Derivation of Le Chatelier’s Mixing
Rde for Flammable Limits
Chad V. Mashuga and DanielA. Crow1
Department of Chemical Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931
In 1891 Le Chatelier [6]firstpro osed an empirical
mixing rulefor predicting theflamma tfle limit of leanfiel
air mixtures - this method is still wide4 used today. This
paper presents a proof to Le Chatelierj mixing rule based
on thermodynamics. A number of assumptions are required
to produce theproof These assumptions are
Theproduct beat ca acittes are constant.
8
The number ofmo s ofgas is constant.
The combustion kinetics of the pure species are
inde endent and unchanged by the presence of other
f
com ustible species.
The adzabatic tem erature rise a t theflamma-
bilz limit is the samebr all s ecies.
g e s e assumptions werehund to be reasonably
valid a t the lower flammability limit and less so at
the u perjlammability limit.
dis paper also considers experimental data that
support some of the assumptions made to arrive a t the
Le Chatelier mixing equation.
INTRODUCTION
Le Chatelier [61 first proposed the following empiri-
cal mixing rule for predicting the flammable limit of
lean fuel air mixtures,
1 lower limits are typically higher than limits obtained
LFL,,,, =
v A
% LFL,
where yi is the mole fraction of the ifhcomponent
considering only the combustible species, and LFL, is
the lower or lean flammable limit of the ith component
in volume percent. Algebraically, L e Chatelier’s
method states that the mixture flammability limit has a
value between the maximum and minimum of the
pure component flammability limits.
Le Chatelier arrived at his mixture rule from his
experiments with methane and other lower hydrocar-
bons. He used a specially designed glass tube to mix
the gases. This tube was 30 mm in diameter and 300
mm long with one open end narrowing to 20 mm so
that it could be closed with one’s thumb. Connected
to the other end of the main tube was a much narrow-
er tube with a diameter of 10 mm and 250 mm 10%.
112 Summer 2000
The narrower tube was graduated into thousandths of
the total volume.
Le Chatelier mixed gases in this tube assembly by
first filling the tube with water and then holding the
tube upright under water and carefully bubbling the
gases through the water into the open end of the
tube. The gas volume was measured using the narrow
tube and was done at atmospheric pressure by align-
ing the water levels inside and outside of the tube. L e
Chatelier then placed his finger over the open end of
the tube and vigorously shook the tube for several
seconds to mix the gases.
To ignite the gases, the tube was quickly inverted
and the water within the tube was allowed to drain to
the bottom. His thumb was then removed, and a small
match or flame was brought into the vicinity of the
opening. A mixture was considered flammable if the
flame descended to the bottom of the test tube.
. Le Chatelier used methane and illuminating gas to
prove Equation (11, although only 3 data points were
used.
This procedure has many drawbacks, although it
was undoubtedly innovative during Le Chatelier’s
time. First, the method determines only the downward
propagating flammability limit, since the flame must
burn downward within the tube. The downward
for combustion propagating upward. Second, the
gases are clearly saturated with water, which may
have an effect on the flammability limits.
Le Chatelier continued his combustion studies and in
1898 published a more detailed study (Le Chatelier and
Boudouard, [71) involving the flammability limits of 31
species. These studies used a 21 liter flask and were
designed to study the flammability of species that are
normally liquid at room temperature. Le Chatelier con-
cluded that, for most of the species tested, the heat pro-
duced by the combustion of one molecular volume of
the mixture at the lower flammability limit is between 9
and 13 cal, with most values between 12 and 13 cal. The
lower flammability limit for most species is typically less
than lo%, so the mixture is composed mostly of air.
Thus, Le Chatelier’s result implies that, assuming con-
stant heat capacity and constant moles, these species
combust at approximatelyequal flame temperatures.
Process Safety Progress (Vol. 19, N0.2)
 Burgess and Wheeler [ll multiplied the lower flam-
mability limit (mole %) by the calorific value
(kcal/mole) to obtain a constant of about 1100 for
most fuels. This also implies that the lean limits have
the same final flame temperature. Egerton and Powl-
ing [31 correlated the lower limit of combustion
against the net molar heat of combustion, further rein-
forcing the concept of an approximate final flame
temperature.
Recently Stull [131, Hansel et al. [51, Melhem [ill,
Crow1 and Mashuga [lo1 used the constant final flame
temperature approach to predict flammable limits.
This approach assumes a constant calculated adiabatic
flame temperature (CAFT) threshold. Mixtures with
calculated adiabatic flame temperatures higher than
this value are considered flammable while those
lower are considered non-flammable.
Other early contributors to experimental evidence
include Eitner [41 and Coward et al. [21. With these
data it was difficult to verify Le Chatelier’s mixing rule
since experiments were unreliable and the criteria for
flammability had not yet been properly defined and
agreed upon. The upper flammable limits were even
more unreliable due to the small apparatus and type
of ignition sources used. Coward et al. [21 was the first
to attempt an examination of the applicability of L e
Chatelier’s rule to both the lower and upper flamma-
ble limits.
More recently Liekhus et al. [91, and others have
compared experimental results to Le Chatelier’s pre-
diction with some success.
Le Chatelier’s empirical mixing rule is still used
extensively today for predicting the lean fuel limits.
This paper presents a proof of the validity of L e
Chatelier’s mixing rule based on thermodynamics and
lists the assumptions and determines the applicability
of the method.
THEORY
Lower FlammabilityLimit
Le Chatelier’s rule can be derived quite quickly
from the results of Le Chatelier and Boudouard [71 and
Burgess and Wheeler 111. If the fraction of the total
heat release by species i is given by
yi
(2)
LFL,
where y, is the mole fraction of gas on a combustible
basis only, and LFL, is the lower flammability limit. If
we assume that the heat release is the same for all
limit mixtures, then the total heat release is given by,
1
(3)
$[&]=IFr_
and L e Chatelier’s rule, Equation (11, is proved by
solving for LFL,, This simplified approach is useful
for comprehension, but does not elucidate the
detailed assumptions inherent in Equation (1). A more
rigorous approach is required.
Process Safety Progress (V01.19, No.2)
Consider a mixture of gas that is initially unburned.
Assume that the gas combusts adiabatically at constant
pressure to its final burned state. From a total energy
balance with constant pressure the adiabatic process
is represented as,
AH=O (4)
where His the total enthalpy. Enthalpy is a state func-
tion. Thus, an adiabatic constant pressure reaction can
be represented by two steps. First an isothermal, con-
stant pressure reaction and second, a constant pres-
sure heating of the reaction products up to the final
temperature of the adiabatic reaction. For the net
process it follows that,
AH = AHc + AH, = ncAhc+ n,Ah, = 0 (5)
where AH, is the total enthalpy change of the com-
bustion reaction at the initial temperature, AHp is the
enthalpy change due to the heating of the products,
n, is the total number of combustible moles, Ah, is
the enthalpy change of the combustion per mole, n is
the number of product moles, and Ahp is the enthaby
change due to the heating of the products per mole.
The energy required to heat the products to its final
adiabatic temperature is found by,
Tad
Ah, = J C r d d T (6)
TI
where CpProd is the heat capacity of the product gas
mixture, TI is the initial temperature, and Tadis the
final adiabatic flame temperature. If the heat capacity
of equation [61 is considered constant then,
Ah, = C,AT (7)
where C ’ is the constant heat capacity and ATis the
adiabatic temperature change. Combining equations
(5) and (7) results in the following ratio,
Assume that the number of moles is constant dur-
ing the combustion, i.e. the initial and final moles are
constant. This assumption is written,
np s nT (9)
where +is the total number of moles. Then by com-
bining equations (8) and (9) results in the following,
C, AT
-nc_ - (10)
‘T (-Ahc)
If an adiabatic temperature threshold, A P , is assumed,
then the left hand side of equation (10) is the mole
fraction of fuel at the flammability limit. In terms of
the LFL,
(11)
Summer 2000 113
 nitrogen heat capacity, the calculated adiabatic flame
Lower Flammability Limit and Heat of temperature at the lower limit and the heats of com-
Combustion bustion values shown. The results compare well to
10 , 1
experimental values.
LFL = 4332 [l/-Ah,] + 0.239
Development of a similar flammable limit equation
for a mixture with multiple fuels requires a modifica-
tion of equation (11). This modification results in,
Oxygencompounds
A Nilmgcn Compounds (12)
x Svlfvrcampoundr
-Lmm negreJsmn

