FLAMMABLE MIXTURE ANALYSIS FOR HAZARDOUS AREA CLASSIFICATION

Allan Bozek P.Eng, MBA Vince Rowe, P.Eng

Member IEEE Member IEEE
EngWorks Inc. Marex Canada Ltd.
1620, 49th Avenue SW 1550, 555 - 4th Avenue SW
Calgary, Canada T2T2T7 Calgary, Canada T2P 3E7

Abstract - The properties of flammable mixtures as they The probability that a flammable atmosphere exists is
apply to a hazardous area classification analysis are dependent on the chemical properties of the flammable
discussed. Mathematical formula and application rules of materials present, as well as the grade and rate of release.
thumb are provided to help estimate the relative density, The extent of the hazard will be influenced by the behavior of
group classification, autoignition temperature, material the flammable material under normal ambient pressure and
flashpoint and the flammability of a mixture. Application temperature conditions, the degree of ventilation within an
guidelines are provided on how to apply the results in the area, the geometry and velocity of the release and the
context of a hazardous area classification analysis. physical topography of an area.
There are several methods for classifying an area once the
Index Terms – Hazardous area classification, flammable flammable materials and physical parameters are identified.
mixture analysis, density, group classification, autoignition, The most common way is to use the direct example approach
flashpoint, flammability. where the facility is classified using diagrams that depict
typical situations. This method of classification is
I. INTRODUCTION incorporated into most industry recommended practices for
hazardous area classification.
The vast majority of flammable materials handled in oil, gas A second method uses the point source approach to
and petrochemical facilities consist of flammable mixtures of classify facilities. Potential release sources are identified and
various compositions. Performing a hazardous area a formal calculation is performed to determine the extent of a
classification risk assessment requires an understanding of classified area. The point source approach is more rigorous
the behavior of flammable mixtures and how they might and thus requires more detailed information on the nature of
influence the extent, group classification and autoignition the flammable materials to obtain a reasonable conclusion.
temperature of the classified area.
Unfortunately, very little guidance is given on mixture III. PROPERTIES OF FLAMMABLE MATERIALS
analysis by the various industry recognized standards and
recommended practices on area classification. The search To assess the risk and the extent of the hazard, several key
for the proper chemical relationships and formula can be properties of the flammable material must be determined.
frustrating. The mixture analysis must be performed with help They include:
of chemical textbooks and other references not specifically
written for the purpose of a hazardous area classification A. Vapor Pressure and Flashpoint
analysis.
The purpose of this paper is to provide guidance on how to The hazard posed by flammable materials is influenced by
analyze the properties of flammable mixtures as they apply to how easily it will mix with air and potentially form a flammable
a hazardous area classification. The key flammable material mixture. This is a function of vapor pressure and
parameters and the test methods used to determine the temperature. Flammable gases have a very low vapor
properties of pure flammable materials are discussed. In the pressure and as such are always in a gaseous state at
absence of actual test results, a series of mathematical ambient temperatures. Flammable liquids in contrast, are in a
relationships and application rules of thumb are provided for state of transition between a liquid and a gas. The hazard
estimating the properties of flammable mixtures. Application posed by a flammable liquid is a function of how easily it
guidelines are also provided to assist in documenting the changes state from a liquid to a vapor at ambient
results within the context of a hazardous area classification temperatures. The temperature at which a liquid provides
analysis. sufficient vapor to form a flammable mixture on the surface of
the liquid is termed its flashpoint. This is the key parameter
II. HAZARDOUS AREA CLASSIFICATION used to classify the potential hazard associated with
OVERVIEW flammable liquids.
The flashpoint of a flammable material is determined
A hazardous area classification analysis is a structured risk experimentally using two recognized methods as illustrated in
assessment process used to determine the probability of a Fig. 1 and 2. The open cup flashpoint test procedure requires
flammable atmosphere being present during normal or heating the flammable material in an open cup and
abnormal operations. The analysis divides the facility layout periodically using an open flame to ignite the surface vapor.
into zones of risk which are then used to determine the When there is sufficient vapor to sustain combustion, the
appropriate equipment and wiring methods for safe operation. flashpoint temperature is recorded.
 The closed cup flashpoint test procedure is similar to the Thermometer
open cup flashpoint test except the flammable material is
sealed within a closed cup environment. The closed cup Open Cup
flashpoint test typically results in a lower flashpoint with
temperature than observed with the open cup test. The Flame Flammable
flashpoint temperatures most often quoted for flammable Liquid
materials in various publications are derived using the closed
cup method.
Flashpoint is used as a basis for categorizing the volatility
of flammable liquids. NFPA 30 [1] categorizes flammable
materials into three classes based on their flashpoint and
boiling point vapor pressure (Table I). Class I materials are Bunsen
those that readily flash to atmosphere at ambient Burner
temperatures and pressures. They are considered highly
volatile and require due consideration with respect to an area
classification.
