Limiting Oxygen Concentrations of Gases
Laurence G. Britton,a Martin P. Clouthier,b,c Benjamin K. Harrison,d and Samuel A. Rodgerse
a
AIChE Fellow, Charleston, WV; lbritton.consult@suddenlink.net (for correspondence)
b
Fauske & Associates, Halifax, NS, Canada
c
Department of Process Engineering and Applied Science, Dalhousie University, Halifax, NS, Canada
d
Department of Chemical and Biomolecular Engineering, University of South Alabama, Mobile, AL
e
Honeywell, Colonial Heights, VA
Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/prs.11806
This article discusses technical and practical aspects of
the limiting oxygen concentration (LOC) including a
detailed appraisal of possible sources of measurement error.
LOC values obtained in the “classical” 5-cm diameter, verti-
cal tube apparatus have been described as nonconservative
owing to flame quenching. However, much of the difference
between classical LOC values and those obtained in closed
vessels using ASTM E2079 is due to the change in the defini-
tion of “ignition.” Formerly defined as propagation of a visi-
ble flame through a vertical tube at least 1.5 m tall, which
in a closed tube would typically generate an overpressure in
excess of 100%, ignition is now defined as an overpressure
that exceeds 7%. The small pressure rise criterion tends to
underestimate the LOC in smaller test vessels, especially for
tests made at elevated pressures and temperatures. More use
should be made of ASTM E2079’s flexibility regarding the use
of larger pressure rise criteria. Having lost sight of the flame,
it is important not to lose sight of the objective, namely to
select test criteria that correctly predict the flammable limits
pertaining to large volumes of gas mixture. Additional
“reference quality” LOC data are needed both to improve the
definition of “ignition” with respect to test vessel volume and
to investigate the accuracy of LOC estimation techniques.
Any large-scale reference quality test program should investi-
gate the effect of low levels of forced turbulence on measured
LOC values.
The NFPA “Explosion Protection Systems” Technical Com-
mittee recently supported the development of two Tentative
Interim Amendments (TIAs) to NFPA 69 “Standard on Explo-
sion Prevention Systems.” The first TIA resolves issues with
the table of LOC values for gases, which had been modified
and over-corrected in the 2008–2014 editions. The second
TIA introduces a simple method for estimating the LOCs of
single gases and gas mixtures based on the equation
LOC 5 LFL 3 S, where LFL is the lower flammable limit and S
the molar stoichiometric ratio of oxygen to fuel. An Appendix
describes the two TIA recommendations while a second
Appendix describes how the estimating methods have been
incorporated into ASTM’s “CHETAH” Program. V C 2016 Ameri-
can Institute of Chemical Engineers Process Saf Prog 35: 107–114,
2016
Additional Information in the form of Appendices A and B may be
found in the online version of this article.
C 2016 American Institute of Chemical Engineers
V ancy can be attributed to a difference in LOC definition, since
Process Safety Progress (Vol.35, No.1)
Keywords: limiting oxygen concentration; limiting oxygen
concentration measurement; flammability; inerting
INTRODUCTION
Chapter 7 of NFPA 69 “Standard on Explosion Prevention
Systems” (2014) presents formal procedures for “Deflagration
Prevention by Oxidant Concentration Reduction.” The gen-
eral practice is usually known as “inerting,” which involves
the addition of inert gas to a mixture of fuel and oxygen so
that the oxygen stays some specified margin below the
“limiting oxygen concentration” or LOC. The LOC is defined
as the smallest concentration of oxygen that can support a
self-propagating flame whatever the concentrations of fuel
and diluent. This article focuses on oxygen and nitrogen
although inerting can be applied to other oxidants and inert
gases. Nitrogen is the most commonly used inert gas, as
described, for example, by Yanisko et al. [1].
Annex C of NFPA 69 contains “additional information” on
inerting and includes a widely used table of LOC values for
gaseous fuels [2]. In the 2008 edition, most of the tabulated
LOC values were decreased by 2 mol % oxygen, regardless
of their initial magnitude. This was prompted by LOC data
recently measured in a large (120-L) test vessel using the cur-
rent standard test method ASTM E2079-07 [3] and considered
state-of-the-art. New LOC data for hydrogen, carbon monox-
ide, methane, and propane [4] were 7.5 6 0.5% smaller than
“classical” values measured using the 5-cm diameter, vertical
tube apparatus. However, the new LOC for ethylene was
15% smaller (8.5 mol % oxygen as opposed to the classical
10.0 mol % value). It was hypothesized that the 5-cm vertical
tube may have caused excessive quenching at the LOC and
to offset this effect, the NFPA 69 Technical Committee
adjusted all classical LOC values downward by 2 mol % oxy-
gen. LOC values measured using ASTM E2079-07 or appara-
tus approximating to its requirements were not adjusted.
Surprisingly, there were no public comments about these
changes although not all Technical Committee members
agreed with the approach. There’s no direct evidence that
the 5-cm vertical tube causes more flame quenching at the
LOC than it does at the lower flammable limit (LFL) and
upper flammable limit (UFL), the likelihood of which was
discounted by the U.S. Bureau of Mines following extensive
testing in larger diameter tubes; see, for example, Lewis and
von Elbe [5].
This article makes the case that much of the LOC discrep-
March 2016 107
the classical 5-cm vertical tube test method required a flame to
propagate the full length of a tube at least 1.5 m tall (which in
a closed tube would typically produce a pressure rise in excess
of 100%) while the ASTM E2079 closed vessel test method
requires only a 7% pressure rise. Indeed, in cases where Zlo-
chower and Green observed a pressure rise of about 30% the
corresponding LOC values (apart from ethylene) were much
the same as the classical ones. Moreover, it’s proposed that the
classical LOC data were subject to a number of experimental
errors that were deliberately avoided by Zlochower and Green.
In all cases where experimental errors resulted in overesti-
mated classical LOC values, the experimental error and the
“definition” error become additive. This is because the new
definition always results in smaller LOC values.
