Journal of Loss Prevention in the Process Industries 15 (2002) 429438

www.elsevier.com/locate/jlp

A mathematical model for predicting the flash point of binary

solutions
Horng-Jang Liaw , Yi-Huah Lee, Chia-Ling Tang, Hua-Hsuan Hsu, Jia-Huey Liu
Department of Occupational Safety and Health, China Medical College, 91 Hseuh-Shih Rd, Taichung, Taiwan

Abstract
A mathematical model which may be used for predicting the flash point of binary solutions has been proposed and subsequently
verified by experimentally-derived data, such data pertaining to an almost-ideal solution as also to highly non-ideal solutions. The
results reveal that the model is able to precisely predict the flash point over the entire composition range of binary solutions for
both ideal solutions and non-ideal solutions by way of utilizing the flash point of the individual components. The highly nonideal solution like octane+ethanol exhibits the minimum flash-point behavior, which leads to the minimum on the flash point vs
composition curve.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Flash point; Lower flammable limit; Vapor-liquid equilibrium; Binary solution; Minimum flash point

1. Introduction
The flash point of a flammable (or combustible) liquid
is the temperature at which the vapor pressure of the
substance is such as to produce a concentration of vapor
in the air that corresponds to the lower flammable limit
(LFL) (Lees, 1996). The flash point is one of the major
physical properties used to determine the fire and
explosion hazards of liquids (Crowl & Louvar, 1990). A
liquid that exhibits a flash point value below ambient
temperature, and can thus give rise to flammable mixtures under ambient conditions, is generally considered
to be more hazardous than one reflecting a higher flash
point (Lees, 1996).
The flash-point specification is one of the major safety
data items specified in the typical material safety data
sheet (MSDS), and can be measured by use of a Flash
Point Analyzer. In addition, the specific value of the
flash point for a pure substance can be estimated by use
of its LFL value and the equation for the saturated vaporpressure variation of the substance with temperature as
an Antoine equation (CCPS/AIChE, 1993). The flash-

Corresponding author. Tel.: +886 4 22053366 ext. 3502; fax: +886

4 22031843.
E-mail address: hjliaw@mail.cmc.edu.tw (H.-J. Liaw).

point data corresponding to various compound solutions

appear to be scarce in the literature; even those listed in
a variety of MSDS sheets are, typically, only valid for
a specific compound composition. In Taiwan, the revocation of the license for the largest chemical waste handler, Shengli Waste Handler, due to their illegal dumping
of waste organic solvents into the Kaoping River
(southern Taiwan) resulting in serious water pollution,
led to the collection of a large quantity of waste organic
solution which could not be handled legally, such that
these waste materials were required to be stored
(temporarily) in a variety of factory sites or in the industrial parks in 2000. In order to assure the safety of storage of such materials, the flash-point data corresponding
to flammable (or combustible) liquid solutions have
clearly become an important issue. Although such data
could be determined by use of a Flash Point Analyzer,
it needs to be understood that such determination
requires a significant amount of time in order to procure
satisfactory data because the various composition ranges
of specific materials used or produced in an industrial
process can be very substantial. In addition to this,
flame-spread rates, which have a direct impact upon the
time available for fire-fighting to limit the area involved,
are dependent upon the fuel-mixture flash point (White,
Beyler, Fulper, & Leonard, 1997). If a flash point-prediction model for the solutions could be successfully

0950-4230/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 0 - 4 2 3 0 ( 0 2 ) 0 0 0 6 8 - 2

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H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

Nomenclature
A, B, C Antoine coefficients;
binary parameter of the three-suffix Margules equation;
Aij
a
defined in Eq. (11);
f
fugacity of pure component, kPa;
G
defined in Table 1;
g
binary parameters of NRTL equation, J/mol;
LFL
lower flammable limit;
P
ambient pressure, kPa;
saturated vapor pressure, kPa;
Psat
saturated vapor pressure of component i at flash point, kPa;
Psat
i,fp
measure of molecular surface areas;
qi
R
gas constant, 8.314 J/mol;
measure of molecular van der Waals volumes;
ri
T
temperature, K;
flash point temperature of pure component i, K;
Ti,fp
u
binary parameters of UNIQUAC equation, J/mol;
molar volume of liquid, m3/mole;
vl
x
liquid-phase composition;
y
vapor-phase composition;
z
coordination number;

