Olin NaClO Handbook
Olin NaClO Handbook
Olin NaClO Handbook
SODIUM
HYPOCHLORITE
MANUAL
January 2016
Locations
Olin has multiple sites throughout North America that manufacture sodium hypochlorite solutions,
commonly referred to as “bleach.” The capabilities of these sites are similar with slight differences in
the grades of product available to meet specific market needs. Olin is uniquely positioned to service
your sodium hypochlorite needs as a true North American manufacturer with production facilities,
terminals and joint ventures located throughout the United States and eastern Canada. Production
sites representing Olin and our chemical distribution business, K. A. Steel Chemicals, are shown on
the map included in this section. With the capability of railcar shipments, we can ship anywhere in this
geography. For more information about your specific needs, contact an Olin representative.
Product Grades
Sodium hypochlorite solution grades are typically defined by differences in product assay and/or
alkalinity content. From an industry perspective, solution strengths of 12.5 and 15.5 weight percent as
NaOCl represent the two most common grades of product. Olin offers a variety of different product
grades depending upon industries served and local market demands with 12.5 and 15.5 weight
percent as NaOCl solutions being the most prevalent. Several of the Olin production facilities
incorporate additional blending systems that provide the ability to customize the assay and alkalinity
component concentrations to meet particular application requirements.
Olin’s sodium hypochlorite solutions are well-suited for use in a variety of industrial and municipal
applications. We offer product certification upon request for various industry and regulatory standards
including the American Water Works Association (AWWA B300), National Sanitation Foundation
(NSF standard 60 requirements), as well as U.S. EPA pesticidal registration. Contact your Olin sales
representative to discuss specifications, certifications, and product grades available in your particular
market.
Table 1
Equivalent
Wt% NaOCl Wt% AvCl2 g/L AvCl2 Trade % Density (Theoretical)
Cl2
(g (g
(g AvCl2/100 (lb Cl2/gal
NaOCl/100g AvCl2/100g (g/L soln.) g/ml lb/gal
mL soln.) soln.)
soln.) soln.)
Note 1 Note 1 Note 1
9.00 8.6 97 9.7 0.81 1.134 9.46
10.04 9.6 110 11.0 0.92 1.150 9.59
10.84 10.3 120 12.0 1.00 1.163 9.69
11.00 10.5 122 12.2 1.02 1.165 9.72
11.23 10.7 125 12.5 1.04 1.169 9.75
12.38 11.8 140 14.0 1.17 1.187 9.90
12.50 11.9 142 14.2 1.18 1.189 9.91
12.76 12.2 145 14.5 1.21 1.193 9.95
13.00 12.4 148 14.8 1.24 1.197 9.98
13.13 12.5 150 15.0 1.25 1.199 10.00
13.87 13.2 160 16.0 1.33 1.211 10.10
14.00 13.3 162 16.2 1.35 1.213 10.12
15.50 14.8 183 18.3 1.52 1.238 10.32
16.00 15.2 190 19.0 1.58 1.246 10.39
16.70 15.9 200 20.0 1.67 1.258 10.49
One of the complicating factors in converting units involves the role of the density in the calculation.
Some units of measure, such as weight percent (wt%), compare the weight of NaOCl (gram) to the
solution weight (100 grams) while other units, such as grams per liter (g/L), compare the weight of the
NaOCl (grams) to the solution volume (liter).
When converting between these units, the density of the solution must be used in the calculation.
Because there is no direct relationship between density and concentration for sodium hypochlorite
Density
Density is a prevalent analytical tool used in petroleum and some chemical industries to quickly
identify contaminations and correlate product quality without the use of expensive laboratory
instrumentation or performance of time-intensive “wet chemistry” tests. Appropriate applications for
use of density determination in sodium hypochlorite should be well-understood and judiciously
chosen. When determining weight-based calculations, performing an actual density analysis is critical
to predicting the most precise assay value for a just-collected sample as discussed in the preceding
paragraphs. However, the unique nuances associated with chemical composition and production, as
well as the decomposition attribute of sodium hypochlorite, can lead to erroneous conclusions when
density is incorrectly used to predict hypochlorite solution assay.
Sodium hypochlorite density is affected by a variety of factors. The sodium hydroxide used in
hypochlorite manufacture includes a number of dissolved components, such as sodium chloride and
sodium carbonate that can vary significantly depending upon the grade and production source used.
Changes in sodium hydroxide sourcing or in the amount remaining in the hypochlorite solution for
stability will measurably change the density of the hypochlorite solution. Chlorination efficiencies also
can affect hypochlorite density, as the amount of salt and chlorate relative to the amount of
hypochlorite will change with chlorination efficiencies. Well-controlled manufacturing processes
typically demonstrate consistent product densities if all other variables are held constant. However, a
change in any variable—sodium hydroxide quality/source, manufacturing technology (automated
versus batch process), or even different production systems from the same manufacturer using the
identical raw materials and technology will result in a different density “fingerprint.”
Sodium hypochlorite strength is time dependent, with all solutions starting to lose assay immediately
after production. Unlike hypochlorite strength, density will remain unchanged over time. For
immediately produced product, density will generally correlate with assay. However, the correlation
will continue to change as the solution ages and will yield increasingly erroneous conclusions the
older the hypochlorite solution is. Other factors such as metallic content of the hypochlorite,
temperature exposure, and solution age become increasingly critical with time because product assay
is significantly affected by these contributors. These attributes provide the rationale explaining why an
aged hypochlorite solution will have a significantly different assay than a freshly produced one, but
density of the solutions will remain unchanged. As a result, hypochlorite solution density (or
specific gravity), should not be specified in chemical purchase specifications or acceptance
criteria because it is not a reliable predictor of sodium hypochlorite strength. When precision
is required for determining strength, assay titration is preferred.
For applications where density must be determined, there are several different test methodologies
available, including density meters, hydrometers, or use of a pipette-and-weigh combination. When
Eye Contact
Immediately flush eyes with copious amounts of water for at least 15 minutes. Hold eye lids open to
facilitate irrigation. If contact lenses are present, begin eye irrigation immediately and remove contact
lenses as soon as practical. Do not delay irrigation while waiting for contact lens removal. Do not add
other agents to the eyes without medical direction. Seek medical attention immediately.
Skin Contact
Immediately flush with copious amounts of water for at least 15 to 20 minutes. If there is sodium
hypochlorite on the head and face, do not remove goggles until this area has been thoroughly flushed
with water. Remove clothing and jewelry that have come into contact with sodium hypochlorite and
continue water flushing. Seek medical attention immediately. Wash all contaminated clothing before
re-use.
Ingestion
Do not induce vomiting, and never give anything by mouth to unconscious persons. Rinse mouth with
water. Seek medical attention immediately.
Inhalation
Move to fresh air and seek immediate medical attention.
Spill Recovery
Spill clean-up methods will vary depending upon factors such as quantity involved, potential for off-
site impact, expertise of the first responders, and whether the spilled material is contained. Special
care must be exercised when attempting to contain, neutralize, and dispose of sodium hypochlorite
spills. Spill mitigation may manifest itself in the form of recovery/reuse, dilution, absorption,
neutralization, or a combination of these actions.
If the end-application is not sensitive to impurities obtained from the spill event, reuse is often a
preferred method because remediation costs are minimized and the initial value of the product is
recovered. In events where small quantities of spillage occur, spill dilution with water may be favored.
However, for large spill quantities, dilution is generally not favored because of the tremendous
increase in total volume resulting from massive water addition.
The strong oxidizing power dictates that any absorbent material must be chemically inert to sodium
hypochlorite. Avoid use of items such as sawdust and rags, which can react with sodium hypochlorite
under certain conditions, and materials such as “floor dry,” which typically contain organic
components. Spill collection equipment, such as shovels or recovery drums, should be verified clean
and void of incompatible residues.
Never introduce sodium hypochlorite to local sanitary treatment plants or bodies of water without
proper approvals. Sodium hypochlorite can irreparably disrupt the biological processes of sewage
treatment operations and will result in harm to aquatic life. Chlorine gas also might be released at the
treatment plant if acidic waters are encountered by the hypochlorite. Processing and containment
area drains should be periodically reviewed to ensure protective features such as engineering and
procedural controls are in place to prevent automatic release.
