Chemical Engineering Science 56 (2001) 38293843

www.elsevier.nl/locate/ces
Prediction of ammability limits at reduced pressures
J. Arnaldos

, J. Casal, E. Planas-Cuchi
Centre dEstudis del Risc Tecnol ogic (CERTEC), Institut dEstudis Catalans-Universitat Polit ecnica de Catalunya,
Diagonal 647, 08028-Barcelona, Catalonia, Spain
Received 27 March 2000; received in revised form 11 October 2000; accepted 1 March 2001
Abstract
This work presents a method to estimate the variation of ammability limits as a function of the pressure of fuelair mixtures at
conditions of reduced pressure, for C
m
H
n
O
x
type fuels. The accuracy of the method has been tested through the comparison with
experimental values of methaneair, ethaneair, propaneair and butaneair mixtures drawn from the bibliography; the agreement
between the predicted values and the experimental data is very good. ? 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Flammability limits; Pressure; Modelling; Fuel; Explosions; Safety
1. Introduction
Knowledge of ammability limits of ammable gas=air
mixtures or ammable gas=air=inert gas mixtures is ex-
tremely important for safety in certain plants and in the
performance of a range of operations (for example, dry-
ing of solids, loading and unloading tanks). Thus, the
values of both upper (UFL) and lower ammability lim-
its (LFL) are available for most gases and vapours mixed
with air at atmospheric pressure and room temperature
(usually 298 K). The best study published in this eld is
probably that by Zabetakis (1965), with a set of values
obtained experimentally with the apparatus developed at
the US Bureau of Mines by Coward and Jones (1952).
Furthermore, for the most common substances,
ammability diagrams of ammable gas=air=inert gas are
also available in the literature. Again, these diagrams are
given for the most common conditions, i.e., 298 K and
atmospheric pressure.
Very few data are available on ammability limits in
conditions other than the aforementioned. However, in a
number of processes mixtures of ammable gas and air,
with or without an inert gas, can exist in dierent con-
ditions, such as relatively high temperatures or reduced
pressure. For example, vacuum is used to increase the
drying rate when low temperatures are required. In these

Corresponding author. Tel.: +34-93-401-6675;