0.0000 0.0005 0.0010 0.0015
l/(-Ahc) Ikl/mole]-’
FIGURE 1. LFL and the standard enthalpy of combustion for 123
compounds.
where LFL is the lean or lower flammable limit for a
single fuel (percent fuel in air).
Egerton and Powling [31 in their studies on the limits
of flame propagation plotted and correlated the lower
flammable limit and the non-reciprocal heat of combus-
tion. Equation (11) proposes that the LFL is proportional
to the reciprocal of the heat of combustion. Suzuki [141
examined the trend of the LFL and the standard
enthalpies of combustion for 123 compounds. These
include 55 hydrocarbons, 48 oxygen-containing com-
pounds, 16 nitrogen-containingcompounds, and 4 sulfur
-containing compounds. Halogenated compounds are
not included because of inadequate knowledge of their
stoichiometry. Figure 1 shows the linear relationship
between the LFL and the reciprocal of the standard
enthalpy of combustion for this data which clearly sup-
ports the form of equation (11).
For many lean mixtures the concentration of fuel is
only a few percent, with the majority of the mixture
nitrogen. The heat capacity of the gas mixture should
be close to the heat capacity for pure nitrogen (29.2
J/mole-K). Table 1 shows flammability limit estimates
using Equation (11) for hydrocarbons and oxygen -
containing compounds. These calculations use the
0.0020 where (LFL/lOO),i, is the lean or lower flammable
limit of a multiple fuel mixture with an adiabatic tem-
perature change of AT*. The equation relating the
energy of a multi fuel combustion reaction and tem-
perature is,
N
i=l
where n, is the total number of combustible moles,
(-Ah,),,, is the heat of combustion of the fuel mix-
ture, niis the number of moles of the ith fuel species,
and (-Ahd, is the heat of combustion of the ifh fuel.
Equation (13) assumes that the net heat of combustiop
is determined from the heat of combustion of the pure
components. This assumes that the combustion kinet-
ics for the pure species are independent and
unchanged due to the presence of other combustible
gas species in the mixture. In actual combustion
processes, the species share common elementary
reactions and the kinetics would b e expected to
change due to the presence of the other combustible
species. Also, cool flames might arise in the mixture
dramatically changing both the kinetics and the tem-
perature increase at the limit.
Writing equation (13) for two species, and dividing
by n, results in,