Class II materials typically do not flash at temperatures that
would normally be considered “ambient”. From an area
classification perspective, Class II flammable materials are
considered when they are stored or handled at temperatures Fig. 1 Open Cup Flashpoint Test Apparatus
above their flashpoint. Class III materials are only a
consideration when they are exposed to very high process Test Cup
temperatures and typically do not factor into a hazardous area Thermometer
classification. In all cases, the properties of the flammable Agitator
material and the process conditions must be assessed prior to
defining the degree and extent of a classified area. Bath
Part 15 (IP15) of the British Institute of Petroleum Model Thermometer
Code of Safe Practice in the Petroleum Industry has a similar
classification for petroleum liquids based on flashpoint. The
petroleum classes defined in Table II are used in conjunction Flammable
Liquid Flame
with a series of typical diagrams that define the degree and
extent of a classified area.
IP15 takes into account the process conditions and adjusts Liquid Bath
the extent of the classification based on if the material is
handled above or below its flashpoint temperature. It also
makes reference to situations where the fluid cannot be easily
classified by flashpoint and addresses the potential hazards
associated with flammable mists and sprays. Under these
circumstances, a judgment call must be made as to the fluid
Heating Vessel
category and the characteristics of the potential hazard. The
point source method of area classification is normally used in
these situations [2]. Fig. 2 Closed Cup Flashpoint Test Apparatus

TABLE I
NFPA CLASSIFICATION OF FLAMMABLE/COMBUSTIBLE TABLE II
MATERIALS IP15 PETROLEUM CLASSES
NFPA Flashpoint (ºC) Examples IP Class Flashpoint (ºC) Application
Class BP = Boiling Point
IA < 22.8, (BP < 37.8) Ethyl Ether, Pentane 0 NA LPGs
IB <22.8, (BP > 37.8) Acetone, Gasoline I <21 Flam. at ambient conditions
IC ≥22.8 and < 37.8 Naphtha, Xylene II(1) ≥21 and ≤ 55 Handled below FP
II >37.8 and < 60 Fuel Oil, Kerosene II(2) ≥21 and ≤ 55 Handled above FP
IIIA ≥ 60 and < 93 Ethylene Glycol III(1) >55 to 100 Handled below FP
IIIB ≥ 93 Asphalt, Transformer Oil III(2) >55 to 100 Handled above FP
Unclassified ≥ 100

B. Relative Vapor Density

The relative vapor density of a flammable gas/vapor is a

key parameter when using the direct example approach
method of area classification. The diagrams selected for a
particular situation are dependent on the relative density of
the gas/vapor as compared to air under standard ambient TABLE III
temperature-pressure conditions. GROUP CLASSIFICATION CRITERIA
For practical applications, a gas/vapor mixture that has a NEC Gas Grouping IEC Gas Grouping
relative vapor density of 0.8 is regarded as lighter-than-air and Group MESG MIC Group MESG MIC
a release would rapidly rise and collect in the upper levels of a (mm) ratio (mm) Ratio
A Acetylene
confined area. Gas/vapor mixtures that have a relative vapor IIC ≤0.50 ≤0.45
B ≤0.45 ≤0.40
density greater than 1.2 are regarded as heavier-than-air and
>0.45 >0.40 >0.50 >0.45
will collect at ground level. In theory, heavier-than-air C
≤0.75 ≤0.80
IIB
≤0.90 ≤0.80
flammable mixtures can travel long distances and result in D >0.75 >0.80 IIA >0.90 >0.80
large areas of potential hazard. Gas/vapor mixtures with a
relative vapor density of between 0.8 and 1.2 can exhibit The group classification for a flammable material can also
properties of both lighter-than-air and heavier-than-air be based on the minimum ignition current (MIC) required to
behavioral characteristics so both possibilities should be ignite the material under stochiometric conditions within a
considered [3] [4]. specified test apparatus. This is derived experimentally with
While gas/vapor density may have an influence on the the results often expressed as a ratio to the minimum ignition
extent of a classification in enclosed areas under ideal energy required for methane. Table III provides the group
conditions, recent experiments using dispersion modeling classifications based on the minimum ignition current ratio
have shown that the relative density has little influence on the (MIC ratio) as compared to methane.
extent of a hazard in a pressurized release. In these
circumstances, the angle of release and how close the D. Lower and Upper Flammable Limits
release point is to the ground has a larger effect. The extent
of a flammable region is determined more by the direction and Flammable gases and vapors are flammable only when
the velocity of the release than by the density of the gas or they are between their lower flammable limits (LFL) and their
vapor released [5]. upper flammable limits (UFL). For area classification
purposes, the LFL is of greater concern as the hazard can be
C. Group Classification of Flammable Materials reduced by controlling the level of ventilation to dilute the
flammable gas to a concentration well below the LFL. The
The group classification assigned to a hazardous location LFL is a key parameter required for all hazardous area
determines the explosionproof or flameproof enclosure design classification ventilation and point source calculations.
requirements and the performance specifications for
intrinsically safe circuits. The design of an explosionproof or
flameproof enclosures is dependent on flamepath tolerances
Flammable
which are in-turn based on the Maximum Experimental Safe
Air Gas Mixture
Gap (MESG) distance defined for a given flammable gas or
vapor. The smaller the MESG defined for a material, the
longer the flamepath required to cool the hot gases Manifold
discharged from an explosionproof assembly during an Hot Air Ignition
ignition event. Typically, the longer the flamepath required, Vessel
the more expensive the enclosure. Electrode Air
The group classifications for flammable gases/vapors are
determined experimentally based on the MESG determined
under test conditions. The NEC group classifications for
flammable materials are based on tests performed by Manifold
Underwriter Laboratories using a Westerberg Explosion Test
Vessel (WETV).