Greek letters
i
i

segment fraction;
fugacity coefficient of species i in solution;
activity coefficient;
defined in Table 1;
binary parameters of Wilson equation, J/mol;
area fraction of component i;
defined in Table 1;

Subscripts
fp
i
m

flash point;
species i;
mixture.

developed, the flash point of various solutions should be

able to be predicted relatively easily with only a little
basic data.
There are two currently-accepted methods for the

Closed cup
Open cup

Pensky Martens
Tagliabue
Cleveland

measurement of the flash point value of a liquid, the

closed cup test and the open cup test (Lees, 1996). Some
standard test methods are as follows:

ASTM D 93-00 (ASTM D 93, 2000)

ASTM D 56-01 (ASTM D 56, 2001)
ASTM D 92-98a (ASTM D 92, 1998)

H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

431

Table 1
Some models for activity coefficients for binary systems
Name

Binary parameters

ln1 and ln2

Three-suffix
Margules
Wilson

A12,A21

lngi (1xi)2[Aij 2xi(AjiAij)] where i 1 j 2 or i 2 j 1

12, 21

ij
ji
lngi ln(xi ijxj) xj(

) where i 1 j 2 or i 2 j 1;
xi ijxj jixi xj
l
vj
lijlii
ij lexp(
)
vi
RT

NRTL

g12 g22, g21 g11

UNIQUAC

u12 u22, u21 u11

Gji
tijGij
gijgjj
;
lngi x2j[tji(
)2
] where i 1 j 2 or i 2 j 1; tij
xi xjGji
(xj xiGij)2
RT
lnGij aijtij
i z
qi
ri
tji
tij
lngi ln qiln j(li lj)qiln(qi qjtji) qjqi(

) where i 1 j 2 or
xi
2 i
rj
qi qjtji qj qitij
uijujj
xiri
xiqi
z
;q
; l (r q )(ri1); z 10
i 2 j 1; lntij
; i
RT
xiri xjrj i xiqi xjqj i 2 i i

The open cup flash point (temperature) value is usually

a few degrees greater than the closed cup flash point
(Lees, 1996).
Affens and McLaren (1972) have developed a model
based upon Raoults law, which was used to estimate the
vapor-phase composition of the hydrocarbons present in
a hydrocarbon solution, in order to predict the flash point
for hydrocarbon solutions. White, Beyler, Fulper and
Leonard (1997) reduced Affens and McLarens model
(1972) to a simpler equation by ignoring the temperature
effect upon LFL, the former group using this equation
to estimate the flash point of two aviation-fuel mixtures:
JP-4/JP-8 and JP-5/JP-8, and, subsequently, to attempt
to correlate the flame-spread rate to the (estimated) flashpoint temperature. It could be construed that it may be
somewhat questionable to apply Affens and McLarens
model (1972) and White et al.s equation (1997) to a
non-ideal solution, for which situation Raoults law
would appear not to apply, although such models can
be used to describe the flash-point variation of an ideal
solution with the solutions composition. The object of
our work here was to establish a flash point-prediction
model that was able to be successfully used to predict
the flash point of binary solutions including both ideal
and non-ideal solutions, such a model being developed
based upon Le Chateliers rule (Le Chatelier, 1891) and
the flammable composition of the vapor phase being
derived from the theory of vapor-liquid equilibrium
(VLE). This model has been subsequently verified by
using the experimentally-derived data provided by the
closed cup test method.
Based upon the definition of flash point as mentioned
above, it becomes necessary to estimate the vapor-phase
composition of flammable substances in order to predict
their flash point. Prior to estimating the vapor-phase
composition by way of the vapor-liquid equilibrium equ-