fax: +34-93-401-7150.
E-mail address: certec@upc.es (J. Arnaldos).
cases, if the moisture is a ammable liquid (as often
happens in the ne chemicals industry) a ammable gas
mixture can be created, with the consequent risk of de-
agration. Variation of the vacuum has been suggested
as a means of moving the operation outside the amma-
bility limits (it is known that if pressure is suciently
decreased, ammable mixtures will not sustain combus-
tion). Unfortunately, as stated before, data on these limits
are very scarce.
A method enabling the prediction of ammability lim-
its as a function of pressure and temperature would there-
fore be of great interest. The purpose of this paper is to
discuss a new mathematical model for the estimation of
UFL and LFL at reduced pressures. The model is based
on that proposed by Lihou (1993), which has been con-
siderably modied to allow more complete calculations.
2. Variation of ammability limits as a function of
temperature
As temperature increases, the range of ammability
limits widens (see Fig. 1). Thus, a mixture, which is not
ammable at room temperature, can become ammable if
temperature increases. The value of LFL decreases when
temperature increases, as less combustion energy will be
required to spread the ame (Drysdale, 1985):
LFL
T
LFL
298
= 1
T 298
T
lim
298
: (1)
0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S0009- 2509( 01)00090- 2
3830 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Fig. 1. Variation of ammability limits as a function of temperature.
Taking T
lim
= 1573 K (minimum temperature which
must be reached to allow ame propagation) (Zabetakis,
1965):
LFL
T
=LFL
298
(1 7:8 10
4
(T 298)): (2)
This expression is similar to the empirical one proposed
by Zabetakis, Lambiris, and Scott (1959) on the basis of
the Burguess and Wheeler law:
LFL
T
=LFL
298
(1 7:21 10
4
(T 298)): (3)
UFL follows a similar relationship (Drysdale, 1985):
UFL
T
=UFL
298
(1 + 7:21 10
4
(T 298)): (4)
According to this expression, a limiting temperature
should also exist for UFL. It is not possible to calcu-
late the adiabatic ame temperature for UFLas can be
done for LFLsince the combustion products cannot be
predetermined (they will be a complex mixture of prod-
ucts with diering degrees of oxidation). However, Stull
(1977) demonstrated theoretically that the ame temper-
ature at UFL is approximately the same as that at LFL.
3. Variation of ammability limits as a function of
pressure
As pressure increases above atmospheric pressure,
ammability limits enlarge their domain. In fact, LFL
decreases only very slightly as pressure increases, but
UFL increases very signicantly (Zabetakis et al., 1959;
Vanderstraeten et al., 1997; Goethals et al., 1999).
Below atmospheric pressure, as pressure decreases (at
constant temperature) the values of the two limits ap-
proach each other and the gap between them is narrowed
until a certain pressure is reached (for methane, for exam-
ple, 125 mm Hg at 293 K) at which they have the same
value (Coward & Jones, 1952; Stull, 1977); at lower pres-
sures, the ame cannot propagate through the mixture.
According to Stull (1977), this is due to the fact that the
concentration of gas is too low to sustain combustion.
In a more recent paper, Lihou (1993) presented a math-
ematical model for the calculation of ammability lim-
its at reduced pressure from their values at atmospheric
pressure and room temperature. This model allows the
calculation of the minimum pressure at which the ame
can propagate through the mixture, although it does not
allow the prediction of the evolution of UFL and LFL as
a function of pressure (Table 1).
The model proposed by Lihou considers that when
a small spherical volume of a ammable gas mixture
reaches a certain temperature and starts to react, then the
hot reaction products expand and the expansion absorbs
part of the combustion energy. Thus, the products un-
dergo a certain cooling. If the temperature of burnt gases
at the ammable mixture (unburnt gases) interface is
still higher than the minimum or limiting temperature for
ame propagation in the ammable mixture, the reaction
will continue towards the mixture. But if the temperature
at the interface is lower than the limiting temperature,
then the reaction cannot propagate. A balance between
heat generation and heat absorption will indicate whether
the limiting temperature has been reached or not:
radiative heat loss =
combustion heat sensible heat gain:
The heat released in the incomplete combustion of 1 kmol
of ammable vapour can be calculated as
Q
c
=fH: (5)
The sensible heat gain required to bring the temperature
of the mixture from ambient temperature (298 K) up to
the ame temperature is
Q
s
=MrC
p
(T 298); (6)
where C
p
, the specic heat of the reacting mixture (con-
sidered equal to that of air at average temperature, T
m
),
can be calculated as
C
p
=
4:18
28:8
(6:713 + 0:04697 10
2
T
m
+ 0:1147
10
5
T
2
m
0:4696 10
9
T
3
m
) (7)
and r is
r =
(M 28:8)y + 28:8
My
: (8)
The radiant heat emitted in time dt can be determined,
for a spherical volume, by the StefanBoltzmann law:
dQ
r
=D
2
T
4
dt: (9)
It may be assumed that the ammable mixture surround-
ing the ame front has an absorptivity of zero. Fur-
thermore, the value of ame emissivity () has been
considered to be unity: a luminous ame is made of in-
candescent particles (=0:95, Siegel and Howell (1992))
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3831
Table 1
Limiting pressures below which the ame does not propagate through the mixture (Lihou, 1993)
Methane Propane Heptane Methanol Toluene Acetone Acetic Acid THF
Pressure (bar) 0.168 0.137 0.101 0.106 0.129 0.126 0.131 0.115
and gases with low emissivity; therefore, supposing that
the ame is a grey body it will always have values of
0:95. Dierent authors (Eisenberg, Lynch, & Breeding,
1975; Raj & Kalekar, 1974) have used values of 1
for the ame in radiation models for hydrocarbon res.
The spherical volume emitting radiation changes with
time. The velocity at which its diameter increases can be
expressed as (Lihou, 1993)
dD
dt
= 2V: (10)
From Eqs. (9) and (10) the following expression is ob-
tained:
dQ
r
=
D
2
T
4
2V
dD: (11)
Integrating between D = 0 and D =S gives
Q
r
=
_
S
0
T
4
2V
D
2
dD =
T
4
S
3
6V
: (12)
For 1 kmol of ammable vapour the nal diameter of the
radiant shell can be calculated from (Stull, 1977)
S =D
_
ET
298
_
1=3
: (13)
By substituting the StefanBoltzmann constant and Eq.
(13) into Eq. (12) the following expression is obtained:
Q
r
=
_
D
3
6
__
1000E
298
__
T
1000
_
5
_
56:7
V
_
: (14)
In this expression, the rst term on the right-hand side
corresponds to the volume of 1 kmol of ammable vapour
mixed with air at 298 K and a pressure P, with a mole
fraction y of vapour in the mixture. By applying the ideal
gas law, this volume can be expressed as
v =
24:77
yP
: (15)
Finally, by substituting this relationship into Eq. (14), the
following expression is obtained, which gives the heat
radiated from the combustion of 1 kmol of ammable
vapour:
Q
r
=
4713E
yPV
_
T
1000
_
5
: (16)
Now, by substituting Eqs. (5), (6) and (16) into the heat
balance:
4713E
yPV
_
T
1000
_
5
=fH 1000MrC
p
_
T
1000
0:298
_
:
(17)
In the model it has been assumed that the ame speed
and the burning velocity have the same value, as it is
very dicult to establish experimentally any dierence
between these two parameters (Drysdale, 1985). Then,
the burning velocity can be expressed as (Lihou, 1993)
V =K
_
D
e
: (18)
K is a constant lightly dependent on the molecular struc-
ture of the fuel. However, the introduction of its exact
value would extraordinarily complicate the model. There-
fore, an average value for all fuels has been taken; in
this way, the knowledge of the value of K is not required
(see Eqs. (20) and (21)) and the proposed model is much
simpler.
The diusivity can be calculated from the following
expression for a mixture of a vapour or gas and air (Reid,
Prausnitz, & Poling, 1987):
D
e
= 0:0043
T
1=3
P(
air
+)
2
_
1
28:8
+
1
M
: (19)
To avoid the use of diusivities, Lihou suggested that
the burning velocity for each substance, V, can be ob-
tained from that corresponding to another one, V
ref
, al-
ready known,
V =K
_
D
e
V
ref
=K
_
D
e
ref
_
V =