The WETV consists of two chambers, one within the other,
and each filled with a stochiometric explosive mixture. The
mixtures are separated by an adjustable 25mm wide joint gap
assembly. The flammable atmosphere is ignited in the inner
chamber and allowed to propagate to the outside chamber.
The opening of the joint gap assembly is reduced until an Fig. 3 Flammable Limits Test Apparatus
internal chamber ignition does not propagate to the external
chamber. The opening of the 25mm wide joint gap at that The %LFL and %UFL values for pure substances are
point is the MESG. The group classification for the flammable derived experimentally using the apparatus described in
material is then assigned based on Table III. ASTM E 681-04 and illustrated in Fig. 3. The concentration
The IEC group classifications are performed in a similar of the flammable material is gradually increased until an
fashion. The size and shape of the explosion chamber differs ignition is observed. The % volume to air is recorded as the
from the WETV but the results are statistically similar. The lower flammable limit. The concentration is further increased
IEC group classification of materials as it relates to MESG is and ignited until the mixture no longer ignites. The %
also provided in Table III. concentration is then recorded as the upper flammable limit.
E. Autoignition Temperature (AIT) surface ignition occurs is not a fundamental fluid property and
is influenced by a number of factors including ambient
The autoignition temperature of a flammable material is conditions as well as the size, geometry and properties of the
required to determine maximum safe operating surface hot surface itself. Hot surface ignition data cannot easily be
temperature for equipment installed in a hazardous location. extrapolated to different situations and the use of a general
The maximum surface operating temperature for electrical rule of thumb based on a minimum autoignition temperature
equipment is defined by a temperature code. The temperature can be very inaccurate [11]. Fig. 5 illustrates the relationship
code is used to determine if the equipment item is suitable for between vapor pressure, upper and lower flammability limits,
installation based on the AIT defined for the hazardous autoignition and hot surface ignition temperature.
location.
There are a number of definitions for autoignition Mirror Flame
temperature in current use. For example, API RP500 defines Viewing Line Arrestor
AIT as: “The minimum temperature required, at normal
atmospheric pressure, to initiate or cause self sustained Syringe
200 ml Erlenmeyer
combustion (independent of any externally heated element).”
[3] Inflatable
Reservoir
API RP505 defines AIT as: “The lowest temperature of a
heated surface at which, under specified conditions, the Thermocouple
Heater Elements
ignition of a flammable substance in the form of a gas or
vapor mixture with air will occur.” [4] Electric Furnace
The API RP505 definition is a modification of the definition
in IEC 60079-4 which is: “Ignition temperature – The lowest
temperature at which ignition occurs when the method
prescribed in this standard is used.” [7] To Instrument
The test method used in IEC 60079-4 consists of heating a Monitors
200ml Erlenmeyer flask in a hot air furnace as illustrated in To Heater Controls
Fig. 4. The flask is heated to the desired temperature, at
which point a liquid or gaseous sample is injected into the
Fig. 4 IEC 60079-4 Autoignition Temperature Test Apparatus
flask. If no flame is observed within 5 minutes, the test is
repeated until the minimum temperature at which ignition
occurs is determined. The process is repeated until a degree Published
Mixture
of correlation exists between several identical tests. This Vapor Autoignition
Temperature Upper Flammable Limit
correlated value is then defined as the autoignition Pressure
V
temperature for the flammable material. a
Curve
ASTM E659 Standard Test Method for Autoignition p
Temperature of Liquid Chemicals defines AIT as: “The o
minimum temperature at which Autoignition occurs under the r
Hot Surface
specified conditions of test.” [8] The test method described in Autoignition Ignition Zone
P
standard ATSM E659 is similar to the test procedure used in r Zone (Curve may shift
based on less ideal
IEC 60079-4 with the exception of the volume and the shape e conditions)
of the flask used. s
Published AIT tables are usually based on the laboratory s
u Flash Point
procedures outlined in IEC 60079-4 and ASTM E659. The Temperature
r Lower Flammable Limit
prescribed methods are relatively simple and the results are e
repeatable, however, they are only accurate for the conditions Mixture/Surface Temperature
under which the testing is performed. Autoignition
temperatures can be influenced by the volume, shape and the Fig. 5 Autoignition and Hot Surface Ignition Temperature as a
material composition of the test apparatus, the method and Function of Temperature and Vapor Pressure
rate of heating, the flame detection method as well as the
percent gas/vapor/air composition of the sample [9]. IV. INDUSTRY REFERENCES
The published AIT tables typically reference the lowest AIT
observed under controlled laboratory conditions. Industry Most area classification standards and recommended
experience however indicates that the actual minimum practices do not incorporate a list of flammable material
temperature at which ignition occurs is much higher. API RP properties. A secondary publication must usually be
2216 Ignition Risk of Hydrocarbon Liquids and Vapors by Hot referenced to obtain the necessary data. The one notable
Surfaces in Open Air concluded that the minimum exception is NFPA 497 Recommended Practice for the
temperature (referred to as the minimum hot surface ignition Classification of Flammable Liquids, Gases, or Vapors and of
temperature) should not be assumed unless the surface Hazardous (Classified) Locations for Electrical Installations in
temperature is approximately 360°F (182°C) above the Chemical Process Areas which incorporates a list of
published AIT [10]. flammable material properties within the context of the
It should be noted that there is no standardized test for hot document [12].
