Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide

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NASA/TM-2004-2 1 3 1 5 1
Fire, Explosion, Compatibility and

Safety Hazards of Hydrogen Peroxide
Dennis D. Davis
Louis A. Dee
Ben Greene
Steven D. Hornung
Mark B. McClure
Kurt A. Rathgeber
White Sands Test Facility

Las Cruces, New Mexico
January 2005
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NASA/TM-2004-213151
Fire, Explosion, Compatibility and

Safety Hazardsof Hydrogen Peroxide
Dennis D. Davis
Louis A. Dee
Ben Greene
Steven D. Hornung
Mark B. McClure
Kurt A. Rathgeber
While Sands Test Facility

Las Cruces, New Mexico
National Aeronautics
and Space Administration
Johnson Space Center

Houston, Texas 77058-3696
January 2005
ACKNOWLEDGEMENTS
The Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide manual was prepared under
NASA contract at White Sands Test Facility in Las Cruces, New Mexico, by the following team
members:
Project Manager
David L. Baker
Project Leader
Ben Greene
Technology and Technical Services Section

Elizabeth Ball
Laura Cerecerez
David Huskey
Lori Kubinski
Jennifer Sterling
Krista West
Della Wilson
WSTF Technical Library
Experts in the field of propellant hazards, both at White Sands Test Facility and other organizations,
helped review and revise this document prior to publication. The expertise of these professionals is
gratefully recognized.
Available from:

NASA Center for Aerospace Information National Technical Information Service

7121 Standard Drive 5285 Port Royal Road

Hanover, MD 21076-1320 Springfield, VA 22161
This report is also available in electronic form at http://ston.jsc.nasa.gov/collections/TRS

I ABSTRACT
High-test hydrogen peroxide (HP) is an energetic liquid with widespread use in a variety of industrial and
aerospace applications. In recent years, there has been increased interest in its use as a "green" or
environmentally benign propellant in spacecraft and defense propulsion and power systems. HP, however,
can be a significant hazard if not properly handled. In addition, hydrogen peroxide is unstable when
exposed to trace contaminants, which may catalyze decomposition and result in violent thermal runaway.
Many advanced and newly developed alloys, polymers, composites and other construction materials (such
as those used in tankage and piping systems) have not been tested for compatibility with hydrogen
peroxide. The reliability of extrapolating from short-term compatibility test results to long-term
compatibility has not yet been fully assessed. Therefore, the users and designers of HP systems must be
aware of these hazards and unknowns and take the appropriate precautions.
PREFACE
' White Sands Test Facility has initiated a hydrogen peroxide hazards characterization program. The goals
of this program are to summarize the existing hazards of HP in one document and conduct additional tests
where needs are identified. Valuable reference sources existed before 1970, but in following years, there
was little work done with hydrogen peroxide until new interest was sparked in the 1990s. The subjects
addressed in this manual are fire, explosion, compatibility hazards and overall safety considerations.
Although a substantial amount of information has been compiled in this manual from numerous sources,
testing in several areas is still being conducted and is anticipated to continue for several years. Perhaps of
greatest importance is the testing of a material's compatibility and extrapolation of this data to useful
' engineering information for the design, construction and operation of hydrogen peroxide systems.
However, the need to prepare and release an HP manual with the current compiled information is evident,
and the decision was made to do so with periodic updates as new data are obtained.
Many additional tests are required to meet the HP hazards program objectives. These tests are anticipated
to yield useful data that will be incorporated into subsequent revisions of the original edition. It is our
goal that this manual provide a guide for scientific and engineering evaluations, as well as solutions to HP
propellant and materials hazards issues.
The user of this manual will note that data herein are most often reported with their corresponding
original units. Conversion factors are provided in the Appendix for the user of this manual as needed.
Lack of consistency with the International System of Units (S1 units) is unavoidable, especially with
original data published many years ago. Unless otherwise specified, HP concentrations reported in
' percent refer to weight percent.
t
t
CONTENTS
SECTION PAGE
Abstract.................................................................................................................................. i
Preface.................................................................................................................................... i
1.0 Hydrogen Peroxide Hazards Introduction .................................................................. 1-1

1.1 Hydrogen Peroxide as a Green Propellant ....................................................................... 1-2
1.2 Early Propulsion and Power Systems .............................................................................. 1-2
1 .3 About This Manual .......................................................................................................... 1-4
1.4 Hazard Assessment .......................................................................................................... 1-5
1.4.1 Hazards Resulting From Fire ................................................................................. 1-6
1.4.2 Hazards Resulting From Explosion ........................................................................ 1-6
1 .5 Overall Hazard ................................................................................................................. 1-8
1 .6 References ........................................................................................................................ 1 -9
2.0 Fire and Explosion Hazards .......................................................................................... 2-1

2.1 Fire Parameters of Hydrogen Peroxide ............................................................................ 2-1
2.1.1 Introduction ............................................................................................................. 2-1
2.1.2 Thermodynamics ..................................................................................................... 2-1
2.1.3 Flash and Fire Points ............................................................................................... 2-2
2.1.4 Minimum Ignition Energies and Ignition Sources .................................................. 2-2

2.2 Hypergolic Behavior of HP Mixtures .............................................................................. 2-2
2.2.1 Heterogeneous Catalysts ......................................................................................... 2-3
2.2.2 Homogeneous Catalysts .......................................................................................... 2-4
2.2.3 Hybrids .................................................................................................................... 2-5
2.3 Hydrogen Peroxide Explosions ........................................................................................ 2-5
2.3.1 Deflagrations and Detonations ................................................................................ 2-5
2.3.2 Adiabetic Compression ........................................................................................... 2-6
2.3.3 Vapor-Phase Explosion Hazards ............................................................................. 2-7
2.3.4 Liquid-Phase Explosion Hazards ............................................................................ 2-9
iii
SECTION PAGE
2.3.5 Hydrogen Peroxide with Additives ......................................................................... 2-15

2.4 Assessment Examples ...................................................................................................... 2-16
2.5 Summary .......................................................................................................................... 2-17
2.6 References ........................................................................................ .................... ............ 2-18
3.0 Materials and Reactivity ............................................................................................... 3-1
3.1 Decomposition of HP ....................................................................................................... 3-2
3. 1.1 Methods of Measuring Decomposition Active Oxygen Loss .............................. 3-4
3.1.2 Methods of Measuring DecompositionMicrocalorimetry .................................. 3-5
3.1.3 Stability ................................................................................................................... 3-9
3.2 Chemical Reaction Hazards ............................................................................................. 3-9
3.2.1 Reactions with Inorganic Materials ........................................................................ 3-10
3.2.2 Reactions with Organic Materials ........................................................................... 3-11

3.2.3 Stabilizers ................................................................................................................ 3-12
3.2.4 Passivation .............................................................................................................. 3-14
3.3 Guide to Data Tables ....................................................................................................... 3-22
3.4 Data Tables ...................................................................................................................... 3-22

3.5 Assessment Examples ...................................................................................................... 3-68
3.6 References ........................................................................................................................ 3-68
4.0 Personnel and Environmental Hazards ....................................................................... 4-1
4.1 Exposure Guidelines ........................................................................................................ 4-1
4. 1.1 Threshold Limit Values of the ACGIH .................................................................. 4-1

4.1.2 Final Rule Limits of OSHA .................................................................................... 4-2
4.1.3 Recommendations of NIOSH ................................................................................. 4-2
4.1.4 SARA Title III ........................................................................................................ 4-3

4.1.5 Spacecraft Maximum Allowable Concentrations ................................................... 4-3
4.2 Toxicity ............................................................................................................................ 4-4
4.2.1 Routes and Results of Exposure to Hydrogen Peroxide ......................................... 4-5
ry
SECTION PAGE
4.2.2 Teratogenic and Reproductive Toxicity .................................................................. 4-6
4.2.3 Carcinogenicity ....................................................................................................... 4-7
4.3 Exposure Remediation and Control ................................................................................. 4-7
4.3.1 Personnel Protection ............................................................................................... 4-7
4.3.2 Medical Aid ............................................................................................................ 4-8
4.3.3 Fire Fighting ............................................................................................................ 4-11
4.3.4 Spills ....................................................................................................................... 4-16
4.4 Environmental Fate of HP ............................................................................................... 4-17
4.4.1 Soil and Sediment ................................................................................................... 4-17
4.4.2 Atmosphere ............................................................................................................. 4-18
4.4.3 Aquatic .................................................................................................................... 4-18
4.5 HP Handling ...................................................................................... ............................... 4-18
4.5.1 Personal Protective Equipment ............................................................................... 4-18
4.5.2 Respiratory Protection ............................................................................................ 4-21
4.5.3 Monitoring Equipment ............................................................................................ 4-23
4.6 Engineering Design .......................................................................................................... 4-26
4.6.1 Process Safety Management ................................................................................... 4-27
4.6.2 Assembly Guidelines .............................................................................................. 4-28
4.7 Cleaning and Passivation ................................................................................................. 4-29
4.7.1 Procedures for the Passivation of Glassware .......................................................... 4-30
4.7.2 Procedures for Passivation of Metals and Materials ............................................... 4-31
4.8 Laboratory Design ........................................................................................................... 4-37
4.8.1 Building Codes ........................................................................................................ 4-37
4.8.2 Other Legal Requirements and Codes .................................................................... 4-37
4.8.3 Environmental ......................................................................................................... 4-37
4.8.4 Controlling HP Vapor Emissions ........................................................................... 4-38
4.8.5 Controlling Liquid Effluents ................................................................................... 4-38
v
SECTION PAGE
4.8.6 Design Features for an HP Testing Laboratory ...................................................... 4-38
4.9 Storage of HP ................................................................................................................... 4-39
4.9.1 Storage Areas and Containers ................................................................................. 4-39
4.10 Shipping of HP (DOT) ................................................................................................... 4-46
4. 10.1 Proper Shipping Name .......................................................................................... 4-50
4.10.2 Packaging Containers ............................................................................................ 4-50

4.11 Waste Disposal ............................................................................................................... 4-52
4.12 Regulatory Enforcement ................................................................................................ 4-52
4.12.1 Department of Transportation (DOT) ................................................................... 4-52
4.12.2 Environmental Protection Agency (EPA) ............................................................. 4-53
4.12.3 OSHA .................................................................................................................... 4-54
4.13 Assessment Examples .................................................................................................... 4-57
4.13.1 Assessment Example 1 ......................................................................................... 4-57
4.14 References ...................................................................................................................... 4-63
Appendix A: Chemical, Physical, and Thermodynamic Properties of

Hydrogen Peroxide Propellants .......................................................................................... A-1
References.............................................................................................................................. A-13
Appendix B: Anal y tical Spectroscopy of Hydrogen Peroxide ......................................... B-1
References.............................................................................................................................. B-7
Appendix C: Hydrogen Peroxide Specifications ............................................................... C-1
References.............................................................................................................................. C-7
Appendix D: Quantitative Determination of Hydrogen Peroxide ................................... D-1
References.............................................................................................................................. D-12
Appendix E: Hydrogen Peroxide Accidents, Close Calls, and Lessons Learned........... E-1
References.............................................................................................................................. E-19
Appendix F: Compatibility Tables from FMC Bulletin 104 ............................................ F-1
V1

References .......... ......................................................................................................... F-22

TABLE PAGE
L I Exposure Limits ............................................................................................................... 1-2
2.1 Heat of Decomposition at 298.16 K and Theoretical Flame Temperature at One

Atmosphere of various Hydrogen Peroxide Concentrations ........................................... 2-1
2.2 Theoretical Combustion Temperatures of Hydrogen Peroxide with various Materials

at One Atmosphere Pressure ........................................................................................... 2-2
3.1 Material reactivity in 83 Percent Solvay HP, 25° C ........................................................ 3-6
3.2 Criteria for Classification of Materials for HP Service on the Basis of Laboratory
Tests ................................................................................................................................ 3-19
3.3 Compatibility of 90% HP with Aluminum AlIoys .......................................................... 3-23
3.4 Compatibility of 98% HP with Aluminum Alloys .......................................................... 3-26
3.5 Compatibility of 90% HP with Stainless Steel Alloys .................................................... 3-27
3.6 Compatibility of 98% HP with Stainless Steel Alloys .................................................... 3-30
3.7 Compatibility of 90% Hp with Pure Metals .................................................................... 3-31
3.8 Compatibility of 90% HP with Miscellaneous Alloys ..................................................... 3-32
3.9 Compatibility of 90% HP with Polyethylene and Halogenated Polyethylene Types of

Plastics ............................................................................................................................. 3-35
3.10 Compatibility of 90% HP with Polyvinylchloride and Copolymers ............................. 3-41
3.11 Compatibility of 90% HP with Silicone Rubbers .......................................................... 3-44
3.12 Compatibility of 90% HP with Rubbers and Plastics-General ...................................... 3-47
3.13 Compatibility of 90% HP with Laminates, Diaphragms and Adhesives ....................... 3-49
3.14 Compatibility of 98% HP with Various Plastics ........................................................... 3-51
3.15 Compatibility of 90% HP with Lubricants .................................................................... 3-53
3.16 Compatibility of 90% HP with Ceramics, Refractories and Miscellaneous Materials.. 3-56
3.17 Compatibility of 90% HP with Porous Materials .......................................................... 3-58
3.18 Results of Evaluation of Protective Coatings for 90% HP Service ............................... 3-60
3.19 Results pf Physical and Chemical Evaluation of Joint Sealing Compounds with 90%
HP .................................................................................................................................. 3-64
4.1 ACGIH Adopted Values for Hydrogen Peroxide .......................................................... 4-2
vii
TABLE PAGE
4.2 Carcinogenicity of HP ................................................................................................... 4-7
4.3 Protective Clothing Summary ........................................................................................ 4 -20
Appendix A
A.1 Physical Constants ......................................................................................................... A-1
A.2 Conversion Factors ........................................................................................................ A-2
A.3 Variation of HP Density (g/cm 3) with Concentration at 298 K ..................................... A-3
A.4 Electrical Conductivity at 298 K ................................................................................... A-4
A.5 Heat Capacity of Gaseous HP Between 298.16 K and 1500 K ..................................... A-6
A.6 Mean Heat Capacity of Hydrogen Peroxide Solutions Between 273 K and 300.0 K ... A-6
A.7 Heat Capacity of Solid HP Between 12 K and 270 K ................................................... A-7
A.8 Heat and Free Energy of Formation of HP in Solution at 298.16 K ............................. A-8
A.9 Refractive Index of HP Solutions at 298 K for the Sodium-D Line .............................. A-8
A.10Total Heat of Vaporization of HP Water Solutions .................................................... A-9
A. I I Dielectric Constant of 90, 98, and 100 Percent HP ....................................................... A-9
A.12 Volume of Oxygen Released by 1 Liter of HP at Atmosphere and 273 K .................... A-9
A.13 Density of 90 Weight Percent HP .................................................................................. A-11
A.14Density of 98 Weight Percent H2O2 .............................................................................. A-11
A.15Total Vapor Pressure of HPH 2O Solutions ................................................................ A-12
A.16Viscosity of 90 Percent HP ............................................................................................ A-13
A. 17 Viscosity of 98 Percent HP ............................................................................................ A-13
Appendix B
B.1 Causes for HP Discoloration ......................................................................................... B-2
Appendix C
C.1 Inactive Specifications ................................................................................................... C-3
C.2 Item Description May 21, 1997 ..................................................................................... C-3
C.3 Item Description June 9, 1999 ....................................................................................... C-4
CA Item Description November 5, 1999 ............................................................................. C-4
viu
TABLE PAGE
C.5 MIL-PRF-16005F (proposed) ........................................................................................ C-5
C.6 MIL-PRF-16005F .......................................................................................................... C-6
C.7 Degussa PROPULSE Products ...................................................................................... C-6
Appendix F
F.1 Criteria for Classification of Materials for H2O2 Service on the Basis of Laboratory
Tests............................................................................................................................... F-2
F.2 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Metals
AltiminurnAlloys .......................................................................................................... F-3
F.3 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Stainless Steel
Alloys............................................................................................................................. F-4
F.4 Results of Compatibility Tests with 90% Hydrogen Peroxide Pure Metals .................. F-5
F.5 Results of Compatibility Tests with 90% Hydrogen Peroxide Metals—

MiscellaneousAlloys ..................................................................................................... F-6
F.6 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Plastics—
Polyethylene and Hologenated (sic) Polyethylene Types ............................................. F-7
F.7 Results of Compatibility Tests with 90% Hydrogen Peroxide Plastics,

Polyvinylchloride and Co-Polymer ............................................................................... F-9
F.8 Results of Compatibility Tests with 90% Hydrogen Peroxide Plastics—Silicone

RubberCompounds ....................................................................................................... F-10
F.9 Results of Compatibility Tests with 90% Hydrogen Peroxide Plastics—General........ F-1 1
F.10 Results of Compatibility Tests with 90% Hydrogen Peroxide Plastics—Laminates,

Diaphragm Materials and Adhesives ............................................................................. F-12
F.1 I Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Porous
Materials........................................................................................................................ F-13
F.12 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Lubricants......... F-14
F.13 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Ceramics,
Refractories and Miscellaneous Materials ..................................................................... F-16
F.14 Results of Evaluation of Protective Coatings for Becco 90% H 2O2 Service ................. F-17
F.15 Evaluation of Clothing Materials for Contact with Becco 90% Hydrogen Peroxide.... F-18
F.16 Clothing Material Not Suitable for Use When Handling Becco 90% Hydrogen
Peroxide......................................................................................................................... F-18
ix
TABLE PAGE
F.17 Protective Clothing and Accessories for Personnel Handling Concentrated Hydrogen
Peroxide......................................................................................................................... F-19
F.18 Outdoor Winter-Weight Protective Clothing for Wear by Personnel at H2O2

HandlingAreas .............................................................................................................. F-19
F.19 Recommended Joint Sealing Compounds for Use with Becco 90% and 98%
HydrogenPeroxide ........................................................................................................ F-20
F.20 Results of Compatibility Tests with Becco 90% Hydrogen Peroxide Aluminum,
Stainless Steel, Plastic ................................................................................................... F-21
FIGURE PAGE
2.1 Effect of Variation of Diluent Gas Composition on Ignition Limit lit Hydrogen
Peroxide-Oxygen-Water Vapor System ........................................................................ 2-8
2.2 Effect of Total Pressure on Ignition Limit ..................................................................... 2-10
2.3 Ignition Limit of Hydrogen Peroxide at Pressures Above Atmosphere ....................... 2-11
2.4 Combination of Temperature and Liquid Composition Producing Equilibrium

Vapors in Explosive Region .......................................................................................... 2-11
2.5 Results of 2-1n. Steel Tube Tests as a Function of Hydrogen Peroxide Temperature
andConcentration .......................................................................................................... 2-14
3.1 Temperature Dependence of reaction rate for Al 5254, SS316, and Electropolished
SS316 with 90 Percent HP ............................................................................................. 3-8
3.2 Arrhenius Plot for 90 Percent Hydrogen Peroxide Decomposition on Al 5254,

SS316, and Electropolished SS316 ................................................................................ 3-8
3.3 Baseline Heat Rates from 90.5 Percent HP in Passivated Glass Containers ................. 3-15
Appendix B
B. l Ultraviolet Absorption Spectrim ................................................................................... B-3
B.2 Raman Spectrum ............................................................................................................ B-3
B.3 Near-Infrared Spectrum of 98% HP .............................................................................. B-4
B.4 Near-Infrared Spectrum of 90% HP .............................................................................. B-4
B.5 Near-Infrared Spectrum of Deionized Water ................................................................. B-5
B.6 Mid-Infrared Spectrum of 98% HP ............................................................................... B-5
B.7 Mid-Infrared Spectrum of 90% HP ............................................................................... B-6
B.8 Mid-Infrared Spectrum of Deionized Water .................................................................. B-6
x

FIGURE PAGE
Appendix D
D. I Apparatus for the Unattended Decomposition of HP ....................................... I.... D-8
D.2 Apparatus for the Collection of Total Carbon in HP ............................................ D-12
X1
Xii
v
I Section 1.0
Hydrogen Peroxide Hazards Introduction
I
1.0 Hydrogen Peroxide Hazards Introduction
I
1.1 Hydrogen Peroxide as a Green Propellant
In recent years, there has been increasing interest in space propellants that are environmentally less
damaging and have reduced toxicity when compared to commonly used solid propellants (ammonium
perchlorate) and liquid hypergols (monomethylhydrazine/nitrogen tetroxide) (Mavis 2000, EPA 2001).
Ideally, green propellants are easier and safer to handle than conventional propellants, and are expected to
drive down the costs associated with propellant transport and storage, and costs in spacecraft
development, ground support and operations. HP has been regarded as a candidate green propellant
because of its relatively benign exhaust products and relatively low vapor pressure when compared to
propellant hydrazine fuels and nitrogen tetroxide oxidizers in bipropellant systems and also when
compared to hydrazine in monopropellant systems. Approximately 1.3 billion lb of HP are used annually
in various industries in North America. HP can be used safely if proper safety precautions are followed.
To reduce air pollution during spacecraft launches and flight, the exhaust products must be benign. HP
produces water and oxygen as a result of its catalytic decomposition (such as might occur when it is used
as a gas generator):
H202(1) —> H 20(l) +''/zO2(g) (1.1)
Monopropellant HP systems produce environmentally friendly water and oxygen as exhaust products. I
When HP reacts in a bipropellant system with hydrocarbon-based fuels such as kerosene, the products of
combustion will include water, carbon monoxide (CO), carbon dioxide (CO,) and other incomplete
products of combustion that are not innocuous in the environment. For example, in the atmosphere CO, is
a naturally occurring "greenhouse" gas. But when produced and released in large quantities, such as in the
combustion of fossil fuels, it can alter climates and contribute to global warming (EPA 2001). Rocket
exhaust products, however, may produce effects that are vanishingly small when compared with other
anthropogenic sources such as aircraft propulsion and fossil fuel combustion, and other natural sources
such as volcanoes, oceans and stratospheric methane oxidation (Lo 2001). Carbon-containing exhausts
also contribute to undesirable plume signatures, such as in defense or classified applications
(Searles 2001).
When HP is used in a bipropellant or hypergolic system where the fuel contains a soluble or dispersable
catalyst, such as manganese acetate or manganese dioxide, the environmental fate and toxicology of that
catalyst must also be considered. A toxicological profile for manganese, a frequently used catalyst in HP
bipropellant systems, has recently been published (ATSDR 2000).
Spilled HP is initially harmful to the environment, but is rapidly decomposed to environmentally friendly
water and oxygen. Toxicity data for exposure of aquatic organisms to HP have been reported and are
discussed in detail in Section 4. On the other hand, HP has been used as a supplemental oxygen source in
the bioremediation of hydrocarbon fuel-contaminated soils (Jacobi 2001, Petigara 2002).
Toxicity is another aspect of "greenness." Table 1.1 shows the exposure limits established by the
American Conference of Governmental Industrial Hygienists (ACGIH) for HP and other common liquid
propellants (ACGIH 2003).
Table 1.1
Exposure Limits (ACGIH 2003)
Propellant TLV-TWA*
(pom)
Hydrogen peroxide (HP) 1
Nitrogen dioxide (NO,) 1
1 Hydrazine
Monomethylhydrazine (MMH)
Unsymmetrical dimethylhydrazine (UDMH)
Methanol
Ethanol
0.01
0.01
0.01
200
1,000
Hydrogen No TLV-TWA listed
*TLV-TWA = Threshold Limit Value-Time Weighted Average
r The allowable exposure limit to HP is not insignificant because the Threshold Limit Value-Time
Weighted Average (TLV-TWA) is comparable to nitrogen dioxide (NO,). Although HP is considered a
green replacement for NOS, its comparative greenness from a toxicity standpoint may only refer to the
inhalation toxicity (Lo 2001). For acute toxicity effects, a 70 percent HP solution has an oral LDsp (the
dosage that, when administered orally, kills 50 percent of the test population) of 75 mg/kg (highly toxic)
in the male rat. The dermal LDso is 690 mg/kg (moderately toxic) in the rabbit. Inhalation data are
difficult to interpret because the vapor and aerosol concentrations of the exposure atmosphere are not
t
clearly understood. The vapor pressure of 98 percent HP (0.2799 KPa at 77 °F (25 °C)) is low by a factor
of about 0.0023 compared to NO, (119.8 KPa at 77 °F (25 °C)). As a result, HP vapor concentrations
relative to NO, are more difficult to reach under similar conditions (Schumb 1955, CPIA 1994).
However, high aerosol concentrations of HP can be lethal (Mattie 1999). Toxicological properties of HP
are discussed in detail in Section 4.
From a health and safety standpoint, HP is corrosive to the eyes, skin, nose and lungs. It can violently
1 decompose with the rapid evolution of heat and steam when contaminated. It is corrosive to the skin and
eyes if there is contact and can cause embolisms in the body if ingested or injected. Accidents and injuries
have occurred as a result of HP explosions and exposures due to improper handling. Health and safety
aspects of HP are discussed in detail in Section 4.
1.2 Early Propulsion and Power Systems
Use of HP as an energy source in propulsion and power systems has long been recognized, but the major
problem has been how to control the release of energy (Harlow 1999). HP is not typically regarded as a
hypergol, but derives its utility from catalytic decomposition by transition metals to produce high
temperature steam and oxygen. Although the decomposition of HP alone produces power that can be used
in monopropellant applications, the output is increased by the addition of a fuel that reacted with the
oxygen produced in the decomposition reaction in bipropellant applications. Ideally, this fuel would be
hypergolic at the steam/oxygen mixture concentrations and temperatures created by the catalytic
reduction of HP. The physical and chemical properties of HP were understood enough by the early 1930s
to put it into practical use as a propellant. Reviews of HP use in early propulsion and power systems have
been published elsewhere (Walter 1954, Schumb 1955, Bloom 1957, NAVAER 1957, Stokes 1998,
Wernimont 1999).
I I-?
One example of how HP was used with another fuel occurred in Germany, where it was used for catapult
launching and for steam generation to drive the pumps of the A-4 (V-2) rocket (Schumb 1955). An
aqueous calcium permanganate solution was sprayed continuously on HP in a decomposition chamber.
This formed finely divided manganese oxide catalyst particles. The V-2 rocket used the decomposed HP
to power fuel pumps delivering liquid oxygen and 75 percent ethanol/25 percent water into the
combustion chamber. In another case, the German V-1 flying bomb was launched from the ground by a
piston-type catapult and was powered by HP decomposed with sodium or calcium permanganate solution.
Each launching used about 220 lb (100 kg) of 80 percent HP and 1 1 lb (5 kg) of calcium permanganate
solution. The two fluids, when sprayed into the breach, generated pressure to activate a piston that
launched the projectile.
Uses of HP for German submarine propulsion were developed but not implemented because of the
shortage of HP in World War 11 (Schumb 1955, NAVAER 1957). By the end of World War 11, the
German Walter Cycle Submarine (Type 18-X) was being constructed for a submerged speed of 24 knots,
with a capacity for about 90 tons of HP. In the propulsion system, HP was pumped into a catalyst
chamber where it was decomposed and fed into a combustion chamber. Here, the oxygen was used to
burn diesel oil. The combustion gases were then cooled with water and used to drive a gas turbine. Details
of the German HP submarines have been published (McKee 1946).
At one time, the U.S. Navy projected the construction of an HP-powered submarine (Blackman 1950). It
was later disclosed that the United Kingdom launched submarines using HP propulsion systems first in
1954 (Schumb 1955). Many accounts of early HP usage by U.S. agencies including the Navy and Air
Force have also been reported (Wolf and McNally 1963).
Torpedoes have been powered using HP propellants (Schumb 1955). A variety of German torpedoes were
developed to use 80 percent HP as an oxidizer with decalin (decahydronaphthalene) as the fuel.
Combustion was initiated by injecting 80 percent hydrazine hydrate containing dissolved copper
compounds as a catalyst, and this fuel mixture was spontaneously ignited with HP. The U.S. Navy also
developed torpedoes with HP propulsion systems, and details on many of these programs and related
accidents were reported (Wolf and McNally 1963).
1n 1946, work started in the UK on the DeHavilland Sprite aircraft that used HP as a monopropellant
(Rothmund 1999). In 1952, the DeHavilland Spectre was used with kerosene and HP. Kerosene and HP
were used as propellants in the UK Gamma fighter aircraft. The DeHavilland Engine Company was
involved in the development of rocket-assisted take off (RATO) propulsion systems suitable for aircraft.
Some of these used HP, including the Sprite engine, which first flew in a Comet in 1951. The Super
Sprite evolved and was in active service with the Royal Air Force in RATO application for the Vickers
Valiant Mk VV bomber. Other launch vehicles in the UK, including the Black Knight and the Black
Arrow, used HP in their propulsion systems (Gould 1991). Bell Aerospace developed a Man Rocket Belt
for the U.S. Army Transportation Corps that used 90 percent HP and first propelled a man in 1961
(Wolf and McNally 1963).
The fictional futuristic "Moonraker" rocket used HP mixed with potassium permanganate to generate
steam. This steam drove turbine pumps that delivered fluorine and hydrogen to the rocket's combustion
chamber (Fleming 1955).
Between 1933 and 1963, the United States used HP in propulsion and power systems. These included the
Mk 16 Mods 6 and 7 torpedoes, Navol (a torpedo alcohol), and the X-1 (a midget submarine using a
diesel engine with 90 percent HP as an oxidizer). The FJ4 aircraft used a rocket engine powered by JP-4
and 90 percent HP. The Douglas D-558 and the Bell Aircraft X-1 used HP to drive pumps. The North
American X-15 rocket aircraft, first flown in 1959, was powered by a liquid propellant engine with a
1-3
pump driven by 90 percent HP flowing throu b gh a silver screen catalyst
J chamber. The Centaur missile
used 90 percent 11P for attitude control and to drive turbopumps on the liquid oxygen and liquid hydrogen
propellant tanks. The Scout missile also used HP in its altitude control system (Wolf and McNally 1963).
HP drives turbines on Soyuz launchers and powers monopropellant thrusters on Soyuz descent modules
(Frolov 1998). The Beal BA-2 used an HP/kerosene propulsion system. A bibliography of HP propellant
applications is published by the Chemical Propulsion Information Agency (CPIA 1995). A more recent
and complete history of propellants including HP in aerospace applications has also been published
(Isakowitz 2000).
1.3 About This Manual
Recent environmentally friendly propellants and improved propulsion systems performance initiatives
have identified high-test HP as a candidate propellant for propulsion and power systems. However, HP
can be hazardous and can result in catastrophic incidents, many of which have been reported over the
years. HP is toxic and corrosive, is a strong oxidizing agent with limited stability, and can slowly or
suddenly decompose violently in the presence of a suitable catalyst. This can result in the evolution of
heat and steam that generate high pressures. However, like any other energetic material, thorough hazard
assessments and engineering controls can allow HP and HP systems to be used safely.
The Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide manual was developed at
W STF to consolidate and update HP hazard assessments. This manual covers a broad range of topics
including fire and explosion hazards, material and fluid compatibility, materials selection, personnel and
environmental hazards, specifications and analytical methods. This manual is intended to be a useful
guide for engineers in selecting materials for use in HP systems. This manual also includes
documentation and discussion of accidents and incidents involving HP and examines the applicability of
certain regulatory compliance documents.
Examples of recent hazard assessments for other propellants that have proven to be useful resources for
the aerospace propellants community are the NASA and American Institute of Aeronautics and
Astronautics (AIAA) hazards manuals on hydrazine, monomethylhydrazine (MMH) and dinitrogen
' ttroxide (NTO) (AIAA 1999a and 1999b). There are several excellent sources of HP hazards
assessments, but they are outdated and may not adequately address recent concerns or current regulatory
requirements (Rocketdyne 1967). They also may not use data and other information necessary for modern
materials selection processes. Some of the hazards, precautions and benefits associated with HP have
been discussed at recent conferences (Proceedings 1998, 1999, 2000, 2001 and 2002). Recognizing the
need for a current reference, a program was initiated at WSTF to produce a modern HP hazards manual.
1 This manual summarizes and references existing hazards data for use of HP propellants and addresses
fire, explosion, materials compatibility and personnel and environmental hazards. Reference information
such as chemical and physical properties, analytical spectroscopy, fluid specifications and analytical
chemistry methods associated with HP propellants are included to aid the user. The manual provides
useful information and assessment examples including sample exercises and calculations to:
• Assess hazards
• Mitigate risks
• Make material selections and assess compatibility issues
• Reduce safety and health risks
• Reduce environmental contamination
1-4
a
This manual presents information that designers, builders and users of HP systems and persons working
with HP can use to avoid or resolve HP hazards. Pertinent research and data are summarized and
presented in a user-friendly way.
New information obtained on the HP hazards will be incorporated into this manual. Every effort will be
made to maintain a complete, up-to-date hazards manual. Users of this manual are cautioned, however,
that although every reasonable effort has been made to present accurate information, the authors and
publisher make no warranty nor do they assume legal responsibility for its correctness or completeness.
Users are urged to assess each situation carefully and to use the information in this manual as a guide.
1.4 Hazard Assessment
Every HP system and application require a hazard assessment. Potential HP applications may be
addressed by mandatory or other applicable codes issued by OSHA, NFPA, EPA and DOT. Since every
system and application may be unique, it is the responsibility of each facility to accurately assess the
hazards. This section presents guidelines for determining if a particular hazard exists.
NASA's Safety Policy requires the use of an organized and systematic approach to identifying and
controlling hazards. Approaches are provided in this manual to aid decision-makers in their
responsibilities for performing HP hazard assessments. These hazard analysis procedures are based on a
method used successfully to evaluate hazards in hydrazine, MMH and NTO hypergol systems, and in
oxygen components and systems. Use of the procedures is demonstrated by working through simple
scenarios. The procedures can also be used as failure analysis tools.
For the purposes of this manual, a hazard means any condition that could result in:
• Injury to personnel
• Damage to property or equipment
• Delay or loss of mission or objective
• Damage to the environment
The assessment of risks associated with a hazard is integral to the hazard assessment process. A risk
means a combination of the probability of occurrence and severity of the consequences of an adverse
condition. A successful hazard assessment follows the steps below:
1. Identifying the hazards.

2. Assessing the risks by considering their probability and severity.
3. Evaluating if the risks are acceptable.
4. If risks are not acceptable, managing them by applying engineering and administrative controls,
upgrading designs, and finally by using personal protective equipment that will minimize the
probability and severity of the risks.
Criteria for potential hazards and the corresponding effects produced are discussed in general terms in this
introductory section and, in subsequent sections, specific hazards of HP are described more thoroughly to
better familiarize the reader. Users of this manual may find there is not always a clear delineation between
hazards; for example, fire and explosion hazards may overlap with each other and with personnel and
environmental hazards. The structure of this manual is not intended to present an impediment to the
hazard assessment process. Examples of detailed hazard assessments are given in each subsequent section
of this manual.
l-5
1 Because of the chemical, physical and toxicological properties of HP, when assessing related hazards one
must consider the general hazards associated with energetic materials, propulsion systems and associated
ground support systems and activities. This manual addresses the following hazards:
• Hazards resulting from fire

• Hazards resulting from explosion
• Material compatibility and reactivity
• Personnel exposure and environmental impact
1.4.1 Hazards Resulting from Fire
Fire is a rapid chemical reaction that produces heat and light. To assess a possible fire hazard, the
following information must be known:
1 • Phases, pressure and temperature of HP

• Atmosphere (HP, diluents, incompatible or reactive materials) and corresponding concentrations
• Ignition sources and the amount of energy that can be released by each source
• HP liquid and vapor are nonflammable, so there is no potential fire hazard from this alone;
flammable, combustible, or reactive material must be present for a fire with I iP to occur
The occurrence of a fire may not constitute a hazard. Fire hazards are determined by assessing the effects
produced by the fire on the system or environment. For the purposes of this manual, the primary effect of
a fire is heat; the rate and duration of the heat released determine the severity of a fire.
1.4.2 Hazards Resulting from Explosion
"An explosion can be viewed as a rapid equilibration of a high-pressure gas with the environment. The
key word in this definition is `rapid.' The equilibration must be so fast that the energy contained in the
high-pressure gas is dissipated into a shock wave" (Grelicki 1976). This manual assumes an explosive
event is produced either directly or indirectly by the release of chemical energy. Explosions are divided
into categories that represent processes HP can undergo and, in some cases, generate high pressures:
• Detonation
• Deflagration
• Thermochemical
• Decomposition generating excessive pressure
Detonation is a chemical reaction coupled with a multiple shock-wave system that propagates at
supersonic velocities in reference to the unreacted vapor (liquid HP does not detonate). To assess an
t explosion hazard due to detonation, the following information must be known:
• Pressure and temperature of HP vapor

• Atmosphere (HP, diluents, incompatible or reactive materials) and their concentrations
• Ignition sources and the amount of energy released by the source
• Type of confinement
To determine if an explosion hazard from a detonation exists, the resulting effects produced by the
detonation must be assessed. The occurrence of a detonation does not necessarily mean an actual
explosion hazard exists. When a detonation occurs, an actual explosion hazard only exists if the
1-6
environment or system can be damaged. On the other hand, when the environment or system can contain
the detonation without loss of environment or system integrity, no explosion hazard exists.
1.4.2.1 Hazards Resulting from Thermal-Chemical Reactions

A thermal-chemical process for HP is a confined exothermic chemical reaction that generates heat and
pressure. To assess an explosion hazard due to a thermal-chemical reaction, the following information
must be known:
• Amount (mass, volume) and concentration of HP (percent)

• Phases and temperatures
• Atmosphere (diluents, incompatible or reactive materials) and corresponding concentrations
• Materials in contact with HP liquid and/or vapor and corresponding surface areas
• Rate of HP decomposition in the bulk liquid
• System thermal capacity and heat transfer properties
• System pressure and gas venting limitations
HP typically undergoes two types of thermal-chemical processes that generate heat and pressure. In one
case, HP confined in a system reacts under a nonisothermal process; the heat produced by the chemical
reaction is greater than the heat lost from the system. In this case, HP temperature increases and
accelerates the reaction and pressure increase rates. This process is commonly viewed as a thermal
runaway reaction. In the other case, HP confined in a system reacts under an isothermal process, in which
heat generated by the chemical reaction is dissipated by the system and the HP temperature remains
constant. As a result, the reaction and pressure increase rates will also be constant.
HP is also highly susceptible to catalytic decomposition by many materials and contaminants, so the HP
decomposition rate can be accelerated by the material in either a nonisothermal or isothermal event.
Because HP can catalytically decompose in both nonisothermal and isothermal processes, a potential
explosion hazard from a thermal-chemical reaction is always present.
An explosion hazard from a thermal-chemical process exists only when the confining system fails and
releases the generated pressure. The severity of the explosion depends on the total pressure in the system
before failure and the rate at which the generated pressure is subsequently released when the system fails.
When the system uses relief valves and burst disks, an explosion hazard exists when the pressure increase
rate exceeds the venting rate.
Rapid compression of some liquids can lead to an explosion, but HP is not known to explosively
decompose as a result of rapid compression.
1.4.2.2 Material Compatibility or Reactivity

HP affects materials by degrading them and changing their chemical and physical properties. Materials
affect HP by accelerating its decomposition and affecting its purity. To assess a fluid compatibility or
reactivity hazard, the following information must be known:
• Amount (mass, volume) and concentration of HP (percent)

• Phases and temperature
• Atmosphere (diluents, incompatible or reactive materials, surface coatings and passivation, as
applicable) and corresponding concentrations
• Surface areas of the materials on which the HP liquid and vapor are decomposing
1-7
• Chemical composition
P and catalytic
Y activityYof the material
• System thermal capacity and heat transfer properties
• Pressure limitations of the system
• Effects of impurities or stabilizer concentrations of HP on the system
' Material compatibility and reactivity hazards exist when the HP degrades the material, altering its
physical or chemical properties, which can lead to loss of system integrity. Some materials decompose
HP and accelerate the reaction, causing the pressures or temperatures generated to lead to loss of system
integrity. if the HP is used in a catalytic propulsion or power system, system performance can be
compromised by impurities in the HP and cause catalyst poisoning or loss of system performance. A loss
of system performance or integrity can lead to other hazards as previously described, such as fire,
' explosion, exposure and injury of personnel, damage to the environment, loss of mission objective and
damage to equipment and property.
1.4.2.3 Personnel and Environmental Hazards
Personnel and environmental hazards include toxicity of HP to humans and its effects on the environment.
To assess personnel and exposure hazards, the following information must be known:
• Amount (mass, volume) and concentration HP (percent)

• Phases of HP
• Temperature of the environment
• Atmosphere and corresponding concentrations
• Presence of reactive or incompatible materials
' Transportation, use and storage conditions
• Allowable exposure limits
• Applicable laws and regulations
The criteria for a toxicity hazard are exposure/contact time and concentration. Personnel exposure to HP
can be chronic (long-term exposure) or acute (short-term exposure). A toxicity hazard is present when
personnel can be exposed to HP vapor concentrations that exceed established exposure limits. HP is also
toxic when physically contacted, injected, or ingested. However, HP is not classified as carcinogenic to
humans as discussed in Section 4 of this manual.
Spilled or released HP is initially hazardous to the environment. Personnel injury and damage to the
environment can occur as secondary effects to a fire, explosion, or material reactivity event. State, federal
and facility regulations specify HP concentrations that pose an exposure hazard to the environment. The
EPA and DOT have established quantities of HP that, when spilled, require authorities to be notified.
1.5 Overall Hazard
iAn overall hazard is increased by the combination of individual hazards. An example of the cumulative
effect hazards can have is illustrated by an incident involving storage of HP described below:
chemical storage facility contained various service buildings and HP in concentrations

iAranging from 35 to 70 percent. An employee discovered a fire outside of the storage yard
where the drums of 35 percent HP were stored on wooden pallets. The fire department
was called, but the fire spread rapidly after it encompassed drums of nitrocellulose. When
the fire fighters arrived, chemicals were burning, drums were exploding, and potentially
hazardous smoke was threatening exposures. Using water and foam streams, fire fighters
I-8
were able to limit damage to outside storage areas and a section of the warehouse.
Investigators believed the fire ignited spontaneously when HP either spilled or leaked
onto the wooden pallets. The fire then spread to the nitrocellulose, which is highly
flammable, causing the fire to spread rapidly. One fire fighter was injured in the event. A
section of the warehouse roof collapsed as a result of the fire. Damage to the structure
and the contents were estimated at $1,193,000 (NFPA 1992).
From this example, it is clear that a proper hazard assessment considers not only the individual hazards,
but the potential effects of the combined hazards as well.
1.6 References
ACGIH, Threshold Limit Values for- Chemical Substances and Physical Agents & Biological Exposure
Indices. ACGIH 2003. American Conference of Governmental Industrial Hygienists,
Cincinnati, Ohio, (2003).
AIAA. Fire, Explosion, Compatibility, and Safety Hazards ofHypergols —Hydrazine. Special Project
Report AIAA SP-084. American Institute of Aeronautics and Astronautics, Reston, Virginia
(I 999a).
AIAA. Fire, Explosion, Compatibility, and Safety Hazards of Hypergols — Monomethylhydrazine. Special
Project Report, AIAA SP-085. American Institute of Aeronautics and Astronautics, Reston,
Virginia (1999b).
ATSDR, Toxicological Profile .for Manganese, U.S. Department of Health and Human Services, Public
Health Service, Agency for Toxic Substances and Disease Registry. Altlanta, Georgia, September
2000.
Blackman, R. V. B., Ed. Jane's Fighting Ships. McGraw-Hill Book Co., Inc. (1950).
Bloom Jr., R. and N. J. Brunsvold. "Anhydrous Hydrogen Peroxide as a Propellant." Chemical

Engineering Progress, Volume 53, No. 11, November 1957.
CPIA, Hydrogen Peroxide Propellant Applications: A Bibliography. CPIA/LS96-01. Columbia, Maryland

(1995).
CPIA, Liquid Propellant Handbook. Chemical Propulsion Information Agency. CPIA/M4. Columbia,
Maryland (1994).
EPA. Final Report: Characterization and Kinetics of Containincmt Oxidation and Hydrogen Peroxide
Decomposition in the Presence of Subsurface Material. 8823402. Environmental Protection
Agency, Washington, DC (2001).
Fleming, L Moonraker. Jonathan Cape Ltd. Great Britain (1955).
Frolov, A. S. "The Analysis of Possible HTP Applications. " Proceedings of the First Hydrogen Peroxide
Propulsion Workshop, Surrey, UK, July 1998.
Gould, R. D. and J. Harlow. "Black Arrow — The First British Satellite Launcher." 42"`t Congress of the
International Astronautical Federation. IAA91-689, Montreal, Canada, October 1991.
1-9
Grelicki, C. "Fundamentals of Fire and Explosion Hazards Evaluation." AICE Today Series, AICE,
1976:p. 2.
Harlow, J. H. "Hydrogen Peroxide Engines: Early Work on Thermal Ignition at Westcott." Proceedings
of the 2nd International Symposium on Hydrogen Peroxide. Purdue University, West
Lafayette, Indiana, November 1999.
Rocketdyne. Hydrogen Peroxide Handbook. Technical Report AFRPL-TR-67-144, Air Force Rocket
Propulsion Laboratory, Edwards AFB, California (1967).
lsakowitz, S. J., J. B. Hopkins, and J. P. Hopkins. International Reference to Space Launch Systems Third
Edition, American Institute of Aeronautics and Astronautics, Washington, DC (2000).
Jacobi, S. "Hydrogen Peroxide Environmental Impact and Toxicity." Proceedings of the First
International Conference on Green Propellants for Space Propulsion, (Special Publication
SP-484). European Space Agency, Noordwijk, Netherlands, June 2001.
Lo, R. E. "Green High Thrust Propulsion: Cryogenic Solid Propellants." Proceedings of the First
International Conference on Green Propellants for Space Propulsion, (Special Publication
Mattie, D. R. "Toxicity of Rocket Fuels: Comparison of Hydrogen Peroxide with Current Propellants."
JANNAF 28`x' Propellant Development & Characterization Subcommittee and 12"' Safety &
Environmental Protection Subcommittee Joint Meeting, (CPIA Publication 687 Volume 1).
San Diego, California, April 1999.
Mavis, D. N., B. J. German, E. C. Branscome, A. P. Frits, and N. C. Yiakas. "An Evaluation of Green
Propellants for an ICBM Post-Boost Propulsion System." 2000 Missile Sciences Conference.
Defense Technical Information System, Monterey, California (2000).
McKee, L. Mechanical Engineering, Vol. 68, (1946):1045.
NAVAER. Handbook, Field Handling of Concentrated Hydrogen Peroxide (Over 52 Weight Percent
Hydrogen Peroxide). NAVAER 06-25-501, Director of the Chief of the Bureau of Aeronautics
(1957).
NFPA Journal, March/April (1992).
1 Petigara, B., N. Blough, and A. Mignerey. "Mechanisms of Hydrogen Peroxide Decomposition in Soils."
American Chemical Society Environmental Science & Technology, Vol. 36 No. 4 (2002).
Proceedings of the I" Hydrogen Peroxide Propulsion Workshop, Surrey, UK (1998).
Proceedings of the 2nd International Hvdrogen Peroxide Propulsion Conference, Purdue University, West
Lafayette, Indiana (1999).
Proceedings of the Y.d International Hydrogen Peroxide Propulsion Conference, NASA Stennis Space
Center, Mississippi (2000).
Proceedings of the First International Conference on Green Propellants for Space Propulsion. (Special
Publication SP-484). European Space Agency, Noordwijk, Netherlands, (2001).
1-10
Proceedings of the 5 ``' International Hydrogen Propulsion Conference, Purdue University, West
Lafayette, Indiana (2002).
Rothmund, C. and J. H. Harlow. "A History of European Liquid Propellant Rocket Engines for Aircraft."
Proceedings of the 35`h AIAAIASME/SAE/ASEE Joint Propulsion Conference and Exhibit. (AIAA
99-2901). Los Angeles, California. June 1999.
Schumb, W. C., C. N. Satterfield, and R. L. Wentworth. Hydrogen Peroxide. American Chemical Society
Monograph Series. Reinhold Publishing Corporation, New York (1955).
Searles, D. S., M. B. Christopher, J. Sinibaldi, M. J. Venner, and C. W. Johnson. "Soot Production

Characteristics for JP-8, JP-8+100, and JP-10." JANNAF Exhaust Plume Technology
Subcommittee, Nellis AFB, Las Vegas, Nevada, May 2001.
Stokes, P. R. "Hydrogen Peroxide for Power and Propulsion." Proceedings of the P Hydrogen Peroxide
Propulsion Worshop. University of Surrey. Surrey Space Centre, UK, July 1998.
Walter, H. Experience with the Application of Hydrogen Peroxide for Production of Power. Jet
Propulsion, May-June 1954.
Wernimont, E., M. Ventura, G. Garboden, and P. Mullens. "Past and Present Uses of Rocket Grade
Hydrogen Peroxide." Proceedings of the 2"`r International Hydogen Peroxide Propulsion
Conference. Purdue University, West Lafayette, Indiana, November 1999.
Wolf, S. and W. A. McNally. Hydrogen Peroxide as a Torpedo Propellant. Naval Underwater Ordnance
Station, NUOS 360, Newport, Rhode Island (1963).
t
1
Section 2.0
Fire and Explosion Hazards

2.0 Fire and Explosion Hazards
2.1 Fire Parameters of Hydrogen Peroxide
2.1.1 Introduction
Concentrated liquid hydrogen peroxide (HP) (>_ 70 percent) is not flammable in the usual sense; however,
it will undergo a self-sustaining thermal decomposition process manifested as a hot, nearly invisible vapor
decomposition front close to the surface of the liquid. This high-temperature front (1005 K for 90
percent HP and - 1200 K for 98 percent HP) can cause ignition of flammable or combustible materials.
Such a scenario could easily occur in a nearby spill area. In addition, combustible materials (including
clothing) wetted by concentrated HP can, in some cases, ignite very easily. Once an HP thermal
decomposition front is established, it will continue until the liquid is consumed or until diluted or cooled
(Kuntz 1966).
HP can enhance the normal hazards associated with flammable and combustible materials as it
exothermically decomposes and evolves oxygen. The rate of HP decomposition and oxygen evolution
increases with temperature, so the process is self-accelerating by decomposing HP. Even if a flammable
or some combustible material is below its flash point and, therefore, normally considered to be in a safe
region, the heat from decomposition of HP could raise the temperature of the material above its flash
point and convert a safe system into an unsafe one. The presence of oxygen from decomposing HP further
enhances this hazard.
2.1.2 Thermodynamics
I
Table 2.1 shows the heat of decomposition at 298.16 K for various HP concentrations and the theoretical
flame temperatures at one atmosphere pressure. The decomposition reaction is expressed by the following
equation:
HzOz(l) -> H20(1) + ``/202(x) (2.1)
The data in Table 2.1 indicate that water dilation effectively lowers the flame temperature of
decomposing HP. An HP fire can be readily initiated if the concentrated oxidizer contacts leather or, in
some cases, cellulose-based materials such as wood, cotton, rayon and linen. This is especially hazardous
if the materials are soiled by substances that catalyze HP decomposition (including metals) (Kuntz 1966).
Table 2.2 shows the theoretical flame temperatures computed for HP with some materials that could be in
the vicinity of a spill. This illustrates the potential for damage from HP fires initiated by materials such as
wood, aliphatic hydrocarbons and common solvents (Kuntz 1966).
Table 2.1
Heat of Decomposition at 298.16 K and Theoretical Flame Temperature at One Atmosphere of Various
Hydrogen Peroxide Concentrations (Selph 1993)
H,0, (%) Heat of Decomposition Flame Temperature
(kJ/mole) (K)'
100 -98.1 1272
98 -97.9 1226
90 -97.1 1030
70 -96.2 536
°Ca1Ca1ateC1 urine eauilibrium thcrmodvnamics.
2-1

Table 2.2
Theoretical Combustion Temperatures of Hydrogen Peroxide with
Various Materials at One Atmosphere Pressure (Selph 1993)
Combustible Material Theoretical Flame Temperature

Wood 2541
Polyethylene 2668
Ethyl Alcohol 2603
The theoretical flame temperatures for hydrogen peroxide combustion of carbonaceous materials are
much higher than those for its decomposition. For example, the heat of reaction for ethyl alcohol and HP
(A 1.4) is 18 times higher than the heat of decomposition of HP (shown in Table 2.1). Thus, it is not
surprising that the flame temperatures for combustion are much higher than for decomposition.
2.1.3 Flash and Fire Points
In 1966, Kuntz performed a series of hot wire ignition experiments with 90 percent HP and determined
the autoignition temperature of 98 percent HP. In 2000, Pinsky used a conventional closed-cup apparatus
to determine the flash points of 90 and 99 percent HP. Neither the vapor above 90 percent HP nor the
liquid could be ignited by a hot (1140 to 1260 K) nichrome wire when the liquid temperature was below
383 K at one atmosphere pressure (101.3 kPa). Ignition was rapid above this temperature (at one
atmosphere) when the source was placed in the vapor just above the liquid. Ignition did not occur when
the source was placed in the bulk liquid under the same conditions (Kuntz 1966). More recently, using a
closed-cup apparatus equipped with a butane flame ignition source, the flash point for 90.6 percent HP
was determined to be 355 to 358 K and 347 K for 99.1 percent HP (Pinsky 2000). At 308 kPa, the
minimum bulk liquid temperature had to be above 390 K for ignition to occur, at 790 kPa the vapor failed
to ignite even at 439 K. Autoignition of 90 percent HP occurred at one atmosphere pressure in stainless
steel when the liquid temperature reached 408 K. The autoignition temperature for 90.6 percent HP was
reported to be 483 K in air and 440 K in oxygen (Pinsky 2000). The autoignition temperature for
99.1 percent HP was reported to be 395 K in both air and oxygen (Pinsky 2000).
2.1.4 Minimum Ignition Energies and Ignition Sources
1 Quenching distances and minimum spark-ignition for HP/H,0 vapor mixtures between 35 and 50 mole
percent HP at pressures between 3.3 and 26.7 kPa have been determined (Marshall 1959). The quenching
distances varied between 0.51 and 1.63 cm with the ignition energies ranging from 0.53 to
25.5 millijoules (mJ). In each case, the vapor temperature was maintained 9 °C above its condensation
temperature. The data trend fits the following equation:

' Em;,, = 3.84 dg3.04 (2.2)
Where:
ER,;,, = ignition energy (mJ)

dg = quenching distance (cm)
' 2.2 Hypergolic Behavior of HP Mixtures
The term hypergolic is used to describe the fuels and oxidizers that ignite spontaneously upon contact
with each other without any external initiating energy. In a propulsion system, if the event is not
sufficiently spontaneous, the propellants will collect in the combustion chamber and then ignite, usually
2-2
causing an explosion. As a result, the engine and its surroundings are damaged or destroyed. The accepted
euphemism for this sequence of events is a "hard start." In the 1940s, German scientific researchers set an
upper limit of 50 milliseconds (ms) on the ignition delay that they could tolerate (Clark 1972). The
current state-of-the-art monomethylhydrazine (MMH)/nitrogen tetroxide (NTO) bipropellant systems
have ignitions delays of 3 to 4 ms (Humble 1999, Sadov 2001). To prove themselves as suitable
replacements, HP/fuel combinations do not necessarily have to meet or exceed the ignition speed of
MMH/NTO, but they should be close. Thus, the 50 ms delay that was acceptable to German researchers
hunting for hypergolic combinations is not considered acceptable to today's researchers. Ignition delays
of 10 ms or less are preferred, but that is not the only factor to consider. Rocket designers also care about
propellant density, stability, oxidizer-to-fuel ratios and, above all, specific impulse (Isp). This document is
not meant to review the virtues of all the systems touting high performance with HP, but it will review the
ignition mechanisms of HP/fuel combinations previously researched or still being developed.
Hydrogen peroxide has been tested with many fuels to determine ignition delays and hypergolicity. The
literature is contradictory on what is and is not considered hypergolic with HP. The discrepancies may be
due to researchers' definitions of hypergolicity, for example, the definition of what is an acceptable or
tolerable ignition delay for the system under development. The one fuel which most sources seem to
agree is hypergolic with HP is hydrazine. Clark reported that hydrazine had been tested and determined
hypergolic with HP by the Jet Propulsion Laboratory (JPL) in the late 1940s (Clark 1972). Other fuels
tested by JPL in the same study—methanol, kerosene and ethylene diamine—required a pyrotechnic
igniter. FMC reported that hydrazine and Aerozine 50 (a 50:50 weight percent blend of hydrazine and
UDMH) are hypergolic with 98 percent HP and MMH is not (McCormick 1965). Another study found
that only five compounds (ethylamine, diethylallylamine, trimethylamine, triethylamine and N-
allylpiperidine), all amines, were found to be hypergolic with HP, and these only unpredictably so and
after delays of around 15 s (Rapp 1952). Hydrazine, Aerozine 50 and unsymmetrical dimethylhydrazine
(UDMH) have been reported as hypergolic with 90 percent HP; however, there are conflicting reports in
the literature about ignition delays and combustion chamber pressure spikes (Rocketdyne 1967). "... It is
concluded that the hypergolicity of HP with various fuels is, at best, marginal. For this reason, many HP
bipropellant systems utilize HP decomposition gases (resulting from the injection of the HP in a catalyst
chamber upstream of the main combustion chamber) as the ignition source" (Rocketdyne 1967). A recent
report summarized the reaction characteristics of HP with a variety of fuels (Melof 2000).
2.2.1 Heterogeneous Catalysts

The term heterogeneous catalyst is used to describe the mode when HP is decomposed with a solid
catalyst and the resulting oxygen-rich steam is mixed with a fuel (Cong 2001). Silver screen-based
catalysts are typically used to decompose HP. Other types of solid catalysts include alumina,
carborundum, or ceramic particles impregnated with calcium or potassium permanganate, manganese
dioxide, or metallic nitrates (Rocketdyne 1967, Bettner 1998).
In the heterogeneous mode, fuel is injected into the flowing, hot oxygen where it will autoignite if it is
heated to its autoignition temperature. Technically speaking, this is not truly a hypergolic combination
since there is a preliminary step to decompose the HP. The literature reviewed mentions kerosene, JP-4,
JP-8 and JP-10 as fuels used with this type of ignition scheme (Anderson 1998, Wernimont 1999, Purcell
2000, Harlow 2002); however, no ignition delay data were presented. This mode of operation is better
suited to continuous thrust operation, not a reaction control system, start-and-stop application because of
the time required to decompose the HP through the catalyst and then mix with the fuel. For example, the
Hydrogen Peroxide Handbook (Rocketdyne 1967) reports that the start transient for an HP catalytic
decomposition for a monopropellant application normally ranges from 50 to 150 ms. It also reports that
this is typical of all of the catalysts used in the decomposition of HP concentrations from 76 to
98 percent. The handbook defines the start transient as the time from HP injection to achievement of
90 percent of the operating chamber pressure. This may not have a direct correlation to a heterogeneous
catalytic mode, but it does indicate that the time delay is significant. The general result of getting the fuel
and oxidizer to combust is achieved; however, the desired result of hypergolic performance is not
achievable.
' 2.2.2 Homogeneous Catalysts
' The term homogeneous catalyst is used to describe the process in which a soluble catalyst, such as an
organometallic transition metal salt, is added to a fuel to make it react spontaneously with HP (Melof
2000, Cong 2001). Transition metal salts act as catalysts, and the organic ligands promote solubility of the
' salt in the fuel base, which is typically alcohol or kerosene. German researchers during World War II
discovered the value of transition metal salts for catalyzing HP decomposition. Fifty years later,
researchers are still using the same or similar additives to make alcohol- or kerosene-based fuels that are
hypergolic with HP.
Chinese researchers working with kerosene-based fuel formulations containing manganese or cobalt salts
reported that hypergolic reactions can be achieved with HP. The main problem encountered involved the
' solubility of metal salts in kerosene. To promote solubility, alcohols, amines and/or aromatic
hydrocarbons were added. Various combinations and formulations were evaluated with 96 percent HP.
Though actual ignition delay times were not measured, it was reported that at least five formulations had
"instantaneous ignition" upon contact with HP. These formulations were then tested in small rocket
thrusters for steady state, hot restart and short pulse mode performance (Cong 2001).
' Researchers at Sandia National Laboratories investigated the reaction characteristics of HP with a number
of fuels, and found that a mixture of ethanolamine and one percent copper (II) chloride rapidly ignited
with 90 percent HP (Melof 2000).
' Russian researchers working with a diaziridine-type fuel also added an organic salt of manganese to
catalyze reaction with HP. The fuel is called Diran-A (Sadov 2002). Drop-on-drop tests indicated a 20 ms
ignition delay between Diran-A and HP, which was later confirmed in thruster tests. After redesign of the
thruster injector, an ignition delay of 8 ms was reported.
The U.S. Navy has developed a family of fuels it terms nontoxic, hypergolic, miscible fuels, or NHMFs
that are designed to be used with rocket-grade HP. NHMF is a series of alcohols, from methanol to
butanol, to which a homogeneous manganese-based catalyst is added to make them hypergolic with HP
(Porras 1999). Drop-on-drop tests with two NHMF formulations and 96.5 percent HP yielded ignition
delays of 16 to 20 ms (Austin 1999). Other researchers working with a basic thruster design reported
' similar ignition delays (Funk 1999); however, their results seemed to depend on their injector design and
combustion chamber geometry. Navy researchers, using high-speed film analysis, reported ignition delays
as low as 4 to 6 ms with specially designed injectors (Purcell 2000).
' A recent study showed promising candidate NHMF formulations for HP propulsion systems using 2-[2-
(2-methoxy) ethoxy] ethoxyacetate- (MEEA-) and acrylate-chelated metal ions dissolved in high energy
' density hydrocarbon fuels such as quadricyclane or bicyclopropylidene. The metal ions included Mn 2+
Fe' `, Ni 2' and Co'`+ (Hitch 2002). Using co-solvents and hydrocarbon fuels to improve miscibility with
HP, ignition delay times as low as 10.8 ms with quadricyclane were achieved.
' To address aging/shelf-life issues associated with NHMF, Purcell continued working with homogeneous
catalysts to develop other new fuels (2000). Approximately 550 combinations of solvents, catalysts and
reactants were studied in drop-on-drop ignition delay tests. Five formulations were selected for
development; two were ether-based fuels with an unspecified additive and three others were amine-based
fuels with additives. All five fuels were fired in thrusters with varying concentrations of HP. Ignition
delays < 4 ms were reported for various conditions. The results indicate that hypergolic ignition with
2-4
homogeneous catalyst-based fuels and HP is achievable. Some may argue that this type of ignition
mechanism is not a true "hypergolic event." However, the propellants do ignite when they come into
contact with each other, making them at the very least "hypergolic-like" (Humble 1999).
2.2.3 Hybrids
Another approach to using HP as an oxidizer in propulsion systems imitates the homogeneous catalyst
mode. These types of systems are called hybrids because a solid fuel is burned with a liquid or gaseous
oxidizer. When used in a hybrid engine, HP is decomposed over a catalyst, and the hot oxygen flows into
a combustion chamber, which doubles as the solid fuel rod. The hot oxygen liquefies, then vaporizes the
solid fuel material, and causes spontaneous combustion. The burning rate of hybrid engines, referred to as
the regression rate, depends on the heat of vaporization of the fuel since only the vaporized fuel can
combust. Polyethylene is the fuel commonly used or compared against when discussing hybrids. Other
fuels used or considered in hybrid engines with HP include hydroxyl-terminated polybutadiene (HTPB),
polymethylmethacrylate (PMMA), nylon, Plexiglass, and polystyrene (Bettner 1998, Brown 1998).
Though hybrids have been demonstrated in pulse mode, the ignition is not fast enough to be considered
hypergolic. A value of 350 ms was reported as the shortest ignition delay (Brown 1998).
2.3 Hydrogen Peroxide Explosions

Although HP solutions are not ordinarily classed as explosives, certain conditions can exist in which
detonations or explosive-like energy releases occur (Rocketdyne 1967). Typically, most explosions
involving HP are the result of HP decomposition, which is highly exothermic and produces large amounts
of water and oxygen gas as shown:
H2O,(I) —> HO( j) ` zOz(g) AH — 97.4 kJ/mole

+ / (2.3)
Water can also be vaporized to form steam. HP is thermodynamically unstable and, even in its most
stabilized form, is decomposing at a slow yet noticeable rate. The decomposition rate is accelerated by
heat, either from an external source or from the HP decomposition itself. HP systems and containers that
are exposed to external heat sources are at risk of exploding if not properly vented. Vents serve three
purposes:
• Prevent overpressurization by exhausting ullage gas
• Prevent accumulation of high concentrations of oxygen
• Remove heat that would otherwise contribute to further decomposition
Contaminants of almost any description can also increase HP decomposition chemically or catalytically
and, in some situations, can lead to explosions. Information on the reactivity and storage hazards of HP is
found in Section 4 of this manual.
An explosion can be defined as a rapid equilibration of pressure between a system and its surroundings
that can produce a shock wave. When considering HP explosions, this can include deflagrations,
detonations, thermal runaways and pressure ruptures. This section will describe the ways in which vapor-
and liquid-phase HP can react with materials and/or react to external stimuli and produce an explosive
event.
2.3.1 Deflagrations and Detonations

Witnesses to explosive events will often report that such-and-such "detonated." It is true that all
detonations are explosions, but the converse is not true — not all explosions are detonations. A quick
review of deflagrations and detonations will clarify the events each term represents. The distinctions may
be lost on the casual observer who sees smoke and fire and pieces of a system flying in many directions,
2-5
but for engineers and safety professionals, the distinctions are significant to the hazards that must be
addressed.
A deflagration is a chemical reaction moving through a flammable mixture at subsonic velocity relative to
the unburned media (Kanury 1976). The energy output from the reaction is transferred to the unburned
media through ordinary heat and mass transfer processes (Grelecki 1976) and is sufficient to enable the
' reaction to propagate and accelerate without energy input from another source. Factors that affect the heat
and mass transfer processes, such as changing constituents in the unburned media or placing obstacles in
the reaction flow path, can help or hinder a deflagration's progress.
' The main hazards from a deflagration are heat and pressure. Deflagration pressures are roughly 5 to
10 times the initial pressure of the unburned media. Deflagrations have less destructive power than
detonations, but are still considered rapid explosive events (Sax 1987).
' A detonation is a chemical reaction that travels at supersonic velocity relative to the unburned media. The
energy output takes the form of and is transferred to the fuel primarily by strong shock (compression)
waves (Fickett 1979, Kinney 1985). After initiation, the thermal energy of the reaction sustains the shock
wave, and the shock wave compresses the unreacted material to sustain the reaction (AIAA 1999).
' Detonations produce extremely high temperatures and pressures within very short time spans. It is the
impulse from the shock wave acting on system materials that is the main detonation hazard. Detonation
pressures can range up to approximately 30 times the initial pressure of the unreacted media depending on
the initial conditions (Benz 1988). Reflected detonation pressures can be two to three times the incident
' pressure (Bodurtha 1980). Consequently, the greatest destruction from a gaseous detonation often occurs
at elbows, tees and closed ends of pipes, where pressure waves can be reflected (Woods 1993).
' Good practices in system design, buildup and operation will minimize many of the risks that can lead to
an explosion in an HP system. Proper material selection, system cleanliness and appropriate vents will
prevent simple pressure ruptures caused by the natural decomposition of HP, which causes slow
temperature and pressure increases. Even if external heat sources or contaminants increase the
decomposition rate, the stated controls are typically adequate to control the pressure rise and prevent an
explosive release. However, there are conditions in which the decomposition can reach an explosive rate.
If the decomposition continues to accelerate due to excessive heat or gross contamination, the HP can
undergo a thermal runaway. A thermal runaway is an exothermic reaction in which the rate of heat
generation exceeds the rate of heat transfer to the surroundings. The increased system temperature leads
' to an increased reaction rate, which in turn produces more heat at an increasing rate, and so on. A thermal
runaway can lead to an explosion when the system is confined and the hot decomposition products
overpressurize the system. Confinement, in this case, can simply mean that the pressurization rate, caused
by the HP decomposition, exceeds the flow capacity of the vent or relief devices. The Hydrogen Peroxide
Handbook (Rocketdyne 1967) points out that explosive HP decomposition rates are usually associated
with the vapor phase, however, separation of the cause/effect relationship between the liquid and vapor
phases is difficult.
2.3.2 Adiabatic Compression
' In addition to material incompatibilities and external heat sources, another not-so-obvious mechanism that
can generate heat in a system and possibly cause decomposition is the flow of HP through a piping
system containing a ullage gas. As the liquid moves toward a closed valve, for example, hot spots can
form by adiabatic heating as the ullage gas is compressed. In hydrazine systems these hot spots can lead
to explosive decomposition. The event is not an adiabatic compression detonation, as it is sometimes
referred to, but rather, a thermal runaway leading to an explosion when confined. The explosion may be
2-6
either a deflagration or a detonation. Confinement, in this case, is provided by the tubing walls and the
inertia of the liquid itself. Adiabatic compression reaction is the appropriate term for this type of
explosive event.
Various researchers through the years have performed adiabatic compression reaction tests. In 1956, the
Naval Air Rocket Test Center conducted tests with 90 and 98 percent HP at both 70 OF (21 °C) and 160 OF
(71 °C). No effects were observed for either concentration at either temperature with it maximum loading
rate of 231,000 lb/s (Nimmerfroh 1999).
FMC reported that 90 percent HP at 70 to 90 OF (21 to 32 °C) had experienced adiabatic compression test
loading rates up to 3,000,000 lb/s with no adverse effects (McCormick 1965).
Tests at WSTF with 90 percent HP from FMC subjected the fluid to loading rates as high as 3,200,000
lb/s.' Initial liquid temperatures ranged from 55 to 82 OF (13 to 28 °C). No adverse effects were observed
The 0.5-in.diameter stainless steel tubes used in the test were slightly bulged; however, that is expected
from the hydrodynamic surge pressures generated (as high as 22 ksi) and is not attributed to any
contribution from HP decomposition.
Apparently, HP does not undergo explosive decomposition when adiabatically compressed.