Neutralization
Neutralization is often favored for larger quantity spills, those which are heavily contaminated and
cannot be re-used, or in situations where the resulting neutralized solution will be sent to a waste
water treatment plant. Neutralization methods for spill events described in this publication are not
intended to treat bodily exposures. Although the result of neutralization is a less-hazardous material,
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the process itself involves other chemicals, rapid reactions, and in some instances the potential to
generate other gases and hazards. When neutralizing hypochlorite solutions, safety must be an
integral component throughout the process. Because of the potential for aggressive reactions, only
well-trained personnel should attempt neutralization. Completing a hazard analysis before work
commences will help identify the critical engineering and procedural controls necessary for safe
neutralization.
There are a number of chemical options for neutralizing sodium hypochlorite, including sodium sulfite,
sodium bisulfite, sodium thiosulfate, hydrogen peroxide, and sulfur dioxide. Regardless of method
chosen, the sequence of neutralization steps is critical. To prevent generation of chlorine gas, always
neutralize the hypochlorite solution before lowering solution pH.
Disposal
Sodium hypochlorite must be properly handled, including during spill clean-up events. Proper clean-
up and disposal requires that liquids, residues, and neutralized materials are handled, stored,
transported, and disposed of in accordance with local, province, state, and federal regulations.
Consult the most current Safety Data Sheet for additional guidance.
Shipping
Each of those listed above plays an important role in the safe shipment of hazardous materials.
Shipping Containers
Sodium hypochlorite solutions are shipped in a wide variety of container sizes, bulk and non-bulk, to
meet customers’ needs. Olin currently ships product only in tank trailer and railcar bulk containers.
Olin personnel are available to help you determine which type of delivery method best suits your
company’s needs.
Tank Trailers
Olin contracts with trucking companies to deliver sodium hypochlorite solutions by tank trailer (cargo
tank). In some areas of the United States, Olin operates its own trucking fleet for delivery of the
product. Tank trailers used in sodium hypochlorite service must meet standards issued by the
regulatory agencies (U.S. DOT, Transport Canada) and include equipment that conforms to the MC-
307, DOT-407, MC-312, and DOT-412 designations. While tank trailer capacities can vary
significantly, they usually contain about 5,000 gallons of product based on over-the-road weight
limitations. The two major trailer constructions are rubber-lined steel and fiberglass reinforced plastic
(FRP) tanks with a compatible resin corrosion barrier. Product unloading configurations include
bottom discharge or a top-unloaded dip-leg arrangement.
Olin sodium hypochlorite trailers typically have a double valve arrangement on the unloading line and
are configured for bottom-unloading. The internal valve is pneumatically or hydraulically operated and
can be closed remotely in case of an emergency. The unloading connections on each tank trailer are
typically located at the rear. A data plate specifying tank fabrication, inspection, and other regulatory
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information is located on the driver’s side of the trailer frame near the front. Transport regulations
require these trailers to be inspected periodically (includes internal and external visual inspections as
well as leak, thickness and pressure testing) and that inspection dates be stenciled on the front head
of the trailer. Tank trailers can be unloaded by the driver or by properly trained employees
(DOT/Transport Canada function-specific) at the customer’s or end user’s facility. Clearly defined
procedures should be followed to ensure communication and coordination between the driver and the
appropriate customer/plant representatives. Delivery tractors are equipped with an air compressor for
pneumatic product transfer. Pumps are not provided with delivery equipment for unloading.
Railcars
In 2007 Olin added railcars to its shipping mode. This proprietary fleet of specially designed railcars
maintains sodium hypochlorite quality throughout the shipment cycle. This Olin innovation, along with
process capabilities, has allowed the creation of a bulk distribution paradigm to reach distant
marketplaces effectively. The typical shipping volume by railcar is approximately 17,500 gallons.
Numerous, important regulatory, environmental, safety, and health informational items are available
on each railcar. Tags and stenciling display required regulatory, car maintenance, and operating
information as well as safety, spill mitigation, and first-aid information along with emergency response
contacts.
Olin’s entire rail fleet is designed for top unloading only. The specific unloading method and additional
requirements are described in separate white papers available for reference and future discussions.
Unloading Stations
Unloading stations for receipt of tank trailer and railcar shipments should be designed with safety and
operational efficiency in mind. In general terms, either delivery mode requires appropriately located
safety shower and eyewash stations, adequate lighting for possible night-time work, filtered pad gas,
adequate secondary containment, chemically compatible transfer hoses and connectors, and a
source of rinse water to facilitate product residue removal. The ideal site design will minimize the
length of hose required for shipping container unloading as well as the pipe run for delivery of product
to the tank.
Tank Trailers
Tank-trailer serviced unloading stations should be laid out to provide easy access to the receiving
pipeline connection. Where possible, drive-through unloading stations wherein backing of the trailer
into the unloading station can be avoided is preferred. In-plant street access should be designed to
accommodate tractor/trailer combinations and incorporate wide intersections. Reinforced concrete
unloading pads sloped to a containment device such as a dedicated sump, French drain, or the like
provide a hard surface for trailer parking and an effective means to collect and contain product
drippage that might occur during the unloading process. Where multiple chemicals are received in the
same area as sodium hypochlorite, engineering and/or procedural provisions should be incorporated
to avoid mixing of incompatibles.
Receiving pipelines for tank trailers are typically installed approximately three feet above grade, (hip
level). A two-inch male, quick connect fitting is standard for customer receiving locations and should
include a block valve to prevent possible chemical drain-back when the delivery hose is disconnected.
Placement of a drain valve in the receiving pipeline can facilitate safe sample collection during the
unloading process. Quick-connect fittings should be of fluoropolymer-lined stainless steel or high
density polyethylene (plastic) construction. To minimize the ”mechanical hammer” and torque stresses
exerted on the receiving connector and pipeline during the unloading process, installation of the
receiving connector at a 22.5- or 45-degree downward angle is suggested. Angled receiving
connectors are especially beneficial when ‘plastic’ components are used.
Railcars
Railcar unloading stations should incorporate level track to maximize product transfers. An elevated
platform with a folding gangway and fall protection cage should be available to enhance worker safety
and expedite efficiency. Pad gas piping and filtration devices, and the receiving pipeline are typically
located within arm’s reach of the unloading platform which limits hose length and associated clutter,
while maximizing convenience for component access.
Railcars require a three-inch, four-bolt flanged connector to attach to the product outlet valve.
Because of the elevated potential for ”mechanical hammer” and other unloading stresses, the transfer
hose requires a robust support system in place to limit stresses on the railcar connection. Because of
these unloading stresses, a fluoropolymer-lined, flanged metal connector is preferred for railcar
unloading. Federal regulation (DOT- 49CFR 177.834 (i) and Transport Canada (CSA B622) require
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shipping containers to be continuously monitored during the entire unloading process by a qualified
person located within 25-feet of the transfer. Where staffing is limited, use of unloading station
surveillance cameras could be considered for monitoring the unloading process.
Figure 1 illustrates the key features required for railcar pad air supplies. A customer-supplied pad air
system for tank trailer unloading is identical except for the use of a 1-inch air hose and pinned crow’s
foot connector (Chicago coupling).
Because of the sensitivity of sodium hypochlorite to pad air contaminants, all system components
including the air compressor, air cooling and water drainers, pre- and after-filters, air drying and point-
of-use pad air filters/condensate drainers should be evaluated to determine appropriate equipment
upgrades. System operation also should be evaluated because oil/water/particulate loads can vary
under start/stop conditions. The minimum requirement for sodium hypochlorite shipping
container pad air is ISO STANDARD 8573 – 1 (ISO Class 1) noted in red inside Table 1. Note
that the air does not have to be “dry” to a specific dew point, only “water droplet free.”
Table 2
International ISO Standards ISO 8573-1
Particulate Water Oil
Class Max. Size Max. Conc. Max. Press. Dew Point Max. Conc.,
µm ppm / mg/m3 °F / °C ppm / mg/m3
1 0.1 0.08 / 0.1 -94 / -70 0.008 / 0.01
2 1 0.80 / 1 -40 / -40 0.08 / 0.1
3 5 4.20 / 5 -4 / -20 0.83 / 1
4 15 6.70 / 8 37 / +3 4.2 / 5
5 40 8.30 / 10 45 / +7 21 / 25
6 - - / - 50 / +10 - / -
High-pressure pad air can over-pressure the shipping container, resulting in activation of the safety
relief device and chemical leakage. The pad air should be regulated to a maximum of 25 psig for both
railcar and tank trailer unloading activities and be protected with a pressure relief device downstream
of the regulator.