surface ignition temperature. The temperature at which hot
 Historically, API 500 and 505 has referenced NFPA 325 V. PROPERTIES OF MIXTURES
Guide to Fire Hazard Properties of Flammable Liquids, Gases
and Volatile Solids as the recommended source of information In a perfect world, a hazardous area classification would be
for flammable material properties. The document was completed using the information provided in the various area
originally intended for fire prevention purposes and does not classification standards and recommended practices and the
incorporate information on MESG, MIC ratio or minimum properties listed in the hazardous material references. All
ignition energy data required for determining the group process materials would be of a homogenous nature with their
classification of a flammable material. properties and flammable characteristics well defined.
As of 1998, NFPA 325 is no longer in print and has been Unfortunately, real world process facilities combine process
superseded by the NFPA Fire Protection Guide to Hazardous streams with different materials thus affecting the properties
Materials [13]. The document combines information from nine and characteristics of the combined mixture.
different NFPA reference documents on hazardous materials. This would not be an issue if the tests for flashpoint,
With NFPA 325 no longer being published, the 2007 edition MESG, %LEL and autoignition could be done for a mixture
of API 500 and 505 now make reference to NFPA 497 as the the same way it is done for a pure substance. This is
recommended source of information for flammable material however impractical in the context of plant design where the
properties. NFPA 497 provides a complete list of chemical cost and effort associated simulating and testing each
parameters including the NFPA flammable material process stream does not justify the end result. Some
classification, flashpoint, autoignition temperature, vapor mathematical means of estimating the properties of a
pressure, density, group classification and the MESG and flammable mixture is required to properly assess the nature of
MIE/MIC for a list of commonly found flammable materials the hazard and define the extent of the classified zones.
used in chemical process facilities. The list, although not Fortunately there are some mathematical relationships that
comprehensive, includes most flammable materials commonly can be used to help predict the properties of flammable
found in upstream production, transportation and refinery mixtures.
facilities.
Area classifications performed using IEC 60079-10 [14] are A. Base assumptions
referred to IEC 60079-20 Electrical Apparatus for Explosive
Gas Atmospheres – Part 20 Data for Flammable Gases and To estimate the properties of a flammable mixture, a
Vapours [15] for a list of flammable material properties. IEC number of key assumptions are required. The first
60079-20 was created specifically for hazardous area assumption is that the mixture is in a gas or vapor state upon
classification purposes and includes a complete set of data for release and it does not exist as mist or spray. The properties
performing an analysis. of flammable mists and sprays are extremely difficult to model
There are minor differences between the data published in and must be treated as a unique case for area classification
NFPA 497 and IEC 60079-20. The differences are related to purposes [5].
the variation in test procedures and apparatus used. TABLE The second assumption is that the flammable materials
IV provides an overview of the differences between the remain in mixture. The behavior of ideal vs. non-ideal
reference publications for a cross sample of flammable mixtures will impact the accuracy of this assumption to a
materials. degree but not enough to render the approximation invalid.
Other sources of flammable material property information
include MSDS (Material Safety Data Sheets US OSHA) and B. Estimating Mixture Relative Density
WHMIS (Workplace Hazardous Materials Information System
– Canada) material data sheets and a number of chemical As previously discussed, the relative density of a mixture
reference texts that tabulate the properties of flammable must be estimated to determine if it is heavier-than-air, lighter-
materials. MSDS and WHMIS data can be valuable because than-air or of neutral buoyancy. The information is
they often provide information on chemicals and products not necessary to determine what direct example approach
normally listed in industry chemical references. They diagram is appropriate for a particular situation. The relative
however omit MIC and MESG information required for the density of a mixture is calculated based on the molar weight
group classification of a flammable material. of the mixture as it compares to the molar weight of air. The
molar weight of air is 28.96 grams/mole at 0°C at sea level.