However, this does not eliminate adiabatic compression from hazard considerations. During
decomposition tests using the Bendix 6HA5 peroxide pump, Wolf and McNally (1963) report that a
rupture occurred which displaced the head of the pump from the body. The cause of this rupture was
attributed to failure of the start solenoid valve to open following closure of the recycle solenoid. The
system thus became momentarily dead-ended. Before the inertia of the relief valve set for 300 psi
could be overcome, the instantaneous pressure rise (far above 3000 psi) initiated a shock wave in the
liquid line. This resulted in a muffled noise. Simultaneously, compression of the peroxide vapor
trapped in the accumulator initiated combustion of the vapor with a silicone rubber diaphragm. This
heated the liquid peroxide and initiated a self-accelerating decomposition reaction. The result was an
extremely large pressure surge in the system, which ruptured the peroxide pump with a loud report
and a flash of flame. As this example illustrates, adiabatic compression of HP vapor is part of an
ignition chain that results in a thermal runaway and resultant explosive release.
2.3.3 Vapor-Phase Explosion Hazards
HP in the vapor-phase is subject to deflagration and detonation processes when the vapor concentration
exceeds 26 mole percent (40 weight percent) at atmospheric pressure (Satterfield 1951). Thus, the
primary factor affecting vapor-phase explosion hazards is the temperature of the liquid HP. Pressure has
not been observed to have an effect (Watkins 2002). The "ignition limit" in this sense is defined as the
minimum HP vapor concentration below which external stimuli cannot initiate a self-propagating reaction
(Satterfield 1959). The propagating reaction in the vapor is not a flame in the typical sense (i.e.
combustion), but rather a rapid decomposition (a thermal runaway). It was determined that the ignition
limit is unaffected by the initiation mechanism (spark or hot wire) or by changes in the ratio of oxygen to
water vapor in the diluent gas (Figure 2.1) (Satterfield 1951). In addition to the spark or hot wire, it was
also observed that an explosion could result from vapor contact with catalytic materials initially at room
temperature (silver, copper platinum, nickel and stainless steel), or by contact with noncatalytic materials
such as aluminum at temperatures of 150 °C or higher. This phenomenon may be what Proud and Field
(2000) were referring to when they stated, "The boiling point is estimated to be 150 °C at atmospheric
pressure, but a direct measurement is not possible since the vapor produced from the liquid is
Rathgeber, K. X-37 Hydrogen Peroxide Adiabatic Compression Reaction Test, Special Test Data Report,
WSTF # 02-37243, NASA Johnson Space Center White Sands Test Facility, Las Cruces, New Mexico, September 2002.
2-7
spontaneously explosive at greater than 26 mole percent and the liquid can explode at temperatures above
130 °C."
28 1 a
• No Explosion
24 Explosion
J A
C
O
20
• A
0 • M•
16
0
A
a^ •
X12
X
O
AAA A
8
% . •
•.
•
4
01
4 18 22 26 3
Hydrogen Peroxide, Mole %
Figure 2.1
Effect of Variation of Diluent Gas Composition on Ignition Limit in the Hydrogen Peroxide-Oxygen-
Water Vapor System (Reproduced from Satterfield 1951)
NOTE: Total pressure 1 atm; ignition with platinum wire at 1350 K
2-8
1
Similarly, tests by DuPont (1958) with liquid HP in open containers showed that the vapor above 90
percent HP exploded at temperatures between 120 °C and 140 °C. The same tests with 98 percent HP
exploded between 100 °C and 140 °C. Satterfield (1951) did experience some spontaneous events but
only when the high vapor concentrations contacted the materials mentioned. By taking extra precautions
with system design, material selection and cleanliness, they were able to contain high HP vapor
concentrations in their test system without spontaneous explosions.
In the same Satterfield (1951) study, it was also determined that the vapor concentration for ignition
increases as the total pressure decreases below atmospheric (Figure 2.2). At 0.26 atm, the ignition limit
increases to 33 mole percent (43 weight percent) and at 0.05 atm, it is 55 mole percent (70 weight
percent). In another study by Satterfield (1959), it was determined that as the pressure increases above
atmospheric to 2 atm, the vapor concentration for ignition decreases to 20.7 mole percent. Between 2 and
6 atm pressure, the ignition limit was found to be constant (Figure 2.3). Satterfield (1959) did not have a
theoretical explanation for the constancy of the limit over this range.
Vapor-phase detonation studies performed by Monger (1964) determined a detonation velocity of 6700
ft/s (2042 m/s) at atmospheric pressure in a minimum concentration of 34.6 mole percent (50 weight
percent) HP. For 50 percent HP vapor at 140 °C and atmospheric pressure, the calculated detonation
velocity is 5003 ft/s (1525 m/s),' which does not agree well with the reported results. Further
investigation would be necessary to clarify the disparity. At 100 percent HP vapor, 140 °C, and
atmospheric pressure the calculated detonation velocity is 6266 ft/s (1910 m/s).' This result agrees with
similar calculations performed by Vasil'ev (1999) who determined the detonation velocity for 100 percent
HP at atmospheric pressure to be 6247 ft/s (1904 m/s). In contrast, the calculated maximum deflagration
velocity (i.e. the sonic velocity of the unburned media) for 50 percent HP at atmospheric pressure is 1414
ft/s (431 m/s). 1 Monger (1964) also reported that detonation velocity measurements at higher
concentrations were unobtainable because of spontaneous ignition of the test mixture. Again, the system
materials of construction probably catalyzed the HP decomposition, which only serves to highlight the
hazard posed by high vapor concentrations of HP. Under ordinary storage and handling conditions
(i.e. atmospheric pressure and ambient temperature), explosive vapor concentrations are not reached
(Rocketdyne 1967). As Figure 2.4 illustrates, only when the liquid temperature for 100 to 75 percent HP
is approximately I 1 °C or higher are explosive vapor concentrations produced at atmospheric pressure
(Satterfield 1951, Laporte Chemicals 1960).
2.3.4 Liquid-Phase Explosion Hazards
The sensitivity of uncontaminated liquid HP to deflagration and detonation processes is primarily a

function of HP concentration (Schumb 1955). Experimental efforts to evaluate HP sensitivity can be
grouped in three areas—impact sensitivity, shock sensitivity and thermal sensitivity.
Calculated by WSTF personnel using the Gordon and McBride (1994 and 1996) computer code, which performs
thermodynamic equilibrium calculations to determine Chapman-Jouguet detonation parameters.
2-9
i
but)
760
720
680
640
600
560
520
U
m̀ 480
440
400
P 360
C1.
320
0f6
H
280
240
200
160
120
80
40
0
16 20 24 28 32 36 40 44 48 52 56
Hydrogen Peroxide in Vapor, Mole %
Figure 2.2
Effect of Total Pressure on Ignition Limit (Reproduced from Satterfield 1951)
NOTE: Up to I atm; hot-wire initiation
2-10
100-
• Interpolated composition at last

901— sparking before ignition
n Interpolated composition at first
sparking before ignition
80 ^
70 — •
M 60'
N
a
N 50
N
d
40—
^ n
O
30 • n
•
20
0 1 1 1 1 1 - I
10 15 20 25 30 35 40
Hydrogen Peroxide in Vapor, Mole %
Figure 2.3
Ignition Limit of Hydrogen Peroxide at Pressures Above Atmosphere
(Reproduced from Satterfield 1959)
NOTE: Dashed line represents data below I atm
100
150
d 140
7
f6
N Equilibrium e0%/jn
E 130 Vapor Concentration 9pO
Above 26 Mol % /nr
rdc Hazardous
120
0
110
Equilibrium Vapor Concentration
Below 26 Mol %
100
100 90 80 70 60 50 au
Hydrogen Peroxide in Aqueous Solution, Weight %
Figure 2.4
Combination of Temperature and Liquid Composition Producing Equilibrium Vapors in Explosive
Region (Reproduced from Satterfield 1951)
NOTE: Total pressure = 1 atm
2-11
r
2.3.4.1 Explosive Yields
Large-scale explosive tests performed at WSTF with Jet A (kersosene) and 90 percent HP gave an
average %TNT yield of 18.3 percent (Boggs 2002). A calculation by the U.S. Bureau of Mines indicates
the explosive energy release for the complete decomposition of 90 percent HP to water and oxygen would
be about 39 percent of the energy released from an equal weight of TNT. The Chemical Propulsion
Information Agency Liquid Propellant Manual (CPIA/M4 1994) indicates the explosive energy release
for the complete decomposition of 98 percent HP to water and oxygen would be about 14 percent that of
TNT based upon gas volumes, internal energy and reaction temperatures (CPIA/M4 1994).
HP is regulated under explosive safety standards (NASA 1993, Department of Defense 1999). These are
discussed in Section 4 of this manual.
2.3.4.2 Impact Sensitivity
The most common method for assessing impact sensitivity is to drop a known weight from a given height
onto a small amount of sample material. In the case of liquids, this is typically performed in a piston-like
device that contains the fluid. The most generally accepted mechanism for reaction initiation is the
conversion of impact energy into heat. In liquids, hot spots are created by adiabatic compression of small
bubbles in the liquid (Shell Chemical Company 1961). The following summary of impact test results with
HP in various configurations and testers supports the conclusion of previous authors: "HP and HP-water
solutions are considered non-impact sensitive in both the solid state (low temperature studies) and the
liquid state up to 212 °F (100 °C)" (Rocketdyne 1967).
• 100 percent HP is not detonated by mechanical impact, such as a drop hammer, or by gunfire
(Schumb 1955).
• Using a BAM Fallhammer test, Degussa Corporation researchers found no sensitivity to impact for
98.7 percent HP applying 40 J of impact energy (Nimmerfroh 1999).
• Bloom and Brunsvold (1957) used a U.S. Bureau of Mines impact device and observed no explosions
with > 98 percent HP up to 212 °F (100 °C) with an impact energy of 30 J. Similar tests by Buffalo
Electro-Chemical Company (BECCO) and Shell Chemical Company (1961), up to and including 90
percent HP, showed no explosions.
• German researchers during World War II used gunfire to test 90 and 100 percent HP and did not
obtain explosions (Nimmerfroh 1999).
90 percent HP was confined in I-quart rectangular aluminum containers with `/4-in. walls. The
containers were filled to 10 percent void. Armor piercing. tracer and incendiary bullets were fired into
the containers at 100 yards from a .50-caliber machine gun. None of the three ammunition types had
any effect other than to pierce the containers (Bellinger 1946).
It is generally concluded that HP is not normally impact sensitive. It should be noted that HP with
additives (or contaminants) capable of being oxidized is highly impact sensitive. This is discussed further
in Section 2.3.5.
2.3.4.3 Mechanical Impact
' Materials exposed to HP have also been subjected to mechanical impact tests. Shell Chemical Company
reported impact test results with 90 percent HP and polyvinyl chloride (PVC), Kel-F, Teflon, and
polyethylene (PE) (200 mesh particle size) (1961). The PVC/HP exploded on impact. Molten PVC and
i
2-12
t
molten polyethylene also exploded. "It can be concluded that containers or hoses made of PVC, PE, or
other carbon-hydrogen compounds can explosively react with concentrated peroxide if they become
molten. This condition could arise, for example, by local contamination of the HP leading to its
decomposition with generation of heat" (Shell Chemical Company 1961).
Tests at WSTF exposed 0.25 g samples of the following materials to HP and then subjected them to
mechanical impact tests with 72 ft-lb of impact energy. No explosions or evidence of explosions were
observed for asphalt, cotton, latex, polyvinyl alcohol, nylon, K-10 paper, plywood, cork, Buna-N and
Neoprene. 1
2.3.4.4 Shock Sensitivity
The primary means of assessing shock sensitivity are to subject HP to the shock from an explosive
initiator and observe the degree to which the HP enhances the output of the initiator (Schumb 1955). The
enhanced output could be the result of a deflagration or detonation of the liquid or vapor. The following is
a summary of shock sensitivity test results with HP in various configurations and tests. Note that the
results are reported with respect to HP concentration.
• Besides concentration, other factors that affect the response of HP to an explosive initiator include
temperature, vessel diameter, degree of confinement and magnitude of initiating explosion (Schumb
1955).
• German researchers in the 1940s reported 96 percent HP or greater was detonable with a velocity
from 6000 to 7000 m/s. Below 96 percent, it was extremely difficult to obtain detonation at ambient
conditions (Nimmerfroh 1999).
• Bloom and Brunsvold (1957) showed that 99 percent HP can be detonated at ambient temperature in
2- or 4-ft length, 1-in. diameter, and 0.17-in. wall thickness with 20-g tetryl booster charge. A 10-g
tetryl charge was unable to propagate a detonation. A 40-g tetryl charge with smaller diameter pipes
was unable to propagate a detonation (Nimmerfroh 1999).
• Card gap tests by Degussa Corporation researchers confirmed a detonation (completely shattered tube
and hole in witness plate) with 98.8 percent HP with a minimal gap (corresponding to one card)
(Nimmerfroh 1999). Other card gap tests, using 30-g tetryl charges separated from the HP by a thin
(0.005 to 0.010 in.) aluminum membrane, indicated no evidence of detonation in 90, 95 and 98
percent HP (DuPont 1958).
• Degussa Corporation researchers, using the BAM 50/60 steel tube test, otherwise known as a 2-in.
steel tube test, obtained detonations in 98.7 percent HP at 12 °C, and in 90 percent HP at 33 °C.
Through 20 years of tests, they have compiled sufficient data to illustrate that temperature plays a
significant role in determining the ability of the HP to propagate a detonation. The temperature
necessary to cause a propagating detonation decreases appreciably with increasing HP concentration
(Figure 2.5) (Nimmerfroh 1999).
• Shock tests were performed with 15 g Hercomite #2 dynamite set off in the geometric center of 30-
gal, 18-in. diameter, aluminum drums containing 250 lb of 90 and 99.5 percent HP at 72 °F and 160
°F (22 °C and 71 °C), respectively. Only minor damage to the aluminum drums was reported
(McCormick 1965).
Greene, B. and Baker, D. L. Mechanical Impact Testing of Hydrogen Peroxide-Exposed Materials. Special Test Data Report.
WSTF # 02-37389, NASA Johnson Space Center White Sands Test Facility, Las Cruces, New Mexico, January 15, 2003.
2-13
• Detonation propagation tests were carried out with 1.5-in. diameter, schedule 80 pipes connected to
30-gal, 18-in. diameter, aluminum drums containing 250 lb of 98 percent HP. Detonations were
initiated in the HP in the pipes but they did not propagate into the larger drums (McCormick 1965).
• Tests carried out by the U.S. Bureau of Mines used 99 percent HP in 1-in. diameter thick walled tubes
connected to '/2-in. diameter tubes. The HP in the 1-in. tubes was detonated by a large booster charge,
but the detonations did not propagate into the '/2 -in. tubes (McCormick 1965).
• Trauzl block tests report enhancement of the explosive effect of the initiator at HP concentrations as
low as 60 percent (Schumb 1955).
Numerous other shock sensitivity tests have been conducted on 90 to 100 percent HP. Schumb (1955)
reports on other attempts, both successful and unsuccessful, at detonating HP with No. 8 blasting caps,
pentaerythritol tetranitrate (PETN) booster charges, aluminum tubes buried in sand. etc.
100
90
80
_ 70
U
60
50
`m
CL
E 40
30
20
10
0
75 80 85 90 95 100
H 2O, Concentration (%)
Figure 2.5
Results of 2-in. Steel Tube Tests as a Function of Hydrogen Peroxide Temperature and Concentration
(Reproduced from Nimmerfroh 1999)
Although some of the data indicate shock sensitivity in HP concentrations above 95 percent, the data are
suspect (DuPont 1958) because of potential vapor-phase detonation contributions and potential
contamination contributions from the explosive initiators themselves (Rocketdyne 1967). Regardless of
the test objective or method, when high HP concentrations have been tested, the end result is an explosion
that is more energetic than the initiator used.
It is generally concluded that HP is not normally shock sensitive, except in high concentrations, under
conditions of heavy confinement and high shock loads (Rocketdyne 1967). It should be noted that HP
I
with additives or contaminants capable of being oxidized are highly shock sensitive. This is discussed
further in Section 2.3.5.
2.3.4.5 Thermal Sensitivity
HP is thermodynamically unstable and decomposes at a measurable rate even in its most compatible
container (Schumb 1955). The addition of heat promotes the decomposition process.
2-14
s
Researchers at DuPont (1958) conducted thermal sensitivity tests with 90 to 98 percent HP. As previously
discussed in Section 2.3.3 and as illustrated in Figure 2.4, the vapor above the liquid becomes explosive at
elevated temperatures. In an effort to determine liquid-phase participation in the vapor-phase explosions,
large-scale tests were performed with approximately 2 gal of HP in passivated stainless steel (type not
specified) drums. The drums were instrumented and heated remotely. The following descriptions and
results are excerpted from the Hydrogen Peroxide Handbook (Rocketdyne 1967) referencing the research
by DuPont (1958).
The drums were heated at a controlled rate, and the temperature-time profile of each was recorded. The
following results were reported on the five tests run.
1. Two gal of 90 percent HP. The drum started belching foam at 271 °F (133 °C). Much liquid was
dispersed, but the stainless steel container was undamaged.
2. Two gal of 95 percent HP. Vapor ignited at 268 °F (131 °C) and burned with several white puffs with
no resulting damage to the stainless steel container.
3. Two gal of 35 percent HP. Vapors ignited at 248 °F (120 °C). Burning continued for 30 s. Both ends
of the drum were bulging and the thermocouple had been ejected from the drum during the test.
4. Two gal of 95 percent HP. Vapors ignited at 295 °F (146 °C) and burned for 3 min. The drum was
undamaged.
5. Two gal of 95.2 percent HP. At 289.4 °F (143 °C) the drum ruptured, spewing high strength liquid
HP. The maximum pressure recorded was 75 psi.
It was concluded from these tests that the liquid does not participate in the vapor-phase reaction, except to
form more vapor from heat soak back. Concentrated liquid HP is susceptible to overheating, which makes
possible the formation of vapor within the liquid phase and consequent "belching." Thermal hazards
increase for liquid HP concentrations above 95 percent, even though direct participation by the liquid
phase in resulting detonations is questionable (Rocketdyne 1967).
As the Hydrogen Peroxide Handbook (Rocketdyne 1967) points out, thermal hazards increase for HP
concentrations above 95 percent. The thermal hazards for lower concentrations can be similar to higher
concentrations when the temperature of the liquid is raised. In reference to explosive limits, 95 percent
aqueous HP can be detonated under very special conditions (very high confinement and a powerful
booster charge). Aqueous 85 percent HP has about the same sensitivity if warmed to 100 °C (Shanley
1958).
In general, HP becomes thermally unstable if it is heated to greater than 100 °C (Klais 1993). Explosive
vapor concentrations are produced at roughly 1 10 °C or higher. As with impact and shock, HP becomes
more thermall y sensitive with the addition of contaminants.
2.3.5 Hydrogen Peroxide with Additives

As reported by numerous sources, HP becomes extremely unstable when mixed with organic and
inorganic materials. McCormick reported that HP solutions can become detonable if they contain soluble
fuels, which give a solution energy greater than 1 kcal/g (1965). As an example, a solution of 70 percent
HP containing in excess of 9 percent by weight diethyleneglycol was found to be shock sensitive.
McCormick stated not to add ethyl alcohol to HP if the solution is to be used in a stainless steel system as
acetic acid will form and the mixture will detonate (1965).
i
2-15
I
Shanley and Perrin found that sensitivity to initiation is about the same for all mixtures having the same
heat of reaction (Shanley 1958). The findings provide an easy basis for predicting the likely range of
explosive compositions of untested mixtures containing HP. It was also suggested that explosion limits
are estimates only, not hard and fast limits. Tests at the boundary show `no-go' for a few trials conducted.
This does not mean there is no hazard at or beyond the boundary, and given enough tests, some
explosions would probably be realized.
Shanley and Greenspan reported on detonability of several mixtures and show ternary plots for
HP/acetone/water, HP/glycerol/water and HP/ethanol/water (1947). Other organic liquids including
acetone, acetic acid, acetic anhydride, aniline, carbitol (diethyleneglycol ethyl ether), dioxane, ethanol,
ethyl acetate, 2-ethoxyethanol, ethylene glycol, glycerol, isopropanol, methanol, methyl methacrylate and
quinoline were tested. Detonations were observed only when the 90 percent HP formed over 30 percent
by volume of the final mixture.
Wolf and McNally (1963) concluded that solutions and emulsions of many organic materials in HP are
highly energetic and quite shock sensitive. For example, 90 percent HP contaminated with as little as 5
percent organic material can be detonated. A mixture containing as little as 55 percent HP with 25 percent
organic material and 20 percent water is likewise detonable.
The overall hazard from HP explosions is pressure. For detonations, the pressurization rates are so fast,
pressure relief devices are not able to respond and protect systems. Thermal runaways and deflagrations,
though slower than detonations, are still very rapid events capable of rupturing propellant systems and
causing collateral damage, even when those systems are equipped with pressure relief devices.
2.4 Assessment Examples
The following scenario is offered as an example of how to avoid HP hazards.
A chemist is directed to take 70 percent HP and distill it to 90 percent. Checking the physical properties
of HP in Appendix A, the chemist notes the boiling point of 70 percent HP is 125 °C and the boiling point
of 90 percent HP is 141.6 °C. Wearing the appropriate personal protective equipment (PPE) and using
clean, passivated glassware, the chemist loads a flask of 70 percent HP into a temperature-controlled bath.
Knowing the boiling point will be slightly depressed at the local ambient pressure, the chemist sets the
temperature for 135 °C and monitors the system. What are the hazards of this operation?
Referring to Figure 2.4, at 70 percent HP and 135 °C, the HP vapor produced is not in the explosive
region (26 mole percent). However, after a short time, as water is driven off, the vapor concentration
above the now higher concentration of liquid HP will eventually move into the explosive region. An
explosion hazard exists. An ignition source is still required for an explosion to occur; however, remember
1 that simple contact with many materials is sufficient to catalyze HP decomposition and initiate an
explosive release.
s Using proper engineering controls, the hazard could have been avoided. Performing this operation in a
fume hood could prevent the accumulation of HP vapors in excess of 26 mole percent. The better solution
is to use a vacuum distillation process, which will reduce the boiling point of 90 percent HP to a safe
temperature. Unfortunately, vacuum distillations are less efficient (larger plate height), thus the yield of
90 percent will be reduced. A standard vacuum pump, equipped with a perfluorocarbon oil, can be used if
it is protected with a regulating valve, a liquid nitrogen trap, dry-ice cooled distillate receiver and a
1 pressure transducer in that order. Use of a thermostatted water bath to heat the distillation pot is
recommended. Check the vapor pressure/temperature curve for 90 percent HP and select a vapor pressure
that is in a safe temperature region for the product. Cool the traps, then evacuate the system to degas the
HP and initiate boiling. Raise the temperature to —50 °C and regulate the pressure to maintain a controlled
2-16
t
distillation rate. When the distillation temperature reaches the value listed in Table A.15, the vapor
pressure/temperature table for 90 percent HP at the measured pressure, stop the distillation and remove
the collected distillate. Restart the distillation and maintain the conditions for collection of 90 percent HP
until approximately 10 percent of the fluid is left in the pot. Stop the distillation, transfer the distillate to a
clean, passivated container, discard the pot residue and decontaminate the system. Be aware that the
distilled product contains no stabilizers.
The following incident summary is offered as evidence of the severity of explosive events resulting from
rapid HP decomposition.
Catalyst bed tests with 98 percent HP were conducted in a test stand at Stennis Space Center, Mississippi.
A leaking shutoff valve allowed small amounts of HP to flow into the catalyst bed between tests.
Personnel reported small, intermittent puffs of steam coming from the nozzle on the downstream side of
the catalyst bed. Due to this leak and the heat soak from previous tests, the catalyst bed housing reached a
temperature of 121 °C. The I -in. diameter supply line between the catalyst bed and the shutoff valve was
also at an elevated temperature, assumed to be approximately 121 °C. Upon initiation of the next test in
the series, an explosion occurred approximately one second after opening the shutoff valve
(Cockrell 2001, Bruce 2002).
Referring again to Figure 2.4, it is known that 98 percent HP liquid between 110 and 150 °C produces
ignitable vapor concentrations of 26 mole percent or greater. When the accumulated vapor in the supply
line was compressed by opening the shutoff valve and/or pushed into the catalyst bed, an explosive
decomposition event was initiated.
As a result of the explosion, the system sustained the following damage (Cockrell 2001,
Bruce 2002):
• The shutoff valve, rated for 3000 psig service, was damaged and deformed
• The supply line, rated for 4200 psig service, was ruptured
• All fourteen, '/2-in. diameter, stainless steel bolts holding the catalyst bed and nozzle together failed in
tension
• The nozzle, weighing 16 lb, was found 100 ft away
2.5 Summary
In summarizing 30 years of researching HP accidents, Wolf and McNally (1963) provide the following
conclusions, which are still relevant 40 years later:
• By itself, HP is a safe material to handle. The record of 30 years' experience with this material has
shown no case wherein permanent injury to personnel resulted from detonation, explosion, fire, or
accidental spillage of high concentration HP alone.
When in contact with contaminants, HP solutions become dangerous. In particular, mixtures of

concentrated peroxide and soluble organics are extremely dangerous.
• There is no magic concentration of HP below which it can be safely used and above which it
suddenly becomes dangerous. Explosions have occurred in systems using concentrations as low as 48
percent and as high as 90 percent. Laboratory investigations of the explosion limits of various HP and
organic mixtures have shown that certain mixtures with even less than 40 percent by weight of HP
can be detonated.
2-17
• The energy content of HP solutions increases with the HP concentration. Also, the higher the
concentration, the smaller the amount of contaminant necessary to produce an explosive mixture.
Thus, while there are no "magic numbers," it is evident that the higher concentrations of HP are less
"tolerant" of errors resulting in contaminated mixtures.
• Last and most important, a safe propellant system can result only from the careful design of all
tankage, plumbing, valves, etc., so as to minimize the possibility of obtaining mixtures of HP with
organic or other contaminants. The system should, insofar as possible, be fail-safe throughout. The
possibility of assembly errors, wiring errors and component failures must be considered and
provisions made such that system safety is not jeopardized.
2.6 References
AIAA. Fire, Explosion, Compatibility, and Safety Hazards ofHypergols —Hydrazine. Special Project
Report AIAA SP-084. American Institute of Aeronautics and Astronautics, Reston, Virginia
(1999).
Anderson, W., M. Bender, D. Crockett, S. Hill, T. Lewis, R. Fuller, P. Morlan, D. Ruttle, P. K. Wu, and
C. McNeal. "Low Cost Propulsion Using a High-Density, Storable, and Clean Propellant
Combination." Proceedings of the I" Hydrogen Peroxide Propulsion Workshop, Surrey, UK, July
1998.
Austin, B. L., S. Frolik, G. Porras, L. J. Etheridge, and J. J. Rusek. "Characterization of Non-Toxic,

Hypergolic Bi-Propellants." Proceedings of the 2`1 International Hydrogen Peroxide Propulsion
Conference. Purdue University, West Lafayette, Indiana,
November 1999.
Bellinger, F., H. B. Friedman, W. H. Bauer, J. W. Eastes, and W. C. Bull. "Chemical Propellants

Corrosion and Stability Studies." Industrial and Engineering Chemistry, Vol 38, 1946:310-320.
Benz, F. J., C. V. Bishop and M. D. Pedley. "Ignition and Thermal Hazards of Selected Aerospace Fluids:
Overview, Data, and Procedures." RD-WSTF-0001, NASA Johnson Space Center White Sands
Test Facility, Las Cruces, New Mexico, October 1988.
Bettner, M. and R. Humble. "Polyethylene and Hydrogen Peroxide Hybrid Testing at the United States
Air Force Academy." Proceedings of the P Hydrogen Peroxide Propulsion Workshop, Surrey,
UK, July 1998.
Bloom, R. and N. Brunsvold. Chem. Eng. Prog., Vol 53, 1957:541.
Bodurtha, F. A. Industrial Explosion Prevention and Protection. New York: McGraw-Hill, (1980).
Boggs, W. H. "Explosive Tests of HBO, and Kerosene (Jet A)," JANNAF Propellant Development and
Characterization/Safety & Environmental Protection Subcommittee Meeting, Colorado Springs,
Colorado, March 2002.
Brown, R., J. Sellers, and M. Paul. "Practical Experience with Hydrogen Peroxide Hybrid Rockets."
Proceedings of the I" Hydrogen Peroxide Propulsion Workshop. Surrey, UK, July 1998.
Bruce, R., G. Taylor, and P. Taliancich. "Rocket Propulsion Ground Testing with High Concentration
Hydrogen Peroxide — Lessons Learned at the NASA Stennis Space Center," Proceedings of'the
I 2-18
5`h International Hydrogen Peroxide Propulsion Conference. Purdue University, West Lafayette,
Indiana (2002).
Clark, J. D. Ignition! An Informal History of Liquid Rocket Propellants. Rutgers University Press, New ,
Brunswick, New Jersey (1972).
Cockrell, M., D. Sewell, R. Ross, G. Liebig, and K. Lohner. "E-3 HBO, Catalyst Bed Test Investigation."
Failure investigation briefing charts, Propulsion Test Directorate, NASA Stennis Space Center,
Mississippi, February 2001.
Cong, Y., T. Zhang, X. Sun, D. Liang, L. Lin, and W. Tan. "Propulsive Performance of Hypergolic
H2O,/Kerosene Bipropellant." Proceedings of the First International Conference on Green
Propellants for Space Propulsion. (Special Publication SP-484). European Space Agency,
Noordwijk, Netherlands, June 2001.
CPIA/M4. Liquid Propellant Manual. Chemical Propulsion Information Agency, Johns Hopkins
University. Columbia, Maryland, May 1994.
Department of Defense. DOD Ammunition and Explosives Safety Standards. DOD 6055.9, Washington,
DC, July 1999.
DuPont de Nemours & Company, Inc., A Report for North American Aviation, Inc., Rocketdyne Division,
Wilmington, Delaware, October 1958.
Fickett, W. and W. C. Davis. Detonation. Los Alamos Series in Basic and Applied Sciences, Univ. of
California Press (1979).
Funk, J. E. and J. Rusek. "Assessment of United States Navy Block 0 NHMF/RGHP Propellants."
Proceedings of the 2"" International Hydrogen Peroxide Propulsion Conference, Purdue
University, West Lafayette, Indiana, November 1999.
Gordon, S. and B. J. McBride. Computer Program for Calculation of Complex Chemical Equilibrium
Compositions and Applications. NASA Reference Publication 1311. (1994 and 1996).
Grelecki, C. "Fundamentals of Fire and Explosion Hazards Evaluation." AIChE Today Series Seminar,
American Institute of Chemical Engineers, New York (1976).
Harlow, J. "The KP Programme or, Whatever did KP do for us?" Proceedings of the 5th International
Hydrogen Peroxide Propulsion Conference, Purdue University, West Lafayette, Indiana,
September 2002.
Hitch, B. T., R. L. Cook, and D. Stokowski. "Hypergolic Agents for H2O? Bipropellants," Technical
Report AFRL-PR-ED-TR-2001-0042, Air Force Research Laboratory, Edwards AFB, California,
June 2002.
Humble, R. W. "Liquid, Hypergolic, Bipropellant Engine System Development Using Methanol and
Hydrogen Peroxide," Proceedings of the 2`1 International Hydrogen Peroxide Propulsion
Kanury, A. M. Introduction to Combustion Phenomena. New York: Gordon and Breach (1976). ,
2-19
I
Kinney, G. F. and K. J. Graham. Explosive Shocks in Air, 2 nd Ed., Springer-Verlag, New York, New York
(1985).
Klais, O. "Hydrogen Peroxide Decomposition in the Presence of Organic Material: A Case Study."
Thermochimica Acta, Vol. 225, 1993:213-222.
Kuntz, R. J., C. J. O'Brian, and N. E. Van Huff. Advanced Propellant Staged Combustion Feasibility
Program, AFRPL-TR-66-6, Part II, Phase 1 Final Report. Air Force Rocket Propulsion
Laboratory, Edwards AFB, California, April 1966.
Laporte Chemicals Ltd., Hydrogen Peroxide Data Manual, Luton, England (1960).
Marshall, J. G., Trans. Far. Soc., Vol. 55, 1959:288.
McCormick, J. C. Hydrogen Peroxide Rocket Manual. Inorganic Chemicals Division, FMC,

Buffalo, New York (1965).
Melof, B. M. and M. C. Grubelich. "Investigation of Hypergolic Fuels with Hydrogen Peroxide." 3"r
International Hydrogen Peroxide Propulsion Conference, NASA Stennis Space Center,
Mississippi, November 2000.
Monger, J., H. J. Baumgartner, G. C. Hood, and C. E. Sanborn. "Detonations in Hydrogen Peroxide

Vapor," J. Chem. Eng. Data, 9(1), 1964:124-7.
1
NASA. Safety Standard for Explosives, Propellants, and Pyrotechnics. NSS 1740.12. Office of Safety and
Mission Assurance, Washington, DC, August 1993.
Nimmerfroh, N., H. Feigenbaum, and E. Walzer. "PRO PU L SE'" Hydrogen Peroxide: History,
Manufacture, Quality, and Toxicity." Proceedings of the 2" `r International Hydrogen Peroxide
Propulsion Conference, Purdue University, West Lafayette, Indiana, November 1999.
' Pinsky, M., H. Gu, D. Covington, D. Tucci, and H. Rosenhouse. "Hazards Evaluation for 90+%
Hydrogen Peroxide." Y d International Hydrogen Peroxide Propulsion Conference, NASA NASA
Stennis Space Center, Mississippi, November 2000.
Porras, G., S. Wulf, J. Funk, and J. J. Rusek. "Non-Toxic Hypergolic Bi-Propellant Engine Design."
Proceedings of the 2"' International Hydrogen Peroxide Propulsion Conference, Purdue
University, West Lafayette, Indiana, November 1999.
Proud, W. G., and J. E. Field. "Shock-Induced Reaction in Hydrogen Peroxide," in Shock Compression of
Condensed Matter — 1999, M. D. Furnish, L. C. Chhabildas, and R. S. Hixson, Eds, American
Institute of Physics (2000).
Purcell, N. "Non-Toxic Hypergolic Liquid Bipropellant 300-lbj: Thrust Test Series." Proceedings of the
3`d International Hydrogen Peroxide Propulsion Conference, NASA Stennis Space Center,
Mississippi, November 2000.
Rapp, L. R. and D. Ressler. Investigation of the Correlation Between Chemical Structures of Propellants
and Self-Ignition for Nitric Acid and Hydrogen Peroxide Oxidizers. Technical Report
ADB201816, Reaction Motors Inc, Rockaway, New Jersey, February 1952.
2-20
Sadov, V. "HP-Based Green Rocket Propellants." Proceedings of the First International Conference on
Green Propellants for Space Propulsion. (Special Publication SP-484), European Space Agency,
Noordwijk, Netherlands, June 2001.
Sadov, V. N. "Self-Ignition of Low-Toxicity Fuel Diran-A with Hydrogen Peroxide in Combustion

Chamber," Proceedings of the 5th International Hydrogen Peroxide Propulsion Conference,
Purdue University, West Lafayette, Indiana,
September 2002.
Satterfield, C. N., G. M. Kavanagh, and H. Resnick. Explosive Characteristics of Hydrogen Peroxide

Vapor (1951). I
Satterfield, C. N., F. Feakes, and N. Sekler. "Ignition Limits of Hydrogen Peroxide Vapor at Pressures
Above Atmospheric," J. Chem. Eng. Data, 4:131 (1959).
Sax, N. 1. and R. J. Lewis Sr., Eds. "Hawley's Condensed Chemical Dictionary." I I 1 ed. New York: Van
Nostrand Reinhold Company (1987).
Schumb, W. C., C. N. Satterfield, and R. L. Wentworth. "Hydrogen Peroxide," ACS Monograph 128,
Reinhold Publishing Company, New York, New York (1955).
Selph, C. C. AFRL Specific Impulse Program, Air Force Research Laboratory, Edwards AFB, California,
October 1993.
Shanley, E. S. and F. P. Greenspan, "Highly Concentrated Hydrogen Peroxide Physical and Chemical
Properties," Industrial and Engineering Chemistry, Vol. 39, No. 12, pps.
1536-1543, December 1947.
Shanley, E. S. and J. R. Perrin. Prediction of the Explosive Behavior of Mixtures of Hydrogen Peroxide.
Jet Propulsion, American Rocket Society, Inc. (1958).
Shell Chemical Company. Concentrated Hydrogen Peroxide — Summary of Research Data on Safety
Limitations, Publication SC:59:44R, Shell Chemical Company, Industrial Chemicals Division,
Revised Ed., September 1961.
Vasil'ev, A. A., A. 1. Valishev, and V. A. Vasil'ev. "Detonation Hazard of Combustible Mixtures —

Ozone, Hydrogen Peroxide," 17th International Colloquium on the Dynamics of Explosions and
Reactive Systems, Heidelberg University, Heidelberg, Germany, July 1999.
Watkins, W., S. Zeppieri, L. Spadaccim, and M. Roeder. "2" d Generation Reusable Launch Vehicle Upper
Stage Project 2 — Chamber and Nozzle Risk Reductions," Hydrogen Peroxide Detonation Studies
Report LS-617 -1, Pratt & Whitney, Liquid Space Propulsion (2002).
Wernimont, E., M. Ventura, G. Garboden, and P. Mullens. "Past and Present Uses of Rocket Grade
Hydrogen Peroxide." Proceedings of the 2"" International Hydrogen Peroxide Propulsion
Conference, Purdue University, West Lafayette, Indiana, November 1999.
Wolf, S. and W. A. McNally. Hydrogen Peroxide as a Torpedo Propellant. Naval Underwater Ordnance
Station, NUOS 360, Newport, Rhode Island (1963).
2-21
Woods, S., D. B. Wilson, R. L. Bunker, D. L. Baker, and N. B. Martin. Fire, Explosion, Compatibility,
and Safety Hazards of Monomethylhydrazine. RD-WSTF-0003, NASA Johnson Space Center
White Sands Test Facility, Las Cruces, New Mexico (1993).
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1
2-23
t Section 3.0
Materials and Reactivity
i
3.0 Materials and Reactivity
This section covers the reactivity of hydrogen peroxide

ide ( HP ) with common materials of construction
in aerospace systems, tanks and other vessels. It also considers the characteristics of chemical
reactions of HP including self-decomposition and the resultant hazards. Although sources of
compatibility data and reactivity data for a number of materials are provided along with a discussion
of the limitations of these data, users of this manual are cautioned to interpret this information only as
a guide to apply it to their intended use conditions. Other sections discuss schemes used for the
classification of materials according to reactivity and a compilation of reactivity data. The reactivity of
a material with HP is classically grouped (Class 1 to 4) according to the extent of HP decomposition or
changes in the material itself. This is defined and explained in detail. The classifications of many
materials and the conditions under which rankings were assigned are discussed in this section.
The interaction (both chemical and physical) of HP with materials is potentially detrimental for the
following reasons:
• Most materials, whether metals or nonmetals, induce or catalyze the decomposition of HP and
degrade the quality of the fluid.
• HP can induce changes in a material through corrosion, absorption, or extraction processes
sufficient to impair the function of catalysts that cause controlled decomposition of HP in
propulsion and power systems.
• HP can induce changes in a material through corrosion, absorption, extraction, or other chemical
reactions sufficient to impair the performance of the material for its intended use in propulsion and
power systems or storage.
• Chemical or physical reactions of HP with materials or contaminants may form products that are
hazardous (explosive when isolated) or can physically interfere with the performance of the
hardware (insoluble reaction products in the system).
• HP can react violently, slowly or suddenly, with some materials or contaminants resulting in
system damage or destruction and personnel injury.
It is important to carefully detail the conditions of the fluid, the system and its environment when
assessing the compatibility or reactivity of a material with HP. Important fluid considerations include
the quantity, phases (liquid and vapor), temperature, concentration, stability (and the stabilizers the
fluid contains) and contaminants that may be present. Important material considerations include the
bulk chemical composition, surface chemical composition, surface physical characteristics,
passivation, cleanliness and the surface area exposed to the liquid and vapor.
A material may be suitable for long-term contact with HP under a variety of environmental conditions
or it may be grossly incompatible for even momentary contact. Factors to consider include exposure
time, temperature, stabilizer packages and acceptance of some degradation of fluid and material. Some
materials can be replaced more easily than they can be made compatible. With this information, the
potential chemical and physical processes of a material in use with HP can be identified and assessed.
The assessment should guide the user whether or not the process causes degradation of a material or
the HP, and whether or not this degradation is acceptable to the intended use conditions.
3-1
3.1 Decomposition of HP
' In a decomposition reaction involving HP, the evolution of gaseous oxygen (0,) and heat can result in
pressure or thermal hazards, depending on the rate of the reaction and the system. The decomposition
reaction can occur in a slow process to form 0, and liquid water or in a rapid process to form 0, and
steam. Other effects that can compromise the functions of a material or HP include degradation of the
material through oxidation, corrosion, or extraction processes.
An important cause of thermal and pressure hazards arises from the exothermic decomposition
reaction:
H202(1) —> H-)O (i) + `'/20, (g) + 97.4 U mole- ' (3.1)
Common modes of HP decomposition include:
' • Intrinsic mode

• Homogeneous- or heterogeneous-catalyzed mode
• Surface-catalyzed or surface-promoted mode
The intrinsic mode occurs in HP containing no other chemical species than HP (HO,) and its
conjugate acids and bases ( H3 O1 + , H 4 0,2+ , HO, - and 0,'-). The concentrations of these species are
determined by the self-ionization equilibrium constants of HP and no amount of purification can
eliminate them. Water (H2O) is almost always present in HP. Because of the dissociation of water by
the equation below:
2H2O !:-, H3OT (

+ OH- 3.2)
hydronium (H30) and hydroxide (OH- ) ions will also be present in concentrations depending on the
water concentration and are not considered impurities or contaminants.
The rate of reaction via the intrinsic decomposition mode is extremely slow at or near room
temperature and is generally ignored in comparison to the two other modes of HP decomposition.
Schumb reported that extremely pure, concentrated and unstabilized HP would decompose at a rate of
approximately 0.5 percent per year at 30 °C (Schumb 1955). An earlier study reported the following
rates of decomposition of 90 percent unstabilized HP at different temperatures (Shanley 1947):
• 30 °C, 1 percent per year

• 66 °C, 1 percent per week
• 100 °C, 2 percent per day
• 140 °C, rapid decomposition with boiling
The rate of decomposition of highly pure, unstabilized HP solutions at temperatures from 50 to 70 °C

has been shown to increase by a factor of 2.2 ±0.1 for a 10-degree rise (Schumb 1955).
A recent stability test indicated that a 98 percent propellant-grade HP is extremely stable when tested
for 24 h at 212 °F (100 °C). This test used a Pyrex flask that had been treated with nitric acid followed
by annealing at 1076 °F (580 °C) for 3 h, then passivated with nitric acid and HP (Huang 2003). The
study further suggested the decomposition rate of this propellant would be less than 0.1 percent per
year if the HP was stored under similar conditions.
3-2
Catalytic decomposition of HP may occur due to the presence of homogeneous (dissolved) species
such as metal ions and organic materials. Catalytic decomposition of HP may also occur due to the
presence of heterogeneous (suspended or colloidal) materials such as metallic or organic particulate
matter. The homogeneous and heterogeneous modes of decomposition are much more rapid than the
intrinsic mode and account for an appreciable fraction of the overall decomposition of HP at normal-
use temperatures. Eliminating or minimizing the contaminating species can control these modes of
decomposition. Stabilizers and inhibitors are used to alter the reactivity or remove effective catalysts.
Use of meticulous cleaning techniques and minimization of contamination by the careful handling and
storage of HP are also critical for these modes of decomposition to be controlled.
The rate of decomposition by the homogeneous and heterogeneous catalyzed modes is called the
background or bulk decomposition rate. This rate is proportional to the amount of HP present and the
concentrations of dissolved or suspended catalysts.
Bulk decomposition rate k b(HP) (3.3)
Where:
Bulk decomposition rate = moles of bulk HP decomposed per second (mol/s)

kb = psuedo-rate constant (mol/sec/kg)
(HP) = amount of HP present (kg)
The psuedo-rate constant (kb) is the sum of the products of the true rate constants and the individual
concentration terms for all the catalytically-active species. It is usually taken as a single combined
value.
The surface-catalyzed or surface-promoted mode occurs through a heterogeneous reaction on the

surface of a material in direct contact with HP liquid or vapor. In this mode, the material acts as a
catalyst, binding HP to its surface and providing a pathway for the decomposition of HP. The rate of
the surface-catalyzed reaction (mol/s) is proportional to the fraction of the catalytic surface covered by
the reactant (6) and the total surface area (SA) of the catalytic material in contact with the liquid or
vapor.
Where:

Surface-catalyzed decomposition rate = k,9(SA)

(3.4) 1
k, = rate constant (mol/sec/m')
6 = fraction of surface area covered by reactant (M)
SA = catalytic surface area (m')
The fraction of surface area coverage, 6, is described by the adsorption isotherm of the catalytic
surface and reactant as well as temperature and pressure conditions. For a concentrated or neat liquid,
9 is usually taken as unity, making the rate of the surface-catalyzed decomposition reaction directly
proportional to the surface area of the catalyst only. The rate of decomposition is not dependent on the
amount of HP present as long as there is enough HP to wet the catalytic surface area and maintain A
equal to 1.
3-3
I
If more than one different catalytic surface is present or the HP is present as both liquid and vapor, the
rates of decomposition for each catalytic combination can be summed. For example, in a tank system,
the walls of the tank (both immersed and above the liquid) and a catalytic impurity dissolved in the HP
are considered three catalytic combinations.
3.1.1 Methods of Measuring Decomposition — Active Oxygen Loss

The parameter most commonly used to express the amount of decomposition of HP is active oxygen
loss (AOL), expressed as percent active oxygen loss (%AOL). Percent AOL is typically determined
experimentally by measuring changes in mass (weight), volume or concentration. Experimental
methods for the determination of AOL by gravimetric and volumetric methods, and for the
determination of HP concentration are discussed in Appendix D of this manual. AOL occurs by the
reaction below.
t HzOz(q —> H2O (,) + /20 2(,) + 97.4 U mole -1 (3.5)
It is important to note that two moles of HP are required to yield one mole of 0, by this reaction.
Percent AOL is the ratio of 0 2 lost by HP to the total available 0, in the HP expressed as a percentage.
Simply stated, %AOL is the weight loss percent of the hydrogen peroxide in the solution and is
calculated as follows.
For the gravimetric determination of %AOL:
%AOL = ( W; - Wr. )100
f
(3.6)
(W; Q0.47
For volumetric determination of %AOL:
%AOL = Vx (T/273.15) x (P/ 760) x 2 x 34 x 100

22,400(W;C;) (3'7)
For concentration determinations of %AOL:
%AOL = -LW- ; C; - W f 100

(3.8)
W;C;
Where:
W; = the initial weight of HP solution

Wf = the final weight of the HP solution
C; = the initial weight fraction of HP in solution (assay %/100%)
Cr = the final weight fraction of HP in solution (assay %/100%)
V = volume (mL) of 0, evolved
T = the temperature in Kelvin
P = the ambient pressure in millimeters (mm) of mercury (Hg)
e 760 = the pressure in mm of Hg at sea level
2 = the number of moles of HP required to produce 1 mole of 0,
34 = the gram molecular weight of HP (g/mol)
100 = the percent conversion factor
22,400 = the volume of 1 mole of 0, in milliliters (ml-) at standard temperature and pressure
0.47 corrects the ratio of 0, lost to decomposed HP, (one mole 0,/two moles HP, 32/(34 x 2))
3-4
22,400 mL/mole converts mL of gas at standard temperature and pressure to moles of gas I
Percent AOL is usually determined by directly exposing a material to HP for a specific time and
temperature, with a standard wetted surface-to-volume (S/V) ratio (see Section 3.1.2.2 for more
information on S/V). Common temperatures used in the past are 86 °F (30 °C) or 151 °F (66 °C);
common time periods are four weeks and one week for the respective test temperatures (FMC 1965).
Decomposition of HP results in the evolution of 0, gas and a corresponding weight loss. Using the
gravimetric equation, the sample/fluid mixture is weighed before and after heating. Using the
volumetric equation, the volume of O 2 evolved is measured.
For other than relative comparisons within a set of identical tests, the %AOL values need to be
normalized for time of contact and wetted S/V ratio. It is extremely important for the users of this
manual to realize that %AOL values that are not calculated under identical conditions or are not
accurately normalized for time of contact and wetted S/V ration may not be compared to each other
with any degree of confidence or accuracy. For these reasons, use of these data in materials selection
processes and in the evaluation of reactivity must be regarded with caution and used only as a guide.
One important reference source lists %AOL values for many materials determined at a S/V ratio of
0.38 in. - ' (Kuntz 1966). This S/V ratio was selected because it is close to that of a 30-gal storage drum.
A sample coupon that is 1 '/2 in. by '/2 in. by 1/16 in. (surface area — 1.75 in. 2) immersed in 4.6 in .3 of
HP has a S/V ratio of 0.38 in. - '. Other S/V ratios such as 0.33 in. - ' have been employed in %AOL
determinations (FMC 1965).
The rate of HP decomposition can be expressed as %AOL per unit of time or can be converted to rate
units of mole/second (mol/s) using the following equation.
HP decomposition rate (mol/s) _ %AOL/100/s x (C;W;)/34 (3.9)
The terms Ci, W; and the value 34 are defined above. Time is expressed in seconds (s).
A similar equation expresses the HP decomposition rate in inverse time units such as reciprocal
seconds (s - ') or reciprocal years (yr'). These inverse time units can be converted to HP decomposition
rates in mol/sec using the equation below (shown for reciprocal seconds).
HP decomposition rate (mol/s) = Rate (s') x (C;W;)/34 (3.10)

The terms Ci, W; and the value 34 are defined above.
A decomposition rate of HP that is calculated from %AOL data is the average decomposition over the
duration of the experiment. The average rate is equal to the instantaneous rate only if the kinetics are
zero-order.
3.1.2 Methods of Measuring Decomposition — Microcalorimetry I

Decomposition reactions of HP can also be determined by microcalorimetry, a very sensitive
instrumental technique that provides real-time data (Pinsky 2000, Gostowski 2000a, Gostowski 2000b,
Davis 2001, Gostowski 2002, Greene 2003, Hornung 2003). Microcalorimetry measures heat flow at
the microwatt (pW) or microjoule (µJ s - ') level, and is particularly suited to measurement of HP
decomposition by equation 3.5.
The heat flow that occurs in this reaction, rather than AOL, is measured by microcalorimetry.
Further details on the microcalorimetry technique are given in Appendix D.
3-5
1 Percent AOL decomposition rates measured at or near room temperature suggest that the background
rates of stabilized peroxide decomposition would result in heat flows of approximately 10 pW per
gram. Contact with incompatible materials, contamination, or purposeful addition of catalysts to
overwhelm the stabilizer system increases the rate of decomposition and results in an increased
instantaneous heat flow. The heat rates are converted into chemical reaction rate using the following
equation:
Decomposition rate (mol/s) = heat rate (µ J/s)/10 6 (µ J/J)/AH, (J/mol) (3.11)
Where AH, – the heat of reaction for the decomposition in (J/mol).
The heat of reaction is approximately 97.4 kJ/mol and varies slightly with assay as indicated in the
Hydrogen Peroxide Rocket Manual (McCormick 1965).
Examples of some material-promoted rates determined by microcalorimetry are shown in Table 3.1
(Davis 2001). The decomposition rates obtained by microcalorimetry are not always directly
comparable to previously published AOL values due to variablity in material formulation, material
surface contamination, fluid composition and concentration, S/V ratios, differences in test time and
temperatures, and the fact that some of the materials tested by microcalorimetry were not available
after the classic AOL measurements were performed. However, because AOL is a measure of oxygen
weight loss due to the material promoted decomposition of HP and microcalorimetry is a measure of
the heat of the reaction causing the oxygen weight loss, it is expected that the two methods produce
similar trends in data. Microcalorimetry work is ongoing and is expected to be an important tool in
assessing material reactivity and for making long-term predictions of HP decomposition.
Table 3.1
Material Reactivity in 83 Percent Solvay" HP, 25 'C (Davis 2001)
Material Material Rate Material Rate
_1
µW cm mol s cm--
PTFE 0.15 1.6 x 10—
FEP 0.34 3.5 x 10 -12
Tefzel ®b 1.06 10.9 x 10-12
Kynar ` 0.58 6.0 x 10 -12
Neoflon U A 0.56 6.0 x 10 -12
Ta 0.80 8.3 x 10 -12
Al(cp) 0.37 3.8 x 10-17
Al 6061 1.04 10.7 x 10 "12
304L SS 9.3 96 x 10 -12
Bulk (82.6%) 0.57 pW g -1 * 5.9 x 10 -12 mol s -1 9-1
a
Solvay' is a registered trademark of Solvay Corporation, Brussels, Belgium.
b Tefzel r is a registered trademark of DuPont de Nemours, Wilmington,
Delaware.
` Kynar" is a registered trademark of Pennsalt Chemicals Corporation,
Philadelphia, Pennsylvania.
d
Neoflon" is a registered trademark of Daikin Kogyo Company, Osaka,
Japan.
* 0.6% AOL yr 1
s
3-6
3.1.2.1 Effect of Temperature
In temperature ranges commonly encountered in propellant storage conditions, the temperature

dependence of the rate of a chemical reaction can be expressed by the following equation
(Shoemaker 1974):
k=Ae -EIT (3.12)
This is the Arrhenius equation, where:
k = the reaction rate

A = the pre-exponential factor
E, = the activation energy
R = the universal gas constant
T = the temperature in Kelvin I
The pre-exponential factor, A, has the same units as the rate constant. Curves characteristic of this
equation for aluminum (Al) 5354, stainless steel (SS) 316 (passivated) and electropolished SS316 with
90 percent HP, are shown in Figure 3.1. These plots are based on data obtained by microcalorimetry,
corrected for background decomposition, and normalized to sample surface area (Hornung 2003). The
sensitivity of the change in rate of these materials with temperature is evident, especially at
temperatures above 300 K.
This equation may also be written in the following logarithmic form:
—E
Ink= E + In A (3.13)
If the log of the rate constant is plotted as a function of the reciprocal of the absolute temperature, a
straight line is obtained as shown in Figure 3.2 (Hornung 2003). For each line, the slope is - EQ/R and
the intercept is In A. Each material will have a unique activation energy and pre-exponential factor.
This plot also illustrates the isokinetic effect; there may be a temperature where the rates from
differing materials are equal. Below that temperature the relative reactivity of the materials will
change. The temperature at which this occurs will change depending on the materials tested. At
temperatures below approximately 273 K the relative ranking of these three materials is reversed. It
should be noted that this extrapolation does not take into account effects such as phase changes, which
can strongly influence the rate.
In practice, the rate of the reaction is determined for at least three temperatures in the range of interest
to determine the activation energy and pre-exponential factor. Extrapolation within this temperature
range is generally valid, however, care must be taken when extrapolating any reaction rate to
temperature extremes. This extrapolation becomes invalid if the mechanism of the chemical reaction
changes by moving from one temperature extreme to another.
3-7
t
60000
U 50000
En
U)
a)
40000
E
0
U
d
m 30000
M
Of
C
0
V) 20000
_-
0
a
E
10000
W
0
0
280 300 320
Temperature, K
Figure 3.1
Temperature Dependence of Reaction Rate for Al 5254, SS316 and
Electropolished SS3I6 with 90 Percent HP
(Adapted from Hornung 2003)
-14
-16 w
•
Aluminum 5254
-18 • SS316
t SS316 Electropolished -
-20
a^
-22
C
-24
-26
-28
-30
40 38 36 34 32 30 28
10.000/T
Figure 3.2
Arrhenius Plot for 90 Percent Hydrogen Peroxide Decomposition on Al 5254, SS316,
and Electropolished SS316 (Hornung 2003)
3-8
3.1.2.2 Surface -to-Volume I
Surface-to-volume (S/V) refers to the ratio of the surface area of an HP-exposed surface to the total
volume of HP in the container. Units of surface-to-volume are typically in.'/in. 3 or in. - ' (cm'/cm3 or
cm-1 ). Early work reported with borosilicate glass on a laboratory scale showed the decomposition rate
of pure HP was roughly proportional to the S/V over a wide S/V range (Roth 1953). Decomposition of
HP in a container with an ullage (as in most storage systems) may be attributed to the following
mechanisms:
• Heterogeneous decomposition of HP liquid on the container surface

• Homogeneous decomposition of HP liquid in the bulk
• Heterogeneous decomposition of HP vapor on the container surface
Because liquid HP is directly exposed to a surface in a container, the surface-catalyzed liquid

decomposition method is the most important contributor to the overall decomposition rate.
Decomposition of HP in the bulk liquid can be controlled by the use of purified HP that is relatively
free of catalytic impurities and to which stabilizers have been added (Schumb 1955). Roth reported
that vapor phase decomposition of HP exposed to borosilicate glass decomposed at about '/4 to 1 /3 the
rate observed for liquid-exposed surfaces, per unit area of surface (Roth 1953). Therefore, in assessing
the relative contributions of the three decomposition mechanisms (described above) to the overall
decomposition rate, heterogeneous decomposition of HP in contact with container surfaces is a
stronger contributor to the overall decomposition rate than homogeneous HP decomposition in the
bulk liquid. In addition, homogeneous vapor phase decomposition is only a fraction of the rate
observed in the surface-catalyzed decomposition.
Another aspect of S/V that may be of great importance in specific situations arises when the S/V ratio
may not be classically applied. For example, a nearly empty storage tank may have a very small
amount of HP in contact with a surface, such as droplets. Droplets may also occur on the walls of a
storage container due to condensation, and may adhere to the walls of a tank under zero gravity
conditions. When HP is newly introduced into an unwet system, a small amount of HP in contact with
a very large surface area will typically result. Despite prior passivation of the system, such
circumstances may lead to bulk depletion of stabilizers in the liquid HP, or initial decomposition
producing heat that may locally increase the HP decomposition rate as the system comes to initial
equilibrium.
3.1.3 Stability
Stability is a measure of the effects of material exposure on the bulk decomposition rate of HP and is a
required measurement in many of the HP specifications (see Appendix Q. Stability and %AOL must
be determined at a temperature of 212 °F (100 °C) for a period of 24 h. Stability is calculated as
follows:
Stability = 100 - %AOL (3.14)
3.2 Chemical Reaction Hazards

HP is a strong oxidizing agent and can chemically react with a variety of organic and inorganic
materials. A chemical reaction involving HP can lead to a number of hazards including:
• Degradation of fluid and material

• Generation of heat and pressure
i
3-9
Formation of shock sensitive compounds
Corrosion of HP containers and systems
Oxidation of metals and materials
A thorough discussion of nonpropellant industrial uses of HP is not within the scope of this manual.
Of concern are hazards resulting from chemical reactions involving HP with materials of construction,
materials likely to be present in case of a spill or release of HP, and reactions that could cause injury to
personnel and the environment (CPIA 1984). Personnel and environmental hazards are discussed in
Section 4 of this manual.
3.2.1 Reactions with Inorganic Materials
HP reacts with a variety of inorganic species. Although HP is typically thought of as an oxidizing

agent, it can also act as the reducing agent. An example of the latter is the reaction of HP with
t permanganate (Mn0 4- ), which is utilized in propulsion and power systems, and in the purity
determination or assay of HP in specification analyses. This reaction and the specifications that
employ it are discussed in Appendix C and are expressed as follows:
2KMnO4 + 5H,0, + 3R SO 4 —> 2MnSO4 + K,SO4 + 8H2O + 50, (3.15)
The counter ion to permanganate (K+ shown in equation 3.15) employed in this reaction is irrelevant to
' the stoichiometry. Potassium permanganate is available as an analytical, reagent-grade standard and is
employed in the analytical titration, but calcium permanganate has typically been used in propulsion
and power systems.
HP reacts as an oxidizing agent with a variety of inorganic species, including metals. In combination
with the appropriate acid, acidic solutions of HP are aggressive in the dissolution of metals and other
substances. "Piranha" solution, which is a 3:1 mixture of sulfuric acid and 30 percent HP (the resultant
peroxydisulfate is the aggressive species), is very effective in removing metallic as well as organic
contaminants from surfaces. However, this solution can be unstable, difficult to store, and has been
reported in many accidents (Dobbs 1990, Matlow 1990, Wnuk 1990).
Some of the reactions of HP with inorganic species are su nmarized below (Schumb 1955,
Kuntz 1966):
• HP reduces chlorine and hypochlorite to chloride. Perchlorates are unaffected making perchloric
acid useful in adjusting the pH of HP solutions.
• HP reduces bromine and bromate to bromide.
• HP oxidizes iodide to iodine; this forms the basis of a "clock" reaction.
• HP is not reactive with sulfur.
t • HP oxidizes sulfide and sulfite to sulfate; concurrent with sulfite oxidation is the formation of
dithionate.
• HP oxidizes selenite to selenate, selenium is slowly oxidized to selenium dioxide, and hydrogen
selenide is rapidly attacked.
• HP, in sufficient concentration, dissolves elemental tellurium to form telluric acid.
• HP may react with ammonia with explosive violence. Example accidents are given in Appendix E.
• HP reacts with nitrite to form nitrate and a peroxynitrous acid intermediate.
• HP is not reactive with nitrate, allowing nitrate to be added to stabilizer cocktails; but can
violently react with nitric acid producing heat and NO x gases (Solvay 2002).
• HP reacts with cyanide to form cyanate and carbonate.
3-10
1
• HP reacts with hydrazine in acid to produce hydroazoic acid; concentrated HP and hydrazine read
explosively after a variable length induction period. Catalysts are important in the latter reaction,
which has been of interest in propulsion system applications.
• HP reacts with elemental phosphorous to form phosphine and phosphoric acid.
• HP does not react with phosphoric acid, allowing the use of phosphate in stabilizer cocktails. In
addition, phosphoric acid has been used in the emergency stabilization of HP as described in
Section 4 of this manual.
• HP may oxidize elemental arsenic to arsenic acid.
• HP is relatively inert toward elemental antimony and its oxides.
• HP may be decomposed by elemental carbon, and more rapidly so with increased surface area and
the presence of catalytic impurities.
• HP oxidizes stannous ion to stannic ion, and the hydrous stannic oxide is inert and valuable in
stabilizer cocktails.
• HP is catalytically decomposed by elemental lead, silver and platinum and silver is one of the
most common catalysts in HP heterogeneous propulsion systems.
• HP is catalytically decomposed by many metals and their oxides including: beryllium, cadmium,
niobium, chromium, cobalt, copper, gold, iron, lead magnesium, manganese, mercury,
molybdenum, nickel (Ni 2+), platinum, silicon, silver, sodium, tin, titanium, tungsten and zinc. Do
not use mercury thermometers with HP as a violent reaction could occur if the thermometer should
break.
• HP is inert toward tantalum and zirconium.
• HP oxidizes zinc to zinc oxide.
• HP oxidizes active metals including magnesium, barium, sodium and potassium.
• HP can react with some inorganic species, such as lithium hydroxide, to form inorganic peroxides.
• HP may be catalytically decomposed by the inorganic constituents in dirt and dusts.
Passivation of metallic surfaces is extremely important in using metals in HP systems. Cleaning and
passivation are described in Section 4 of this manual.
The reactivity of HP toward inorganic materials must be considered in the construction of HP systems,
cleaning and storage. A number of accidents have been reported as the result of the reaction of HP
with inorganic materials (Wolf and McNally 1963, Conner 1993).
3.2.2 Reactions with Organic Materials I