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The primary isolation valve (see Figure 1) marks the piping specification breakpoint between
components designed for standard pad air service and components designed for sodium hypochlorite
vapor, and should be constructed of lined steel as discussed below. All components downstream of
this valve must be designed to accommodate possible exposure to sodium hypochlorite vapors.
Downstream of the point-of-use filter, lined metallic piping or titanium must be used. Iron, galvanized
steel, copper or other common pad air piping materials will corrode and re-introduce contaminants
downstream of the filter. These materials should be avoided in their unlined versions downstream of
the point-of-use filter location. For a lined piping system, the liner offers the chemical resistance
needed while the metallic piping provides the structural strength. Liners such as polyethylene, Teflon®
polymer (PFA, FEP, PTFE), PVDF (fluorinated polyvinylidene or Kynar® polymer) and PVC/CPVC
(polyvinylchloride/chlorinated polyvinylchloride), etc., are compatible with sodium hypochlorite. A
careful evaluation of material of construction compatibility with sodium hypochlorite should be
completed during the liner selection process because product vapors can potentially back feed into
the pad air piping system under certain conditions.
The preferred hose fitting for the railcar padding connection is a four-bolt, 150-pound, two-inch flange
permanently affixed to the hose. A flanged adapter equipped with a quick-connect fitting for
attachment to the pad air hose is a variation that may be a desired alternative. Fluoropolymer-lined
stainless steel fittings are preferred as they offer enhanced mechanical strength, are chemically
compatible and can safely manage stored energy and stresses. Tank trailers are typically connected
to the pad air supply hose via a one-inch “crow’s foot” connector (or Chicago coupling) appropriately
pinned to ensure a secure connection.
A timely and effective preventive maintenance program (see Table 3 Inspection Guidelines) is critical
for ensuring delivery of clean, water-droplet-free and oil-free pad air to the shipping container over the
long term. Several general guidelines are applicable regardless of equipment or operating conditions.
Maintenance guidelines issued from the compressor manufacturer should be consulted and typically
represent the minimum frequency at which maintenance should be performed. In addition to
performing scheduled component maintenance, a ”white-rag” test should be performed at least once
monthly to provide redundant verification of proper system operation. When performed correctly, a
clean ”white rag” should be used to collect the compressed gas stream at regular, full-flow rates for a
duration of –one to two minutes. Any discoloration will provide indications of a malfunctioning filtration
system.
In addition to providing clean, filtered pad gas (air), all air sources should be regulated to prevent
potential overpressurization of the shipping container. A 25psig pressure regulator setting (maximum)
is suggested for both tank trailer and railcar unloading stations. Installation of a safety relief valve,
installed downstream of the pressure regulator, can provide an added layer of protection against over-
pressurization should the regulator fail.
Pumps
Pumps are typically selected based upon service. Centrifugal, diaphragm, canned, and magnetically
driven pumps are more common for high-volume transfers or for recirculation-type activities whereas
positive-displacement and peristaltic designs are more common in metering applications. Regardless
of application, all internally wetted components must be sodium hypochlorite-compatible materials,
and the use of all metals except titanium must be avoided. Non-metallic materials such as Teflon®,
Tefzel®, Halar®, or Kynar® polymers, and polyvinylchloride are common internal components for
pumps.
Design features are influenced by the type of pump selected. Positive displacement pumps should
incorporate a pressure relief device to protect against ‘dead-heading’ situations whereas mechanically
sealed centrifugal pumps should employ a seal/shaft shroud to help prevent potential seal leakage
from being slung onto nearby personnel or equipment. A low-amp cut-off switch should be considered
for magnetically driven pumps to protect against “burn-out” resulting from operating under damaging
low or no-flow conditions.
Although piston, gear, and peristaltic positive displacement pumps are most frequently used in
metering situations, all pump styles have been used successfully in these situations. The overriding
factor in determining which type of pump to use may lie in past plant experience. The pump type most
familiar to maintenance personnel and for which spare parts are readily available may be the best
choice. A centrifugal pump coupled with a measuring device (rotameter, mag meter, or mass flow
meter, etc.) may prove easier to calibrate and more compatible with automated control systems than
metering pumps. Without an independent flow-measurement device, metering pumps require routine
calibration to ensure accurate output.
“Vapor lock” caused by entrained gas can be a problem with centrifugal, diaphragm, and peristaltic
pumps, especially in low-flow metering applications. Typically, entrained gas is a result of trace-metal-
induced product decomposition (oxygen gas formation), so efforts to eliminate the source of such
contamination would be the preferred solution. However, this problem can be minimized by sloping
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pump intake piping so that entrained gas bubbles move away from the pump suction or by employing
other means of separating entrained gases before liquid reaches pump suction.
Valves
Selection of valve type will depend upon the intended application. Materials of construction range from
fluoropolymer-lined steel valves to plastic. Where cavity valves, such as ball or plug designs are used,
a vented valve design should be employed to prevent pressure buildup and potential valve or piping
damage resulting from metallic-induced decomposition of sodium hypochlorite and associated buildup
of decomposition gases. Vented valve body designs will also be critical in pipe runs wherein sodium
hypochlorite liquid or residues may remain trapped between closed valves. Storage tank outlets
should be equipped with positive shut-off capability and avoid the use of “butterfly” designs. Flanged
or glued valves are preferred over threaded valves as they eliminate the threaded area, which is a
potential leakage point.
Piping
When making initial decisions about piping, it is critical to select the appropriate material of
construction because sodium hypochlorite is incompatible with all metals except titanium. Use of
nonmetallic materials throughout is often embraced when only economic and compatibility
perspectives are considered. However, the role of external stresses in pipe life, effective means to
mitigate their detrimental effects, and the mechanical abilities of the organization should be evaluated
before choosing pipeline materials. Exposures to direct sunlight and wide temperature extremes, to
identify just two common examples, are external stresses that can weaken non-metallic piping and
lead to premature component failure. Consideration for lined-steel or titanium at critical points in the
piping system where mechanical stresses are a routine part of the operation may be warranted, such
as the quick-connect hose fittings for unloading and the initial portion of the fixed unloading line.
Employing a more robust pipeline inspection, maintaining detailed records of installation dates and
significant inspection findings, and assigning a scheduled replacement cycle should be every user’s
goal when non-metallic components are favored.
Design Considerations
Installation
Where possible, pipe runs should be installed to eliminate the presence of low points because product
left standing in pipelines can experience product decomposition (oxygen generation and chlorate
formation) when not in use. Where low points cannot be avoided, installation of drain valves
discharging to a suitable containment system should be considered. Piping feeding metering pumps
creates a special situation wherein oxygen gas formation can result in pump vapor lock. Installation of
suction piping sloped up away from the pump can minimize gas collection and associated cavitation
concerns. Placement of underground piping inside of an impermeable trench with adequate
removable covers will afford convenience in performing mechanical inspections and maintenance,
while providing secondary containment. Threaded pipe should be avoided as the pipe wall section
containing the threads is thinner and more prone to failure or leakage.
Glues
Sodium hypochlorite will attack the fumed silica additive used as a thickening agent in some glues or
cements intended to join PVC/CPVC (polyvinyl chloride and chlorinated polyvinyl chloride)
components. Because of the likelihood of joint separation or leakage, only glues/cements which are
fumed silica-free should be used. Containers for these glues typically indicate their compatibility with
oxidizers and alkalis. Proper preparation of the surface and application techniques for the primer and
cement are important, but often overlooked, aspects of pipe installation. Proper preparation of the
glued joint is critical to long-term performance. Diligently follow the glue manufacturer’s guidance for
all assembly steps.
Labeling
Labeling of pipelines provides critial information regarding the intended contents and associated
product hazards. General pipeline labeling indicating the product and flow direction can be especially
helpful when performing line-tracing activities. The labeling of receiving pipelines is particularly
important because it can provide an additional layer of protection against accidental delivery of the
wrong chemical by providing a visual reference of intended contents for delivery and unloading staff.