TABLE IV The following formula is the basis for the calculation:
FLAMMABLE PROPERTIES COMPARISON BETWEEN
NFPA 497 and IEC 60079-20 n
Flammable
Ref. %LFL %UFL
AIT
MESG RDair = ∑ Mi,xi
Material ºC i (1)
NFPA 5 15 630 1.12 28.96
Methane where
IEC 4.4 17 537 0.92
NFPA 1.5 7.8 243 0.93
Pentane RDair = Relative density of the mixture compared to air
IEC 1.4 7.8 258 0.93
NFPA 4 75 520 0.28 Mi = molar weight of the individual constituent
Hydrogen xi = corresponding mole fraction
IEC 4 77 560 0.28
Hydrogen NFPA 4 44 260 0.90
Sulfide IEC 4 45.5 270 0.89
 The results are then compared to the values in TABLE V system will counteract as far as possible, the effect of the
and then applied to the appropriate area classification disturbance on the system. This principle is applied to
diagram. estimating the MESG and subsequent group classification of
TABLE V a flammable mixture. The mathematical relationship for
RELATIVE DENSITY CATEGORIZATION estimating MESG using Le Chatelier’s principle is as follows:
RDair < 0.8 Lighter than air
0.8 ≥ RDair ≤ 1.2 Neutral buoyancy
RDair > 1.2 Heavier than air 1
MESGmix= (2)
Consider the mixture illustrated in TABLE VI. Calculate the
molar weight of the mixture and determine if it is lighter or
∑ xi
i MESGi
heavier than air. where
MESGmix = Estimated MESG of the mixture
TABLE VI
EXAMPLE: ESTIMATING RELATIVE DENSITY
MESGi = MESG of the individual constituent
Material Mi xi Mi x i xi = corresponding mole fraction
Methane 16.04 50% 8.02
Ethane 30.07 10% 3.0 Consider the example of a flammable mixture consisting of
H2S 34.08 15% 5.11 50% Diethyl Ether, a Group C, (IIB) classified material as
Nitrogen 28.02 15% 4.2 illustrated in TABLE VII.
Heptane 100.2 5% 5.0
Octane 114.22 5% 5.71 TABLE VII
Total 100% 31.04 ESTIMATING MESG EXAMPLE
Material xi MESG (mm) Group
The molar weight calculated for the mixture is 31.04. When Diethyl Ether 50% 0.83 C, (IIB)
divided by the molar weight of air (28.96) the mixture has a Methanol 20% 0.92 D, (IIA)
relative density of 1.07 indicating the mixture has neutral Nitrogen 15% -
buoyancy. This information would then be used to judge the Isopropyl Ether 10% 0.94 D, (IIA)
extent of the transient vapor zone associated with the Methyl Ether 5% 0.84 C, (IIB)
appropriate area classification diagram.
It should be noted that most industry references for Applying Le Chatelier’s principle to the mixture:
flammable materials do not provide information on the molar
weight of materials. A chemistry textbook must be referenced
to source this information. 1
MESGmix =
C. Estimating the Group Classification of Mixtures 0.5 0.2 0.15 0.1 0.05
∞
+ + + +
0.83 0.92 0.94 0.84
Determining the group classification of a mixture is
essential for determining the appropriate hazardous location
electrical equipment specifications. For most upstream MESGmix = 1.014
production and downstream refinery facilities handling
hydrocarbon mixtures, the group classification is typically Using TABLE III, the gas mixture is thus classified group D,
group D under the division system and group IIA under the (IIA).
zone system of area classification. It is interesting to note that the MESG value obtained for
The two flammable materials that most often influence the the mixture using Le Chatelier’s principle has a value greater
group classification of a hydrocarbon processing facility are than all MESGs for each of the individual material
H2S and hydrogen. API RP500, RP505 and IP15 provide components. This is due to the effect nitrogen gas has on
some guidance in determining the group classification of calculating the MESG of the mixture. Inert gases will
facilities handling H2S and hydrogen. Generally, a group C influence the MESG of a mixture by reducing the oxidant
or IIB group classification is not justified unless H2S quality of the mixture. Le Chatelier’s principle will tend to
comprises at least 25% of the flammable mixture stream. A overemphasize the effect of the inert gas on the MESG of an
group B or IIC classification is not justified unless the inert-flammable gas mixture and will produce odd results
hydrogen component of a flammable stream exceeds 30%. when used with mixtures that contain a large percentage of
For most hydrocarbon processing facilities, the H2S and inert gas.
hydrogen rule of thumb guidelines are sufficient to determine The same is true of mixtures that contain oxygen in excess
the group classification. For chemical processing facilities of a nominal 21% concentration. The higher concentration of
handling flammable mixtures other than hydrocarbons, the oxygen increases the volatility of the ignition producing higher
group classification is more complex. In these situations, Le pressures which in turn render the MESG test values for the
Chatelier’s principle can be applied. individual components invalid. Materials such as carbon
Le Chatelier studied the influence of pressure, temperature monoxide or carbon disulfide that do not incorporate hydrogen
and concentration on systems at equilibrium. Le Chatelier bonds can also result in erroneous results. Laboratory test
postulated that when a system at equilibrium is disturbed, the results has shown that Le Chatelier’s principle is reasonably
accurate provided the following situations are avoided: Le Chatelier’s principle provides flammability limits that are
[16][17] close to the experimental values of simple hydrocarbon
mixtures with sufficient accuracy for most area classification
1. Flammable mixtures where a significant portion of the analysis. The approximation is valid with mixtures in air at
gas is an inert. ambient pressures [18].