D
e
D
e
ref
V
ref
: (20)
Thus, substituting D
e
and D
e
ref
according to Eq. (19) into
Eq. (20),
V =
_
(
air
+
ref
)
(
air
+)
_
M
ref
(M + 28:8)
M(M
ref
+ 28:8)
_
1=4
_
V
ref
: (21)
The value of can be obtained (Reid et al., 1987) from
the atomic volumes of the dierent atoms forming the gas
molecule. For air, v
air
= 29:9 10
3
m
3
kmol
1
; there-
fore,
air
=0:31 m kmol
1=3
. As an example, the value of
for a generic fuel C
m
H
n
O
x
is calculated as
=
3

mv
C
+nv
H
+xv
O
; (22)
where v
C
= 0:0148 m
3
atom
1
; v
H
= 0:0037 m
3
atom
1
and v
O
= 0:0074 m
3
atom
1
.
The burning velocity thus obtained corresponds to at-
mospheric pressure. At reduced pressure, burning veloc-
ity is slightly higher (Spalding, 1979):
V
reduced pressure
=V
_
1
P
_
0:1
: (23)
The burning velocity for any concentration (V
y
) can also
be expressed as a function of burning velocity for the
3832 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
stoichiometric mixture, V
s
, and of mole fraction of
ammable vapour for the mixture, y:
V
y
=V
s
_
a
_
y
s
_
2
+b
_
y
s
_
+c
_
: (24)
By combining Eqs. (23) and (24) we can obtain an ex-
pression for the burning velocity as a function of pressure
and concentration:
V
y
=V
s
_
a
_
y
s
_
2
+b
_
y
s
_
+c
_ _
1
P
_
0:1
: (25)
Substituting this expression into Eq. (17) we obtain
4713E
yP
0:9
V
s
(a(y=s)
2
+b(y=s) +c)
_
T
1000
_
5
=fH 1000MrC
p
_
T
1000
0:298
_
: (26)
3.1. Minimal pressure below which the ammability
limits do not exist
The concentration at which the two limits concur (the
mixture then becoming non-ammable) can essentially
be considered as equal to the stoichiometric concentra-
tion (y = s). Substituting the ame temperature corre-
sponding to UFL (which gives a more conservative value
for pressure) into Eq. (26), the minimal pressure below
which the mixture cannot be ammable is (Lihou, 1993)
as follows:
P
min
=
_
4713E
s
(T
u
=1000)
5
sV
s
(f
s
H 1000Mr
s
C
p
u
((T
u
=1000) 0:298))
_
1:11
:
(27)
4. Variation of ammability limits at reduced pressures
Although the method described above provides useful
information, it would be of great interest to know the
complete variation of ammability limits as a function of
pressure, at lowpressures. As stated above, when pressure
decreases LFL increases gradually and UFL decreases,
until both concur when the concentration of the mixture,
y, is equal to the stoichiometric concentration, s. Below
a new method is presented enabling the prediction of this
variation.
For LFL:
P =
_
4713E

(T

=1000)
5
y(a

(y=s)
2
+b

(y=s) +c

)V
s
(f

H 1000MrC
p

((T

=1000) 0:298))
_
1:11
: (28)
For UFL:
P =
_
4713E
u
(T
u
=1000)
5
y(a
u
(y=s)
2
+b
u
(y=s) +c
u
)V
s
(f
u
H 1000MrC
p
u
((T
u
=1000) 0:298))
_
1:11
: (29)
By giving several values to P, from atmospheric pressure
to minimal pressure (P
min
), this implicit equation can be
solved with respect to concentration y. Thus, the variation
of both limits as a function of pressure can be obtained.
4.1. Calculation of parameters a; b; c, at LFL and UFL
The method proposed by Lihou allows prediction of
burning velocity for a given compound from the burning
velocity of another substance (which will be referred to
below as the reference substance and will be indicated
by subscript ref). As burning velocity varies with the con-
centration of the mixture, a value can be obtained for the
burning velocity for a given concentration. Lihou, for the
reference substance, provided a value of burning veloc-
ity (V

ref
) for the ammability limits (supposing that at
298 K and 1 atm it has the same value for both limits) and
another one for the stoichiometric concentration (V
s
ref
).
Thus, according to Eq. (21), these two velocities (V

and
V
s
) can be directly obtained for a given substance.
In order to obtain the burning velocity for concentra-
tions other than these two, Eq. (24) must be applied.
Therefore, parameters a; b; c, must be known (a