ation, it is necessary to evaluate the liquid-phase activity

coefficients. For moderately non-ideal binary solutions,
the earlier-established relevant equations, Margules and
van Laar, are easier to handle mathematically than are
the more recently-developed equations, such as that
developed by Wilson (1964), and the Non Random Two
Liquid (NRTL) (Renon & Prausnitz, 1968) and the Universal Quasi Chemical (UNIQUAC) (Abrams & Prausnitz, 1975) examples (Reid, Prausnitz, & Sherwood,
1977). For a strongly non-ideal binary mixture, e.g., solutions of alcohols with hydrocarbons, the equation of
Wilson (1964) is probably the most useful method for
evaluating the liquid-phase activity coefficient, because,
unlike the NRTL equation (Renon & Prausnitz, 1968),
it contains only two adjustable parameters and it is mathematically simpler to manipulate than the case for the
UNIQUAC equation (Reid, Prausnitz & Sherwood,
1977). For such mixtures, the three-suffix Margules equation and the van Laar equation are likely to represent
the data with significantly less success (Reid, Prausnitz & Sherwood, 1977). In addition to the activity coefficients, the respective vapor pressures of both components in solution are also necessary thermodynamic
properties for the estimation of the vapor-phase composition. Further, the vapor pressure can be estimated by
use of the Antoine equation, the Antoine coefficients for
different substances being listed in various appropriate
chemical-engineering handbooks (Reid, Prausnitz &
Sherwood, 1977; Boublik, Fried, & Hala, 1984) and/or
by way of reference to the relevant literature.

2. Experimental details
The Flash Point Analyzer, HFP 362-Tag, manufactured by Walter Herzog GmbH (Germany) was used to

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H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

measure the flash point of binary liquid solutions associated with different compositions as tested. The Flash
Point Analyzer is operated according to the standard test
method, ASTM D56 (ASTM D56, 2001) with the following set of selected parameters: start test 5 K, end of
test 20 K, test interval-1 0.5 K, test interval-2 1.0 K,
heat rate-1 1 K/min, heat rate-2 3 K/min.
Octane, heptane, 1-butanol, and methanol were
HPLC/Spectro-grade reagents, supplied by the Tedia Co.
Inc. Methyl acetate was obtained from Lancaster, and
ethanol (99.5 vol%) purchased from NASA enterprises.

3. Models for predicting the flash point of binary

solutions
3.1. Mathematical formulation for the flash pointprediction model
The Le Chateliers rule (1891) for the flammable (or
combustible) vapor-air mixture of two components is
as follows:
1

y1
y2
yi

LFLi LFL1 LFL2

(1)

where yi is the composition of a flammable substance i

in the vapor phase, and LFLi the lower flammable limit
(LFL) of the pure component i. From the definition of
flash point, the LFL of component i, LFLi, is expressed
relative to its saturated vapor pressure at flash point,
Psat
i,fp, as:
LFLi

Psat
i,fp
P

yi

xigiPsat
i
P

(5)

Substituting Eq. (2) and the above equation into Eq. (1):
1

x1g1Psat
x2g2Psat
xigiPsat
i
1
2

sat
sat
Pi,fp
P1,fp
Psat
2,fp

(6)

The saturated vapor pressure variation with temperature

for a pure substance i can be estimated by the Antoine
equation:
Bi
logPsat
i Ai
T Ci

(7)

The vapor pressure of pure substance i at its flash point

Psat
i,fp, as presented in Eq. (6), can be estimated by substituting Ti,fp, the flash point of component i, into the Antoine equation.
The activity coefficients gi, which were presented in
Eq. (6), can be estimated by the use of several equations,
such as the three-suffix Margules equation, the Wilson
equation (Wilson, 1964), the NRTL equation (Renon &
Prausnitz, 1968), or the UNIQUAC equation (Abrams &
Prausnitz, 1975), such equations, which were used for
this study, being listed in Table 1.
The flash point-prediction model developed for the
binary solution included the modified equation of Le
Chatelier, the Antoine equation, and a model for estimating activity coefficients. These are described using Eqs.
(6) and (7) and the equations listed in Table 1. The temperature, which satisfies these equations, is deemed by
us to be the flash point of the solution.