1
HP is reactive with a variety of organic materials, and may form potentially unstable organic peroxides
or peroxy acids. A common precaution is to keep reactive organic materials away from HP. Some of
the reactions of HP with organic species are summarized below (Schumb 1955):
HP reacts with hydrocarbons under a number of conditions. HP and simple hydrocarbons

including kerosene and Rocket Propellant 1 (RP-1) form the basis of many propulsion systems.
HP does not react on contact with saturated paraffins such as polyethylene; however, at higher
temperatures paraffins make an excellent fuel and form the basis of hybrid propulsion systems.
Emulsions or mechanical dispersions of paraffins in HP may be detonated. Hybrid propellants are
discussed in Section 2 of this manual.
HP can react with unsaturated carbon-carbon bonds (R,CCR,) to form epoxides (R COCR-,) which
may undergo further oxidation to form unstable organic peroxides (R,000CR,). Propylene,
1,2-butadiene and methylacetylene have been used in combination with HP in propulsion systems
(Dunn 1996).
3-11
HP does not visibly react with ethanol in cold mixtures, but mixtures in certain concentration
ranges can be violently detonated. HP and alcohols (ROH) have been used in propulsion and
power systems, and the hazards of these mixtures are discussed in Section 2 of this manual
(Wolf and McNally 1963). Ferric ion catalyzes the reaction of HP and ethanol forming acetic acid
and carbon dioxide.
• HP can react with tertiary alcohols (R3 COH) to form alkyl hydroperoxides (R30OOH).
• HP reacts with polyols such as glycerol to form formic acid through glyceric acid and glycollic
acid intermediates.
• HP reacts with carboxylic acids to form peroxy acids, and further oxidation may occur with small
chain carboxylic acids.
• HP reacts with aldehydes (RCHO) to form hydroxy alkyl peroxides (RCH(OH)OOCH(OH)R).
• HP oxidizes organic amines. Aniline is oxidized to nitrobenzene and azoxybenzene. Primary
amines are vigorously decomposed. Secondary amines (R,NH) react energetically to form
hydroxylamines (R,,NOH). Tertiary amines (R3N) are oxidized to amine oxides (R3NO).
• HP reacts with unsymmetrical dimethylhydrazine (UDMH). HP and UDMH have been used in
propulsion systems (Dunn 1996).
• HP may oxidize nitriles (RCN) to amides (RCONH,).
' 0 HP may oxidize mercaptans (RSH) to disulfides (RSSR), although a catalyst is generally required.
• HP is generally not reactive with carbohydrates in the absence of a catalyst, but detonable
mixtures can be formed.
• HP does not react with benzene and toluene in the absence of a catalyst, and iron catalyzes the
formation of phenols.
• HP reacts with furfural, a heterocyclic unsaturated aldehyde that has been used in combination
with HP in propulsion systems (Dunn 1996).
A number of accidents resulting in damage to equipment, facilities and injury or death of personnel,
have been reported as a result of the reaction of HP with organic materials. Reported reaction materials
include petroleum residues, organic surfactants, hydrocarbon oils, acetone, U-DETA (a mixed amine
fuel (MAF) consisting of unsymmetrical dimethylhydrazine (UDMH) and diethylenetriamine) and
mixed organic wastes (Wolf and McNally 1963, Koppel 1974, Brewer 1975, Darnall 1978, De Forest
1987, OSHA 1992, Klais 1993).
3.2.3 Stabilizers
Although the rate of HP decomposition in highly purified solutions is very low, if there were a total
absence of catalytically active materials present as impurities no stabilizers would be needed to ensure
long-term storage at ordinary temperatures without appreciable decomposition (Schumb 1955,
Kuntz 1966). Decomposition of HP in storage and in use is minimized by the following:
• Initial production of highly pure HP

• Addition of substances, called stabilizers, that counter the decomposition effects of catalytic
impurities or container surfaces
• Control of the environment
• Proper cleaning and passivation of vessels
Stabilization of HP consists of inactivating catalytically active substances that may be present in

solution or on the walls of containers. Stabilization does not slow the autodecomposition of HP. In
practice, the nature of the contamination or the specific catalysts that may be present are not known,
and what is known as a "stabilizer cocktail" is added to the HP by the manufacturer. Constituents of
stabilizer cocktails and their allowable limits in HP are discussed in Appendix C. Limitations on
3-12
acceptable stabilizers are set partly by any adverse effect the HP may have on the stabilizers (oxidation
of organic stabilizers) and by the negative effects of the stabilizers on the HP (formation of
precipitates affecting HP flow characteristics) or chemical or physical poisoning of catalyst beds.
A variety of organic and inorganic stabilizers have been tested with HP. Organic stabilizers are
typically not preferred in propellant HP because carbon formed in the combustion process can poison
catalyst beds. The most widely used stabilizers in propellant applications are sodium or potassium
stannate and sodium pyrophosphate. Another stabilizer that has been used with some success is
8-hydroxy-quinoline (oxine), but its use in modern propellant-grade fluid has not been widely
examined. Sodium nitrate is sometimes present in the stabilizer cocktail, although its function is for
passivation rather than stabilization.
3.2.3.1 Sodium or Potassium Stannate
Sodium stannate (Na,SnO 3 . 3H2O) or postassium stannate (K,SnO 3 -3H2O) hydrolyzes in HP to form a
colloidal-hydrated stannic oxide (SnO, xH2O). Stabilization is achieved by the adsorption of catalytic
metallic cations, such as ferric ion (Fe) and cupric ion (Cu 2+), by the colloid. It has been shown that
sodium stannate greatly improves the stability of 90 percent HP stored in borosilicate glass
(Monger 1965). Caution must be exercised in the quantity of sodium stannate added because the pH of
the system will increase due to hydrolysis of sodium stannate and result in reduced HP stability.
Schumb reported a table of optimum proportions of stannate for stabilization of 85 percent HP against
Fe 3+ (Schumb 1955). Schumb showed that an optimum amount of stannic oxide (SnO,) added as
Na,SnO 3 . 3H2O ranges from 1 to 60 ppm, and the ratio of stannate to ferric ion may vary from 13 to
26 for iron concentrations above 0.3 ppm (Kuntz 1966). Sodium stannate is not an equally effective
stabilizer for all metallic cation impurities, and it has been reported that up to 65 ppm of Sn02 (added
as stannate) is necessary to stabilize the activity of as little as 0.1 ppm cupric ion (Cu 2+)
(Schumb 1955).
A recent study examined the effect of tin on the stabilization of 98 percent HP solutions (Huang 2002).
It was reported that stannate at an equivalent concentration of 2.7 ppm tin (Sri) resulted in no change
to the measured stability of the HP with up to 190 ppm of added Fe. The order of catalytic activity
toward 98 percent HP of 5 metal cations was found to be Mn 2+ > Cu'`+ > Fe 3+ > Cr3+ > N i'+. It was also
proposed in this study that 98 percent HP may be more stable to nickel alloy surfaces than 90 percent
HP. This could be the result of an inert, protective metal oxide layer formed on contact of the surface
with 98 percent HP that was not formed on contact with 90 percent HP.
3.2.3.2 Sodium Pyrophosphate
Sodium pyrophosphate (Na 4 PIO T IOH,,O) appears to achieve stabilization by the precipitation or
complexation of catalytic metallic cations, such as Fe 3+ and Cu''. Schumb reported the optimum
proportion of pyrophosphate for stabilization against Fe 3+ (Schumb 1949). Maximum stabilization for
iron-contaminated HP occurs at a ratio of PI-O7 4- to Fe 3+ of 3.8 to 9.0 (Kuntz 1966).
Pyrophosphate gradually hydrolyzes according to the following reaction:
I
P207 4- + H2O -> 2HPO42- (3.16)
Therefore, pyrophosphate initially added is not indefinitely effective as a stabilizer.
3-13
3.2.3.3 8-Hydroxyquinoline
A commonly used organic stabilizer is (or was) 8-hydroxyquinoline (oxine). Schumb reports that its
use has often been in conjunction with a soluble phosphate or pyrophosphate, and the mechanism of
the stabilization process has not been fully elucidated (although it is likely to complex and stabilize
ferric impurities) (1955). Oxine is slowly oxidized by HP, as an organic additive would be expected,
so prolonged storage may reduce the oxine concentration.
Other organic compounds may have utility as stabilizer components when used as parts of proprietary
stabilizer "cocktails."
3.2.3.4 Corrosion Inhibitors
Corrosion of containers by HP and its contaminants has been reported and studied (Schumb 1955,
Lewis 1961, Davidson 1989). When the corrosion resistance of a container breaks down, it may be a
result of a local flaw in the oxidized surface of the container. Nitrate (as the sodium or ammonium
r salt) is sometimes added to HP to help inhibit corrosion by maintaining container surface passivation.
Sulfate and chloride may cause localized corrosion (pitting) of aluminum and stainless steel container
surfaces by the dissolution of aluminum, and nitrate has been found to inhibit these effects
(Davidson 1989, Kuntz 1966). Nitrate appears to inhibit corrosion by penetrating to the bottom of a
I
growing pit more effectively than the bulk HP, and converting the exposed surface to the inert oxide
that stops pit growth (Davidson 1989). Inhibition of pitting corrosion of aluminum in chloride-
contaminated HP by nitrate may be due to competition for active sites on the protective oxide film and
within growing pits.
3.2.3.5 Emergency Stabilization
Phosphoric acid has been used as an emergency stabilizer, and has been added to HP suspected to be
undergoing uncontrolled decomposition in containers (NAVAER 1957). However, the addition of
phosphoric acid stabilizer may not be sufficient to stop uncontrolled decomposition. Procedures for
emergency stabilization are discussed in Section 4 of this manual and extreme caution must be used if
employed.
3.2.4 Passivation
Surfaces that come into contact with HP must be specially treated prior to use to prevent
decomposition of HP. Processes that make the surface inactive toward decomposition of HP are
known as passivation processes. Passivation of a metal or alloy typically results in the formation of an
oxide surface. The passivation process occurs at the surface of the material, and has no effect on its
bulk chemical composition. Should the surface of a passivated material become disturbed while in
contact with HP (such as by mechanical means of flaking or scratching), nonpassivated material would
be exposed resulting in potential hazards. Procedures for passivation of various materials are discussed
in Section 4 of this manual.
The effectiveness of passivation can be studied using microcalorimetry as described in Section 3.1.2
and Appendix D. Figure 3.3 illustrates the effect of temperature on the baseline decomposition rates of
HP in passivated glass containers determined by microcalorimetry (Greene 2003).
3-14
40
—^ 25 C
35
35 C
q 55 C
q 60 C
30
m 25 q ^^-
0
U
20
15
z 10
v v v
5
0

0 200
Time, Hours
Figure 3.3
Baseline Heat Rates from 90.5 Percent HP in Passivated Glass Containers (Greene 2003)
Observations of these data include
• Even at the lowest temperature, decomposition of HP is observed in the passivated glass

containers.
• The decomposition rate of HP increases with temperature.
• The decomposition rate slows with time.
The effectiveness of passivation and the ultimate acceptance or rejection of a component or assembly
must be gauged by some method of observing HP decomposition, visual or otherwise.
Electropolished surfaces are a special case. These are typically cleaned but not passivated, as
passivation would physically and chemically destroy the electropolished surface.
3.2.4.1 Material Selection
The primary criteria for selection of materials for use with HP are compatibility classifications that
include the effect of the fluid on the material and the effect of the material on the fluid. Assessments of
material degradation in HP need to be based on the concentration, exposure time and temperature.
The effect of material degradation is to make the material unsuitable for its intended use through
alteration of its dimensions (corrosion, swelling, shrinkage), physical properties (tensile strengths,
softening, hardening, blistering, deterioration, dissolution of plasticizers), or chemical characteristics
(conversion to another material). The effect of fluid degradation is to make the fluid unsuitable for its
intended use through alteration of its performance, purity, chemical composition, stability, stabilizer
concentration, and its potential to poison a catalyst bed. The final evaluation of a material for its
suitability for HP service is based on experience during use (FMC 1965, FMC 1966, Kuntz 1966).
In general, increased temperature leads to increased incompatibility of materials (increased reactivity

of HP). Materials that are compatible at ambient temperature may be incompatible at elevated
temperatures. Some caution should be observed when only high temperature compatibility data are
3-15
available. A high temperature used to accelerate the reaction rate of HP with a material may cause the
reaction to proceed by a mechanism different from that of a lower temperature. Thus, accelerated rate
data might not extrapolate well to actual material use conditions.
The concentration of HP is another factor in compatibility assessment. In general, the higher the
concentration of HP the more aggressive it is toward materials. However, the stabilizer content of the
HP given concentrations is also a factor because more highly stabilized HP at a given concentration
might be expected to be more compatible with a given material than with less stabilized HP at the
same concentration. A recent study proposed that 98 percent HP may be more stable to nickel alloy
surfaces than 90 percent HP (Huang 2002). This could be the result of an inert, protective metal oxide
layer formed on contact of the surface with 98 percent HP that was not formed on contact with
1 90 percent HP.
The time a material is exposed to HP also can influence its compatibility rating. Compatibility tests
conducted for only short times may lead to inaccurate extrapolations for long-term compatibility
ratings. Rate processes, such as corrosion, can be reported as an average rate over the total exposure
time or as an instantaneous rate at a specified time. If the rate process (instantaneous rate) changes
during the exposure, the average and instantaneous rates will not be equal.
The presence of contaminants caused by exposure (both dissolved and suspended) has been shown to
adversely affect the compatibility of materials and the performance of hardware in the presence of HP.
The effect of HP on the test material is determined visually, such as the observation of corrosion,
staining, bronzing, pitting, swelling, bleaching, blistering and surface disintegration.
1 Liquid and powdered materials (including solids that might yield finely divided particles in HP
service) are usually evaluated for impact sensitivity. Impact sensitivity is determined by subjecting the
exposed test material and HP to the impact of a weight dropped from a specified height (FMC 1966).
Laboratory tests are used to indicate the suitability of a material for an intended application. For
example, O-rings that become brittle or metals that corrode during immersion testing are not suitable
for use in HP service. However, some materials cannot be evaluated adequately, such as protective
coatings, protective clothing and joint sealing compounds. Specialized tests for these materials are
required.
Protective coating materials are first tested by coating them on standard-sized strips and subjecting
them to the standard compatibility immersion test. An additional test involves filling a coated steel cup
with HP, inverting a second coated cup on top of the cup containing the HP, and maintaining two such
sets at 86 °F (30 °C) and 151 °F (66 °C) for one year and one week, respectively. A final laboratory
test is performed by half-filling a coated 5-gal container with HP and allowing the test container to
I stand at room temperature in a controlled temperature environment. The concentration of the HP is

determined initially and then bimonthly for both the one-year cup test and the container test
(FMC 1966).
Protective clothing material tests are performed by dropping HP on the material in the às-received'
and ìn-soiled' conditions. The "soil" used is 0.005 N potassium permanganate (KMnO 4) solution
because it reacts violently with HP, permitting determination of the ignition and self-quenching
properties of the protective clothing (FMC 1966).
Joint-sealing compound tests are first performed after immersion and impact testing, and then in the
configuration the compound is used (FMC 1966).
3-16
The final evaluation of a material for its suitability with HP is based on experience during use. The
recommendations of materials classification for HP service are generally based on the results of
laboratory tests and practical experience. Practical experience may show results that do not agree with
those of the laboratory tests. Whenever this is the case, greater consideration is given to practical
experience. Criteria established for laboratory tests are based as much as possible on correlation with
practical experience (FMC 1966, Kuntz 1966).
3.2.4.2 Classification System

Materials for use in HP systems are traditionally classified as belonging to one of four classes
(FMC 1965, FMC 1966, Kuntz 1966, Rocketdyne 1967). The criteria for classification are based on
three things: the effect of direct contact of the material on the rate of decomposition of the HP; the
residual effect of the material on the HP after removal of the material; and changes in the properties of
the material. The classes are described as follows:
• Class I — Materials Satisfactory for Unrestricted Use with HP. Such service includes long-term
contact with HP. Typical use is for storage containers.
• Class 2 — Materials Satisfactory for Repeated Short-Time COntaCt with HP. Such materials are
used for transient contact with HP prior to storage of the HP, or hinited contact with HP prior to
use. Such contact is not to exceed 4 h at 160 °F (72°C) or 1 week at 70 °F (22 °C). Typical uses
are for valves and pumps in HP transfer lines and feed tanks.
• Class 3 — Materials that Should be Used Only for Short-Time Contact with HP. These materials
should be used only where neither Class 1 nor Class 2 materials would suffice. These materials
can be used for repeated contact, but a single use period should not exceed 1 min at 160 °F (71 °C)
or 1 h at 70 °F (22 °C) prior to immediate use because contamination of the HP may be otherwise
sufficient to render it unsuitable for storage. An example of a Class 3 application is materials for
use in a flow system. The HP should be consumed in the application or disposed of after the test
because contamination of HP solutions with Class 3 material is usually sufficient to render the
contaminated HP unsuitable for storage. Many Class 3 materials indicate satisfactory room
temperature service; however, the material should be checked prior to use.
• Class 4 — Materials Not Recommended for Use with HP. These materials cause excessive
decomposition of HP even on short-time contact, are attacked or deteriorate on contact, yield
corrosion or deterioration products that cause excessive decomposition of HP on subsequent
contact, or form impact-sensitive materials with concentrated HP.
The criteria for classification of materials for HP service on the basis of laboratory tests is shown in
FMC Bulletin No. 104, Table 1 (1965) (reproduced in Table 3.2 below).
The decomposition rate of HP can be calculated from %AOL as follows, and decomposition rates
corresponding to %AOL acceptance criteria are shown in Table 3.2.
Chemical Rate (mol/sec/cm2) _ %AOL/100 x 1/t x d/MW x I/(S/V) (3.17)
Where:
t = time in seconds
d = density of HP (1.44 g/cm 3 at 25 °C)
MW = molecular weight of HP (34 g/mol)
S/V — surface-to-volume ratio (cm')
3-17
Table 3.2 lists the test evaluation criteria used for classification of materials for HP service
(Kuntz 1966). The nominal dimensions of the materials were 1 '/z in. by %z in. by '/16 in. and the
materials were immersed in a nominal volume of 75 mL of electroytically-produced HP.
Application of the criteria in Table 3.2 to the results of compatibility tests are subject to the following
considerations (FMC 1966, Kuntz 1966):
• If there is any doubt as to whether a material should be in a given category, the material should be
placed in the lower category.
• If the results of practical experience are different from the results of laboratory tests, greater
weight should be given to the practical experience.
' • The main distinction between Class 2 and Class 3 rankings is their possible effect on the stability
of HP. If there is any doubt as to whether the stability of HP might be affected, the material is
placed in Class 3. Slight deterioration of the material causing foreign matter to enter the HP might
cause decreased stability of the HP.
' • Numerical limits for Classes 1 through 4 are approximate. Class 1 materials fall within narrow
limits, while Class 2 materials fall within broader limits. In general, the higher the active O, loss
for a particular material, the less reproducible the results.
iAny material that is impact-sensitive when in contact with HP in any proportion is considered a
Class 4 material. The criteria of impact sensitivity of a material in contact with HP are the incidence of
any positive detonation on the basis of at least 10 trials. A mixture that gives negative results in
10 tests is considered to be tentatively non-impact sensitive unless later tests produce a positive result.
3.2.4.3 Compatibility Data

Most materials suitable for use (Class 1 and 2) have been extensively tested (FMC 1966, Kuntz 1966).
Some of these materials are no longer manufactured, and for those that are, further testing is prudent to
verify these classifications because of lot-to-lot variations or formulation changes without name
changes, which may have occurred over the years. New materials or variations of older materials
should also be tested. Insufficient information about a material that was previously tested may trigger
the need for additional testing. Furthermore, the historical AOL compatibility data were obtained
using HP produced by an electrolytic process (FMC 1966, Kuntz 1966). Current HP propellants are
produced using the anthroquinone process (Wernimont 1999, Wernimont 2001). The information
' provided in the tables below and in Appendix F is meant to offer only general guidance to material
selection. The data should not be used for quantitative purposes because of changes in both the
materials and the fluids, and possible variations in the test methodologies that are currently preferred
by the users. This necessitates that materials coming into contact or expected to come into contact with
HP be tested on a case-by-case basis.
1
3-18
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Materials that have been shown to meet Class 1 or Class 2 criteria and are currently available include:
• 1000- and 5000-series low copper aluminum alloys (primarily 1060, 1160, 1260 and 5254)
• 300 series stainless steels, primarily 316
• Tantalum'
• Zirconium
• Teflon PTFE
• Teflon PFA
• Viton PVDF
• Polyethylene
• Mylar
Data tables showing the compatibility of HP with various materials have been reproduced and are
shown at the end of this section (Kuntz 1966). Additional data tables showing the compatibility of HP
with various materials have been reproduced and are shown in Appendix F (FMC 1965). The user of
this manual should refer to both the table in this section and the tables in Appendix F to obtain the
widest scope of guidance information. A brief explanation of the data presented in the tables is given
below. In determining the compatibility of solid materials that will be used in a continuously wetted
condition, a sample strip (having the dimensions of 1 `/z in. by `/z in. by 1/16 in.) is usually immersed in
75 mL of the HP solution (Rocketdyne 1967). A strip of this dimension has a S/V of 0.33 in. - '. These
are the nominal dimensions and volumes used in the immersion testing, and simulate the wetted
surface of a standard drum (approximately 30 gal capacity) containing 250 lb of HP. In testing the
compatibility of liquids with HP, a 5-mL sample is normally used. In testing the compatibility of
greases with HP, a 5-mL sample is usually smeared on the inside of the test flask. In tests with liquids
and greases, the S/V cannot be calculated because the sample may dissolve in the fluid.
More recently, NASA Stennis Space Center compiled a database of approximately 20 materials with
compatibility classifications and recommendations (Warren 2003). At the time of publication of this
manual, this information was being incorporated into a draft NASA Stennis Space Center Hydrogen
Peroxide Design Guide. Further information can be obtained by contacting Stanley C. Warren at
NASA/VA60 at Stennis Space Center (228) 688-7111.
3.3 Guide to Data Tables
The following data tables showing the compatibility of HP with various materials have been
reproduced from Kuntz (1966). In addition to the tables presented in Section 3, more data is presented
in Appendix F.
The compatibility of aluminum alloys with 90 percent HP is shown in Table 3.3. There was a wide
variability in the classification of these alloys between Classes 1 and 4.
The compatibility of aluminum alloys with 98 percent HP is shown in Table 3.4. These were mostly
Class 1 materials.
The compatibility of stainless steel alloys with 90 percent HP is shown in Table 3.5. There was a wide
variability in the classification of these alloys between Classes 2 and 4.
The user of this manual should be aware that some commercial alloys of tantalum contain tungsten, which is a Class 4
material (Kuntz 1966, ASM 1980). Additionally, the user should be aware that any material must be well characterized and
tested prior to use, as the presence of incompatible impurities could have deleterious results to the use of HP.
3-21
The compatibility of stainless steel alloys with 98 percent HP is shown in Table 3.6. These were
typically Class 2 and 3 materials.
The compatibility of pure metals with 90 percent HP is shown in Table 3.7. These were typically Class
4 materials.
The compatibility of miscellaneous alloys with 90 percent HP is shown in Table 3.8. These were
typically Class 3 and 4 materials.
The compatibility of polyethylene and halogenated polyethylene types of plastics with 90 percent HP
is shown in Table 3.9. There was a wide variability in the classification of these materials between
Classes 1 and 4.
The compatibility of polyvinylchloride and copolymers with 90 percent HP is shown in Table 3.10.
There was a wide variability in the classification of these materials between Classes 2 and 4.
1 The compatibility of silicone rubbers with 90 percent HP is shown in Table 3.11. There was a wide
variability in the classification of these materials between Classes 2 and 4.
The compatibility of general rubbers and plastics with 90 percent HP is shown in Table 3.12. There
was a wide variability in the classification of these materials between Classes 1 and 4.
The compatibility of laminates, diaphragms and adhesives with 90 percent HP is shown in Table 3.13.
There was a wide variability in the classification of these materials between Classes 1 and 4.
The compatibility of various plastics with 98 percent HP is shown in Table 3.14. There was a wide
The compatibility of lubricants with 90 percent HP is shown in Table 3.15. There was a wide
The compatibility of ceramics, refractories and miscellaneous materials with 90 percent HP is shown
in Table 3.16. There was a wide variability in the classification of these materials between
Classes 1 and 4.
The compatibility of porous materials with 90 percent HP is shown in Table 3.17. There was a wide
The results of evaluation of protective coatings for 90% HP service are shown in Table 3.18. There
was a wide variability in the results of evaluation of these materials.
The results of physical and chemical evaluation of joint sealing compounds with 90 percent HP
service are shown in Table 3.19. There was a wide variability in the results of evaluation of these
materials.
3.4 Data Tables
The following data tables show the compatibility of HP with various materials (reproduced without
corrections or changes from Kuntz 1966).
3-22
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- - - - - - .. - - - - - - - - - - - - Table 3.9
Compatibility of 90% HP with Polyethylene and Halogenated Polyethylene Types of Plastics' (continued)
Effect of Material on H20 2
wt %AOL I
Material C lass ification %/mo %/wk Stability After Effect of H20 2 on Material Source Comm ents
@ 30 °C @ 66 °C Test 2 Material
Furane CF9070 4 Disintegrated Whitro Assoc. ot recommended
Black
Ha lgene 2 4.6 one Palo Lab Supplies Seals
Hypalon S-2 4 100 Sample destroyed Dupont Unsatisfactory
(I h)
Hypalon Ga ket 4 74.2 2 Severe attack Metal Hose & U nsa tisfactOlY
Tubing
Hypalon , grey V-54- 4 100 Bliste red and Raybestos- Unsatisfactory (FMC
B, grey V-56-A, and swo llen Manhattan 1965 and Shell 1965)
black V-163-4
Hyp lon O-ring 3 19 74.4 Moderate surface Go hen Rubber ot recommended
(G R 90-5) attack Co.
Irrathene 101 2 3.0 96.6 o ne at room temp. ; General Electric Seals and gaskets
(i rradiated can ignite Co.
polyethylene) at > 160°F
Kel-F 3.5 one Minn . Mining & Gaskets, sea ls, eats
(unplasticized) Mfg.
Kel-F 800 2.93 98 one Minn. Mining & High temp . service,
Mfg. seals, sea ts
Kel-F 800 4.5 97. Very light arne Ga kets, sea ls, seats
(Lot 5649) hardening
Kel-F 820 (G4028) 2 9.0 96.4 Slight hardening sa me Gaskets, seals, seats
Kel-F 3700 gum 3 8.8 93 .2 Blistering and sa me Gaskets, seals, seats
bleaching
50% Kel-F 3700, 2 3.6 97.0 Slight blistering same Gaskets, seal , eats
50% Kel-F 800
Kel-F 5550 2 26.3 95.7 Slightly tacky same Gaskets, sea l , seats
(unpigmented)
Kel-F 5550 gum 3 18.5 Blistering and sa me ot recommended
di sto11ed
3-36

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Table 3.9
C ompa tibility of 90% HP w ith P o lye th y le ne and H a logen a ted P o lyeth y le ne T y pes o f Pi a ti cs· (continued)
Effect of Materia l on H20 2
wt % AO L I
Mate rial C lass ificatio n %/mo %/wk Stabili ty After Effect of H20 2 on Materi al Source Co mments
@ 30 °C @ 66 °C Test 2 Material
4
Tefl on Fuel ce1l 2 4 .0 94 V. sl. bl eaching Die lectrix Corp. Ex pul sio n bladder
Tefl on T FE cell 2 3.6 97.5 Bleached Chemengin eers, Ex pul s ion bladder
Inc.
Tefl on TFE3 I 1.5 98 one Du-Pont Bladder m aterial
Vi cone 185 2 3.8 2.8 99 Slight bl eaching N011h Ameri can Bladder m aterial
Av.
Vicone 185 2 0. 1 3.4 99 V. s1. bleaching orth Ameri can Excelle nt elasto mer
Av .
Vicone 185 2 0.6 1.1 7 99 V. s1. bleaching orth American Bladder m aterial
Av.
Vicone 3 1-2 2 12 98 Slight Bleaching orth American Ex puls io n bladde r
Av.
Viny lidon-F luoride 1 0. 5 98 onc Pall Fil t Corp. Fil ter media
V in y Iido n-FIuoride 2 1.3 97 Two out of three Pall Fi lt Corp. Fil te r media
sa mpl es showed low
stabili ty
Vito n A (27 1_7)7 2 Good erv ice to 3 Parker Hannefin O-ring , sea ls,
days at 15 1°F dia phragm s
Vi to n A (27 1-7) 4 Blisters after 3 days
at 15 1°F
Vi to n A (03- 2 15.6 95 one eals, Inc. O-ri ngs
100EA3 1)
Viro n A (03- 2 15.4 98 one B.F. Goodrich O-rings, sea l
IOOER3 I)
Vi to n A (4 1 IA4) 3 80.6 95 Blistered and Hewitt Robb in ot reco m mended for
swelled service above 120 OF
3-39
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Table 3.10
Compatibi lity of 90% j--lP with Polyv inylchloride and Copo lymers· (Kuntz 1966)
Effect of Material on H20 Z
wt'llo AOL I
Materi al Clas ification %/wk at 66 °C Stability After Te t 2 Effect of H Z0 2 o n Material Materia l Source
Alanol tubing 3 10J Embri ttled a lge Co mpany
Boltaron 6200 (grey) 2 3 one The Bolta Co.
Geon 11 83 4 8.5 (4 days) 85.6 (4 days) MiLky white , blistered and B.F. Goodrich
di storted
Geon 404 (ye ll ow) 3 8.0 Bleached and became B.F. Goodrich
brittle
Geon PYD Pipe 2 1.3( ) 85 Slight bleaching B.F. Goodrich
Grey 3 10.6 97 Slight bleaching B.F. Goodrich
I.P.S. Uscal ite 4 7.2 89.8 Severely attacked and Stritt & Prie be
blistered
4
Korosea l I J 6 3 23 Bl eached and hardened B.F. Goodrich
Korosea l 11 7 5 (molded) 3 16 Bleached and hardened B.F. Goodrich
Korosea l 700 6 2 2 .9 Slightly wollen , stiffe ned B.F. Goodrich
and bleached
Korosea l 700 w ith 4 14.9 0 Blistered and bl eached Prince Rubbe r o.
Hycar 1041 pIa ticizer
Lucofl ex (tra nslucent) 3 10.1 Bli stered and bl eached Lucofl ex Plasti c
Fabricating Co.
Lucoflex (white) 3 11.2 Darkened, s light blistering Lucoflex Plastic
Fabricating o.
Marvina12 18-200 4 10012 h Sample beca me tacky after U. S. Rubber Co.
I hour
Marvinol 2 18-20 I 4 100/1 h Deformed, chaJTed U. S. Rubber Co .
Marvinol F-3005 4 100/ 1 h Sample became tacky U. S. Rubber Co .
Marvinol R-60 10 4 100/1 h Sample deformed, became U. S. Rubber Co .
tacky
Pliovic9 2 Goodyea r Tire & Co .
3-4 1
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The following assessment examples were developed to familiarize the user of this manual with practical
questions and example calculations that are typically encountered when working with HP decomposition
rates and the prediction of resultant system pressures.
1. HP in a 50 percent solution decomposed at a rate of 1 percent per h. What is the concentration of

HP after 1 h?
Amount decomposed after 1 h - 1%/100% x 50% = 0.5%

After 1 h, the concentration is 50% - 0.5% = 49.5%
2. Calculate the decomposition rate of HP at room temperature in which a stainless steel alloy
having the dimensions of 1 %z in. by '/z in. by 1/16 in. is immersed in 75 mL of fluid and yields a
%AOL of 1.0 in a one-week test.
Chemical Rate (mol/sec/cm') = %AOL/100 x 1/t x d/MW x 1/ (SN)
' 1/t = 1/(7 days x 24 h/day x 60 min/h x 60 sec/min) = 1/604,800 sec

d = 1.44 g/cm 3 at 25 °C
MW = 34 g/mol
S/V (in) = ((2 x 1 '/2 x ''/z) + (2 x % x V16) +
2
(2 x 1 `/z x vie)) in2 /(75 mL x 1 cm3 /mL x 1 in/2.54 3 cm 3 /in 3) in .3 = 1.75 in . /4.58 in. 3 =
0.38 in.-^
S/V (cm 1 ) = 0.38 in. - ' x 2.54-1 cm-1 /in-1 = 0.15 cm-1
Chemical Rate (mol/sec/em) = 1.0/100 x 1/604,800 sec x 1.44g/cm 3 x Imol/34 g x 1/0.15cm-^

4.7 x 10-9 mol/sec/cm'
Calculate the pressure (psi) in an unvented, 30-gal storage drum containing 29 gal of 90 percent
HP (density = 1.37 g/mL) at 30 °C after 1 week. The 1-week AOL value at 30 °C for the drum
material is 1.0%. State the assumptions.
Assume the S/V ratio for the drum is the same as that for the %AOL determination.
' Assume the HP is already saturated with O,.
Assume atmospheric pressure.
Calculate the ullage in the drum: 30 gal - 29 gal = 1 gal

Convert to metric: 1 gal x 3.8 L/gal = 3.8 L
Calculate the amount of O, evolved:
' The total mass of HP (volume x density x fractional purity): 29 gal x 3.8 L/gal x 1.37 g/mL x
1000 mL/L x 0.90 = 135,877 g HP
' The fraction of HP decomposed: %AOL/100 = 1.0/100 = 0.01

The amount of O,_ produced from the decomposed O,: 0.01 x 135,877 g HP x 32 g 0,/68 g HP =
639.4g0,
Converting O, to moles: 639.4 g O, x 1 mol 0 2 /32 g O, = 19.98 mol O,
3-68
Calculate the pressure of O, using the Ideal Gas Law: PV = nRT.
Where:
V = 3.8 L (ullage)
n = 19.98 mol
R = 0.08206 L-atm/mo1-K
T = 30 °C = 30 +273 = 303 K
Solving for P and inserting the values:

P = nRT/V = (19.98mo1)(0.08206 L•atm/mol-K)(303 K)/3.8 L = 130.7 atm
Converting atm to psi where 1 atm = 14.7 psi:

130.7 atm x 14.7psi/atm = 1900 psi
The user will note this a significant pressure and consequently the importance of being familiar
with calculations using AOL values, ullage, purity of HP, and temperature. In addition, the user
can see why high purity HP is always stored in vented containers.
3.6 References
ASM. Metals Handbook Ninth Edition. Volume 3 Properties and Selection: Stainless Steels,
Tool Materials and Special-Purpose Metals. ASM Handbook Committee. American
Society for Metals. Metals Park, Ohio (1980).
Aerojet-General Corporation. Compatibility of O-ring Materials with 90% HBO,_. Rpt. No. 1847,
Liquid Rocket Plant, Sacramento, California. Undated document.
Bell Aerosystems Company. Compilation of Materials Compatibility Test Data with Propellants.
Rpt. No. 2084-939-001, Contract AF 33 (657)-8555, December 1962.
Brewer, A. D. "Peroxide/acetone Mixture Hazard." Chemistry in Britain, 1 1(9)335 (1975).
Conner, W. V. Hydrogen Peroxide Safety Issues. RFP-4599. UC-707 Health and Safety,
DOE/OSTI-4500 (Rev. 75), EG and G Rocky Flats, Inc., Golden, Colorado (1993).
CPIA. Hazards of Chemical Rockets and Propellants, CPIA Publication 394 Volume III, CPIA,
Laurel, Maryland (1984).
Davis, D. D., S. D. Hornung, and D. L. Baker. Hydrogen Peroxide Decomposition, Proceedings

of the First International Conference on Green Propellants for Space Propulsion.
(Special Publication SP-484). European Space Agency, Noordwijk, Netherlands,
June 2001,
Darnall, D. W. "Explosive Peroxides." Chemical and Engineering News, Vol. 56, Issue 47, '
1978:47.
Davidson, C. M. and D. J. Drexler. Electrochemical Comparisons of Corrosion Inhibitor

Performance in Aluminum-Hydrogen Peroxide Systems. Corrosion, July 1989.
3-69
De Forest, P. and R. Rothchild. "Fiber Analysis
Y Usingg
Heated Hydrogen Peroxide." Chemical &
Engineering News, Vol. 65, Issue 31, 1987:2.
Dobbs, D. A., R. G. Bergman, and K. H. Theopold. "Piranha Solution Explosion." Chemical &
Engineering News Vol. 68, Issue 17, 1990:2.
iDunn, B. Alternate Propellants for SSTO Launchers. Adapted from a Presentation at: Space
Access 96. Phoenix, Arizona, April 1996,
FMC. Materials of Construction for Equipment in Use with Hydrogen Peroxide. Bulletin No.
104, Second Issue. FMC, Buffalo, New York (1965).
FMC. Materials of Construction for Equipment in Use with Hydrogen Peroxide. Bulletin No.
104, 1966 Revision. FMC, Industrial Chemicals Group, 1735 Market Street,
Philadelphia, Pennsylvania 19103 (1966).
Gostowski, R. Compatibility of Materials with Reactive Fluids. Proceedings of the 3 "d

International Hydrogen Peroxide Propulsion Conference, NASA Stennis Space Center,
Mississippi, November 2000a.
Gostowski, R. "Assessment of the Compatibility of Composite Materials with High-Test

Hydrogen Peroxide." Proceedings of the 3 Yd International Hydrogen Peroxide
Propulsion Conference, NASA Stennis Space Center, Mississippi, November 2000b.
Gostowski, R., Y. Villegas, and C. A. Smith. "Compatibility of Materials with Hydrogen

Peroxide: Isothermal Microcalorimetry." Abstracts of Papers, 223rd ACS National
Meeting, Orlando, Florida, April 2002.
Greene, B., S. D. Hornung, K. A. Rathgeber, M. B. McClure, L.W. Starritt, and D. L. Baker.

"Hydrogen Peroxide Testing Capabilities at NASA Johnson Space Center White Sands
Test Facility." JANNAF Propulsion and Subcommittee Meeting, Charlottesville, Virginia
(2003).
Hornung, S. D., D. D. Davis, and D. L. Baker. "Hydrogen Peroxide — Material Compatibility

Studied by Microcalorimetry." JANNAF Propulsion and Subcommittee Meeting,
Charlottesville, Virginia (2003).
Huang, K., S. Yuan, and M. Pinsky. "A Study of Concentrated (98%) HBO,: Compatibility with
Ni Alloys and Reserve Stability of Some Metal Contaminants." Proceedings of the 5 h
International Hydrogen Peroxide Propulsion Conference, Purdue University, West
Lafayette, Indiana, September 2002.
Huang, K. and S. Yuan. "Stability Study of Concentrated Hydrogen Peroxide." JANNAF

Propulsion and Subcommittee Meeting, Colorado Springs, Colorado (2003).
' Klais, O. "Hydrogen Peroxide Decomposition in the Presence of Organic Material. A Case
Study." ThermochimicaActa, 225 (1993).
' Koppel, H. C. Violent Explosions. Chemical & Engineering News, Vol. 52, Issue 39, 1974:3.
' 3-70
Kuntz, R. J., C. J. O'Brien, and N.E. Van Huff. Advanced Propellant Staged Combustion
Feasibility Program Part 1. Technical Report. AFRPL-TR-66-5, Part I Final Report,
Air Force Rocket Propulsion Laboratory, Edwards AFB, California (1966).
Lewis, T. J. "The Corrosion of Aluminum in Concentrated Hydrogen Peroxide." J0111-nal of

Applied Chemistry, Volume 11, November 1961.
Matlow, S. L. "Mixtures of Sulfuric Acid and Hydrogen Peroxide." Chemical & Engineering
News, Vol. 68, Issue 30 1990:2.
McCormick, J. C. Hydrogen Peroxide Rocket Manrtal. Inorganic Chemicals Division, FMC,

Monger, J. M., and G. C. Hood. Concentrated Storable Hydrogen Peroxide. Quarterly Progress
Report No. 4, S-13961. Shell Development Co., Emeryville, California. Contract
DA-04-200-AMC-569(Z), February-April 1965.
NAVAER. Handbook, Field Handling of Concentrated Hydrogen Peroxide (Over 52 Weight

Percent Hydrogen Peroxide). NAVAER 06-25-501, Director of the Chief of the Bureau
of Aeronautics (1957).
OSHA. Accident File Number 17006381, Occupational Safety and Health Administration
(1992).
Pinsky, M., H. Gu, D. Covington, D. Tucci, and H. Rosenhouse. "Thermophysical Properties of

FMC ?90% HTP Hydrogen Peroxide for Hazards Evaluation and Emergency Relief
Design for Safe Shipping and Storage." Proceedings of the 3 "d International Hydrogen
Peroxide Propulsion Conference, NASA Stennis Space Center, Mississippi,
November 2000.
Rocketdyne. Hydrogen Peroxide Handbook. Technical Report AFRPL-TR-67-144, Air Force

Rocket Propulsion Laboratory, Edwards AFB, California (1967).
Roth, E. M. and E. S. Shanley. "Stability of Pure Hydrogen Peroxide." Industrial and

Engineering Chemistry, Vol. 45, 1953:2343-49.
Schumb, W. C. "Stability of Concentrated Hydrogen Peroxide Solutions." Industrial and

Engineering Chemistry, Vol. 45, 1949:992.
Schumb, W., C. Satterfield, and R. Wentworth. "Hydrogen Peroxide." American Chemical

Society Monograph Series (1955).
Shanley, E. S. and F. P. Greenspan. "Highly Concentrated Hydrogen Peroxide." Industrial and

Engineering Chemistry, Vol. 39 (1947).
Shell Chemical Company. Concentrated Hydrogen Peroxide — Properties, Uses, Storage,

Handling, Industrial Chemical Div., 2 nd ed., SC:62-63, June 1965.
Shoemaker, D. P., C. W. Garland, and J. L. Steinfeld. "Experiments in Physical Chemistry."

McGraw-Hill, Inc. (1974).
3-71
1
Î
Solvay. Technical Data Sheet Nitric Acid with Hydrogen Peroxide: Reaction Hazards. Solva yY
Interox, Inc. HH1064, July 2002.
Warren, S.W. Hydrogen Peroxide Design Guide. NASA Stennis Space Center, Mississippi.
Draft document/unpublished results (2003).
Wernimont, E., M. Ventura, G. Garboden, and P. Mullens. Past and Present Uses of Rocket
Grade Hydrogen Peroxide. Proceedings of the Second International Hydrogen Peroxide
Propulsion Conference. Purdue University, West Lafayette, Indiana, November 1999.
Wernimont E. and M. Ventura. "Reviewf Hydrogen Per xide Specification MIL

oo M] -P-1
-P-16005. "
AIAA-01-3251, 37`h AIAAIASME/SAEIASEEJoint Propulsion Conference and Exhibit.
Salt Lake City, Utah, July 2001.
Wnuk, T. "Cleaning Glass Funnels." Chemical & Engineering News, Vol. 68, Issue 26, 1990:2.
Wolf, S., and W. A. McNally. Hydrogen Peroxide as a Torpedo Propellant. Naval Underwater
Ordnance Station, NUOS 360, Newport, Rhode Island (1963).
Î
Î
I
3-72
i
Section 4.0
Personnel and Environmental Hazards
I
4.0 Personnel and Environmental Hazards
This section discusses personnel and environmental hazards associated with exposures to or releases
of HP. Exposure rules, recommendations and guidelines of ACGIH, OSHA and NIOSH are presented.
This section addresses toxicity, exposure remediation and control, handling precautions, personal
protective equipment, monitoring equipment, and general safety aspects of engineering design.
Commercially available detectors are reviewed. Transportation issues governed by the DOT and
regulatory environmental requirements set by the EPA including waste disposal are also discussed.
HP is a colorless, oxidizing, corrosive liquid. It decomposes to form water and oxygen. It has been
reported to have no odor (Weiss 1986, ASP 1998, FMC 2002), a slightly sharp odor (Weiss 1986), a
slightly acrid odor (NFPA 49) and a bitter taste (ATSDR 2002).
4.1 Exposure Guidelines
A variety of guidelines has been established to help protect the worker and public from exposure to
hazardous chemicals. OSHA, ACGIH and NIOSH have published exposure limits. While OSHA
limits are always enforceable by law, other, more stringent, limits may be enforced if the employer
adopts these limits based on knowledge of the hazards. For example, NASA uses OSHA or ACGIH
limits, whichever are more stringent. The regulations established by OSHA are often based on the
recommendations of organizations such as ACGIH or NIOSH. The limits recommended by ACGIH
and NIOSH are the most up-to-date exposure limits published and are typically reevaluated annually.
The public must also be protected from hazards associated with industry, and Title III of the
Superfund Amendments and Reauthorization Act (SARA) ensures a community's right to know which
hazardous materials are present in their community. This enables community emergency response
authorities and local fire departments to protect themselves when responding to a fire, explosion, gas
or other chemical release, or emergency.
4.1.1 Threshold Limit Values of the ACGIH
Threshold Limit Values (TI-W") refer to airborne concentrations of substances and represent
conditions under which it is believed that nearly all workers may be repeatedly exposed day after day
without adverse health effects. TLVs are based on available information from industrial experience;
from experimental human and animal studies; and when possible, from a combination of the three.
The basis on which the values are established may differ from substance to substance; protection
against impairment from health may be a guiding factor for some, whereas reasonable freedom from
irritation, narcosis, nuisance, or other forms of stress may form the basis for others (ACGIH 2003).
The TLVs are recommended limits and should be used as guidelines for good practices. Although
serious adverse health effects are not believed likely as a result of exposure to the threshold limit
concentrations, the most prudent practice is to maintain exposure as low as reasonably achievable.
There are three categories of TLVs:
• Threshold Limit Value-Time Weighted Average (TLV-TWA). The time-weighted average

concentration for a conventional 8-h workday and a 40-h work week, to which it is believed that
nearly all workers may be repeatedly exposed, day after day, without adverse effect.
4-1
II
Threshold Limit Value-Short Term Exposure Limit (TLV-STEL). The concentration to which it is
believed that workers can be exposed continuously for 15 min without suffering from adverse
effects. A 15-min TWA would not be exceeded at any time during a workday even if the 8-h TWA
is within the TLV-TWA.
• Threshold Limit Value-Ceiling (TLV-C). The concentration that should not be exceeded during
any part of the working exposure.
A summary of the ACGIH adopted values for HP is shown in Table 4.1.
The ACGIH also allows Excursion Limits as follows (ACGIH 2003). Excursions in worker exposure
levels may exceed three times the TLV-TWA for no more than a total of 30 min during a workday,
and under no circumstances should they exceed five times the TLV-TWA, provided that the TLV-
TWA is not exceeded.
As applied to HP, Excursion Limits would be allowed by the ACGIH as follows. Excursions in worker
exposure levels may exceed 3 ppm for no more than a total of 30 minutes during a workday, and under
no circumstances should they exceed 5 ppm, provided that the 8-h
TLV-TWA of 1 ppm is not exceeded.
Table 4.1
ACGIH Adopted Values for Hydrogen Peroxide (ACGIH 2003)
TLV-TWA TLV-STEL TLV-C Notations TLV Basis — Critical Effects
1 ppm -- - A3 Irritation; pulmonary edema; central
' nervous system
A3 is a Confirmed Animal Carcinogen with Unknown Relevance to Humans. The agent is carcinogenic in
experimental animals at a relatively high dose, by route(s) of administration, at sites(s) of histology type(s), or by
mechanism(s) that may not be relevant to worker exposure. Available epidemiological studies do not confirm an
' increased risk of cancer in exposed humans. Available evidence does not suggest that the agent is likely to cause
cancer in humans except under uncommon or unlikely routes or levels of exposure.
1 4.1.2 Final Rule Limits of OSHA

OSHA has established Final Rule Limits, which are exposure limits enforceable under federal
authority (29 CFR 1910.1000). This information is published in the Federal Register, the source for
the most up-to-date OSHA regulations.
The OSHA Final Rule Limit value that applies to HP is the Permissible Exposure Limit (PEL).
L The PELs are 8-h TWAs unless otherwise noted and are determined from breathing-zone air samples.
There are no other notations for HP. The OSHA PEL is 1 ppm (1.4 mg/m 3) for HP as listed in 29 CFR
1910.1000 Table Z-1, Limits for Air Contaminants.
4.1.3 Recommendations of NIOSH
NIOSH develops and periodically revises Recommended Exposure Limits (RELs) for hazardous
substances or conditions in the workplace. NIOSH also recommends appropriate preventive measures
' to reduce or eliminate the adverse health and safety effects of these hazards.
4-2
r
To formulate these recommendations, NIOSH evaluates available medical, biological,
g engineering,
g g,
chemical, trade and other information relevant to the hazard. These recommendations are then
published and transmitted to OSHA and the Mine Safety and Health Administration (MSHA) for use
in promulgating legal standards. Guidelines published by NIOSH are defined as follows:
• Recommended Exposure Limits (RELs). A time-weighted average concentration for up to a 10-h

workday during a 40-h week (NIOSH 2003). The NIOSH REL as an 8-h TWA for HP is 1 ppm
(1.4 mg/m3) (NIOSH 2003).
• Immediately Dangerous to Life and Health (IDLH) Limit. A condition that poses a threat of
exposure to airborne contaminants when that exposure is likely to cause death, immediate or
delayed permanent adverse health effects, or prevent escape from such an environment. Although
the IDLH limit is based on a 30-min exposure, it is not meant to imply that workers should stay in
the work environment any longer than necessary. In fact, every effort should be made to exit
immediately (NIOSH 1987). The NIOSH IDLH for HP is 75 ppm (NIOSH 2003).
NIOSH has compiled a convenient CD-ROM of recommendations including: OSHA; ACGIH; a

International Safety Cards; the NIOSH Manual of Analytical Methods; the NIOSH Pocket Guide to
Chemical Hazards; OSHA Sampling and Analytical Methods; Recommendations for Chemical
Protective Clothing; Specific Medical Tests Published for OSHA Regulated Substances; Toxicological
Review of Selected Chemicals; and the 2000 Emergency Response Guidebook. The CD is available
from NIOSH at (800) 35-NIOSH or www.cdc.gov/niosh (NIOSH 2003).
4.1.4 SARA Title III
The Superfund Amendments and Reauthorization Act (SARA) Title III ensures a community's right to
know what hazardous materials are present in their community. This enables community emergency
response authorities and local fire departments to protect themselves when responding to a fire,
explosion, gas or other chemical release or emergency.
• HP is not listed under part 302 of the Superfund, Emergency Planning and Community Right-to
Know Programs "Designation, Reportable Quantities, and Notification"
(40 CFR 302.4).
• HP is listed under part 355 of Emergency Planning and Notification (40 CFR 355.40). The
Reportable Quantity (RQ) of HP (> 52 percent) is 1000 lb, and the Threshold Planning Quantity
(TPQ) is 1000 lb. Spillage of an RQ of HP requires notification of the Environmental Protection
Agency. If a facility has, within its boundaries, an amount of HP equal to or in excess of its TPQ,
the facility is subject to the Emergency Planning and Community Right-to-Know Act (EPCRA)
emergency planning requirements. In addition, the facility must notify both the State Emergency
Response Committee (SERC) and the Local Emergency Planning Committee (LEPC) of this fact.
The facility must also appoint an emergency response coordinator who will work with the LEPC
on developing and implementing the local emergency plan at the facility.
4.1.5 Spacecraft Maximum Allowable Concentrations

One of NASA's highest safety priorities is to protect the safety of astronauts and pilots. Consequently,
exposure limits have been evaluated and established for continuous exposure to spacecraft
contaminants for up to 180 days (for normal Space Station operations and for short-term emergency
exposures to high concentrations of contaminants). OSHA and other regulatory agencies have not set
exposure limits for the duration of exposures in space or in microgravity conditions. Because of the
experience of the National Research Council (NRC) Committee on Toxicology, NASA requested that
4-3
1
r
the NRC establish guidelines for developing spacecraft maximum allowable concentrations (SMACs)
for airborne contaminants (NRC 1972, NRC 1992). Sources and types of data for establishment of
SMACs for airborne contaminants include chemical and physical characteristics, in vitro toxicity
studies, animal toxicity studies, clinical and epidemiological observations, pharmacokinetics and
metabolism and biological markers
(NRC 2000).
SMACs are intended to provide guidance on chemical exposures during normal operations of
w spacecraft as well as emergency situations. Short-term (I to 24 h) SMACs refer to concentrations of

airborne substances that will not compromise the performance of specific tasks by the astronauts
during emergency conditions or cause serious or permanent toxic effects. Such exposures might cause
reversible effects, such as mild skin or eye irritation, but they are not expected to impair judgment or
interfere with proper emergency response procedures. Long-term (up to 180 days) SMACs are
intended to avoid adverse health effects and to prevent decremental change in crew performance under
t continuous exposure in the closed environment of the space station for as long as 180 days.
The seven-day SMAC value for HP is 0.28 mg/m 3 (0.20 ppm under ambient conditions) (Materials
and Processes Technical Information Service (MAPTIS)).
t4.2 Toxicity
Recent reviews of the toxicity of HP have been published (ECETOC 1993, Mattie 1998 and 1999,
Nimmerfroh 1999, SCNNFP 2002).
Factors affecting the toxicity potential of HP are route of exposure, concentration and duration of
exposure. Probable routes of exposure include inhalation, dermal absorption, eye or mucous
membrane contact and injection. The duration of exposure can be described as subacute, acute,
subchronic, or chronic (Klaassen and Eaton 1991). Acute exposure refers to short-term exposure at
relatively high concentrations, whereas chronic exposure refers to long-term exposure at relatively low
concentrations. When the route of exposure is inhalation, acute exposure usually refers to a single,
high-concentration duration. When the route of exposure is through ingestion, acute exposure refers to
a single dose. Typically, acute exposure produces noticeable, almost immediate effects, but can also
produce delayed adverse effects that may or may not resemble the effects of chronic exposure.
Repeated exposure to low concentrations of a substance can produce subacute (one month or less),
1 subchronic (one to three months), or chronic (more than three months) effects.
A measure of dosage employed in toxicity studies is the median lethal dose (LD 50). The LD 50 is the
dosage that, when taken into the body by ingestion or absorption, will kill 50 percent of the test-animal
population. The LD50 is expressed as a ratio of the mass of the dosage substance to the mass of the
organism (e.g. mg/kg) and must also express the route or means of exposure. The LD; O for oral
ingestion of 70 percent HP was reported to be 805 mg/kg for 14 days for rats (FMC 1996). The LD;O
for oral ingestion of HP (concentration and time not provided) was reported to be 2000 mg/kg for mice
(NIOSH 2002). The dermal LD 50 of 70 percent HP was reported to be greater than 6.5 g/kg for rabbits
(all the rabbits survived) (FMC 1979). The dermal LD 50 for intravenous injection of 90 percent HP is
690 mg/kg in the rabbit (Hrubetz 1951).
A measure of dosage employed in toxicity studies is the median lethal concentration (LC 50). The LC50
is the concentration of a contaminant in the air or in a body of water that will kill 50 percent of the
test-animal population. The LC 50 is expressed in airborne or water concentration units, such as ppm.
When reporting an LC 50, the length of exposure and the concentration must be indicated, An inhalation
LC50 for 50 percent HP was reported to be greater than 0.17 mg/L for 14 days for rats (all the rats
4-4
survived this exposure) (FMC 1990). The LC50 was reported to be 1418 ppm for 4 h for rats
(NIOSH 2002).
Another measure of dosage employed in toxicity studies is the lethal concentation-low (LCr„). The
LC Lo is the lowest concentration of a contaminant in air that causes death. The LC D,, for HP (time not
available) was reported to be 227 ppm for mice (Stokinger 1962, NIOSH 2002).
The EC 50 is the concentration of a sample that causes a 50 percent decrease in the light emitted by
luminescent bacteria. The bacteria are exposed to the toxic sample, and the amount of light they emit
is measured by a photometer. Healthy bacteria will emit a greater amount of light, so the amount of
light measured indicates the health of the bacteria and thus the toxicity of the sample. The more toxic
the sample, the less light will be produced by the bacteria. The EC 50 for daphnia magna was 7.7 mg/L
for a 24-h exposure (FMC 2002).
4.2.1 Routes and Results of Exposure to Hydrogen Peroxide
Routes of exposure to HP include inhalation, ingestion, dermal and ocular contact, parenteral,
intravenous and injection.
4.2.1.1 Inhalation
Inhalation of HP mist or vapor can irritate and inflame mucous membranes. Prolonged exposures can
result in burns and blisters of the mucous membranes, dyspnea (difficulty in breathing) and coughing
and lung edema (fluid accumulation and swelling). Effects may be delayed for a few hours and
aggravated by physical effort; with concentrated solutions there may be more severe irritation and
inflammation of the respiratory tract. Aerosols of 90 percent HP concentrations can be lethal (Punte
1953). Respiratory irritation through nasal inhalation occurred in a group of human volunteers exposed
to HP vapors. The irritation depended upon exposure concentration and, to a lesser extent, exposure
duration (between 5 min and 4 h) (Kondrashov 1977).
4.2.1.2 Oral Ingestion
Ingestion of HP may cause distension of the abdomen and even internal damage from the rapid
generation of gases. Ingestion results in gastrointestinal irritation, the severity of which depends on the
concentration of the solution. There is also a risk of gas embolism (presence of gas bubbles in the
bloodstream that obstruct circulation). In most reported cases, the exposures were to concentrated
solutions of 30 to 40 percent (Ruse 1997). Ingestion of the more concentrated solutions (> 10 percent
HP, but particularly 30 to 40 percent and above) should be regarded as serious because of the risk of
more severe irritation. The risk of gas embolism is probably also increased with the concentrated
solutions, although a large quantity of a dilute solution may also produce embolisms (Cina 1994).
Death may occur within minutes of ingestion (Dickson 1994). Most cases of ingestion of dilute HP
result in only mild effects. Frothy vomiting may occur due to the liberation of oxygen. Of 270 cases of
HP ingestion in one study, only 24 percent required medical referral (Dickson 1994).
4.2.1.3 Dermal I
Exposure of the skin to HP can cause irritations, burns and blisters, depending on concentration and
time of exposure. Brief contact will cause reversible bleaching. Reversible bleaching has been
attributed to the following mechanism (General Kinetics, LLC 2003):
4-5
1
• HP is absorbed into the skin upon contact
t • HP decomposes on contact with blood and forms oxygen bubbles

• Oxygen bubbles impede the flow of blood in capillaries, giving the skin a white appearance
• Oxygen bubbles are subsequently absorbed or dissolved, allowing blood to flow unobstructed
through the capillaries, restoring color
The National Transportation Safety Board (NTSB 1998) reported that HP spilled on workers' hands
caused burns. Seventy percent HP was shown to be corrosive to the skin of rabbits, where application
of the fluid produced lesions that were consistent with third degree burns after 48 h (FMC 1989).
4.2.1.4 Parenteral
Parenteral or direct introduction of HP into the body through the venous system (such as by injection)
can result in vomiting, pain at the injection site, ventricular fibrillation, embolism of heart and lung
tissue, hemolytic anemia, renal failure and/or death (Ruse 1997).
4.2.1.5 Ocular
Exposure of the eyes to HP can cause severe damage and blindness. The damage may take days or
weeks to develop. Exposure to the eyes will result in irritation with a burning sensation, conjunctival
hyperemia, lacrimation and severe pain that resolves within a few hours. With more concentrated
solutions, effects may take up to 24 h to resolve. There are rare cases of temporary corneal injury
resulting from application of a three percent solution to the eye (on contact lenses) including
punctuated staining of the cornea, decreased vision, corneal opacity and edema (Ruse 1997). Seventy
1 percent HP is corrosive to the eyes of rabbits (FMC 1979).
4.2.2 Teratogenic and Reproductive Toxicity
A teratology study is designed to assess the potential of a chemical to cause birth defects. There was
insufficient data to determine if HP is a teratogen (ECETOC 1993).
Limited reproductive data have been reported in the literature (Mattie 1998 and 1999). A one percent
dose of HP (10,000 mg/kg) for 21 days had no effect on the fertility of male mice (Wales 1959). Rats
exposed to 0.005 to 50 mg/kg HP by lavage for six months showed that at the high dose, the female
reproductive cycle was affected and sperm motility decreased. Only three out of nine female rats
produced litters and there was a decrease in the body weights of pups (Antonova 1974).
4.2.3 Carcinogenicity
There is limited evidence that HP is carcinogenic to mice when administered at high concentrations in
their drinking water (IARC 1985). However, the International Agency for Research on Cancer (IARC)
concluded that the carcinogenicity of HP in humans could not be classified (therefore, it is classifiable
as a Group 3 Carcinogen by IARC)(ATSDR 2002). HP is not listed as a carcinogen by the National
Toxicology Program (NTP) or by OSHA (NTP 2004, 29 CFR.1910). The ACGIH assigns an A3
(Confirmed Animal Carcinogen) notation to HP (ACGIH 2003). Table 4.2 summarizes the
carinogenicity status of HP.
Long-term HP exposure of the stomach and intestines of mice may progress to cancer (Mattie 1998
and 1999). In exposed rats, only nonmalignant papillomas of forestomach are found, not malignant
tumors. HP is not an initiator of skin cancer, but may be a weak promoter of skin and intestinal
4-6
t
tumors. The mechanism for HP carcinogenicity appears to be nongenotoxic (not a direct effect on
genetic material). The tumors are at the site of direct contact with HP after continuous inflammation
and hyperplasia (pathology) for a period of time (ECETOC 1993).
4.2.3.1 Ecotoxicity
The following ecotoxico logical data for HP have been reported for the aquatic environment:
• Toxicity was not observed for fingerling trout exposed to 40 ppm in salt water (time period not
specified) (Weiss 1986).
• The LC50 for channel catfish was 37.4 mg/L for a 96-h exposure (FMC 2002).
• The LC50 for the fathead minnow was 16.4 mg/L for a 96-h exposure (FMC 2002).
• The EC50 for daphnia magna was 7.7 mg/L for a 24-h exposure (FMC 2002).
• The LC50 for daphnia pulex was 2.4 mg/L for a 48-h exposure (FMC 2002).
• The LC 50 for the freshwater snail was 17.7 mg/L for a 96-h exposure (FMC 2002).
• There are no data available for toxicity to waterfowl (Weiss 1986).
• There is no Biological Oxidation Demand (BOD) (Weiss 1986).
• There is no potential for concentration of HP in the food chain (Weiss 1986).
4.3 Exposure Remediation and Control
Engineering design, engineering controls, adherence to established standard operating procedures, use
of properly selected personal protective equipment, emergency planning and the training and
cooperation of all personnel in good safety practices can mitigate hazards from operations with HP.
Workers should know the hazards of HP and other chemicals in the vicinity, and use the
Table 4.2
Carcinogenicity of HP (IARC 1985, ATSDR 2002, ACGIH 2003, NTP 2004, 29 CFR.1910)
NTP Status IARC Status OSHA Status ACGIH
Hydrogen Not Listed Group 3 Not Listed A3 (Confirmed Animal
Peroxide Carcinogen)
appropriate precautionary and protective measures established for the workplace. They should also be
familiar with the location and contents of the Material Safety Data Sheet (MSDS) for HP, and take the
time to become familiar with the assessment guidelines provided in this manual before working with
or around HP.
4.3.1 Personnel Protection
Always avoid underestimating risks. The following general guidelines can protect personnel from
exposure to HP:
Avoid breathing dust, vapor, or fumes from an HP-contaminated area.

Avoid skin and eye contact with HP or HP-contaminated materials.
Do not touch or otherwise handle leaking containers of HP without personal protective equipment
including chemically compatible gloves, skin, eye and face protection, plus suitable respiratory
protection.
4-7
Wear compatible, chemically protective clothing in the presence of HP. Never wear leather, which
can ignite and vigorously burn when exposed to HP.
Use a supplied air respirator, such as a self-contained breathing apparatus (SCBA), air line
respirator, or level A or B protective equipment when in the vicinity of HP vapor concentrations at
or above the acceptable exposure limits.
1 Wear a SCBA when fighting fires involving HP.
Always use prudent precautions such as:
• Never return HP to the original container to avoid potential contamination.

• Minimize the quantity of HP used in tests, storage, or analyses in a manner that is consistent with
meeting the program objectives.
• Ensure areas where HP is used or stored are appropriately ventilated and there are compatible
containment devices to prevent uncontrolled release of HP.
• Have a source of water to cool containers of HP should decomposition occur, or to dilute liquid if
it is spilled.
• Never work alone with HP.
• Ensure that no sources of ignition that could cause a fire in the area are present.
• Know the location and use of emergency equipment.
• Ensure HP is stored in appropriately vented containers and never put HP in a sealed vessel.
• Follow the specified procedures for HP emergencies, including evacuation routes, spill cleanup
procedures and waste disposal.
• Ensure that an established emergency shutdown procedure is immediately available during an HP
test.
• Keep HP appropriately segregated from flammable or combustible chemicals and materials.
• Store HP only in areas approved for its storage.
• Do not deliberately smell or taste HP.
' Do not store, handle, transport, or consume food, beverages, or their containers in areas where HP
is stored or used.
• Do not use HP for any aspect of use other than for what it was intended (propellant HP is not for
use as mouthwash, bleaching agent or antiseptic).
• Always minimize the quantity of HP waste generated in a manner that is consistent with meeting
the objectives of the tests.
• Ensure labels on containers of HP are legible and are not defaced.
• Do not eat, drink, smoke, chew gum, orally consume tobacco products, or apply cosmetics, hand
lotion, or lip balm in areas where HP is present, and wash hands before conducting these activities.
• Wash hands after working with HP or with materials that HP has been in contact with, even when
protective gloves have been worn.
4.3.2 Medical Aid
First aid and medical treatment procedures for exposure to HP must be evaluated by qualified
personnel. It is essential that response and medical personnel be briefed on the nature of the exposure
and provided with the information necessary to make qualified medical decisions. Providing the
MSDS to medical personnel is essential. Medical personnel need to be apprised that HP is a strong
oxidizing agent, that contact with the eyes is likely to cause permanent corneal damage (especially if
not rinsed thoroughly and immediately), and that ophthalmologic evaluation may be necessary. In the
event of ingestion, medical personnel must consider corrosive and irritant effects on the
4-8
gastrointestinal tract, as well as internal distension due to oxygen evolution. Injection of HP may cause
complications similar to ingestion.
4.3.2.1 Emergency
The 2000 Emergency Response Guidebook, Guide 143: Oxidizers, Unstable, (ERG 2000) provides the
following directions for basic first aid involving aqueous solutions of HP at concentrations greater
than 60 percent:
• Move victim to fresh air. Call 911 or emergency medical service.