; b

and
c

for concentrations below the stoichiometric concentra-

tion and a
u
; b
u
and c
u
for concentrations above it).
There are three unknown parameters in Eq. (24); as
we know three values of the burning velocity for three
dierent concentrations, then three equations can be set
up to obtain these three values. As previously mentioned,
the method proposed by Lihou provides two of them, the
third one must be determined. The burning velocity as a
function of concentration has been published for methane
and propane (Stull, 1977), the two reference substances
chosen by Lihou. Thus, another value can be obtained
for each range of concentrations. The values y=0:8s and
y = 1:2s were selected.
Then, the aforementioned parameters can be deter-
mined by solving the following two equation systems:
1 =a

+b

+c

;
V
0:8s
V
s
=a

0:8
2
+b

0:8 +c

;
V

V
s
=a

s
_
2
+b

s
_
+c

; (30)
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3833
1 =a
u
+b
u
+c
u
;
V
1:2s
V
s
=a
u
1:2
2
+b
u
1:2 +c
u
;
V

V
s
=a
u
_
u
s
_
2
+b
u
_
u
s
_
+c
u
: (31)
According to this, the burning velocities for each amma-
bility limit, as a function of pressure and concentration,
are
V

=V
s
_
a

_
y
s
_
2
+b

_
y
s
_
+c

__
1
P
_
0:1
; (32)
V
u
=V
s
_
a
u
_
u
s
_
2
+b
u
_
u
s
_
+c
u
__
1
P
_
0:1
: (33)
5. Calculation of ame temperature
To solve the heat balance at dierent pressures (thus
obtaining the ammability limits at each pressure), the
ame temperatures T

and T
u
corresponding to LFL and
UFL at 298 K and 1 atm must be known. To nd the
temperature corresponding to LFL it is necessary to solve
Eq. (28) for P =1 and y =; and to nd the temperature
for UFL, Eq. (29) must be solved for P = 1 and y = u.
Both equations are implicit with respect to temperature.
As stated by Lihou (1993), the ame temperature at
P
min
is equal to T
u
; therefore, T
u
does not change with
pressure at vacuum conditions, while the ame temper-
ature at LFL changes from T

(at atmospheric pressure)

to T
u
(at P
min
). This inuence of pressure must be taken
into account to obtain accurate results close to real data.
T

can be expressed as a function of both T

u
and con-
centration (which changes with pressure) through the fol-
lowing expression:
T

=T
u
_
y
s
_
0:2
: (34)
The error involved when using this expression to calculate
LFL ranges between 5.2% and 2:4%, with an average
value of 1:7% (lower than the experimental error which
can be introduced when determining T
u
). Fig. 2 shows
the deviation of the values obtained with Eq. (34) with
respect to the experimental data.
6. General methodology for C
m
H
n
O
x
type fuels
In the following paragraphs a general procedure is pre-
sented to determine the variation of ammability limits
Fig. 2. Deviation of T

as calculated from Eq. (34) with respect to

experimental data (at 298 K and 1 atm).
as a function of pressure for any C
m
H
n
O
x
type gas fuel
(see Fig. 3).
The data required (available in the literature for most
substances) are summarised in Table 2.
6.1. Calculation of ame temperature at LFL and UFL
Calculation of the mass ratio of reaction mixture to
ammable vapour at LFL and UFL at 298 K and 1 atm,
from Eq. (8):
r

=
(M 28:8) + 28:8
M
; (35)
r
u
=
(M 28:8)u + 28:8
Mu
: (36)
Calculation of the fraction of ammable vapour burnt
at LFL and UFL, at 298 K and 1 atm:
Of course, for LFL and the stoichiometric concentra-
tion, as there is an excess of air (for the stoichiometric
concentration it is considered that there is 5% excess
air) this fraction will be 1,
f

= 1; (37)
f
u
=
0:8(1 y)
y(4m+n 2x)
: (38)
Calculation of the mole fraction of reaction products
with respect to reactants for the concentrations corre-
sponding to LFL and UFL at 298 K and 1 atm:
E

= 1 + 0:25n + 0:5x; (39)