(2)

where P is the ambient pressure. The composition of

flammable substance i in the vapor phase, yi, can be
derived from the vapor-liquid equilibrium (VLE).
For every component i in the mixture, the condition
for equilibrium between a liquid phase and a vapor phase
at the same T and P is given by:
iP xigifi
yi

or

(i 1,2,%,N)

(3)

3.2. Reduced model under an ideal solution

assumption
For the ideal solution, the activity coefficients of the
liquid phase are equal to unity, and the flash point-prediction model may be reduced to a simpler form. Under
this condition, the vapor-liquid equilibrium equation, Eq.
(5), was able to be reduced to Raoults law for this study,
this being described as:

At low pressure, the vapor phase can be approximated

as an ideal gas, then the vapor phase solutions fugacity
coefficient for component i is reduced to:

yi

i 1

Therefore, the modified equation of Le Chatelier, Eq.

(6), was reduced to:

and the fugacity of pure liquid i at the temperature and

pressure of the system can be simplified as:
fiPsat
i
where Psat
is the vapor pressure of pure i at the system
i
temperature. Therefore, the vapor-liquid equilibrium
relation is reduced as:
yiP xigiPsat
i

(4)

xiPsat
i
P

x1Psat
x2Psat
xiPsat
i
1
2

Psat
Psat
Psat
i,fp
1,fp
2,fp

(8)

(9)

this being the equation used by White et al. (1997) to

estimate the flash point of aviation-fuel mixtures, JP4/JP-8 and JP-5/JP-8. The Antoine equation, Eq. (7), was
and
still deemed by us to be useful to estimate Psat
i
for
this
reduced
model.
Therefore,
the
reduced
Psat
i,fp

H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

model for the flash point-prediction under an ideal solution assumption can be described using Eqs. (7) and (9).
3.3. Affens and McLarens model
Affens and McLaren (1972) derived a model to predict the flash point of hydrocarbon solutions using Le
Chateliers rule (1891) and Raoults law:

1642(Ti,fp 230)
xi10a
1
1642(T 230)

(10)

where
a

(Ti,fp

Bi(Ti,fpT)
230)(T 230)

(11)

The temperature, T, satisfied Eq. (10) and Eq. (11)

describes the flash point of the solution.

4. The flash point of a binary solution

4.1. The parameters used to predict the flash point of
a binary solution
In this study, the flash point prediction model proposed in section 3.1 was used to predict the flash point
of the following binary solutions: octane+heptane,
methanol+methyl acetate, octane+1-butanol, and
octane+ethanol. The prediction results obtained were
compared with the corresponding experimentallyderived data. The binary solution of octane + heptane
behaves as an almost ideal solution at 94kPa (Wisniak,
Reich, & Segura, 1999). By contrast, the binary systems
of methanol+methyl acetate, octane+1-butanol and
octane+ethanol behave as highly non-ideal solutions, and
they all exhibit minimum boiling azeotropic behavior at
101.3kPa (Hiaki, Taniguchi, Tsuji, Hongo, & Kojima,
1996; Tu, Wu, & Liu, 1997; Hiaki, Tatsuhana, Tsuji, &
Hongo, 1999). The liquid-phase activity coefficients for
octane+heptane and octane+ethanol solutions were estimated by use of the NRTL equation (Renon & Prausnitz,
1968), and those for octane+1-butanol solution were
deduced by use of the Wilson equation (Wilson, 1964).
The activity coefficients for methanol + methyl acetate
solution were estimated by the use of four different
equations including: the three-suffix Margules, NRTL,
Wilson and UNIQUAC equations, and subsequently
were used in the flash point-prediction model to predict
the flash-point variation curves, and the results, based
upon different activity coefficient equations, were compared. The parameters pertaining to the flash point-prediction model include the Antoine coefficients, the parameters of certain equations necessary to estimate the
activity coefficients, such as the three-suffix Margules,
Wilson, NRTL, or UNIQUAC equations and the flash