For maximum impact, receiving pipelines should be clearly identified near the delivery hose
attachment point and include the words, “Sodium Hypochlorite” and “UN 1791.” This label terminology
incorporates the information found in bills-of-lading and other delivery paperwork, and therefore allows
the delivery driver and site unloading staff to compare delivery documents against the receiving
pipeline label and shipping container placard. Consult The Chlorine Institute’s bulletin, “Avoiding
Accidental Mixing of Sodium Hypochlorite,” at www.chlorineinstitute.org for additional details.
Materials of Construction
There are a number of acceptable materials of construction for sodium hypochlorite piping systems.
Each material of construction presents unique attributes, and in some instances requires special care
in installation and inspection to help ensure successful long-term use. Structural strength, chemical
resistance, and operational conditions are important factors to consider when selecting piping
materials of construction.
Because of their superior structural strength, metals are widely used in piping service for many alkali
chemicals. However, unlike many alkalis, sodium hypochlorite is highly reactive with most metals and
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metal alloys and is compatible only with titanium or tantalum metal. Lined-steel piping using
thermoplastics such as polypropylene, polyvinylidene fluoride (PVDF or Kynar® polymer) or
polytetrafluoroethylene (PTFE or Teflon® polymer) as the liner is often used as an alternative pipe
material for portions of the systems where mechanical stresses or impacts are expected. The initial
portion of the receiving pipeline, especially near the hose connector where external stresses are
expected to be more significant, is often chosen for lined metal.
PVC and CPVC are chemically compatible, nonmetallic materials often used in lower-mechanical
stress applications. Certain specialty grades of polyethylene also have been successfully used in
sodium hypochlorite service. Pipe specifications should be at least schedule 80 or higher for most
applications. Mechanical impact from hazards such as liquid/gas mechanical hammer, temperature
expansion/contraction cycles, pressure surges from pump start-up and operation, sunlight/ultraviolet
light degradation, and potential foot or vehicular contact should be carefully considered when
selecting PVC/CPVC for sodium hypochlorite service. PVC/CPVC materials are sensitive to these
types of external stresses and if not properly installed, supported, and inspected, can often fail
unexpectedly during use.
For end-use applications such as dosing meters, small diameter PVC/CPVC piping is often used. As
with larger diameter piping, proper support is required. A protective enclosure such as a conduit or
equivalent device should be used where foot or vehicular traffic is likely.
Most polyvinyl chloride monomers have recommended temperature ranges which should not be
exceeded. In many instances, ambient conditions exceed these recommendations and elevate the
risk of fracture. A related factor is ultraviolet damage as a result of long-term sunlight exposure.
Repeated sunlight exposure will weaken monomer bonds, making the pipe more prone to fracture.
Consult with your pipe vendor for added guidance.
Fiberglass reinforced plastic (FRP) has been used successfully in hypochlorite service, but it requires
extreme diligence in carefully managing all aspects of fabrication and installation. Successful service
is typically dependent upon fabricator experience (those specializing in manufacturing pipe expressly
intended for sodium hypochlorite), selecting the correct resin composition and the curing process
(avoiding cobalt napthenate chemical cures), and using certified installers that employ stringent
quality assurance methods, to name several critical aspects.
Tanks
The tank selection process has a number of important components to consider. While many are
obvious, others are not intuitive because of the unique attributes of sodium hypochlorite. Tanks should
be located to minimize piping runs, accommodate shipping container movement for inbound
deliveries, and be installed in secure areas to avoid tampering/vandalism concerns. Local, state, and
federal environmental regulations should be reviewed before tank installation. Local building codes
and fire regulations also may influence tank farm construction and location.
A part of the process of the purchase and installation of a new storage tank should be planning for
future inspection and replacement. Accurate records about the particulars of the tank design
(drawings and notes) and materials of construction should be provided to those responsible for
ongoing maintenance and inspection of each tank. The tank vendor should be asked to supply
recommendations for initial inspection scheduling and tank life expectancy. Proper replacement timing
should always be intended to replace the vessel well before the end of its expected useful life.
Design Considerations
Sizing
As part of the storage system strategy, the vessel should be large enough to easily accommodate a
full inbound bulk shipping container and compensate for likely transit times and tank heels. A general
rule of thumb is to size the tank at least 1.5 times as large as the full bulk shipping container to
maximize freight savings and have ample room to avoid tank overflows during filling. However,
consumption rates also should be considered because of the decomposition nature of the product.
For low volume requirements or where the tank is subjected to high ambient temperature and sunlight
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exposure, a smaller tank volume might be appropriate. Vertical tank designs, rather than horizontal,
are preferred.
Venting
Adequate venting is critical for ensuring a rapid release of air surge when tanks are filled via
pneumatic transfer. The tank will be subjected to a nearly immediate, large volume of compressed air
at the end of the shipping container unloading process using pad air as the motive force. Compressed
air surges approaching 1200 SCFM, (Standard Cubic Feet per Minute) are typical from tank trailers,
for example. Without an adequately sized vent, the tank will temporarily act as a pressure vessel,
which can lead to tank wall flexing to accommodate the pressure load. Repeated flex cycles can
weaken tank walls and could lead to catastrophic tank failure.
As a general guide, tank vent diameters should be at least twice (2X) the size of the inlet piping
diameter. Factors such as the length of the vent piping and number of turns can impede the release of
compressed air and will require further upsizing of the vent. Consult your tank vendor for specific
guidance.
Overflows
If the tank becomes over-filled, overflow nozzles allow chemical that normally would spray out of the
tank vent or man-way opening in a wide and undirected pattern to be safely channeled via directional
piping into the containment system. Overflow nozzles and directional piping are generally sized at
least 1.5 times (1.5X) larger than the inlet pipe to ensure adequate capacity. Overflow nozzles should
be installed below the roof line and on the sidewall of the tank. This overflow piping should discharge
near ground level in an area and direction away from the typical area occupied by personnel.
Receiving Pipeline
Two-inch piping is typical for tank trailer-serviced locations, while three-inch diameter pipelines are
often used for railcar unloading to facilitate rapid product transfer. Pipe diameter guidance will vary
depending upon site layout.
Outlet Nozzles
Selection of tanks with a low-point drain should be considered. Low-point drains offer the benefits of
complete product heel removal for applications that are sensitive to product decomposition
byproducts, such as chlorate. Low-point drains also facilitate periodic internal tank inspection and
cleaning activities.
Non-metallic tanks are also easily stressed from axial and lateral forces originating from factors such
as the act of tank filling and the expansion/contraction of attached discharge piping as ambient
temperatures change. Unsupported discharge piping connected to a heavy valve can exert significant
torque on the tank’s outlet fitting area that can culminate in sidewall cracks/damage. Rigid
connections tend to concentrate these stresses in the nozzle area of the tank. Installation of proper
piping support and/or use of flexible connectors may help eliminate many of these potential tank
Level Measurement
A level measurement system is important for maintaining process operation and for avoiding a
possible overflow condition during inbound delivery. Gauging systems range from simple visual
readings to complex remote readouts. Under certain scenarios, the inventory may be read directly
from the “shadow” of a translucent, clear-tinted “poly” tank equipped with markers molded into the
side wall. External “sight glasses” can provide effective level indications. However, similar to reading
inventories from the ”shadow” of a translucent tank, use of external ”sight glasses” may also lead to
erroneous readings under certain lighting conditions. External “sight glasses,” such as polyethylene or
polypropylene tubing, also present an opportunity for catastrophic loss of tank contents upon “sight
glass” failure or damage. Differential pressure or electronic level indicators are frequently used for
tank level measurement. Level indicators that are not immersed in the product typically perform best,
but all electronic level transmitters should be assigned a scheduled, periodic recalibration cycle to
ensure accurate readings over the long term. Equipping the indicator to activate an alarm or automatic
shutoff at preset inventory levels can provide an important additional layer of protection against
accidental tank overflow conditions. The reliability of the high level alarm or automatic shutoff can be
enhanced by using an activation device independent of the regular level transmitter (redundancy).
Posting the maximum allowable storage tank volume in a location clearly visible to unloading
personnel will facilitate calculation of available volume for incoming chemical. This, coupled with a
local level readout, will allow the unloading staff (and delivery driver for tank trailer shipments) to
monitor tank levels more effectively during unloading.