2. Mixtures that incorporate oxygen as one of the
components. E. Flammability of Mixtures
3. Mixtures that contain greater than 5% carbon monoxide.
4. Mixtures that contain acetylene. There are often situations where gas or fluid mixtures
contain flammables in low concentrations. The question
D. Estimating LFL and UFL of Mixtures arises whether the mixture as a whole is flammable and
therefore must be considered as part of an area classification.
Estimating the lower flammable limit of a mixture is required To determine the flammability of a mixture, an assessment
for point source calculation methods and for determining the must be made to determine if the mixture contains sufficient
level of adequate ventilation in an enclosed area using the flammables to exceed the lower flammable limit of the mixture
fugitive emissions calculation procedure described in as a whole. The calculation procedure is relatively easy for
appendix B of API RP 500 and 505. Upper flammable limits mixtures in a gaseous state. It is more complex for fluid
are seldom used as a basis for area classification. mixtures where the flammable components may flash to
The LFL of a mixture may be estimated by applying a atmosphere based on ambient, operating or storage
derivation of Le Chatelier’s principle. The derivation uses only temperatures.
the flammable components of the mixture with their mole
fractions adjusted to their relative percentage of the 1) Flammability of a Gas Stream: The flammability of
flammable mix as follows: a process gas stream may be determined by first estimating
the %LFL of the mixture using Le Chatelier’s principle and
then comparing the %LFL to the total %flammables contained
1 in the mixture. If the %flammables exceed the %LFL, the
%LFLmix= (3) mixture is considered flammable [19]. Consider the example
∑ xiflam in TABLE IX where a relatively small percentage of
flammables make up a gas mixture:
i %LFLi
where
%LFLmix = Estimated LEL of the mixture
TABLE IX
%LFLi = %LFL of the individual constituent EXAMPLE: DETERMINING THE FLAMMABILITY OF A GAS
xiflam = Corresponding mole fraction on a STREAM
flammable bases Material % Vol xiflam LFL
Methane 3 54.5% 5.0%
Butane 1.5 27.3% 1.9%
Consider the flammable mixture example previously used Ethane 1 18.2% 3.0%
for estimating MESG. Air 94.5
100%
TABLE VIII Estimating the %LFL for the mixture using Le Chatelier’s
EXAMPLE: ESTIMATING %LFL
principle:
Material xi xiflam LFL
Diethyl Ether 50% 58.8% 1.7%
Methanol 20% 23.5% 6.0% 1
Nitrogen 15% - %LFLmix = X 100 = 3.2%
Isopropyl Ether 10% 11.8% 1.4% 0.545 0.273 0.182
Methyl Ether 5% 5.9% 3.4% + +
0.05 0.019 0.03
100% 100%
The flammable percent volume of the mixture is:
1
%LFLmix = X 100 %Flammix = 3% + 1.5% + 1% = 5.5%
0.588 0.235 0.118 0.059 Since the %Flammix exceeds the %LFLmix the mixture is
+ + +
0.017 0.06 0.014 0.034 considered flammable and must be considered within the
context of an area classification.
%LFLmix = 2% 2) Flammability of a Process Fluid Stream:
Determining the flammability of a process fluid stream
requires estimating the flashpoint of the mixture. A common
The UFL of a mixture can also estimated using Le industry practice for estimating the flashpoint of mixtures is to
Chatelier’s principle in a similar way.
use the lowest published flashpoint for any of the pure
components. If the flashpoint temperature for the single
Actual Vapour
lowest pure component in the mixture is exceeded at ambient, Pressure Tf,B
process or storage handling conditions, the mixture is PsatB Ideal
considered flammable.
This assumption is thought to provide a conservative value Ideal
for the flashpoint of a mixture however; further research has PsatA Tf,A
Actual Flashpoint
shown that this assumption is not always valid. Mixtures can
exhibit lower flashpoints than any of the pure component
values depending on if the mixture is classed as ideal or non- xi xi
ideal. (mole fraction) (mole fraction)
An ideal mixture is defined as a mixture where all molecular
interactions are the same as if the individual components Fig. 7 Vapor Pressure and Flashpoint Behavior of Non-Ideal
were in their pure state at the same pressure and temperature Mixtures
as the mixture [20]. The mixture will follow the properties of
Raoult’s law which allows the thermodynamic properties of F. Autoignition Temperature
the mixture to be predicted based on the properties of the
individual components. Estimating an AIT for a mixture is a challenging problem
Using this principle, the vapor pressure and flashpoint of a due to the complex nature of the autoignition-combustion
mixture can be estimated diagrammatically as illustrated in process. There are no established mathematical relationships
Fig 6. The vapor pressure or the flashpoint of a mixture is to help in this regard. The only way to determine the AIT of a
directly influenced by the mole fraction of the individual mixture is by laboratory test.
constituents of the mixture. If AIT data for a mixture is not available and the situation
precludes testing, often the lowest AIT of any pure component
in the flammable mixture is used as the AIT. This typically
results in a very conservative AIT value and may not reflect
PsatB Tf,B the true nature of the hazard.