433

points of pure substances. The Antoine coefficients for

these species were adapted from the literature (Reid,
Prausnitz & Sherwood, 1977; Boublik, Fried & Hala,
1984; Riddick, Bunger, & Sakano, 1986; Hiaki, Tatsuhana, Tsuji & Hongo, 1999; Wisniak, Reich & Segura,
1999) and are listed in Table 2, the parameters of the
three-suffix Margules, Wilson, NRTL or UNIQUAC
equations for these solutions being abstracted from the
relevant literature (Hiaki, Taniguchi, Tsuji, Hongo &
Kojima, 1996; Tu, Wu & Liu, 1997; Hiaki, Tatsuhana,
Tsuji & Hongo, 1999; Wisniak, Reich & Segura, 1999)
and are listed in Table 3. The flash points of pure substances used in this study were obtained by way of testing with the Flash Point Analyzer. The equation used by
White et al. (1997), as deemed by us to be equivalent
to our reduced model under an ideal-solution assumption
(as mentioned in section 3.2 above), as also Affens and
McLarens model (1972) (as introduced in section 3.3)
were also used to predict the flash-point variation for
comparison with experimentally-derived data. In the prediction of the flash-point variation by use of above-mentioned two models, the authors elected to ignore the
equations listed in Table 1 and the data listed in Table
3 in order to estimate the liquid-phase activity coefficients but chose to set those values to unity, although
we did also use the Antoine coefficients as listed in
Table 2 in order to estimate the vapor pressure.
4.2. The flash-point variation of an almost-ideal
solution
Fig. 1 compares the flash-point variation between the
model predictive curves and the experimentally-derived
data for the binary solution of octane + heptane, which
reflects an example of an almost-ideal solutions
behavior at 94kPa (Wisniak, Reich & Segura, 1999). The
curve predicted by the flash point-prediction model as
proposed in this work appears to be consistent with the
experimentally-derived data, which demonstrates that
the flash point-prediction model is able to successfully
predict the flash-point variation of an almost-ideal solution. Fig. 1 also displays the predictive curves simulated by Affens and McLarens model (1972) and White
et al.s equation (1972) (should be equivalent to the
reduced model under an ideal solution assumption as
mentioned in section 3.2), both of which models set
activity coefficients equal to unity. Fig. 1 reveals that
the predictive curves based upon Affens and McLarens
model (1972) and White et al.s equation (1997) almost
overlap with that result predicted by the flash point-prediction model for an almost-ideal solution, such as an
octane+heptane solution. Such an outcome is attributed
to the observation that the liquid-phase activity coefficients of an almost-ideal solution, such as
octane+heptane, lie close to unity (see Fig. 2), which is
subject to accepting the assumption of Raoults law, in

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H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

Table 2
Antoine coefficients of the componentsab
Material

lit.

1-butanola
Ethanola
Heptanea
Octanea
Methanola
Methyl acetateb

6.54068
7.24222
6.02023
6.04394
7.20519
16.1295

1335.028
1595.811
1263.909
1351.938
1581.993
2601.92

96.496
46.702
56.718
64.030
33.289
56.15

c
c
d
e
f
g

log(P/kPa)=A-B/[(T/K)+C]
ln(P/mmHg)=A-B/[(T/K)+C]
c
Boublik, Fried and Hala (1984)
d
Wisniak, Reich and Segura (1999)
e
Hiaki, Tatsuhana, Tsuji and Hongo (1999)
f
Riddick, Bunger and Sakano (1986)
g
Reid, Prausnitz and Sherwood (1977)
b

Table 3
Parameters of the Margules, NRTL, Wilson and UNIQUAC equations for the experimental binary systems
Parametersa system
Three-suffix Margules
Methanol (1) + methyl acetate
NRTL equation
Octane (1) + heptane (2)
Octane (1) + ethanol (2)
Methanol (1) + methyl acetate
Wilson equation
Octane (1) + 1-butanol (2)
Methanol (1) + methyl acetate
UNIQUAC equation
Methanol (1) + methyl acetate
a
b
c
d
e

A12

A21

a12

lit.