• Apply artificial respiration if victim is not breathing.
• Administer oxygen if breathing is difficult.
• Remove and isolate contaminated clothing and shoes.
• In case of contact with substance, immediately flush skin or eyes with running water for at least 20
min.
• Keep the victim warm and quiet.
• Ensure that medical personnel are aware of the material(s) involved and take precautions to protect
themselves.
• The site emergency center should be notified while first aid is being administered. If no one else is
available to send for help, treat the exposure victim first, then get help.
4.3.2.2 Rescue Instructions
Remove an incapacitated worker from further exposure and implement appropriate emergency
procedures (for example, those listed on the MSDS required by OSHA's Hazard Communication
Standard (29 CFR 1910.1200)). These procedures may include thorough washing of the victim's
exposed areas with copious amounts of water, ophthalmologic evaluation in the case of eye exposure,
and use of a nastogastric or orogastric tube for the relief of distension in case of ingestion. Emergency
and medical personnel must also take precautions to avoid exposing themselves to HP that may be
present on the victim's skin or clothing, body fluids and to HP or its vapors that may be present in the
area. All workers should be familiar with emergency procedures, the location and proper use of
emergency equipment, and methods of protecting themselves during rescue operations (OSHA 1996,
FMC 2002). Secondary exposure can take any form: inhalation, dermal contact, exposure of eyes and
mucous membranes, ingestion, or injection.
The rescuers must also regard other hazards in the area, such as the potential for oxygen deficiency,
oxygen enrichment, a flammable atmosphere, or any other chemical or physical hazard that may
endanger themselves, and take the appropriate measures to avoid becoming victims themselves.
4.3.2.3 Inhalation Exposure
In the event of an inhalation exposurc. rescuers must not enter the exposure area without appropriate
personal protective equipment including respiratory protection and chemically protective clothing.
Move the victim to fresh air and get medical attention immediately. If breathing has stopped, qualified
personnel may administer artificial respiration using a bag valve mask (BVM). Qualified personnel
must be made aware of severe risks of mouth-to-mouth resuscitation.
4.3.2.4 Dermal Exposure I

4-9
For a large splash or contact with the skin, the exposed person should move away from the
contaminated area and immediately flush the exposed and surrounding areas with copious amounts of
fresh potable tepid water while removing clothing to improve the effectiveness of flushing. Thorough
flushing for at least 15 min in an emergency shower at a flow rate of 20 gal per min (gal/min) should
be performed while medical personnel are notified (ANSI 1998). If an ANSI-compliant emergency
shower is not immediately available, use another source of water such as a drench hose. Every
consideration should be made in pre-planning for this kind of exposure and placement of an
emergency shower or eyewash unit in the vicinity of a potential exposure. Medical personnel will
advise whether to continue flushing until their arrival based on their assessment of the exposure.
4.3.2.5 Eye Exposure
Any splash to the eyes must be immediately flushed with copious amounts of fresh potable tepid
water. Thorough flushing for at least 15 min in an emergency eyewash at a flow rate of 3 gal/min
should be performed while medical personnel are notified (ANSI 1998). If an ANSI-compliant
emergency eyewash is not immediately available, use another source of water such as a personal
eyewash or a drench hose, taking care that the force of flushing fluid does not cause additional injury
to the eyes. Every consideration should be made in pre-planning for this kind of exposure and
placement of an emergency eyewash unit in the vicinity of a potential exposure. Medical personnel
will advise whether to continue flushing until their arrival based on their assessment of the exposure.
' An early source states, "if water is not available for flushing, saliva can be used to absorb the HP and
decrease the effect upon the tender eye membranes" (McCormick 1965). To avoid having to resort to
this practice, ensure that a suitable supply of flushing water is available.
Another early source (Kuntz 1966) suggests that a rinse with three percent boric acid may follow
flushing with water for 15 min.
4.3.2.6 Ingestion
Rinse the mouth immediately with copious amounts of fresh potable water while medical personnel
are notified. Dilute the swallowed fluid by giving one or two glasses of water if the victim is
conscious. Never attempt to make an unconscious victim swallow water. Vomiting SHOULD NOT
BE INDUCED because it may cause additional injury to the upper throat, esophagus and larynx
(Furr 2000). Additionally, vomiting should not be induced to avoid the potential for HP liquid and/or
vapor to enter the lungs. Trained emergency personnel may be advised to insert a gastric tube to
prevent pressure build-up.
Other first aid considerations for HP ingestion include (Ruse 1997):
• Gastric decontamination is not worthwhile for ingestion of HP due to its rapid dissociation.
• Asymptomatic patients who have ingested only a small quantity of low concentrated solutions
(three to six percent) probably do not require treatment.
• Any patient with haematemesis, abdominal discomfort, persistent vomiting, central nervous
system (CNS) or respiratory effects must be admitted.
• If gastric distension is severe, a fine bore gastric tube may be passed to aid the release of gas.
• Endoscopy should be considered in patients with haematemesis or persistent vomiting or if the
solution was > 10 percent.
• Patients with severe clinical effects require abdominal and chest x-rays.
4-10
• The Trendelenburg position (head down, elevated foot of bed) should be avoided since this may
trap air in the apex of the right ventricle and cause obstruction of blood flow (Henry 1996).
• Monitor the electrocardiogram in severe cases.
• Ventilation may be required in patients with severe respiratory effects.
• Hyperbaric oxygen therapy has been suggested for patients with evidence of cerebral embolism
due to HP (Sherman 1994).
An early source discussed how concentrated HP may cause bleaching and swelling of the lips and
mouth, and how swallowing may cause bleeding from the lining of the stomach, which could be in
danger of rupture from violent gas evolution (Kuntz 1966). It was also stated for ingestion, "if the
mouth is bumt, the pain and swelling can be alleviated somewhat by sucking ice. Refer further
treatment to a physician."
4.3.3 Fire Fighting
HP is nonflammable according to OSHA, National Fire Protection Association (NFPA), and DOT
definitions. However, HP vapor at greater than 26 mol percent may be detonable and HP liquid may
promote the combustion of flammable and combustible materials. Oxygen evolved from HP may also
promote combustion of flammable and combustible materials. Additionally, contact of HP with
incompatible materials or elevated temperatures may cause rapid decomposition producing oxygen
and heat, which support combustion and may cause overpressurization if contained. A severe
detonation hazard may exist when HP is mixed with organic materials.
The NFPA rates the degree of hazard severity. Ratings range from zero (indicating minimal hazard) to
four (indicating severe hazard). Definitions of pertinent ratings are given below:
Flammability: NFPA rating 0
• Materials that will not burn under typical fire conditions, including intrinsically noncombustible
materials such as concrete, stone and sand.
• Materials that will not burn in air when exposed to a temperature of 1500 T (816 °C) for a period
of five min in accordance with Annex D (of NFPA 704).
Instability: NFPA rating 3
• Materials that in themselves are capable of detonation or explosive decomposition or explosive

reaction, but that require a strong initiating source or that must be heated under confinement
before initiation.
• Materials that have an instantaneous power density (product of heat of reaction and reaction rate)
at 482 T (250 °C) at or above 100 W/mL and below 1000 W/mL.
• Materials sensitive to thermal or mechanical shock at elevated temperatures and pressures.
The NFPA provides the following hazards information for HP aqueous solutions, stabilized (> 60%)
(NFPA 49):
• DOT Class: Class 5. 1, Oxidizer

• ID No. UN 2015
• Shipping Label: OXIDIZER AND CORROSIVE
• Statement of Hazards: Corrosive. Strong oxidizer
4-11
• Emergency
g Y Response
Pp Personal Protective Equipment: Wearsspecial protective
p clothin g and
positive pressure self-contained breathing apparatus.
• Spill or Leak Procedures: Stop or control the leak, if this can be done without undue risk. Use
water spray to cool and disperse vapors and protect personnel.
• Fire Fighting Procedures: Extinguish fire using agents suitable for surrounding fire. Use flooding
quantities of water. Fight fire from protected location or maximum distance possible.
• Health Hazards: Corrosive. Causes severe eye and skin burns.
• Fire and Explosion Hazards: Strong oxidizer. Not combustible, but promotes combustion in
combination with combustibles. Closed containers may rupture violently when heated. May cause
spontaneous combustion if allowed to remain in contact with readily oxidizable materials.
• Instability and Reactivity Hazards: Reacts violently with alkalies, oxidizable materials, finely
divided metals, alcohols, permanganates. Contaminated HP can decompose at a rate that will
exceed the venting capacity of the container. Decomposition can be self-accelerating and result in
explosive rupture of the container.
• Storage Recommendations: Store in a cool, dry, well-ventilated location. Separate from alkalies,
oxidizable materials, finely divided metals, alcohols, permanganates. See also NFPA 430, Code
for the Storage of Liquid and Solid Oxidizers.
• Usual Shipping Containers: Glass or polyethylene bottles, carboys, polyethylene-lined' or
aluminum drums with special vent caps; bulk packaging in aluminum tank trucks or rail cars and
bulk in tank barges.
• Physical Properties: Colorless liquid, slightly acrid odor.
• Boiling Point: 258 OF (126 °C) (70 percent solution).
• Specific Gravity: 1.44 @ 77 O F (25 °C).2
• Solubility In Water: soluble.
• Vapor Pressure: 8 mm mercury @ 77 OF (25 °C).3
NFPA assigns HP a health hazard rating of 3, which includes the criteria described below (NFPA
704).
• Materials that, under emergency conditions, can cause serious or permanent injury.
• Gases whose LC50 for acute inhalation toxicity is greater than 1000 ppm but less than or equal to
3000 ppm.
• Any liquid whose saturated vapor concentration at 20 °C (68 °F) is equal to or greater than its
LC50 for acute inhalation toxicity, if its LC50 is less than or equal to 3000 ppm and that does not
meet the criteria for degree of hazard four.
• Dusts and mists whose LC50 for acute inhalation toxicity is greater than 0.5 mg/L but less than or
equal to 2 mg/L.
• Materials whose LD 50 for acute dermal toxicity is greater than 40 mg/kg but less than or equal to
200 mg/kg.
• Materials that are corrosive to the respiratory tract.
• Materials that are corrosive to the eye or cause irreversible corneal opacity.
• Materials that are corrosive to skin.
• Cryogenic gases that cause frostbite and irreversible tissue damage.
• Compressed liquefied gases with boiling points at or below -55 °C (-66.5 °F) that cause frostbite
and irreversible tissue damage.
The reader should regard this with caution as a lined drum may be allowable by law but also constitutes a serious hazard as
discussed in Section 4.10.
z Concentration not specified.
3 Vapor composition and liquid concentration not specified.
4-12
i
Materials whose LD 50 for acute oral toxicity is greater than 5 mg/kg but less than orequal to
50 mg/kg.
I
t
1
4-13
4.3.3.1 Emergency Response Guidebook Fire Recommendations
The 2000 Emergency Response Guidebook, Guide 143: Oxidizers, Unstable, (ERG 2000) provides
information on the potential hazards of fire or explosion and of health that emergency response
personnel should be aware of in emergencies involving:
• Hydrogen peroxide, aqueous solution, stabilized, with more than 60 percent hydrogen peroxide,
2015'
• Hydrogen peroxide, stabilized, 20151
Potential Hazards — Fire or Explosion
• May explode from friction, heat or contamination

• These substances will accelerate burning when involved in a fire
• May ignite combustibles (wood, paper, oil, clothing, etc.)
• Some will react explosively with hydrocarbon (fuels)
• Containers may explode when heated
• Runoff may create fire or explosion hazard
Potential Hazards — Health
• Toxic. Inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause
severe injury, burns, or death.
• Fire may produce irritating and/or toxic gases.
• Toxic fumes or dust may accumulate in confined areas (basement, tanks, hopper/tank cars, etc.).
• Runoff from fire control or dilution water may cause pollution.
Public Safety - General
• Call the Emergency Response Telephone number on the Shipping Paper first. If the Shipping
Paper is not available or there is no answer, refer to appropriate telephone number listed on the
inside back cover.
• Isolate spill or leak area immediately for at least 160 to 330 ft (50 to 100 m) in all directions.
• Keep unauthorized personnel away.
• Stay upwind.
• Keep out of low areas.
Ventilate closed spaces before entering.
Public Safety - Protective Clothing
• Wear positive pressure, self-contained breathing apparatus (SCBA).

• Wear chemical protective clothing, which is specially recommended by the manufacturer. It may
provide little or no thermal protection.
• Structural fire fighters' protective clothing provides limited protection in fire situations ONLY; it
is not effective in spill situations.
Public Safety - Evacuation — Spill
2015 refers to the United Nations identification number, UN 2015.
4-14
1
See the Table of Initial Isolation and Protective Action Distances for highlighted substanes. 1 For non-
highlighted substances, increase in the downwind direction, as necessary, the isolation distance shown
under "Public Safety."`'
Public Safety - Evacuation - Fire
If tank, rail car, or tank truck is involved in a fire, ISOLATE for 800 m ('/z mile) in all directions.
Also, consider initial evacuation for 800 in (%z mile) in all directions.
Extinguishing Fires
For small fires, use water. Do not use dry chemicals or foams. CO, or Halon 3 may provide limited
control.
For large fires, the Emergency Response Guidebook recommends the following:
• Flood fire area with water from a distance
• Do not move cargo or vehicle if cargo has been exposed to heat
• Move containers from fire area if you can do so without risk
• Do not get water inside containers; a violent reaction may occur
• Cool containers with flooding quantities of water until well after fire is out
• Dike fire-control water for later disposal
• Always stay away from tanks engulfed in fire
• For massive fires, use manned hose holders or monitor nozzles; if this is impossible, withdraw
from area and let fire burn
4.3.3.2 OSHA Fire Recommendations
OSHA provides the following guidelines for fighting fires involving HP (OSHA 1996):
• To extinguish small fires using water only, no dry chemical or carbon dioxide.
• Flood fire area with water from a distance to fight large fires involving HP.
• Fires involving HP should be fought upwind from the maximum distance possible. Keep
unnecessary people away, isolate the hazard area and deny entry. Isolate the area for 800 m (%
mile) in all directions if a tank, rail car, or tank truck is involved in the fire.
• For a massive fire in a cargo area, use unmanned hose holders or monitor nozzles; if this is
impossible, withdraw from the area and let the fire burn. Emergency personnel should stay out of
low areas.
• Vapors are an explosion and poison hazard indoors, outdoors, or in sewers.
• This substance may ignite other combustible materials such as wood, paper, oil, etc. Mixed with
fuel they may react violently or even explode.
• Explosions can be caused by friction,4 heat or contamination. Containers of HP may explode in the
heat of the fire and should be moved from the fire area if it is possible to do so safely. If this is not
possible, cool fire exposed containers from the sides with water until well after the fire is out. Stay
away from the ends of containers.
1 HP is not a highlighted substance.

See above.
3 Use of Halon in modern fire extinguishment systems has been discontinued due to its negative effect on the environment,
which is primarily ozone depletion.
4
No supporting information on explosion initiation due to friction is provided.
4-15

t
• Firefighters
g should wear a full set of protective
P clothingg and self-contained breathingg
when fighting fires involving HP.
4.3.4 Spills
Because HP can be harmful to the environment, spills should be diluted with water and held in a pond
or dike area until it is decomposed. if combustible materials are exposed to HP, they should be
immediately drenched with water to prevent ignition and fire.
HP spills or releases, depending on the quantity, are regulated by specific standards. Notification of
the EPA or the United States Coast Guard may be necessary. Spilled HP may result in vapor
concentrations in air that exceed safe limits and endanger the environment via soil or water pollution.
Therefore, prompt cleanup or remediation of spilled HP is very important. The appropriate local or
national pollution, fire and emergency response authorities must immediately be notified in the event
of an HP spill or release to the environment. Assistance and guidelines for handling spills or releases
of HP can be obtained from CHEMTREC at (800) 424-9300. To report a spill of a reportable quantity
of HP, contact the following National Response Center at (800) 424-8802. The National Response
Center is a combined EPA and Coast Guard point of contact for federal regulatory agencies.
' Spills during transportation require notification of the RSPA. RSPA's hazardous materials inspection
and enforcement program is carried out by the Office of Hazardous Materials Enforcement (OHMS),
which is under the general direction of the Associate Administrator for Hazardous Materials Safety.
' OHME also enforces the requirement to submit a telephonic and/or written report (DOT Form 5800.1)
following the unintentional release of hazardous materials in transportation. If you have any questions
regarding DOT, call (800) HMR-4922, (800) 467-4922, or (202) 366-4488 (Washington, DC).
Spilled HP is not only a toxicity hazard, but it presents fire, explosion and compatibility hazards.
Because HP is highly reactive and is catalytically decomposed by various substances, these hazards
must be carefully assessed before cleaning up a spill is attempted. Sections 2 and 3 of this manual
provide additional information concerning fire, explosion and compatibility hazards.
4.3.4.1 Emergency Response Guidebook Spill Recommendations
The Emergency Response Guidebook (ERG 2000) provides the following guidelines for dealing with
an HP spill or leak:
• Keep combustibles (wood, paper, oil, etc.) away from spilled material
• Do not touch damaged containers or spilled material unless wearing appropriate protective
clothing
• Use water spray to reduce vapors or divert vapor cloud drift
• Prevent entry into waterways, sewers, basements or confined areas
Small Spills
Flush area with flooding quantities of water.
Large Spills
DO NOT CLEAN UP OR DISPOSE OF HP EXCEPT UNDER SUPERVISION OF AN HP

SPECIALIST. Additional information in the Emergency Response Guidebook (ERG 2000) provides
for spills involving aqueous solutions of HP at concentrations greater than 60 percent.
4-16
1
Evacuation — Spill
• "Oxidizers
Chapter 143—(Unstable)—of " Emergency Response Guidebook gives evacuation
the
and isolation procedures for spilled HP (ERG 2000)
• Isolate the spill or leak area immediately for at least 160 to 330 ft (50 to 100 m) in all directions
• Keep unauthorized personnel away
• Stay upwind
• Keep out of low areas
• Ventilate closed spaces before entering
• If a tank, rail car or tank truck is involved in a fire, isolate for 800 m ('/z mile) in all directions;
also, consider initial evacuation for 800 m (`/z mile) in all directions
4.3.4.2 OSHA Spill Recommendations
OSHA (1996) provides the following guidelines for HP spills or leaks.
In the event of a spill or leak involving HP, persons not wearing protective equipment and clothing
should be restricted from contaminated areas until cleanup has been completed. The following steps
should be undertaken following a spill or leak:
• Notify safety personnel.
• Remove all sources of heat and ignition.
• Ventilate the area of the spill or leak.
• Keep combustibles (wood, paper, oil, etc.) away from the spilled material.
• Water spray may be used to reduce vapors, but the spray may not prevent ignition in closed
spaces.
• For small liquid spills, flood the area with large amounts of water.
• For large liquid spills, flood the area with large amounts of water and dike far ahead of the spill to
contain the HP for later reclamation or disposal.
4.4 Environmental Fate of HP
4.4.1 Soil and Sediment
HP can be introduced to the soil or sediment through spills, atmospheric deposition such as rainwater,
or intentional introduction such as in environmental contamination remediation (Jacobi 2001, Petigara
2002; Valentine 1998). HP is thought to affect soil composition if its decomposition within the soil
leads to the formation of hydroxyl radical (OH) through a Fenton-type reaction:
H2O,+M"+—>OH+ Off +M" +1 (4.1)

+1
Where M n- and M" represent the reduced and oxidized form of a redox-active metal such as iron
(Fe). The half-life of HP in soils ranges from minutes to hours depending on microbiological and
metal contaminants (FMC 2002). 1
HP is sometimes used to supply oxygen to facilitate aerobic biological degradation or oxidation of
contaminants in soils (Huling 1990).
4-17
4.4.2 Atmosphere
Degradation of HP in the atmosphere by photolysis and by chemical reaction with organic substances
has been reported (Jacobi 2001). Direct photolysis occurs with radiation at wavelengths at 280 to
380 nm:

2H2O2 + by --> H2O + OH + HO,_ (4.2)
OH + HO," —> H2 O + OZ
The tropospheric half-life of HP was reported to be 10 to 20 h (Kleinman 1986). The half-life of HP in

air was reported to be 10 to 20 h (FMC 2002).
HP and its mixtures with methanols have been used to remove multiple air pollutants, nitrogen oxide,
sulfur trioxide and carbon-containing compounds from combustion-generated flue gas
(Zamansky 1996).
4.4.3 Aquatic
The half-life of HP in the aquatic environment ranges from 8 h to 20 days (FMC 2002). HP in surface
waters may be decomposed by transition metal catalysis or biodegradation or by biological organisms
such as plankton.
Direct photolysis was not reported to have a major role in aquatic decomposition (Jacobi 2001).
However, it was reported that when 10 mL of 90 percent HP, free from inhibitors, was exposed at 25
°C to radiation from a 100-watt mercury vapor lamp (rated as emitting 2.2 watts of radiation in the
near UV (3200-3800 angstroms)), the resulting HP decomposition rate was 0.25 percent per h. This
rate was about 70 times that observed in the absence of radiation under the same conditions (Schumb
1955). Further investigations would be required to elucidate the apparent discrepancy in results
reported by Jacobi and Schumb.
The half-life of HP in natural waters was reported to range from a few hours to several days (Cooper
1989).
4.5 HP Handling
4.5.1 Personal Protective Equipment
t Personal protective equipment (PPE) for working with HP or any other hazardous material is selected
on the basis of a hazard assessment. OSHA provides guidelines for performing a PPE hazard
assessment and making equipment selections (29 CFR 1910.132). In brief, the PPE selection process
is described below:
Assess the workplace to determine if hazards are present, or are likely to be present, which necessitate
the use of personal protective equipment (PPE). If such hazards are present or likely to be present:
• Select the types of PPE that will protect the personnel from the hazards identified in the hazard
assessment.
• Communicate selection decisions to the affected personnel.
• Select PPE that properly fits each affected employee.
• Train the personnel in what PPE is necessary and how to properly don, doff, adjust and wear PPE.
4-18
• Communicate the limitations of the PPE.
• Communicate the proper care, maintenance, useful life and disposal of the PPE.
Personnel are required to demonstrate an understanding of the training and the ability to use PPE
properly before being allowed to perform x^ ork requiring the use of PPE. Finally, the hazard
assessment process should be documented through a written certification that identifies the workplace
evaluated; the person certifying that the evaluation has been performed; the date(s) of the hazard
assessment (which identifies the document as a certification of hazard assessment).
Consequently, PPE selection is dependent on the specific operation being performed, the potential for
exposure to occur, the details of the potential exposure, and the compatibility of the PPE with HP. For
example, PPE selected for offloading hundreds of gals of HP from tanker to tanker or tanker to drums
may differ from the PPE selected for transferring HP from a 1-gal jug to small ampules, or for
working with mL quantities in a laboratory fume hood.
4.5.1.1 Eye and Face Protection
OSHA standard 29 CFR 1910.133 provides guidelines for the selection and use of eye and face
protective equipment. This standard incorporates a previous revision of the American National
Standards Institute Z87.1 Occupational and Educational Eye and Face Protection Devices (29 CFR
1910.6). The selection chart shown in the "Non-mandatory Compliance Guidelines for Hazard
Assessment and Personal Protective Equipment Selection" (29 CFR 1910 Subpart I App B) offers the
guidelines below:
• All protective eyewear must meet the impact resistance criteria set forth by ANSI (ANSI 2003).
• Safety glasses or spectacles with side shields shall be worn to protect against flying objects. These
are not recommended for protection against chemical exposure.
• Goggles with no ventilation shall be worn when there is an irritating mist hazard.
• Goggles with no ventilation or with indirect ventilation shall be worn when there is a chemical
exposure by splash hazard.
• Face shields may be worn over goggles for additional protection. Face shields are a secondary
protector and shall be used only with primary protectors, such as over safety glasses with side
shields for protection against impact, or over goggles for protection against chemical splash. Face
shields with crown, chin and neck protectors are also available.
4.5.1.2 Chemical and Protective Clothing
No one protective material is suitable for protection against all types of hazards or chemicals. Some
types of protective material may react with HP, violently or otherwise. For example, steel-toed leather
footwear, while meeting the requirements of the American National Standards Institute Z41-1999 for
protection against impact, metatarsal injury, compression and puncture, may catch on fire upon contact
with HP. Another example is poly(vinylalcohol) (PVA) gloves. While suitable for use with a number
of organic solvents, PVA may dissolve upon contact with HP. This section of the manual provides
guidelines on the PPE selection process for HP.
There are standard test methods to determine the suitability of protective clothing (ASTM 1996,
ASTM 1997, ASTM 2000). HP suppliers also provide recommended protective clothing (AKZO
Nobel 2001, FMC 2002). A summary of protective clothing for use when working with HP is given in
Table 4.3.
4-19
There is also a specific test method for evaluating protective clothing materials for HP service (FMC
1966). This test involves dripping HP onto swatches of the test material in an "as received" and in a
"soiled" condition. "Soiling" is accomplished by exposing the material to a 0.005N KMn0 4 solution,
then drying it in an oven. While dripping HP on the material at a rate of 4 mL per min for one h,
t
changes in the surface, smoking where HP contacts the materials, sparks and time to ignition are
noted. It is also noted whether the material will support combustion when removed from the dripping
HP. Results of FMC testing are given in Appendix F.
Table 4.3
Protective Clothing Summary (AKZO Nobel 2001, FMC 2002)
HP Concentration Protective Clothing Material
30 percent > 6 h, 70 °F (21 °C): 4H oa and Silver Shield ®b (gloves, aprons, sleeves
and booties) (North Safety Products 2001)
30 percent Neoprene, natural latex or rubber, butyl and nitrile gloves are rated
"good" (CDC 1997)
30 to 70 percent 8 h: Butyl rubber (gloves, suits, boots), natural
rubber (gloves), nitrite (gloves, suits, boots), polyethylene (PE) (gloves,
suits, boots), Viton ®` (gloves, suits), CPF3 d (suits), Responder a (suits),
Tychem ` (Tychem 10,000 suits). Recommendations are NOT valid for
very thin natural rubber, neoprene, nitrile and PVC gloves (0.3 mm or
less) (NIOSH 1999)
(8 h = More than 8 h of resistance to breakthrough > 0.1 µg/cm'-/m)
4 h: Polyvinyl chloride (gloves, suits, boots), 4H and Silver Shield gloves.
Recommendations are NOT valid for very thin natural rubber, neoprene,
nitrile and PVC gloves (0.3 mm or less) (NIOSH 1999).
(4 h = At least 4 but less than 8 h of resistance to breakthrough > 0.1 p
g/cm2/min)
30 to 70 percent > 8 h: Butyl rubber, natural rubber, nitrile rubber, Viton, Responder
> 4 h: Polyvinyl Chloride, 4H (PE/EVAL)
1-4 h (Caution): Neoprene
< 1 h (not recommmended, degradation may occur): Polyvinyl alcohol
(OSHA 1996)
> 60 percent PVC or rubber rainsuit (body), (AKZO Nobel 2001)
> 90 percent Gortex ®9 polyester or acrylic (full cover clothing), approved rubber or
nitrite (gloves and shoes) (FMC 2002)
4HJ is a registered trademark of Safety 4 A/S Corporation, Denmark. 4H is a polyethylene/poly(ethylvinyl) alcohol
laminate.
b Silver Shield® is a registered trademark of Siebe North, Inc. Corporation, Charleston, South Carolina.
Viton° and Tychem'9 are registered trademarks of DuPont de Nemours Company, Wilmington, Delaware. Viton is a
poly(vinylidene fluoride-co-h exafluoropropylene) material.
d CPF3 8' is a registered trademark of the Kappler Company, Arlington, Washington. CPF3 is a multilayer barrier film
laminated to a polypropylene substrate.
Responder° is a registered trademark of Life-Guard, Inc., Guntersville, Alabama. Responder is a multicomponent
Level A protective ensemble.
f OSHA also states the following, which is applicable to all PPE:
To evaluate the use of these PPE materials with hydrogen peroxide, users should consult the best available
performance data and manufacturers' recommendations. Significant differences have been demonstrated in the
chemical resistance of generically similar PPE materials (e.g., butyl) produced by different manufacturers. In
addition, the chemical resistance of a mixture may be significantly different from that of any of its neat components.
B
Gortex® is a registered trademark of DuPont de Nemours Compariv. Wilmington, Delaware.
4-20
1
OSHA Non-mandatory Compliance Guidelines for Hazard Assessment and Personal Protective
Equipment Selection (29 CFR 1910 Subpart I App B) offers the following guidelines with respect to
selection of gloves for protection against chemical hazards:
• The toxic properties of the chemical(s) must be determined; in particular, the ability of the
chemical to cause local effects on the skin and/or to pass through the skin and cause systemic
effects.
• Generally, any "chemical resistant" glove can be used for dry powders.
• For mixtures and formulated products (unless specific test data are available), a glove should be
selected on the basis of the chemical component with the shortest breakthrough time, since it is
possible for solvents to carry active ingredients through polymeric materials.
• Employees must be able to remove the gloves in such a manner as to prevent skin contamination.
Any chemical-resistant clothing that is used should be periodically evaluated to determine its
effectiveness in preventing dermal contact. Safety showers and eye wash stations should be located
close to operations that involve hydrogen peroxide.
4.5.1.3 Protective Footwear
Protection from HP must be considered in the selection of protective footwear. OSHA standard 29
CFR 1910.136 and the American National Standards Institute Z41-1999 (which is incorporated as
specified in 29 CFR 1910.6) set forth specific requirements for protection against impact, metatarsal
injury, compression, puncture and electrical hazards. Such hazards may be necessary in the following
situations: for protection during transport of HP tanks, drums, cylinders, hand held carts or dollies;
when working with or around different kinds of ground support equipment; and performing
inspections, maintenance and construction work around areas where HP is present. The standards,
however, make no mention of chemical resistance. Like any other PPE selection, chemical resistance
is an extremely important consideration in the selection of protective footwear. For example, ANSI
Z41-compliant footwear made of leather may catch on fire upon contact with HP. This can cause not
only immediate injury to personnel but create additional hazards as well (see Section 4.3.3 Fire
Fighting). Therefore, the selection of the appropriate footwear for work with HP must be made after
first assessing the hazards involved. The guidelines below are offered. I
• Wear ANSI Z41-compliant footwear when there is any danger of injury to the feet due to falling
or rolling objects, objects piercing the shoe sole, and where employees' feet are exposed to
electrical hazards.
• Ensure the footwear is compatible with HP if it is assessed that exposure of the footwear to liquid
HP is possible. The portions of the footwear that could be exposed to HP could be neoprene or
butyl rubber, for example.
• A protective covering over footwear may be assessed as appropriate in certain instances, such as a
PVC bootie worn in the laboratory when working with small quantities of HP.
4.5.2 Respiratory Protection
OSHA standard 29 CFR-1910.1000 states the following:
Administrative or engineering controls must first be determined and implemented whenever

feasible. When such controls are not feasible to achieve full compliance, protective equipment
or any other protective measures shall be used to keep the exposure of employees to air
contaminants within the limits prescribed in this section. Any equipment and/or technical
4-21
measures used for this purpose must be approved
PP for each P articular use b Y a competent
P
industrial hygienist or other technically qualified person. Whenever respirators are used, their
' use shall comply with OSHA 1910.134.
Approved respirators must be worn when the concentration of HP vapor exceeds the allowable limits.
The allowable limit established by OSHA is a PEL of 1 ppm (29 CFR 1910.1000). The allowable limit
established by the ACGIH is a TLV-TWA of 1 ppm (ACGIH 2003). The recommended exposure limit
(REL) established by NIOSH is a TWA of 1 ppm (NIOSH 2003). A facility may establish its own
limit, if it is more stringent than the PEL, TLV-TWA, or REL and the facility has sufficient
knowledge of the hazards to do so. As stated above, when respirators are used, their use must comply
with 29 CFR 1910.134. This OSHA respiratory standard has very specific requirements for the
' selection of appropriate respiratory protective equipment and the qualification of personnel (medical
and otherwise) to wear and use them. The requirements listed below for respiratory protection against
HP apply.
• Identify and evaluate the respiratory hazard(s) in the workplace.

• The evaluation shall include a reasonable estimate of employee exposures to respiratory hazard(s)
and an identification of the contaminant's chemical state and physical form.
• Where the employer cannot identify or reasonably estimate the employee exposure, the employer
shall consider the atmosphere to be IDLH.
• Respirators must be NIOSH-certified and shall be used in compliance with the conditions of its
certification.
• Respirator selection shall be from a sufficient number of respirator models and sizes so that the
respirator is acceptable to, and correctly fits, the user. Be aware that HP mists may be present
along with HP vapor.
• Supplied-air respirators or SCBA (air purifying respirators are not allowed for protection against
HP) should be made available.
IThe NIOSH/OSHA Respirator Recommendations for HP (NIOSH 2003) are:
• Up to 10 ppm (Assigned Protection Factor (APF) = 10): Any supplied-air respirator.

' 0 Up to 25 ppm (APF = 25): Any supplied-air respirator operated in a continuous-flow mode.
• Up to 50 ppm (APE = 50): Any self-contained breathing apparatus with a full face piece or any
supplied-air respirator with a full face piece.
' • Up to 75 ppm (APF = 2000): Any supplied-air respirator that has a full face piece and is operated
in a pressure-demand or other positive-pressure mode.
• Emergency or planned entry into unknown concentrations or IDLH conditions (APE = 10,000):
Any self-contained breathing apparatus that has a full face piece and is operated in a
pressure-demand or other positive-pressure mode or any supplied-air respirator that has a full face
piece and is operated in a pressure-demand or other positive-pressure mode in combination with
an auxiliary self-contained positive-pressure breathing apparatus.
• Escape (APE = 50): Any air-purifying, full-face piece respirator (gas mask) with a chin-style,
front- or back-mounted canister providing protection against the compound of concern' or any
appropriate escape-type, self-contained breathing apparatus.
• Respirators provided only for escape from IDLH atmospheres shall be NIOSH-certified for escape
from the atmosphere in which they will be used.
HP is not compatible with and could be explosive with the carbon absorbent material in an air-purifying respirator. No
approved canister for protection against HP vapor is available from Mine Safety Appliances
(http://www.msanet.com/day/20.html), which is a primary supplier of NIOSH and other regulatory agency-approved
respiratory protective equipment.
4-22
4.5.3 Monitoring9 Equipment
4.5.3.1 Commercial Monitoring Equipment
Operations involving HP can potentially expose personnel to HP vapors in excess of allowable

exposure limits. Monitoring equipment can be used to determine if an area is safe before personnel are
allowed to enter without respiratory protective equipment. After personnel enter an area where
exposure is possible, monitors can be used continuously. Monitors can be used for making industrial
hygiene surveys and serve to determine or confirm the effectiveness of the engineering control
measures.
Various methods used to measure HP in air include:
• Direct reading instruments in which sampling and analysis are performed within the instrument
itself and the information is displayed on a meter or digital readout.
• Collection of an air sample in which a measured volume of air is processed and the analytical
determination is later performed by instrumental or chemical analysis.
• Colorimetric devices in which a chemical reaction in a tube or dosimeter produces a color or a
color change measurable on a direct reading on the scale of the tube or by color comparison.
The selection of a direct reading instrument, air sample collection/laboratory analysis method or
colorimetric device requires a thorough understanding of the intended application, the personnel
monitoring requirements that may be required by various regulations, and the reason for monitoring.
Direct reading instruments are typically used for real-time measurements while air sample
collection/laboratory analysis methods may be required by OSHA or NIOSH health regulations.
Before selecting any direct reading instrument, the following factors should be evaluated:
• Operating characteristics
• Simplicity of use and operation
• Accuracy and precision
• Interference susceptibility (both positive and negative)
• Ease of calibration and maintenance
• Size and weight
• Portability and orientation sensitivity
• Zero stability and drift
• Span stability and drift
• Battery life
• Warm-up time
• Relative humidity effects
• Temperature effects
A comparison of techniques used to monitor HP in air was reported (Puskar and Plese 1996). The
techniques that were evaluated were a Draeger tube, ion mobility spectrometer and OSHA Method
V 1-6 (wet chemical method). The principal difficulties encountered with the instruments were
calibration and effects of relative humidity. Relative humidity was also found to be a problem with the
Draeger tube. The OSHA method suffered from the disadvantage of not being a real-time method.
Exposure assessment of vapor emissions during HP propulsion testing has been performed and
reported (Meske 2000a and 2000b). In a test firing of 90 percent HP with a liquid hydrocarbon fuel
(JP8), a direct reading Model C 16 ATI PortSens II monitor using an HP electrochemical sensor was
4-23
' used to monitor HP concentrations. Immediately after the test fire, and within close proximity to the
test stand, concentrations of HP were above established exposure limits.
Exposure assessment of vapor emissions during HP propulsion testing was reported in other accounts
of test firing of 90 percent HP with a liquid hydrocarbon fuel (JP8) (Brever 1999, Wright 2000).
Personal and area air samples were collected in accordance with OSHA Method VI-6, which is a
partially validated method (OSHA 1977). Air samples were collected in midget fritted glass impingers
containing titanium oxysulfate (TiOSO 4 ) collecting solution. Then the solution was prepared and
analyzed colorimetrically. Airborne concentrations of HP near the test cell were found to exceed
established exposure limits. Administrative controls such as observation of wind direction and post-
test wait time were sufficient to control personnel exposure.
Information on commercially available direct reading instruments for HP can be obtained from the
following companies.
• Global Detection Systems

1233 Confederate Rd.
Houston, Texas 77055-6306
(713)984-1437
Fax: (713) 984-0955
• PureAire Monitoring Systems

5420 Newport Dr., Ste. 57
Rolling Meadows, Illinois 60008.
(847) 788-8050.
http://www.pureairemonitoring.com
• Draeger Safety, Inc.

GDS Houston Office
10450 Stancliff, Ste. 220
Houston, Texas 77099
(281)498-1082
http://www.draeger.com/us/ST/Ag.jsp
' AFC International, Inc.

P.O. Box 894, DeMotte, IN 46310
715 SW Almond St, Ste. A
' DeMotte, Indiana 46310
(800) 952-3293 or (219) 987-6825
Fax: (219) 987-6826
http://www.afcintl.com/index.html
I Bionics (PureAire monitoring systems, Inc.)

5420 Newport Dr., Ste. 57
Rolling Meadows, Illinois 60008
(847)788-8000
Fax: (847) 788-8080
http://www.bionics-instrument.com/about.htm
4-24
• CEA Instruments, Inc.
16 Chestnut St.
Emerson, New Jersey 07630
(888)893-9640
http://www.ceainstr.com/
Information on commercially available sampling tubes and kits can be obtained from the following
companies:
• Draeger Safety, Inc.

GDS Houston Office
10450 Stancliff, Ste. 220
Houston, Texas 77099
(281) 498-1082
http://www.draeger.com/us/ST/Agisp
• SKC Inc
863 Valley View Rd.,
Eighty Four, Pennsylvania 15330
(724)941-9701(800)752-8472
http://www.skcinc.com/diffusion/dosimeter.litml
• Analytical Technology, Inc.

Box 879/680 Hollow Road
Oaks, Pennsylvania 19456
(610)917-0991(800)959-0299
Fax: (610) 917-0992
http://www.analyticaltechnology.com
Commercially available test strips for the determination of HP on wetted surfaces or in rinsates are
available for concentration ranges from 0.5 to 25 mg/L and 0 to 100 mg/L. Information on
commercially available test strips for the determination of HP can be obtained from the following
companies:
• EMD Chemicals
Gibbstown, New Jersey 08027
http://www.emdchemicals.com
• Ben Meadows
P.O. Box 80549
Atlanta, Georgia 30366
(800)241-6401 Fax: (800) 241-2068
http://www.benmeadows.com
• Lab Safety Supply

P.O. Box 1368
Jamesville, Wisconsin 53547
(800) 356-0783
http://www.labsafety.com
4-25
4.5.3.2 Regulatory Agency Procedures
OSHA Method ID 126SG is a partially validated method in which 100 L of air is passed at 0.5 L/min
through a midget fritted glass bubbler containing 15 mL TiOSO 4 (OSHA 1993). The resulting solution
is analyzed using a polarograph. For more information, consult
http://www.osha-sic.gov/dts/chemicalsampling/data/CH_246600.html.
4.6 Engineering Design
Safe handling of HP requires proper system designs (Hall 1989). The oxidizing and corrosive
properties of HP, coupled with its sensitivity to decomposition by contamination or incompatible
materials (and the gas that is generated as a result) make it necessary to very carefully choose
materials HP will come into contact with. Systems must be designed to relieve excess pressure and
avoid areas where bubbles could accumulate and to allow leaked HP to drain in a manner that does not
cause further damage.
Because decomposition of HP may happen on a surface, small systems may have problems in pipes,
pumps and valves where surface-to-volume ratios are likely to be greater than those found in tanks and
other containers (Mackenzie 1990). These problems can be exacerbated if components with rough
surfaces are present. In such cases, the gas evolution per unit volume in a system of HP can be much
higher in pumps, pipes and valves than those found in tanks and other containers. Additionally, typical
pipeline systems for liquids rarely have headspace. Because of this, even low rates of gas evolution
can rapidly raise the pressure inside a pipeline system. Although this is not necessarily a problem
when the system is flowing, when the system is stationary, pressure bursts can occur. Bursts can also
occur when HP is sealed in pipe sections that are between valves if procedural controls are not used to
prevent this "liquid lock"condition and where no positive pressure relief is provided to protect the
system if a procedural error does occur. Individual valves can also have internally sealed dead spaces.
Such spaces must be avoided, provided with relief, or be capable of being provided with a flow path
that could provide relief. For example, ball valves for HP service (of a design with a seal on both sides
of the ball) are drilled to provide a small hole in the upstream face of the valve to vent the dead space
when the valve is closed.
Operating a centrifugal pump against a closed head, such as without flow, may mechanically or
frictionally heat HP (McKenzie 1990). High temperature and rough or relatively high surface areas,
such as from fins, can cause rapid decomposition of HP.
A good engineering design must take into account that gas (oxygen) evolution may occur within an
HP system, and provide relief accordingly. Knowledge of the expected decomposition or pressure
evolution rates may assist the engineer in the proper sizing of pressure relief systems. In a situation
where HP undergoes rapid decomposition (such as what may occur if the fluid contacts an
incompatible material, surface, or if contamination is introduced), heat and pressure may not dissipate
and the rising temperature of the HP can cause the decomposition rate to accelerate. When this occurs,
HP may violently decompose and evolve large volumes of oxygen and steam in what might
approximate adiabatic conditions. This can result in a catastrophic event such as an explosion.
Choosing the appropriate materials, ensuring they are properly passivated, preventing contamination,
and selecting the appropriate pressure relief system is extremely important in the design of HP
systems. All components must be compatible and properly passivated before use.
The hot steam- and oxygen-enriched environment downstream of a catalyst bed can be very aggressive
towards materials. Design engineers must take this into consideration, as applicable.
4-26
Valves and other assembled components should be carefully examined for void spaces and for
potentially incompatible materials of construction. Incompatible materials that are coated with
compatible materials should be carefully evaluated before use.
System design should minimize the number of sealed connections to reduce potential leak points.
Sealed connections should be high integrity designs. Designs that use threads in contact with the
media should be avoided. Threads or other entrapment areas that are in contact with the media are a
concern due to the large surface area compared to the media volume. This results in an increased
oxygen gas generation rate coupled with a location where the oxygen accumulates and is trapped. Use
of tapered pipe thread fittings should be avoided because the threads contact the media and there are
concerns about debris that is generated during assembly. The use of threaded port with O-Ring gaskets
designs, sometimes called AN Boss fittings (SAE J 1926-1, SAE AS5202, MS 33649) should be
avoided because the threads contact the media. Bending of pipes and tubing is recommended over
mechanical elbow fittings to reduce leak points. Welded joints are preferable to mechanically sealed
joints.
In the presence of HP, dissimilar metals in contact may electrolytically corrode (NAVAER 1957).
Although the more concentrated the HP the less the corrosion, contact of dissimilar metals even with
90 percent HP should be avoided. Sometimes, one metal can be insulated from the other by a plastic.
If two dissimilar metals must be in contact, the one that corrodes (the anodic metal) should have a
larger surface area than the other (the cathodic metal). For example, aluminum is corroded (anodic)
with stainless steel (cathodic).
Weld spatter on the inside of the equipment should be avoided and the amount of weld exposed to HP
should be minimized (NAVAER 1957). Good machining practices are also important because a
smooth surface or fine finish causes less decomposition of HP than does a rough or poorly machined
surface.
Honing and grinding must be performed carefully and every precaution must be taken to avoid
transferring or embedding impurities from one system to another (General Kinetics, LLC 2003).
Casting can embed impurities in a surface, and hardening and welding processes can result in a surface
that is less compatible with HP than the original base material.
4.6.1 Process Safety Management
An HP system must be managed in accordance with 29 CFR 1910.1 19, "Process Safety Management
of Highly Hazardous Chemicals," when quantities of HP (>_ 52 percent) are greater than or equal to
7500 lb. This is the Threshold Quantity in Appendix A "List of Highly Hazardous Chemicals, Toxics
and Reactives (Mandatory)" of 29 CFR 1910.1 19. This OSHA standard contains requirements for
preventing or minimizing the consequences of catastrophic releases of toxic, reactive, flammable, or
explosive chemicals, which may result in toxic, fire or explosion hazards. It is a performance-oriented
standard and it requires that best practices, including engineering design, be employed as applicable.
While it is not within the scope of this manual to provide a complete review of this OSHA standard,
one of the requirements applicable to this section is the compilation of written process safety
information that includes:
• Materials of constriction
• Piping and instrument diagrams (P&IDs)
• Electrical classification
• Relief system design and design basis
4-27
• Ventilation system design
• Design codes and standards employed
• Material and energy balances for processes built after May 26, 1992
• Safety systems (e.g. interlocks, detection or suppression systems)
• Documentation of equipment compliance with recognized and generally accepted good
engineering practice
• Documentation of existing equipment designed and constructed in accordance with codes,
standards, or practices that are no longer in general use that the equipment is designed,
maintained, inspected, tested and operating in a safe manner
Stennis Space Center, where extensive HP testing has been performed, is developing a Hydrogen
' Peroxide Design Guide based on best practices and the facility's experience. At the time of publication
of this manual, the document was in draft form and contained information on design philosophy and
requirements for Class 1 and Class 2 HP systems, plus a number of appendices. The draft design guide
' can be obtained by contacting Stanley C. Warren at NASA/VA60 at Stennis Space Center (228) 688-
7111. The guide includes:
• Reference material and related literature

• Design checklist
• HP material compatibility
• Past experiences
• Cleaning methodologies
• Welding fabrication and weld examination/inspection of HP systems
• Hardware currently used in HP systems and hardware identified as potential candidates for use
given further technical evaluation
• HP decomposition and rates of reaction
4.6.2 Assembly Guidelines
Guidelines for assembly of propulsion systems (CPIA 1984) are listed below:
• Only clean, degreased tools should be used.

• Operators should wear clean, lint-free gloves and outer garments.
• Small components should be assembled in a clean, dust-free room.
• Keep all openings and clean surfaces covered with polyethylene film until the system has been
assembled.
- Polyethylene film is easily shredded wherever it is bent or creased sharply. Whenever there
are sharp corners, threads or knife-edges are to be covered. ACLAR 33-C film of 0.025 to
0.05 mm thickness should be used as the inner liner.
- Careful use of grease-free and oxide-free metals and tools, avoidance of internal surface
handling, fingerprints, and accumulation of lint, dust and metal particles are important during
the assembly process.
- Use a clean, dry purge gas during the assembly process.
- All systems are to be kept clean by closing or covering all openings with plastic film.
- Every system should be pressure-checked at operating pressure to ensure there are no leaks.
Additional design guidelines are provided in the EKA Hydrogen Peroxide Product Information
Manual and are listed below:
4-28
• Use a minimum number of valves.
• Where several valves in a series cannot be avoided, a small safety valve for liquid or a small
rupture disc can be used to provide pressure relief in the system. Blind flanges installed on the
discharge side of a properly drilled ball valve can still result in over-pressure conditions. Avoid
this combination.
• Run a small recirculation line with restriction orifice from the discharge side of the pump back to
the tank.
• Avoid locating shutoff valves and bypass valves next to control valves.
• Ball valves should be specially cleaned and drilled to prevent overpressure conditions. Make sure
the design keeps HP from coming into contact, directly or indirectly (via return lines or the like),
with unsuitable materials of construction or process liquids.
• Valves and pumps requiring lubricants should be avoided. Lubricated power ends on pumps are
acceptable when maintained properly.
• Pipes should be plainly marked to identify their contents.
• TIG (Tungsten-Inert-Gas) or MIG (Metal-Inert-Gas) welding with shielding gas (e.g. argon) must
always be used for aluminum welding. Tungsten electrodes should be used for TIG welding of
aluminum. It is important that the filler metal has the same composition as the base metal and is
free of moisture and other impurities.
• TIG welding with shielding gas should be used for stainless steel welding. The piping must be
well-filled with shielding gas to ensure a good weld on the inside.
4.7 Cleaning and Passivation
The stability of HP solutions is sensitive to impurities and the surface effects of its containers. While
stabilizers are used to help mitigate HP self-decomposition, it is of utmost importance that containers
or any surfaces HP may contact are specially cleaned and passivated. In a cleaning procedure, the
contaminants are removed from the surface, while in a passivation procedure, the surface is typically
chemically treated to produce an oxide layer. The surface of a passivated component is not
representative of the bulk composition of the component. Details on the chemistry of the passivation
process are discussed in Section 3 of this manual.
There are many safety precautions to be taken when preparing solutions for passivation, performing
the passivation process, and disposing of solutions used in the passivation process. Safety issues that
may arise when cleaning and passivating include:
• Exposure to detergents, solvents, acids and bases used in the process.

• Violent reaction of HP with incompatible solvents.
• Ignition of combustible materials.
• Violent decomposition of HP to steam and oxygen by dirt. impurities or contaminants on the parts
to be cleaned and passivated.
1
• Violent decomposition of HP if attempting to passivate inherently incompatible materials such as
carbon-based steels, nickel, chromium, bronze, or copper.
• Excessive pressure build-up in closed or improperly vented systems.
The specific safety precautions of working with organic solvents and detergents used in degreasing
and hydrofluoric and nitric acids used in pickling and passivation are not discussed in this manual.
However, it is important to realize that HP is a strong oxidizing agent and is incompatible with a
variety of organic solvents. An example of an extremely incompatible solvent is acetone, with which
HP may form explosive acetone peroxide (Schumb 1955). Other hydrocarbon-based solvents may
4-29
catch on fire when mixed with HP. Rags, paper and leather must be kept away from HP at all times.
Properly segregate and promptly dispose of cleaning solution wastes.
The procedures described below are used for cleaning and passivating containers used to store or test
HP. It is very important to verify that a surface has been properly passivated. Means to evaluate the
effectiveness of passivation include observation of discoloration, bubbles, gas streamers, heat, or
pressure generation when the surface is exposed to HP. It is also important to note that not all cleaning
and passivation procedures are alike. The user of this manual must evaluate the various cleaning and
passsivation procedures, including those recommended by the HP manufacturer, before selecting the
appropriate procedure(s).
4.7.1 Procedures for the Passivation of Glassware
MIL-PRF-16005F specifies the method of passivating Pyrex volumetric glassware in preparation
1 for the stability test. Glassware is filled with concentrated American Chemical Society (ACS)
reagent grade nitric acid, covered with pure aluminum foil with an inverted beaker placed over the
aluminum cover. The flask is placed in a boiling water or steam bath. The nitric acid is poured off
and the flask is rinsed with distilled water immediately followed with an HP rinse. Distilled water
is not allowed to dry in the flask. The flask is screened by performing the stability test using
samples. Flasks that give inconsistent results are rejected. Flasks that give consistent results shall
only be used for HP samples.
1 • MIL-P-16005E (inactive) specifies the method of passivating Pyrex volumetric glassware in

preparation for the stability test. This procedure was the same as that specified in the current MIL-
PRF-16005F (above).
MIL-H-22868 (Wep) (inactive) specifies the method of passivating Pyrex volumetric glassware in
preparation for the stability test. Glassware is filled with concentrated certified pure (c.p.) nitric
acid and maintained at 100 °C for 24 h. The tops of the flasks are covered with small beakers. The
acid is removed and the flasks are rinsed with distilled water, followed immediately with an HP
rinse. The flasks are screened by performing the stability test using peroxide from the same
container in each flask. Flasks that give inconsistent results are rejected. The flasks are then to be
used for no other purpose but to contain HP. Even distilled water cannot be allowed to dry in the
flasks, but must be rinsed out immediately with HP.
FMC Bulletin 104 describes a method for passivation of glassware (FMC 1966). Prior to use, all
glassware, including thermometers and hydrometers, should be cleaned as follows:
' - If heavily soiled, immerse in a 10 percent sodium hydroxide (NaOH) for 1 h at room
temperature. If the glassware is relatively clean, the use of sodium hydroxide for cleaning may
actually decrease the inertness of the surface to hydrogen peroxide. This step may be omitted
' and a detergent substituted.
Rinse in clean potable water.
- Immerse in 35 percent sulfuric acid for at least 1 h at room temperature.
- Air dry or dry in an oven at 230 °F (110 °C).
' - Passivated glassware can be stored ready for immediate use by covering the opening with
aluminum foil.
• A technical data sheet from Solvay Interox, Houston, Texas, describes a method for passivation of
laboratory equipment that will come into contact with peroxygens, and is most applicable to glass
containers (Solvay 2001). The inside of the container is first washed with any common detergent
4-30
for cleaning glassware. Detergent residues are then rinsed from the container thoroughly with
1
demineralized water (or water of equivalent purity). A one part (70 percent) nitric acid to one part
demineralized water (or water of equivalent purity) by volume is stored in the container for at least
24 h at ambient temperature. Just prior to using the container, the 1:1 nitric acid solution is
removed and all residues are rinsed with demineralized water (or water of equivalent purity).
The Hydrogen Peroxide Handbook (Rocketdyne 1967) describes a procedure for passivation of
laboratory-type equipment including thermometers and hygrometers. Heavily soiled glassware is
immersed in 10 percent sodium hydroxide (NaOH) for 1 h at room temperature. If the glasssware
is relatively clean, commercial detergent is used instead. The glassware is then rinsed thoroughly
in potable water. Chemical passivation is next performed by immersion in 35 percent sulfuric acid
for at least 1 h at room temperature. After the glassware is thoroughly rinsed in distilled or
deionized water, it is dried with clean air or nitrogen or in an oven at 230 °F (110 °C). The
passivated glassware is then stored after wrapping and sealing in clean plastic or metal foil bags.
Bottles, flasks, or other containers can be stored by covering the opening tightly with aluminum
foil.
• CPIA describes a procedure for passivation of glassware (CPIA 1984). Glassware is sequentially
immersed in 10 percent sodium hydroxide for 1 h at room temperature, rinsed in tap water,
immersed in 35 percent sulfuric acid for 1 h minimum at room temperature, then rinsed in distilled
or deionized water and dried.
A recent study describes a passivation procedure where a Pyrex glass flask used for the stability
test is treated with nitric acid followed by annealing at 1076 °F (580 °C) for 3 h, then passivated
with nitric acid and a 98 percent propellant-grade HP (Huang 2003).
4.7.2 Procedures for Passivation of Metals and Materials
It is important to note that not all cleaning and passivation procedures are alike. The user of this
manual must evaluate the various cleaning and passsivation procedures, including those recommended
by the HP manufacturer, before selecting the appropriate procedure(s).
4.7.2.1 Passivation of Metal Surfaces
The Hydrogen Peroxide Passivation Procedure (Solvay 2003) is for metal surfaces and consists of
several steps:
• Grinding to remove weld spatter and smooth out scratches.

• Degreasing with a trisodium phosphate/sodium metasilicate solution to remove oil and grease
films.
• Pickling with a sodium hydroxide solution to chemically clean the surface.
• Passivating with a nitric acid solution to form an oxide film.
• Testing with dilute HP solution to ensure successful treatment.
The Chemical Propulsion Information Agency (CPIA 1984) has described procedures for passivating
materials:
4-31
Stainless Steel
After cleaning, immerse or fill with 70 percent nitric acid and allow to stand for 5 h at room
temperature. Then remove and rinse with distilled or deionized water. Condition with 70 to 90 percent
HP for 4 h. Criteria for inspection and special treatments such as with nitric acid/hydrofluoric acid
mixtures are also described.
Aluminum
After cleaning, immerse or till with 0.25 percent sodium hydroxide solution and allow to stand for
20 min at room temperature. Then, remove and rinse with distilled or deionized water. Immerse or fill
with 45 percent nitric acid and let stand for 1 h at room temperature and rinse again with distilled or
particle-free distilled deionized water. Then, condition with 70 to 90 percent HP for 4 h. Criteria for
inspection to observe bubble formation and discoloration and special treatments are also described.
Finally, the part is removed from the HP, flushed with distilled water, inspected under specific criteria,
then oven or air dried (tanks need not be dried).
Non-metals
Plastics, O-rings and gaskets are sequentially wiped as clean as possible with a lint-free rag,
degreased by agitating in a 1 percent detergent solution at 120 °F (49 °C), then rinsed thoroughly
in distilled water and allowed to air dry.
To obtain a higher degree of cleanliness, the following procedure is followed for plastic and
elastomeric parts: wipe as clean as possible with a lint-free rag; degrease with trichloroethylene;
scrub with 0.2 percent detergent water solution; flush with distilled water; immerse in 20 percent
nitric acid for 1 It at room temperature; flush with distilled water: immerse in 35 percent HP for 24
h; then immerse in 90 percent HP for 24 h.
' Systems Cleaning
• Removable (Small) parts. Parts such as valves and piping are disassembled (except for plastic
inserts that might be damaged by removal), and aluminum and stainless steel parts are processed
separately throughout the passivation procedure. Parts are sequentially wiped free of loose dirt and
grease, degreased by 1, 1, 1 -trichloroethane vapor or solvent (other degreasing solvents are listed in
' Appendix F of this reference) for 30 min. Criteria for cleaning plastics with solvents are given.
Solvent absorption must be considered. Degreased parts are rinsed with alcohol and handled with
clean gloves. Parts and equipment are then rinsed with distilled or particle-free deionized water.
' Non-Removable Components. Stainless steel tanks, after cleaning, are examined and brushed with
an AISI 300-series stainless steel brush if welding scale or dirt is found. The tank is then filled
with 3 percent hydrofluoric acid (HF) and 10 percent nitric acid and left to stand for 3 h at 65 to 75
°F (18 to 24 °C), drained, rinsed with clear water, and brushed again. If the tank is small, it is
tilled with approximately 70 percent nitric acid and left to stand for 4 to 5 h at room temperature
before draining and rinsing with water. If the tank is large, it is passivated for one to two days
' before draining and rinsing with distilled or deionized water. If possible, the tank is then
conditioned with 35 percent HP for one to three days before filling with propellant grade HP. (The
criterion for passivation is that there are no bubbles or streamers noticed, and the tank is quiet and
' cool.) The 35 percent HP is pumped out and the tank is rinsed with distilled water, then tilled with
70 to 90 percent HP. The tank is monitored for rising temperature or excessive gassing of the HP
for at least 6 h and up to 24 h, if possible.
4-32
Aluminum and aluminum alloy tanks holding less than 100 gal, after cleaning, are filled with
0.25 percent sodium hydroxide and agitated. Chlorinated solvents and/or solvent residues must be
absent. The tank is drained and washed thoroughly, then passivated with 45 percent nitric acid for
2 to 4 h, or filled with 5 percent nitric acid at 70 OF (21 °C) for 18 to 24 h, then rinsed thoroughly
with water. If possible, the tank is conditioned with 35 percent HP for one to three days before it is
filled with propellant HP. The tank is rinsed with deionized water, then filled with 70 to 90 percent
HP. The tank is monitored for rising temperature or excessive gassing of the HP for a minimum of
6 h.
• Aluminum and aluminum alloy tanks holding 100 gal or greater, after cleaning, may be treated
using the procedure described for stainless steel tanks above, or a spray passivation procedure
obtained from the HP manufacturer may be used.
Cleaning and passivation procedures are described in the Hydrogen Peroxide Handbook (Rocketdyne
1967). The sequence of these procedures is typically degreasing, cleaning, pickling, basic passivation,
and propellant conditioning prior to system assembly:
Degreasing and Cleaning
Degrease excessively greasy metal parts by cold flushing for 30 min (with a solvent such as
trichloroethylene or tetrachoroethylene, repeated with a clean solvent as necessary), or using a
solvent vapor degreaser for at least 10 min. Metal parts are then cleaned with a hot (140 to 160 OF
(60 to 71 °C)) detergent solution or a mild alkaline commercial cleaner (a 0.07 N NaOH solution
has been used for anodized aluminum). The metal parts are then cleaned by agitation in the
cleaning solution, scrubbing with a stiff nylon brush or pumping the solution through the part. The
metal parts are then rinsed thoroughly in warm potable water.
Nonmetallic parts such as O-rings, gaskets and hoses are degreased by immersion or scrubbing at
140 to 160 OF (60 to 71 °C) with a commercial detergent or mild alkaline cleaner, followed by a
thorough rinsing with warm distilled or deionized water. Teflon, polyethylene, Kel-F, or Viton,
(except when bonded to metal), may be cleaned with a solvent provided the immersion time is
short (-5 s). Residual solvent or water on the surface of parts that are not chemically cleaned is
removed immediately with clean dry nitrogen or air.
It is noted that after a part is degreased and cleaned, it should only be handled with clean gloves or
tongs, and that any means of recontamination should be avoided after this point.
Descaling
Metal parts that have scale from welding, heat treatment, or impurities from casting or forging
should be descaled or "pickled." Descaling solutions should not be used after finish-machining of
precision surfaces without protection or on parts that do not have heavy oxide or foreign material
deposits in the form of rust or scale. The contact time with the descaling solution should be limited
to the time necessary to clean the part or the established maximum allowable time. Only plastic-
coated or nonmetallic gaskets should be exposed to nitric-hydrofluoric acid descaling baths to
prevent excessive metal loss by corrosion.
• Stainless steel parts should be pickled for no longer than 1 h at 60 to 80 OF (16 to 27 °C) with an
aqueous solution of 3 percent technical grade hydrofluoric acid and 10 percent nitric acid. It is
cautioned that a close visual check be maintained during descaling to prevent material pitting or
4-33
' excessive etching. After pickling, theart
P should be rinsed thoroughly
g Y with potable
P water, and
loosely adhering smut or flux may be removed by spraying with water or scrubbing with a
' stainless steel or hemp brush. If the parts are to be passivated immediately after pickling, they
need not be dried. The parts may be dried completely by purging with dry hydrocarbon-free air or
nitrogen or in an oven at 140 to 150 OF
(60 to 66 °C).
• Nonanodized aluminum and aluminum alloy parts may be pickled by immersion in an aqueous
solution of I percent HF and 10 percent nitric acid for 30 s to 5 min at 115 OF (46 °C) maximum.
It is cautioned that a close visual observation be maintained during pickling to prevent material
pitting or excessive etching. After pickling, the parts should be rinsed thoroughly with potable
' water. It is also noted that a 35 percent sulfuric acid solution at about 115 OF (46 °C) can be used
as an alternate pickling solution for aluminum and aluminum alloys.
' Basic Passivation

Immediately after cleaning or pickling, the metal parts should be subjected to "Basic Passivation."
Plastic and synthetic rubbers should not be subjected to this step in the passivation procedure.
• Stainless steel parts should be immersed in 45 percent nitric acid at 60 to 80 OF (16 to 27 °C) for a
minimum of 30 min. The parts should then be rinsed thoroughly with deionized or distilled water.
Unless the part is immediately placed in the propellant-conditioning solution (described below), it
should be drained and dried by purging with dry, filtered, hydrocarbon-free nitrogen or air, or
dried in a dust-free oven at 140 to 150 OF (60 to 66 °C). Then the part should be protected from
' recontamination by sealing in a clean plastic bag.
• The nitric acid passivation solution should be used for AISI 300 and 400 series stainless steels.
' The resultant protective films will normally not be visible, but the surfaces should be uniform in
appearance, and free from scale, corrosion, pitting and contaminants. The normal discoloration
from welding is permitted, provided there is no scale or rust associated with the discoloration.
' • Electropolishing of stainless steel parts (except for AM 355) is sometimes recommended as an
alternative method for stainless steel passivation. After electropolishing, the parts should be
cleaned with detergent, then rinsed thoroughly with deionized or distilled water, and dried in an
' oven.
• Aluminum and aluminum alloy parts may be passivated with 45 percent nitric acid at room
temperature for 1 h, although 35 percent nitric acid may also be used. Following exposure to nitric
acid, the parts should be rinsed thoroughly with deionized water or distilled water. Unless the part
is immediately placed in the propellant-conditioning solution (described below), it should be
' drained and dried by purging with dry, filtered, hydrocarbon-free nitrogen or air, or dried in a
dust-free oven at 140 to 150 O F (60 to 66 °C). Machined aluminum barstock parts do not normally
require pickling or passivating, and can be prepared for service by degreasing and thoroughly
rinsing. Welded, cast, or corroded parts require pickling, cleaning and passivating. Anodized
' aluminum parts are not descaled or passivated, and should be prepared for service by degreasing
and thorough rinsing.
Propellant Conditioning
4-34
i
Metal parts should be conditioned in propellant HP following cleaning and acid treatment to check
passivation ("activity testing") and to further passivate active sites on the materials. The
nonmetallic parts are propellant-conditioned following cleaning. Most procedures recommend
initial propellant conditioning with 30 to 35 percent HP prior to conditioning with HP of the grade
to which the parts will eventually be exposed to. Propellant conditioning should be performed on
both unassembled parts and components, and the assembled systems for a minimum of 3 to 6 h.
Materials, parts and components such as valves and pumps should be assembled prior to activity
testing. The passivated surfaces should be exposed by either immersion or filling with the desired
HP solution. Low openings in composite assemblies may be closed with passivated plugs of the
same material or polyethylene-covered rubber stoppers; however, there must be a vent to allow
evolved oxygen to escape. All sliding surfaces must be completely wetted, such as by valve
actuation, with HP.
The criteria for acceptance of passivation by the activity test is no reaction of the material with the
HP (no observable bubbles). If, at the end of the activity check, the gas bubble rate is minimal,
unexposed surfaces are cool to the touch, and gas bubbles are not confined to a particular location,
then the material or part is considered acceptable. If rapid bubbling, clouding of solution, or a
local hot spot is observed, the solution should be discarded and the active part repassivated. If
practical, the location of the active part should be noted for future observation. A component or
part should be rejected if it fails three consecutive activity tests. If a part shows only marginal
unacceptable reaction, it should be removed from the HP, rinsed several times with distilled or
deionized water, and reconditioned with fresh HP. If it continues to demonstrate marginal
unacceptability, it should be repassivated. Parts which cause discoloration of the HP must be
reimmersed in fresh HP, and if discoloration continues, the part should be rejected and the
discolored HP solution disposed of immediately. Any part that shows blackening, rust streaks, or
signs of excessive corrosion should be rejected.
• After materials, parts and assemblies have passed the activity checks in HP, they should be rinsed
thoroughly in distilled or deionized water and dried with clean dry air or nitrogen. Heat may be
used to dry plastic and metal materials below 120 °F (49 'Q. All dried parts are handled with
tongs or clean neoprene gloves until assembled or packaged as described below.
System Assembly
1
After a system is assembled from parts that have undergone and passed activity testing, the whole
system should be conditioned. This is done by tilling the system with 30 to 35 percent HP and
checking the system activity. The system should be vented and all valves and sliding surfaces
should be wetted with HP. The test should be conducted for 4 h unless it is terminated if a local
heated area or excessive gas evolution is observed. It may be desirable to measure the actual gas
1
1
evolution rate.
• if the above step is successful, the next step is to condition the system with HP of the grade it will
eventually be used with. Following this, the system is considered passivated and ready for HP
service. All passivated systems should be protected against further contamination. Additionally,
the system should be continuously surveyed during use for evidence of excessive HP
decomposition.
4-35
Handling and Storage of Passivated Materials
• Parts that have been cleaned and passivated should be handled, stored, or packaged in a manner
that prevents contamination. Immediately following cleaning and passivation, large valves, piping
sections, vessels, flex joints, subassemblies and other prefabricated parts should be dried. Ends
and openings should be capped, plugged or flanged and sealed with clean compatible sealing
material. Small valves and components should be purged with dry nitrogen and wrapped and
sealed in clean plastic or metal foil bags. Parts should be kept sealed until installation.
• Small items should be sealed in clean preformed envelopes, rolls, or sheets of polyethylene film,
polyethylene-backed paper, polyethylene-backed cloth, or polyethylene-backed aluminum foil,
vinyl, Koroseal, Saran, or Mylar. Materials for short-term storage of passivated items can also
include aluminum foil (or aluminum-backed cloth), paper and cellophane.
1 • For long-term or indefinite storage, small passivated items should be dried and packaged as soon
as practicable after passivation and activity testing. Any openings of the items should be sealed
with clean new polyethylene or aluminum caps, and used closures will be discarded to prevent
reuse. The materials should be enclosed in a clean envelope and sealed to stop free passage of air.
The envelope should then be wrapped in heavy paper or placed in a protective container.
4.7.2.2 Passivation for Storage
For systems intended for long-term storage of HP under sealed conditions, allowances must be made
for ullage space and wall strength in order to confine the gas liberated by decomposition of HP
(AFRPL 1966). The means of HP decomposition in this situation are: dissolved and suspended
contaminants in the liquid phase; catalytic activity of container surfaces exposed to liquid HP,
catalytic activity of container surfaces exposed to HP vapor.
Monger reported procedures for passivating surfaces for the storage of 90 percent HP (1965):
• Surface preparation for electrolytic tin consisted of 1 percent caustic followed by 1 percent nitric
acid for 10 min each
• Surface preparation for Aluminum 1260 and 5052 1 percent caustic followed by 35 percent nitric
acid for 20 h each
The nitric acid was said to remove some contaminants and to give an acidic surface that was essential
in obtaining low activities. Treatments were followed by thorough rinsing with deionized distilled
water and by final passivation with 90 percent HP.
FMC Bulletin 104 describes detailed procedures for passivating materials including aluminum,
stainless steel, plastics and glassware (FMC 1966). It also describes procedures for passivity checks of
components and flow systems including the measurement of temperature and rate of decomposition.
For example, three criteria were provisionally established for the suitability of individual components
of flow systems for HP service after passivation:
Maximum loss of concentration of the HP is 0.7 percent
I Maximum temperature rise above ambient during the test is 5 °F (2.7 °C)
Minimum stability of the HP following the test is 90 percent
e 4-36
It was recommended that the above testing be done with the HP solution to be handled at a
temperature of at least 70 °F (21 °C) for a period of 24 h.
4.7.2.3 Passivation of Other Materials
The NAVAER Handbook for Field Handling of Concentrated Hydrogen Peroxide (Over 52 Weight
Percent Hydrogen Peroxide) also describes procedures for passivating materials (NAVAER 1957). It
states that anodized aluminum parts should be carefully handled to keep them clean and to prevent
scratching of the anodized surface. Prior to use they should be degreased, rinsed with distilled water
and conditioned in HP. They should not be treated with sodium hydroxide, as this will remove the
anodized surface.
4.8 Laboratory Design
There are several excellent sources for details in the design of laboratories (Fur y 2000, National
Academy of Sciences 2000, Alaimo 2001). Laboratories engaged in the analysis and testing of HP
propellants should consider the details described below.
4.8.1 Building Codes
• International Conference of Building Officials (ICBO)

• Building Officials and Code Administrators (BOCA) International
• Southern Building Code Congress (SBCC) International
4.8.2 Other Legal Requirements and Codes
• ANSI American National Standards Institute

I
• NFPA National Fire Protection Agency
• OSHA Occupational Safety and Health Administration
• ASHRAE American Society for Heating, Refrigeration and Air-Conditioning Engineers
• AIHA American Industrial Hygiene Association
• ASTM American Society for Testing and Materials
4.8.3 Environmental
The laboratory design team should become familiar with the requirements of the relevant
environmental guidelines to ensure the facility is compliant. Relevant references include:
• The Resource Conservation and Recovery Act (RCRA) addresses waste disposal and reduction.
The RCRA is the primary federal statute regulating the control and disposal of solid and hazardous
wastes. Federal facilities may have many regulatory responsibilities under RCRA, including
obtaining permits, identifying and listing hazardous wastes, adhering to proper procedures when
transporting or disposing of wastes, developing risk management plans and maintaining records.
RCRA also contains requirements for underground storage tanks. These standards cover tank
design, operation, cleanup and closure.
• The State Air Toxics Acts concern air quality and its effects on human health. A state may
mandate pollution control requirements for sources of air pollution. Facilities may have regulatory
responsibilities including obtaining emission permits, installing pollution and emission control
devices, developing risk management plans and maintaining records.
4-37
• The Clean Water Act (CWA) is the primary federal statute regulating the protection of the nation's
waters. Federal facilities may have regulatory responsibilities under the Clean Water Act,
including obtaining discharge permits, developing risk management plans and maintaining
records.
• Title III of the Superfund Ammendments and Reauthorization Act (SARA) protects a
community's right to know which hazardous materials are present in its community. This
knowledge enables community emergency response authorities and local fire departments to
protect themselves when responding to a fire, explosion, gas or other chemical release or
emergency.
4.8.4 Controlling HP Vapor Emissions
HP vapor is not listed by the Clean Air Act (CAA) as a hazardous air pollutant (HAP). A specific state
air toxic regulation, however, may apply. For example, the state of New Mexico mandates that a
quantity of 1.5 lb/h or greater of HP cannot be released to the atmosphere without prior permitting
(NMAC 2002). Where source reduction is not practical, emission control devices, such as packed-bed
scrubbers can be used to reduce vapor emissions.
4.8.5 Controlling Liquid Effluents
Requirements for controlling the discharge of HP are set by the local sewer authority or publicly
owned treatment works (POTW). Early communication with the sewer authority or the POTW about
the intention, if any, of the laboratory to discharge small quantities of HP will help to ensure
environmental compliance.
Typically when disposing of HP, dilute it with 20 to 30 volumes of water before pouring it down an
approved drain and leave the water flowing for at least 5 min after disposal.
Methods for decomposing HP in the laboratory have been reported. HP may be diluted to 5 percent,
then an excess of sodium metabisulfate can be gradually added while stirring. The resulting reaction is
exothermic (Armour 1996). The reaction solution may be acidified with HCl to increase the rate.
Postassium iodide and starch can be added as an indicator after treatment with sodium metabisulfate to
test the completeness of the reaction; a blue color indicates there is excess HP (Lunn 1994). The
reaction of HP with sodium metabisulfate is:
2 H2O, + S,OS ' - --> 2 SO4 2-+ H2O + 2H+ (4.3)
If containerized and shipped for disposal by an approved facility, HP is assigned waste codes of D002
"Corrosive" and D001 "Ignitable."
4.8.6 Design Features for an HP Testing Laboratory
The design features described below are recommended for a laboratory in which HP is tested.
• A ventilation system (including fume hoods) that is compliant with ANSI/AIHA Z9.5-2003. This
' standard establishes guidelines for the design and operation of laboratory ventilation systems to
help personnel avoid overexposure to harmful or potentially harmful contaminants in the
laboratory. The standard addresses recommended requirements for operation of laboratory fume
4-38
hoods, ductwork, fans and storage facilities. Also addressed are methods for dealing with potential
catastrophes and maintaining safe noise levels.
• Emergency showers and eyewashes (ANSI Z358.1-1998).