Ethylene’s classical LOC value of 10.0 mol % oxygen
derives from two studies reviewed by Coward and Jones [6];
the first involved mixtures of ethylene, oxygen, and nitrogen
while the second involved mixtures of ethylene, air, and nitro-
gen. In both cases, a 5-cm vertical tube apparatus was used.
In the first case, a fuel-oxygen flammability diagram was pre-
sented that directly gave the LOC as 10.0% oxygen. In the sec-
ond case, a flammability diagram of fuel versus added
nitrogen was presented, showing the LOC was reached after
the addition of 50% nitrogen. No grid was shown but the eth-
ylene concentration at the LOC appears to be about 3.5%.
The LOC is therefore approximately 9.7% oxygen, which is
roughly the same value found in the other study. Since a 5-
cm vertical tube should not quench near-LOC ethylene flames
to a greater extent than CO, H2, CH4, and C3H8, we propose
instead that both classical studies were flawed; the fact that
different workers found roughly the same LOC value is con-
sidered to be a coincidence rather than a confirmation. We’ll
explore sources of error later in this article but one reason
why two similarly high LOC values should have been
obtained for ethylene is that two similarly weak ignition sour-
ces might have been used. The most frequently used ignition
source was a continuous arc as opposed to a discrete spark
having a high power density; it’s plausible that “weak
ignition” errors are more pronounced at the LOC than at the
more commonly measured LFL. Another possible reason is
that unlike most hydrocarbons, ethylene’s LOC occurs at a Figure 1. Schematic Cartesian flammability diagrams for (a)
fuel concentration not far above the LFL; the so-called “nose” propane and (b) carbon monoxide in air plus diluent
region shown in typical flammability diagrams such as those (Adapted from Ref. 6, with permission from U.S. Bureau of
of Kuchta [7] is relatively elongated and narrow. Conse- Mines). [Color figure can be viewed in the online issue,
quently, an insufficient number of tests might have been per- which is available at wileyonlinelibrary.com.]
formed near the optimum LOC composition.
Following publication of the 2014 edition of NFPA 69, we
proposed two Tentative Interim Amendments (TIAs) that LOC in Relation to Flammability Diagrams
were favorably received by the Technical Committee. The Let’s first consider the LOC in relation to a flammability
first TIA changes the LOC adjustment process and the associ- diagram. The LFL is the smallest concentration of fuel that
ated table of LOC values; this effectively increases all of the can propagate a flame when mixed with an oxidant and is
classical LOC values that were previously overcorrected. The found to be approximately the same for both oxygen and
second TIA describes a technique for estimating LOC values air. This is because the oxidant (oxygen) and diluent (nitro-
from LFL values, plus worked examples showing how to gen) have almost identical heat capacities and in both cases
estimate LOCs of gas mixtures starting either from measured there’s an overabundance of oxygen, since the oxygen con-
LOC or LFL values. The detailed TIAs are presented in centration greatly exceeds the “stoichiometric” concentration
Appendix A. The LFL and LOC of single fuels can be calcu- needed for complete combustion. As additional nitrogen is
lated for many fuels using ASTM’s “CHETAH” Program with- added to the mixture, there’s negligible increase in the LFL
out reference to test data. Appendix B describes how until the oxygen concentration is decreased sufficiently to
CHETAH has been updated to allow similar estimates to be become rate controlling. Beyond this point, the lower limit
made for mixtures. concentration of fuel increases above the LFL and the flam-
mable region forms the familiar “nose” of a flammability dia-
gram. This is illustrated for propane by Figure 1a. At the
DISCUSSION LOC, the LFL curve joins the UFL curve as shown in Figures
We will now discuss technical aspects of the LOC concept 1 and 2. As illustrated by Figure 1b for carbon monoxide,
and practical application, including a critical review of cur- fuels whose diffusivities are closer to that of oxygen exhibit
rent LOC measuring techniques. LOC values closer to the point P. As discussed later, this

108 March 2016 Published on behalf of the AIChE DOI 10.1002/prs Process Safety Progress (Vol.35, No.1)

Figure 2. Ethylene triangular flammability diagram. [Color
figure can be viewed in the online issue, which is available
at wileyonlinelibrary.com.]
point represents the oxygen concentration needed to com-
pletely burn the LFL concentration of fuel. Since Figure 1 is
plotted as a Cartesian fuel-oxygen flammability diagram, the
“nose” region is underemphasized compared with either tri-
angular flammability diagrams or those that depict the vol-
ume of added nitrogen needed to inert various
concentrations of fuels in air.
By definition, the LOC is independent of the concentra-
tions of fuel and diluent so there are actually two possible
LOC locations, the “lower” near the LFL concentration of fuel
and the “upper” at the UFL in oxygen. For example, carbon
monoxide’s UFL in oxygen is about 95%; since the diluent
concentration is zero for fuels in oxygen, the “upper” LOC is
about 5% oxygen regardless of the type of diluent. The
“upper” LOC is increasingly likely to be the lower of the two
values when the diluent is more effective than nitrogen
(such as H2O or CO2) and the fuel has a high UFL. The
state-of-the-art LOC tests described earlier [4] did not include
investigation of the “upper” LOCs for hydrogen or CO in
oxygen so the results only strictly apply to the “lower” LOC
such as fuel mixtures with air.
The existence of an “upper” LOC is implied by Figure 41
of Kuchta [7], which shows a flammability diagram for mix-
tures of hydrogen and air with either N2 or CO2 diluent. As
expected, the LOC was shown to occur at a fuel concentra-
tion near the LFL although only a marginally greater oxygen
concentration was required at the UFL in air. Although not
discussed by Kuchta, various mixtures of fuels with enriched
air or oxygen may exhibit an “upper” LOC that is less than
the “lower” LOC, especially when the diluent is more effec-
tive than nitrogen. UFL data for fuels in oxygen are scarce
but a few additional examples together with their approxi-
mate “upper” LOC values are: methanol (7%), acetaldehyde
(7%), and trichloroethylene (9%). The UFL data were taken
from Table 6 of Kuchta [7]. Using current ASTM closed vessel
test methodology, it’s expected that the UFL values would be
increased leading to smaller “upper LOC” values. In the case
of “electronic” gases such as dichlorosilane, both the “upper”
and “lower” LOC values are so small that they would be dif-
ficult to differentiate experimentally. Discussion of flamma-
bility diagrams is resumed later.