(2)

0.93946

0.81157

179.68
651.91
224.99

0.3
0.47
0.27101

(2)

226.87
604.97
86.237

667.10
116.30

(2)

114.33
451.90

(2)

71.429

329.34

d
b

NRTL: A12=(g12-g22)/R, A21=(g21-g11)/R; Wilson: A12=(12-11)/R, A21=(21-22)/R; UNIQUAC: A12=(u12-u22)/R, A21=(u21-u11)/R

Tu, Wu and Liu (1997)
Wisniak et al. (1999)
Hiaki et al. (1999)
Hiaki, Taniguchi, Tsuji, Hongo and Kojima (1996)

which condition the flash point-prediction model can be

simplified to White et al.s equation (1972), which would
also be equivalent to our reduced model under the
assumption of an ideal solution as mentioned in section
3.2. It is also apparent from Fig. 1 that the flash pointprediction model and the simpler analogues, i.e., Affens
and McLarens model (1972) and White et al.s equation
(1977), are all able to effectively describe the flash point
of an almost-ideal solution.
4.3. The flash-point variation of a highly non-ideal
solution
The flash points of differing binary solutions covering
the entire composition range of methanol in methyl acetate, which forms a minimum boiling azeotrope at 101.3
kPa (Tu, Wu & Liu, 1997), were tested. The results were
plotted against the predictive curves from the flash point-

prediction models using different equations for estimating the activity coefficients of the curves depicted in Fig.
3. It can be clearly seen that the experimental results are
in excellent agreement with the predictive curves, which
use the NRTL, Wilson or UNIQUAC equations to estimate activity coefficients. The predictive curves simulated by Affens and McLarens model (1972) and White
et al.s equation (1997), are also displayed in Fig. 3.
From this Figure, it is apparent that the predictive curves
based upon Affens and McLarens model (1972) and
White et al.s equation (1997) deviate from the experimentally-derived data for this highly non-ideal solution,
methanol+methyl acetate. The estimated activity coefficients for this solution based upon the NRTL equation,
as displayed in Fig. 2, appear to deviate highly from
unity, suggesting that this deviation arises from the fact
that the behavior of this binary solution deviated highly
from that of an ideal solution, and that the application

H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

Fig. 1. Comparison of the flash point-prediction curves with experimentally-derived data for octane (1) + heptane (2) solution.

Fig. 2. Activity coefficient-liquid composition diagram for octane (1)

+ heptane (2), methanol (1) + methyl acetate (2), octane (1) + 1-butanol
(2) and octane (1) + ethanol (2) solutions at their flash-point conditions.

of Raoults law, which is the main assumption of Affens

and McLarens model (1972) and White et al.s equation
(1997), was not valid for such a solution.
Fig. 3 also depicts the results of comparing the predictive curves of the flash point-prediction model using different equations for estimating the corresponding
activity coefficients. It is apparent that the predictive

435

Fig. 3. Comparison of the flash point-prediction curves with experimentally-derived data for methanol (1) + methyl acetate (2) solution.
A: three-suffix Margules equation; B: NRTL equation; C: Wilson equation; D: UNIQUAC equation.

curves provided by the flash point-prediction model are

very similar to their analogues generated when using one
of the NRTL, Wilson or UNIQUAC equations to estimate the relevant activity coefficients, these predictive
curves all describing the experimentally-derived data
well. The resultant predictive curve for the flash pointprediction model using the three-suffix Margules equation to estimate the activity coefficients, described the
experimentally-derived data much more satisfactorily
than was the case for Affens and McLarens model
(1972) and White et al.s equation (1997), although the
predictive curve did deviate slightly from the experimentally-derived data. It was previously concluded by Reid,
Prausnitz and Sherwood (1977) that the NRTL, Wilson
and UNIQUAC equations were more effective than the
three-suffix Margules equation at describing the activity
coefficients for strongly non-ideal solutions, this being
the reason that the predictive curves of the flash pointprediction model based upon the NRTL, Wilson or
UNIQUAC equations were able to describe the experimentally-derived data more effectively than was the
case when the prediction model was based upon the
three-suffix Margules equation.
In addition to the predictive results for the almostideal solution, octane+heptane, and the highly non-ideal
solution, methanol+methyl acetate, the flash point-prediction model is also able to precisely predict the results
for other highly non-ideal solutions, including octane+1butanol and octane+ethanol, as reflected by a comparison
of the predictive results with the experimentally-derived
data, both of which solutions exhibiting minimum boil-

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H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

Fig. 4. Comparison of the flash point-prediction curves with experimentally-derived data for octane (1) + 1-butanol (2) solution.