• Suitable storage areas for HP (ventilated) and segregated from flammable, combustible materials,
or incompatible materials. HP should be stored in its original, vented container, and in clean,
ventilated storage cabinets. HP must be stored away from common laboratory chemicals including
alcohols, amines, hydrazines, ketones, hydrocarbons, iron, copper, manganese, heavy metals,
cyanides and reducing agents.
• Water should meet the purity standards defined by ASTM D 1193, Type I or be free of interfering
substances.
• Laboratory and storage areas should be constructed of materials that are compatible with HP and
tree of potential catalytic materials that may form, such as rust.
• Dedicated fume hoods, free of oxidizable materials and solvents, with work surfaces constructed
of welded stainless steel or lined with a compatible material.
• Lipped cup sinks to prevent a spill of HP from entering the drain system.
• Suitably sized containers that can be used for passivation of laboratory equipment (glassware,
tubing) and enable the users to easily fill and drain them.
• An ample supply of water to dilute a spill and a supply spill control equipment, including
polyethylene spill pillows to absorb diluted spilled liquid.
• A supply of air that is clean and free of dust.
• Flooring and lab benches that will not abrade to produce contaminant dust.
4.9 Storage of HP
4.9.1 Storage Areas and Containers
4.9.1.1 Storage Areas and Containers — General Considerations
Because HP is an oxidizer, is corrosive, and evolves oxygen, storage areas should be located away
I
from flammable or combustible material such as wood, paper and vegetation, and should be well-
ventilated. HP should never be stored in the vicinity of flammable materials such as liquid fuels or
solvents. The storage area should be kept clean and free of dirt and debris to minimize the possibility
of contamination of the outside of storage vessels or, in a worst case, contaminate the inside of storage
vessels. When HP decomposes, it produces oxygen and heat, so the danger of a fire is present when a
fuel is available. if HP does come into contact with a combustible material, it can start a fire; however,
it may take a prolonged time for a fire to break out. A supply of water should be available in a storage
area for fire extinguishing purposes as well as to cool containers of HP that may become heated. The
heating may result from a fire, thermal decomposition, or decomposition induced by some mechanism
such as contamination. The storage area should also be protected from extremes of temperature
because HP solutions of concentrations less than 45 percent expand during freezing, while solutions
above 65 percent contract during freezing (Rocketdyne 1967). The area should be diked to prevent an
uncontrolled release of HP into the environment, and there should be sufficient water supply to dilute
spilled HP while maintaining containment.
HP storage areas should have a drainage system that prevents released 14P from mixing with
incompatible materials. The drainage system should be kept free of dirt and debris, and not be
interconnected in any way with a drainage system for flammable or combustible liquids.
4-39
' The utmost care must be taken to prevent contamination of HP when opening or transferring fluid to
or from storage vessels. Contamination can induce decomposition that leads to heat and pressure build
' up with potential catastrophic results. The best practice is never to return used HP to its original
storage container.
' Design the storage area with adequate room so vehicular traffic cannot damage HP storage containers.
Provide enough room for delivery vehicles or forklifts to easily enter the area, maneuver in the area,
and exit the area.
IThere are also temperature considerations for the safe storage of HP (Schumb 1955, NAVAER 1957).
Solutions > 65 percent HP will contract upon freezing, so there is no danger of concentrated HP
bursting containers by expansion upon freezing.
When HP solutions are cooled, they will generally remain liquid (supercool) to well below their
freezing points. HP at concentrations > 50 percent have been observed to supercool at 10 to 50 °C
below their freezing points; however, safe sampling, pumping, or transportation operations should not
rely on the HP supercooling phenomenon.
4.9.1.2 National Fire Prevention Association Requirements
The NFPA Code 430 has primary applicability to the storage and handling of HP depending on the
concentration. According to this standard:
• 8 to 27.5 percent HP is a Class 1 Oxidizer

• 27.5 to 52 percent HP is a Class 2 Oxidizer
• 52 to 91 percent HP is a Class 3 Oxidizer
• > 91 percent HP is a Class 4 Oxidizer
' Storage requirements for HP in retail establishments are not addressed in this manual. Refer to NFPA
430 for these requirements. The definitions for Class 3 and 4 oxidizers, which cover the concentrations
of HP primarily discussed in this manual, are given below:
• Class 3: An oxidizer that will cause a severe increase in the burning rate of combustible materials
with which it comes into contact or that will undergo vigorous self-sustained decomposition due to
contamination or exposure to heat.
• Class 4: An oxidizer that can undergo an explosive reaction due to contamination or exposure to
thermal or physical shock. In addition, the oxidizer will cause a severe increase in the burning rate
of combustible materials with which it comes into contact.
The basic requirements for storage of Class 3 or 4 oxidizers (52 percent to greater than 91 percent HP)
are as follows:
Hazard Management
• The design of a new or significantly modified facility for storage of oxidizers shall be reviewed by
the authority having jurisdiction.
• Emergency plans shall be prepared for each facility. These plans shall be reviewed and training
' exercises shall be conducted (at least annually) in cooperation with local emergency organizations.
4-40
I
Identification o Materials in Storage
ge
• All storage areas containing oxidizers shall be conspicuously identified by the words "Class
(appropriate clasification number) Oxidizers."
• Where oxidizers having different classifications are stored in the same area, the area shall be
marked for the most severe hazard class present.
• All packages shall be approved and individually marked with the chemical name (Hydrogen
Peroxide) of the oxidizer.
Storage Containers, Tanks and Bins
Where a storage container for solid and liquid oxidizers also functions as the shipping container, the
container shall meet the requirements of the U.S. Department of Transportation, 49 CFR 100 to end, or
the Canadian Ministry of Transport Regulations.
Tanks for the storage of bulk liquid oxidizers and bins for the storage of bulk solid oxidizers shall
meet the requirements below.
• Materials of construction shall be compatible with the oxidizer being stored.

• Tanks and bins shall be designed and constructed in accordance with federal, state and local
regulations or, as a minimum, in accordance with nationally recognized engineering practices
(e.g., American Society of Mechanical Engineers [ASME], American Petroleum Institute [API]).
• Tanks and bins shall be equipped with a vent or other relief device to prevent overpressurization
due to decomposition or fire exposure.
• Bulk liquid storage is defined as the storage of more than 600 U.S. gal (2271 L) in a single
container.
• With the exception of Class 4 oxidizer, outside storage tank size shall not be limited by this code.
Storage Arrangements
The arrangement and quantity of oxidizers in storage shall depend upon their classification, type
of container, type of storage (segregated, cutoff or detached), and fire protection as specified in
succeeding sections (NFPA 430) and in the manufacturer's or processor's instructions.
- Segregated storage is in an area where the materials are stored separated by physical means
such as walls, shelves, or bins.
- Cutoff storage is in a room within a building and having at least one exterior wall.
- Detached storage is in a separate building, having no common walls with another building.
The arrangement and quantity of oxidizers in storage shall be permitted to deviate from the
requirements of succeeding sections where specially engineered fire prevention or fire
protection systems acceptable to the authority having jurisdiction are provided.
Oxidizers shall be stored to avoid contact with incompatible materials such as ordinary
combustibles, combustible or flammable liquids, greases, and those materials that have the
potential to react with the oxidizer or promote or initiate its decomposition. These incompatible
materials shall not include approved packaging materials, pallets, or other dunnage. The exception
is that HP (Classes 2 through 4) stored in drums shall not be stored on wooden pallets.
Special care shall be taken to prevent any contamination of oxidizers in storage.
Where oxidizers are stored in segregated warehouses with flammable liquids, the oxidizer
containers and flammable liquid drums shall be separated by at least 25 ft. The separation shall be
maintained by dikes, drains, or floor slopes to prevent flammable liquid leakage from encroaching
on the separation.
4-41
Where Class 2, 3 or 4 liquid
qliquid
oxidizers are stored means shall be provided
P to prevent
P the q
oxidizer from flowing out of a cutoff area into an area containing incompatible materials.
Storage Limitations
Where two or more different classes of oxidizers are stored in the same segregated, cutoff or detached
area, the maximum quantity permitted for each class shall be limited to the sum of the maximum
proportion permitted for that class. The total of the proportional amounts shall not exceed 100 percent.
Other Considerations
1 • In storage facility design, consideration shall be given to the need to provide for containment.
Containment on-site or off-site shall be required where necessary to protect the environment from
oxidizers, fire extinguishing agents, and their liquid decomposition products.
• Approval of the arrangement of storage shall take into consideration the potential evolution of
large quantities of smoke and toxic fumes, especially as storage affects manual fire fighting
operations, building egress, and evacuation of adjacent occupancies or communities.
Employee Instruction
• Personnel involved in operations where oxidizers are stored shall receive instruction in handling
the materials in a safe manner, including the recommendations of the manufacturer and processor.
• Particular attention shall be given to proper disposal of spilled material to prevent contamination.
Heating and Electrical Installations
• Heating shall be arranged so that stored materials cannot be placed in direct contact with heating
' units, piping, or ducts. Oxidizers shall be separated so that they cannot be heated to within 25 OF
(14 °C) of their decomposition temperature or to 120 OF (49 °C), whichever is lower.
• Electrical installations shall be in conformance with NFPA 70, National Electrical Code.
Smoking
• Smoking shall be prohibited in all storage areas containing oxidizers.

'0 "No Smoking" signs shall be placed conspicuously within and at all entrances to storage areas.
Maintenance and Repairs
r• The performance of maintenance work in an oxidizer storage area shall be subject to prior review
and approval by supervisory personnel.
• Cutting and welding procedures shall be in conformance with NFPA 51B.
Fire Protection
' Fire hydrants and water supplies shall be provided as required by the authority having jurisdiction.
Hydrants shall be installed in accordance with NFPA 24, Standard for the Installation of Private
Fire Service Mains and Their Appurtenances.
• The need for automatic sprinkler protection shall be determined by the nature of the materials, the
manner of storage, and the construction of the buildings under consideration. Where automatic
sprinkler systems are required, the systems shall be installed in conformance with NFPA 13.
i
4-42
i
• Dry-pipe and double-interlock pre-action Y stems shallsprinklersprotection
not be permitted
P for P of
buildings or areas containing oxidizers.
• Water supplies shall be adequate for the protection of the oxidizer storage by hose streams and
automatic sprinklers. The water system shall be capable of providing not less than 750 gal/min
where protection is by means of hose streams, or 500 gal/min hose streams in excess of the
automatic sprinkler water demand. Duration of the water supply shall be a minimum of 2 h.
• Water-based fire protection systems shall be inspected, tested and maintained in accordance with
NFPA 25.
• Manual fire-fighting equipment in the form of portable water extinguishers or water hose reel
stations shall be provided in accordance with the requirements of NFPA 10 and NFPA 14.
• The placement and use of dry chemical extinguishers containing ammonium compounds (Class A,
B and C) shall be prohibited in areas where oxidizers that can release chlorine are stored. (This is
not applicable to areas in which only HP is stored.)
• Halon extinguishers shall not be used in areas where oxidizers are stored.
Construction
Combustible construction materials that have the potential to come into contact with oxidizers shall be
protected with a compatible coating to prevent impregnation of the combustible materials by the
oxidizers.
Housekeeping and Waste Disposal
• Accumulation of combustible waste in oxidizer storage areas shall be prohibited.

• Spilled oxidizers and leaking or broken containers shall be removed immediately to a safe area to
await disposal in conformance with applicable regulations and instructions from the manufacturer
and processor. Spilled materials shall be placed in a clean, separate container and shall not be
returned to the original container. The disposal of such materials shall not be combined with that
of ordinary trash.
• Used, empty, combustible containers shall be stored in a detached area or an area with sprinklers.
• Operations shall be arranged to prevent fugitive dust accumulation.
• Absorptive combustible packing materials used to contain water-soluble oxidizers that have
become wet during fire or nonfire conditions and wooden pallets that are exposed to water
solutions of an oxidizer shall be relocated to a safe outside area and shall be disposed of properly.
Dust Collection Systems
If provided, dust collection systems shall meet the requirements of NFPA 91. Separate systems shall
be provided for incompatible materials.
The basic requirements for storage of 52 to 91 percent HP (Class 3 oxidizer) in quantities in

I
excess of 200 lb (91 kg) are as follows:
• The storage of Class 3 oxidizers shall be segregated, cutoff or detached.

• Class 3 oxidizer storage shall be located on the ground floor only.
• Cutoff walls shall have a fire resistance rating of at least 2 h.
• Storage of Class 3 oxidizers shall be in accordance with Tables 5-2.4(a) and (b) of NFPA 430.
4-43
• The buildingg limit (tons)

tons shall
be permitted
p to be twice the quantities
q O
shown in Table 5-2.4 b of
NFPA 430 if all of the following conditions are met:
Storage is cutoff or detached.
- Noncombustible containers are used or buildings are noncombustible.
- Storage is located in non-retail occupancies.
• Storage in glass carboys shall be one carboy high.
• Bulk storage in open bins or piles shall not be permitted.
• Maximum storage height for buildings without sprinklers shall be in accordance with
Table 5-2.4(a) of NFPA 430.
• Maximum storage height for buildings with sprinklers shall be in accordance with
Table 5-4.1 of NFPA 430.
IBuilding Construction
'• Buildings used for the storage of liquid Class 3 oxidizers shall not have basements.
• Construction materials that can come in contact with oxidizers shall be noncombustible.
• Storage areas for oxidizing materials in combustible containers shall be provided with means to
vent fumes in a fire emergency. Storage of HP in combustible containers should be avoided.
Sprinkler Protection
' • Sprinkler protection for Class 3 oxidizers shall be designed in accordance with Table 5-4.1 of
NFPA 430.
• Sprinkler protection shall be installed in accordance with NFPA 13.
• Ceiling sprinklers shall have heads rated at 286 °F (141 °C).
• In-rack sprinklers shall have heads rated at 165 °F (74 °C) and shall be designed to provide 30 psi
(207 kPa) on the most hydraulically remote six heads on each level. The in-rack sprinklers shall be
spaced on 8-ft to 10-ft centers at rack uprights.
Note: NFPA 430 makes allowances for storage in non-sprinklered buildings. The user of this manual
' should consult NFPA 430 for specific details.
Detached Storage
To be considered detached, a building for storage of Class 3 oxidizers shall be separated from
flammable or combustible liquid storage, flammable gas storage, combustible material in the open,
and any inhabited building, passenger railroad, public highway, or other tanks. The minimum
separation distance shall be 50 ft for a building with sprinklers and 75 ft for a building without
sprinklers.
' Storage of greater than 91 percent HP (Class 4 oxidizer) in quantities in excess of 10 lb (4.5 kg) is
as follows:
• The storage of Class 4 oxidizers shall be detached.

• Storage in glass carboys shall be one carboy high.
• Storage in drums or in containers or in cases shall not exceed the limits outlined in Table 6-2.2 of
NFPA 430.
4-44
i
Building Construction and Location
• Buildings shall be one story without a basement. Construction materials that could come in contact
with oxidizers shall be noncombustible.
• Storage areas shall be provided with means to vent fumes in an emergency.
• A storage building or storage tank shall be located not less than the minimum distance provided in
Table 6-3.4 of NFPA 430 from flammable liquid storage, combustible material in the open, and
any inhabited building, passenger railroad, public highway, property line, or tank other than
oxidizer storage.
• Where tanks are not separated from each other by 10 percent of the distance specified in
Table 6-3.4 of NFPA 430 for the largest tank, the total contents of all tanks shall be used when
using Table 6-3.4 of NFPA 430.
Sprinkler Protection
• Sprinkler protection for Class 4 oxidizers shall be installed on a deluge sprinkler system to provide
water density of 0.35 gal/min/ft'- (14.4 L/min/m') over the entire storage area.
• Sprinkler protection shall be installed in accordance with NFPA 13.
Additional recommendations for HP storage areas are to:
• Establish an inspection checklist and schedule.

• Establish a receiving procedure.
• Inspect drums for signs of leaks and instability such as heat or noise.
• Monitor for signs of corrosion.
• Provide ramps and suitable surfaces for operating forklifts or other powered industrial trucks (29
CFR 1910.178).
• Provide adequate exits and exit routes (29 CFR 1910.33).
• Exit routes must be kept free and unobstructed (29 CFR 1910.37).
• Provide area monitoring for HP vapors.
• Ensure there are appropriate emergency shower and eyewash units at suitable location within the
area, and ensure these are inspected and maintained regularly (ANSI Z358.1-1998).
• Provide an automatic fire extinguishing system.
• Provide for security against unauthorized personnel.
• Ensure storage tanks or vessels have pressure and/or temperature sensors if possible. An oxygen
mass flow meter might also be used (Ross 2002)
• Ensure smoke detectors are in the area.
• Equip containment areas with sight glasses or liquid leak detectors.
• Ensure an established emergency plan is in place and personnel are adequately trained (29 CFR
1910.38).
4.9.1.3 Quantity and Distance Requirements for Storage
NASA explosives quantity-distance (QD) requirements exist for procurement, transport, storage,
handling and use of HP. These requirements are contained in NSS 1740.12 "Safety Standard for
Explosives, Propellants, and Pyrotechnics" (NASA 1993). The data from NSS 1740.12 are not
reproduced in this manual; however, these data exist and are readily available. Consult explosive
specialists at your NASA location when determining the applicable NSS 1740.12 requirements for HP.
Explosive specialists will also consult DOD 6055.9 "DOD Ammunition and Explosives Safety
4-45
Standards" as required (Department of Defense 1999). The user of this manual should be aware that
NSS 1740.12 will be re-issued as NASA-STD-8719.12 when it is updated, according to the NASA
Technical Standards Program website (http://standards.nasa.gov ) (website updated on December 18,
2002).
4.9.1.4 Stabilization of Contaminated HP
Gross contamination of HP may occur if contaminated fluid is reintroduced into the container or
' tankage system, incompatible material or objects are inadvertently dropped into the fluid, or the
containment system was not properly cleaned and passivated. Rapid evolution of heat and generation
of pressure (due to oxygen generation) by decomposing HP is one of the first warning signs of gross
' contamination. To counteract this and prevent thermal runaway, addition of phosphoric acid to the
bulk HP has been recommended, secondary to dilution with water and dumping (NAVAER 1957,
McCormick 1965).
One procedure recommended the addition of one gallon of 6 percent phosphoric acid for each 500 gal
of contaminated HP. This procedure indicated that no mixing was necessary because the turbulence
would disperse the stabilizer (NAVAER 1957).
Another procedure recommended the addition of 1 Ib of 85 percent (concentrated) phosphoric acid per
100 gal of contaminated HP. An example adding 5 lb of phosphoric acid to 6000 lb (500 gal) of
' 90 percent HP that was contaminated during a recycle test of aircraft booster pumps, resulting in a
stability increase in the HP within a few hours, was cited (McCormick 1965).
One drawback to the addition of phosphoric acid to HP is that it may render the fluid unsuitable for its
intended use, such as for use in silver screen catalyst beds. Over-stabilization of HP resulting in poor
system performance or poisoning of catalyst beds, such as silver, may occur as a result of the addition
of phosphoric acid stabilizer. In addition, phosphoric acid has a limited capacity to stabilize
contaminated HP and its use for emergency stabilization must be carefully considered.
4.10 Shipping of HP (DOT)

HP must be shipped in a safe and reliable manner in order to avoid hazards associated with injury to
personnel, fire and explosion, releases to the environment, and damage to equipment and facilities,
while maintaining the quality of the propellant. While some of the applicable regulatory requirements
are described below, HP manufacturers, suppliers and hazardous material transportation specialists
should be consulted for best practices since some of the authorized packagings should not be used for
HP propellants.
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United States Department of Transportation
Shipment of HP in the United States must conform to the hazardous materials regulations set forth by
the U.S. Department of Transportation (DOT). A summary of the DOT regulations current as of
2/10/04 applicable to propellant HP is as follows:
Hazardous Material Description

• Proper shipping name: Hydrogen peroxide, stabilized or Hydrogen peroxide aqueous
solutions, stabilized with more than 60 percent hydrogen peroxide (see Proper Shipping Name
below for additional information)
• Hazard Class or Division: 5. I
• Identification Numbers: UN2015
• Packaging Group: I
• Label Codes shown below: 5.1 (Oxidizer), 8 (Corrosive)
CORROSIVE
Special Provisions (49 CFR 172.101 "Special Provisions"): 12, A3, A6, B53, B80, B81, B85, T10,
TP2, TP6, TP24, TP37
Note: Special provisions with an "A" prefix refer to air shipment and are not applicable because
shipment of HP by air is forbidden.
• Packaging Section:
• Exceptions: None
• Non-Bulk (< 119 gal): 49 CFR 173.201 "Non-bulk packagings for liquid hazardous
materials in Packing Group F
• Outer packaging
• 1 A 1 or 1 A2 steel drums
• 1 B 1 or 1 B2 aluminum drums
• Others: Not permitted by special provision
• Inner packaging
• Glass, plastic receptacles, metal receptacles, glass ampoules
• Single Packagings:
• Steel Drums: I A 1 or I A2
• Aluminum Drums: 1 B 1 or 1 B2
• Bulk (>_ 199 gal): 49 CFR 173.243 "Bulk packaging for certain high hazard liquids and
dual hazard materials which pose a moderate hazard."
• See regulation for details
4-47
Quantity Limitations:
• Passenger Aircraft/rail: Forbidden
• Cargo Aircraft only: Forbidden
Vessel Storage:
Location: D (Stowage category "D" means the material must be stowed on deck only on a
cargo vessel and on a passenger vessel carrying a number of passengers limited to no
more than 25 passengers or one passenger per each 3 m of overall vessel length. The
material is prohibited on passenger vessels in which the limiting number of passengers is
exceeded.)
Other (as specified in 49 CFR 176.84 "Other requirements for stowage and segregation for
1
cargo vessels and passenger vessels:")
• 25 Shade from radiant heat
66 Stow "separated from" flammable solids
75 Stow "separated from" permanganates.
106 Stow "separated from" powdered metal
Special Provisions
The special provisions applicable to HP, not including those with an "A"-prefix because transportation
by air is forbidden, are described as follows:
Note: A code containing the letter "B" refers to a special provision which applies only to bulk
(quantities >_ 119 gal) packaging requirements. Unless otherwise provided, these do not apply to IM
portable tanks.
I • 12 In concentrations greater than 40 percent, this material has strong oxidizing properties and
is capable of starting fires in contact with combustible materials. If appropriate, a package
containing this material must conform to the additional labeling requirements of 49 CFR
172.402 "Additional labeling requirements."
• B53 Packagings must be made of either aluminum or steel.
• B80 Each cargo tank must have a minimum design pressure of 276 kPa (40 psig).
• B81 Venting and pressure relief devices for tank car tanks and cargo tanks must be approved
by the Associate Administrator.
• B85 Cargo tanks must be marked with the name of the lading in accordance with the
requirements of 49 CFR 172.302 "General marking requirements for bulk packagings."
Note: "T" codes apply to transportation in UN and IM portable tanks.
T10 Minimum test pressure: 4 bar.

Minimum shell thickness (in mm-reference steel) (49 CFR 178.274 "Specifications for UN
portable tanks" (d)): 6mm
Pressure-relief requirements (49 CFR 178.275(g)(3)). Portable tanks must have a pressure
relief device consistent with the requirements of 49 CFR 178.275 "Specification for UN
Portable Tanks intended for the transportation of liquid and solid hazardous materials." Except
for a portable tank in dedicated service that is fitted with an approved relief device constructed
of materials compatible with the hazardous material, the relief device system must include a
frangible disc preceding (such as between the lading and the reclosing pressure relief device) a
reclosing pressure relief device. A pressure gauge or suitable tell-tale indicator for the
detection of disc rupture, pin-holing or leakage must be provided in the space between the
frangible disc and the pressure relief device to allow the portable tank operator to check to
4-48
determine if the disc is leak free. The frangible
g disc must rupture
P at a nominal pressure
P 10
percent above the start-to-discharge pressure of the reclosable pressure relief device.
• Bottom opening requirements (49 CFR 178.275(d): Prohibited).
Note: "TP" codes apply to portable tank special provisions.
• TP2 The maximum degree of filling must not exceed the degree of filling determined by the
following:
Degree of filling — 95/(1+ a(t, - if))
Where:
t r is the maximum mean bulk temperature during transport; and
if is the temperature in degrees Celsius of the liquid during filling, and is the mean
coefficient of cubical expansion of the liquid between the mean temperature of the liquid
during filling (i f) and the maximum mean bulk temperature during transportation (t r) both
in degrees Celsius
• Liquids transported under ambient conditions may be calculated using the formula:
a = (d15-d50)/35d5O
Where:
d 15 and d5o are the densities (in units of mass per unit volume) of the liquid at 15 °C (59
°F) and 50 °C (122 °F), respectively.
• TP6 To prevent the tank from bursting in an event, including fire engulfment (the conditions
prescribed in CGA pamphlet S-1.2 (CGA Pamphlet S-1.2, Safety Relief Device Standards Part
2 - Cargo and Portable Tanks for Compressed Gases, 1980).
49 CFR 171.7 "Reference Material" may be used to consider the fire engulfment condition, it
must be equipped with pressure relief devices that are adequate in relation to the capacity of
the tank and the nature of the hazardous material transported.
• TP24 The portable tank may be fitted with a device to prevent the build up of excess pressure
due to the slow decomposition of the hazardous material being transported. The device must
be in the vapor space when the tank is filled under maximum tilling conditions. This device
must also prevent an unacceptable amount of leakage of liquid in the case of overturning.
• TP37 IM portable tanks are only authorized for the shipment of HP solutions in water i
containing 72 percent or less HP by weight. Pressure relief devices shall be designed to
prevent the entry of foreign matter, the leakage of liquid and the development of any
dangerous excess pressure. In addition, the portable tank must be designed so that internal
surfaces may be effectively cleaned and passivated. For solutions with a HP concentration >
60 percent and < 70 percent, each tank must be equipped with pressure relief devices with a
total venting capacity of 32 SCFM/pound of HP solution.
4-49
' 4.10.1 Proper Shipping Name
A provision in 49 CFR 172.101(c)(6) states: "When a proper shipping name includes a concentration
range as part of the shipping description, the actual concentration, if it is within the range stated, may
be used in place of the concentration range." For example, the proper shipping name for the highest
HP concentration solution in 49 CFR 172.101 is Hydrogen peroxide, stabilized or Hydrogen peroxide
aqueous solutions, stabilized with more than 60 percent hydrogen peroxide. Accordingly, the
following are all correct shipping names for 98 percent HP (5.1 UN2015, PGI, Oxidizer, Corrosive):
• Hydrogen peroxide, stabilized

• Hydrogen peroxide aqueous solutions, stabilized with more than 60 percent hydrogen peroxide
• Hydrogen peroxide aqueous solutions, stabilized with 98 percent hydrogen peroxide
4.10.2 Packaging Containers
Venting of packaging containers to reduce internal pressure which may develop by the evolution of
Gas from the contents is permitted only when:
• Transportation by aircraft is not involved.

• The evolved gases are not poisonous, likely to create a flammable mixture with air or be an
asphyxiant under normal conditions of transportation.
• The packaging is designed to preclude an unintentional release of hazardous materials from the
receptacle.
• For shipments in bulk packaging, venting is authorized for the specific hazardous material by a
special provision in the 49 CFR 172.101 Table or by the applicable bulk packaging specification
in 49 CFR 178.
Accordingly, packaging containers for HP must be vented.
The packaging requirements for shipping HP were clearly spelled out in paragraph 5 of
MIL-P-16005E, and exceeded those required by the DOT. The specific packaging requirements for HP
were as follows:
• Drums shall conform to DOT Specification 42D, aluminum of not over 55-gal capacity with a
vented closure in the top head. The closure shall be wire sealed to prevent removal in transit. Side
closures shall not be permitted.
• Cargo tanks shall conform to DOT Specification MC 31-H2O, or MC 312-H2O, of types 1060,
1260, 5254, or 5652 aluminum alloy with approved venting and pressure relief devices approved
by the Bureau of Explosives.
• Tank cars shall conform to DOT Specification 103-A-AL-W-H2O, of types 1060, 1260, 5254, or
' 5652 aluminum alloy with venting arrangement approved by the Bureau of Explosives.
However, when MIL-P-16005E was cancelled, responsibility for the selection of suitable DOT-
' approved packagings became that of the user and the shipping organization. Some of the issues
associated with the selection of packagings include:
• Even though certain packaging is specified by the DOT, it is the responsibility of the person
offering a hazardous material for transportation to ensure that such packaging is compatible with
the lading (particularly as it applies to corrosion, permeability, softening, premature aging and
embrittlement).
4-50

• A test method "Procedure for Testingg Chemical Compatibility

P Y and Rate of Permeation in Plastic
Packagings and Receptacles" must be performed on each plastic packaging or receptacle used for
Packing Group I materials.
• DOT-allowed combination packaging may create unsafe conditions.
DOT drum specifications provided in 49 CFR 178.504 "Standards for steel drums" and
49 CFR 178.505 "Standards for aluminum drums" include:
• 1 A 1 for a non-removable head steel drum and 1 A2 for a removable head steel drum
• 1 B 1 for a non-removable head aluminum drum and 1 B2 for a removable head aluminum drum
• Construction requirements
• Maximum capacity 450 L (119 gal) capacity and maximum net mass 400 kg (882 lb)
• Details on rolling hoops required for capacities > 60 L (16 gal)
• Dimensions of openings for filling, emptying and venting in the bodies or heads
• Closure requirements
• 49 CFR 178.504(7) "Standard for Steel Drums" states: "If materials used for body, heads, closures
and fittings are not in themselves compatible with the contents to be transported, suitable internal
protective coatings or treatments must be applied. These coatings or treatments must retain their
protective properties under normal conditions of transport."
Thorough discussions of some of the concerns and problems associated with the shipping of propellant
HP have been reported and are summarized in part as follows (General Kinetics, LLC 2003, Pinsky
2000, Wernimont 1999 and 2001):
• Decades of knowledge and experience that had been put into the very clearly stated transportation
requirements of MIL-P-16005E may be lost and conforming only to the DOT requirements may
pose a threat to safety in transportation and use.
• Grades of aluminum alloys that had been clearly specified for the construction of drums, cargo
tanks and tank cars are no longer specified.
• it has become the responsibility of the HP manufacturer to determine the most appropriate
packagings.
• The highest concentrations of HP specified by the DOT in the Hazardous Materials Table (49 CFR
172.101) are > 60 percent. The DOT requirements were not intended to apply to propellant HP nor
do the minimum requirements adequately apply to propellant HP.
• An allowable non-bulk combination packaging is an outer 1 A 1 or 1 A2 steel drum with an inner
plastic receptacle. This allows an inner plastic receptacle, such as a bag or liner, to contain the HP
in a steel drum. This allowed combination packaging creates a situation where HP is separated
from incompatible steel with a very thin but compatible liner.
An example of a DOT-allowable non-bulk combination packaging for propellant HP and the resultant
hazards is a carbon steel drum with a removable head and a polyethylene liner (Wernimont 2001).
Such a combination is hazardous for several reasons
Failure of the polyethylene liner could allow direct contact of the HP with a carbon steel drum.
The HP could decompose and release enough heat to initiate combustion of the polyethylene liner
and lead to overpressurization and a possible drum failure.
Dropping the drum on its head clamp could result in clamp failure and spillage of HP to the
environment. This might result in a fire external to the drum.
4-51
t Another example of a DOT-allowable non-bulk combination packaging is use of a stainless steel drum
and Teflon liner (Wernimont 2001). Such a combination is a potential hazard for several reasons:
• Failure of the Teflon liner could permit prolonged contact of HP with the stainless steel, resulting
in leaching of iron, nickel and chromium into the HP.
• The contaminated HP could begin to decompose and pressurize the drum. If the contamination is
sufficient, overpressurization may cause structural failure of the drum even if a vent is provided.
Examples of packagings for propellant HP that conform to DOT requirements but may cause
hazardous conditions include (General Kinetics, LLC 2003):
• Unlined stainless steel drum with a non-removable head

• Polyethylene-lined stainless steel drum with a non-removable head
• Polymeric bag-lined carbon steel drum with a removable head
These examples further demonstrate the need to understand HP and packaging materials properties in
addition to the DOT requirements in order to safely ship HP.
Other Transportation Hazards
Other hazards associated with transportation include (Wernimont 2001, General Kinetics, LLC 2003):
• Pallets should be compatible with HP. Containers of HP should never be shipped on wood pallets
since a fire could result if the propellant is spilled. Additionally, if a wood pallet catches on fire,
f the fire external to the container could cause it to heat and overpressurize.
• Secondary containment is desirable, but the secondary containment must be compatible with HP.
• Inversion of a container must be avoided because the venting device may fill with HP and thereby
impair its function.
• Use of an incompatible Class 4 crimp material such as lead for drum locks must be avoided.
4.11 Waste Disposal
HP waste is given the waste code D002, "Corrosive" and D001, "Ignitable." Facilities desiring to treat
their own waste must conform to the waste disposal regulations found in 40 CFR 264.
Facilities, however, may find other uses for HP before it is declared waste. Properly diluted to the
desired concentration and provided it is not undesirably contaminated, HP can be used in a number of
productive ways, such as a reagent for laboratory use, synthetic chemical intermediate, industrial
cleaner or bleaching agent, or disinfectant.
Typically, when disposing of HP, dilute it with 20 to 30 volumes of water before pouring it down an
approved drain and leave the water flowing for at least 5 min after disposal.
4.12 Regulatory Enforcement
4.12.1 Department of Transportation (DOT)
The RSPA primary mission under the federal laws governing the transportation of hazardous materials
is to protect the nation adequately against the risks to life and property which are inherent in the
transportation of hazardous materials in commerce. It is the task of RSPA's inspection and
4-52
1
enforcement staff to determine compliance with the safety and training g tandards by inspecting
p g entities
that offer hazardous materials for transportation; and that manufacture, requalify, rebuild, repair,
recondition, or retest packaging (other than cargo tanks and tank cars) used to transport hazardous
materials. RSPA's hazardous materials inspection and enforcement program is carried out by OHME,
which is under the general direction of the Associate Administrator for Hazardous Materials Safety.
OHME also enforces the following requirements: 1) to have valid authority when operating under a
DOT exemption or approval; 2) to be registered with RSPA as a shipper or carrier of hazardous
materials; and 3) to submit a telephonic and/or written report (DOT Form 5800.1) following the
unintentional release of hazardous materials in transportation. If you have any questions regarding
DOT, call (800) HMR-4922, (800) 467-4922, or (202) 366-4488 (Washington, DC).
DOT regulates transportation of HP, which is classified as a hazardous material in accordance with 49
CFR. The specific rules are determined by the HP concentration. HP is specifically regulated in
concentrations of
• More than 60 percent, stabilized

• More than 40 percent but not more than 60 percent, stabilized as necessary
• Not less than 20 percent but not more than 40 percent, stabilized as necessary
• Not less than 8 percent but less than 20 percent, stabilized as necessary
This manual concerns itself primarily with propellant grades of HP, which are typically concentrations
greater than 70 percent. For concentrations of HP greater than 60 percent, the DOT regulations
described in Section 4.10 apply.
4.12.2 Environmental Protection Agency
EPA requirements for emergency planning, reportable quantities of hazardous releases, community
right-to-know, and hazardous waste management may change over time. Users of this manual are
therefore advised to determine periodically whether new information is available. The information
below was verified to be current as of the Federal Register dated February 4, 2003.
Emergency Planning Requirements
Employers owning or operating a facility at which there are the threshold planning quantity of 1000 lb
or more of > 52 percent HP must comply with EPA's emergency planning requirements (40 CFR
355.30).
Reportable Quantity Requirements for HP Releases
A hazardous substance release is defined by EPA as any spilling, leaking, pumping, pouring, emitting,
emptying, discharging, injecting, escaping, leaching, dumping, or disposing into the environment
(including the abandonment or discarding of contaminated containers) of hazardous substances.
In the event of a release that is above the reportable quantity for that chemical, employers are required
to notify the proper federal, state and local authorities (40 CFR 355.40). The reportable quantity of HP
is 1000 lb. If an amount equal to or greater than this quantity is released within a 24-h period in a
manner that will expose persons outside the facility, employers are required to do the following:
I
4-53
Notify the National Response Center immediately at (800) 424-8802 or at (202) 426-2675 or
(202) 267- 2675 (Washington, DC). The facsimile number is (202) 267-2165 and the telex number
is 892427 (40 CFR 302.6).
Notify the emergency response commission of the state likely to be affected by the release
(40 CFR 355.40).
Notify the community emergency coordinator to the local emergency planning committee (or
relevant local emergency response personnel) of any area likely to be affected by the release
(40 CFR 355.40).
Community Right-to-Know Requirements
Employers are not required by the EPA in 40 CFR Part 372.30 to submit a Toxic Chemical Release
Inventory form (Form R) to the EPA reporting the amount of HP emitted or released from their facility
annually.
CERCLA (Comprehensive Environmental Response Compensation and Liability Act)
HP is not listed under CERCLA (40 CFR 302.4).
Resource Conservation and Recovery Act (RCRA)
A waste is classified as hazardous under RCRA Subtitle C if it exhibits any of the characteristics of
ignitability, corrosivity, reactivity, or toxicity, or if it contains specific constituents that are listed as
hazardous.
HP wastes are regulated by RCRA as characteristically ignitable (D001) waste according to

40 CFR 261.21 "Characteristics of Ignitability," that states in part, a waste exhibits the characteristic
of ignitability if "it is an oxidizer as defined in 49 CFR 173.151." 40 CFR 261.21 was verified to be
current as of the Federal Register dated July 1, 2003. Although
49 CFR 173.151 "Exceptions for Class 4" pertains to flammable materials and does not provide a
definition for oxidizer, a definition for oxidizer is found in 49 CFR 173.127 "Class 5, Division 5.1 —
Definition and Assignment of Packing Groups." Therein, "oxidizer (Division 5.1) means a material
that may, generally by yielding oxygen, cause or enhance the combustion of other materials." Despite
the fact that 40 CFR 261.21 references the non-applicable
49 CFR 173.151, the RCRA Orientation Manual states "substances meeting the Department of
Transportation's definition of oxidizer as ignitable wastes" (RCRA 2002).
HP wastes are also regulated by RCRA as characteristically corrosive (D002) waste

(40 CFR 261.22).
In summary, HP wastes are given two EPA waste codes: D001 (ignitable) and D002 (corrosive).
4.12.3 OSHA
Relevant regulatory labor enforcement by OSHA includes the standards described below:
• 29 CFR 1910.1 19. Process Safety Management of Highly Hazardous Chemicals, and Appendix A
List of Highly Hazardous Chemicals, Toxics and Reactives (Mandatory). Appendix A of this
standard regulates HP (52 percent by weight or greater) at a threshold quantity (TQ) of 7500 lb.
The TQ in pounds is the amount necessary to be covered by the process safety management
4-54
i
standard. This standard contains requirements
q for preventing or minimizing the consequences of
catastrophic releases of toxic, reactive, flammable, or explosive chemicals. These releases may
result in toxic, fire or explosion hazards.
29 CFR 1910.120. Hazardous Waste Operations and Emergency Response. This standard
provides requirements for response efforts by employees from outside an immediate release area
or by other designated responders (mutual aid groups, local fire departments, etc.) to an
occurrence that results, or is likely to result, in an uncontrolled release of a hazardous substance.
This includes HAZMAT personnel. HP is a hazardous substance as defined by this standard.
Treatment of HP waste is also covered by this standard.
29 CFR 1910.132. Personal Protective Equipment General Requirements. This standard requires
protective equipment—including personal protective equipment for eyes, face, head and
extremities—protective clothing, respiratory devices, and protective shields and barriers. These
shall be provided, used and maintained in a sanitary and reliable condition wherever it is
necessary. Hazards that may necessitate use include: chemical hazards, radiological hazards, or
I
mechanical irritants encountered in a manner capable of causing injury or impairment in the
function of any part of the body through absorption, inhalation or physical contact. A discussion of
PPE for use with HP is given in Section 4.5.1 of this manual.
29 CFR 1910.133. Eye and Face Protection. This standard sets forth requirements for protection
of eye or face hazards from flying particles, molten metal, liquid chemicals, acids or caustic
liquids, chemical gases or vapors, or potentially injurious light radiation using appropriate eye or
face protection. The American National Standard ANSI Z87.1-68 and Z87.1-89 "Practice of
Occupational and Educational Eye and Face Protection" is incorporated into this standard by
1910.6 "Incorporation by Reference." A discussion of eye and face protection for use with HP is
given in Section 4.5.1.3 of this manual.
• 29 CRF 1910.134. Respiratory Protection. This standard requires the use of appropriate
respirators when engineering and administrative controls are insufficient to protect the worker
from unallowable airborne concentrations of vapor. The specific elements of a respiratory
protection program are addressed in Section 4.5.2 of this manual.
29 CFR 1910.136. Occupational Foot Protection. Although this standard addresses requirements
for footwear that is protective against foot injuries due to falling or rolling objects, or objects
piercing the sole, and where employees' feet are exposed to electrical hazards, it does not address
chemical protective hazards. Knowledge of HP hazards is essential to the application of this
standard. A discussion of foot protection for use with HP is given in Section 4.5.1.2 of this
manual.
• 29 CFR 1910.138. Hand Protection. This standard sets forth requirements for the selection and
use of appropriate hand protection when employees' hands are exposed to hazards such as those
from skin absorption of harmful substances, severe cuts or lacerations, severe abrasions,
punctures, chemical burns, thermal burns and harmful temperature extremes.
• 29 CFR 1910.141. Sanitation. This standard sets forth requirements for sanitation in permanent
places of employment. Although not specifically addressed in this standard, HP is a toxic material
and there are corresponding requirements for washing facilities and eating and drinking areas.
s
4-55
29 CFR 1910-15 1. Medical Services and First Aid. This standard provides for the ready
availability of medical personnel for advice and consultation on matters of plant health. In the
absence of an infirmary, clinic, or hospital in near proximity to the workplace used for the
treatment of all injured employees, this standard provides for a person or persons adequately
trained to render first aid and maintain adequate first aid supplies. Additionally, the standard
requires that where the eyes or body of any person may be exposed to injurious corrosive
materials, suitable facilities for quick drenching or flushing of the eyes and body shall be provided
within the work area for immediate emergency use. The "American National Standard for
Emergency Eyewash and Shower Equipment," ANSI Z358.1-1998, is not incorporated by
reference (1910.6 "Incorporation by Reference") into 1910.151.
' 29 CFR 1910.1000. Air Contaminants. This standard requires an employee's exposure to any
substance listed in Tables Z-1, Z-2, or Z-3 of this section shall be limited in accordance with the
requirements of the following paragraphs of this section. Table Z- 1, "Limits For Air
Contaminants," lists the PEL as an 8-h TWA limit for HP exposure as 1 ppm (25 °C and 760 torr)
and 1.4 mg/m3 (approximate). OSHA lists no skin designation for these airborne concentrations of
HP.
• 29 CFR 1910.1020. Access to Employee Exposure and Medical Records. This standard provides
employees and their designated representatives a right of access to relevant exposure and medical
records. It also provides representatives of the assistant secretary a right of access to these records
in order to fulfill responsibilities under OSHA. Access by employees, their representatives and the
assistant secretary is necessary to yield both direct and indirect improvements in the detection,
treatment and prevention of occupational disease.
29 CFR 1910.1200. Hazard Comm uutication. This standard is intended to address

comprehensively the following: the issue of evaluating the potential hazards of chemicals;
communicating information concerning hazards and appropriate protective measures to
employees; and to preempt any legal requirements of a state or political subdivision of a state
pertaining to this subject. Evaluating the potential hazards of chemicals and communicating
information concerning hazards and appropriate protective measures to employees may include
provisions for the following: developing and maintaining a written hazard communication
program for the workplace (including lists of hazardous chemicals present); labeling of chemical
containers in the workplace, as well as containers of chemicals being shipped to other workplaces;
preparation and distribution of material safety data sheets to employees and downstream
employers; and development and implementation of employee training programs regarding
hazards of chemicals and protective measures.
• 29 CFR 1910.1450. Occupational Exposure to Hazardous Chemicals in Laboratories. This

standard provides for the employer to develop and implement protective practices to prevent
employee exposure to a hazardous chemical in a laboratory. It applies to HP by its definition of a
hazardous chemical, in addition to the listing of HP in 29 CFR 1910.1000 Table Z-1.
The Occupational Safety and Health Administration (OSHA) has cited employers for failure to
comply with regulations in case reports involving HP. For more information see OSHA Region 1
News Release BOS 2000-171, http://www.osha.gov/media/oshnews/nov00/regl-20001120.html.
4-56
4.13.1 Assessment Example 1
Prepare a MSDS for 98 percent HP using OSHA form 174 (available at

http://www.osha.gov/Publications/MSDS/msdsform.htmi and following) and the information provided
in this manual.
Blank MSDS Form
Material Safety Data Sheet U.S. Department of Labor

May be used to comply with OSHA's Hazard Occupational Safety and Health
Communication Standard, 29 CFR 1910.1200. StandardAdministration
must be consulted for specific requirements. (Nonmandatory Form)
Form Approved
OMB No. 1218-0072
IDENTITY (As Used on Label and List) Note: Blank spaces are not permitted. If any
item is not applicable, or no information is
available, the space must be marked to indicate
that.
Section 1
Manufacturer's Name Emergency Telephone Number
Address (Number, Street, City, State and ZIP Code) Telephone Number for Information
Date Prepared
Signature of Preparer (optional)
Section 11 - Hazard Ingredients/

Identity Information
azardous Components (Specific Chemical Identity; OSHA PEL ACGIH TLV Other Limits
ommon Name(s)) Recommended
%(optional)
Section III - Phvsical/Chemical Characteristics

Boiling Point Specific Gravity (H2O = 1
Vapor Pressure mm Hg.) Meltinp, Point
V apor Densi (Air = 1) EEvaporation Rate (Butyl Acetate=l
Solubility in Water
App earance and Odor
Section IV - Fire and Fxnlosion Hazard Data

Flash Point (Method Used) lammable Limits LEL EL
xtin u shing Media

Special Fire Fighting Procedures
Un usual Fire and Explosion Hazards
4-57
îectton V - liata

Stability nstable itions to Avoid
Stable
rials to Avoid)
ition or Byproducts
ay Occur s to Avoid
ill Not Occur
Section VI - Health Hazard Data

R oute(s) of Ent nhalation? Skin? n estion?
H ealth Hazards (Acute and Chronic)
SHA
C arcinogenic]. ty: TP? ARC Monographs?
^ egulated?
Signs and Symptoms of Exposure
M edical Conditions Generally Aggravated by Exposure
E mergency and First Aid Procedures
Section V11 - Yrecautions for Sate Handling and Use

Steps to Be Taken in Case Material is Released or Spilled
Waste Disposal Method
3recautions to Be taken in Handling and Storing
Precautions
Section VIII - Control Measures

R espiratory Protection (S eci T e)
V entilation tocal Exhaust ISpecial
M echanical (General O ther
P rotective Gloves e Protection
,O ther Protective Clothing or Equipment
ork/Hygienic Practices
4-58
Complete MSDS Form Example
Material Safety Data Sheet U.S. Department of Labor

May be used to comply with OSHA's Hazard Occupational Safety and Health
Communication Standard, 29 CFR 1910.1200 Administration
Standard must be consulted for specific (Nonmandatory Form)
requirements. Form Approved
OMB No. 1218-0072
IDENTITY (As Used on Label and List) Note: Blank spaces are not permitted. If
Hydrogen Peroxide, 98 percent any item is not applicable, or no
information is available, the space must be
marked to indicate that.
Section I
Manufacturer's Name Emergency Telephone Number
Insert company name CHEMTREC 800 424-9300
Address (Number, Street, City, State and ZIP Telephone Number for Information (xxx)
Code) xx-xxxx
98 HP Way Date Prepared 2110103
City, State Zip Signature of Preparer (opt io nal
Section II - Hazard Ingredients/

Identitv Information
Hazardous Components (Specific Chemical OSHA PEL ACGIH TLV Other Limits
dentity; Common Name(s)) Recommended
%(o tional
Hydrogen Peroxide, CAS No. 7722-84-1 1 pprn 1 ppm A
> 90
Water, CAS No. 7732-18-5 NA NA A
<10
Section III - Phvsical/Chemical Characteristics

-Point 149 °C (300 °F
g
Boilin J Specific Gravity H2O= 1 1.45
Vapor Pressure (mm Hg.) 3 mm Hg at 30 °C (86
êlting Point - 2.5 °C (27.5 °F)
°F)
4-59
Evaporation Rate (Butyl Acetate-1) less
Vapor Density (Air = 1) not available
than water
Solubility in Water 100 wei ht ercent
App earance and Odor clear, colorless liquid with sharp odor
Section IV - Fire and Exnlosion Hazard Data

Flash Point (Method Used) Flammable LEL UEL
o flash (Pensky-Martens Closed Tester) Limits none none
None
E xtinguishing Media use water in fightingfires
Special Fire Fighting Procedures wear self contained breathing apparatus (SCBA
Unusual Fire and Explosion Hazards Hydrogen peroxide will promote combustion of
ammable or combustible materials. Containers may build up pressure when exposed to
eat.
Section V - Reactivity Data

Stability unstable U nstable yes C onditions to Avoid Exposure to heat,
Stable contamination, contact with incompatible
materials that could cause violent
decomposition, contact with flammable or
combustible materials, that could cause
fire or explosion.
Incompatibility (Materials to Avoid)
Reducing agents, organic chemicals, bases, flammable or combustible materials, dirt,
Bather, iron, copper, silver, platinum and other heavy metals that could cause catalytic
decomposition
Hazardous Decomposition or Byproducts
Decomposition may be violently exothermic and will produce oxygen and water.
Hazardous May Occur no Conditions to Avoid: contact with
Polymerization NA W ill Not Occur yes 17ammable or combustible materials and
incom atible materials
Section VI - Health Hazard Data

Route(s) of Ent nhalation? yes Skin? Yes n estion? yes
Health Hazards (Acute and Chronic)
Corrosive to the skin, eyes, nose, throat and pings. May cause severe health problems or
death if ingested
SHA
Carcinogenicity: egulated?
TP? Not listed IARC Monographs? No of regulated
unknown
s
arcino en.
Signs and Symptoms of Exposure
P is corrosive and causes skin, eye, nose, throat and lung effects: Exposure may cause a
burning sensation and whiteness of the exposed area and tissue damage.
Medical Conditions Generally Aggravated by Exposure
Generally aggravated by exposure
4-60
:mergency and First Aid Procedures
eek medical attention and remove the victim to fresh air. In case of ingestion, give 1 to 2
lasses of water if the victim is conscious. Do not induce vomiting.
Section VII - Precautions for Safe Handling

and Use
Steps to Be Taken in Case Material is Released or Spilled
Refer to Emergency Response Guide 143.
Waste Disposal Method
Dilute with water to 3 percent or less. Dispose of in accordance with local authorities
Precautions to Be taken in Handling and Storing
Wear personal protective equipment at all times. Store in a ventilated area free of debris and
flammable or combustible materials.
Dther Precautions
Storage containers must be vented or autodecomposition to water and oxygen will generate
excessive pressure.
Section VIII — Control Measures

I^
Respiratory Protection (Specify Type) SCBA, Air-line
Ventilation Local Exhaust fume hood S ecial
Mechanical General Other
ye Protection yes, splash goggles and
Protective Gloves yes
ace shield
Other Protective Clothing or Equipment compatible protective clothing including protective
boot over leather footwear
Work/Hygienic Practices: Avoid contact with liquid or vapor. Wash hands frequently with
water.
I^
I^
4-61
Given the following scenario, select the appropriate personal protective equipment that should be
worn.
Two persons are to isolate and remove a 6-ft long, 8-in. outside diameter aluminum and stainless steel
tube weighing 150 lb, from an HP system for field decontamination with an available water supply.
The tubing contains an unknown amount of residual 98 percent HP.
Identified Hazards
98 percent HP: possible vapor inhalation and exposure of the skin or eyes to liquid
Tube: heavy weight could cause injury to the body or feet by impact, compression, or rollover
Other Considerations
PPE must be compatible with 98 percent HP
PPE Selection
• SCBA or air-line for respiratory protection if vapor concentrations are in excess of allowable
limits
• Steel-toed neoprene boots with metatarsal guards for foot protection
• Poly(vinylchoride) or neoprene splash suit and gloves
Discuss the preparations and precautions necessary for a facility to receive and sample a drum of
propellant HP. Be familiar with the manufacturer's procedures and recommendations.
• It is the policy of many organizations that all handling, sampling and transferring operations
should have two trained persons present.
• Receiving/inspection
- Inspect drum for signs of leakage, excess venting, noise, or heat
- Match drum identity to shipping papers
- Obtain MSDS, certificate of analysis and other documentation for traceability.
• Unload the drum from truck using approved lifting equipment (dolly or forklift)
- Personnel wear footwear compatible with HP and appropriate for protection against impact,
compression, or rollover: steel-toed neoprene boots with metatarsal protection
- Keep the drum in an upright position.
• Transport drum to sampling/storage area (secured to trailer in an upright position).
• The sampling storage area must be free of dirt, vegetation and combustible material, have a supply
of flushing water, and an emergency shower and eyewash. Preferably the sampling area should be
inside a clean building.
• Ensure the area around the bung is clean and free of particulate matter. Wipe clean if not.
• All persons must wear appropriate protective clothing for protection against HP liquid, such as
splash goggles and face shield, gloves, splash gear (PVC or neoprene outerwear), and neoprene
boots.
• Ensure there is an adequate supply of purified wash water immediately available.
4-62
• Ensure that loose objects such as pens, badges, pins, jewelry and tools are removed so they cannot
fall into the drum when the bung is opened.
• If there is a drum lock, ensure it is removed and that no pieces or residues can fall into the drum.
Some drum locks may be made of lead, which is a Class 4 material.
• Remove the bung with an appropriate wrench.
• Do not allow the bung to come into contact with potential contaminants; place in a clean
poly(tetrafluoethylene) (PTFE) bag if possible.
• Sample the HP using a scrupulously clean and passivated PTFE sampling tube attached to a
vacuum source, such as a syringe, so that liquid flows directly from the drum through the
sampling tube into a cleaned, passivated sampling container. The sampling container should be
Pyrex glass or PTFE if possible. The sampling container must have been maintained clean and
closed since the time it was passivated. Some sampling devices are supplied by the manufacturer.
• Replace the bung on the drum and the cap of the sampling container and tighten them.
• Ensure no HP has spilled and if it has, flush the area with water and dispose of water in
accordance with the facility's waste stream profile.
• The sampling tube is HP-contaminated and must be rinsed with deionized water.
• Rinse water must be disposed in accordance with the facility's waste stream profile.
• Place the sampling container in a suitable secondary container, such as a rubber-carrying bucket,
for transport to the laboratory for analysis.
• Transport the drum, upright, to its appropriate storage location.
4.14 References
29 CFR 1910 Subpart I Appendix B. Code of Federal Regulations Title 29, Occupational Safety and
Health Administration, Department of Labor, Part 1910, Occupational Safety and Health
Standards, Subpart 1, Appendix B, OSHA Non-mandatory Compliance Guidelines for Hazard
Assessment and Personal Protective Equipment Selection. U.S. Printing Office, Washington,
DC (2002, or latest revision).
29 CFR 1910.6. Code of Federal Regulations Title 29, Occupational Safety and Health
Administration, Department of Labor, Part 1910, Occupational Safety and Health Standards,
Section 6, Incorporation by Reference. U.S. Printing Office, Washington, DC (2002, or latest
revision).
Section 33, Exit Routes, Emergency Action Plans, and Fire Prevention Plans. U.S. Printing
Office, Washington, DC (2002, or latest revision).
Administration. Department of Labor, Part 1910, Occupational Safety and Health Standards,
Section 37, Maintenance, Safeguards, and Operational Features for Exit Routes. U.S. Printing
Administration. Department of Labor, Part 1910, Occupational Safety and Health Standards,
Section 38, Employee Emergency Plans. U.S. Printing Office, Washington, DC (2002, or
latest revision).
4-63
29 CFR 1910.1 19. Code of Federal Regulations Title 29, Occupational SafetY and Health
' Section 119, Process Safety Management of Highly Hazardous Chemicals. U.S. Printing
' 29 CFR 1910.120. Code of Federal Regulations Title 29, Occupational Safety and Health
Section 120, Hazardous Waste Operations and Emergency Response. U.S. Printing Office,
' Washington, DC (2002, or latest revision).
' Administration, Department of Labor, Part 1910, Occupational Safety and Health Standards,
Section 132, Personal Protective Equipment General Requirements. U.S. Printing Office,
Washington, DC (2002, or latest revision).
Section 133, Eye and Face Protection. U.S. Printing Office, Washington, DC (2002, or latest
revision).
Section 134, Respiratory Protection. U.S. Printing Office, Washington, DC (2002, or latest
revision).
Section 136, Occupational Foot Protection. U.S. Printing Office, Washington, DC (2002, or
' latest revision).
Section 138, Hand Protection. U.S. Printing Office, Washington, DC (2002, or latest
revision).
Section 141, Sanitation. U.S. Printing Office, Washington, DC (2002, or latest revision).
Section 151, Medical Services and First Aid. U.S. Printing Office, Washington, DC (2002, or
latest revision).
' 29 CFR 1910.178. Code of Federal Regulations Title 29, Occupational Safety and Health
Section 178, Powered Industrial Trucks. U.S. Printing Office, Washington, DC (2002, or
' latest revision).
4-64
1
29 CFR 19 10. Code of Federal Regulation Title 29, Occupational Safety and Health Administration,
Department of Labor, Part 1910, Occupational Safety and Health Standards, Subpart Z, Toxic
and Hazardous Substances. U.S. Printing Office, Washington, DC (2002, or latest revision).
Section 1000, Air Contaminants. U.S. Printing Office, Washington, DC (2002, or latest
revision).
29 CFR 1910.1000 Table Z-1. Code of Federal Regulations Title 29, Occupational Safety and Health
Section 1000, Table Z-1, Limits for Air Contaminants. U.S. Printing Office, Washington, DC
(2002, or latest revision).
Section 1020, Access to Employee Exposure and Medical Records. U.S. Printing Office,
Washington, DC (latest revision).
Section 1200, Hazard Communication. U.S. Printing Office, Washington, DC (2002, or latest
revision).
t
Section 1450, Occupational Exposure to Hazardous Chemicals in Laboratories. U.S. Printing
40 CFR 261.21. Code of Federal Regulations Title 40, Environmental Protection Agency, Part 261,
Compliance Assurance Monitoring, Section 21, Characteristic oflgnitability. U.S. Printing
Compliance Assurance Monitoring, Section 22, Characteristic of Corrosivity. U.S. Printing
40 CFR 264. Code of Federal Regulations Title 40, Environmental Protection Agency, Part 264,
Standards for Owners and Operators of Hazardous Waste Treatment, Storage, and Disposal
Facilities. U.S. Printing Office, Washington, DC (1980, or latest revision).
Designation, Reportable Quantities, and Notification, Section 4, Designation of Hazardous
Substances. U.S. Printing Office, Washington, DC (2002, or latest revision).
Designation, Reportable Quantities, and Notification, Section 6, Notification Requirements.
U.S. Printing Office, Washington, DC (2002, or latest revision).
4-65
1
40 CFR 355.30. Code of Federal Regulations Title 40, Environmental Protection Agency, Section 355,
Emergency Planning and Notification Section 30, Emergency Planning. U.S. Printing Office,
40 CFR 355.40. Code of Federal Regulations Title 40, Environmental Protection Agency, Section 355,
Emergency Planning and Notification Section 40, Emergency Release Notifcation. U.S.
Printing Office, Washington, DC (2002, or latest revision).
Toxic Chemical Release Reporting, Section 30, Reporting Requirements and Schedule for
Reporting. U.S. Printing Office, Washington, DC (2002, or latest revision).
49 CFR. Code of Federal Regulations Title 49, Department of Transportation, Parts 100 to end. U.S.
Printing Office, Washington, DC, (2002, or latest revision).
49 CFR 171.7. Code of Federal Regulations Title 49, Department of Transportation, Part 171,
Reference Material. U.S. Printing Office, Washington, DC, (latest revision).
49 CFR 178.345-11. Code of Federal Regulations Title 49, Department of Transportation, Part 178,
Specifications for Packagings, Section 345-11, Tank Outlets. U.S. Printing Office,
Washington, DC, (1996, or latest revision).
Hazardous Materials Table, Special Provisions, Hazardous Materials Communications,
Emergency Response Information, and Training Requirements, Section 101, Hazardous
Materials Table. U.S. Printing Office, Washington, DC (2003, or latest revision).
' Hazardous Materials Table, Special Provisions, Hazardous Materials Communications,
Emergency Response Information, and Training Requirements, Section 302, General Marking
Requirements for Bulk Packagings. U.S. Printing Office, Washington, DC (latest revision).
Hazardous Materials Table, Special Provisions, Hazardous Materials Communications,
Emergency Response Information, and Training Requirements, Section 402, Additional
Labeling Requirements. U.S. Printing Office, Washington, DC (latest revision).
Shippers--General Requirements for Shipments and Packagings, Section 127, Class S,
Division 5.1 - Definition and Assignment of Packing Groups. U.S. Printing Office,
' 49 CFR 173.151. Code of Federal Regulations Title 49, Department of Transportation, Part 173,
Shippers--General Requirements for Shipments and Packagings, Section 151, Exceptions for
' Class 4. U.S. Printing Office, Washington, DC (1997, or latest revision).
' Shippers--General Requirements For Shipments and Packagings, Section 201, Non-bulk
Packagings for Liquid Hazardous Materials in Packing Group I. U.S. Printing Office,
i
4-66
Shippers--General Requirements For Shipments and Packagings, Section 243, Bulk Packaging
for Certain High Hazard Liquids and Dual Hazard Materials which Pose a Moderate Hazard.
U.S. Printing Office, Washington, DC (2002, or latest revision).
Carriage By Vessel, Other Requirements for Stowage and Segregation for Cargo Vessels and
Passenger Vessels. U.S. Printing Office, Washington, DC (latest revision).
Specifications For Packagings, Specifications for UN Portable Tanks. U.S. Printing Office,
Specifications For Packagings, Specifications for UN Portable Tanks Intended for the
Transportation of Liquid and Solid Hazardous Materials. U.S. Printing Office, Washington,
1
DC (latest revision).
Specifications For Packagings, Standards for steel drums. U.S. Printing Office, Washington,
DC (latest revision).
Specifications For Packagings, Standards for aluminum drums. U.S. Printing Office,
ACGIH. TL Vs and BEIs Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices. American Conference of Governmental Industrial Hygienists,
ACGIH, Cincinnati, Ohio (2003).
AFRPL. Storable Concentrated Hydrogen Peroxide. AFRPL-TR-66-262, Air Force Rocket Propulsion
Laboratory. Shell Development Company (1966).
I
1
AKZO Nobel. Material Safety Data Sheet: Hydrogen Peroxide, Aqueous Solution (Greater than 60%
by Wt.), SDS-002.60. Eka Chemicals Inc., Marietta, Georgia (2001).
Alaimo, R. A., Ed. Handbook of Chemical Safety and Health. Oxford University Press, New York,
New York (2001).
ANSI. American National Standard for Emergency Eyewash and Shower Equipment. American
National Standards Institute Z358.1-1998 1 New York, New York. National Safety Council,
Itasca, Illinois (1998).
ANSI. American National Standard,for Personal Protection — Protective Footwear. American