A rule of thumb often used to estimating the AIT of
hydrocarbon mixtures is to take the lowest AIT of any
component exceeding 5% (by volume) of the total mixture.
PsatA Tf,A This is based on the assumption that the autoignition
Vapour Pressure Flashpoint
temperature of a mixture will be influenced more by the
properties of the major components than by the minor
xi xi components in the mixture. This assumption has not been
(mole fraction) (mole fraction) verified and additional research in this area is required.
Rules in the NEC and the CEC require the maximum
Fig. 6 Vapor Pressure and Flashpoint Behavior of Ideal surface operating temperature of electrical equipment to be
Mixtures less than the ignition temperature of the specific gas or vapor
in a hazardous area. While the rules do not specify the use of
Mixtures that exhibit ideal behavior include water-alcohol AIT’s (as opposed to hot surface ignition temperature), the
and heptane-hexane hydrocarbon mixtures. use of published AIT’s has been standard practice.
Non-ideal mixtures deviate from Raoult’s law in a positive In some situations it may make sense to use a temperature
or negative manner depending on the molecular attraction of other than the published AIT based on documented
the mixture components. Fig. 7 illustrates the behavior of a engineering judgment. A real life example involves the
mixture that deviates in positive manner from Raoult’s law. installation of MI heat tracing on high temperature process
Note that under certain conditions, the flashpoint of the piping in heavy oil upgrader facilities. In these situations, it is
mixture may be less than the flashpoint of either component in common for process piping to operate at elevated
the mixture. temperatures in the range of 325°C in areas where diluents
Most mixtures exhibit non-ideal behavior to a degree. (predominantly hexane - AIT 215°C), are present.
Methanol hydrocarbon mixtures are highly non-ideal and have Historically, the heat trace design would have been limited to
been shown to exhibit flashpoint temperature lower than a maximum surface operating temperature of 215°C on a pipe
either component. This complicates the development of a that normally operates at 325°C. This results in multiple
simple rule of thumb for determining the flammability of a fluid passes of a lower wattage electric heat trace to limit the
mixture. Unless a mixture can be positively confirmed to maximum surface operating temperature of the tracer to less
exhibit ideal behavior in accordance with Raoult’s law, the than 215°C.
mixture must be assumed to be flammable with the flashpoint Recent upgrader facility designs have made documented
lower than what is published for any of the flammable engineering decisions to allow the maximum design
components. The only reliable way of determining the temperature of the heat trace to be as high as the operating
flashpoint and hence the flammability of a fluid mixture is by temperature of the hot piping. This allows more flexibility in
test procedure. the design of the heat trace system and typically reduces the
number of tracer circuits required to meet the process piping
heating requirements.
 VI. APPLICATION GUIDELINES the molar weight of air at ambient temperatures and
pressures. Determining the group classification, estimating
The hazardous area classification for a facility is usually the LFL, UFL, and predicting the flammability of a gas mixture
documented using layout drawings and details that define the can be done using Le Chatelier’s principle.
degree and extent of the classified areas. The drawings also The complex nature of the autoignition process precludes
provide pertinent information on the group classification and the use of a simple mathematical model or industry rule of
autoignition temperature defined for the facility. For complex thumb that can be used to estimate the AIT of a flammable
facilities that incorporate a variety of flammable mixture mixture. Additional research is required to develop a basis for
streams, the drawings are usually supplemented by an an industry accepted practice for estimating the autoignition
engineering document that summarizes the basis for the area temperature of flammable mixtures.
classification. The hazardous area classification study report
should include: X. REFERENCES

1) A description of the process and the flammable [1] NFPA 30, Flammable and Combustible Liquids Code,
materials handled. National Fire Protection Association, Quincy, MA., 2003.
2) A list of the codes, standards, recommended
practices and material references used in the [2] Institute of Petroleum, Model Code of Safe Practice –
analysis. Part 15, Area Classification Code for Installations
3) A list of assumptions used to classify the facility Handling Flammable Fluids, 3rd Edition, Energy Institute
including the basis for normal and abnormal (2003), Portland Press.
operations. This would also include a section on
flammable mixtures and how their material properties [3] ANSI/API RP 500, Recommended Practice for
were estimated. Classification of Locations for Electrical Installations at
4) A hazardous materials worksheet that documents Petroleum Facilities Classified as Class I, Division 1 and
the properties of the flammable materials handled Division 2, American Petroleum Institute, Washington,
within the facility. The flashpoint, group DC, 1998.
classification, autoignition temperature, LFL/UFL and
hazard classification is summarized for each process [4] ANSI/API RP 505, Recommended Practice for
stream. Classification of Locations for Electrical Installations at
5) A source of release worksheet that identifies the Petroleum Facilities Classified as Class I, Zone 0, Zone
most likely release points within a facility. 1, and Zone 2, American Petroleum Institute,
6) The basis for the group classification and Washington, DC, 1998.
autoignition temperature for the overall facility.