Process Safety Progress (Vol.35, No.1) Published on behalf of the AIChE
Process Applications of LOC and MOC
The LOC was formerly known as the minimum oxygen con-
centration (MOC). However, to avoid confusion the term “MOC”
should be reserved for certain process applications where fuel
concentrations are held at or above some minimum value.
The LOC can be determined at any stated conditions of
pressure and temperature provided it allows for all possible
concentrations of fuel and diluent. For example, Figure 2
shows ethylene’s LOC at 608C and 16 psia (1.10 bara). The
test conditions were intended to simulate a typical Gulf Coast
vent header [8]. Ethylene’s LOC was found to be 8 mol %
oxygen rather than the classical LOC value of 10 mol %. This
was despite using oxygen analysis plus a robust 100% pres-
sure rise criterion to denote ignition. Furthermore, testing
under identical test conditions had given methane’s LOC as
12% oxygen, the same as the classical value. The apparent
decrease of ethylene’s LOC couldn’t be accounted for by the
elevated temperature of 608C and marginally elevated pres-
sure. Publication of the findings led to the further investiga-
tion of ethylene’s LOC as discussed earlier.
LOC values are commonly measured and tabulated for
atmospheric pressure conditions although a specified elevated
temperature is required for less volatile fuels. As shown in
Appendix A, several of the LOC values in NFPA 69 were meas-
ured at 608C. This is the high end of the range considered by
UN/DOT as normal transportation temperatures. It’s also a con-
venient “standard” LOC test temperature for fuels such as low
molecular weight polar solvents that could otherwise create
errors owing to condensation during a test. Another “standard”
elevated temperature, which is likewise based on transporta-
tion regulations and the NFPA 704 “Flammability Hazard Class”
demarcations, is 938C (2008F). The use of “standard” elevated
temperatures is encouraged to facilitate tabulation and compar-
ison of LOC values.
For application to partial oxidation reactors, the term
“MOC” is used when operating with a specified minimum
fuel concentration. It differs from “LOC” insofar as the fuel
concentration is constrained and only diluent concentration
is an independent variable. With a specified minimum fuel
concentration, a process can be designed to operate in the
nonflammable region above the UFL curve as shown in Fig-
ure 2. Partial oxidation processes are typically controlled by
oxygen concentration and the operating envelope is con-
trolled above the pertinent MOC range using appropriate
safety factors. When the fuel concentration is constrained at
a relatively high value as required for commercial processes,
the MOC greatly exceeds the LOC and the two terms cannot
be used interchangeably. The MOC can be a function of
multiple time-dependent process conditions, in which case
calculation of this variable may need to be programmed into
the digital control system using a complex polynomial or
other equation derived from extensive test work.
Paragraph 7.7.2.6 of NFPA 69 presently exempts “partial oxi-
dation processes” from operating under the low oxygen
requirements of Paragraph 7.7.2.5, which would otherwise
make such processes unviable. However, the processes could
arguably be exempted entirely from Subsection 7.7.2 “Systems
Operated Below The Limiting Oxidant Concentration (LOC),”
since during steady operation they are better described by Sub-
section 7.7.3 “Systems Operated Above The Upper Flammable
Limit (UFL).” The LOC is only relevant to partial oxidation
processes during procedures such as start-up after opening
equipment to the air; during steady operation, the LOC
becomes irrelevant and the process is controlled below the
prevailing MOC.
Preferential Diffusion at the LOC
The “lower” LOC occurs at the optimum fuel/oxygen ratio
for upwards flame propagation. The optimum mixture may
DOI 10.1002/prs March 2016 109
be greater or less than stoichiometric depending on the rela-
tive diffusivities of fuel and oxygen. As summarized by Lewis
and von Elbe [5]: “the more diffusive constituent (either fuel
or oxygen) is always stoichiometrically deficient.” The stand-
ard binary diffusion coefficient of oxygen in nitrogen at 1
atm and 298 K is 0.22 cm2/s. Normal butane with a diffusion
coefficient of 0.10 cm2/s is much less diffusive than oxygen
and its flammability diagram shows an upturned “nose” at
the LOC. In this case, the optimum fuel concentration occurs
at 140% of stoichiometric. Oxygen diffuses into the flame
front and maintains optimum (stoichiometric) conditions
locally despite the overall mixture being fuel rich. Con-
versely, hydrogen with a diffusion coefficient 0.78 cm2/s is
far more diffusive than oxygen and the optimum mixture
occurs at only 70% of stoichiometric.
When the fuel and oxygen diffuse at similar rates, for
example, carbon monoxide, ethylene, or methanol, the effect
of “preferential diffusion” is marginal although the LOC
“nose” may still be observed for upwardly propagating
flames. Complex interactions involving preferential diffusion
plus gravitational effects are described by Lewis and von
Elbe [5] with respect to the measurement of upward flame
propagation limits.
Possible Effects of Turbulence
Owing to preferential diffusion effects, the oxygen con-
centration at the flame front is governed by local mixing and
differs from the overall gas composition or “measured LOC.”
Consequently, one might expect low levels of forced turbu-
lence to alter the measured LOC by affecting local mixing at
the flame front. If the lowest LOC values are obtained under
quiescent conditions, forced turbulence should generally
increase the measured LOC. If so, one should minimize
flow-induced turbulence during standard LOC tests using a
large, unstirred apparatus with central ignition rather than a
closed, vertical tube ignited at the lower end. A more inter-
esting outcome is if forced mixing typically decreases the
LOC and brings the measured value into closer alignment
with the value estimated using the approximation that “the
LOC is that concentration of oxygen that will completely
combust the LFL concentration of fuel.” This condition is
given by the equation LOC5LFL3 S and is represented by
the point P shown in Figures 1a and 1b.