TABLE 1. Properties of Selected Hydrocarbons and Oxygen-containing Compounds.

Experimental LFL 4 Ta,@LFL Calculated LFL from Equation (11)

Compound (vol.%) (kJ/mole) (K) ‘pN2 (ATad LFL) ’
-Ahc

Methane 5.3 -890.3 1481 4.9

Acetylene 2.5 -1299.6 1268 2.8
Ethylene 2.7 -1411.2 1370 2.8
Ethane 3.0 -1559.8 1534 2.9
Propyne 2.2 -1935.8 1431 2.2
1-Butene 1.6 -2716.8 1479 1.6
1-Hexene 1.2 -4032.5 1583 1.1
Ethanol 3.3 -1409.2 1492 3.1
Dimethyl ether 3.4 - 1460.5 1565 3.1
Acetone 2.6 -1821.4 1541 2.5

Heat of combustion and LFL data from Suzuki (1994).

Calculated flame temperatures at the LFL’s from Melhem (1997).

114 Summer 2000 Process Safety Progress (Vo1.19, No. 2)

 Substituting equation (14) into equation (12) results EXAMPLE
in, A vapor is comprised of 63.5% ethyl acetate, 20.8%
C, AT * ethyl alcohol, and 15.6% toluene by volume on an air

(%)mix n C (-4
= nl 1
+ +Ah2
n C [ 1
(15) -free basis. The flammability limits for each are shown
in Table 2 below. Estimate the lower flammability
limit of the mixture.
Recognizing the molar ratios in the denominator of TABLE 2. Lower Flammability Limits for Example 1
equation (15) are equivalent to the mole fractions o n
a fuel only basis results in the following definitions, LFL (Lewis and
von Elbe, [81 LFL (NFPA [12]
y I = Jn and y2 = -nl Compound fuel in air) (vol. % fuel in air)
(16) (~01%
nc nc
Ethyl Acetate 2.5 2.0
Equations (16) are substituted into Equation (15) and
Ethyl Alcohol 4.3 3.3
the numerator and denominator are divided by C)P.
Toluene 1.4 1.2
This assumes a constant heat capacity and a constant
adiabatic temperature threshold, A P.The result is