7) A summary of any fugitive emission and ventilation [5] Propst, John, E., Volatility and Mists—Electrical Area
calculations. Classification's Important Variables, IEEE Transactions
8) Recommendations for gas detector placement on Industry Applications, Vol. 36, No. 2, March/April
including information on what flammable gases are 2000.
to be detected and the calibration procedure required
for gas detector maintenance. [6] ASTM E 681-04, Standard Test Method for
9) A list of recommendations for operation and Concentration Limits of Flammability of Chemicals,
maintenance activities performed in classified areas. American Society for Testing and Materials,
10) The area classification layout drawings should Conshohocken, PA, 2004.
incorporate a note that references the study report
as the bases for the area classification design. [7] IEC 60079-4, Electrical Apparatus for Explosive Gas
Atmospheres Part 4: Method of Test for Ignition
The hazardous area classification study report provides Temperature, International Electrotechnical Commission,
essential information for understanding the basis for the Geneva, Switzerland 1975.
original hazardous area classification and for planning any
future modifications to the area classification design for the [8] ASTM E659-78, Standard Test Method for Autoignition
facility. Temperature of Liquid Chemicals, American Society for
Testing and Materials, Conshohocken, PA, 2005.
VII. CONCLUSION
[9] NFPA 325, Guide to Fire Hazard Properties of
Performing a hazardous area classification risk analysis Flammable Liquids, Gases and Volatile Solids, National
requires an understanding of how flammable mixtures Fire Protection Association Quincy, MA., 1994.
behave. In an ideal world, the properties of a flammable
mixture would be determined by test procedure; however, this [10] API RP 2216, Ignition Risk of Hydrocarbon Liquids and
is impractical in most cases. Methods are required to Vapors by Hot Surfaces in Open Air, American
estimate the properties of flammable mixtures to support a Petroleum Institute, Washington, DC, 2003.
hazardous area classification analysis.
Predicting the relative vapor density of a mixture is a simple
calculation that compares the molar weight of the mixture to
[11] Colwell, J.D., Reza, A., Hot Surface Ignition of [19] Crowl, Daniel, A., Understanding Explosions, American
Automotive and Aviation Fluids, Fire Technology, 41, Institute of Chemical Engineers, New York, New York,
105-123, 2005. 2003

[12] NFPA 497, Recommended Practice for the Classification [20] Perry’s, Chilton, Kirkpatrick, Perry’s Chemical Engineers
of Flammable Liquids, Gases, or Vapors and of Handbook, McGraw-Hill Inc. New York, New York, 1963.
Hazardous (Classified) Locations for Electrical
Installations in Chemical Process Areas, National Fire
Protection Association Quincy, MA., 2004.

[13] Fire Protection Guide to Hazardous Materials, National H. VITA

Fire Protection Association, Quincy, MA., 2002.
Allan Bozek, P.Eng., MBA, is a Principal with EngWorks Inc.
[14] IEC 60079-10, Electrical Apparatus for Explosive Gas providing consulting engineering services to the oil and gas
Atmospheres – Part 10 Classification of Hazardous industry. He is a registered professional engineer in the
Areas, International Electrotechnical Commission, provinces of Alberta and British Columbia, Canada and has
Geneva, Switzerland, 2002. been a member of the IEEE since 1989. Allan’s areas of
expertise include hazardous area classification, power
[15] IEC 60079-20, Electrical Apparatus for Explosive Gas systems design, protective relaying and grounding for large
Atmospheres – Part 20 Data for Flammable Gases and scale industrial and petrochemical facilities. Mr. Bozek
Vapours, related to the use of Electrical Apparatus, graduated from the University of Waterloo in 1986 with BASc
International Electrotechnical Commission, Geneva, in Systems Design Engineering and a MBA from the
Switzerland, 2000. University of Calgary in 1999. Allan may be contacted at
ABozek@EngWorks.ca
[16] Briesch, Edward, NEC Group Classification of Mixtures,
American Institute of Chemical Engineers, 34th Loss Vince Rowe retired from Shell Canada in 1994 and continues
Prevention Symposium, Atlanta, Georgia, March 8, 2000. to be active in the Oil and Gas industry as a consultant. He
provides training on electrical installations and maintenance in
[17] Report on Proposals NFPA 497, Report of the classified locations. He is a partner with Marex Canada
Committee on Electrical Equipment in Chemical Limited and a member of the steering committee for the
Atmospheres, F2007. Canadian Electrical Code. He is Chairman of the Hazardous
Location and Electric Heating sections and one of the
[18] Hristova, M., Tchaoushev, S., Calculation of Flash Points initiators of the Objective Based Industrial Electrical code for
and Flammability Limits of Substances and Mixtures, Canadian Industry. Mr. Rowe graduated from the University
Journal of the University of Chemical Technology and of Manitoba in 1960 with a Bsc in Electrical Engineering.
Metallurgy, 41, 3, Pg 291-296, 2006. Vince may be contacted at Vince.Rowe@shaw.ca