The 7% Solution
Over the years, various pressure rise criteria have been
proposed for identifying an “ignition” when testing for flam-
mable limits in closed vessels [9]. A 7% pressure rise criterion
was originally proposed because 1 psig approximates to the
overpressure threshold for breaking window glass. Also, a
7% overpressure exceeds the background pressure rise
caused by firing igniters in typical laboratory test vessels con-
taining common gas mixtures below their LFLs. Although a
fixed value fails to address the wide range of limit flame tem-
peratures and molar expansions exhibited by disparate fuels,
the 7% pressure rise criterion seemed to be a conservative
yet reasonable solution and was adopted by ASTM. In 2005,
members of the ASTM E27 “Hazard Potential of Chemicals”
committee published an article discussing the evolution of
flammability test standards including the new LOC standard
ASTM E2079 [10].
In April 2007, the ASTM subcommittee responsible for gas
flammability standards held a teleconference to discuss vari-
ous problems being experienced when applying the 7%
pressure rise criterion. Several proposals were made includ-
ing the use of a pressure rise criterion that decreased with
increasing vessel size, an additional criterion of “cusp”
behavior in a plot of concentration versus pressure rise and
110 March 2016 Published on behalf of the AIChE
some minimum temperature rise recorded by sensitive ther-
mocouples. The following year these and other ideas were
published by Brandes and Ural [11].
For laboratory testing, it’s important to match the over-
pressure criterion adopted with the size of the test vessel,
the type of ignition source and other factors. After the igniter
is fired, there’s always some combustion in excess of the
heat released by the igniter, even if the test mixture is sub-
stantially outside the flammable envelope. An overdriven
flame may propagate a significant distance before self-
extinguishing and this results in an overpressure that in a
laboratory test vessel can amount to several percent of the
initial pressure. Even if no hot flame is apparent, reaction
may nevertheless occur in the rising plume of hot gas mix-
ture above the igniter. Whenever this is significant, the pres-
sure rise corresponding to mixtures just outside the
flammable envelope should be set as a DP “baseline” to
which the standard 7% pressure rise is added. The sum
might result in a practical pressure rise criterion of about
12% or more.
The 120-L state-of-the-art LOC tests were run at normal
atmospheric conditions using test gases having large ignition
temperatures (CO, H2, CH4, C2H4, and C3H8); additionally,
the large size of the 120-L vessel minimized background
pressure effects caused by overdriven flames. These particu-
lar test gases are less prone to overdriving than fuels with
small ignition temperatures such as oxygenated solvents.
Large and highly variable “baseline” pressures are exhibited
by various alcohols, aldehydes, ketones, and ethers, particu-
larly if tests are made in relatively small vessels at elevated
temperatures and pressures. In such cases and especially
where cool flame phenomena occur, it might be necessary to
set the pressure rise criterion between 30 and 100%.
Although not prominent, “Note 1” of ASTM E2079 allows
users to adopt a larger pressure rise criterion where neces-
sary and references Britton [12] who made a number of rec-
ommendations after working with oxygenated fuels
including aldehydes.
Errors in LOC and MOC Measurement
Since the LOC involves a ternary mixture, it’s inherently
more prone to measurement error than either the LFL or the
UFL, especially when mixtures are made up by partial pres-
sures without oxygen analysis to confirm the calculated com-
position. The following list should help improve the poor
reproducibility sometimes found for gas flammability data
obtained using the same standard methods:
Pressure Rise Criterion Is Too Small
ASTM E2079-07 allows test vessels as small as 4 L with an
aspect ratio  2 to be used for LOC testing with an ignition
pressure rise criterion of 7%. As discussed earlier, ASTM
E2079 allows a larger pressure rise criterion to be used
where appropriate.
Ignition Source Is Weak
Energy is usually dissipated inside closed test apparatus
using a fuse wire, since, unlike spark igniters, these can be
used at high pressure and aren’t easily shorted out. The
exploding fuse wire should dissipate a high power density.
Although energy dissipation from fuse wires isn’t as fast or
as localized as from a high voltage spark these limitations
are offset by using energies of tens of Joules. The stored
energy needs to be dissipated within the rise time of the
flame kernel, which can be as short as a few milliseconds.
Much of the stored energy can be lost in the circuit unless
the power cables and connectors are heavy-gauge, low-
resistance types designed for high currents. Higher
DOI 10.1002/prs Process Safety Progress (Vol.35, No.1)
resistances and capacitances increase the RC time constant of
the circuit and can lead to extended discharge times. The
combination of long discharge times, large circuit losses, and
a reduced oxygen atmosphere may result in the wire not
exploding but instead functioning as a glowing wire. The
time constant is decreased using higher voltages, shorter
cables, and lower storage capacitances. The 5.3-L apparatus
described in [8,12] was equipped with switched parallel fuse
wires that were each designed to dissipate 30 Joules of
energy within 5 ms, as confirmed by high speed digital V-I
measurements across the igniter itself. Prior to upgrades in
the 1980s most of the stored energy had been lost heating
the power cables and much of what remained might have
been dissipated wastefully, after flames had already become
self-sustaining.
Compressed Air Isn’t “Air”
It’s important to define the LOC and other flammable lim-
its on a dry gas basis since, depending on temperature and
relative humidity, atmospheric air can contain several mole
percent of water vapor. Since water vapor would otherwise
act as an inert component, testing on a dry gas basis pro-
duces conservative results. Although argon (0.93 mol %) is
usually neglected, it’s effectively grouped with nitrogen
when oxygen is specifically analyzed. Compressed air is usu-
ally not “standard” air; for example, CGA Grade D com-
pressed air cylinders (OSHA breathing air) can contain
between 19.5–23.5 mol % oxygen plus up to 0.1 mol % car-
bon dioxide. Although CGA Grade J (specialty/analytical
grade) has much tighter restrictions on trace gases, it con-
tains the same range of oxygen concentrations as Grade D.