Labeling
Tanks should be clearly labeled to identify chemical contents. Labels or stencils noting the entire,
formal product name, e.g. “sodium hypochlorite,” are preferred and especially beneficial to contractors
and others not intimately familiar with the tank farm. Avoid use of “Chlorine” or “Liquid Chlorine” for
identification as these terms are inaccurate and confusing. A misunderstanding may lead to
unnecessary or inappropriate precautions being taken by emergency response personnel in an actual
chemical incident. Such distractions and confusion can prevent prompt action to address the
emergency condition to which they have responded. Labels should comply with OSHA’s Globally
Harmonized System of Classification and labeling of Chemicals (GHS) or with Canada’s WHMIS
(Workplace Hazardous Materials Information System) for Canadian sites. Certain local regulations,
codes, or agencies may also dictate label content.
Tie Downs
Tanks should be adequately secured using tie downs installed from the factory to prevent tank
movement from high winds or seismic activity.
Materials of Construction
Titanium
There are a limited number of materials that are chemically compatible with sodium hypochlorite.
25 | O l i n C h l o r A l k a l i P r o d u c t s – S o d i u m H y p o c h l o r i t e M a n u a l
These materials can be categorized into metallic and nonmetallic systems. Titanium and tantalum are
the only chemically compatible metals and offer the longest lifetime. Their high cost generally limits
use except in those situations where the benefits justify the cost for critical systems components such
as reactors for product manufacture and internal components of pumps, meters, valves, etc.
Rubber-lined Steel
Rubber-lined steel tanks are often selected for high capacity vessels or ones that are subjected to
multiple fill/discharge cycles. The lining should be of a 100 percent chlorobutyl rubber composition
that has been successfully used for hypochlorite service. Rubber-lined storage tanks require a simple,
but specialized mechanical integrity test (IP-4-13 “Procedure for Spark Testing Elastomeric Sheet
Lining”) to evaluate lining integrity on a periodic basis. Exposure of lining to the product can result in
the exposed rubber surface dislodging or flaking over time. This dislodging or flaking phenomenon is
often more pronounced for tank/liner combinations that have been exposed to different chemical
service. For sensitive applications, a particulate filter on the tank discharge nozzle may be required.
Fiberglass Reinforced Plastic (FRP) is frequently used in storage applications and offers good
mechanical strength and a failure mechanism that is typically preceded by small leaks that warn of its
weakened condition. However, fabricator experience, resin, curing mechanism, and stored product
strength are important variables influencing vessel performance. FRP vessels are sensitive to
ultraviolet (UV) degradation and should incorporate the use of a UV inhibitor for tanks located
outdoors.
Hand-laid application of the reinforcement mat or chopped strand filament winding is preferred over
continuous filament wound construction. Should the corrosion barrier fail, continuous wound filament
reinforcement is at a higher risk of chemical attack via product wicking which increases the risk of
catastrophic failure. Avoid the use of cobalt napthenate as a curing agent because cobalt may
catalyze hypochlorite decomposition.
FRP tanks also can be lined with a fluoropolymer such as PTFE, PVDF, etc. or PVC to produce a dual
laminate vessel. Dual laminate construction offers the mechanical strength of FRP combined with a
robust, chemically compatible internal liner.
Poly Tanks
High-density polyethylene (HDPE), cross-linked (XHDPE) and linear (HDLPE), have been
successfully used in sodium hypochlorite service and are typically known as ‘poly’ or ‘plastic’ tanks.
However, fabricator experience, resin, product strength, “mechanical hammer,” temperature, sunlight
exposure, and pipe connection methods are important variables influencing vessel performance. If
cross-linked HDPE is used, it is important to confirm that the resin chosen is suitable for sodium
hypochlorite. Additionally, tanks should comply with ASTM D-1998, “Standard Specification for
Upright Polyethylene Storage Tanks.”
”Poly” tanks have excellent chemical resistance, but their mechanical strength is generally less robust
than alternative materials that are typically used when tank volumes exceed 10,000 gallons. Lateral
expansion and contraction of the tank wall is a significant concern with “poly” tanks as the walls will
tend to flex depending upon the product level inside the tank. The “mechanical hammer” associated
Fabricator Evaluation
The fabrication and lining processes are critical to long-term success when storing sodium
hypochlorite. Industry experience has shown merely utilizing chemically compatible material alone is
not a guarantee for lengthy tank service lifetimes. The aggressiveness of sodium hypochlorite
dictates that special evaluations of the fabricator and the material of construction should be
performed, regardless of the type of construction chosen. Fabricators should be selected based
upon 1) their experience in fabricating tanks intended for this product, 2) the performance record of
their tanks in sodium hypochlorite service, and 3) the fabrication process used.
Operation
Cleaning
Tank cleaning frequencies will be affected by factors such as the purity of the incoming product,
consumption volumes, and internal tank inspection cycles. Tank rinsing may be desired for removal of
sedimentation that can occur over time, as well as removal of residual metallic contaminants that may
adhere to tank walls after the product has been consumed. Tank cleaning and flushing needs should
be considered at the design stage so consideration can be given to the addition of a full tank drain
nozzle. A ground-level man-way also could allow for more complete removal of sediment and other
materials with use of a high-velocity water stream without the need for vessel entry.
Inspection
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future inspection and replacement scheduling. Without an understanding of the performance
characteristics of a particular material of construction and tank design under your specific storage
conditions, it is impossible to make wise decisions about the timing of future tank inspections and
replacement. Your tank vendor’s initial recommendations for the frequency of these activities may be
effectively modified by using information from well-documented inspections.
Containment Systems
A well-designed handling system should incorporate an effective secondary containment system to
contain potential drips or spills in product storage and unloading areas. Secondary containment
regulations often vary by location, so it will be important to review local codes/city ordinances, as well
as province, state, and federal requirements when considering storage of sodium hypochlorite,
whether the tank is indoors or outdoors. As a general guide, containment systems should be capable
of holding at least 110 percent of the largest tank capacity found in the contained area. Incompatible
chemicals--especially those that release hazardous gases when mixed—should be separated by walls
within the overall containment area and in the drain-system piping.
There are a number of options for secondary containment systems including concrete, double-walled
tanks and open-top containment tanks. Concrete is typically the preferred choice for bulk storage
containment systems. A well-designed system will employ reinforced floors and walls. The concrete
should be sealed with an industrial coating to extend containment lifetime and to limit the potential of
chemical migration through cracks or open expansion joints. The effectiveness of industrial coatings
will be largely influenced by the overall condition of the concrete, amount of surface preparation
before application, and the type of coating applied. Two-part epoxy coatings intended for strong
alkalis are preferred. The use of cinder blocks for containment walls should be avoided because of
their porous nature and relatively weak strength. For newly poured concrete systems, the concrete
should be allowed to fully cure and to potentially settle before surface coatings are applied.
Good maintenance and housekeeping practices that eliminate small piping or pump leaks soon after
they develop and that keep the area clean and dry will extend the life of the enclosure. Maintenance
becomes critical as minor imperfections that allow chemical to contact the concrete structure may not
be adequately rinsed away from rainfall or housekeeping events.
Double-walled tanks are often considered for vessels if there is limited room for the tank and
containment system. Use of a liquid-detection monitor in the open space between the tanks can
provide notification of internal vessel failure. The double-walled feature does, however, impede the
ability to perform important visual inspections of the tank wall.
For small capacity process or “day” tanks, an oversized, open-top containment tank can be used as
the secondary containment system. This style of containment system is available from most
nonmetallic tank fabricators and is often favored for indoor locations with limited free space or where
the presence of a concrete containment dike may make future tank replacement difficult.
Shipping container unloading stations also should incorporate secondary containment to collect leaks,
spills, or wash-down water. Reinforced concrete is generally the preferred material of choice for tank
trailer unloading station containment systems because most unloading areas must be able to
accommodate vehicular traffic weight loads. For railcar unloading, the presence of railroad ties and
the occasional need for track maintenance make removable containment pans preferable to concrete
Transfer Hoses
Bulk shipments of sodium hypochlorite will require a flexible hose to connect the shipping container to
the storage tank’s receiving pipeline. Although most tank trailer-serviced customers rely upon the
carrier to provide the transfer hose, use of customer-provided hoses remains an option. Railcar
deliveries require customers to supply the transfer hose.