E
u
=
(4:2 0:2u)m+ (1:26 0:26u)n (1:68 + 0:32u)x 0:84(1 u)
(4m+n 2x)(1:05 0:05u)
: (40)
3834 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Fig. 3. General methodology for C
m
H
n
O
x
type fuels.
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3835
Table 2
Data required for the new methodology
Denition Nomenclature
Number of carbon atoms in the molecule m
Number of hydrogen atoms in the molecule n
Number of oxygen atoms in the molecule x
Molecular weight of ammable vapour M (kg kmol
1
)
Molar heat of combustion H (kJ kmol
1
)
Lower ammability limit at 298 K and 1 atm
Stoichiometric concentration ammable vapour=air
a
s = 1=[1 + (4:762m + 1:191n 2:381x)1:05]
Upper ammability limit at 298 K and 1 atm u
Molecular weight of the reference substance M
ref
(kg kmol
1
)
Burning velocity at the limits for the reference V

ref
(m s
1
)
Burning velocity at the stoichiometric conc. for the reference V
s
ref
(m s
1
)
Burning velocity for the reference at y = 0:8s V
0:8s
ref
(m s
1
)
Burning velocity for the reference at y = 1:2s V
1:2s
ref
(m s
1
)
Cube root of molar volume of the reference
ref
(m kmol
1=3
)
a
Supposing an air excess of 5%.
Calculation of burning velocities at LFL and UFL from
the value of the burning velocity of the reference sub-
stance at LFL and UFL:
V

=V

ref
(
air
+
ref
)
(
air
+)
_
M
ref
(M + 28:8)
M(M
ref
+ 28:8)
_
1=4
: (41)
Heat balance as a function of temperature (taking into
account that specic heat also depends on tempera-
ture):
1=
4713E

_
T

1000
_
5
V

_
f

H1000Mr

_
4:18
28:8
_
_
6:713+0:0469710
2
_
(T

+298)
2
_
+0:114710
5
_
(T

+298)
2
_
2
0:469610
9
_
(T

+298)
2
_
3
_
__
T

1000
_
0:298
_
_;
(42)
1=
4713E
u
_
T
u
1000
_
5
uV

_
f
u
H1000Mr
u
_
4:18
28:8
_
_
6:713 + 0:0469710
2
_
(T
u
+298)
2
_
+0:114710
5
_
(T
u
+298)
2
_
2
0:4696 10
9
_
(T
u
+298)
2
_
3
_
__
T
u
1000
_
0:298
_
_:
(43)
These two expressions allow the calculation of T

and
T
u
, respectively.
6.2. Calculation of ammability limits as a function of
pressure
With the calculated values of temperatures T

and T
u
,
the specic heats for both limits are calculated from
Eq. (7). Then the burning velocitiesrequired to de-
termine parameters a; b and care obtained as follows:
V
s
=V
s
ref
(
air
+
ref
)
(
air
+)
_
M
ref
(M + 28:8)
M(M
ref
+ 28:8)
_
1=4
; (44)
V
0:8s
=V
0:8s
ref
(
air
+
ref
)
(
air
+)
_
M
ref
(M + 28:8)
M(M
ref
+ 28:8)
_
1=4
; (45)
V
1:2s
=V
1:2s
ref
(
air
+
ref
)
(
air
+)
_
M
ref
(M + 28:8)
M(M
ref
+ 28:8)
_
1=4
: (46)
Now, by solving the equation systems (30) and (31) the
parameters a; b and c can be obtained.
The next step is the determination of the parameters r,
f and E as a function of y:
r =
(M 28:8)y + 28:8
My
; (47)
f

= 1;
f
s
= 1;
f
u
=
0:8(1 y)
y(4m+n 2y)
; (48)
E

= 1 y + 0:25ny + 0:5xy;
E
s
=
5m+ 1:5n 2x
5m+ 1:25n 2:5x + 1
;
E
u
=
(4:2 0:2y)m+ (1:26 0:26y)n (1:68 + 0:32y)x 0:84(1 y)
(4m+n 2x)(1:05 0:05y)
: (49)
Although, when determining the entire range of variation
of ammability limits as a function of pressure the min-
imal pressure value is also obtained, this value can also
be calculated previously by substituting the values given
by Eqs. (47)(49) for the stoichiometric concentration
into Eq. (27).
3836 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Table 3
Burning velocity and cube root of molar volume for the reference substances
Reference M
ref
V

ref
V
s
ref
V
0:8s
ref
V
1:2s
ref

ref
(kg kmol
1
) (m s
1
) (m s
1
) (m s
1
) (m s
1
) (m kmol
1=3
)
Methane 16 0.08 0.33 0.231 0.309 0.3093
Propane 44 0.06 0.35 0.29 0.327 0.4198
Table 4
Data for the fuels studied
Combustible m n x M H s u
(kg kmol
1
) (kJ kmol
1
) (m kmol
1=3
)
Methane 1 4 0 16 802,703 0.3093 0.06
a
0.091 0.132
a
Ethane 2 6 0 30 1,560,700 0.3727 0.0285 0.054 0.131
Propane 3 8 0 44 2,042,043 0.4198 0.024 0.0385 0.095
Butane 4 10 0 58 2,877,600 0.4582 0.018 0.0298 0.0835
Heptane 7 16 0 100 4,503,508 0.546 0.011 0.0179 0.067
Methanol 1 4 1 32 665,239 0.3332 0.067 0.118 0.36
Toluene 7 8 0 92 3,773,679 0.5107 0.012 0.0217 0.07
Acetone 3 6 1 58 1,690,139 0.4198 0.0215 0.0476 0.13
Acetic acid 2 4 2 60 832,930 0.3996 0.054 0.0909 0.16
THF 4 8 1 72 2,510,590 0.4582 0.02 0.0351 0.118
a
These values, given by Lihou, do not correspond to the reference temperature of 298 K but to a temperature of 293 K. Thus, the reference
temperature in the equations given in the text (298 K) must be changed to 293 K when the limits of methane are calculated.
Table 5
Parameters r; f and E for the dierent fuels at ammability limits
Combustible r