Dry “synthetic air” made up for test purposes should contain
the “standard” concentration of oxygen in air
(20.94 6 0.1 mol %) as required under Section 6.3 of ASTM
E681-09 (2015). This requirement is currently absent from
ASTM E 2079. Moreover, this requirement is missing from
two of the five ASTM standards that address the flammability
of dust clouds.
Wrong Strain Gauge
When making up mixtures using the method of partial
pressures a sensitive strain gauge must be used rather than
the high range strain gauge used to measure the deflagration
pressure rise. Calibrations can drift so both zero and span
should be routinely checked. Also, if the gauges are exposed
to elevated temperature they must be temperature
compensated.
Mixture Isn’t Mixed
ASTM E2079 doesn’t require the test vessel to be
equipped with a mixer or gas analyzer although it requires
“uniform mixing of the components before attempting
ignition.” However, the 120-L test vessel used by Zlochower
and Green [4] was equipped with an internal fan and sam-
ples were taken to confirm that thorough mixing was accom-
plished. Smaller vessels such as the 20-L apparatus are
difficult to retrofit with a mixing device but lack of a mixer
may cause errors, especially when testing liquids or vapors
subject to condensation during testing.
Fuel Condenses
After adding the test liquid and allowing it to evaporate,
oxidant and diluent gases are added from cylinders and the
cold gas jets often re-condense some of the vapor. Addition
of diluent is sometimes used to assist mixing, in which case
it’s done last. Condensation decreases the fuel in the vapor
phase and to reach the target pressure more gas is added
resulting in too much oxidant or diluent depending on the
order of addition. Condensed liquid can become trapped in
Process Safety Progress (Vol.35, No.1) Published on behalf of the AIChE
connected lines and crevices such as strain gauge casings
and even if the vessel is stirred, which is often not done at
all, trapped liquid is mostly unaffected. The result is usually
an underestimate of the concentration of oxidant since the
target pressure is based on the initial measurement of fuel
partial pressure. In an extreme case, it might be impossible
to make steady pressure measurements until all the adventi-
tious cold traps are filled with liquid. To minimize condensa-
tion problems, Britton [12] used a twin vessel method with
both vessels placed inside a convection oven, including all
connected lines and gauges. Only the oxygen analyzer was
outside the oven and the sampling line was extensively heat
traced. In general, the test temperature must exceed the
value calculated to produce the required vapor pressure of
fuel. Standard elevated temperatures considered by ASTM
2079 are 60 and 938C.
No Oxygen Analyzer
The previous two sources of error can be mitigated using
an oxygen analyzer. To obtain a reliable reading from the
test vessel using a paramagnetic analyzer or other flow
instrument, the test mixture must be made up at an elevated
pressure. For potentially condensable liquids, the fuel vapor
pressure needs to be considered in relation to the test tem-
perature. Oxygen analysis isn’t required by ASTM E2079
although a single confirmatory oxygen analysis is required
by EN 14756 [13] and this value must agree to within
60.2 mol % of the calculated concentration. As a practical
matter, if paramagnetic oxygen analysis is used to confirm
the calculated oxygen concentration in the test mixture, the
initial pressure must be adequate to generate the required
flow rate and sampling time of the analyzer. For 5-L test ves-
sels, an initial pressure of 25 psia (1.7 bara) might be neces-
sary and the temperature must be adequate to maintain the
fuel as a vapor during this sampling period. Since paramag-
netic analyzers respond to oxygen partial pressure, the sen-
sor unit is maintained at a fixed pressure and temperature. If
the sample flow rate and temperature aren’t properly
selected, the analyzer will give erroneous readings.
Cool Flames Occur
Britton [12] showed that at elevated temperatures and
pressures, it’s impractical to use a 7% pressure rise as an
ignition criterion for gases subject to cool flame phenomena,
whether or not this is added to a small “baseline” DP value.
On fuel-oxygen flammability diagrams the phenomena may
form a “second lobe” on the fuel-rich side of the LOC “nose.”
Calculations showed gas compositions in this “second lobe”
had adiabatic flame temperatures less than 1,000 K which are
inadequate to support hot flame propagation. Recommenda-
tions for avoiding these problems were later incorporated
into ASTM E2079-07. The significance of cool flames is that
the reaction might transition to a two-stage ignition or an
autoignition. However, although autoignition is not pre-
vented by operating below either the LOC or MOC, a
flame by definition cannot propagate into properly inerted
equipment connected to the zone where such phenomena
occur [12].
Irreproducible Positive Results
ASTM E2079 requires the LOC to be calculated as the
average of the lowest oxygen concentration at which ignition
occurs L and the highest oxygen at which ignition doesn’t
occur H. In case the lowest observed L is wrong owing to
one of the many possible errors, ASTM E2079 provides that
at the LOC the difference between H and L should not
exceed 0.5 mol % oxygen. In some test standards, a single
positive result is allowed to outweigh any number of nega-
tive results with no requirement for even a single
DOI 10.1002/prs March 2016 111
confirmation! Using ASTM E2079, if H 2 L exceeds 0.5 mol
% oxygen and the gap cannot be narrowed with more test-
ing, the lower value can be discarded.