Hoses should be constructed of sodium hypochlorite-compatible materials and be rated to withstand
the working pressures expected during the transfer process. Hose construction must avoid any wetted
metallic surfaces, such as pipe nipples or quick-connect fittings, because of the corrosive nature of
sodium hypochlorite and the sensitivity of this product to experience metallic-induced decomposition.
From a mechanical integrity standpoint, metallic connector components that have a fluoropolymer or
HDPE lining on the wetted surface are the preferred construction. Polyethylene, including the Ultra-
High Molecular Weight Polyethylene (UHMWPE or UHMW) subset and polypropylene are common
tube materials of construction. The choice of material should be discussed with your hose vendor
regarding expected service conditions including, but not limited to, strength of sodium hypochlorite
and likely temperature ranges to be experienced throughout a calendar year. The potential for
external surface abrasion can also influence the type of protective sheath, if any, chosen for the hose.
Hoses should undergo a visual inspection prior to each use to identify and prevent potential failures.
Use of an inspection checklist by a knowledgeable inspector trained in defect identification helps
maximize inspection effectiveness. The Association for Rubber Products Manufacturers’ bulletin, IP-
11-7, (www.arpminc.com ) can provide added details regarding maintenance, testing and inspection
of chemical hoses.
Proper storage of chemical hose can influence useful lifetime. Storage wherein the hose can be laid
out straight, has continuous support, is purged of chemical residue, and is located out of direct
sunlight exposure is preferred. An enclosed hose carrier such as an oversized pipe can address these
issues and if positioned properly can minimize the ergonomic concerns associated with ground
storage of hoses. Proper storage can be especially important in areas where hoses can potentially be
subjected to vehicular traffic.
As with all expendable unloading system components, a replacement schedule is essential to ensure
hoses are retired before normal wear and tear leads to failure. For hoses with non-metallic fittings,
these are likely the weakest points and should be replaced on a more frequent basis. The hose body
29 | O l i n C h l o r A l k a l i P r o d u c t s – S o d i u m H y p o c h l o r i t e M a n u a l
itself is likely to be the determining factor for the replacement schedule for hoses with fluoropolymer-
lined fittings.
Incompatible Chemicals
The excellent oxidizing property of sodium hypochlorite requires that special care be taken to avoid
incompatible chemical contact, also known as accidental mixing. Accidental mixing may result in
personnel injury or environmental damage as a result of introducing sodium hypochlorite residues to a
wide variety of incompatible chemicals. Although reactions vary depending upon the chemical
composition, sodium hypochlorite will generate chlorine gas upon exposure to acids, acid residues, or
other chemicals that may lower the pH of the hypochlorite solution. Production of oxygen gas and
significant amounts of heat may accompany other reactions with sodium hypochlorite.
The opportunities for incompatible chemical contact at a storage facility are many and variable but
typically can be grouped into three categories: 1) the shipping container unloading process, 2)
secondary containment for unloading and storage, and 3) small-container handling. Unloading
stations often consolidate bulk chemical receipt into a single area that shares a common
containment/drainage system.
1. A common unloading area is often favored for new facilities because construction costs are
reduced and the footprint of the unloading area can be minimized. However, such an unloading
station enhances the risk of unloading the wrong chemical into a given storage tank due to the
close proximity of other product unloading connections. This highlights the importance of
installing and maintaining proper labeling of all unloading connections. Common unloading
stations generally share a single containment system sump and drain piping. Any spill or
incidental drippage will mix in the containment, sump, or drain piping.
Because unloading sodium hypochlorite into a tank containing an acidic product (or unloading
an acidic product into the sodium hypochlorite tank) may lead to a significant release of chlorine
gas, engineering controls should be employed in addition to administrative controls to prevent
such scenarios. Use of locked connections and unloading checklists are but two examples of
these controls. With outdoor storage tanks, such releases not only will potentially affect
employees in the area but may affect neighboring properties and personnel at great distance
from the release.
2. Well-designed containment systems employ elements to keep sodium hypochlorite separate
from incompatible chemicals both in the containment dike and in the discharge piping system.
Separate containment systems sharing a common drain are often designed to include locked
drain valves for each containment area. The locked valve concept can provide an administrative
control against incompatible contact and allows the facility to evaluate options for handling the
collected liquid before it contacts potential incompatible chemicals or residues. Such a design
typically requires a Process Hazard Analysis (PHA) evaluation to assess risks and means of
handling incompatible chemicals in common drain systems. Since introduction of incompatible
chemicals can potentially result in generation of chlorine gas, the PHA should consider both in-
plant and off-site impacts.
Storage areas for non-bulk containers, such as tote bins or drums, also should be reviewed for
potential of incompatible chemical contact. Such an evaluation not only covers the use/feed
Olin Chlor Alkali Products – Sodium Hypochlorite Manual | 30
area, but also the staging area where larger numbers of containers are typically stored
temporarily before being unloaded.
3. Small-containers can present a source of incompatible chemicals. Buckets or pans used for
incidental drip collection at an unloading station or small containers and sample thieves and
related devices used in product sampling can appear empty and clean but may have
incompatible chemical residues. All small containers used in sodium hypochlorite service should
be expressly designated for this use and clearly labeled “Sodium Hypochlorite Only.”
The Chlorine Institute (www.chlorineinstitute.org) bulletin, “Sodium Hypochlorite Incompatibility Chart,”
provides a list of chemical families that are incompatible with sodium hypochlorite.
Stability
All sodium hypochlorite solutions continually decompose on standing after they are produced. There
are many factors affecting the stability of hypochlorite solutions, and as such there is not a standard
shelf life for this product.
Decomposition of hypochlorite solutions cannot be avoided, but the rate of decomposition can be
altered. The major factors affecting stability are: temperature, hypochlorite/ionic strength, and contact
with catalyzing metallic impurities. Other factors such as pH, exposure to sunlight, organic impurities,
and other contaminants can contribute to losses as well.
In most situations, the temperature and concentration at which the sodium hypochlorite solutions are
stored have the most impact on their stability because decomposition is slowed as concentration and
temperature decrease, assuming all other conditions are similar and unchanged. As a general rule,
lower concentration solutions are more stable than higher strength solutions, assuming that other
conditions such as temperatures, pH and metal ion concentrations are similar. Studies of sodium
hypochlorite solutions have shown that the decomposition rate increases by a factor of approximately
two to four times for every 10°C (18°F), (see Graph 1 below for 13 wt% Sodium Hypochlorite). In
order to determine your best option for minimizing product decomposition, each application should be
reviewed based on hypochlorite strength, storage temperature, and storage time.
Closely related to temperature exposure is ultraviolet light-induced decomposition. Shielding of
storage systems, qualification samples, and the like from sunlight exposure can eliminate this
variable.
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Graph 1
Exposure to certain metals also can affect stability of sodium hypochlorite, with nickel, cobalt, copper,
and iron having the greatest impact, respectively. Graph 2, Metal-induced Assay Loss, depicts the
significance of trace metallic exposure to hypochlorite stability. While cobalt is particularly reactive
with sodium hypochlorite solutions, it is rarely found in day-to-day operations and shipments, and
therefore is typically not a significant contributor in most applications. On the other hand, nickel is
often encountered since stainless metals are used in many chemical handling applications. Simply
transferring sodium hypochlorite through an unlined stainless steel hose connector can initiate the
decomposition reaction because of the presence of the nickel component in stainless steels.
The major sources of metallic contamination are the quality of caustic soda and dilution water used in
the manufacturing process, and the exposure to metals during delivery and handling. Many
manufacturing processes incorporate various types of filtration to control and/or remove metallic
contamination. However, for certain applications such as product bottling, additional filtration steps
may be required to further reduce metallic contents. Customer-controlled exposure opportunities
encompass all areas of product handling beginning at the unloading process and continuing through
to product formulation and use. Because of the potential significant impact to product quality, a
rigorous management of all handling processes will be required to ensure all wetted surfaces are
metals-free (except for titanium and tantalum), as discussed in preceding handbook sections.