r
u
f

f
u
E

E
u
Methane 29.2 12.84 1 0.658 1 1
Propane 27.618 7.235 1 0.381 1.024 1.036
Heptane 26.894 5.011 1 0.253 1.033 1.051
Methanol 13.53 2.6 1 0.237 1.0335 1.0434
Toluene 26.77 5.159 1 0.295 1.012 1.02
Acetone 23.62 4.326 1 0.335 1.0215 1.0438
Acetic acid 9.41 3.52 1 0.525 1.054 1.0846
THF 20.6 3.99 1 0.272 1.03 1.0482
Table 6
Parameters r; f and E for the dierent fuels, as a function of concentration
Combustible r f
u
a
E

E
u
Methane (1:8=y 0:8) 0:1(1 y)=y 1 1
Propane (0:345 + 0:655=y) 0:04(1 y)=y (1 + y) (1:092 0:092y)=(1:05 0:05y)
Heptane (0:712 + 0:288=y) 0:0182(1 y)=y (1 3y) (1:107 0:107y)=(1:05 0:05y)
Methanol (0:1 + 0:9=y) 0:1333(1 y)=y (1 + 0:5y) (1:12 0:12y)=(1:05 0:05y)
Toluene (0:686 + 0:313=y) 0:0222(1 y)=y (1 + y) (1:073 0:073y)=(1:05 0:05y)
Acetone (0:503 + 0:497=y) 0:05(1 y)=y (1 + y) (1:1025 0:1025y)=(1:05 0:05y)
Acetic acid (0:52 + 0:48=y) 0:1(1 y)=y (1 + y) (1:155 0:155y)=(1:05 0:05y)
THF (0:6 + 0:4=y) 0:0364(1 y)=y (1 + 1:5y) (1:107 0:107y)=(1:05 0:05y)
a
f

is in all cases 1, as explained above.

Table 7
Burning velocity and parameters a; b and c (reference: propane)
Combustible V

V
s
V
0:8s
V
1:2s
a

a
u
b
u
c
u
(m s
1
) (m s
1
) (m s
1
) (m s
1
)
Methane 0.08 0.47 0.39 0.44 11:07 20.77 8:71 6:361 13.674 6:313
Heptane 0.048 0.28 0.232 0.262 7:04 13.53 5:49 0.0068 0:335 1.328
Methanol 0.0705 0.411 0.341 0.384 4:615 9.162 3:547 0:0455 0:22 1.265
Toluene 0.05 0.294 0.243 0.274 4:04 8.127 3:087 0:0256 0:2636 1.289
Acetone 0.0585 0.341 0.283 0.319 1:893 4.263 1:37 0:104 0.0917 1.195
Acetic acid 0.06 0.35 0.29 0.327 5:75 11.21 4:46 1:375 2.705 0:33
THF 0.0547 0.319 0.264 0.298 4:66 9.243 3:583 0:0144 0:288 1.303
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3837
Table 8
Flame temperature at ammability limits (reference: propane)
Combustible T