Complex Liquid Fuel Mixtures
Commercial liquid fuels are better characterized by distil-
lation ranges than by flash points; this is due to the wide
boiling point range of the components (which may run into
the hundreds). In such cases, it’s neither practical nor appro-
priate to test the entire mixture. For applications such as
inerted naphtha, kerosene, or diesel storage tanks, a suitable
LOC value is normally assumed rather than measured. Even
if commercial fuel mixtures contain aromatic components,
inerting to below 5–6 mol % oxygen usually meets NFPA 69
requirements. If a representative LOC value is necessary, a
specialized test needs to be conducted so that minor compo-
nents in the liquid phase are not under-represented in the
vapor phase once the system has achieved vapor-liquid equi-
librium. The problem of providing an adequate liquid reser-
voir is discussed by Britton and Smith [14] in relation to
storage tanks at high elevation, where the lower prevailing
pressure significantly decreases the “flash point.” Numerous
unexpected land-based diesel and kerosene tank fires have
occurred at high altitude. Perhaps the most critical applica-
tion is the LOC of aviation fuels which must address the
worst case with respect to both temperature and pressure.
Special large scale tests are described in the literature.
Fuel Reacts Rapidly with Oxidant
For some process applications involving reactive gas mix-
tures, the LOC or MOC must be measured in a flow system.
Aromatics with chlorine oxidant are particularly difficult.
Testing techniques are highly specialized and beyond the
scope of this article.
“Experimental Error” Versus “Definition of Ignition
Error”
There are two sources of discrepancy between classical
LOC values and current LOC values. Of these, the definition
of ignition error (propagating flame in tube vs. 7% pressure
rise in closed vessel) might account for up to about 10% of
the absolute LOC (for example 1 mol % oxygen when the
LOC is 10 mol % and 0.5 mol % oxygen when the LOC is
5%) and is generally negative, so that “new” LOC values are
less than classical values. Assuming the new LOC values are
correct and that experimental errors in classical data account
are normally random (such as composition errors) rather than
biased (such as weak ignition errors), the discrepancy caused
by experimental errors may or may not be additive to the def-
inition error. For a particular igniter, the repeatability of ASTM
E2079 should be within 0.5 mol % oxygen so experimental
errors associated with classical LOC determinations should not
be better than 60.5 mol % oxygen. With respect to the recent
large-scale ASTM tests, the average observed discrepancy was
about 7.5% of absolute LOC but increased to about 15% for
ethylene. The latter case could correspond to a condition
where all the errors were large and additive.
Additional testing in a 5-cm vertical tube would determine
whether or not the discrepancy found for ethylene was due
to flame quenching. If ethylene cannot propagate, a flame
below 10% oxygen using an adequate ignition source the
quenching thesis will have been validated, and vice versa.
LOC Estimation
If complete combustion occurs and if the LFL does not
decrease as diluent is added, the LOC cannot be smaller than
the product of LFL and the stoichiometric ratio S. Equation 1
112 March 2016 Published on behalf of the AIChE
should, therefore, predict the LOC conservatively in all cases,
provided the LFL value is reliable.
LOC5LFL3S (1)
According to Eq. 1, the location of the LOC is at point P
on Figures 1a and 1b. Where identical test methods are used
to measure LFL and LOC, Eq. 1 typically underestimates the
LOC by up to about 2 mol % oxygen. This conservative
result is usually satisfactory because a safety factor of at least
2 mol % oxygen is required by NFPA 69 and very precise
LOC values are typically not needed. In some cases, Eq. 1
overestimates the LOC, but usually this is due to the assumed
LFL value being too high. There are a few cases (such as CO
as shown in Figure 1b) where the LOC is apparently overes-
timated by about 1 mol % oxygen but this is less than the
minimum applied safety factor.
Britton [8] cited Bodurtha [15] as the source of Eq. 1 and
commented that a likely source of error when applying the
equation is that any error in LFL becomes multiplied by S,
which for aromatics and other fuels with relatively high
molecular weights can have a value up to 10 or more. For
example, styrene is easily condensable and has a small LFL
(0.9 mol %) which could easily be overestimated during a
test. The LFL commonly given in the literature is 1.1 mol %.
Application of Eq. 1 multiplies the error by 10 and the LOC
(9 mol %) is estimated as 11 mol %. This type of error is
illustrated by Table 2 of Hansen and Crowl [16].
When the fuel concentration at the LOC exceeds stoichio-
metric, the LOC is effectively a rich limit, with excess fuel
acting as a second diluent. Were the excess fuel partially oxi-
dized to CO, the assignment of S would become compli-
cated. However, one of the few fuels whose measured LOC
is less than the product LFL3 S is CO itself, which cannot be
partially oxidized in the flame. Since the excess CO contrib-
utes no heat, its involvement must be to enhance transport
properties despite the similarity in the diffusion rates of CO
and oxygen. The oxidation rate of CO is slow unless a
source of hydrogen is present—in which case the fuel system
is referred to as “moist” CO. Hydrogen acts as a catalyst and
the rate of oxidation of CO is controlled not via reaction
with oxygen but with OH radicals. Figure 1b, adapted from
Figure 13 of Coward and Jones [6], shows that the LOC of
moist CO occurs at about 17% fuel or 4–5 mol% above the
LFL concentration. The original Coward and Jones flammabil-
ity diagram shows the “nose” region far more clearly than
Figure 1b since it plots CO concentration versus “nitrogen
added to the original atmosphere” rather than oxygen
concentration.
Effects of Elevated Temperature and Pressure
Equation 1 can be applied to elevated temperatures by
adjusting the LFL value. Procedures for correcting the LFL
using a linear interpolation technique are discussed by Brit-
ton and Frurip [17]. The technique requires the lower limit
flame temperature to be known or estimated.
As discussed by Britton and Frurip [17], although the
effects of elevated pressure on LFL are relatively small, Eq. 1
predicts that the effects of pressure on LOC will be S times
as large. Consequently, while the effect on LFL might be less
than experimental error (0.1–0.2 mol % fuel) the effect on
LOC for relatively high molecular weight fuels might be of
the order 1 mol % and, therefore, significant.
Figure 41 of Zabetakis [18] shows that for natural gas, eth-
ane, and propane, the LOC decreases with increasing pres-
sure, although the gradients are relatively small. Britton and
Frurip [17] observed that one practical effect of elevated
pressure would have been to offset heat losses in the small
diameter test vessels used and this should account for at least
DOI 10.1002/prs Process Safety Progress (Vol.35, No.1)
part of the observed LOC decrease with increased pressure.