120
100
80
g/L Avail. Cl2
Ni
60
Co
Cu
40
Fe
20
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours
Solution pH also can affect sodium hypochlorite stability. For most sites receiving inbound sodium
hypochlorite, pH is not a significant stability factor as the importance of alkalinity (the ultimate source
of pH) is well-understood by most commercial producers. Because of this, adequate alkalinity (and the
resulting pH level) is added at the point of manufacture. However, alkalinity levels can become an
important consideration for customers who significantly change the solution composition, such as in
major product dilution, formulation, or during spill neutralization activities. The adage, “if a little is
good, then a lot will be better,” does not correlate with sodium hypochlorite stability and alkalinity/pH
levels. In fact, stability can be adversely affected by either too little or too much alkalinity. Alkalinity
levels of at least 0.1 – 0.2 weight % as NaOH are needed for stability. As alkalinity increases, solution
instability also increases.
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Dilution
Dilution of sodium hypochlorite is often chosen by customers to slow the rate of product
decomposition while in storage or to meet assay-specific applications. Although many sources of
water can be used for sodium hypochlorite dilution, the most important aspects to consider when
choosing a dilution water source are generally hardness and metals content. Hard water (high calcium
and magnesium content) can cause precipitates and scaling to occur in sodium hypochlorite solutions.
Exposure of sodium hypochlorite to dissolved metals in dilution water can accelerate product
decomposition similar to physical contact with metallic components and /or may alter the color of the
hypochlorite solution. In general, as water quality improves, product scaling and precipitation are
reduced and decomposition rates decrease.
The dilution water should be analyzed to develop an impurity profile. Depending upon impurities, a
treatment system may be required to upgrade water quality to help minimize quality problems with the
diluted product. A reputable water treatment specialist can
determine the best treatment method and capacity to Component Concentration
generate purified water for your particular application. For Nickel < 10 ppb
most applications, water impurities should not exceed the
general quality requirements noted in the adjacent chart. For Copper < 10 ppb
sodium hypochlorite bottling operations, additional water Cobalt < 10 ppb
treatment and product filtration may be required. Iron < 10 ppb
Another consideration for significant strength dilutions is the Silica < 0.2 ppm
excess alkalinity in the diluted product. For minor dilutions, Conductivity < 10 µS/cm
the excess actual sodium hydroxide content in the product
Total Dissolved Solids < 5 ppm
should be sufficient to maintain the minimum level of about
0.1 wt% to ensure product stability. With more significant Total Hardness < 5 ppm
dilutions, a small addition of caustic soda (sodium hydroxide)
may be required to achieve the minimum level necessary for a stable product. The quality of the
caustic soda added can also negatively impact sodium hypochlorite quality, especially in the areas of
trace metals and salts.
Unlike dilution of hypochlorite with water which is non-exothermic, addition of significant quantities of
caustic soda will result in a temperature gain of the solution. Solution cooling capabilities may be
required for large volume alkali additions to minimize temperature-induced product decomposition.
Chemistry
Manufacturing
Sodium hypochlorite solutions are most often produced today using an automated continuous
process. In the early development of commercial production, the batch process was based on the
same approach used to scrub various fugitive chlorine streams as piping and equipment were purged
for maintenance and other procedures. All of these processes involve the bubbling of gaseous
chlorine or direct injection of liquid chlorine into a dilute caustic solution. To avoid over-chlorination
and to maintain the excess alkalinity required to produce a stable hypochlorite solution, chlorine
addition must be discontinued prior to complete depletion of the caustic present in the solution.
Olin Chlor Alkali Products – Sodium Hypochlorite Manual | 34
Conventional sodium hypochlorite follows the manufacturing chemical reaction below which combines
caustic soda and chlorine to produce one mole of sodium chloride (NaCl) for each mole of sodium
hypochlorite (NaOCl). (A mole is a measure of the number of molecules of a compound). This one-to-
one ratio of production products often garners the name of ‘equimolar sodium hypochlorite’ as a
result.
Oxidation Power
The major uses for sodium hypochlorite solutions are directly related to its oxidation power. Before the
development of sodium hypochlorite solutions, chlorine was used directly for many of these
applications. With the storage advantages of an aqueous solution, sodium hypochlorite solutions have
replaced chlorine in many of these typical uses.
This leads to the obvious question: How much chlorine (Cl2) is available in a sodium hypochlorite
(NaOCl) solution? Equations 2 and 3 below show that one mole of NaOCl can oxidize two moles of
potassium iodide to form one mole of Cl2. (In other words a mole of sodium hypochlorite will oxidize
the same amount of iodide as will a mole of chlorine). The molecular weight of NaOCl is 74.5 (23 + 16
+ 35.5); the molecular weight of chlorine (Cl2) is 71 (2 × 35.5). The term, available chlorine, was
coined to describe this relationship in the sodium hypochlorite context. The ratio of molecular weights
(74.5/71), or 1.05, quantifies this relationship.
To relate gallons of sodium hypochlorite solution to pounds of chlorine, the hypochlorite’s strength as
expressed in units of available Cl2 must be converted to the equivalent pounds of chlorine to answer
the question above using the equation:
Avail. Cl2 g/L (A) X 3.785 liters/gal X 2.205 lbs/1000 grams = lbs Avail. Cl2 /gal solution
Eq. 4
For example, 120 g/L available Cl2 X 3.785 X 2.205/1000 = 1 pound available Cl2/gallon of solution.
Expressed differently, one gallon of sodium hypochlorite solution having 120g/L available chlorine
provides the equivalent oxidizing power of one pound of chlorine, (120 g/L available Cl2 = 1 lb chlorine
per gallon of solution). The unique one-to-one ratio provides a convenient basis point when other
hypochlorite solution strengths (in grams per liter of available Cl2) are considered.
When evaluating other hypochlorite solutions for chlorine equivalency using available chlorine, always
divide the grams per liter available chlorine by 120 g/L. For example, (150 g/L available Cl2 /120 g/L
avail. Cl2) = 1.25. In this example, one gallon of 150 g/L available Cl2 solution yields the equivalent of
1.25 pounds of chlorine gas. This ratio will then indicate how much more (or less) equivalent chlorine
35 | O l i n C h l o r A l k a l i P r o d u c t s – S o d i u m H y p o c h l o r i t e M a n u a l
is present in a given hypochlorite solution compared to a fixed amount of chlorine gas. Refer to Table
1 for additional details.
Similar calculations can be performed using wt% NaOCl provided the solution density is known.
Decomposition
The conditions and impurities in the sodium hypochlorite solution determine the reaction(s) defining
the solution composition resulting from decomposition of the NaOCl molecules. The thermal
decomposition route primarily results in production of chloride and chlorate ions.
The presence of trace metals catalyzes the sodium hypochlorite decomposition according the
following equation, which produces oxygen and salt. Small bubbles of the gas emanating from
particles, often barely visible to the naked eye or even microscopic, within the solution and rising to
the surface are often telltale evidence of this problematic reaction. Small amounts of nickel, cobalt,
and copper are particularly reactive even at parts per billion (ppb) levels. Oxygen generation and the
corresponding loss in assay (NaOCl) will continue until all hypochlorite has been decomposed or until
the trace metal(s) has been removed from the solution. Operational and safety concerns associated
with this reaction are discussed in greater detail in the preceding Stability section.
Titration/Chemical Analysis
The chemistry involved in the typical analysis used to determine the assay of NaOCl in a sodium
hypochlorite solution is shown below. The color of the iodine molecule (I2) provides a visual cue to the
endpoint of the manual titration procedure used for this analytical process.
The yellow-to-clear titration end-point using iodine is difficult to determine accurately. Addition of
starch indicator with the potassium iodide will significantly improve the accuracy of this titration by
providing a more distinct blue-to-clear colorimetric end-point.
Table 4
Crystallization Points
(Chlorine Institute Data)
Weight % NaOCl Crystallization Point (Deg. F.) Crystallization Point (Deg. C.)
15.5 -21.5 -29.6
12 -3 -19.4
6 18.5 -7.5
Product Assay
A simple titration test is used to determine sodium hypochlorite strength and, if performed correctly,
will yield highly accurate data. The titration is based upon the principle of ion substitution in a pH-
buffered environment, where the substitution element (iodine) is more easily titrated than the
hypochlorite ion. Advances in technology have resulted in the adoption of autotitrators for analyses
because they offer excellent reproducibility and are well-suited for facilities performing high volumes
of testing. However, the procedure can also be performed manually using a burette for titration. As
with all titrations, use of good lab protocols and attention to detail will be important in obtaining
accurate, reproducible results.