T
u
(K) (K)
Methane 878.4 968.4
Heptane 802.3 883.0
Methanol 835.5 886.1
Toluene 793.0 899.9
Acetone 767.1 909.8
Acetic acid 808.6 893.9
THF 824.3 916.3
Table 9
Specic heat at ammability limits and minimal pressure (reference:
propane)
Combustible C
p
C
pu
P
min
(kJ kg
1
K
1
) (kJ kg
1
K
1
) (bar)
Methane 1.058 1.066 0.1314
Heptane 1.051 1.059 0.125
Methanol 1.053 1.058 0.0863
Toluene 1.05 1.06 0.126
Acetone 1.047 1.06 0.1202
Acetic acid 1.05 1.059 0.122
THF 1.052 1.06 0.119
To determine the complete range of variation of
ammability limits the values from Eqs. (47)(49) (as
a function of y) and the values of ame temperature (in
the case of LFL with the correction of Eq. (34)) must be
substituted into Eqs. (28) and (29). Thus, two implicit
equations of y are obtained, which can be solved by
attributing values to the pressure in the range between
P = 1 and P =P
min
.
Lihou proposed two reference substances: methane and
propane. In order to be in a position to compare our results
with Lihous, ammability limits as a function of pres-
sure were calculated for the same fuels proposed by him
(methane, propane, heptane, methanol, toluene, acetone,
acetic acid and tetrahydrofuran (THF)), using methane
as a reference in one case and propane in the other. The
results obtained are described below.
7. Results obtained for dierent fuels
The data corresponding to the reference substances
proposed by Lihou, which are used in the following cal-
culations, can be seen in Table 3. The data required for
the dierent fuels studied are summarised in Table 4.
To determine the ame temperature at the ammabil-
ity limits, a set of parameters (which do not depend on
the reference substance) must be obtained (see Table 5).
And to establish the general equation of the heat balance
as a function of pressure and concentration, we need to
determine the expressions for r, f and E (these parame-
ters do not depend on the reference substance) as a func-
tion of y for LFL and UFL (see Table 6).
7.1. Determination of the ammability curves using a
reference substance
For the case of propane as a reference substance, the
values of burning velocity and parameters a; b and c have
been summarised, for the various fuels selected, in Ta-
ble 7. Two implicit equations (Eqs. (42) and (43)) were
solved, yielding the results shown in Table 8. With these
temperature values, specic heats can be determined (see
Table 9) at ammability limits, as well as the minimal
pressure at which the mixture becomes non-ammable.
The results nally obtained (i.e., the ammability limits
as a function of concentration and pressure) are plotted
in Fig. 4.
The procedure was also applied to the same fuels taking
methane as a reference substance. The values obtained
for the various parameters are summarised in Tables 10,
11 and 12. The results corresponding to the variation of
ammability limits as a function of pressure are plotted
in Fig. 5.
The results obtained for a given fuel are very similar
with the two reference substances, and show the same
trend with only slightly dierent values. Fig. 6 shows
the variation of ammability limits for heptane using
methane and propane, respectively, as references. LFL
varies very slightly when pressure decreases, this varia-
tion increasing somewhat near minimal pressure. How-
ever, UFL shows a signicant variation over the whole
range of pressures studied. It can also be observed that
the values obtained when propane is used as a refer-
ence substance are always below those obtained when
using methane; the zone corresponding to ammability
conditions is therefore larger when propane is used as a
reference substance, the minimal pressure being lower.
Minimal pressure was lower for all the fuels studied when
propane was used as a reference (Fig. 7).
The same trend was found for all the fuels studied.
Therefore, while no experimental values are available, the
use of propane as a reference substance is a sound option,
as it will always provide more conservative results.
Flame emissivity was used to study the sensibility of
the method. The variation of P
min
as a function of emissiv-
ity was analysed for the dierent hydrocarbons studied,
using propane as the reference substance. The data cor-
responding to ve representative compounds have been
plotted in Fig. 8. These data show that the ame emis-
sivity has a practically negligible inuence on the value
of P
min
, even in the case of low luminosity ames with
0:5 (Siegel & Howell, 1992); the deviation of the
value of P
min
at = 1 with respect to the value obtained
at =0:5 was lower than 2% for most hydrocarbons, and
4.4% in the worst case (methanol).
3838 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Fig. 4. Variation of ammability limits for dierent fuelair mixtures, as a function of pressure, taking propane as a reference substance.
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3839
Table 10
Burning velocity and parameters a; b and c (reference: methane)
Combustible V

V
s
V
0:8s
V
1:2s
a

a
u
b
u
c
u
(m s
1
) (m s
1
) (m s
1
) (m s
1
)
Propane 0.06 0.25 0.172 0.23 0:0744 1.6964 0:622 0:0906 0:2028 1.2933
Heptane 0.0477 0.197 0.138 0.184 2:5743 6.1337 2:5594 0.0214 0:377 1.3557
Methanol 0.07 0.288 0.2019 0.27 1:141 3.5493 1:4083 0:0298 0:2464 1.2762
Toluene 0.05 0.206 0.1442 0.1929 0:7718 2.8883 1:1164 0:0119 0:2907 1.3027
Acetone 0.058 0.2394 0.1676 0.2242 0.3389 0.8895 0:2284 0:0791 0:143 1.2221
Acetic acid 0.059 0.242 0.1696 0.2269 1:785 4.7081 1:923 1:2205 2.3737 0:1531
THF 0.054 0.2237 0.1566 0.2095 1:1486 3.5675 1:4189 0:0014 0:3149 1.3163
Table 11
Flame temperature at ammability limits (reference: methane)
Combustible T