It was also observed that as pressures were increased up to
about 20 bar the measured LOC values tended toward those
predicted by Eq. 1.
ASTM’s CHETAH program is discussed in Appendix B.
The program allows LFL values to be estimated for many
organic fuels, either at a standard temperature of 298 K or at
a user defined elevated temperature. The LOC is estimated
from this LFL using Eq. 1. Pressure is not addressed and
without additional information on the topic it’s assumed that,
at least within certain limits, the effect of increased pressure
is marginal. Elevated pressure may actually increase the
accuracy of Eq. 1 since this is typically conservative for
organic fuels at atmospheric pressure.
Estimated LOC Values for Mixtures
Proposed TIA changes to NFPA 69 involve (1) revisions to
Annex Table C.1(a) and (2) a new section explaining how to
estimate the LOC of individual fuels or fuel mixtures. The
TIA proposals are detailed in Appendix A of this article.
Methods for estimating the LOC of fuel mixtures differ
depending on whether or not LOC values are available. Even
if only LFL values are available the LOC of mixtures can be
estimated. Methods exist for estimating LFL and hence LOC
at elevated temperature.
Prior to the general acceptance of these LOC mixture esti-
mation methods, many users have designed explosion protec-
tion based on controlling below the smallest LOC of the
component materials, clearly wasting a good deal of inerting
gas. Such waste is especially severe for large throughput waste
combustors such as flares, where headers are run under inert
conditions rather than fuel-rich conditions. A large underesti-
mation of mixture LOC will in such cases lead to the use of
excessive amounts of inert gas which could in turn lead to
additional natural gas input to the flare. The new approach
allows LOC estimates for complex mixtures and provides a sig-
nificant improvement over the assumption that a gas mixture’s
LOC is represented by the smallest LOC of any component.
Hybrid Approach
Although many LOC values are tabulated in NFPA 69, the
list is far from comprehensive. Appendix A describes the
general methodology for estimating the LOCs of mixtures
starting either with LOC values or LFL values. However, in
some cases a user may have “reliable” LOC values for some
components but only obsolete or unknown LOC values for
other components of a mixture. In such cases, a “hybrid”
approach may be used that combines the “reliable” LOC val-
ues with LOC values estimated using Eq. 1, which are gener-
ally conservative. The approach is very similar to the one
described in Appendix A and involves a temporary conver-
sion of all the LOC values to “pseudo-LFL” values using Eq.
1. These are then combined using Le Chatelier’s rule and
reconverted to a mixture LOC.
Elevated Temperatures
If the LOC is required at an elevated temperature, tabu-
lated LOCs can seldom be used directly. If the fuel compo-
nents all consist of carbon and hydrogen, with or without
nitrogen and chlorine, ASTM’s CHETAH program can be
especially helpful. CHETAH currently only allows calcula-
tions for fuels that burn to carbon dioxide and water, with or
without nitrogen and hydrochloric acid in the products. As
discussed in Appendix B, CHETAH requires no user input
apart from the fuel and temperature of interest to provide
estimates of the LFLs of single fuels and mixed fuels at the
user-defined temperature. Equation 1 is used to estimate the
corresponding LOCs. The method employed by CHETAH
Process Safety Progress (Vol.35, No.1) Published on behalf of the AIChE
tends to smooth out individual LFL errors in the literature
plus the effects these would have on the estimated LOC.
CONCLUSIONS
Flammable limits are used not only in safety analysis but
also in combustion science. In both cases, it’s important that
limits measured in the laboratory agree closely with the lim-
its observed in large volumes of gas. Although wider flam-
mable limits might be claimed to be “more conservative” it’s
not the job of a test laboratory to include safety factors in
the test method. Such safety factors should be included dur-
ing application of data, not during measurement. With
respect to closed vessel tests, having lost sight of the flame
it’s important not to lose sight of the objective, namely to
select test criteria that correctly predict the flammable limits
pertaining to large volumes of gas mixture [9].
Since these sentiments were published in 2002, European
test methods have continued to generate flammable limit data
outside the envelope of compositions within which flames
can propagate through large volumes of test mixture. Mean-
while, although the 7% pressure rise “ignition criterion” used
in ASTM E2079 has been shown to be valid during 120-L
“reference quality” tests, the scope of these tests was limited
to only five gases under normal atmospheric conditions. Also,
it’s been found that the 7% pressure rise criterion must often
be increased when using smaller test vessels, especially at ele-
vated temperatures and pressures. The need for a larger pres-
sure rise criterion under certain conditions is recognized by
ASTM E2079. Not only is there a provision for a “baseline”
pressure rise to which the standard 7% value is added, but
the pressure rise criterion can be substantially increased based
on “exploratory tests in the vicinity of limit mixtures.” How-
ever, since the procedure for selecting nonstandard pressure
rise criteria is vague, test laboratories may prefer to err on the
side of a conservative result. Some specific conclusions are:
1. Additional tests should be conducted in NIOSH’s 120-L
vessel or a similar large test vessel capable of producing
“reference quality” LFL and LOC data. Test gases should
include a variety of “CHON” fuels including examples of
fuels with low ignition temperatures. Tests should be
repeated under stirred conditions to address the effect of
mild turbulence, which might increase or (more impor-
tantly) decrease the measured LOC value. The test pro-
gram should preferably include elevated initial
temperatures or pressures. The LFL and LOC data would
be extremely helpful for evaluating LOC estimation tech-
niques such as those discussed in this article.
2. Additional testing should also be carried out using smaller
vessels that better represent those used by testing labora-
tories; typical volumes are between 5 and 20 L. Such test-
ing would help standardize the pressure rise criterion
with respect to test vessel volume rather than type of
igniter and type of fuel. The latter variables can be sepa-
rately addressed using the “adjustable baseline” proce-
dure currently described in ASTM E2079.