National Standards Institute Z41-1999, New York, New York. National Safety Council,
Itasca, Illinois (1999).
ANSI. Occupational and Educational Eye and Face Protection Devices. American National Standards
Institute Z87.1-2003, American Society of Safety Engineers, Des Plaines, Illinois (2003).
4-67
ANSI. American National Standard for Laboratory Ventilation. American National Standard
ANSI/AIHA Z9.5-3003, New York, New York. Fairfax, Virginia: American Industrial
Hygiene Association (2003).
Antonova, A. "Argumentation Hygienique De La Concentration Limite Admissible en Peroxyde

' d'Hydrogene Dans Les Reservoirs d'Eau." O. Gigiena I sanit., 1974, Vol. 10, pp. 20-22.
Armour, M. A. Hazardous Laboratory Chemicals Disposal Guide, 2 nd ed. Lewis Publishers, New
' York (1996).
ASP. Hydrogen Peroxide (45%59.5%). Material Safety Data Sheet No. 001, Revision A, CR8432.
Advanced Sterilization Products (1998).
ASTM. Standard Test Method for Resistance of Protective Clothing to Penetration by Liquids. ASTM
Method F903-96, American Society for Testing and Materials, Philadelphia, Pennsylvania
(1996).
ASTM. Standard Test Method for Pressure Testing Gas Vapor Protective Ensembles. ASTM Method
F1052-87. American Society for Testing and Materials, Philadelphia, Pennsylvania (1997).
ASTM. Standard Specification for Reagent Water. ASTM Method D 1193-99. American Society for
Testing and Materials, Philadelphia, Pennsylvania (1999).
ASTM. Standard Test Method for Resistance of Protective Clothing Materials to Permeation by
Hazardous Liquid Chemicals. ASTM Method F739-00. American Society for Testing and
' Materials, Philadelphia, Pennsylvania (2000).
ATSDR. ToxFAQs for Hydrogen Peroxide. Agency for Toxic Substances and Disease Registry, April
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r
1
4-75
i
Appendix A
Chemical, Physical and Thermodynamic Properties
of Hydrogen Peroxide Propellants
I
A1.0 General Information for Hydrogen Peroxide Propellants
Chemical Name: Hydrogen Peroxide

Chemical Formula: H2O,
Molecular Weight: 34.0146
Appearance:
Solid: Colorless
Liquid: Colorless
Gas: Colorless
Odor: None or sli<uhtly sharp, similar to dilute ozone or halogens
A1.1 Units and Conversion Factors
In order to make this property data convenient to readers with a variety of backgrounds the following
tables of physical constants and conversion factors are provided.
Table A.1
Physical Constants (Rocketdyne 1967, Dean 1999)
Unit Remark Value
gC Standard Gravitational 32.1740 ft/sec-
Acceleration 980.665 cm/sec'-
1 atm Standard Atmosphere 101325.0 pascal
R Molar Gas Constant 8.31439 absolute J/K-g mole
VP=nRT 1.98719 cal/K-g mole
R=VP/Tn 0.0820567 L-atm/K-g mole
R=L-atm/°K-g mole 59.47 cu ft-atm/R-lb mole
10.73 cu ft-psia/R-lb mole
(PV)oc = (RT)oc Pressure-Volume Product for 22.414 L-atm/g mole
Ideal Gas at 0 °C 2271.16 abs J/g mole
To c Ice Point 273.16 K
491.688 R
0K Absolute Zero (Kelvin) -273.16 °C
0R Absolute Zero (Rankin) -459.69 OF
L Avogadro Constant 6.022136 x 10 23 mol -I
A Angstrom IWo m
A-1
1 Table A.2
Conversion Factors (Rocketdyne 1967, Dean 1999)
1 calorie 4.1840 abs J
1 Btu 1055.040 abs J
252.161 calories
I in. 2.5400 cm
I pound (Avoidupois) 453.5924 grams
OF ((°C*9)/5)+32
°C 5/9(°F-32)
Pounds per square in. 14.6918*atm
mm Hg 760*atm
1 1 atm
133.3224 pascal
1333.2237 dynes/cm'
101.3 kPa
1,013,250 dynes/cm2
14.69618 psi
760 mm Hg
I gal (US) 0.133680555 ft'
3785.43449 cm3
1 lb (US) 453.5924277 g
Btu/lb 2.324444 x 103 J/kilogram
cal/g 4.184 x 103 J/kilogram
Watt 0.2388 cal/sec
Joule 1 Watt-sec
A1.2 Physical Constants for Hydrogen Peroxide Propellants
Melting Point
100 percent (Giguere 1974) 272.75 K
98 percent (McCormick 1965) 270.7 K
90 percent (Ibid.) 261.6 K
Boiling Point
100 percent (Schumb 1955) 423.36 K
98 percent (McCormick 1965) 421.6 K
Triple Point
100 percent (Giguere 1954) 272.74 K
I Density
100 percent (Schumb 1955)
98 percent (Raleigh 1969)
90 percent (McCormick 1965)
1.4425 g/mL @ 298 K
1.4309 g/mL @ 298 K
1.387 g/mL @ 298 K
70 percent (Ibid.) 1.283 g/mL @ 298 K
A-2
Table A.3
Variation of HP Density (g/cm') with Concentration at 298 K (Kindron 1949, Easton 1952)
H-O2 0 10 20 30 40
(%/W)a
0 0.9970 1.0322 1.0692 1.1080 1.1487
1 1.0004 1.0358 1.0730 1.1120 1.1529
2 1.0039 1.0394 1.0768 1.1160 1.1571
3 1.0074 1.0431 1.0806 1.1200 1.1613
4 1.0109 1.0468 1.0845 1.1240 1.1655
5 1.0144 1.0505 1.0884 1.1281 1.1698
6 1.0179 1.0542 1.0923 1.1322 1.1741
7 1.0214 1.0579 1.0962 1.1363 1.1784
8 1.0250 1.0616 1.1001 1.1404 1.1827
9 1.0286 1.0654 1.1040 1.1445 1.1871
50 60 70 80 90
0 1.1915 1.2365 1.2839 1.3338 1.3866
1 1.1959 1.2411 1.2888 1.3390 1.3921
2 1.2003 1.2458 1.2937 1.3442 1.3976
3 1.2047 1.2505 1.2986 1.3494 1.4031
4 1.2092 1.2552 1.3035 1.3546 1.4086
5 1.2137 1.2599 1.3085 1.3598 1.4141
6 1.2182 1.2647 1.3135 1.3651 1.4197
7 1.2227 1.2695 1.3185 1.3704 1.4253
8 1.2273 1.2743 1.3236 1.3758 1.4309
9 1.2319 1.2791 1.3287 1.3812 1.4365
" 100 %/w = 1.4422 g/cm
Refractive Index @ 298 K for the Sodium D-Line (Giguere 1949)

100 percent 1.4067
t
98 percent 1.4049
90 percent 1.3980
70 percent 1.3814
Viscosity
100 percent (Raleigh 1969) 1.156 cp @ 298 K
98 percent (McCormick 1965) 1.156cp@298K
90 percent (Ibid.) 1.158cp@298K
70 percent (Ibid.) 1.123 cp @ 298 K
Surface Tension
100 percent (Schumb 1955) 80.4 dynes/cm @ 293 K
98 percent (McCormick 1965) 80.1 dynes/cm @ 293 K
90 percent (Ibid.) 79.14 dynes/cm @ 293 K
70 percent (Ibid.) 77.20 dynes/cm @ 293 K
A-3
i
t Vapor Pressure
100 percent (Scatchard 1952) 0.260 kPa @ 298 K
98 percent (McCormick 1965) 0.2799 kPa @ 298 K
90 percent (Ibid.) 0.443 kPa @ 298 K
70 percent (Ibid.) 0.93 kPa @ 298 K
Specific Conductance
100 percent (Schumb 1955) 4 x 10-7 ohm-cm @ 298 K
98 percent (Ibid.) 0.8 x 10-7 ohm-cm @ 298 K
Critical Properties
Temperature
100 percent (Scatchard 1952) 730 K
98 percent (CPIA/M4 1994) 728.4 K
90 percent (McCormick 1965) 718 K
70 percent (Ibid.) 693 K
Pressure
100 percent (Scatchard 1952) 2.17 x 104 kPa
98 percent (CPIA/M4 1994) 2.21 x 104 kPa
90 percent (McCormick 1965) 2.45 x 104 kPa
70 percent (Ibid.) 2.37 x 104 kPa
Thermal Conductivity
Btu-ft/h-ft'-°F @77 OF = 0.339 (CPIA/M4 1994)

Btu-ft/h-ft'-°F @32 OF = 0.321 (CPIA/M4 1994)
Table AA
I Weight Percent H,01

Electrical Conductivity at 298 K
Specific Conductivity
(ohm- I cm- I x 106)
Reference
99.9 0.39 Roth 1950

99.2 0.4 Gross 1950
99.0 0.49" Kuntz 1966
98.7 0.72 Schumb 1949
98.5 0.82 Ibid.
90.0 2.2a Kuntz 1966
1 79.7
66.8
58.5
40.5
3.3
5.1
5.3
5.5
Schumb 1949
Ibid.
Ibid.
Ibid.
26.4 4.0 Ibid.
11.8 2.3 Ibid.
0 0.5 Ibid.
' Considered to be extremely reliable. Testing was performed on "super pure" 99.9 percent H 2 0 2 diluted with purified
water.
I A-4
I
Liquid Compressibility
Adiabatic (CPIA/M4 1994)

90 percent 2.548 x 10-' kPa @ 298 K
70 percent 2.955 x 10-' I Pa @ 298 K
Isothermal (Rocketdyne 1967)

100 percent 2.651 x 10-' kPa @ 293 K
Sonic Velocity
Liquid
100 percent (Rocketdyne 1967) 1781 m/s @ 298 K
98 percent (Ibid.) 1775 m/s @ 298 K
90 percent (McCormick 1965) 1752.5 m/s @ 298 K
70 percent (Ibid.) 1690.3 m/s @ 298 K
Bond Distances
O-O (Abrahams 1951) 1.49±0.01 A
O-H (Giguere 1952) 0.97±0.01 A
Bond Angles (Penney 1934)

O-O-H 100°
Azimuthal Angle 900
A-5
w
I A1.3 Thermodynamic Data for Hydrogen Peroxide Propellants
Table A.5
Heat Capacity of Gaseous HP Between 298.16 K and 1500 K (Giguere 1955a)
Temperature (K) Heat Capacity ( J/mole-K)
298.16 43.14
300 43.22
350 45.94
400 48.45
500 52.55
600 55.69
700 57.99
800 59.83
900 61.46
1000 62.84
1100 64.14
1200 65.31
1300 66.40
1400 67.40
1500 68.32
Table A.6
Mean Heat Capacity of Hydrogen Peroxide Solutions Between 273 K and 300.0 K
(Giguere 1955b)
Wt. Percent HO, Heat Capacity
( J/mole-K)
100 89.37
98 88.70
90 86.27
80 83.64
70 81.50
60 79.50
50 77.86
40 76.44
30 75.48
20 74.81
10 74.77
0 75.56
A-6
Table A.7
Heat Capacity of Solid HP Between 12 K and 270 K (Giguere 1954)
Temperature Heat Capacity
(K) (J/mole-K)
12 0.2594
15 0.5188
20 1.234
30 3.648
40 6.895
50 10.48
60 14.11
70 17.52
80 20.48
90 23.30
100 25.71
120 29.97
140 33.64
160 36.91
180 39.98
200 43.02
220 46.21
240 49.61
260 52.82a
270 54.48A
Corrected for premelting
Heat of Fusion
100 percent (Giguere 1954) 0.368 kJ/g
98 percent (Rocketdyne 1967) 0.361 kJ/g
90 percent (CPIA/M4 1994) 0.344 kJ/g
70 percent (Ibid.) 0.300 kJ/g
Heat of Vaporization at 298 K

100 percent (Raleigh 1969) 1.517 kJ/g
98 percent (Kuntz 1966) 1.539 kJ/g
90 percent (CPIA/M4 1994) 1.630 kJ/g
70 percent (Ibid.) 1.830 kJ/g
Heat of Decomposition at 298.16 K (Kuntz 1966):
HBO,)( q = H-)O) , ) +'/202(g) (A.1)
100 percent -98.07 kJ/mole

A-7
I
Heat and free energy of formation (Schumb 1955):
H2(g) + O,tgt + nH2O(1) = H2O2(1) + nHzO tq (A.2)

I
' Table A.8

Heat and Free Energy of Formation of HP in Solution at 298.16 K (Schumb 1955)
Wt. Percent H_,O, Heat of Formation Free Energy of Formation
(kJ/mole) (kJ/mole)
100 187.65 120.42
90 188.32 120.96
80 188.95 121.63
70 189.49 122.42
60 189.95 123.34
50 190.33 124.31
40 190.62 125.44
30 190.83 126.69
20 190.96 128.24
10 191.04 130.50
0 191.08
I Table A.9
Refractive Index of HP Solutions at 298 K for the Sodium-D Line (Kuntz 1966)
H 2 O, Percent 0.0 0.2 0.4 0.6 0.8
90 1.3 980 981 983 985 986
91 988 990 992 993 995
92 997 999 *000a *0023 *0043
93 1.4 006 007 009 011 013
94 014 016 018 020 021
95 023 025 027 028 030
96 032 034 035 037 039
97 041 042 044 046 048
98 049 051 053 055 056
' 99 058 060 062 063 065
100 067
I irst two diuits are 1.4
A-8
Table A.10
Total Heat of Vaporization of HP - Water Solutions (Kuntz 1966)
Composition, Wt. Percent H2O, 298 K At normal boiling point
(kJ/g) (kJ/g)
100 1.517 1.358
98 1.539 1.376
90 1.628 1.464
80 1.732 1.569
70 1.832 1.669
60 1.928 1.766
50 2.019 1.854
40 2.107 1.941
30 2.192 2.021
20 2.276 2.105
10 2.359 2.180
0 2.442 2.255
Table A.11
Dielectric Constant of 90, 98 and 100 Percent HP (Gross 1950)
Temperature H2O,
(K) (%)
90 98 100
243 110.7 106.8 105.7
253 102.6 99.0 98.1
263 95.1 91.7 90.8
273 88.6 85.3 84.4
283 82.6 79.4 78.5
293 77.1 74.0 73.2
303 72.2 69.4 68.5
Table A.12
Volume of Oxygen Released by 1 Liter of HP at 1.0 .Atmosphere and 273 K (Raleiuh 1969)
H2O, Volume O,
(%) (L)
100 484.65
90 419.16 j
80 358.17
70 301.46
60 248.66
50 199.49
40 153.66
30 110.97
20 71.21
10 34.26
0 0.00
A1.4 Heats of Reaction of Hydrogen Peroxide Propellants with Fuels
The heating values are calculated for the combustion of hydrogen peroxide with some common fuels.
The reactions are assumed to go completely to H 2O, CO, and N,_ and are based on the following values
of heats of formation:
Hydrazine(j) (Baker 1999) 50.37 kJ/mole

MMH(j) (Ibid.) 54.836 kJ/mole
UDMH()) (Ibid.) 51.626 kJ/mole
CO2(g) (Ibid.) -393.522 kJ/mole
H2O(„) (Ibid.) -241.826 kJ/mole
C,HSOHtb (Dean 1999) -277.6 U/mole
H,0 100% (N1ST Report 8504 1964) -187.8 kJ/mole
H2O,-98% (Ibid.) -187.9 kJ/mole
H2O2-90% aq. (Ibid.) -188.4 kJ/mole
H2O2-70% aq. (Ibid.) -189.6 U/mole
Hydrazine:
N2H4 + 2H2O2 —> 4H2O + N2
MMH
2CH3N(H)NH2 + l OH2O,_ —> 2CO 2 + 16H,0 + 2N2
UDMH:
(CH3)2NNH2 + 8H2O 2 —> 2CO, + 12H2O + N2
100 percent -2238.2 U/mole
C2HSOH:
C,H SOH + 6H2O, —> 2CO 2 + 9H2O
90 percent -1761.1 U/mole
A-10
A1.5 Temperature
p Dependency
p Tables for Hydrogen Peroxide Propellant
Yp
Properties
Table A.13
Density of 90 Weight Percent HP (Kuntz 1966)
Temperature Density
(K) (g/cm3)
273 - - 1.4136
283 1.4026
293 1.3919
298 1.3867
298 1.3866
323 1.3605
323 1.3597
349.5 L334
358.2 1.325
366.2 1.315
369 1.307
398.7 1.283
415.5 1.251
448 1.220
466 1.212
Table A.14
Density of 98 Weight Percent H ?O, (Kuntz 1966)
I
Temperature Density ,
(K) (g/cm3)
273 1.4594
283 1.4477
293 1.4374
298 1.4311
298 1.4309
300 1.4294
307 1.4213
318 1.4196
323 1.4038
323 1.4024
328 1.4003
338 1.3888
348 1.3813
357 1.3693
367 1.3564
369 1.3470
378 1.3460
1
A- I I
Table A.15
Total Vapor Pressure of HP-11,0 Solutions (Kuntz 1966)
Temperature 90% 98% 100 Percent
(K) (kPa) (kPa) (kPa)
277 0.102 0.0614 0.0531
289 0.236 0.1469 0.1296
300 0.507 0.3296 0.2930
311 1.029 0.6902 0.6199
322 1.980 1.365 1.236
333 3.623 2.561 2.336
344 6.352 4.589 4.211
355 10.71 7.888 7.274
366 17.41 13.05 12.10
377 27.42 20.88 19.43
389 41.95 32.34 30.25
400 62.48 48.84 45.78
411 90.81 71.78 67.50
422 129.1 103.1 97.22
433 180.0 145.1 137.1
444 246.2 200.2 189.5
455 331.1 271.2 257.3
466 438.3 361.6 343.6
477 572.0 475.0 452.0
489 736.4 615.2 586.4
500 937.0 786.7 750.9
511 1178 994.3 950.1
527 1467 1243 1189
533 1808 1539 1473
544 2208 1886 1807
555 2675 2293 2199
566 3215 2765 2653
577 3836 3301 3177
589 4547 3932 3776
600 5357 4641 4460
611 6275 5446 5236
622 7309 6356 6111
633 8481 7378 7095
644 9791 8522 8198
655 11246 9798 9425
666 12880 11218 10784
677 14693 12790 12294
689 16700 14535 13962
700 18913 16451 15796
711 21333 18548 17810
722 - 20857 20023
730 - - 21692
A-12
Table A.16
Viscosity of 90 Percent HP (Kuntz 1966)
Temperature Viscosity
(K) (centipoise)
273 1.887
273 1.872
293 1.260
298 1.156
323 0.803
323 0.801
373 0.479
398 0.402
423 0.362
436 0.311
Table A.17
Viscosity of 98 Percent HP (Kuntz 1966)
Temperature Viscosity
(K) (centipoise)
273 1.839
273 1.812
293 1.252
293 1.250
298 1.156
303 1.068
313 0.920
323 0.816
323 0.812
333 0.724
343 0.645
353 0.583
358 0.555
A2.0 References
Abrahams, S. C., R. L. Collin, and W. N. Lipscomb. Acta Cryst. Vol. 4, 1951:15.
Baker, D. L., D. D. Davis, L. A. Dee, B. Greene, C. H. Hart, and S. S. Woods. Fire, Explosion,
Compatibility, and Safety Hazards of Nitrogen Tetroxide, RD-WSTF-0017, NASA Johnson
Space Center White Sands Test Facility, Las Cruces, New Mexico (1999).
CPIA/M4. Liquid Propellant Manual. Chemical Propulsion Information Agency, Johns Hopkins
University. Columbia, Maryland, May 1994.
Dean, J. A. Lange's Handbook of Chemistry, 15 `h edition. McGraw-Hill, Inc. New York, New York
(1999).
A-13
Easton, M. F., A. G. Mitchell, and W. F. K. Wynn-Jones. "The Behaviour of Mixtures of Hydrogen
Peroxide and Water" Trans. Faraday Soc., Vol. 48, 1952:796.
Giguere, P. A. and P. Geoffrion. Can. J. Res., Vol. 27B, 1949:168.
Giguere, P. A. and O. Bain. J. Phys. Chem., Vol. 56, 1952:340.
Giguere, P. A., L D. Liu, J. S. Dugdale, and J. A. Morrison. "Hydrogen Peroxide: The Low
Temperature Heat Capacity of the Solid and the Third law Entropy." Can. J. Chem. Vol. 32,
1954:117.
Giguere, P. A. and I. D. Liu. Am. Chem. Soc. J., Vol. 77 Sec. 4, 1955x:6477.
Giguere, P. A., B. G. Morissette, A. W. Ommos, and O. K'nop. "Hydrogen Peroxideand Its Analogues
VII. Calorimetric Properties of the Systems H2O — H2O ? and DSO — DO," Can. J. Chem.,
Vol. 33, 1955b:804-20.
Giguere, P. A. J. Chem. Ed., Vol. 51, 1974:470.
Gross, P. M. and R. C. Taylor. J Am. Chem. Soc., Vol. 72, 1950:2075.
Kindron. R. R. and E. S. Shanley. unpublished, Becco Chemical Division, Buffalo, New York (1949).
Program, AFRPL-TR-66-6, Part II, Phase 1 Final Report. Air Force Rocket Propulsion
McCormick, J. C. Hydrogen Peroxide Rocket Manual. Inorganic Chemicals Division, FMC,

NIST Report 8504. Preliminary Report on the Thermodynamic Properties of Selected Light-Element
and Some Related Compounds. National Institute of Standards and Technology (NIST). U. S.
Government Printing Office. Washington, DC (1964).
Penney, W. G. and G. B. B. M. Sutherland. Trans. Faraday Soc., Vol. 30, 1934:637.
Raleigh, C. W. Hydrogen Peroxide Physical Properties. Technical Bulletin 67. FMC (1969).
Roth, E. M. and E. S. Shanley. Ind. Eng. Chem., Vol. 72, 1950:2075.
Scatchard, G., G. M. Kavanagh, and L. B. Ticknor. "Vapor-Liquid Equilibrium. VIII. Hydrogen

Peroxide-Water Mixtures." J. Am. Chem. Soc., Vol. 74, 1952:3715.
Schumb, W. C. Ind. Eng. Chem., Vol. 41, 1949:992.
Schumb, W. C., C. N. Satterfield, and R. L. Wentworth. Hydrogen Peroxide. ACS Monograph

No. 128, Reinhold Publishing Corp., New York (1955).
A-14
1
A-15
1
1
Appendix B
Analytical Spectroscopy of Hydrogen Peroxide
131.0 Analytical
Y Spectroscopy
p pY of Hydrogen Peroxide
There have been a variety of spectroscopic studies of HP performed for a number of reasons.
Primary applications include:
• Atmospheric monitoring of air pollution

• Structural characterization of the HP molecule
• Trace analytical determination of HP in air and water including forensic studies
• Propellant characterization
Many common laboratory spectroscopic techniques have been applied to the characterization of
HP. These techniques include:
• Nuclear magnetic resonance (NMR) (Galasso 1984, Giamello 1996)

• Raman spectroscopy (Giguere 1984)
• Infrared (IR) spectroscopy (Bailey 1938, Lannon 1971)
• Ultraviolet (UV) spectroscopy (Schumb 1955, Molina 1997)
• Visible spectroscopy
• Microwave absorption spectroscopy (Massey 1952, Massey 1954)
• Refractive Index (RI) (Giguere 1943a, Giguere 1949, McPherson 2002)
• Magneto-optic rotation (Giguere 1943b)
• X-ray crystalographic studies (Abrahams 1952, Banna 1976)
This section discusses the analytical spectroscopy of HP that is useful for propellant
I
characterization.
131.1 Refractive Index
Use of refractive index (RI) has been investigated for the rapid determination of HP purity (Rusek
1996, McPherson 2002). The RI of HP-water solutions at 77 °F (25 °C) using the sodium D-line
was correlated with results of the classic potassium permanganate titration method (McPherson
2002). The method was found to be rapid and precise, but tended to underestimate the HP
concentrations by 0.5 to slightly over 2 percent using RI-concentration data currently in the
literature (Giguere 1943 and 1949). It was recommended that further correlation studies be
performed.
It is imperative that the refractometer and any associated equipment be properly cleaned prior to
taking any HP readings because HP may react and decompose during the measurement process.
Furthermore, any HP readings must be taken immediately after being placed onto the R1 window
to avoid analytical error due to its decomposition.
131.2 Ultraviolet Spectroscopy
The extinction coefficients for ultraviolet radiation of HP liquid and vapor have been reported and
are shown in Figure B.I below (Schumb 1955). It was concluded the absorption coefficient for
both the liquid and the vapor were the same within the precision of the reported results.
I
B-1
131.3 Visible Spectroscopy
HP is colorless to the eye (4000-800010. It has been observed, however, that in bulk solutions
such as in an aluminum drum HP may appear to have a weak green to blue hue (Schumb 1955).
This may be attributeed to the properties of the aluminum container wall, by bubbles in the liquid,
' and by the presence of suspended material such as that derived from stabilizers. Table B.1
summarizes causes for HP discoloration due to metallic impurities reported by NAVAER (1957).
Table B.1
Causes for HP Discoloration (NAVAER 1957)
Color Cause —
Light pink to deep purple Chromium or nickel impurity
Blue Copper impurity
Yellow Iron (or titanium impurities)
1 131.4 Raman Spectroscopy
' The Raman spectrum of HP (Figure B.2) was been obtained (Giguere 1984). Raman spectroscopy
has been to obtain a calibration curve for HP in water and to determine the concentration of HP in
' a sample during a forensic investigation (Bartick 2001).
B1.5 Infrared Spectroscopy

Infrared absorption spectra of HP have been obtained (Bailey 1938, Bain 1955). Infrared has
primarily been used for structural determination and for the determination of vibrational,
stretching and rotational modes.
' Figures B.3 through B.8 are qualitative infrared spectra of 98 percent HP, 90 percent HP and
deionized water obtained at WSTF in April 2003, using a Nicolet Magna 750 infrared
spectrometer. These were obtained on a drop of each fluid between quartz windows for the near-
infrared spectra (Figures B.3 through B.5) and between ZnSe windows for the mid-infrared
spectra (Figures B.6 through B.8). The spectra of deionized water in these regions is necessary for
the spectroscopist to evaluate and compare the HP spectra to, because water is the major impurity
in the HP. Potentially useful absorbance bands for HP in the mid-infrared are at approximately
2800, 1340, and 879 cm' s (Figures B.6 and B.7). Noting the low values of the y-axis (absorbance
scale), there were no strongly absorbing peaks due to HP in the near—infrared under the
conditions these spectra were collected (Figures B.3 and B.4).
131.6 Spectroscopic Methods for the Trace Components in HP

' Various spectroscopic methods have been used to quantify trace components, including
stabilizers and impurities in HP. These methods include inductively coupled plasma-mass
' spectrometry (1CP-MS), and are discussed in the Analytical Methods section.
13-2
Ultraviolet Absorption Spectrum
1000
100
FE
0 10
V
0 1
U
0.1
w
—° 0.01
a+
0 0.001
2
0.0001
4200 3800 3400 3000 2600 2200 1800
Wavelength, Angstroms
Figure B.1
Ultraviolet Absorption Spectrum (Schumb 1955)
Raman Spectrum
(99 1 0 liquid H2O2, -40 deg-C)
100
a^
w
0
-500 500 1500 2500 3500
Raman Shift, cm-1
Figure B.2
Raman Spectrum (Schumb 1955)
B-3
0.009
0.008
0.007
0.006
c 0.005
aò
Q 0.004
0.003
0.002
0.001
-0.000
11000 10000 9000 8000 7000 6000 5000

Wavenumbers(cm-1)
Figure B.3
Near-Infrared Spectrum of 98% HP (WSTF))
0.034 =FMC 90% H202
0.032 =
0.030 =
0.028 =
0.026
0.024
0.022
0.020
c
m 0.018
0 0.016-
¢ 0.014-
0.012 -
0.010 -
0.008 -
0.006 -
0.004 -
0.002 -
-0.000-
11000 10000 9000 8000 7000 6000 5000

W avenumbers (cm-1)
Figure B.4
Near-Infrared Spectrum of 90% HP (WSTF)'
1 Data obtained at Johnson Space Center White Sands Test Facility, April 2003.
B-4
0.09
0.08
0.07
0.06
d
0.05
a
ò
a
0.04
0.03
0.02
0.01
0.00
11000 10000 9000 5000 7000 6000 5000

Wavenumbers (cm-1)
Figure B.5
Near-Infrared Spectrum of Deionized Water (WSTF)t
1.4
1.3-
1.2-
1.1 -
1.0-
0.9 -
0.8-
m
n 0.7-
2 0.6-
0.5-
0.4-
0.3-
0.2-
0.1-
0.0-
3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Figure B.6
Mid-Infrared Spectrum of 98% HP (WSTF)'
' Data obtained at Johnson Space Center White Sands Test Facility, April 2003.
B-5
1.3
1.2
1.1
1.0
0.9
0.8
m
aò 0.7
Q 0.6
0.5
0.4
0.3
0.2
0.1
0.0
3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Figure B.7
Mid-Infrared Spectrum of 90% HP (WSTF)'
s
a
3500 3000 2500 2000 1500 1000

Wavenumbers(cm-1)
Figure B.8
Mid-Infrared Spectrum of Deionized Water (WSTF)'
1 Data obtained at Johnson Space Center White Sands Test Facility, April 2003.
B-6
B2. 0 References '
Abrahams, S. C. "The Crystal

rY Structure of Hydrogen Peroxide." Acta C ry tallograPhica, Vol. 4,
1952:15-20.
Banna, M. S. "The X-ray Photoelectron Spectrum of Hydrogen Peroxide." Canadian Journal of

Chemistry, Vol. 54, 1976:3811-3813.
Bailey, C. R. and R. R. Gordon. "The Infra-Red Absorption Spectrum of Hydrogen Peroxide."

Trans. Faraday Soc, Vol. 34, 1938:1133.
Bain, O. and P. A. Giguere. "Hydrogen Peroxide and Its Analogues VI. Infrared Spectra of H2O2,
D,O,, and HDO,." Can. J. Chem., Vol. 33, 1955:527.
Bartick, E. G., R. A. Merrill, and K. H. Mount. "Analysis of a Suspect Explosive Component:

Hydrogen Peroxide in Hair Coloring Developer." Forensic Science Communications,
Volume 3, Number 4, October 2001.
Galasso, V. "Ab Initio SOS CI Calculations of the Effect of Internal Rotation on the NMR
Parameters of Hydrogen Peroxide." Journal of Chemical Physics Letters, Vol. 108,
1984:435-438.
Giamello, E. "The Interaction Between Hydrogen Peroxide and Metal Oxides. EPR
Investigations." Applications of Magnetic Resonance, Vol. 10, 1996:173-192.
Giguere, P. A. "The Refractive Indices of Hydrogen Peroxide and Its Aqueous Solutions", Can. J.
Res. Vol. 21 Sec. B, 1943a:156.
Giguere, P. A. and H. Feeny. "The Magneto-Optic Rotation of Hydrogen Peroxide ", Can. J. Res.,
1
Vol. 21 Sec. A, 1943b:69.
Giguere, P. A. and Geoffrion, P. "Refractive Index of Hydrogen Peroxide Solutions. A Revision ",
Can. J. Res. Vol. 27 Sec. B., 1949:168-173.
Giguere, P. A. "Hydrogen Bonding in Hydrogen Peroxide and Water. A Raman Study of the
Liquid State." Journal of Raman Spectroscopy, Vol. 15, 1984:199-204.
Lannon, J. A. "Infrared Spectrum of Solid and Matrix-Isolated Hydrogen Peroxide and

Deuterium Peroxide." Journal of Chemical Physics. Vol. 54, 1971:2212-2223.
Massey, J. T. and D. R. Bianco. "Microwave Absorption Spectrum of H 2O2." Physical Rev., Vol.
85, 1952:717.
Massey, J. T. and D. R. Bianco. "The Microwave Spectrum of Hydrogen Peroxide." J. Chem. '
Phys., Vol. 22, 1954:442.
B-7
McPherson, M. D. Comparison of Concentration Determination Methods .for Propellant-
Grade
Hydrogen Peroxide: Classical Potassium Permanganate Titration versus Refractive
' Index. Paper # 056-02, Aerojet Missile and Space Propulsion, Sacramento, California
(2002).
Molina, L. T. "Ultraviolet Absorption Spectrum of Hydrogen Peroxide Vapor." Geophysical

I Research Letters, Vol. 4, 1997:580-582.
NAVAER. Handbook, Field Handling of Concentrated Hvdrogen Peroxide (Over 52 Weight

Percent Hydrogen Peroxide). NAVAER 06-25-501, Director of the Chief of the Bureau
of Aeronautics (1957).
' Rusek, J.J. "New Decomposition Catalysts and Characterization Techniques for Rocket-Grade
Hydrogen Peroxide." Journal of Propulsion and Power, Vol. 12, N3, May-June 1996.
I
Schumb, W., C. Satterfield, and R. Wentworth. "Hydrogen Peroxide." American Chemical
^ Society Monograph Series (1955).
Î
Î
B-8
1
B-9
1
I
I Appendix C
Hydrogen Peroxide Specifications
1
C1.0 Introduction
This section presents a brief history related to the development of the various hydrogen peroxide (HP)
formulations that have been used and the specifications that describe their quality requirements.
C2.0 Background
French chemist Louis-Jacques Thenard initially produced HP in 1818 by adding nitric acid to barium
I
peroxide. The inorganic electrolysis of ammonium bisulfate produced HP, and was the primary
production method until the development of the organic oxidation of alkylhydroanthraquinone
method. The main impurity, regardless of the production method, is water. The water content can
moderate the reaction temperature during catalytic decomposition so it is not always desirable to
remove all the water from HP; this has caused most specifications to have different allowable water
concentrations. Organic impurities from the anthraquinone production led to organic carbon
specification limits being applied. The decomposition of HP during storage has always been a concern,
so limits on impurities that can catalyze the decomposition have been incorporated into modern
specifications. The use of stabilizing compounds that can act as passivating agents in containers or
sequester impurities have created limits for this class of compounds. A test that can evaluate both the
effectiveness of stabilizers or the lack of catalytic impurities is what is referred to as the active oxygen
loss (AOL) test. The AOL test has been incorporated into most specifications. Finally, most
specifications include limits on evaporation residue and particulate.
The use of HP in torpedoes led to the military specification MIL-H-22868 (Wep), Hydrogen Peroxide,
E-Stabilized, 70 percent and 90 percent (For- Torpedo Use). This document was dated March 21, 1961
and was declared inactive July 31, 1996 (MIL-H-22868 (OS)). This specification covered 70 percent
and 90 percent concentrations, and the stabilizer levels were considerably higher than in the propellant
HP specification, MIL-P-16005E, Propellant, Hydrogen Peroxide. The propellant HP specification
MIL-P-16005E covered 90 and 98 percent HP was first issued January 31, 1968 and was declared
inactive in June 1988 coincident with termination of the Scout Vehicle Program (Wernimont 2000,
Grams 2002). Both of these military specifications had AOL, chloride, sulfate, tin, phosphate, nitrate
and evaporation residue limits; and also detailed wet chemical methods for the determination of most
of these impurities and additives that do not reflect current laboratory practices. Current laboratory
practices are discussed in the Analytical Methods Appendix of this manual. A review of MIL-P-
16005E has been presented (Wernimont 2000).
During the period of time where the military specifications were not being actively maintained,
Semiconductor Equipment and Materials International developed a specification for the semiconductor
industry, SEMI C30-1 101 (SEMI 2001). This document was initiated in 1978, and the current revision
is dated August 27, 2001. This document would normally not be of interest to users of propellant HP
because the concentration of the hydrogen peroxide is only 30 percent, but it is of interest to users of
this manual because it reflects changes in analytical protocols that occurred after the military
specifications were written. For example, the SEMI specification grade five limits most impurities to
30 parts-per-billion (ppb) or less, so the recommended analytical techniques are sufficiently sensitive
for the anticipated low impurity levels in future HP specifications.
Several manufacturers of HP also released their own product descriptions. Solvay lnterox supplied
domestically produced 70 percent HP and imported 85 percent grade HP, Degussa supplied
PROPULSE" 890 (89 percent HP), PROPULSE 900 (90 percent HP) and PROPULSE 980 (98 percent
1
HP) materials. FMC, Philadelphia, Pennsylvania, supplied a variety of HP solutions in concentrations
up to 98 percent.
i
C-1
1
The Directorate of Aerospace Fuels issued interim sets of Item Descriptions between 1997 and 1999
(Item Description 1997, 1999a, 1999b). Some of these item descriptions reflect vendor influence from
that period as different companies started providing incrementally higher concentrations of the product.
For example, the Degussa stability AOL data was reported at 16 h and 96 °C, where the original military
specifications and FMC use the 24 h, 100 °C data (Degussa 2003a, Degussa 2003b. Degussa 2003c, MIL-
H-22868 (Wep), MIL-P- I 6005E).
The first of the Item Descriptions was dated May 21, 1997 and had descriptions for Type 70 (70 percent
HP) and Type 85 (85 percent HP) (Item Description 1997). This Item Description had no test methods
listed, only a table of chemical and physical properties. No stability was specified either.
1 The second Item Description was issued June 9, 1999 and this version also listed a Type 90 (90 percent
HP) material (Item Description 1999a). This Item Description listed test methods for residue of ignition
and stability determined at 16 h and 96 °C for the Type 90 only.
1 The third Item Description was issued November 5, 1999 and it lists Type 70, 85, and 90 materials (Item
Description 1999b). This item description lists test methods for stability determined at 24 h, 100 °C and
evaporation residue. But the primary difference is that the chemical and physical property table has
revised values from the June 9, 1999 version.
The Defense Energy Support Center (DESC) issued draft versions of MIL-PRF-16005F (as of February
21, 2003) for review that reflected the current need for a specification that includes the higher
concentrations needed for propellant applications, redefined impurity levels and more modern analytical
protocols (DESC 2000, 2002a, 2002b). The suspense date for comments on the December 2002 draft
version of the military specification was February 28, 2003. MIL-PRF-16005F was issued on August 1,
2003.
t C3.0 HP Specification Requirements

The tables in this section have been culled from various specifications noted in Section C2.0. The reader
is cautioned to take care in looking at the units in each table; transitions from mg/kg to mg/L with
hydrogen peroxide may lead to confusion as the density varies with the concentration. Every effort was
taken by the authors of this manual to ensure the units in these tables match their original sources.
1
Table C.1 is taken from the inactive military specifications.
Table C.1
Inactive Specifications (MIL-H-22868 and MIL-P-16005E)
Properties Units MIL-H-22868 MIL-H-22868 MIL-P-16005E MIL-P-16005E
Grade 70E Grade 90E Type I Type II
HP assay % by weight 69.5 to 7 1. 0 89.5 to 91.0 90.0 to 91.0 98.0 to 99.0
Aluminum mg/L NR* NR 0.5 max 0.5 max
Chloride ing/L 1.0 max 1.0 max 1.0 max 1.0 max
Ammonium mg/L NR NR 3.0 max 3.0 max
Nitrate mg/L 90 to 130 90 to 130 3.0 to 5.0 3.0 to 5.0
Phosphate mg/L 25 to 33 25 to 33 0.2 max 0.2 max
Sulfate mg/L 10 max 10 max 3.0 max 3.0 max
Tin rng/L 28 to 36 28 to 36 1.0 to 4.0 1.0 to 4.0
Carbon mg/L NR NR 200 max 200 max
Evaporation mg/L 325 max 325 max 20 max 20 max
Residue
AOL % active O 2.0 max 2.0 max 2.0 max 2.0 max
100 °C/24 h
Particulate mg/L NR NR 1.0 max 1.0 max
Acidity Apparent pH 1.2 to 1.6 0.0 to 0.4 NR NR
Surface Dynes/cm 72 min 74 min NR NR
Tension At 20°C
*NR = No Requircmcni
Table C.2 is the first Item Description issued May 21, 1997.
Table C.2
Item Description May 21, 1997 (Item Description 1997)
Properties Units Type 70 Type 85
HP assay % by weight 71.0 to 73.0 85.0 to 87.0
Aluminum mg/kg 0.4 max 0.4 max
Chloride mg/kg 0.8 max 0.7 max
Ammonium mg/kg 2.3 max 2.2 max
Nitrate mg/kg 2.3 to 3.9 2.2 to 3.7
Phosphate mg/kg 0.16 max 0.15 max
Sulfate mg/kg 2.3 max 2.2 max
Tin mg/kg 0.8 to 3.1 0.7 to 2.9
Carbon mg/kg 155 max 147 max
Evaporation Residue mg/kg 15 max 14.6 max
Particulate mg/kg 0.8 max 0.7 max
Chromium mg/kg 0.11 max 0.11 max
Lead mg/kg 0.04 max 0.04 max
Manganese mg/kg 0.04 max 0.04 max
Iron mg/kg 0.11 max 0.11 max
Copper mg/kg 0.04 max 0.04 max
Nickel mg/kg 0.04 max 0.04 max
C-3
1
I Table C.3 is the second Item Description issued June 9, 1999.
Table C.3
Item Description June 9. 1999 (Item Description I999a)
Properties Units Type 70 Type 85 Type 90
HP assay % by weight 71.0 to 73.0 85.0 to 87.0 89.0 to 91.0
' Aluminum mg/kg 0.4 max 0.4 max 1 max
Chloride mg/kg 0.8 max 0.7 max 2 max
Ammonium mg/kg 2.3 max 2.2 max 2 max
Nitrate mg/kg 2.3 to 3.9 2.2 to 3.7 10 max
Phosphate mg/kg 0.16 max 0.15 max 0.5 max
Sulfate mg/kg 2.3 max 2.2 max 5 max
Tin mg/kg 0.8 to 3.1 0.7 to 2.9 3 to 6
Carbon mg/kg 155 max 147 max 100 max
Evaporation Residue mg/kg 15 max 14.6 max NR
' Residue of ignition mg/L NR NR 20 max
Stability (16 h/96 °C) % loss of NR NR 2 max
active O
Particulate mg/kg 0.8 max 0.7 max NR
' Chromium mg/kg 0.11 max 0.11 max NR
Lead mg/kg 0.04 max 0.04 max NR
Manganese mg/kg 0.04 max 0.04 max NR
Iron mg/kg 0.11 max 0.11 max NR
Copper mg/kg 0.04 max 0.04 max NR
Nickel mg/kg 0.04 max 0.04 max NR
*NR = No Requirement
Table CA is the third Item Description issued November 5, 1999.
Table CA
Item Description November 5. 1999 (Item Description 1999b)
Aluminum mg/kg 0.2 max 0.2 max 0.2 max
Chloride mg/kg 0.2 max 0.2 max 0.2 max
Ammonium mg/kg 1.0 max 1.0 max 1.0 max
Nitrate mg/kg 1.7 to 2.7 2.2 to 3.5 2.2 to 3.5
' Sulfate mg/kg 0.2 max 0.2 max 0.2 max
Tin mg/kg 1.0 to 2.1 1.0 to 3.0 1.0 to 3.0
' Evaporation Residue mg/kg 7 max 10 max 10 max
Stability (16 h/96 °C) % loss of 2 max 2 max 2 max
active O
Chromium mg/kg 0.02 max 0.02 max 0.02 max
Lead mg/kg 0.02 max 0.02 max 0.02 max
Manganese mg/kg 0.02 max 0.02 max 0.02 max
Iron tng/kg 0.02 max 0.02 max 0.02 max
Copper mg/kg 0.02 max 0.02 max 0.02 max
Nickel mg/k<-, 0.02 max 0.02 max 0.02 max
C-4
Table C.5 was the proposed performance specification (DESC 2002b).
Table C.5
MIL-PRF-16005F (proposed) (DESC 2002b. proposed comments due February 28, 2003)
Properties Units Type 70 Type 85 Type 90 Type 90 Type 98
Grade ES Grade ES Grade ES Grade HP Grade HP
HP assay % by weight 71.0 to 73.0 85.0 to 87.0 89.5 to 91.0 90.0 to 91.0 98.0-99.0
Aluminum mg/L 0.2 max 0.2 max 1.5 max 0.35 max 0.35 max
Chloride mg/kg 0.8 max 0.2 max 2 max 0.5 max 0.5 max
Ammonium mg/kg 2.3 max 3.0 max 3.0 max 3.0 max 3.0 max
Nitrate mg/kg 3.9 max 5.0 max 3.0 to 10 5.0 max 5.0 max
Phosphate mg/kg 0.2 max 0.2 max 0.5 max 0.2 max 0.2 max
Sulfate mg/kg 2.3 max 0.5 max 5 max 0.5 max 0.5 max
Tin mg/L 0.8 to 3.1 1.0 to 4.0 2.5 to 7.0 1.0 to 4.0 1.0 to 4.0
Carbon mg/kg 155 max 30 max 75 max 40 max 40 max
Evaporation Residue mg/kg 15 max 10 max NR 20 max 20 max
AOL (100 °C/24 h) % active O 2 max 2 max 2 max 2 max 2 max
Chromium mg/L 0.1 1 max 0.03 max NR 0.03 max 0.03 max
Lead mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Manganese mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Iron mg/L 0.11 max 0.03 max NR 0.03 max 0.03 max
Copper mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Nickel mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Antimony mg/L NR NR NR 0.03 max 0.03 max
Arsenic mg/L NR NR NR 0.03 max 0.03 max
Gold mg/L NR NR NR 0.03 max 0.03 max
Zinc mg/L NR NR NR 0.03 max 0.03 max
Titanium mg/L NR NR NR 0.03 max 0.03 max
*NR = No RequircmCnt
C-5
Table C.6 is the current performance specification MIL-PRF- I 6005F.
Table C.6
MIL-PRF-16005F (August 1, 2003)
Properties Units Type 70 Type 85 Type 90 Type 90 Type 98
Grade ES Grade ES Grade ES Grade HP Grade HP
HP assay % by weight 71.0 to 73.0 85.0 to 87.0 90.0 to 91.5 90.0 to 91.5 98.0-99.0
' Aluminum mg/L 0.2 max 0.2 max 1.0 max 0.35 max 0.35 max
Chloride mg/kg 0.8 max 0.2 max 2 max 0.5 max 0.5 max
Ammonium mg/kg 2.3 max 3.0 max 3.0 max 3.0 max 3.0 max
Nitrate' mg/kg 3.9 max 5.0 max 7.5 max 5.0 max 5.0 max
Phosphate mg/kg 0.2 max 0.2 max 0.5 max 0.2 max 0.2 max
Sulfate mg/kg 2.3 max 0.5 max 5 max 0.5 max 0.5 max
' Tin mg/L 0.8 to 3.1 1.0 to 4.0 0.7 to 7.0 1.0 to 4.0 1.0 to 4.0
Carbon mg/L 200 max 40 max 105 max 40 max 40 max
Evaporation Residue mg/kg 15 max 10 max NR 20 max 20 max
AOL (100 °C/24 h) % active O 2 max 2 max 2 max 2 max 2 max
Chromium mg/L 0.11 max 0.03 max NR 0.03 max 0.03 max
Lead mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Manganese mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Iron mg/L 0.11 max 0.03 max NR 0.03 max 0.03 max
Copper mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
Nickel mg/L 0.04 max 0.03 max NR 0.03 max 0.03 max
' Antimony mg/L NR NR NR 0.03 max 0.03 max
Arsenic mg/L NR NR NR 0.03 max 0.03 max
Gold mg/L NR NR NR 0.03 max 0.03 max
Zinc mg/L NR NR NR 0.03 max 0.03 max
Titanium mg/L NR NR NR 0.03 max 0.03 max
*NR = No Re uirement
High purity grade shall be available with a minimum level of 2.0 mg/kg nitrates when requested.
Table C.7 is current (as of April 10, 2003) Degussa PROPULSE HP specifications.
Table C.7
Degussa PROPULSE Products (Degussa 2003a, 2003b and 2003c)
Properties Units m PROPULSE 890 PROPULSE 900 PROPULSE 980
Nitrate mg/kg 7.2 max 7.2 max 7.2 max
Sulfate mg/kg 3.6 max 3.6 max 3.6 max
Tin mg/kg 2 to 5 2 to 5 2 to 5
Residue of Ignition mg/kg 15 max 15 max 15 max
AOL (96 °C/16 h) % AOL 2 max 2 max 2 max
Table C.8 is the current (as of April 10, 2003) FMC product specification.
C-6
Table C.8
FMC Prop ulsion Grade HP Products
HP assay % by weight 71.0 to 73.0 90.0 to 92.0 98.0 min
Nitrate mg/kg 1.7 to 2.7 2.2 to 3.5 2.1 to 3.5
Sulfate mg/kg 0.2 max 0.3 max 0.35 max
Tin mg/kg 1.0 to 2.1 1.0 to 2.9 0.7 to 2.7
Evaporation Residue mg/kg 10 max 15 max 14 max
AOL (100 °C/24 h) % active O 2 max 2 max 2 max
Particulate mg/kg 0.8 max 0.7 max 0.6 max
Chromium mg/kg 0.02 max 0.02 max 0.02 max
Lead mg/kg 0.02 max 0.02 max 0.02 max
Manganese mg/kg 0.02 max 0.02 max 0.02 max
Iron mg/kg 0.02 max 0.03 max 0.035 max
Copper mg/kg 0.02 max 0.02 max 0.02 max
Nickel mg/kg 0.02 max 0.02 max 0.02 max
C4.0 References
Degussa. Specifications. PROPULSE 890 Hydrogen Peroxide. (Document received April 2003)
2003a.
2003b.
2003c.
DESC. Performance Specification: Propellant, Hydrogen Peroxide (Draft MIL-PRF-1600F). Defense

Energy Support Center, Fort Belvoir, Virginia, October 2000.
DESC. Performance Specification: Propellant, Hydrogen Peroxide (Draft MIL-PRF-16005F).

Defense Energy Support Center, Fort Belvoir, Virginia, September 2002a.
DESC. Performance Specification: Propellant, Hydrogen Peroxide (Draft MIL-PRF-16005F).

Defense Energy Support Center, Fort Belvoir, Virginia, December 2002b.
Grams, K. "Status of the Military Specification for Hydrogen Peroxide MIL-PRF-16005."

5th International Hydrogen Peroxide Propulsion Conference, Purdue University, West
Item Description, Propellant, Hydrogen Peroxide. Directorate of Aerospace Fluids. Kelly AFB,
Texas, May 1997.
C-7
t
Item Description, Propellant, Hydrogen Peroxide. Directorate of Aerospace Fluids. Kelly AFB, Texas,
June 1999a.
Item Description, Propellant, Hydrogen Peroxide. Directorate of Aerospace Fluids. Kelly AFB, Texas,
I November 1999b.
MIL-H-22868 (Wep). Military Specification: Hydrogen Peroxide, E-Stabilized, 70 percent and

1
MIL-H-22868 (OS). Notice of Inactivation for New Design. Hydrogen Peroxide, E-Stabilized, 70 percent
and 90 percent (For Torpedo Use), Project 6810-N091, United States Navy - OS, Washington, DC,
July 1996.
MIL-P-16005E. Military Specification: Propellant, Hydrogen Peroxide. Military Specification, United

States Department of Defense, March 1968.

SEMI C30-1101. Specifications and Guidelines for Hydrogen Peroxide. Semiconductor Equipment and
Materials International, San Jose, California (2001).
Wernimont, E. and M. Ventura. "Critical Review of MIL-P-16005E." 3"d International Hydrogen

Peroxide Propulsion Conference, NASA Stennis Space Center, Mississippi, November 2000.
1
1
1
1
C-9
1
Appendix D
Quantitative Determination of Hydrogen Peroxide
1
f
D1.0 Introduction I
This appendix presents a brief history of analytical methods used to verify the quality requirements
defined for HP in the various specifications.
D2.0 Background I
The primary impurity in HP is water, and all specifications have defined different water levels in the
fluid. Consequently, the purity or assay of HP is one of the most common analytical procedures
performed. The stability of HP is an important issue relating to both quality and safety, and the
verification of stability has been incorporated into many of the specifications as the active oxygen loss
(AOL) test. Some impurities catalyze the decomposition of HP, and the methodologies of analyzing low
concentrations of these impurities have been incorporated into most specifications as well. Another aspect
is the addition of stabilizers to HP to reduce the decomposition rate, therefore, methodologies for
verification of stabilizer packages have been of importance. Since the development of the organic
oxidation method of alkylhydroanthraquinone for the production of HP, determining the carbon content of
HP has become a common analytical requirement. Additionally, determination of evaporation residue has
been employed for some time as part of various specifications.
The long-term use of HP coupled with the advances in instrumental analytical chemistry have changed
the preferred analytical methods considerably. Many of the classical wet chemical techniques used
historically have been replaced with modern instrumental techniques. In analyses where wet chemical
techniques are still used, the environmental aspects of the wastes produced may be factors that influence
the selection of one technique over another.
Recommendations concerning analytical methods provided by the Interagency Hydrogen Peroxide j

Analysis Methods Working Group were helpful in the update of the draft MIL-PU-16005F to the current
MIL-PRF-16005F (Aerojet 2002, DESC 2002). 1
D3.0 HP Purity (Assay)
This section covers analytical techniques for the determination of percent level and higher concentrations
of HP. Techniques for the trace determination of HP are covered in Section D4.0.
I
D3.1 Potassium Permanganate Titration I
Potassium permanganate (KMnO4) titration has been widely used for the determination of HP assay
(Schumb 1955, WSTF Job Instruction (WJI) CHEMLAB.0275.A, l Degussa 2001, Solvay 2001a, U.S.
Peroxide Undated a). This titration method was also used in specification
MIL-H-22868 (Wep). The reaction is as follows:
2KMnO4 + 5H2O, + 3H,SO4 --> 2MnSO4 + K,SO4 + 8H2O + 50, (D.1)
In-house document. WJI-CHEMLAB.0275.A. Purity Determination of Concentrated Hydrogen Peroxide. December 6, 1999.
D-1
Potassium permanganate is commonly standardized against primary standard grade sodium oxalate
(Na2C2O4 ) using the following reaction:
5Na,C 2O4 + 2KMnO4 + 8H,SO4 —> 5Na,SO4 + 2MnSO4 + K,SO4 + 8H 2O + 1 OCO, (D.2)
The potassium permanganate titration is the referee technique for assay in MIL-PRF-16005F. The
reaction is catalyzed by the manganous ion so it is helpful to add some manganese sulfate (MnSO4)
solution to the acidified HP solution before the addition of titrant. Not all the above references state this in
their procedures, but other references call for using manganous salt (SEMI 2001, MIL-H-22868 (Wep)).
The standardization must be performed at a temperature of 60 °C. The titration may be done classically
with a burette using the purple color of the first excess permanganate ion as an indicator, but is also
suitable for use in automatic titration equipment with a redox electrode to increase efficiency and
throughput.
D3.2 Cerium Titration
The use of cerium (Ce41) in redox titrations is also a common technique (Solvay 2001 b, U.S. Peroxide
undated b, Schumb 1955). MIL-P-16005E listed ceric titration as the referee technique. The reaction is as
follows:
H2O, + 2Ce(SO4 ) 2 ---> O, + Ce2(SO4 ) 3 + H,SO4 (D.3)
The ceric titration is essentially equivalent to the permanganate assay, but the recommended
standardization techniques (ACS 2000, ASTM 2001) with primary standard grade arsenic trioxide
1
coupled with use of osmium tetroxide in the indicator raise issues with toxicity and waste disposal. Use of
arsenic and osmium tetroxide in this technique makes the permanganate method more desirable. Like the
permanganate titration, it is a process that could be performed using automatic titration equipment with a
redox electrode to increase efficiency and throughput.
D3.3 lodometric Titration
If an excess of potassium iodide (KI) solution is added to acidified HP with a molybdate catalyst, the
iodine formed may then be titrated with standardized thiosulfate solution using starch as an indicator
(U.S. Peroxide undated c, Schumb 1955). The reactions are as follows:

H2O, + 2KI + H,SO4 --> I2 + K,SO4 + 2H2O (D.4)

I2 + 2Na,S 2O3 —> Na,S4O6 + 2NaI (D.5)
Being a back-titration technique, the increase in error propagation makes it less desirable than the
permanganate method. Schumb reports this method as being less accurate than the permanganate titration
(Schumb 1955).
D3.4 Density
Pure HP has a density that is about 47 percent higher than water, and this characteristic makes the use of
density to determine the purity of HP a reasonable method. Classically, pycnometers, hydrometers, or a
D-2
I
Westphal balance have been used in the determination of HP purity by density (Schumb 1955). Modern
digital density meters could be employed as well to increase efficiency and throughput. However, bubble
formation by decomposing HP could easily lead to erroneous results with the density techniques. Density
determination is an alternative assay method in
MIL-PRF-16005F.
D3.5 Refractive Index
Refractive index (RI) can be a rapid and simple technique that is useful for determining HP
concentrations. Results using this technique were published earlier (Giguere 1943, Giguere 1949, Rusek
1996). The RI technique was recently revisited using an automatic digital refractometer, but reported a
discrepancy at higher concentrations (> 95 percent) of HP when compared to the permanganate titration
(McPherson 2002). As with other techniques, decomposition of HP on wetted surfaces, or water
absorption into the HP, can induce error. The RI method has potential to be a suitable alternative method
for purity, although it is not listed in MIL-PRF-16005F.
D4.0 Trace Methods for the Determination of HP in Air and Water

This section focuses on analytical methods suitable for the determination of HP in air for industrial
hygiene monitoring. It also includes information on pollution evaluation and control that should be of
interest to the users of this manual. Numerous methods have been developed and applied to biochemical
studies and atmospheric monitoring. This is due to the importance of HP as an intermediate in catalyzed
biological processes and upper atmospheric chemistry. However, these will not be discussed in this
manual. As discussed in Section 4 of this manual, the limits for HP in air are 1 ppm TLV-TWA (ACG1H
2003), 1 ppm REL and 75 ppm IDLH (NIOSH 2002), and 1 ppm PEL (29 CFR 1910.1000 Table Z-1,
Limits for Air Contaminants). These are the concentrations of HP in air of interest in this section. The
determination of concentrations of HP in water will be evaluated on a case-by-case basis by the users of
this manual.
Considerations in sampling and analysis of HP include its relatively short half-life in air and water, and its
sensitivity to decomposition (ECETOC 1993). These subjects are discussed in Sections 3 and 4 of this
manual.
D4.1 HP in Air
HP in air is commonly determined by the use of color indicating tubes, direct reading monitors, or by
preconcentration in a liquid phase followed by a wet chemical analysis. Color indicating tubes are
available from sources including Draeger and SKC, Inc. and operate on the principle that HP in air drawn
through a clear tube containing a reagent produces a color change. The length of the color change down
the tube is proportional to the airborne HP concentration, and may be read directly from a scale on the
tube.
A survey of direct reading monitors is provided in Section 4 of this manual.
OSHA Method VI-6 is a partially validated method in which air samples are collected in midget-fritted
glass impingers containing titanium oxysulfate (TiOSO.,) collecting solution (OSHA 1977). The solution
D-3
is then prepared in water and analyzed colorimetrically for the yellow peroxo-titanium complex at 410 nm
using a visible spectrometer. Concentrations of HP are determined by: 1) comparing the sample to
standards prepared with HP (from a 30 percent solution) and the TiOSO 4 reagent and 2) taking into
consideration the volume of air collected and the flow rate.
OSHA Method ID 126SG is a partially validated method in which 100 L of air is passed at 0.5 L/min
through a midget-fritted glass bubbler containing 15 mL TiOSO 4 (OSHA 1993). The resulting solution is
analyzed using a polarograph. The polarograph is the alternate detection method for the visible
spectrometer specified in OSHA Method V1-6 referenced above. A portable infrared spectrometer is used
to detect HP directly in air as an alternative in OSHA Method ID 126SG (OSHA 1993).
A method for the collection of HP vapor using titanyl-coated sorbent media packed in tubes offered
advantages over the OSHA method using liquid in a midget-fritted glass bubbler (Hecht 1999).
A comparison of techniques used to monitor HP in air was reported (Puskar 1996). The techniques that
were evaluated were a Draeger tube, ion mobility spectrometer and OSHA Method V1-6 (OSHA 1977).
D4.2 HP in Water
Concentrations of HP that are of interest in the discharge of waste to the publicly owned treatment works
(POTW) are set by the local sewer authority. Early communication with the sewer authority or the POTW
about the intention, if any, of the facility to discharge small quantities of HP will help to ensure
environmental compliance.
Perhaps the easiest method for qualitative determination of HP in water is by the addition of potassium
iodide and starch. The resultant blue color produced by oxidation of iodide to iodine and the formation of
the tri-iodide/starch complex is a qualitative indication of the oxidizing agent (HP). Test strips, described
below, utilize starch-iodide or other color indicating chemistry.
A sensitive qualitative test for HP is the decolorizing of black lead sulfide, forming white lead sulfate
(Schumb 1955).
HP concentrations in water may be determined by a spectrophotometric method that measures the

absorbance of a colored peroxo-cobalt complex at 260 nm (Messchelen 1977). The method is reported to
be useful in the HP concentration range of 0.02 to 0.2 mg/L (U.S. Peroxide undated d).
A number of methods have been reported for the determination of HP in water using the peroxidase
enzyme catalyzed reaction with HP. U.S. Peroxide reports that a spectrophotometric method for the
determination of HP in water measures the absorbance of a colorimetric indicator at 596 nm following the
catalyzed reaction of HP with peroxidase enzyme (U.S. Peroxide undated e).
A number of dip-and-read test strips and test kits are available to detect HP in water. Test strips are
reported by the manufacturers to be useful for HP concentrations from 0.5 to 500 mg/L. Test strips are
available from suppliers listed in Section 4 of this manual. These utilize a peroxidase enzyme, starch-
iodide, or iron phenanthrolate color comparison method. Test kits are reported by the manufacturers to be
useful for HP concentrations from 0.1 to 40 mg/L. These utilize a
N,N-diethyl-p-phenylenediamine (DPD) or starch-iodide thiosulfate method and a disk color or drop
count colorimetric comparitor method. Test kits are available from the following sources.
D-4
• VWR Scientific
1310 Goshen Parkway
West Chester, Pennsylvania 19380
(800) 932-5000
Fax: (800) 926-1166
http://www.vwr.com
Hach Company
PO Box 389
Loveland, Colorado 80539
(800) 227-4224
(970)669-3050
http://www.hach.com
D5.0 Common Anions I

The anions of interest are present in HP for a variety of reasons and are of concern. The anions currently
limited in MIL-PRF-16005F are chloride, nitrate, phosphate and sulfate. Reagent grade sodium nitrate,
potassium stannate trihydrate and sodium stannate trihydrate are the only approved additives for the high
purity grades of propellant HP. Sodium and potassium have no established limits in the current
specification, but there is a limit for nitrate. Chloride and sulfate have always been species limited by
specifications because of their associated corrosive properties towards aluminum.
D5.1 Chloride
The MIL-P-16005E method for chloride was a colorimetric analysis based on the following reactions:
Hg(SCN)2 + 2CF H HgClz + 2SCN ('D.6)
Fe 31 + 2SCN - —> Fe(SCN)z (D.7)
In these reactions, chloride initially reacts with the mercuric thiocyanate (Hg(SCN)2), displacing
3+) to produce the amber-colored ferric
thiocyanate ion (SCN -) that in turn reacts with ferric ion (Fe
thiocyanate complex that is analyzed at 460 nm using visible spectrophotometry. In this analysis, the
intensity of the amber color is proportional to the original chloride concentration.
The method for determination of chloride in MIL-PRF-16005F is ion chromatography. To prepare the
sample for analysis, one of two methods may be used. The first method is by evaporation, in which a
known quantity of HP is evaporated in a porcelain or glass evaporation dish over a steam bath. The
residue is rinsed into a 50-mL flask and diluted with water prior to analysis. The second method is by
decomposition, in which a known quantity of HP is recirculated, unattended through a length of
poly(tetrafluoroethylene) tubing through which a platinum wire is threaded (WJI-CHEMLAB.0274.A,'
Greene 2002, McClure 2002). The resulting water sample produced by the platinum-catalyzed
decomposition of HP is diluted with pure water so that the correlation between the original HP sample
In-house document. WJI-CHEMLAB.0274.A. Decomposition of Concentrated Hydrogen Peroxide.