SOLUTION
The lower flammability data are shown in Table 2.
T h e fuel composition is already o n a fuel only
basis, i.e. air excluded. Equation (19) is used to pre-
dict the LFL of the mixture. Using the limit data from
Lewis and von Elbe [81results in,

LFL,, =
-x
A*E
i=l
1
v.
Yi
-
- 0.635
~

2.5
1
0.208
+- 4.3
+-+- +
. 0.156
~

1.4
= 2.41%

An identical calculation using the l i t data from NFF'A

The terms in the brackets are the pure component
LFLs defined by equation (11). Thus,
[121 results in a mixture value of I.%%, a fairly si@icant
ddference from the previous value. This demonstrates the
sensitivity of the result to the initial limit values.
The experimentally determined value of the LFL is
2.04% (Lewis and Von Elbe, [8D.

Upper Flammability Limit

An equivalent form of Le Chatelier's equation for
the upper flammable limit (UFL) is commonly applied,
Final algebraic transformation of equation [181
results in t he simple mixing rule proposed b y L e (20)
Chatelier that estimates the lower o r lean limit of a
mixture of flammables in air.

1
LFL,,,, = (19) Figure 2 shows the dependence of the UFL and the
IYL L Y2
LFL, LFL, Upper Flammability Limit and Heat of
Combustion
The result is readily applied to an y number of 100 - 1

.X= - A
species. The assumptions required to arrive at this 90
80 -
equation include,
the product heat capacities are constant
E
=
e
-0
\o
kq
7n

50
--
.

A
the number of moles of gas is constant A 40
the combustion kinetics of the pure species are f 30
4 20
independent and unchanged by the presence of other B 10
combustible species. 0
the adiabatic temperature rise at the flammability 0.000 0.001 0.001 0.002 0.002
limit is the same for all species. l/(-AhJ [kJ/mol]-'
An example calculation will illustrate the use of the FIGURE 2. UFL and the standard enthalpies of combustion for 123
L e Chatelier method of estimating the lower o r lean
compounds.
flammable limit from pure component data.

Process Safety Progress (Vol. 19, No.2) Summer 2000 115

standard enthalpy of combustion for the same 123
compounds as Figure 1. The data are quite scattered
which makes it difficult to assess the functionality
between the UFL and the enthalpy of combustion. How-
ever, a large number of the compounds on the lower left
do appear to fit a straight line. Most of the species in Fig-
ure 2 are hydrocarbons.
For the UFL, the fuel represents a large percentage of
the mixture. These mixtures can contain a complex mix-
ture of fuel, oxygen and nitrogen resulting in wide varia-
tion from the initial to final heat capacities and molar
quantities. These conditions violate the assumptions
used to formulate equation (20). Decomposition kinetics,
soot formation, cool flames, and other complex effects
may also play an important role at the upper limit.
Additional Considerations
Proper usage of LaChatelier’s rule requires flamma-
bility limit data at the same temperature and pressure.
Also, flammability data reported in the literature may
be from disparate sources, with wide variability in the
data. Combining data together from these disparate
sources may cause unsatisfactory results, which may
not be obvious to the user.
SUMMARY
This paper provides a proof of Le Chatelier’s empir-
ical rule based on thermodynamics. The proof shows
the important assumptions inherent in the rule an d
the conditions under which L e Chatelier’s rule can be
applied. Furthermore, the result shows that Le Chate-
lier’s rule is a special form of the cakulated adiabatic
flame temperature method, which is widely used
today to predict flammability limits.
Comparison with experimental data shows that Le
Chatelier’srule is moderately good at estimating the lower
flammability limit, and poor to moderate at estimating the
upper flammability h i t , depending on the species.
ACKNOWLEDGEMENT
The authors wish to thank Larry Britton for his
commentary and assistance.
NOTATION
Heat capacity at constant pressure
C,
Ah Enthalpy change d u e to the heating of the
products per mole
Ahc Enthalpy change of combustion per mole
H Total enthalpy
AH Total enthalpy change
AHc Total enthalpy change due to combustion
LFL Lower or lean flammable limit in volume per-
cent fuel in air
n Number of moles
116 Summer 2000
N Number of flammable species
T Temperature
AT Temperature change
AT* Adiabatic temperature threshold or limit tem-
perature increase
UFL Upper flammable limit in volume percent fuel
in air
y Mole fraction on a combustible basis
superscripts
Prod Products
Subscripts
ad Adiabatic
i Species i
mix Mixture
p Products
T Total
1 Initial
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Summer 2000 117