3. The simple LOC estimation method based on Eq. 1, that is,
LOC5LFL3 S, is generally conservative when applied to
individual fuel components. In the few cases where the
LOC is overestimated, and where this is not due to an erro-
neously large LFL value, the error appears to be less than
the minimum application safety factor required by NFPA 69.
Where the estimation method is applied to fuel mixtures,
most component LOCs will be conservatively estimated and
these should normally offset the occasional nonconserva-
tive estimate for individual mixture components.
4. Since Eq. 1 multiples any LFL error by S, which may be
as high as 10 or more, it’s important to select realistic LFL
data. The use of erroneously high LFL data will give LOC
DOI 10.1002/prs March 2016 113
 predictions that are much too high and also nonconserva-
tive; examples include aromatics and other readily con-
densable fuel species with large S values. Conversely,
overly conservative LOC values may result in unnecessary
expense, particularly when the application involves large
volumes of gas such as a vent header going to a flare or
other destruction device.
5. Apart from ethylene, whose “classical” LOC value is consid-
ered to have been the result of flawed measurement rather
than a systemic “quenching” problem with the 5-cm vertical
tube apparatus, much of the difference between classical
LOC values and values measured using ASTM E2079 can be
attributed to different definitions of “ignition.” Owing to its
more conservative definition of “ignition” ASTM E2079 has
a negative bias relative to the 5-cm vertical tube apparatus
so values obtained using ASTM E2079 should normally be
less than those found by classical methods.
6. LOC values presented in Table C.1(a) of Annex C of the
last two editions of NFPA 69 contained classical LOC val-
ues that had each been adjusted downwards by 2 mol %
oxygen, regardless of the initial magnitudes. The adjust-
ment was driven primarily by the reported behavior of
ethylene. Proposed revisions to Table C.1(a) are dis-
cussed in Appendix A of this article. The proposals first
replace classical LOC data with recent 120-L vessel LOC
data obtained using ASTM E2079. They subsequently
reduce the overcorrection of the previous two editions of
NFPA 69 by limiting the downward LOC adjustment to
the smaller of either a 1.5 mol % reduction or a 15%
reduction of the classical LOC value. The same adjust-
ments are applied for both nitrogen and CO2 diluent gas,
although there’s presently no 120-L vessel data for an
adjustment of the classical values with CO2 diluent.
7. Appendix A discusses simple estimation techniques for the
LOC of mixtures. The estimates can begin with LOC values,
LFL values, or a mixed set containing only some LOC values.
The estimates can be made for elevated temperature condi-
tions using corrected LFL values. The procedures have been
proposed as revisions to NFPA 69.
LITERATURE CITED
1. P. Yanisko, S. Zheng, J. Dumoit, B. Carlson, et al., Nitro-
gen: A security blanket for the chemical industry, Chem
Eng Prog 107 (2011), 50–55.
2. National Fire Protection Association, NFPA 69, Standard
on Explosion Prevention Systems, National Fire Protec-
tion Association, Quincy, MA, 2014.
114 March 2016 Published on behalf of the AIChE
3. ASTM International, ASTM E2079, Standard Test Methods
for Limiting Oxygen (Oxidant) Concentration in Gases
and Vapors, ASTM International.
4. I.A. Zlochower and G.M. Green, The limiting oxygen
concentration and flammability limits of gases and gas
mixtures, J Loss Prev Process Ind 22 (2009), 499–505.
5. B. Lewis and G. von Elbe, Combustion, Flames and
Explosions of Gases, Elsevier, 2012.
6. H.F. Coward and G.W. Jones, Limits of Flammability of
Gases and Vapors, Technical Report 503, U.S. Bureau of
Mines, 1952.
7. J.M. Kuchta, Investigation of Fire and Explosion Acci-
dents in the Chemical, Mining, and Fuel-related Indus-
tries, Technical Report 680, U.S. Bureau of Mines.
8. L.G. Britton, Operating atmospheric vent collection head-
ers using methane gas enrichment, Process Saf Prog 15
(1996), 194–212.
9. L.G. Britton, Two hundred years of flammable limits, Pro-
cess Saf Prog 21 (2002), 1–11.
10. L.G. Britton, K.L. Cashdollar, W. Fenlon, D. Frurip, J.
Going, B.K. Harrison, J. Niemeier, and E.A. Ural, The role
of ASTM E27 methods in hazard assessment part II: Flam-
mability and ignitability, Process Saf Prog 24 (2005), 12–
28.
11. E. Brandes and E.A. Ural, Towards a global standard for
flammability determination, Proceedings of the 42nd
Annual Loss Prevention Symposium–Global Safety Con-
gress, Paper 2E, April 6, 2008.
12. L.G. Britton, Flammability hazards of lower aliphatic alde-
hydes at elevated pressure and temperature, Process Saf
Prog 17 (1998), 138–148.
13. European Committee for Standardization, EN 14756,
Determination of the Limiting Oxygen Concentration
(LOC) for Flammable Gases and Vapours, European
Committee for Standardization, Brussels, 2006.
14. L.G. Britton and J.A. Smith, Static hazards of the VAST,
J Loss Prev Process Ind 25 (2012), 309–328.
15. F.T. Bodurtha, Industrial Explosion Prevention and Pro-
tection, McGraw-Hill, New York, 1980.
16. T.J. Hansen and D.A. Crowl, Estimation of the flammabil-
ity zone boundaries for flammable gases, Process Saf
Prog 29 (2010), 209–215.
17. L.G. Britton and D.J. Frurip, Further uses of the heat of
oxidation in chemical hazard assessment, Process Saf
Prog 22 (2003), 1–19.
18. M.G. Zabetakis, Flammability Characteristics of Combusti-
ble Gases and Vapors, Technical Report 627, U.S. Bureau
of Mines, 1965.
DOI 10.1002/prs Process Safety Progress (Vol.35, No.1)