December 6, 1999.
D-5
1
weight and the final volume of solution is known. Typically, 50 g of HP are decomposed and diluted to
50 mL of water. This solution is then submitted for ion chromatographic analysis, and chloride, nitrate,
sulfate and phosphate are then determined after a single injection. The apparatus for this unattended
decomposition is shown in Figure D-1.
f
PERISTALTIC ICE BOX
RIEUGE
PUMP
Figure D.1
Apparatus for the Unattended Decomposition of HP
D5.2 Nitrate
The MIL-P-16005E method for the determination of nitrate used a multiple step process. The HP sample
was first decomposed under basic conditions and brought to dryness. The nitrate-containing residue was
then reacted with phenol-2,4-disulfonic acid to produce the nitro-derivative. The resultant solution was
then made basic with ammonium hydroxide and the resultant yellow solutions analyzed at 410 nm using
visible spectrophotometry. Here, the intensity of the yellow color is proportional to the original nitrate
concentration. The MIL-PRF-16005F method for the determination of nitrate uses the decomposed
solutions described in D5.1 followed by anion ion chromatography.
D5.3 Phosphate
The MIL-P-16005E method for phosphate was ASTM Method F61-65T. This ASTM method was
reapproved in 1985 and withdrawn in 1993 (ASTM 1993). The method involved the acidic decomposition
of HP and reaction of the resulting solution with ammonium molybdate to produce heteropoly
phosphomolybdic acid (PMA). The PMA was then reduced with hydrazine to give the molybdenum blue
color. These blue-colored samples were then analyzed at 825 nm using visible spectrophotometry with the
intensity of the blue color being proportional to the original phosphate concentration. The MIL-PRF-
16005F specification uses the decomposed solutions described in Section D5.1 followed by anion ion
chromatography.
D5.4 Sulfate
' The MIL-P-16005E method for sulfate used a multiple step process. The HP sample was first
decomposed under basic conditions and brought to dryness. The sulfate-containing residue was then
diluted with hydrochloric acid, glycerin and 95 percent ethanol or isopropyl alcohol, then reacted with a
D-6
1
barium chloride solution to precipitate barium sulfate. These samples were analyzed for turbidity samples
at 420 nm using a visible spectrophotometer. The MIL-PRF-16005F specification uses the decomposed
solutions described in D5.1 followed by anion ion chromatography.
D6.0 Ammonium, Sodium and Potassium I

The MIL-P-16005E method for ammonium used a multiple step process. The HP sample was first
decomposed under acidic conditions, the solution was then made basic with sodium hydroxide, then
Nessler's reagent (a solution of mercuric iodide (Hgh), potassium iodide (KI) and potassium hydroxide
(KOH)) was added to form the yellow complex by the reaction below:
2 K,HgI4 + NH 3 + 3 OH- —> Hg,OINH, + 2 HO + 4 K+ + 7 F (D.8)
This solution was then analyzed at 420 nm using visible spectrophotometry with the intensity of the
yellow color being proportional to the original ammonium concentration. The
MIL-PR-F- 16005F specification uses the decomposed solutions described in D5.1 followed by cation
chromatography.
Although sodium and potassium are not usually limited in the specifications, they may be analyzed on the
same ion chromatographic injection as ammonium.
D7.0 HP Stability
The stability of HP has been listed in almost every specification issued. Classically, stability is
determined by the gravimetric AOL technique over a 24-h period at 100 °C. One important drawback to
this test is that it requires 24 h to perform, which is time consuming. An additional drawback is that the
test temperature of 100 °C may not be easily achievable using a water bath at locations other than sea
level. The use of gas evolution rates instead of weight loss is a technique that can save time on this
analysis (Solvay 2001c). Because the weight loss of decomposing HP is due to oxygen gas formation,
there is a simple relationship between the two techniques. An earlier comparison of the gas evolution and
gravimetric techniques was made and found that, although the methods could be compared, care must be
taken to ensure that quantities and surface to volume ratios are matched (McClure 2002). The
decomposition rate sometimes varied during a test period, and the observation was made that this rate
sometimes began rapidly then slowed. Passivation of the containers and their materials of construction
can have a tremendous influence on this test as well.
Microcalorimetry has been investigated as a tool to evaluate the compatibility of HP with materials and,
because the technique has sufficient sensitivity to examine baseline decomposition of HP, it could, in
theory, be used to evaluate stability as well (Greene 2003). The correlation between heat flow and
decomposition rate could allow this method to be used, but the time it takes to get microcalorimetric
readings and the cost of the instrument compared to the other techniques has kept microcalorimetric data
in the research and materials compatibility area. This technique is not an alternative method for HP
stability determination in MIL-PRF-16005F. Further details on the technique of microcalorimetry are
described in D7.3 below. I
D-7
D7.1 Gravimetric Active Oxygen Loss (AOL)
The gravimetric AOL test is straightforward and has not changed significantly with the versions of
specifications issued. The equipment needed to perform the test is minimal and likely to already be
present in most laboratories. Most of the specifications call for a 24-h period at 100 °C, although the
Degussa specification calls for a 16-h period at 96 °C. The specifications that call out the lower
temperature, shorter time period value, do not have a correction factor in them to correlate the values to
more stringent (higher temperature, longer time) conditions. The MIL-PRF-16005F specification has the
24-h time period and 100 °C temperature in it. In this method, 50-mL aliquots of HP are placed in 50-mL
volumetric flasks that have been passivated with nitric acid and prescreened to give consistent results. The
initial and the final weights are determined and recorded. The results are then calculated by the following
equation:
100(Wi — Wz)
A%Oz = (D.9)
0.470C W
Where:
t A%O, = percent active oxygen loss

W = initial net weight
W, = final net weight
C = weight fraction of sample (concentration /100)
D7.2 Gas Evolution AOL
The gas evolution variation of the AOL test as described by Solvay Interox is a test run at 100 °C for a
60-min period (Solvay 2001 c). Solvay Interox does not recommend this technique for concentrations of
HP over 75 percent, and strongly warns against allowing the sample to evaporate or concentrate because
of the risk of explosion. In this method, a 25-mL sample is placed in a passivated reaction tube with an
overall length of 6 in. (15 cm), an external diameter of 1 in. (2.5 cm), and a 24/40 tapered ground glass
joint connecting it to a condenser. The reaction tube is passivated with a 1:1 dilution of 85 percent
phosphoric acid with water. Results are reported at a rate of mL/min of oxygen gas evolved. A
comparison of this technique to the MIL-P-16005E technique found that it was not comparable until the
glassware and fluid volume used was the same as the military specification method (McClure 2002). With
the variable of fluid to volume ratios removed, the agreement was as good as one would assume from the
gas law correlation of gas weight to volume. However, it is still useful to get several gas volume
measurements from a flask to ensure that the value was representative of the overall rate. This technique
does have the advantage of generating data more rapidly than the 24-h test, but is not an alternative AOL
method in MIL-PRF-16005F.
D7.2.1 Oxygen Mass Flow Rate Determination
A method for monitoring oxygen evolution as a means to determine peroxide stability has been reported
(Ross 2002). The use of oxygen flow measurements at tank vent lines has been reported to provide a
sensitive technique for monitoring HP reaction events and can provide an earlier indication of an
abnormal decomposition than measuring temperature rise. This is because oxygen generation is not only
directly related to peroxide decomposition, but occurs immediately. For example, the bulk decomposition
of 1 percent HP per week in a tank or drum can produce oxygen in excess of 30 cc/min. This oxygen flow
I
D-8
rate corresponds to an equivalent temperature rise of approximately 20 millidegrees C, which is difficult
to measure reliably. Under heat exchange (non-adiabatic) conditions that could be expected to exist in a
tank or drum environment, there would be no measurable temperature rise. Temperature changes from the
surrounding environment and heat lost to the peroxide also mask potential problems. Analytical
simulations based on sub-scale tank experiments were conducted to determine if the mass flow rate of
oxygen generated from an HP tank can monitor decomposition and warn if a runaway reaction was
imminent. Simulations also determine whether the measurement temperature rise or oxygen evolution
was the most useful to monitoring abnormal decomposition. The results of the study showed that oxygen
generation measurements had advantages over temperature measurements.
D7.3 Microcalorimetry
Isothermal microcalorimetry is a specialized immersion test used at WSTF that is particularly suited to
measure HP decomposition (Gostowski 2000a, Gostowski 2000b, Davis 2001, Gostowski 2002, Greene
2003, Hornung 2003). Isothermal microcalorimetry is an ultra-sensitive technique that measures heat flow
at the microWatt (µW or µd s') level. This technique uses a water bath controlled to less than 0.01 °C as a
heat sink and a Peltier-effect device to measure the heat flow from the sample to the heat sink. At room
temperature, HP decomposes at a rate of approximately 2 µW/g in a passivated glass container, which is
well within the capabilities of the technique. Approximately 30 g of HP per sample are used in this test.
This technique provides real-time data on the decomposition of HP, which can change with time. Data
taken at three or more temperatures on a given sample can be used to characterize the temperature
dependence of the reaction rate in terms of the activation energy and preexponential factor. This allows
calculation of the decomposition rate at temperatures up to approximately 100 °C and determination of
I
the amount of oxygen evolved or HP lost. This potentially allows a comparison to the other techniques
discussed in this section. As mentioned in Section D7.0, this technique was not incorporated into
MIL-PPF-16005F, but it is a powerful technique for evaluating the decomposition of HP.
D8.0 Evaporation Residue n

The evaporation residue measurement is mostly unchanged from the MIL-P-16005E to the
MIL-PR-F- 16005 F. The method first decomposes a 300-mL sample in 500 mL of purified water over
platinum. This volume is then reduced to less than 50mL and transferred to a tared platinum dish. The
dish is vacuum baked for a minimum of I h at 105 to 1 10 °C and reweighed. A
500-mL sample of the purified water is also done as a blank. The blank result is then subtracted from the
sample result, and reported in mg/L.
D-9
D9.0 Total Carbon
The MIL-P- 16005E method for total carbon was an arduous multistep process as follows: a 50-mL
portion of the HP sample along with 50 mL of purified water was placed into a three-necked reaction
flask equipped with a dropping funnel and a West condenser. Five mL of 0.08N sodium hydroxide was
added from the dropping funnel, then with water circulating and the flask in an ice bath, a drop of dilute
silver nitrate solution was added through the top of the West condenser and allowed to react with the HP
solution. The addition of dilute silver nitrate solution in drops continued until the catalyzed
t decomposition of HP to water and oxygen ceased. Next, 10 mL of the 10 percent silver nitrate solution
and 50 mL of 9N sulfuric acid solution were added to rinse the sides of the flask. The next series of steps
took the flask as prepared above with the decomposed HP in it and oxidized and desorbed any
carbonaceous materials. The flask was assembled into the system as shown in Figure D-2.
ASBESTOS
SILICA COMBUSTION TUBE KOROSEAL STOPPERS
GRA4ULAP ZINC
you
11 —
COM.RUSTION
FURNANCE
U-BFIID
—u
TRAP
COLLECTION
FIASK
DROPPI4G
FUNNEL
KECK
FILLING
FLASK
x
ri
v
PIG MAN un
FLOW
!RÌ' ER
Figure D.2
Apparatus for the Collection of Total Carbon in HP
The tube furnace was filled with cupric oxide heated to 750 °C and the collection flask was filled with 50
mL of a barium hydroxide solution. The flow meter was supplied with oxygen gas, meeting MIL-PRF-
25508E type I requirements. After the oxygen gas flow was initiated, the flask was heated to 70 to 80 °C
and, sequentially, three 100-mL aliquots of saturated potassium persulfate were added from the dropping
funnel until the brown color observed on addition faded. The effluent gas mixture then passed through the
cupric oxide at 750 °C and the granular zinc trap to remove any noncarbonaceous acidic gases, then into
the barium hydroxide solution. The barium hydroxide solution was then titrated with the standardized
0.15- to 0.20-N hydrochloric acid solution to a phenolphthalein endpoint. A blank was analyzed in the
same manner as the HP sample, with the substitution of 50mL of carbon dioxide-free water for the HP.
The MIL-PRF-16005F specification calls for the use of ASTM D 2579 (revised 1993, discontinued 2002)
for the measurement of total organic carbon in water. A neat sample of HP (not decomposed) is used for
D-10
I
the determination of total carbon. The total carbon procedure used at WSTF is a modern catalytic
combustion total organic carbon analyzer (Greene 2003). The microliter-sized sample is injected into a
heated catalyst bed and the carbon dioxide (CO,) in the effluent gas is quantified as it flows through an
infrared detector that is standardized with a potassium acid phthalate solution. ASTM G 144-01 is an
active method that also uses catalytic combustion TOC with infrared detection (ASTM 2001). The use of
modem TOC analyzers can save significant time compared to the original method by integrating all the
individual pieces in Figure D-2 and by infrared detection to increase sensitivity and allow the sample size
to be reduced.
D10.0 Metals I
Metallic species found in HP are also of concern. The metals currently limited in the
MIL-PRF-16005F specification are aluminum, tin, chromium, lead, manganese, iron, copper, nickel,
antimony, arsenic, gold, zinc and titanium. Sodium nitrate, potassium stannate trihydrate and sodium
stannate trihydrate are the only approved additives listed in MIL-PRF-16005F. Sodium and potassium
have no established limits, but stannate added as a stabilizer does (see Table C.6). The use of aluminum
containers for HP storage and the potential for aluminum to contaminate the HP is reflected in the
somewhat higher allowable amount of aluminum in the specification. The other metals may be limited
because of their deleterious effects on the fluid. The original MIL-P-16005E listed only aluminum and
tin. The MIL-H-22868 (Wep) specification lists only tin. Due to the amount of labor required to measure
each of these potentially catalytic metallic impurities by colorimetric or other classical wet chemical
techniques, the stability was a convenient way to measure if the entire sample is free enough of any
catalytic impurities without listing or limiting them specifically.
The MIL-PRF-16005F specification lists two different ASTM documents for the analysis of the referee
method. The first method, ASTM D 5673, is for the analysis of water by inductively coupled plasma-
mass spectrometry (ICP-MS). The MIL-PRF-16005F specification uses neat HP for introduction to the
instrument; at WSTF, HP is decomposed as described in D5.1 or diluted with purified water before
analysis by ICP-MS. The decomposition process is done over platinum, which is not an analyte, and by
decomposing the sample to water. This allows for the matrix to be matched to the standards. If the HP is
analyzed without decomposition or significant dilution (such as 1:100), the internal standard protocols
defined in ASTM 5673 should be followed. The second method listed is ASTM D 3919, which is for the
analysis of water by graphite furnace atomic absorption spectrophotometry (GF-AAS) (ASTM 1999). The
MIL-PRF-16005F specification requires the use of neat HP instead of water using this method. The GF-
AAS technique is slower than using ICP-MS, but the instruments are less expensive than an ICP-MS and
may be more readily available in many laboratories.
D10.1 Aluminum I
The MIL-P-16005E aluminum analysis began by decomposing the HP sample thermally, without acid or
base. The residue was then dissolved with 2 mL of 2N hydrochloric acid, diluted to a 50-mL volume with
1 mL of 1 percent thioglycolic acid and 15.0 mL of Aluminon buffer. The resulting orange/red
alum 1num/Aluminon complex solution was then analyzed at 520 rim using visible spectrophotometry,
with the intensity of the orange/red color being proportional to the aluminum concentration. The MIL-
PRF-16005F specification techniques for aluminum are discussed in Section 10.0.
D-11
1
ID10.2 Tin
The MIL-P- 16005Etin analysis was a colorimetric technique referenced as ASTM F62-65T
(revised 1984, withdrawn 1990). The initial HP sample was decomposed by heating it with sulfuric acid
and platinum, then the residue was dissolved in an ammonium chloride solution with a pH of 0.85. After
extracting the ammonium chloride solution with chloroform, 8-hydroxyquinoline solution was added to
form a complex with the tin. This complex was then extracted with chloroform and analyzed at 385 nin
using visible spectrophotometry.
The MIL-H-22868 (Wep) tin analysis is a polarographic technique. The MIL-PRF-16005F specification
techniques for tin are discussed in Section 10.0. The tin content of the HP in the MIL-PRF-16005F is
about one or two orders of magnitude above the metallic impurities discussed in Section D10.3. The
WSTF protocol for the tin analysis is to dilute the HP (1:100) into the same matrix as the standards and
then to analyze it by ICP-MS for tin (Greene 2003).
D10.3 Chromium, Lead, Manganese, Iron, Copper, Nickel, Antimony, Arsenic,

Gold, Zinc and Titanium
These species are all listed in the MIL-PRF-16005F specification and were not listed in either the MIL-P-
16005E or MIL-H-22868 (Wep) specifications. There are no historical analytical techniques to discuss.
The MIL-PRF-16005F specification techniques for these species are discussed in Section 10.0.
D11.0 References
29 CFR 19 10. 1000 Table Z-1. Code of Federal Regulations Title 29, Occupational Safety and Health
Section 1000, Table Z-1, Limitsfor Air Contaminants. U.S. Printing Office, Washington, DC
ACGIH. TL Vs and BEls Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices. American Conference of Governmental Industrial Hygienists,
ACGIH, Cincinnati, Ohio (2003).
ACS. Committee on Analytical Reagents. "Reagent Chemicals: American Chemical Society

Specification," Official from January 1, 2000, American Chemical Society, 9 `h Edition (2000).
Aerojet. Recommendations from the Interagency Hydrogen Peroxide Analysis Methods Working Group,
Aerojet, Sacramento, California, April 2002.
ASTM. Method of Test for Tin in Electronic Grade Hydrogen Peroxide Solutions.
ASTM F62-65T (revised 1984, withdrawn 1990), American Society for Testing and Materials
International (1984).
D-12
ASTM. Standard Test Method for Phosphate in Electronic Grade Hydrogen Peroxide Solutions. ASTM
F61-65T (revised 1985, withdrawn 1993), American Society for Testing and Materials
ASTM. Standard Test Method for Total Organic Carbon in Water. ASTM D 2579-93el (Withdrawn
2002), American Society for Testing and Materials International (1993).
ASTM. Standard Practice for Measu ring Trace Elements in Water by Graphite Furnace Atomic
Absorption Spectrophotometry. ASTM D 3919-99, American Society for Testing and Materials
ASTM. Standard Practice_for Preparation, Standardization, and Storage or Standard and Reagent
Solutions for Chemical Analysis. ASTM E 200-97 (Reapproved 2001), American Society for
Testing and Materials International (2001).
ASTM. Standard Test Method.for Determination of Residual Contamination of Materials and

Components by Total Carbon Analysis Using a High Temperature Combustion Analyzer. ASTM
G 144-01, American Society for Testing and Materials International (2002).
ASTM. Standard Test Method for Elements in Water by Inductively Coupled Plasma-Mass Spectrometry.
ASTM D 5673-02, American Society for Testing and Materials International (2002).
Davis, D. D., S. D. Hornung, and D. L. Baker. "Hydrogen Peroxide Decomposition", Proceedings of the
First International Conference on Green Propellants for Space Propulsion. (Special Publication
SP-484). Noordwijk, Netherlands, European Space Agency, June 2001.
DESC. Performance Specification: Propellant, Hydrogen Peroxide (Draft MIL-PRF-1600F). Defense

Energy Support Center, Fort Belvoir, Virginia 22060-6222. December 2002.
Degussa. Application of Products, Analytical Method for H 202, Determination of Hydrogen Peroxide
Concentration, Degussa, February 2001.
ECETOC. 1993. Joint Assessment of Commodity Chemical No. 22: Hydrogen Peroxide, CAS No. 7722-
84-1, Brussels, Belgium (1993).
Giguere, P. A. "Refractive Indices of Hydrogen Peroxide and its Aqueous Solutions." Canadian Journal
of Research, Vol. 21, Sec. B, 1943:156-162.
Giguere, P. A. and P. Geoffrion. "Refractive Index of Hydrogen Peroxide Solutions. A Revision."

Canadian Jou rnal of Research, Vol. 27, Sec. B, 1949:168-173.
Gostowski, R. "Compatibility of Materials with Reactive Fluids." Proceedings of the 3 rd International

Hydrogen Peroxide Propulsion Conference, NASA Stennis Space Center, Mississippi, November
2000a.
Gostowski, R. "Assessment of the Compatibility of Composite Materials with High-Test Hydrogen

Peroxide." Proceedings gl'the 3"' International Hydrogen Peroxide Propulsion Conference,
NASA Stennis Space Center, Mississippi, November 2000b.
i
D-13
Gostowski, R., Y. Villegas, and C. A. Smith. "Compatibility of Materials with Hydrogen Peroxide:
Isothermal Microcalorimetry." Abstracts of Papers, 223rd ACS National Meeting, Orlando,
Florida, April 2002.
Greene, B., M. B. McClure, and H. T. Johnson. "Destruction of Hypergolic Chemicals in a Liquid

Propellant Testing Laboratory." Division of Chemical Health & Safety (Cosponsored with
Division of Environmental Chemistry). 224th American Chemical Society National Meeting.
Boston, Massachussetts. August 2002.
Greene, B., S. D. Hornung, K. A. Rathgeber, M. B. McClure, L. W. Starritt, and D. L. Baker. "Hydrogen

Peroxide Testing Capabilities at NASA Johnson Space Center White Sands Test Facility."
Presented at the JANNAF Propulsion and Subcommittee Meeting, Charlottesville, Virginia
(2003).
Hecht, G., S. Aubert, F. Gerardin, and M. Hery. "Workplace Monitoring of Hydrogen Peroxide Using
Titanyl-Coated Sorbents." Journal of Environmental Monitoring. Vol. 1, 1999:149-152.
Hornung, S. D., D. D. Davis, and D. L. Baker. Hydrogen Peroxide — Material Compatibility Studied by
Microcalorimetry. Presented at the JANNAF Propulsion and Subcommittee Meeting,
Charlottesville, Virginia (2003).
McClure, M. B. and H. T. Johnson. "Comparison of Two Techniques for Determining the Stability of
' Hydrogen Peroxide," JANNAF 30"' Propellant Development and Characterization Subcommittee
Meeting, Colorado Springs, Colorado, March 2002.
McPherson, M. D. Comparison on Concentration Determination Methods for Propellant-Grade

Hydrogen Peroxide: Classical Potassium Permanganate Titration versus Refractive Index.
Aerojet Paper #056-02, Aerojet General, Sacramento, California (2002).
' Messchelen, W. "Spectrophotometric Determination of Residual Hydrogen Peroxide." Water and

Sewerage Works. August 1977.
1 MIL-H-22868 (Wep). Military Specification: Hydrogen Peroxide, E-Stabilized, 70 percent and

MIL-P-16005E. Military Specification: Propellant, Hydrogen Peroxide. Military Specification, United

States Department of Defense, Washington, DC, March 1968.
iMIL-PRF-25508E. Military Specification: Propellant, Oxygen. Military Specification, United States

Department of Defense, Washington, DC, October 1995.

NIOSH. Pocket Guide to Chemical Hazards and Other Databases. DHHS (NIOSH) Publication No.
2002-140, June 2002.
D-14
OSHA. OSHA Method No. VI-6. Hydrogen Peroxide. Partially validated method, 1977, revised 1978. 1
OSHA. OSHA Method ID 126SG. Chemical Sampling Information Hydrogen Peroxide (90 116), revised
1993.
Puskar, M. A. and M. R. Plese. "Evaluation of Real-Time Techniques to Measure Hydrogen Peroxide in
Air at the Permissible Exposure Limit." AIHA Journal (57) American Industrial Hygiene
Association, September 1996.
Ross, H. R. "Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability."
Proceedings of the 5th International Hydrogen Peroxide Propulsion Conference, Purdue
University, West Lafayette, Indiana, September 2002.
Rusek, J.J. "New Decomposition Catalysts and Characterization Techniques for Rocket-Grade Hydrogen
Peroxide." Journal of Propulsion and Power, Vol. 12, N3, May-June 1996.
SEMI C30-1 101. Specifications and Guidelines for Hvdrogen Peroxide. Semiconductor Equipment and
Materials International, 3081 Zanker Road, San Jose, California 95134 (2001).
Schumb, W., C. Satterfield, and R. Wentworth. "Hydrogen Peroxide." American Chemical Society
Monograph Series (1955).
Solvay. Technical Data Sheet Determination of Hydrogen Peroxide Concentration (30% to 70%) Solvay
Interox, HH-121, 2001 a. http://www.solvayinterox.com/pdfs/techdata/Hh-121.pdf.
Solvay. Technical Data Sheet Determination of Hydrogen Peroxide Ceric Sulfate Method, Solvay
Interox, HH-5201, 2001b. http://www.solvayinterox.com/pdfs/techdata/HH-5201.pdf.
Solvay. Technical Data Sheet Determination of Gasometric Stability of Hydrogen Peroxide (H 202) at 100
'C. Solvay Interox XX-116, November, 2001 c. http://www.solvayinterox.com/pdfs/techdata/XX-
1 16.PDF.
U.S. Peroxide. Product Information: High Level Assay Analvtical Method (Permanganate Titration), U.
S. Peroxide Head Office, Laguna Niguel, California. Undated a.
http://www.h2o2.com/intro/highrange.html.
U.S. Peroxide. Product Information: Ceric Sulfate Titration Analytical Method, U. S. Peroxide Head
Office, Laguna Niguel, California. Undated b. http://www.h2o2.com/intro/cerie.html.
U.S. Peroxide. Product Information: Iodometric Tit ration, U. S. Peroxide Head Office, Laguna Niguel,
California. Undated c. http://www.h2o2.com/intro/lodometric.html.
U.S. Peroxide. Product Information: Hydrogen Peroxide (0.02-0.2 mg/L) Cobalt-Bicarbonate-

I
Spectrophotometric U. S. Peroxide Head Office, Laguna Niguel, California. Undated d.
http://www.h2o2.com/intro/lowlevelcobalt.litml.
U.S. Peroxide. Product Information: Hydrogen Peroxide (0.02-0.2 mg/L) Peroxidase Enzyme -
Spectrophotometric U. S. Peroxide Head Office, Laguna Niguel, California. Undated e.
http://www.h2o2.com/intro/lowlevelenzyme.html.
D-15
Appendix E
Hydrogen Peroxide Accidents, Close Calls and Lessons Learned
E1.0 Hydrogen Peroxide Accidents
Close Calls and Lessons Learned
E1.1 Improper Transportation of Undeclared HP on Commercial Airlines
The National Transportation Safety Board (NTSB 1998) reported a hazardous materials incident brief
(Accident No. DCA-99-MZ-001) that occurred on October 28, 1998. Briefly, 2 gal of a
35-percent hydrogen peroxide solution in water spilled in a cargo compartment of a passenger airplane
flying from Orlando, Florida, to Memphis, Tennessee. The solution leaked from two undeclared 1-gal
plastic bottles that had split open. The bottles were in an ice chest that belonged to a passenger on the
flight. The leaking hydrogen peroxide contaminated three mail sacks and an undetermined number of
bags. The leak was not discovered until cargo handlers in Memphis began to unload the baggage.
Thinking that the spilled liquid was water, the cargo handlers ignored it and transferred some of the
baggage to other passenger-carrying flights departing for Seattle, Washington. When the flight arrived
in Seattle, two bags in a cargo compartment were smoldering, including one that had come from the
original flight. As a result of the spill, several people required treatment. In Memphis, 1 1 employees
were treated at the airport's first aid station because their hands (that were tingling and turning white)
had been exposed to the hydrogen peroxide, and two more employees went to a local clinic where they
were treated and released. In Seattle, the employee who removed the smoldering bags from the cargo
compartment was exposed to fumes. He went to a hospital for treatment
(littp://www.ntsb.gov/publictn/2000/hzb000 Lhtm).
E1.2 Ground Testing
E1.2.1 The forged body of a valve selected as the main HP flow control valve presented several
problems when it was cleaned for HP service. The valve was made of compatible material (stainless
steel), but still experienced problems. Iron deposits (either from contaminated sand casts or
contaminated blasting media) resulted in corrosion spots over the entire valve body upon cleaning and
passivation. The valve had to be polished and treated with a strong acid etching paste to remove the
impurities from welded areas (Bruce 2002, Ross 2001). The lesson learned was to thoroughly evaluate
a component's materials of construction compatibility, manufacturing process, and intended use with
HP.
E1.2.2 Exhaust clouds with an unknown concentration of HP were in the test area immediately after
the firing of an HP/JP8 (kerosene) engine. An engineer in close proximity to the cell inhaled HP
vapors. He was examined and released once it was determined no injury had occurred (Bruce 2002,
Ross 2001). The lesson learned was that either area-wide monitoring or portable monitoring devices
must be obtained to measure the concentration of HP in the air following tests or decomposition of HP
in facility catalyst beds.
E1.2.3 HP in exhaust clouds may condense on surrounding surfaces. In this case, mist from one of i
these clouds became trapped within the taped cable connectors of the test cell and a technician came
into contact with the HP upon removal of the connectors. This reinforced standard operations practices
of wearing gloves and eye protection whenever working on a system exposed to HP. The test stand is
also manually rinsed with water prior to personnel entering the area after each test (Bruce 2002).
E1.2.4 Entrapment of 98 percent HP in components made of Class 1 materials was identified as an

issue because HP can eventually decompose the materials and could also pose a hazard to personnel
when breaking and entering a system. A double-diaphragm pump was used to transfer HP. The design
allowed HP to be trapped within the main pump cavities and manifolds. Modifications to the pump in
this case included drain ports on both the inlet and outlet manifolds, and mounting such that the pump
could be rotated to aid in draining following HP transfer. In addition, pressure transducers that would
preclude entrapment were installed, and lines were routed to facilitate drainage throughout the entire
system (Bruce 2002, Ross 2001).
E1.2.5 During a test of a catalalyst bed assembly using HP, a rapid decomposition event occurred
approximately one second into the test (Bruce 2002). The test article and the facility were damaged but
no injuries were sustained by personnel. An investigation was conducted and it was determined that
after the test, but before the incident, a leaking shutoff valve allowed liquid HP to acctttnulate in a hot
(approximately 250 °F (121 °C)) supply line just upstream of the catalyst. Liquid HP in the
temperature range from 212 to 300 °F (100 to 149 °C) will create an ignitable vapor for 98 percent HP.
When the accumulated vapor was compressed by the opening of the valve for the last test, a rapid
decomposition occurred. Several lessons were learned from this, resulting in operational changes at
the test facility. These changes included:
• Placing thermocouples in selected locations to monitor hardware temperatures.

• Allowing hardware to cool to a safe temperature before any further testing is performed when
' elevated temperatures are detected.
• Purging the test article, if necessary, with an inert gas prior to testing to ensure there is no vapor
accumulation.
• Replacing several valves in the system so that more reliable valves were used.
E1.3 HP Storage
Four drums of 98 percent HP were discovered to be expelling their contents from vent holes and from
around the top clamping rings of the drums (Bruce 2002). Although it was never confirmed that
decomposing HP was being expelled, out of an abundance of caution, the contents of the drums were
safely pumped into a disposal area and disposed. Seven additional drums were similarly disposed
when they were found to be suspiciously warm. The vendor-supplied drums were stainless steel with a
polyethylene lining, and failed to support the facility's long-term storage requirements. The facility
discontinued use of polyethylene-lined drums for long term storage, and vendor container desings
were subsequently reviewed, inspected and approved prior to acceptance.
E1.4 HP Incompatibility
A failure of a Class 1 material (Teflon) lining a Class 4 (iron) pump component at a NASA facility
caused HP to rapidly decompose. This caused the pump to overpressurize, resulting in rupture in the
pump, piping and valves, and subsequent release of approximately 40,000 lb of 90 percent HP into a
containment area (Accident Report 2001, Bruce 2002). The sequence of events was believed to be as
follows:
Transfer of HP from a container to a storage tank through the pump with the failed liner was
performed. During pumping, there was sufficient flowing HP to remove the heat produced by
decomposing HP.
Once the pumping was stopped, there was no flowing HP to remove the heat. HP at the exposed
valve surface in the pump continued to decompose, generating heat and leading to a self-
accelerating decomposition reaction. The temperature increased until the HP remaining in the
pump boiled.
E-2
Vapor generated could not be relieved from the system fast enough, causing further increases in
• temperature and pressure.
• A loud rumbling sound from the tank was heard by area personnel, who evacuated the area
immediately.
• A white cloud was released from the elbow above the pump.
• Black smoke was released from a valve between the pump and the storage tank. The temperature
is believed to have been high enough (-500 °C) to burn the Teflon liner, which can produce black,
soot-like particles. These particles can travel through the discharge pipe into the storage tank.
• The temperature increased to the point where the Teflon liner began to melt.
• The Teflon liner completely melted, and the elbow obtruded above the pump discharge.
• The pressure continued to build in the system even after blowing past several gaskets.
• All the HP in the piping decomposed, the Teflon liner of the valve completely burned, and some
melted portions of the Teflon dropped down into the pump casing.
• HP in the pump casing began to decompose and the pressure and temperature in the vapor space
increased.
• The pump casing split open due to overpressure, which drove the pump impeller into the motor
coupling and then ejected the motor winding 29 m away.
• The suction side of the pump casing ripped away with sufficient force that the of the suction
piping connected to the storage tank ripped off the nozzle.
• Approximately 40,000 lb of HP began pouring out of the tank into the containment area.
Subsequently, the facility has discontinued the use of Class 4 materials in any HP system even if there
is a Class 1 liner between the material and the HP. Additional observations in the accident report
included:
• All systems designed and operating on a NASA facility should meet NASA's design and safety
requirements, which may differ from industry standards.
• NASA should invest in the fundamental characterization of hazardous and reactive propellants and
develop in-house expertise prior to the design, construction and operation of facilities.
• Project teams should be made part of the design, safety and readiness review process with
signatory concurrence.
• Material and fluid composition must be controlled to prevent adverse interactions leading to a
thermal event.
• Selection of facility location and quantity/distance requirements must be sufficient.
• Appropriate PPE must be worn.
• Safety training probably paid off. Employees at the scene evacuated immediately upon hearing
dangerous sounds from the tank, which probably saved their lives and prevented serious injury.
• Appropriate instrumentation, such as remote temperature and pressure sensors, could possibly
have detected a problem early enough to preclude an explosion. Interlocked controls should
function in tandem with this instrumentation.
E1.5 Storage Incident
A 55-gal drum containing an unknown quantity of 70 percent HP caught fire and subsequently
exploded. A witness escaped the fireball (Cocchario 1998).
E-3 I
I
A 30-gal drum of 70 percent HP exploded in a Quonset but (a semicircular-roofed building). The drum
was contaminated following a dynamometer shot, and had been monitored for two days outside the but
prior to the explosion before it was moved inside. The explosion moved a Quonset but from its
' foundation. The rise in temperature inside the but may have led to increased activity of the
contaminant and the subsequent explosion (Wolf and McNally 1963).
A chemical storage facility contained various service buildings and HP in concentrations ranging from
' 35 to 70 percent. An employee discovered a fire in the outside of the storage yard where the drums of
35 percent HP were stored on wood pallets. The fire department was called, but the fire spread rapidly
after it involved drums of nitrocellulose. When the fire fighters arrived, chemicals were burning,
drums were exploding, and potentially hazardous smoke was threatening exposures. Using water and
foam streams, fire fighters were able to limit damage to outside storage areas and a section of the
warehouse. Investigators believed the fire ignited spontaneously when HP either spilled or leaked onto
the wood pallets. The fire then spread to the nitrocellulose, which is highly flammable, causing the fire
' to spread rapidly. One fire fighter was injured in the event. A section of the warehouse roof collapsed
as a result of the fire. Damage to the structure and the contents were estimated at $1,193,000 (NFPA
1992).
E1.8 Peroxide Tank Explosion
' An outdoor metal tank containing up to 300 gal of high concentration HP exploded at a laser-testing
facility in California. No one was hurt. The HP in the tank had begun to rapidly decompose,
generating sufficient pressure to blow the tank into three pieces of shrapnel, which damaged the side
' of a nearby building. The tank had a pressure-relief system, but was not adequate to handle the
situation that occurred. It was believed that the tank had accumulated Basic Hydrogen Peroxide (BHP,
an HP solution containing potassium hydroxide, lithium hydroxide and sodium hydroxide) over a
period of three months of laser testing that used fluid from the tank that was returned to the tank after
' testing. The preliminary finding was that overpressure in the tank was caused by the rapid
decomposition of the HP due to long-term storage, reuse and consequent contamination of the HP in
the tank (Donnelly 1999).
' E1.9 Industrial Accident
HP was being used to bleach a surfactant in a continuous process in a chemical factory. The process
involved addition of 50 percent HP to water before it was combined with a hot molten surfactant in a
pressurized mixer. After about 30 s on the day of the accident, the pressure in the mixer rose very
rapidly and a few seconds later an explosion was heard followed by shaking of the building. A large
fire evolved from the area around the mixer. It took several hours for the fire brigade to get the fire
under control due to the runoff of large quantities of heating fluid that caught fire and spread across
the unit. The fire caused glass tubes used in the reaction system to break, releasing processed paraffins.
As there was no access to isolation valves, the whole system was drained, pouring several tons of
heating fluid and paraffins into the unit. No one was injured, but the heat damaged the construction so
severely the building had to be rebuilt. The cause of the accident was thought to be an uncontrolled
' exothermic reaction between concentrated HP and the organic surfactant, without sufficient pressure
relief (Klais 1993).
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E1.10 Manufacturing Explosion
losion I
An incident involved the explosion of an HP (concentration unknown) tank in a manufacturing plant.
The explosion occurred as the HP was being gravity fed out of a tank. The tank began to "bump"
(bubble from escaping gas), and exploded as the feed rate was increased. The tank was completely
destroyed and two operators received chemical and thermal burns (Cocchario 1998).
E1.11 Torpedo Explosions
The Navy has experienced several "steamer" incidents with torpedos. A "steamer" occurs when
(through malfunction or improper servicing) the peroxide tank vent is closed off, allowing the pressure
within the tank to build up. This pressure eventually gets high enough to open a spring-loaded delivery
valve and liquid HP is delivered to the decomposition chamber. There, HP is converted to oxygen and
steam, which passes through the turbine and out the torpedo exhaust valve. Under such conditions, the
HP continues to decompose until the tank pressure falls low enough to allow the delivery valve to re-
seat. Manual venting of the tank can be accomplished to stop the process immediately. Torpedo-
related accidents documented are described below.
E1.11.1 A destructive incident with an Mk 16 Mod 1 torpedo, which used a propellant combination of
48 percent HP, a standard torpedo alcohol, and a calcium permanganate catalyst, occurred on
September 22, 1945. During a range run, the torpedo sunk after striking a barge. The following day it
was recovered with the head badly smashed. A short time later, liquids were observed seeping from
the tail and the afterbody was found to be warm. The liquid storage compartments were vented, the
afterbody was cooled by hosing, and the gyro was removed. The plugs were then replaced. About six
hours later, the torpedo exploded violently (Wolf and McNally 1963).
E1.11.2 One sailor was discharged with 100 percent disability following a "steamer" incident on the
USS Swordfish. [n this case, the sailor was confined in the torpedo compartment for about 20 min. No
one pulled the plug in the safety valve manifold, which would have vented the tank, and the "steamer"
continued until the decomposition pressure returned to normal (Wolf and McNally 1963).
E1.11.3 One Torpedo Mk 16 Mod 7 was jettisoned because the HP was considered dangerously
active. The torpedo was not recovered; hence, the cause of the high decomposition rate is unknown.
The peroxide in another torpedo was discarded because of an indicated high decomposition rate. Later
investigation disclosed a broken check valve between the Navol (alcohol fuel) and water
compartments. Several Navol tanks have been returned to Naval Underwater Ordinance Station as
"active." In this case, investigation showed that an aluminum washer in the check valve had corroded.
This residue restricted operation of the vent valve until sufficient pressure had built up to loosen the
valve. At this point, a rapid and prolonged venting of the Navol tank occurred, causing the indicator
panel to show an excessive gassing rate (one valve stuck in this manner required 600 psi to open).
Teflon washers have since replaced the aluminum washers. There has been one case of a mild
contamination while a visual indicator was being used during snorkeling. The drain hose used with
this device had been placed in a pail of water and during the snorkeling operation the water was forced
back through the device into the Navol tank (Wolf and McNally 1963).
E1.12 X-1 Midget Submarine Incident
The diesel engine system of the X-1 craft (a midget submarine) used 90 percent HP as an oxidant. On
May 20, 1957, an explosion on the X-1 parted the nose section of the submarine (where the HP was
stored exterior to the pressure hull) from the rest of the craft. Personnel, alerted by hissing steam from
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' the vent line, had vacated the submarine prior to the explosion. The cause was attributed to failure of
the bag that contained the HP. HP entered the space normally occupied by seawater, where
' contamination from rust, grease and oil resulted in violent decomposition and burning of the bag.
Vents could not accommodate the rapid formation of gas. Rising pressure eventually caused a rupture
of the bag compartment (Wolf and McNally 1963).
' E1.13 Research Torpedo Configuration
Accidents were experienced in the RETORC (Research Torpedo Configuration) program. Under this
program, experimental vehicle configurations varied as new techniques were evaluated. The complete
systems test vehicle (TV-3) uses diesel fuel with 90 percent HP as an oxidant. A multifluid pump
' transfers the propellants through a silver screen catalyst chamber, which decomposes the HP prior to
combustion. In early 90 percent HP pump experiments, a filter in the water line (water was used to
flush away any peroxide seeping past the pump piston) exploded when the water was turned on after
the HP flow had started. Some HP apparently reached the filter, which had previously been used to
' filter oil. Damage was confined to the filter and the faucet in the water supply (Wolf and
McNally 1963).
1 E1.14 Decomposition Test
During HP decomposition tests using the Bendix 6HA5 peroxide pump, a rupture occurred which
displaced the head of the pump from the body. The cause of this rupture was attributed to failure of the
start solenoid valve to open following closure of the recycle solenoid, thus resulting in a momentary
dead-ended system. The instantaneous pressure rise (far above 3,000 psi, where the relief valve was
set) initiated a shock wave in the liquid line. This resulted in a muffled noise. Simultaneously,
compression of the HP vapor trapped in the accumulator initiated combustion of the vapor with a
silicone rubber diaphragm. This heated the liquid HP and initiated a self-accelerating decomposition
reaction. The result was an extremely large pressure surge in the system that ruptured the HP pump
with a loud report and a flash of flame. To prevent recurrence of this incident, interlocking of the
switches was incorporated into the system circuitry so that the pump drive could not start without first
having energized the start solenoid. The silicone rubber was also replaced by a more suitable material
E1.15 TV-3 Engine
During a dynamometer test of a complete TV-3 engine mounted in an afterbody with all auxiliaries
hooked up, an explosion occurred shortly after the signal to fire. The force of the explosion
fragmented the decomposition chamber and badly damaged the engine and auxiliaries. There was no
injury to personnel. Following investigation and tests, it was concluded the explosion occurred in the
catalyst bed and was the result of contamination with an organic solution of soap. Soap solution
(50 percent by weight potassium oleate in a solvent of propanol and ethylene glycol) is used in the
TV-3 system as an additive in the seawater diluent to prevent salt deposits. Steps taken to prevent
recurrence of this incident include a membrane seal (rupture disc) at the outlet of the catalyst pack and
a three-way valve to divert soap solution flow from the combustion system at start-up (Wolf and
McNally 1963).
E1.16 F-104 Incident
On October 20, 1959, an explosion occurred in an F-104 aircraft during reaction control ground tests.
No personnel were injured but damage to the aircraft took two and a half months to repair. The failure
E-6
was caused by rupture of a Teflon bladder. This allowed HP to be drawn through the nitrogen
pressurizing and vent system to a filter that exploded violently. Corrective measures were taken to
isolate the vent from the pressurizing system and to remove the offending filter (Wolf and
McNally 1963).
E1.17 Bell X-1 Aircraft Incident
The X-1 was powered by a pump-driven low-pressure rocket system. HP flowing through a
I
manganese dioxide catalyst chamber drove the pump. NASA reported that no HP injuries were
encountered in the X-1 program, but one small HP explosion was experienced when a pressure
transducer exploded in flight. This transducer was not HP-compatible and had been installed in error.
Resulting damage was minor and confined to the instrument compartment (Wolf and McNally 1963).
E1.18 X-15 Incidents
The X-15 is powered by a liquid propellant engine, with the pump driven by 90 percent HP flowing
through a silver screen catalyst chamber. HP also drives the twin power units, which generate
hydraulic pressure and the electric supply. Two explosions occurred during the X-15 program
E1.18.1 The HP pump supply tank exploded while the X-15 was being purged with nitrogen
following a ground run and jettison of remaining propellants. One mechanic was injured when a piece
of metal struck him in the leg. The cause of the explosion was traced to a new external nitrogen gas
filter, which was not properly cleaned following hydrostatic testing with oil by the manufacturer. The
purge gas glow carried some of the oil to the HP tank, where it reacted violently with a small amount
of residual 90 percent HP (Wolf and McNally 1963).
E1.18.2 An explosion and fire caused several million dollars in damage to an X-15 aircraft and
support equipment. No personnel were injured. During a ground run in the test stand, a tank of
anhydrous ammonia burst and ruptured the HP tank. The resulting explosion drove the forward two-
thirds of the plane about 20 ft ahead and left the tail and engine attached to the stand. All propellants
were consumed in a short raging fire, after which the pilot was removed from the closed cockpit
uninjured. The explosion was caused by failure of a pressurizing valve in the ammonia tank system
E1.18.3 The NASA Flight Research Center reported one accident on July 20, 1961, in which an
employee received third degree burns of the face and eyes while handling 90 percent HP. After six
months treatment by an eye specialist, the man regained his full 20-15 vision (Wolf and
McNally 1963).
E1.19 Aerojet Incident
An explosion involving 90 percent HP and JP-5 rocket fuel occurred at the Aerojet-General Corp.
plant, Azusa, California, on March 30, 1959. There was no permanent injury to personnel. The basic
cause of this explosion was a "hard" start occasioned by an accumulation of rocket fuel in the
combustion chamber prior to introduction of the HP. An initial explosion inside the test motor
ruptured the HP feed line, allowing 500 lb of HP to spray and accumulate in the test bay. The second
explosion twisted the outlet flange off a fuel tank, dumping fuel into the test bay. A large fuel-air fire ,
followed immediately (Wolf and McNally 1963).
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E1.20 Fatal Mixture of a Fuel and an Oxidizer
A chemist was killed when he inadvertently poured HP into a laboratory sink. The HP reacted
violently with some U-DETA (a mixed amine fuel consisting of unsymmetrical dimethylhydrazine and
diethylenetriamine) remaining in the trap underneath the sink and the trap exploded (Wolf and
McNally 1963).
E1.21 HP/Acetone Mixture Hazard
A sulfur heterocycle was dissolved in acetone and an excess of 35 percent HP was added cautiously
with cooling. The solution was then left to stand in a cool place for three days. A crop of white
crystals, which it was presumed were the expected sulfone product, appeared. These were collected,
washed and dried in a vacuum oven. About one hour later, the vacuum oven exploded with extreme
violence, causing widespread damage within a radius of a few feet and being completely destroyed
itself in the process. No injuries resulted due to the absence of workers at the moment of the explosion.
It was suggested that the white crystalline solid was a peroxide of acetone that detonated on drying
(Brewer 1975).
1 E1.22 Violent Explosion
Three instances of very violent explosions occurred while oxidizing tetrahydrothiophene by the
dropwise addition of 37 percent HP over reasonably long periods. The reaction mixtures were tested
for the presence of peroxides before any workup. The reactions that exploded were behind safety
shields so there were no injuries; however, the resulting concussions were reported to be particularly
severe (Koppel 1974).
E1.23 Storing Hydrogen Peroxide in Plastic Bottles
A potentially dangerous situation that exists in storing 30 percent HP in plastic bottles was reported.
Left standing for one year or more, plastic bottles used to store 0.5 to 1 L of 30 percent HP became
brittle. One bottle that had been packaged four years earlier could be crushed and fractured into small
pieces by squeezing with the hand (Clemens 1986). The type of plastic was not specified in this report.
E1.24 Mixture of Ammonium Hydroxide and Hydrogen Peroxide
A mixture of ammonium hydroxide and HP were found to be very effective in cleaning silicon
surfaces. A batch of this reagent was mixed by a junior chemist in a 5-gal glass container and plugged
(against the directive of the senior chemist to mix only small quantities and never have it in a closed
container). The reagent exploded, driving shards of glass into a wall at the opposite side of the
laboratory (about 60 ft away). Fortunately, no one was in the laboratory at the time of the explosion.
The investigator noted that the following reaction might have occurred (Matlow 1990):
2NH3(aq) + 3H 2 01-(aq) —> N-) (g) +6H,0(1) (E.1)
The resultant pressure rise due to formation of gaseous nitrogen in the closed container may have
resulted in the explosion.
E-8
E1.25 Piranha Solution Explosions
Two violent explosions experienced with a sample of "piranha" solution used routinely in many
laboratories to clean badly soiled glass frits and other surfaces were reported.
The first explosion occurred in a bottle of a mixture of 150 ml of concentrated sulfuric acid
and 150 ml of 30 percent HP. One week after the solution was prepared, it spontaneously
detonated in the hood, destroying the glass container in which it was stored, as well as other
bottles of chemicals stored in the hood. It was believed the bottle was only loosely capped, but
it was possible that an oxidizable organic material could have been added to the bottle
(Dobbs 1990).
The other incident occurred when a student was cleaning glass frits by a standard procedure of
drawing small volumes (about 20 ml) of a freshly prepared mixture of concentrated sulfuric
acid and 30 percent HP through the frits by applying vacuum suction. This operation was
eventually followed by washing with deionized water and finally acetone (keeping the
solutions separate). On this occasion, a violent explosion occurred, which shattered the heavy
walled filter flask and caused multiple cuts in the face, chest and forearms of the student. A
partially lowered hood sash, safety glasses, lab coat, and heavy rubber gloves provided some
protection. It was believed the cause of the explosion was inadvertent mixing of the highly
oxidizing sulfuric acid/HP mixture with an unknown amount of acetone residue. It was the
authors' interpretation of these events that sulfuric acid/HP solutions are susceptible to
spontaneous and unpredictable chemical detonation, that they be handled carefully, that they
not be stored for any length of time, and, if possible, not be prepared or used at all
(Dobbs 1990).
E1.26 Cleaning Glass Funnels
Safe procedures for cleaning glass funnels with sulfuric acid/HP solutions have been described. In one
incident, less than I ml of acetone was inadvertently added to a freshly prepared sulfuric acid/HP
solution, and there was an immediate fire, but no explosion (Wnuk 1990).
E1.27 Fiber Analysis Using Heated Hydrogen Peroxide
A violent explosion took place after a student (pursuing an independent research project) attempted to
follow a standard U.K. forensic procedure for fiber analysis. The student had used 0.1 g of a jute rope
sample, 20 ml of glacial acetic acid and 20 ml of 30 percent HP. After heating the mixture in a flask in
a boiling water bath on a hotplate, a detonation occurred. The ceramic top of the hotplate blew apart
into rather massive fragments that were thought responsible for the cracking and damage of the
laminated safety glass of the fume hood sash. Fortunately, the hood sash was down and the blast and
fragments confined to the hood with no injuries. In this case, the mishap was attributed in part to the
use of a more concentrated HP solution than was called for in the procedure. This was due to the
nomenclature employed by the UK procedure that was unfamiliar to the student: a "20 volume" HP
solution was called for, not 20 percent. A "20 volume" HP solution refers to the amount of HP that can
evolve 20 ml of oxygen for each ml of solution, and actually corresponds to 6 percent HP. Other
factors, such as possible metal ions in the fiber sample or accidental contaminants, may also have
played a role in the explosion. In addition, the shattering of the ceramic hotplate top suggested this
possible shrapnel source might best be avoided where explosion hazards may occur (De Forest 1987).
E1.28 Laboratory Storage of Hydrogen Peroxide
E-9
An incident in which a "winchester" (dark glass bottle) of 35 percent HP exploded during the night
' was reported, fortunately causing little damage and no injury. The HP had been stored on an open
shelf in a dark winchester with a plastic screw cap for just over two years. The explosion was
attributed to the slow decomposition of HP forming oxygen, which finally built up excessive pressure.
' The authors cautioned that a shelf life be established and that a pressure relief device be considered
advisable (Clark 1974).
' E1.29 Explosive Peroxides
A very violent explosion occurred in a university chemistry laboratory, apparently due to the
' formation of explosive peroxides in a mixed organic waste/30 percent HP solution that had been
accumulating in a fume hood for three to four weeks. The waste solution was generated by the
combination of polyacrylamide gels, toluene and 2-ethoxyethanol (a glycol ether). The explosion
caused complete destruction of the hood and moved a cinder-block wall located 30 ft from the blast.
' Kick-out panels and glass were blown out of the laboratory and chemicals on shelves in the adjacent
laboratory were knocked to the floor. Fortunately, the explosion occurred when the labs were vacant,
avoiding injury to personnel. It was suggested that addition of HP to the gels to solubilize them could
result in the formation of peracids, azo- and nitro-compounds, and that excess HP could react with the
ether to form an organic peroxide. It was recommended that either alternate methods be used for
solubilization of the gels or that the peroxides be immediately destroyed (Darnall 1978).
' E1.30 Vacuuming HP into an Unsuitable Container
One incident occurred at Rocky Flats, where leaking 35 percent HP in a glove box containing
plutonium was vacuumed into a pickup vessel that contained a solution high in iron, copper and
nickel. The hydrogen peroxide began to foam in the pickup vessel. Within a few minutes, a stream of
liquid ejected from the one-inch pressure relief valve on top of the pickup vessel and the glove box
' was pressurized sufficiently to cause its walls to flex outward and eject plutonium into the room. The
importance of cleanliness of equipment in clean-up of HP spills cannot be overemphasized
(Conner 1993).
f E1.31 Excessive Lubrication
A facility system design and instrumentation requirements contained numerous threaded fittings,
which were adversely affected by the passivation process for HP service (Bruce 1999). It became
apparent that the passivation process was etching the threaded and sealing surfaces and significantly
increased the occurrence of stainless steel threads galling. Therefore, additional lubricant was used
during assembly and resulted in surplus lubricant being injected into the system as connections were
made or broken. The surplus lubricant was compatible with HP, but potentially could have had
detrimental effects on test articles downstream. Lessons learned included the following:
• Modifying the cleaning process to eliminate an additional acid passivation step (acceptable for the
stated application) to minimize the surface etching effects.
• Changing the lubricant from an industry-acceptable silicone lubricant to a lubricant for oxygen
service hardware.
• Reviewing work practices and instructing personnel to apply lubricant in accordance with standard
oxygen service applications: More is not always better.
E1.32 Galvanic Corrosion of Aluminum Seals
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t
All tubing connections on a test stand used 37° flared fittings (Bruce 1999). Aluminum flare seals
were initially procured instead of stainless steel to meet project schedules. Galvanic corrosion between
the aluminum flare seals and the stainless steel tubing used in the system. The aluminum seals
corroded and formed aluminum oxides. Although this oxide was not detrimental to the HP, it
presented a problem when breaking and entering systems, and degraded sealing properties. The lesson
learned was to evaluate piping and tubing needs and place orders for special items early in a project.
E1.33 Ingestions
E1.33.1 Cerebral infarction, believed to have resulted from gas embolisation of the cerebral
vasculature, has been reported in an 84-year-old man who took 30 mL of 35 percent HP diluted in 100
to 300 mL of water (Sherman 1994).
E1.33.2 Multiple brain embolisms occurred in a 63-year-old who ingested 120 mL of a 35 percent
solution. He recovered (Ijichi 1997).
E1.33.3 Ingestion of 240 mL of 35 percent HP in a 49-year-old female caused death 78 h later

(Litovitz 1995).
E1.33.4 About 100 to 170 mL of 35 percent HP was ingested by a 2-year-old, who died after being
taken off life-support four days later of hypoxic encephalopathy (Christensen 1992).
E1.33.5 A near-fatal ingestion of HP was previously reported (Giberson 1989). In this incident, the
contents of a I-pt bottle of 35 percent HP were unintentionally ingested. The patient had stopped to
obtain a drink of water, but mistakenly consumed the residual and unknown volume of a well-marked
bottle of HP and, within minutes, vomited, collapsed and experienced a brief tonic-clonic seizure. The
patient survived, although respiratory failure has been the alleged cause of death in other reported
fatalities of HP ingestion (Zecevic 1979). Aggressive airway management was critical because
respiratory failure and arrest appear to be the proximate cause of death after HP ingestion.
E1.33.6 In another case, one cup of 35 percent HP was accidentally ingested (Dye 2002). The victim
immediately developed shortness of breath and a sore throat, followed by vomiting and coughing up of
a foamy substance with a small amount of blood. Shortly thereafter, severe pain between the scapulae
developed. Air was found in the soft tissues of the neck and there was significant esophageal injury.
E1.33.7 In a press release issued by the Food and Drug Administration (FDA 1989), the agency
warned against the use of HP for human consumption. Thirty-five percent HP had been illegally
promoted to treat AIDS and cancer, or had been mistaken for water and was drunk. At least one death
and several iniuries requiring hospitalization have been reported.
E1.34 Parenteral Incidents
E1.34.1 One hundred mL of three percent HP administered intravenously resulted in the death of a
seven-month-old child (Lubec 1996).
E1.34.2 Two mL (strength unknown) in a dialysis catheter caused abdominal pain, hypertension,
collapse and coma within 1 h. The victim made some improvement with hyperbaric oxygen by the
eighth day, then went into cardiac arrest and had convulsions. The victim recovered in the following
week, went into cardiac arrest again, and died 19 days postinjection (Litovitz 1997).
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' E2.0 OSHA Accidents
The following descriptions of HP accidents were adapted from the OSHA website, www.osha.gov . To
' access general accident information on the OSHA website, go to www.osha.gov . In the righthand
column, click on "Accident Investigation Search." In the search field of the new page, type "hydrogen
peroxide" or another keyword of interest. This will produce a list of accidents related to your search.
' The specific OSHA website of each of the HP accidents described below is referenced and was
verified as correct on February 10, 2004.
' E2.1 Employee Burned when Chemical Mixture Explodes
Employee #1 accidentally mixed HP and sodium thiosulfate, which resulted in an immediate

' explosion. He sustained chemical burns, for which he was hospitalized (OSHAa).
E2.2 Three Employees Burned in Chemical Reaction and Explosion
At 5:00 p.m. on June 27, 1998, Employee #1, age 20, was assigned to read the chemical levels in two
nickel plating dip tanks to determine if any needed to be replenished. He was transferring chemicals
from the bulk chemical storage containers to the dip tanks when he poured Electro-Brite Cobra
Etch—containing hydrogen peroxide, a strong oxidizing agent into a partially filled jug that
contained residues of sulfuric acid, a strong corrosive. A violent reaction involving heat and pressure
resulted and Employees #1 through #3 suffered various degrees of chemical burns to the face and
body. Employee #1 had mistakenly interpreted that the ingredients for the two chemicals he was
replenishing were of the same sulfuric acid composition and thus appropriate to mix (OSHAb).
' E2.3 One Employee Killed, 2 Injured in Stripper Vessel Explosion
The employer is a manufacturer of epoxidized soybean oil that is used to make flexible plastic from
' refined soybean oil. Food grade vegetable oil is fused with hydrogen peroxide, resulting in epoxidized
oil. After the main reaction process, the product goes to a vacuum vessel centrifuge. Oil from the
centrifuge then moves to a stripper vessel where steam removes water, acetic acid and hydrogen
peroxide product remnants. The steam from the stripper is injected using a vacuum and, in turn,
' condenses back into a receiving pot after it has moved to an overhead condenser or heat
exchanger/converter located above the stripper. From this condenser, residual acids are stripped out
and moved to the acid receiver, a neutralization tank and recovery site for acetic acid residue. An
' acidic water line goes from the condenser/ converter to the receiver. Employee #3 and a coworker
were checking steam traps on the first floor by tapping on them, but they were not removing any of the
condensate. They got two new traps ready as replacements after a batch in the vessel was processed.
Condensate was drained out of the steam lines and, after the drain valves were closed, the traps were
apparently working and the stripper vessel's temperature began to rise to its set point. Employees #1
and #2 went to the second floor to check the stripper. Employee #2 was looking through a sightglass
' atop the stripper to ensure that excessive water was not coming in and to check what was happening in
the stripper. All appeared normal when suddenly the acidic water line near the ceiling, which
contained water, acetic acid and hydrogen peroxide, exploded, blowing out the second story wall.
Employee #1 was found dead on an adjacent roof area. He had been walking toward the receiver area
near the south wall to turn on the steam valves, but it is not known if he had reached them before the
explosion occurred. Employee #2 was about 20 ft away looking into the stripper sightglass; he was
struck by flying debris and exposed to excessive noise. Employee #3, who was walking 8 ft away from
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the bottom portion of the stripper on the first floor below, also suffered injuries from flying debris.
Both were hospitalized. The employer was issued citations for violations of 29 CFR 1910-119
"Process Safety Management of Highly Hazardous Chemicals" and 29 CFR 1910.120 "Hazardous
Waste and Emergency Response" (OSHAc).
E2.4 Three Employees Injured When Tank Explodes
Employees #1, #2 and #3—a printer, inspector and rotary operator, respectively, at a large textile
finishing mill—were in an area with a 160 gal capacity stainless steel tank containing 50 percent HP
used in the bleaching process. Apparently, the tank had become contaminated and had been sitting
half-full and idle for a week when it exploded. All three employees were struck by flying debris.
Employee #1 suffered leg fractures, Employee #2 sustained foot lacerations, and Employee #3
sustained puncture wounds on his hands. The source of contamination and the cause of the rupture
could not be determined from the evidence that remained after the explosion. The tank had one feed
line, a dispensing line going in, and an overflow vent on top. This bleaching process had been in
production for a year. The employer was cited for violation of 29 CFR 1910.132 "Personal Protective
Equipment - General Requirements" and 29 CFR. 1910.1200 "Hazard Communication' (OSHAd).
E2.5 Employee Burned in Chemical Explosion
Employee #1 was working in a plating shop with one supervisor and a coworker. The supervisor
usually mixed 35 percent hydrogen peroxide into the slurry tank, which was mixed with chemicals in
the plating tank of cadmic cyanide solution. The hydrogen peroxide precipitated out impurities in the
tank solution, which was diluted to remove the solids. The supervisor asked Employee #1 to get one to
three gallons of hydrogen peroxide then go to the slurry tank. Employee #1 poured the hydrogen
peroxide into a nearly dry slurry tank. The small amount of liquid in the tank and hydrogen peroxide
exothermically reacted and resulted in a chemical vapor explosion that splashed Employee #1 on the
face and neck. The supervisor and coworker were witnesses, but did not actually see the accident
(OSHAe).
E2.6 Employee Burned in Chemical Explosion
Employee #I was performing his normal job duties as a chemical operator, operating a 20 ft tall
reactor. The primary chemical, 2-ethylhexanol, had been piped into the reactor. Phosphoric anhydride
(powder form) had been dumped into the reactor by hand through a 20-in. hatch. HP was then added,
and a flash fire resulted. Employee #1 suffered chemical burns from the explosion and required
hospitalization (OSHAf).
E2.7 Fourteen Employees Exposed to Carbon Monoxide and Hydrogen
At approximately 8:30 p.m., Employee #1, who works for a manufacturer that makes multilayer circuit
boards by a multistep dip operation, inadvertently mixed 55 gal of 50 percent hydrogen peroxide into
1 10 gal of 30 percent formaldehyde. This resulted in a carbon monoxide and hydrogen release. The
facility was evacuated, and the local fire department and ambulance responded. Employees #1 through
#14, three of whom were from two temporary employment agencies, were treated for inhalation and
released. Employee #1 evidently had not looked at the label on the 55 gal drum. Both hydrogen
peroxide and formaldehyde are in similar black 55 gal poly drums with labels on one side (OSHAg).
E2.8 Employees Overexposed to Chemicals
E-13
1
f At approximately 8:30 a.m. on November 11, 1995, a hospital pharmacy technician was in the
t pharmacy storage room helping Employee #1, a delivery driver, load a freezer with frozen antibiotics.
Other hospital employees were sorting medication and cleaning up. The pharmacy technician
determined that the pharmacy secretary, who was helping in the cleanup by pouring expired
1
medication down the sink, had poured a half pint of an 89 percent phenol solution down the sink.
Other chemicals that went down the sink include aluminum hydroxide, Alupent syrup, albuterol syrup,
3 percent HP, Riopan, Neomycin and Actifed. Some of the employees smelled phenol. Employees
were evacuated and the fire department responded. Employees were sent to the hospital. Employee #1
indicated that he had a headache and trouble breathing. The doctor's first report indicates cenhalgia, a
inhalation injury and first- and possibly second-degree burns to the face. Major factors contributing to
accident were that the pharmacy secretary was never trained to handle hazardous substances; the task
was not routine; and there were no supervisory personnel present to evaluate and prevent this incident.
The employer was cited for violation of 29 CFR 1910.1 19 "Process Safety Management of Highly
Hazardous Chemicals" (OSHAh).
1 E2.9 Employees Injured in Hydrogen Peroxide Tank Explosion
On August 28, 1994, at 9:10 p.m., in a caffeine production department, Employees #1 and #2 were
adding HP to a tank of wastewater containing a dilute solution of cyanide and caustics. The HP was
being added by gravity from the floor above. The HP tank began to "bump" (bubble from escaping
gas), so the employees opened the valve more fully to increase HP addition speed when an explosion
occurred which totally destroyed the peroxide tank. Employee #1 was treated for chemical and thermal
burns on his hands and released. Employee #2 was admitted to Lawrence Memorial Hospital in New
London, Conn., with multiple burns and serious eye damage. On August 30, the employee's eye
recovery prognosis was "good." A later prognosis was "excellent." The ophthalmologist expects 100
percent recovery in both eyes (OSHAi).
E2.10 Employee's Eye Burned in Exothermic Explosion
Employee #1, of a printed circuit board manufacturer, was pouring liquid from a mislabeled drum.
Ammonium hydroxide solution reacted with HP and caused an exothermic reaction, resulting in the
chemicals splashing into the face and eyes of Employee #1. He incurred some damage to his eye while
he was flushing his eyes under an eyewash during the second of three explosions from the exothermic
reaction. The exposure occurred in the water treatment area, where drums are rinsed prior to reuse or
reclaiming. The explosive reaction occurred in a 5 gal bucket and the first of three explosions occurred
within a few seconds after the ammonia-containing liquid entered the bucket containing 35 percent
peroxide. The reuse of the peroxide-labeled drum was in direct violation of the employer's written
r safety program and Employee #1's eye protection also violated the employer's safety program. The
employer's eyewash/shower was within 10 feet of the incident (OSHAj).
E2.11 Chemist Dies in Chemical Explosion
Employee #1, a chemist, was working with a mixture of an aminomtrofurazan (ANF) that included the
chemicals methylene chloride, HP, trifluoroacetic anhydride and diaminofurazan. The chemicals were
being mixed in a 2-L flask. When the mixing was complete, apparently Employee #1 was removing
the flask from the mechanical stirrer when an explosion occurred. The explosion ruptured the flask,
which expelled glass shards; one penetrated into Employee #1's neck, cutting the carotid artery. The
employee suffered many other cuts and died. He was working alone; there were no witnesses.
Employee #1 was wearing safety glasses, a lab coat, gloves and safety shoes. He was also wearing a
glass shield to protect himself from any potential explosions. He apparently removed the glass shield,
E-14
however, to prevent obstruction of his vision while he removed the flask from the mechanical stirrer.
Employee #1 had graduated from a university after majoring in chemistry. He received training on
corporation safety procedures with his job and followed specific "safe operating procedures" for the
mixture of ANF (OSHAk).
E2.12 Employees Injured in Chemical/Petroleum Explosion
Employee #2, accompanied by Employee #1, drove a Cusco vacuum tank truck onto Cherokee Brick
1
Property. Their job was to empty eight 55-gal drums of 50 percent HP into the tank on their truck and
transport it to a wastewater storage tank, where it would be inserted to clean the water. The employees
emptied the HP into the truck tank, which contained petroleum residue. They transported the HP to the
storage tank and were preparing to back up to the tank when their truck tank exploded. Both
Employees #1 and #2 were hospitalized for lacerations, abrasions and internal iniuries. The employers
were cited for violations of 29 CFR 1910.1200 "Hazard Communication" and 29 CFR 1910.120
"Hazardous Waste Operations and Emergency Response" (OSHA]).
E2.13 Employees Injured During Chemical Explosion
As an employee transported a plastic drum containing 55 gal of a solution of sulfuric acid (96 percent),
HP and 746 W (stabilizer) from the W1P area to the Electrolysis department, an explosion occurred.
Employees #1 through #5 were hospitalized (for chemical burns). The employer was cited for
violations of 29 CFR 1910.106 "Flammable and Combustible Liquids," 29 CFR 1910.178 "Powered
Industrial Trucks," and 29 CFR 1910.1200 "Hazard Communication" (OSHAm).
E2.14 Employee and Coworkers Exposed to Chlorine Gas I