T
u
(K) (K)
Propane 796 921
Heptane 802 882
Methanol 835 885
Toluene 793 900
Acetone 766 908.5
Acetic acid 806 891
THF 822.5 914
Table 12
Specic heat at ammability limits and minimal pressure (reference:
methane)
Combustible C
p
C
pu
P
min
(kJ kg
1
K
1
) (kJ kg
1
K
1
) (bar)
Propane 1.0503 1.0622 0.185
Heptane 1.0508 1.0585 0.184
Methanol 1.054 1.0588 0.127
Toluene 1.05 1.0602 0.186
Acetone 1.0474 1.061 0.176
Acetic acid 1.0512 1.0594 0.18
THF 1.0527 1.0616 0.174
In order to test the new method, the results calculated
were compared to the experimental data available in the
literature. In Fig. 9 the results predicted by the method
(using as substances of reference propane, in the case of
the methane, and methane for the other gases) are plotted
together with the experimental results published by Stull
(1977) for methane at 298 K, and published by Latte
and Delbourgo (1952) for ethane, propane and butane at
298 K. The calculated values t very well with the exper-
imental ones; a slight dierence is observed in P
min
val-
ues, the calculated values being somewhat conservative
near this pressure.
8. Conclusions
The method proposed by Lihou (1993) for calculating
the minimum pressure at which a fuelair mixture be-
comes non-ammable has been considerably improved
and extended to determine the variation of ammability
limits as a function of pressure, at reduced pressure con-
ditions.
The application of this new methodology has demon-
strated that ame temperature at UFL is not a function
of pressure, while at LFL it varies with pressure. A cor-
relation is proposed to calculate the ame temperature at
LFL as a function of ame temperature at UFL and of
pressure.
A new general methodology has been developed for
C
m
H
n
O
x
type fuels to obtain the ammability limits as a
function of pressure. The comparison of the results ob-
tained from the method with experimental values taken
from literature has shown that using propane as the ref-
erence substance leads to more conservative results (and,
therefore, safer operating conditions) than if methane is
taken as a reference substance.
The proposed method has produced results that closely
match the experimental values available on the variation
of ammability limits as a function of reduced pressures.
Notation
a; b; c parameters in Eq. (24)
C
p
specic heat of reactant mixture, consid-
ered equal to that of air at the average tem-
perature (T
m
) of the mixture, kJ kg
1
K
1
C
pu
specic heat of air at the average tempera-
ture between T
u
and 298 K, kJ kg
1
K
1
C
p
specic heat of air at the average tempera-
ture between T

and 298 K, kJ kg
1
K
1
D
e
diusivity, m
2
s
1
D diameter of spherical volume of reactant
emitting radiation, m
E molar ratio of reaction products to reac-
tants, dimensionless
E
s
molar ratio of reaction products to reactants
when the concentration of the mixture is
stoichiometric, dimensionless
3840 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Fig. 5. Variation of ammability limits for dierent fuelair mixtures, as a function of pressure, taking methane as a reference substance.
J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843 3841
Fig. 6. Comparison of the results obtained for heptane using the two
reference substances.
Fig. 7. Minimal pressure for the various fuels and for the two reference
substances (propane and methane).
Fig. 8. Minimal pressure as a function of ame emissivity.
f fraction of ammable vapour burnt, dimen-
sionless
H molar heat of combustion, kJ kmol
1
K proportionality constant, s
0:5
M molecular weight of ammable vapour,
kg kmol
1
m number of carbon atoms in the molecule of
the substance of interest
n number of hydrogen atoms in the molecule
of the substance of interest
P pressure, bar
P
min
pressure below which the mixture cannot
be ammable, bar
Q
c
combustion heat. Heat released in the com-
bustion of 1 kmol of ammable vapour, kJ
Q
r
radiative heat loss for a spherical volume,
kJ
Q
s
sensible heat gain required to increase the
temperature of the mixture up to the ame
temperature, kJ
r mass ratio of reaction mixture to ammable
vapour, dimensionless
s mole fraction of ammable vapour in the
stoichiometric mixture, dimensionless
S nal diameter of the radiant spherical vol-
ume per kmol of ammable vapour, m
T ame temperature for a given mixture, K
T
m
average temperature of the mixture, T
m
=
(T + 298)=2, K
T
lim
minimum temperature which must be
reached to allow ame propagation, K
u mole fraction of ammable vapour in the
UFL mixture, dimensionless
V burning velocity, m s
1
V

burning velocity at the ammability limits,

m s
1
V
1:2s
burning velocity for a concentration y =
1:2s; m s
1
V
0:8s
burning velocity for a concentration y =
0:8s; m s
1
V
y
burning velocity for any concentration
y; m s
1
v molar volume, m
3
kmol
1
x number of oxygen atoms in the molecule
y mole fraction of ammable vapour in any
mixture, dimensionless
Greek letters
emissivity, dimensionless
cube root of molar volume at boiling point,
m kmol
1=3
StefanBoltzmann constant (=56:7
10
12
kW m
2
K
4
)
mole fraction of ammable vapour in the
LFL mixture, dimensionless
3842 J. Arnaldos et al. / Chemical Engineering Science 56 (2001) 38293843
Fig. 9. Comparison of the ammability limits predicted by the new method and the experimental ones at 298 K. (a) Methane: reference propane:
(b) propane: reference methane, (c) ethane: reference methane, (d) butane: reference methane.
Subscripts=superscripts
indicates LFL conditions (as a superindex
it also indicates the same conditions)
u indicates UFL conditions (as a superindex
it also indicates the same conditions)
s indicates stoichiometric conditions (as a
superindex it also indicates the same con-
ditions)
ref corresponds to the reference substance
air corresponds to the air
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