Sample handling in the areas of time, temperature, ultraviolet light, and metals exposure can have a
significant impact on analytical results when determining sodium hypochlorite assay. To minimize
decomposition from these influences, samples should be collected using sampling devices, bottles,
and bottle cap inserts that are nonmetallic on the wetted surface, and that are dedicated to sodium
hypochlorite use. Avoid exposure to sunlight and immediately analyze the samples upon collection.
When assay testing may be delayed, samples should be refrigerated / chilled to retard temperature-
induced product decomposition and corresponding loss of assay. Storage temperatures in the 35- 40
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degree F. range are common. It will be important to record the temperature of the chilled solution if
specific gravity-based calculations are made.
When collecting samples from sample ports, an adequate purging process should be implemented to
ensure a representative sample is obtained. Sample bottles should avoid being filled liquid-full to
accommodate potential volume expansion if cold product is sampled and allowed to warm before
testing. Adequate “head space” also will minimize the potential for sample bottle damage resulting
from metallic-induced product decomposition and the associated pressure build-up of oxygen gas.
The procedure in the following reference section is based upon the Chlorine Institute’s test method,
“Potentiometric Titration of Sodium Hypochlorite Solutions.” This procedure offers the flexibility of
using a weighed sample or a volumetric sample.
Residual Alkalinity
All sodium hypochlorite solutions require residual alkalinity, particularly sodium hydroxide, to ensure
product stability and to avoid generation of chlorine gas. Sodium hydroxide and sodium carbonate are
the typical alkalinity sources. Sodium carbonate is not as effective in stabilizing hypochlorite solutions,
and is typically not intentionally added to achieve higher alkalinity contents. Alkalinity determination
becomes particularly important in dilution activities or in chlorine-scrubbing applications where dilute
sodium hypochlorite is being produced. Once the available chlorine has been neutralized with
hydrogen peroxide, a simple acid–base titration is performed to determine alkalinity. If the
determination of amount of sodium hydroxide and sodium carbonate is needed, the titration is
essentially the same but has two endpoints. Use of pH testing to determine alkalinity levels is not
recommended because of the inability of pH test methods (probes or litmus papers) to yield accurate,
reproducible test results. The Chlorine Institute’s test method, “Determination of Sodium Hydroxide
and Sodium Carbonate,” follows in the reference section. Like the assay analysis, this test can be
performed by manual or auto titration.
Sample Preparation
(Sample Preparation - Direct Weight Method)
1. Tare-weigh (zero) a 250-mL Erlenmeyer flask on a calibrated analytical balance capable of weighing to at
least +/- 0.001g.
2. Secure lid on sample container and thoroughly mix.
3. Transfer 0.6 g of sample to the tared Erlenmeyer flask and record weight to the nearest +/- 0.001g.
4. Add approximately 10mL of deionized (DI) water for dissolving KI crystals.
(Sample Preparation – Volume Addition Method)
1. Tare-weigh (zero) a 250-mL volumetric flask (without the stopper) on a calibrated analytical balance
capable of weighing to at least +/- 0.001 g.
2. Secure lid on sample container and thoroughly mix.
3. Transfer 25-mL of sample from the container into the tared 250-mL volumetric flask.
4. Dilute to the final 250-mL volumes using DI water; insert the stopper into the flask; mix well.
5. Transfer 10 mL of the diluted sample into a 250-mL Erlenmeyer flask.
Sample Analysis
1. Place a magnetic stir bar in the Erlenmeyer flask.
2. Add 2–3 grams of Potassium Iodide (KI) crystals; gently swirl to dissolve all crystals.
3. Add 10 mL of glacial acetic acid; gently swirl to mix.
4. Rinse sides of flask down with DI water.
5. Titrate with 0.1N Sodium Thiosulfate until solution is a pale yellow color.
6. Add starch indicator and continue titration until the solution turns from blue to colorless.
7. Record the volume of Sodium Thiosulfate used.
Calculations
Weight percent sodium hypochlorite (wt% NaOCl) and weight percent available chlorine (wt% AvCl2)
can be determined from the assay titration. The calculations will differ depending upon whether a
direct weight or a volume aliquot of the sample was used in the analysis.
Using Direct Sample Weight
Wt% NaOCl = (mL Thiosulfate × N Thiosulfate × 3.722)/Sample weight (g)
Wt % AvCl2 = (mL Thiosulfate × N Thiosulfate × 3.5453)/Sample weight (g)
Using Aliquot Sample Volume
mL Aliquot = 25/250 x 10 = 1 ml
Wt % NaOCl = (mL Thiosulfate × N Thiosulfate X 3.722)/(mL Aliquot × Density)
Wt% AvCl2 = (mL Thiosulfate × N Thiosulfate × 3.5453)/(mL Aliquot × Density)
Reagents
Sodium Thiosulfate (Na2S2O3) solution standard, 0.1 normality Potassium Iodide (KI), granular,
certified ACS reagent grade
Glacial Acetic Acid, 98.8%, certified ACS grade
Starch indicator
Deionized (DI) water
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Residual Alkalinity Analytical Detail
Proper PPE should be worn when performing analytical work with sodium hypochlorite and chemical
reagents. Consult the most current Safety Data Sheet (SDS) for laboratory reagents as well as the
Chlorine Institute’s Pamphlet 65 before performing analytical work.
In determining the complete alkalinity analysis of sodium hypochlorite solutions, the hypochlorite ion is
first neutralized by the addition of hydrogen peroxide. Analysis involves a double-end point titration
wherein the first titration end-point represents the amount of hydroxide present. The second end-point
denotes the alkalinity contribution of the carbonate ion. It will be important to use fresh hydrogen
peroxide to ensure complete neutralization. Hypochlorite solution strengths in excess of ~ 15 weight
% as NaOCl will require additional hydrogen peroxide additions. Use of pH testing to determine the
amount of alkalinity should be avoided because of the inability to produce accurate results.
This test method was obtained from the Chlorine Institute’s Pamphlet 96, “Sodium Hypochlorite
Manual” and re-formatted. Consult the most current copy of The Chlorine Institute’s Pamphlet 96 to
ensure the most up-to-date method is used.
Sample Preparation
Prefill an 300-mL Erlenmeyer flask with ~ 50mL of deionized water
Weigh filled flask and tare
Pipette a 5-mL aliquot of the hypochlorite solution into the Erlenmeyer flask
Record flask weight to the nearest 0.1 gram
Add 20-mL of neutral, 3% hydrogen peroxide, stirring gently
Add 3 drops of phenolphthalein indicator
While gently stirring, titrate solution with 0.1N hydrochloric acid solution until all pink color is
dispersed
Record mL of hydrochloric acid used to achieve clear solution (A)
Add 3 drops of methyl orange indicator and continue titration while stirring until the yellow color
changes to red
Record mL of hydrochloric acid used to achieve red color (B)
Calculations
Wt% NaOH = [(A-B) x N X 4]/sample weight (W)
Reagents
0.1N hydrochloric acid
Deionized (DI) water
Reagent grade, pH neutral hydrogen peroxide solution (3%)
Phenolphthalein indicator
Methyl orange indicator
Olin Chlor Alkali Products – Sodium Hypochlorite Manual | 40
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Quick References
The Chlorine Institute
1300 Wilson Blvd.
Suite 525 Arlington, VA 22209
(703)-894-4140
www.chlorineinstitute.org
Pamphlet 96, ”Sodium Hypochlorite Manual”
”Avoiding Accidental Mixing of Sodium Hypochlorite” bulletin
“Sodium Hypochlorite Incompatibility Chart”
41 | O l i n C h l o r A l k a l i P r o d u c t s – S o d i u m H y p o c h l o r i t e M a n u a l
ASTM International
100 Barr Harbor Drive
West Conshohocken, PA 19428
(877)-909-2786
www.astm.org
Emergency Contacts
In the event of an accident or chemical incident, refer to your site’s emergency preparedness plan and
the most current Safety Data Sheet (SDS). Should a chemical leak or spill occur, immediately contact
the applicable regulatory agency and implement your Site Control Plan (SCP).
As a hazardous chemical, sodium hypochlorite spills equating to 100 pounds of active ingredient as
NaOCl (~ 80 gallons of 12.5 wt% as NaOCl solution) or more require the immediate notification of the
National Response Center at 800-242-8802 within 15 minutes of the spill occurrence in the U.S.
Consult local and regional regulatory agencies for other notification requirements unique to your
particular geography.
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