Helium and hydrogen sulfate were added to a waste pit on top of HP. A chemical reaction occurred
and a gas, believed to be chlorine, was released. Employee #1 and approximately 56 others were taken
to hospitals or doctors for observation. None were hospitalized. The company was trying to clean out
excess chemicals, but was doing so in a haphazard manner. The employer was issued a citation for
violations of TBCCR 1910 and 29 CFR 1910.1200 "Hazard Communication" (OSHAn).
E2.15 Chemical Reaction Caused Explosion; Employees Burned
Employees #1 and #2 were disposing of some silver cyanide liquid waste. A flash explosion took
place as they were pouring the third of three 15-gal containers of the chemical waste into a 55-gal
container. Employee #1 received chemical burns to his hands. Employee #2 suffered chemical burns to
his leg. At least 21 others employees were hospitalized for possible injury from skin or respiratory
exposure to silver cyanide and HP. HP was the material that was mixed with the silver cyanide. The
chemical reaction ruptured the 55-gal polypropylene container. The employer was cited for violations
of the OSHA general duty clause 5(a)(1), 29 CFR 1910.094 "Ventilation," 29 CFR 1910.132
"Personal Protective Equipment - General Requirements," and 29 CFR 1910.151 "Medical Services
and First Aid" (OSHAo).
E2.16 Chemical Reaction Caused Drum to Explode, Employees Injured
The employees were pouring chemical waste from a small container into a larger drum for subsequent
disposal. The drum contained silver cyandide (sic). The smaller container held HP. As the two
chemicals were mixed, the drum's internal pressure rapidly rose. The drum ruptured, splashing its
contents on Employees #1 and #2. They were hospitalized with chemical burns. Up to 48 other
E-15
t persons, including company employees,
Y transients and rescue workers were taken to the hospital
P for
observation due to possible exposure to toxic smoke and fumes from the explosion. The primary cause
of the accident was the mislabelling of the HP container.
Additional details: Employees #1 and #2 were disposing of some silver cyanide liquid waste. A flash
' explosion took place as they were pouring the third of three 15-gal containers of the chemical waste
into a 55-gal container. Employee #1 received chemical burns to his hands. Employee #2 suffered
chemical burns to his leg. At least 21 others employees were hospitalized for possible injury from skin
' or respiratory exposure to silver cyanide and HP. HP was the material that was mixed with the silver
cyanide. The chemical reaction ruptured the 55-gal polypropylene container. The employer was cited
for violations of the OSHA general duty clause 5(a)(1), 29 CFR 1910.094 "Ventilation," 29 CFR
1910.132 "Personal Protective Equipment - General Requirements," and 29 CFR 1910.151 "Medical
Services and First Aid" (OSHAp).
E2.17 Employees Inhaled Vapors From Hcc/h202 (sic) Reaction
Employee #1 was preparing a hydrogen chloride/HP bath for cleaning semi-conductor wafers. The
chemicals should have been combined in a water solution, but were not. An unwanted chemical
' reaction resulted. A total of 56 employees, all of whom worked in the clean room, were evacuated.
The reaction occurred at a wet bench for the dump/rinse tank, located in the photo area. The
employees complained of headaches, nausea, coughing and dizziness. The accident resulted from an
inadequate written work practice program regarding the mixing of chemicals for the cleaning bath.
The employer was cited for violation of 29 CFR1 1910.1000 "Air Contaminants" (OSHAq).
E3.0 Historical Accidents

The following incidents ocurred during a 10-year period before and during World War 11, and are
described here from memory by Helmuth Walter (Walter 1954). Descriptions are directly quoted from
the original publication 1.
E3.1 Fatal Monopropellant Mixture
"A very serious accident occurred to several physicists who tried to develop an HP monopropellant
around 1935 (Walter 1953). These men were in the services of the German Army Command. They
used a stoichiometric solution of 80 percent HP and alcohol (type not specified). The solution seemed
to be stable, and 100 lb had been carried in a glass flask over 400 miles in an automobile to its
destination. A test apparatus had been built and consisted of a pressure vessel, pipes, check valves, and
a combustion chamber made of 18-8 stainless steel. The whole apparatus, including the pressure
vessel, detonated soon after ignition. Armoured plates were pierced by fragments and three persons
were killed.
E3.2 HP in the Face
"It happened (-1939), for instance, that one of my co-workers caught a 2-in jet of 80 percent HP right
in his face. He was thoroughly rinsed with water immediately thereafter. His face became white and
Walter, H. "Experience with the Application of Hydrogen Peroxide for Production of Power." Eighth Annual Convention
of the American Rocket Society, New York, New York 1953. Jet Propusion. May-June 1954.
' E-16
swollen, and he could not open his eyelids. He was running some fever for a few days, but his eyesight
was entirely unharmed. He recovered very quickly, and no traces were left on his face.
E3.3 Explosion
"An accident which could have been fatal occurred when I tried to separate the mercury column of a
pressurized flowmeter from hydrogen peroxide by acetylene tetra-bromide (1, 1, 2,2-
tetrabromoethane), because the use of membranes had given us a great deal of trouble in getting
correct measurements. The liquids' did not mix, but the contact on the surface was sufficient to cause
an explosion of the strong aluminum-alloy pressure vessel of approximately 1/2-gal capacity. The
windows were blown out, but no one was hurt, although the explosion occurred about 20 in. above my
head. Looking back on this experiment, the whole undertaking was rather foolish. However, it took a
few more incidents to show fully the potential danger of solutions and mixtures of organic compounds
with hydrogen peroxide.
E3.4 Incompatible Hydrocarbon Grease in a Pump
"There was, for example, the hydrogen peroxide pump used for the 4000-hp marine power plant. The
entire pump had been made of 18-8 stainless steel. It happened that the stuffing box, packed and
greased in the conventional way, blew out several times. Each time, it had been too tight and became
too hot. Small quantities of hydrogen peroxide had reacted with the hydrocarbons of the grease. The
casing had not been destroyed, but the screws were broken. Later, a grease was developed of paraffin
and talcum which gave no trouble when it was applied. In addition, dynamic seals and Buna rubber
sealing rings were developed.'
E3.5 Hydrogen Peroxide/Kerosene Explosion
"Tests were made to ignite hydrogen peroxide and kerosene in a torpedo combustion chamber. This
caused, on one occasion, a fairly heavy explosion in the test cell, so that we stuck to the previously
developed catalytic ignition which had never given us any trouble before or after. This catalytic
ignititon was later improved by using self-igniting fuel (hydrazine-hydrate) plus alcohol in solution.
E3.6 Incompatible Storage Container
"An aluminum pressure vessel (1500 psi) exploded one night. It had been left filled (approximately
5 gal) overnight because, for some reason, the test could not be made the previous day. Afterword it
was found that the aluminum alloy contained copper. ; Similar events occurred later, occassionally, if
small quantities of hydrogen peroxide were left in the container after a test. Sometimes the hydrogen
peroxide decomposed without any explosion; sometimes it was possible to cool the vessel off with a
jet of water.
E3.7 Test by Fire after a Transportation Accident
"Tests were made to heat a pressure vessel filled with hydrogen peroxide over an open fire. The vessel
exploded as soon as the vapor pressure was high enough in the same way as a water and steam-filled
vessel exploded. No additional effect was noted. This test was made because a 10-ton track, loaded
1 Although it is implied that the liquids that did mix were HP and 1,1,2,2-tetrabromoethane, it should be noted that mercury
is also a liquid and a Class 4 material capable of causing an explosion with HP.
While no further information on the Buna rubber formulation was given, Buna-N is a Class 4 material.
3 While the alloy fonmulation was not given, copper is a Class 4 material.
E-17
with H2O—filled aluminum containers, had run into a tree, after the driver had fallen asleep, and
caught fire. The fire was soon under control and no explosion occurred. Over a 10-year period,
thousands of tons of hydrogen peroxide were transported, at first by trucks and later by rail in special
cars, without any accidents except for the above incident.
E3.8 Storage Facilities, Emergency Stabilization and Recycling
"Storage facilities were still in the development stage during this period (1936). The material of the
tanks was pure aluminum in most cases. Coating the inside of the containers with paraffin and hard
polyvinyl chloride, for instance, was tried, but unprotected aluminum proved to be satisfactory, if kept
clean. At the same time, the stabilizers were improved and finally a purer product was made by dual
f distillation. In the few instances I recall, when a large storage tank started to show an elevated
temperature, which is invariably connected with decomposition and which occurs very slowly in large
tanks, the process was brought to halt temporarily by acid' additions. If the quantity of hydrogen
peroxide was large enough, it was sent back to the producer and re-distilled. In most cases, however, it
was mixed with higher per cent hydrogen peroxide and immediately used for tests.2
E3.9 HP Assisted Take-Off (ATO) Units
"The 500-kg rnonfuel ATO unit was in mass production before the war began. It was perfectly safe to
make the actual thrust run with hydrogen peroxide during an actual take-off. In 1940 there were two or
1 three reports of failures. In every case, one of the two devices failed to work and the planes crashed.
(The pilot had lost control because he could not counteract the momentum.) In each case, the cause
was found in the electric switching device which had failed. At no time was the use of hydrogen
peroxide for ATO's considered to be dangerous. The only other accident which occurred, to my
knowledge, happened shortly before the war, when a Heinkel airplane took off in an attempt to break
the world long-distance record. It was equipped with four 500-kg ATO's. During take-off, the
undercarriage broke down. The two ATO devices in use took off after the crash, while the two other
remained filled and ready under the wing. There was no fire or explosion and the crew was unhurt.
This accident shows that hydrogen peroxide does not add to the hazards of flying.
E3.10 HP/Liquid Catalyst/Gasoline-Assisted Take-Off Fatal Explosion
"Just before the self-igniting fuel was ready for application, we developed and built protoypes of a
1000/1500-kg ATO, which worked on hydrogen peroxide, liquid catalyst, and gasoline, i.e., with full
combustion plus decomposition. The unit could be shut down at any time, which could not be done
with the previously described ATO's. The fuel was ignited and combustion maintained by a constant
t flow of a liquid catalyst. This device was used on many occasions for flight tests, but never in the
field. For instance, a guided missile (Enzian) was propelled by it and four of them helped to get the
newly developed Ju 287 jet-engined bomber off the ground. Four 1000-kg ATO's were used for
additional thrust. Some of these devices were taken to England after the war where one of them was
tested and caused a fatal explosion in which our former designer, Dr. Schmidt, and two Englishmen
were killed. As usual, in most fatal accidents, several unfavorable factors worked together to cause the
death of several people. It must, however, be admitted that this type of rocket with three different
fluids, which had to be controlled with the right sequence, was more complicated, less reliable, and
1 The type of acid is not specified; phosphoric acid has been used more recently for emergency stabilization.
2 As long as this did not put higher percent propellant out of specification, this recycling activity might be regarded at the
present time as greening the green!
3 World War II.
4
The composition of the liquid catalyst was not stated.
E-18
required more skilled personnel, than the rockets developed previously and later. This device was also
electrically started and controlled. About ] 000 actual laboratory and flight tests were made safely
before his accident occurred.
E3.11 Torpedo Explosions
"In connection with the torpedo development, I can report about two accidents. One not very heavy
explosion occurred while the torpedo was still inside the tube. Several men were injured, though not
fatally. I do not recall the exact cause, but it was easily corrected and never happened again. However,
a second explosion, which caused the death of three men, happened inside a torpedo which had been
salvaged after it had been lying on the sea bottom for at least one month. As soon as the men started to
dismantle it, an oxplosion occurred, caused probably by a mixture of kerosene and hydrogen peroxide.
E3.12 Submarine Engine Incident - Liquid Accumulation/Decomposition
"In this (submarine) engine, the 80 percent HO, was first decomposed into a harmless steam and
oxygen gas, which was then combined with fuel oil in a burner. Until a reliable solid catalyst was
developed, the start of the decomposition had to be watched and any accumulation of liquid avoided.
On one occasion, such an accumulation, followed by a sudden decomposition, caused the handhole of
the decomposition chamber to be blown out. However, there were no fatal consequences because the
operators were at all times outside the engine room.
E3.13 Submarine Engine Incident - Fire Due to Spill onto an Incompatible

Material
"On another occasion, a fire was started by a leaking hydrogen-peroxide bag' due to the fact that the
steel compartments were, by mistake, painted with a mercury paint. This occurred while the submarine
was in dry dock and while there was no sea water around this bag. The reaction was rather violent. The
hydrogen peroxide started to burn the bag, but the fire was quickly extinguished by flooding the dock.
E3.14 Submarine Engine Incident - Fires and Vapor Exposure from Leaking HP
"The catalyst during that period (1940 and 1941) was still unsatisfactory. Several times a fire started
after the turbine had warmed up, caused by vapor leaking through the glands of the turbine and
igniting the lube oil of the bearings. Great pains were taken to avoid any hydrogen peroxide leaking
into the operators' compartment. In spite of this, it happened that a small quantity of hydrogen
peroxide leaked into the operator's compartment and started to slowly decompose in the bilge. The
atmosphere became unbearable for the crew. The submarine had to be surfaced quickly and was nearly
lost due to further mistakes being made. The piping and leaking gage was changed and no further
mishaps occurred. During 1941 alone, 80 sea trials were made with at least 1000 tons of hydrogen
peroxide being used, and it was generally ackowledged that hydrogen peroxide could be used on ships
and that it was possible to handle and control the submarine at speeds up to 26 1/2 knots, submerged."
E4.0 References
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Space Center, Mississippi. Incident on August 20, 2001.
' HP may have been stored in a flexible polyvinylchloride bag.

The composition of the catalyst was not given.
E-19
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E-20
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E-21 I
r
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i
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Annual Convention of the American Rocket Society, New York, New York 1953. Jet
Propusion. May-June 1954.
Wolf, S., and W. A. McNally. Hydrogen Peroxide as a Torpedo Propellant. Naval Underwater
Ordnance Station, NUOS 360, Newport, Rhode Island (1963).
Wnuk, T. "Cleaning Glass Funnels." Chemical & Engineering News, Vol. 68(26)1990:2,
Zecevic, D. and Z. Gasparec. "Death Caused by Hydrogen Peroxide." Z Rechtsmed, Vol. 84, 1979,
pp 57-59.
I E-22
.1
Appendix F
' Compatibility Tables from FMC Bulletin 104
r
F1.0 Compatibility Tables from FMC Bulletin 104
This appendix contains compatibility data that were electronically reproduced (with permission from
FMC) from FMC Bulletin No. 104, 1966 Revision (FMC 1966). It is provided to the user of this
manual as information supplementary and complimentary to the compatibility tables shown in
Section 3. For further information concerning the data, test methods and discussion of this reproduced
FMC data, the user should refer to the original source (FMC 1966).
Following is the disclaimer statement printed in the original FMC Bulletin (FMC 1966). It is repeated
here so that the user of this manual understands the original intent of the information.
This document is a reprint of the Technical Data Bulletin No. 104 1966 Revision. FMC is
making this Bulletin available at the request of many of its customers and others who are
interested in reviewing this information. No attempt has been made to update the original
document. FMC has included no new data or information regarding updated methods in this
reprint. The information provided in the Bulletin 104 is not meant to be inclusive of all the
requirements needed to understand how to safely use of hydrogen peroxide (sic). Rather, the
information included in the Bulletin was meant to offer general guidance of material selection,
testing, preparation, and handling of concentrated hydrogen peroxide. Since the original
publication date, material suppliers, government regulations, toxicological information and
other factors have changed and certain methods & procedures are no longer in practice. Each
component that comes in contact with hydrogen peroxide should be tested and approved
individually on a case-by-case basis. The referenced information as well as other information
should be thoroughly understood prior to the commencement of any work. Please contact
FMC or your current hydrogen peroxide supplier for updated information on current materials,
practices and procedures. FMC disclaims any responsibility for any event or occurrence that
results from the use of information contained in the 1966 Revision of the Bulletin and each
recipient of this Bulletin acknowledges that use of this information is at such a recipient's sole
risk and liability.
F-I
F2.0 Data Tables
Table F.1
Criteria for Classification of Materials for H2O, Service on the Basis of Laboratory Tests
Max. Amount Min. Stab.

of AOL/Week of H2O2
After
Class Material j0°C 66°c lest
1 Metals 0.2 5.0 95% No other effect on H 2 O2 or :material and
non-impact sensitive to 3 kg-meter impact
at 212°F
1 Bladder mat' 1. 0.2 5.0 95%
Plastics
For drums
and liners,
Diaphragms
For gaskets 0.4 6.0 95%
tubing, etc.
"0" rings
1 Oils and 1.0 10.0 95%

Greases
2 Metals 6.0 80.0 90% No other effect or. He O=, Slight bronzing
stainless of the metal allowable, but no corrosion.
steel
2 Plastics, 6.0 80 , 0 90% No other effect on H2O2. Slight bleaching,
"0" rings swelling, embrittlement or occasional
Expulsion blistering accepted. Non-impact sensitive
devices to 3 kg-meter impact at 212°F
2 Elastomers
Bladder mat'1. 6.5 95.0 90% No other effect on H202. Slight bleaching,
or loss of small amount of elasticity of
the material accepted. Non-Impact sensitive
to 3 kg-meter impact at 212°F
2 Oils and 6.0 80.0 90% No other effect on H2O2. Non-impact sensi-
Greases tive to 3 kg-meter impact at 212°F
3 Metals 11.0 100/24 15%(1) Bronzing and staining, but not rusting or
hrs, other corrosion. products. Slight attack
may be allowed.
3 Plastics 11.0 100/24 15%(1) May become partially bleached, distorted,
hrs, disintegrated, after 1 week on test. Non-
impact sensitive to 3 kg-meter impact at
212°F
3 Elastomers 11.0 100/24
/ 15% 1 Surface may be embrittled, bleached,
hrs, blistered or lose elasticity. Non-impact
sensitive to 3 kg-peter impact at 212°F
3 Oils and 11.0 100/24 15%(1 Non-Impact sensitive to 3 kg-meter impact
Greases hrs. at 212°F.
Excessive H2 O2 decomposition approaching
catalytic rate.
4 Metals Meals - pitted and corroded during or after
,eer
Plastics Plastics - disintegrated, burned, blistered
Elastomers Elastomers - burned, swollen, dissolved,
s n egrated, blistered, gummy, loss of
elasticity.
Oils and Oils and Greases - melted, disintegrated,
Greases burned. Any material which is Impact sensi-
tive to 3 kg-meter impact at 212°F
(1) After 30°C test.
F-2

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Table F.4
Results of Compatibility Tests with 90% Hydrogen Peroxide
Pure Metals
Effect of Sample on H20 2 Apparent Effect

Classifl- % AOL per $ Stability of H202 or. the Source of
materia- cation. Week a: 66 °C After Test Sam:,_e Ma-,erlal
Aluminum (1) -- -- -- -- --
Beryllium 4 100 0 Pitted
Cadmium 4 100 0 Pitted
Columblum 4 100 Pitted Heraus - Germany
Chromium 4 100 0 None
Cobalt 4 100 0 None
Copper 4 100 0 None
Gold 4 100 0 None
Iron (1) 4 100 0 Basted
Lead 4 100 0 Dissolved
Magnesi, :m 4 100 0 None
Manganese 4 100 0 None
Mercury 4 100 0 None
Molybdenum 4 100 0 Dissolved
Nickel 4 100 0 None
Platinum 4 100 0 None
Silicon 2 3.5 97 S1. surface General Electric

dulling Company
Silver 4 100 0 Attacked
Sodium 4 100 -- Violent de-

composition and
flame
Tantalum 1(2) -- -- None Fansteel Met. Corp.
Tin - C.P. 2 28.7 -- None Baxer Chem. Co.
Titanium 4 100 0 Pitted Rem-Cru Titanium, Inc.
Tungsten. 4 100 0 Dissolved
Zinc 4 100 0 Pitted
Zirconium 1 3.2 -- None National Lead Co.
(1) See specific alloy.
(2) Based on service experience
F-5
Table F.5
Metals — Miscellaneous Alloys
Effect of Sample
On H2O2
AOL Stab.
per Week After
Material Class at 66°C Test;, Apparent Effect Source of Material
Aluminum Oxide Frame- 4 100 One Rust Spot Linde Company

plated on Armco 1"l ? PH
Beryllium-Rronze + 100 0 None --
Berylli'am-Nickel + 100 0 None --
Chemalloy H-3 + 100 0 Pitted Electro-Alloys Div.
Chlorimet + 100 0 None Durimet
Dow Metal JIA + 100 0 None Dow Chemical Company
Dow Metal MA + 100 0 None Dow Chemical Company
Durlron (cast) + 100 0 None Durlron
Elgiloy 4 100 0 Bronzed Elgin Watch Company
Farweld "0" + 100 0 None Fansteel Met. Corp.
'4975 5 90.0 -- None Carbide & Carbor.
Hastel;oy "B" + 100/16 hrs. -- None Haynes-Stellite Corp.
1 Hastelloy "C"
Hastelloy "D"
Haynes-Stellite #3
u #6
4
4
+
100 /16 hrs.
100/3 hrs.
100/48 hrs.
100 hrs.
1003 hrs.
--
--
--
--
--
None
Bronzed
None
None
None
Haynes-Stellite Corp.
#^5 3.00 /1 hr. -- Bronzed

Illlum G + 100 O Rusted Tlliu:n Corporation
Inconel 4 100 0 None International Nickel
.1 Corp.
5 100/72 hrs, -- Discolored 11
Inconel "X" (Full Hard)
Kennametal K-138 4 100 0 None Kennametal, Inc.
K -3H + 100 0 None
K-501 4 100 0 None
K-M 4 100 0 None
Monel 4 100 0 None International Nickel Corp.
Multimet N-155 4 100/16 hrs. 0 None Haynes-Stellite Corp.
Ni-Resist Alloy 4 100 0 Rased International Nickel Corp.
Refractalloy 26 3 45.3 -- None Westinghouse
Re,ractalloy 70 5 100 -- None Westinghouse
Steel, Mild 4 100 0 Rusted commercial
Super-Alloy, S-588 4 100 0 None Allegheny Ludlum
Super-Alloy, S-590 4 100 0 None
Tantung 4 100 0 None
Timken 16 - 25 - 6 3 50 -- Sl. bronzing Timken Roller Brg. Co.
Ucc-Star " J " Metal 4 100/4 hrs. -- Bronzed Union Carbide
Utiloy 3 4 100/2 hrs. -- None Utility Steel Foundry
Utiloy 20 4 100/2 hrs. -- None
Utiloy H 4 100/3 hrs- -- 14are
Utiloy NH 4 100/2 'hrs. -- None
Worthi;,e 3 100 -- Bronzed Worthington Corp.
19-9 DL 3 100 -- Bronzed Universal Cyclops Steel
Nickel 'base alloy Rene' 4 100 0 Bronzed Muskegon
Haynes-Stellite 3 65.0 0 Haynes Stellite Corp.
72.7 0 Bronzed
Haynes-Stellite L#3 4 100 0 Bronzed
L6 4 100 0 Bronzed
F17-3 4 97.8 0 Bronzed
C5087-3 4 100 0 Bronzed
01712-3 H2 O2 evaporated completely
M1516-3 4 26.10 0 Bronzed
L1316- 3 4 100 0 Bronzed
Titanium B120 VCA 4 100 0 Sev, discolored Crucible Steel Co.
4
11 it
Titanium C120 AV 100 0 Sev. discolored
Kanegin plated mild steel

Sample 3 3 82.1 88.8 S1. stained Keystone Chromium
Sample 7 3 51.2 95.1 S1. stained
Sample 13 3 60.3 92.5 S1, stained
Tin plated 2 0.6(1) 96.7 Sl. stained
Kaneg'_n plated 2 0.6(1) 96.3 S1. stained
Mild steel 2 0,9(1) 94.2 S1, stained
(1) Seven day room temp. 20 - 22°C (68 - 72°F) toss.
F-6

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Table F.7
Plastics, Polyvinylchloride and Co-Polymer
Effect of Sample on F202 Apparent Effect
% AOL per %Stability of H2 02 Source of
Material Class Week at 66 °C After Test on the Sample Material
Alanol tubing 3 10.3 -- Embrittled Nalge Company
Boltron 6200 (grey) 2 3 -- None The Bolta Company
Geon 118 4 8.5 (4 days) 85.6(4 days) Milky white, blistered B. F. Goodrich
and distorted
Geon 404 (yellow)
(y ) 3 8.0 Bleached & became B. F. Ooodrich
brittle
Geon PVC 2 -- 85 Slight bleaching B. F. Ooodrich
I.P.S. Uscallte 4 7.2 89.8 Severely attacked Stritt & Priebe
-- and blistered
Koroseal 116 3 23 Bleached &11 hardened B. F. Goodrich
Koroseal 117(molded) 3 16 -- " F. Goodrich
Koroseal 700 2 2.9 -- Slightly swollen, B. F. Goodrich
stiffened & bleached
Koroseal 700 with Hycar 4 14.9 0 Blistered & bleached Prince Rubber Co.
1041 plasticizer
Koroseal pipe (grey) 3 10.6 97 S1, bleaching B. F. Goodrich
Lucoflex translucent)
i 3 10.1 -- Blistered & bleached Lucoflex ?laztic Fab. Co.
Lucoflex (wh te) 3 11.2 -- Darkened, slight same
blistering
Marvinal 218-200 4 100/2 hrs. -- Became tacky after U. S. Rubber Co.
one hour
Marvino: 218-201 4 100/1 hr. -- Deformed, charred U. S. Rubber Co.
Marvinol NF-3005 4 100/1 hr. -- Became tacky U. S. Rubber Co.
Marvinol NR-6010 4 10011 hr. -- Deformed, became tacky U. S. Rubber Co.
PVC - Rigid 2 5.3 90.4 Bleached & slightly Vanco Company
blistered
PVC - Rigid 2 7.5 96.0 Bleached Whitehead
Polpinylchloride 2 10.5 86.0 Mod. bleached Walworth Pipe
2 1.2 9 8.4
PVC 3 13.1 87.7 No change Prince Rubber Co.
PVC sheet dark grey 3 13 87 Slight bleaching Prince Rubber Co.
Saran 2 12.3 -- Bleached Dow Chemical Co.
Saran Rubber Q-187 4 -- -- Burned Dow Chemical Co.
Transflex Tubing 4 1.1 -- Blistered badly Irvington Varnisn &
-_ Insulation Company
T ygon B-20 3 2.3 Bleached, blistered U. S. Stoneware
& distorted slightly
Tygor. B-32 3 2.2 -- same same
Tygor.B-72 3 1.0 -- same same
Tygon 5-22-1 4 -- -- Blistered, swollen same
Tygon TL-103 4 -- -- same same
Tygon2807 4 -- -- Disintegrated same
Tygon 3400 4 -- -- Embrittled & swollen same
Tygon 3603 4 -- -- Swollen same
Tygon 3604A 2* -- -- Became opaque same
Tygon 3604B 2* -- -- same
Vinyl 79139 2 1.7 -- Slightly opaque U. S. Rubber Co.
small blisters
Vinylite VO 1914 2 1.5 -- Bleached, sl, blister U. S. Rubber Co.
Vinylite VU 1940 2 1.6 -- Bleached U. S. Rubber Co.
Vinylite VS 1310 3 2.3 -- Turned opaque, slight Bakelite Division
blisters
Vinylite W 1900 3 2.5 -- same Bakelite Division
Vinylite UE 1907 3 3.0 -- same âkeli:e Division
Vinylite VU 1920 3 2.0 -- same Bakelite Division
Vinylite VU 1 93 0 3 2.4 -- same Bakelite Division
Vinylite VU 1940 3 2.0 -- same 3akellte Division
* Based on service experience
F-9
Table F.8
t Material
Plastics - Silicone Rubber Compounds
Effect of Sample on H2O2
% AOL per %Stability
Class Week at 66°C After Test
Apparent Effect
Of H2O2
or. the Sample
Source of
Material
Fluorosilicone LS-53 2 16.7 91.3 None Dow Corning

GE 407B-217-1 4 34.3 -- Hardened General Electric Co.
GE 1240 2 72,4 -- None General Electric Co.
GE 81223 2 27.7 -- None
GE 12601 4 99.5 -- Hardened
GE 12602 None
u
GE 12650 (unpigmented) 2 446.5 -- Slight swelling
n
GE 12650 ((pigmented 3 89 -- sl, bleaching,
red) swelled, distorted
G^ 12670 4 47.5 -- Hardened
GE 12670 (,pigmented 4 45 - Cracked, bleached
brown)
u „ n
OE 15060 (pigmented) 3 31.9 -- Blistered & warped
slightly
GE 15080 3 32.2 -- Blistered
u n n
GE X-7181 3 18.3 -- Slightly hardened
Parkone White 467-1 4 29.6 -- Hardened and broke Parker Appliance
"0" ring
SE 450 (unpigmented) 2 13.3 -- Very slight bleach- General Electric Co.
ing and swelling
Silastic 152 3 17.8 68,1 Slightly bleached Dow Corning
Silastic 160 3 37.8 -- Lost elasticity Dow Corning
Silastic 160 4 71 -- Embrittled Linear Inc.
11
011 ring
Silastic 181 3 39.3 -- Slightly blistered Linear Inc.
Sila3tic 240 2 24.9 -- None Dow Corning
Silastic 250 4 92.6 -- Curled Dow Corning
Silastic 675 3 5.0 -- Blistered and Dow Corning
embrittled
Silastic 6-128 2 6.7 99.7 Bleached, very Dow Corning
slightly blistered
Silastic 7-180 3 17.7 -- Embrittled Dow Corning
Silastic 9711 2 7.4 99.1 Slightly bleached Dow Corning
Silastic 9711 2 5.7 98 Slight bleaching Dow Corning
Silastic HR-9711 Slightly bleached Hewitt Robbins
Silastic 9711 welded 2 13.6 96.0 Weld uneffected. Dow Corning
with 5-2200 Slight bleaching
and mottling
Silastic S-2000-4-480 2 16.1 95.5 Bleached and Dow Corning
mottled slightly
Silicone 407-B-217-1 3 34.5 Embrittled F. S. Bacon Lab.
Silicone 407-B-437-1 2 20,3 None F. S. Bacon Lab.
Silicone HT 656 3 17.4 95.7 Blistered Conn. Hard Rubber Co.
Silicone SR 5550 2 32.4 -- None Conn. Hard Rubber Co.
Silicone SR 5570 2 30.9 -- None Conn. Hard Rubber Co.
SR 5550 2 45.0 -- None E. I. DuPont
SR 5570 2 46.5 -- None F. I. DuPont
X-71a1 3 18.3 -- Lost some elasticity Stalwart Rubber Co
Silicone Y-1749 2 12.3 -- Small white blisters Carbide & Carbon Co.
Silicone TH-1131 2 15 94 Bleacned slightly Stillman Rubber
Silicone TH-1047 2 10.3 97 No effect Stillman Rubber
1
Î
Î
I
F-10
Table F.9
Rubbers and Plastics — General
Effect o: Sam le on H.0; ' Apparent Effect
AOL per Stability of H2O2 Source of
Material Class Week at 66°C After Test on the Sample Material
Acrylon Rubber BA-12 4 -- -- H2O2 turned black. American Monomer Co.
Sample partially dis-
solved in 2 days
Acrylon EA -5 4 -- -- same same
Adiprene C 4 100 0 Decomposed in 1 hr. Hewitt Robins
Blsilon #50 2 9.7 -- Slightly blistered Bishop Mfg.
Buna N 4
Butyl Rubber A 3405 4 100 -- Softened to sticky Esso Lab.
mass overr.lgnt
Butyl Rubber SR-384 4 5.0 -- Sample became very
tacky
Cycolac (natural color) 4 7.6 -- Hmbrittled, swelled, Marbon Chem. Div.
solution turned
yellow
Estane Plastic 4 6 55 Disintegrated B. F. Goodrich
Delrin 4 100 -- Dissolved DuPont
Garlock #5681 (Teflon. 4 100,% in -- Sample fell apart Garlock Packing
Impregnated asbestos) one hour
Hcar PA 478-1-1 4 100/24 hrs. -- Dissolved completely F. S. Bacon Labs.
black)
Haveg 41 (Asbestos 4 100 -- Partially dissolved Haveg Corp.
filled phenolic)
Haveg 60 (phenolic 4 100 -- Dissolved Haveg Corp.
Hysol 4-77C clear 4 100 -- Bleached, distorted Houghton Labs.
Hysol 4-77D amber 4 100 -- Blistered, distorted Houghton Laos.
Hysol 4-77E 4 100 -- Blistered, distorted Houghton Labs.
Hysol 4-77F 4 100 -- Blistered, distorted Houghton Labs.
Hysol 4-78A (white 4 100 -- Blistered, distorted Houghton Labs.
Hysol 4-78B (brown 4 100 -- Blistered, distorted Houghton Laos.
Hysol 4-78C (amber))) 4 100 -- Blistered, distorted Houghton Labs.
Hysol 4-78D (amber) -- "11 11
11
Hysol 6000 B (amber) -- Partially dissolved
Kralite 3 26.7 -- Swollen and U. S. Rubber Co.
distorted
Lexan 2 2.1 97 Slight bleaching General Electric
Melmac # 1077 4 100 -- Partially dissolved Meet,. Prod. Co.
Mylar A 1 5.0 -- None DuPont
Mylar B 1 1.7 -- None DuPont
Neoprene Pure Gum 4 -- -- Ignited and burned Spray Dip Co.
Neoprene SR 365-B 4 100 -- Ignited and burned --
Nylon 4 100 -- Ignited and burned DuPont
Phenol-Formaldehyde 4 100 -- Sample burned Durez
Plexiglas 4 100 -- Softened and partial Rohm & Haas
solution
Polystyrene (Polyflex) 2 9.1 -- None Plax Corp.
Thiokol EC- 801-LP2 4 100 0 Burst into flame Thiokol Corp.
Thiokol 3000 FA 4 100 -- Dissolved Thiokol Corp.
Thiokol 3000 ST 4 -- -- - Thiokol Corp.
Thiokol 1620 AH 4 -- -- __ Thiokol Corp.
Polyurethan
Green 3 8.5 50.2 Partly dissolved Dunlop
Tan 3 56.0 - 59.9 Completely dis- B. F. Goodrich
solved
Black 4 98.5 0 Completely dissolved B. F. Goodrich
F-II
F
Table F.10
' Plastics - Laminates, Diaphragm Materials and Adhesives
Effect of Sample on H2O2
4 Stab. Apparent Effect
% AOL per After of H2O2 Source of
Material class Week at 66 °C Test on the Sample Material
Chemelic MI-411 2* 11.5 -- Bleached during U. S. Gasket

(Teflon Fibreglas) screening
Duroid 5600 (fiber- 3 44.7 70.1 None Rogers Corp.
reinforced Teflon)
Fairprene PS57-167 3 29 91.6 Moderate blistering DuPont
(Viton A, 116 Glass) and surface attack
Fairprer.e FS 57-168 2 23 -94.5 Moderate surface DuPont
(Viton A, Dacron) attack
Fairprene (Viton A) --
5806 2 48,4 None DuPont
5807 2 53.9 None DuPont
58C9 2 7.5 None DuPont
Fairprene 80-080(1/32") 2 4,0 -- None DuPont
Kel-F-Dacron Diaphragm- 4 95 -- Coating and Dacron Vernay Labs. Inc.
-110164 -- separated In 2 days -
^ Kel -F 5160 Diaphragm 2 30.6 -- Slightly blistered Nichols ang. Co.
and tacky
Kel-F 5500 (grey) 2 13.7 Slightly blistered Nichols Eng. Co.
Diaphragm and tacky
Kel-F 5500 (grey) 2 43.8 -- None Nichols Eng. Co,
Dacron diaphragm
Korda Flex (Teflon 2 2.5 97 None Chicago Gasket Co.
coated glass fabric)
Silicone Rubber 4 39.0 60 Disintegrated Continental Can Co.
Silastic DC-9711 on 3 9.7 96 .4 Blistered and Kirkhill Rubber Co.
Dacron diaphragm distorted
Vinyl coated Fiber- 3 49.8 -- None Birma Mfg. Company
glass (grey-greer.)
971 1 Silicone 3 15.5 69.1 None Kirkhill Rubber Company
seal washer
DC A 4094
adhesive (Dow
Corning Silicate
base) on
aluminum
9711 Silicone 3 11.6 83.4 None Kirkhill Rubber Company
seal washer
DC Chemloc
607 adhesive
on aluminum
Polyester Fiberglass
Duracor 1000 3 25.9 15.7 Bleached Will Corporation
Duracor 2000-5 3 18,6 81.7 Bleached W111 Corporation
Duracor 6000-4 3 21,4 70,0 Bleached Will Corporation
Duracor 6000-8 3 49.5 39.8 Bleached Will Corporation
Duracor-E 3 15.0 10.7 Dissolved Will Corporation
Polyester Fiberglass
Red 3 12.0 79.7 Discolored and Buffalo Forge Co.
nigtly
Straw 3 22.0 28.0 Discolored and Buffalo Forge Co.
highly bleached
Glass Resins 1 1.3 97.5 Bleached Owens - Illinois
Technical Center
Rigldo r, 3 27.4 67 Slightly dissolved Heil process and
Equipment Company
' After 24 hours screening at 66°C
Î
F-12
Table F.11
Results of Compatibility Tests with Becco 90% Hydrogen Peroxide
Porous Materials
Effect of Sample or. Hz Oz
Stab, Apparent Effect
% AOL per After of H2 O2 Source of
Material Class Week at 66°C Test on the Sample Vaterlal
Al-Si Mag, Porous 3 100/3 days -- None Lava Corporation

Ceramic #1393 of America
Alimir.um Oxide 2 19 -- None Norton Abrasives Co.
Porous-RA -98
Ar7nalon - 3 70 -- Bleached DuPont
Teflon Felt
(impregnated)
Armalon - 3 28 -- Bleached DuPont
Dacron Cloth 2 5 -- Resiliency de- Nat. Filter Media
Dac-2100 creased Corp.
Dac-2101 2 3 -- Resiliency de- Nat. Filter Media
creased Corp.
Dac-2102 2 6 -- Resiliency de- Nat. Filter Media
creased Corp.
Filtros C Stone 2 Classification 'cased None Filtros Corp.
(55 Micron) on experience
Glass Cloth 2 18 -- None Nat. Filter Media
G-206-C Corp.
Porcloy - 302 SS 3 100 -- None Ber.dlx Filter Div.
Wire
Porous Kel-F 2 9.8 98.0 Less brittle Pall Filtration Co.
(15 micron Fore)
Porous Porcelain 2 16 -- None Selas Corp. of America
(1.4 Micron)
Porous Teflon 2 14.0 96.5 None Pall Filtration Co.
(9 Micron Pore)
Rigimesh J SS 4 100 -- Deep bronzing Pall Filtration Co.
Wire
Sintered 300 Series 4 10012 hrs. -- Brorzed and California Institute
S.S. Powder rusted of Technology
Compact
Sintered 302 SS 4 100/2j -- Bronzed Amplex Division
Powder Compact hours
Sintered 316 SS 4 100/24 hrs. -- Bronzed heavily Titeflex Ir.c.
Powder Compact
Sintered 316 SS 4 100/24 hrs. -- Bronzed Pall Filtration Co.
Powder Compact
Sintered 3028 4 10012 hrs. -- -- S-K-C Research Assoc..
SS. Powder
Compact
Sintered 316 & C'e 4 1005 hrs. -- -- Rensselaer Poly. Inst.
SS. Powder
Compact
Teflon Cloth 3 20 79 Completely Pall Filtration Co.
(25 Grade) bleached
Teflon Cloth - 2 17 98 None Pall Filtration Co.
Repeat
(25 Grade)
Teflon Cloth 3 15.3 83.1 Completely Pall Filtration Co.
(40 Grade) bleached
Teflon Felt
(Impregnated)
Teflon Cloth 3 100 None Bleached white Nat. Filter Media
T-2300 Remaining Corp,
Teflon Cloth 2 28.2 -- None Nat. Filter Media
T-2305 Corp.
Zirconium silicate 2 17 97 None Selas Corp.
(10 micron)
F-13
Table F.12
Lubricants
Effect of Sample
On the H2O2
% AOL per Week Impact
Material Class at 66 °C Sensitive Source of Material
Alkaterge C 4 -- Yes Comm. Solvents

Amino Silane Oil and Grease 4 -- Yes --
Apiezon Hardwax W 4 Excess. -- J. G. Biddle
Arochlor 1221 4 -- Yes Monsanto Chem. Co.
Arochlor 1248 4 Yes Monsanto Chem. Co.
Bardahl 4 -- Yes Bardahl Corporation
Carrum 200 4 5.2 Yes Esso Labs.
Ceresin Wax 4 -- Yes --
CFE-1 4 -- Yes Carbide & Carbon
Dichloro-bis-tri-fluoromethyl 3 3.3 No(1) Hooker Electro-Chem. Co.
benzene
Oro
Dich:. hexafluorobutene 3 9.2 No 1
Fluorolube FS 2 4.2 No 1 Hooker Electro -Chem. CO,
Fluorolube FS plus 5% fluoro- 2 No 1
lube light grease
Fluorolube heavy grease 2 1.7 No(1)
102!4
Fluorolube oil 10213 2 1.0 No 1
Fluorolube S 2 2.5 No 1
Fluorolube T 2 8.5 No 1
Fluorolube 011, S-30 2 -- No 2
Fluorolube Grease, Hg-1200 2 No 2
Fluorolube Grease, GH -660 2 -- No 2
Formulation
F -9 4 -- Yes Monsanto Chem. Co.
os-16 4 -- Yes
OS-22 4 -- Yes
03-23 4 -- Yes
OS-27 4 -- Yes
OS-2 4 -- Yes
03-30 4 -- Yes
03-32 4 -- Yes
09 -33 4 -- Yea
Os-34 4 -- Yes
11
OS- 35 4 -- Yes "
OS -37 4 -- Yes "

CP-3398-2 4 -- Yes
Skydrol (uncolored) 4 1.0 Yes
Halocarbon Oil 8 -25 AV 2 1.8 No(l) Halocarbon Products
Halocarbon grease, series No(2) -- Halocarbon Products
25-10
Halocarbon Hi-Temp No(2) -- Halocarbon Products
Stopcock Grease
Halocarbon Oil 10-21
Halocarbon Oil 11-14
2
2
2.9
2.1
No S Ill
No ( 1
Halocarbon Products
Halocarbon Products
Halocarbon Stop Cock Grease 2 1.8 No(2 Halocarbon Products
Hexachlorocutadiene 3 3.7 No (1 Hooker Electro-Chem. Co.
Hexachloropropylene 4 100 -- Hooker Electro-Chem. Co.
Hydraulic fluid RPM 4 1.4 Yes Standard Oil of California
Hydraulic Oil Houghton 3 7.1(3) -- Houghton Co.
Safe 520
F-14
Table F.12
Lubricants (continued)
Effect of Sample
on the H2O2
% AOL per Week Impact
Material Class at 66°C Sensitive Source of Material
Kel-F Alkane 2 1.0 No(2) Minnesota Mining and

Manufacturing Co.
Kel-F Oil Cut No. 1 2 1.7 No(1) Minnesota Mining and
Manufacturing Co.
Kel-F Oil No. 10 2 3.2 No(1) Minnesota Mining and
Manufacturing Co.
Kel-F No. 90 Grease 2 33.2 No(2) Minnesota Miring and
Manufacturing Co.
Lindol HF (tricresyl 4 -- Yes Celanese Corp.
phosphate)
Lindol HFX 4 -- Yee Celanese Corp.
Liqui-Moly concentrate 4 -- Yes Climax Molybdenum
Lubriseal 4 -- Yes Arthur H. Thomas Co.
Mineral Oil 4 -- Yes Various suppliers
Paraffin. 4 -- Yes Various sources
Perfluorolube grease 2 10.5 No(1) DuPont
FCD-759
Perfluorolube Oil FC - 331 2 1.4 No 1 DuPont
FC-33 2 2 1.7 No 1 DuPont
FC-33 2 1.4 No 1 DuPont
FC- 33^ 2 o.8 No 1 DuPont
FC-335 2 1.0 No 1 DuPont
Petrolatum 4 -- Yes Various sources
Polychloropentane 4 -- Yes Hooker Electro-Chem. Co
(stabilized)
Renex 4 -- Yes Atlas Powder Company
Silicone XF 224 4 -- Yes Dow Corning
Silicone Oil DC - 7 4 -- Yes Dow Corning
DC-44 4 -- Yes Dow Corning
Silicone 011 GE 2V3733 4 -- Yes General Electric
GE 51346 4 -- Yes General Electric
Tectyl 4 -- Yes --
1,1,2,2 tetrafluoroethyl 4 -- Yes DuPont
dodecylether
Tributyl Phosphate 4 - Yes Comm. Solvents
Ucon Hydroiube U-4 4 8.4 -- Carbide & Carbon Chem,
(Ppt. formed)
1 Nor.-impact sensitive to 1 kgm, at Room Temperature

2 Non-impact sensitive to 100 ft. lb . at Room Temperature
3 Non-impact sensitive at 1 Kgm^ at Room Temperature but clouded during 150°F 7 day test.
F-15
Table F.13
Ceramics, Refractories and Miscellaneous Materials
Effect of Sample
on H202 Apparent Effect
% AOL per Stabi ity of H202
Material Class Week at 66 °C After Test on the Sar.:ple Source of Material
Agate (natural) 3 i00 -- None --
Agate (polished) 3 100 -- None Buffalo Meter Co.
Al-S1-N.ag 2 17.5 -- None American Lava Co.

(porcelain)
Alundum LA 116 2 19.1 -- None Norton Company
Boron Nitride 4 -- -- -- --
Carboloy 44 -A 4 100 0 None General Electric

Company
Carboloy 55 -A 4 100 0 Etched General Electric

Company
Carboloy 78 4 100 0 None General Electric

Company
Carboloy 999 4 100 0 None General Electric

Company
Ceramic AB-2 2 8.5 -- None Coors
Ceramic Al-200 2 12.6 -- None Coors
Charcoal 4 -- -- Burned --
Crys.alor. 4 100 -- None Norton Company

(silicon Caroide)
Graphitar No. 30 4 -- -- Dissolved at Lee Company

room temperature
Graphite P -5A6 4 100 -- None Pure Bond Co.

Silver impregnated
Graphite P -55 4 100 -- None Pure Bond Co.

Copper impregnated
Graphite P -59L 4 100 -- None Pure Bond Co.

Copper impregnated
Graphite P - 692 4 Excessive -- None Pure Bond Co.
Karbate 4 100 0 None National Carbon Div.
Norbide 2 15.6 -- None Norton Company
Snthetic Sapphire 1 0.8 -- None Linde Company

polished)
KT Silicon 2 1.2 95.5 None Carborundum Company

carbide
Zirconi•xm silicate 2 7.6 97 None Selas Corp.
F-16
Table F.14
Results of Evaluation of Protective Coatings for Becco 90% H2O, Service
A. RECOMMENDED FCR LONG TIME CONTACT AND SPLASH RSSISTANCE,

Trade Name Supplier Pormulation Applications Class Re ma: ;ca
Teflon Dielectrix T.F.-2. Dispersion coating 1 Difficult to obtain non-
permeable coati rig
Teflon Bladder 1 Tends to be brittle. Multi-
thinlayers are rewarding.
Kel-F M. W. Kellog Co. Kel-P Dispersion coating 1 Uniform coatings possible
Kel-F Metal Cladding Kel-F Spray coated on 1 Uniform coatings possible
1060 a'-'uminum
Kel-F Metal Cladding Kel-P Spray coated on 1 Unifurn coatings possible
5254 aluminum
Kel-P Metal Cladding Kel-F Spray coated on 1 Uniform coatings possible
5652 aluuminum
Omni David Clark Co, Viton A Glass or teflon cloth 2 No effect upon exposure to
impregnated with 9096 H, 0e for 7 days at 66°C
Viton A ( 15 1 "F)
Glass lining Ffaudler Corp. Clear glass, light Po:ned glass Lining 1 No effect upon material
grey
Glass lining Ffaudler Corp. Cobalt glass Formed glass lining 1 No effect upon material
Kanegir, Keystone Chromium Electroless nickel Plating 2 Very slight bronzing after
upon mild steel elevated H2 08 service
Tin plated Sealed tin plating Plating 2 No effect upor. material
Kanegln
B. RECOMMENDED FOR SPLASH RESISTANCE SERVICE

Omni David Clark Co. Viton A Glass, dacron, or 2 Curtains, equipment covers
teflon cloth im-
pregnated with Viton
Teflon DuPont T.F.E. sneet Ai1ma 1 Drop cloths, Curtains, covers
for equipment
Viton A DuPont Viton A Sheet form 2 Curtains, cover cloths, etc.
Metallic Various aluminum non- Paint Excellent field experience
aluminum volatile carrier for painting :seta': surfaces
Aluminum Various aluminum foil and Foil and film 1-2 Coverings for various items
toll film Wrapping
Plastic Nat. Eng. Plastic paint Paint 2 Pa:nting of metal surfaces
metal No. 22 Products
Myiar DuPont Plastic Film 1 Coverings, splash shields
Scotch Pak Various Plastic Film 1 Cove.-Inge, splash shields
Kanegin Keystone Chromium Electrolese nickel Plating 2 Excellent coating for mild
steel and other metals,
Tin plated Tin plated kanegin Plating 2 Very low He Oz loss upon Ha Oz
Kanegin contact.
NOTE: The aluminum alloys all show good splash resistance.

Any non flammable plastics or metals listed Sr. the previous tables having Class 1 thru 3 are
suitable for use as splash resistant materials.
C. THE FOLLOWING MATERIALS ARL NOT iECG.'METNDED

Mate ria1 Company
Gaon Latex 31X B. F. Goodrich
Flexcoat No. 1 Black Bison Chemicals Co. Buffalo, N.Y.
Lithgow LC-600 (Grey) L'!thgow Corporation
Amercoat Red American Pipe a Construction Co.
?rlfcoat Medium Grey Prufcoat Labs.
Lithgow LC (600) (Brown.) Lithgaw Corporation
Veloforn P-10 CPP504 Firestone Rubber Company
condo 5-255 A Cords Chemical Corp.
Ccrdo Plastic Coatinng (3-1 Resin 1 H-26 Activator) Cordo C'nemlcal Corp.
Chromalloy
Unichrome Drum Lining B-124-17 United Chromium Inc.
Ucilon, System E Coating United Chromium Inc.
EX65B Paint American Paint Campary
Sealer EC9C1 with accelerator Minnesota Mining and Mfg. Company
Penton lining on 1060 aluminum Buffalo Lining and Fabricating Co.
F-17
' Table F.15
Evaluation of Clothing Materials for Contact with Becco 90% Hydrogen Peroxide
Active Oxygen
Loss of H2O2 Inflammability
% per Week Drip Tests
ample Source 30°C(1) b6°C Clean Soiled Remarks
PER_ 1o;,BLF.
Dacron
;4onofilament U.S. Rubber Co. 1.0 12.1 No effect No effect 2 Apparently no damage
Heavy :1le G..,d. Borg Co. 0.5 13.0 No effect No effect 2 Apparently no damage
Staple fabric Travis Fabrics, 0.8 13.4 No effect No effect 2 Apparently no damage
Inc.
Saran
..0—n-Ofilament Saran Yarns Co. 0.5 6.0 No effect No effect(2) Apparently no damage
Dacron-fool
Deering Milliken 0.7 7-1 No effect No effect Weakened
D nel Burlington Mills No effect Burred Partially dissolved at
66°c (151°F)
Saran(staple) Saran Yarns Co. 1.3 4.0 No effect Burned
Vinyon N"_ Milburn Co. 1.9 4.0 No effect Burned
I MPE R-1EABLE
Polvvirvl- Milburn Co. 0.2 3.6 Not tested Hardens on prolonged
chloride contact at 66°C (151°F),
' bleaches
Flexigrip. Flexigrip, Inc. 110 4.3 No effect Distorts Hardens on prolonged
zipper (vinyl) contact at 66°C (151°F)
(1) One month test period.
2 Some Dacron samples when soiled with catalyst may burn upon contact with 90% H2O2.
Table F.16
Clothing Material Not Suitable for Use When Handling Becco 90% Hydrogen Peroxide
Sample Effect of Sample on H 2 O2 Effect of H2 D2 on Sample
PERMEABLE
Cotton-drill Moderate decomposition Burns readily when soiled
Cotton - Rayon Moderate decomposition Burns readily when soiled
50% 50%
Dacron - Viscose Moderate decomposition Weakens considerably
50% 50%
Leather --- Burns readily
Linen - bleached Moderate decomposition Burns readily
Linen - unbleached Moderate decomposition Burns readily when soiled
Rayon Moderate decomposition Burns readily when soiled
Silk, degummed fibre --- Dissolved
Wool Moderate decomposition Weakens considerably,
crumbled when touched
I14PBR;,1EABLE

Aluminized cotton duck Moderate decomposition Burns readily when soiled
Î
F-18
Table F.17
Protective Clothing and Accessories for Personnel Handling Concentrated Hydrogen Peroxide
Item Description Source

Shirts, Trousers Dacron fabric-Polystyrene buttons, no Worklon, Inc.
front or side pockets, no cuffs New York 1, N,Y.
Dynel Fabric Mine Safety Appl. Co.
1008 Dynel Che -cleave medium wt. Chem-Wear Inc., Darlen, Conn.
Sells ny p as `_ic, 7EF pâsT^5uc a umerous commercial sources
U ndershirts Dacron AlanacKnitting Mills, N.Y., N.Y.
Special lot, minimum order 10 doz.
Dacron-cotton (can be Ignited if soiled) Carml-Ainsbrooke Corp.
Ca Illinois
Sh orts Dacron arm - ns rob a orp.
Manhattan Shirt
Socks Knit Darcon - No elastic, wn e o s on g, o., oxv e, enn. '
Dynel Fabric Numerous commercial sources
Sh oes o Neoprene Coated, 90 Iron Age Div., Childs & Co., Inc.
Steel toe Pittsburgh 12, Pa.
Rubbers Full, Neoprene with tongue Numerous commercial sources
Boots Neoprene, knee lengt. Numerous commercial sources
Goggles No. 93 AV 'large nose, clear Willson Willson Products, Inc.
Monogoggle Reading, Pa.
Model 293607 SAF-I-CHEM, Series 29 U. S. Safety Service Co,
clear lens Kansas City, Mo.
Face Sh e c No. 324 clear Se'_lstrom face shield Watson Company, Buffalo N.Y.
Gloves Sureseal, gauntlet, Vinyl or Neoprene Surety Rubber Company
No, 116 lightweight for laboratory use. Carrollton, Ohio
No, 136 medi.im weight for work use.
Apron 6 mil vinyl plastic. Surgeon's type, Milburn Company
extra long, overlapping In back, ties Detroit 7, Michigan
in front.
Cove:,a'_ls Vinyl plastic. One piece lightweight Mine Safety Appliance Company
disposable unit. Gre- color.
C aps Dacronaor c, Basebail type, with re- Worklon, Inc.
movable sunshade for neck.
Dynel Fabric. Chem-Wear
Mine Safet y Appliance Compan y
Hood mil vinyl me,;nacry ate window, detach- Milburn Co.
able head 'band, adJustable for size. I rolt ^, Michlgar.
Impermeable er n^"tayns er, :le oprene coated S. ao er o.
Jacket Nylon, MRS-107 Washington, Ind,
impermeable er n y ns er, O-1
— U. S. Ruîêr o.
Overalls
Table F.18
Outdoor Winter-weight Protective Clothing for Wear by Personnel at HBO, Handling Areas
Item Description Source
Shirts 55% Dacron - 45% ''Wool Worclon, Inc,
5 ort-t e shirt of st rene buttons. New York 1 N.Y.
Trousers acron - 4 Wool No pocxe`s, cuffs Worklon Inc.
Cap acron pile lining, ou..e^r mare Borg Fa r c^^-W. Bores
Dela y sn Wiec.
Jacket 10 Dacron pile lining, outer material Borg Fabric Div.
rants
-
r' """"^'—n +r n r^ter--. -_
Boots Neoprene, Insulated boots. Similar to -Hood Rubber Company

U. S. Arne all rubber, Insulated Watertown, Mass.
combat boots
F-19
I
Table F.19
Recommended Joint Sealing Compounds for Use with Becco 90% and 98% Hydrogen Peroxide
:Jane Supplier Formulation Class Remarks
Dixseel Dixon Corporation Teflon. 1 Suitable for small pipe

service
T-Film Eco Engineering Co. Dispersion teflon 1 Suitable for small pipe
- water service
Teflon tape Various Teflon 1 Suitable for most appli-

cations
NOTE: Use sparingly to prevent carry off into the N 2 0 2 stream.

Avoid threaded connections, use AN flares and flanges.
Compounds Not Recommended
Compound Supplier
Calbar CB Pipe Seal Calbar Paint & Varnish Company
Crane Thread Lubricant Crane Company
Fel-Fro, C -5 Felt Products Mfg. Company
Graphite Paste Key Graphite
Goop (Blue) Carl A. Pearson Company
Goop (Silver) Carl A. Pearson Company
Cyl-Seal West Chester Chemical Company
Molybdenite Pipe Dope
Permatex, Aviation Form A Gasket #3

OS-18 Lubricant Monsanto Chemical Company
Pecora Compound Pecora Paint Company
Plastic Metal #22 National Eng. Products
Rutland Pipe Dope Rutland Fire Clay Company
SkydroI Monsanto Chemical Company
Weco No-Gall Well Equipment Manufacturing Co.
X-Pando X-Pando Corporation
Kel-F Grease #90 Minnesota Mining and Manufactur-

ing Company
Tin Plating on Aluminum 6061

Alcoa Thread Lubricant Alcoa
Rectorseal No. 15 Rector Well Equipment Company,

Inc.
F-20
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1
I F3.0 References
FMC. Materials of Constructionfor Equipment in Use with Hydrogen Peroxide. Bulletin No. 104,
1966 Revision. FMC, Industrial Chemicals Group, Philadelphia, Pennsylvania (1966).
J
1
1
I F-22
I
Form Approved
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1. REPORT DATE (DD-MM-YYYY)
01-01-2005
4. TITLE AND SUBTITLE
2. REPORT TYPE
NASA Technical Manual
3. DATES COVERED (From - To)
5a. CONTRACT NUMBER

Fire, Explosion, Compatibility, and Safety Hazards of Hydrogen Peroxide NASA-9-99100
5b. GRANT NUMBER
1 6. AUTHOR(S)
5c. PROGRAM ELEMENT NUMBER
1
5d. PROJECT NUMBER
David Baker, Ben Greene, Mark McClure, Steve Hornung, Kurt Rathgeber
5e. TASK NUMBER
1 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

5f. WORK UNIT NUMBER
8. PERFORMING ORGANIZATION
1 Lvndon B. Johnson Space Center REPORT NUMBER
S-936
1 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING/MONITOR'S ACRONYM(S)
1
National Aeronautics ad Space Administration
Washington, DC 20546-0001
11. SPONSORING/MONITORING
REPORT NUMBER
1 12. DISTRIBUTION/AVAILABILITY STATEMENT

Category: 20, Available from the NASA Center for AeroSpace Information (CASI)
TM-2004-213145
1 7121 Standard
Hanover, MD 21076-1320
13. SUPPLEMENTARY NOTES
1 14. ABSTRACT
1
High-test hydrogen peroxide (HP) is an energetic liquid with widespread use in a variety of industrial and aerospace applications. In
recent years, there has been increased interest in its use as a "green" or environmentally benign propellant in spacecraft and defense
propulsion and power systems. HP, however, can be a significant hazard if not properly handled. In addition, hydrogen peroxide is
unstable when exposed to trace contaminants, which may catalyze decomposition and result in violent thermal runaway. Many
1 advanced and newly developed alloys, polymers, composites, and other construction materials (such as those used in tankage and
piping systems) have not been tested for compatibility with hydrogen peroxide. The reliability of extrapolating from short-term
compatibility test results to long-term compatibility has not yet been fully assessed. Therefore, the users and designers of HP systems
must be aware of these hazards and unknowns and take the appropriate precautions.
1 15. SUBJECT TERMS
1 MMRB, tlujd dynamics, CFD, computational fluid dynamics, Laser Doppler Velocimeter, fluid jet, fluid shear level, torque
1 16. SECURITY CLASSIFICATION OF:

a. REPORT b. ABSTRACT c. THIS PAGE
Restriction/Classification Cancelled
17. LIMITATION OF
ABSTRACT
18. NUMBER 19b. NAME OF RESPONSIBLE PERSON
OF
PAGES David L. Baker
19b. TELEPHONE NUMBER (Include area code)
i Restr d 3 Ooo (505) 524-5605

Standard Form 298 (Rev. 8-98)
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This report is also available in electronic form at http://ston.jsc.nasa.gov/collections/TRS

1.0 Hydrogen Peroxide Hazards Introduction .................................................................. 1-1

2.0 Fire and Explosion Hazards .......................................................................................... 2-1

2.1.4 Minimum Ignition Energies and Ignition Sources .................................................. 2-2

2.3.5 Hydrogen Peroxide with Additives ......................................................................... 2-15

3.2.2 Reactions with Organic Materials ........................................................................... 3-11

3.2.4 Passivation .............................................................................................................. 3-14

3.3 Guide to Data Tables ....................................................................................................... 3-22

3.4 Data Tables ...................................................................................................................... 3-22

4.1 Exposure Guidelines ........................................................................................................ 4-1

4. 1.1 Threshold Limit Values of the ACGIH .................................................................. 4-1

4.1.3 Recommendations of NIOSH ................................................................................. 4-2

4.1.4 SARA Title III ........................................................................................................ 4-3

4.2 Toxicity ............................................................................................................................ 4-4

4.2.1 Routes and Results of Exposure to Hydrogen Peroxide ......................................... 4-5

4.2.2 Teratogenic and Reproductive Toxicity .................................................................. 4-6

4.2.3 Carcinogenicity ....................................................................................................... 4-7

4.3 Exposure Remediation and Control ................................................................................. 4-7

4.3.1 Personnel Protection ............................................................................................... 4-7

4.3.2 Medical Aid ............................................................................................................ 4-8

4.3.3 Fire Fighting ............................................................................................................ 4-11

4.3.4 Spills ....................................................................................................................... 4-16

4.4 Environmental Fate of HP ............................................................................................... 4-17

4.4.1 Soil and Sediment ................................................................................................... 4-17

4.4.2 Atmosphere ............................................................................................................. 4-18

4.4.3 Aquatic .................................................................................................................... 4-18

4.5 HP Handling ...................................................................................... ............................... 4-18

4.5.1 Personal Protective Equipment ............................................................................... 4-18

4.5.2 Respiratory Protection ............................................................................................ 4-21

4.5.3 Monitoring Equipment ............................................................................................ 4-23

4.6 Engineering Design .......................................................................................................... 4-26

4.6.1 Process Safety Management ................................................................................... 4-27

4.6.2 Assembly Guidelines .............................................................................................. 4-28

4.7 Cleaning and Passivation ................................................................................................. 4-29

4.7.1 Procedures for the Passivation of Glassware .......................................................... 4-30

4.7.2 Procedures for Passivation of Metals and Materials ............................................... 4-31

4.8 Laboratory Design ........................................................................................................... 4-37

4.8.1 Building Codes ........................................................................................................ 4-37

4.8.2 Other Legal Requirements and Codes .................................................................... 4-37

4.8.3 Environmental ......................................................................................................... 4-37

4.8.4 Controlling HP Vapor Emissions ........................................................................... 4-38

4.8.5 Controlling Liquid Effluents ................................................................................... 4-38

4.8.6 Design Features for an HP Testing Laboratory ...................................................... 4-38

4.9 Storage of HP ................................................................................................................... 4-39

4.9.1 Storage Areas and Containers ................................................................................. 4-39

4.10 Shipping of HP (DOT) ................................................................................................... 4-46

4. 10.1 Proper Shipping Name .......................................................................................... 4-50

4.10.2 Packaging Containers ............................................................................................ 4-50

4.12 Regulatory Enforcement ................................................................................................ 4-52