ing azeotropes at 101.3 kPa (Hiaki, Taniguchi, Tsuji,

Hongo & Kojima, 1996; Hiaki, Tatsuhana, Tsuji &
Hongo, 1999), such results being displayed in Figs. 4
and 5. As was the case for the mix of methanol+methyl
acetate solution, the predictive curves based upon Affens
and McLarens model (1972) and White et al.s equation
(1997) were unable to satisfactorily equate with the
experimentally-derived data corresponding to the highly
non-ideal
solutions
octane+1-butanol
and

Fig. 5. Comparison of the flash point-prediction curves with experimentally-derived data for octane (1) + ethanol (2) solution.

octane+ethanol. The reason for this substantial deviation

between the experimentally-derived data and the predictive curves based upon Affens and McLarens model
(1972) and White et al.s equation (1997) is the same as
that for a solution of methanol + methyl acetate: Raoults
law is unable to effectively describe the behavior of a
non-ideal solution, this also being referred to in Fig. 2
where the estimated activity coefficients for these solutions were demonstrated to deviate notably from unity.
It is thus likely that it can be concluded that Affens and
McLarens model (1972) and White et al.s equation
(1997) are not satisfactory to predict the flash point of
a highly non-ideal solution, although they may be used
to predict the flash point for an almost-ideal solution.
The more powerful model, the flash point-prediction
model as proposed in this manuscript, is thus necessary
for predicting the flash-point behavior of a non-ideal solution.
In deriving the flash point-prediction model, it was
assumed that the liquid phase and vapor phase of a solution are in equilibrium. The estimation of the flash point
using the flash point-prediction model is only adequate
for the data determined by the closed cup test method,
which condition is presumed under the assumption of a
vapor-liquid equilibrium, and may not be appropriate to
apply to the data obtained from the open cup test
method, which condition deviates from the assumption
of an existing vapor-liquid equilibrium and the presence
of a vapor-concentration gradient existing.
4.4. The flash point for a binary solution reflecting a
positive deviation from an ideal solution
The experimentally-derived data recorded here indicate that the flash point of a binary solution that reveals
a positive deviation from an ideal solution, e.g.,
methanol+methyl
acetate,
octane+1-butanol,
or
octane+ethanol, is typically lower than that predicted by
the model based upon Raoults law as White et al.s equation (1997) or Affens and McLarens model (1972)
would suggest (see Figs. 3, 4 and 5). Such difference is
attributed to the observation that the vapor pressure of
flammable substances in a solution which demonstrates
a positive deviation from an ideal solution is higher than
that predicted by Raoults law, such that the flash point
temperature will be lower than the predictive equivalent
based upon an ideal solution. The more that a solution
deviates positively from ideality, the larger the difference in flash point between the experimentally-derived
data and the predictive analogue based upon the assumption of an ideal solution. Accordingly, the addition of a
small quantity of a low-flash-point substance to another
relatively high-flash-point substance and one for which
such a mixture produces a solution with a highly positive
deviation from an ideal solution, will result in a solution
reflecting a substantial reduction of the flash point as

H.-J. Liaw et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 429438

compared to the relatively high-flash-point component.

The binary solutions methanol+methyl acetate,
octane+1-butanol and octane+ethanol are examples of
such an outcome (see Figs. 3, 4 and 5). Clearly thus,
responsible personnel must be very cautious regarding
the safe storage/handling of a solution containing even
only a small quantity of a low-flash-point contaminant.
Such mixing would be likely to form a highly non-ideal
solution with a positive deviation from the (chemical)
behavior of an ideal solution, such deviation resulting in
a solution reflecting a substantial reduction of the flash
point from the analogous value for the parent solution.
4.5. Minimum flash-point behavior
It has been suggested above that the value of the flash
point for an ideal solution, such as octane+heptane, lies
somewhere between the corresponding values for the
individual components as revealed by the experimentally-derived data (Fig. 1). The surprising finding for the
solution of octane+ethanol, however, was that the flash
point of the solution over a wide composition range was
lower than that recorded for the individual solution
components, i.e., this solution exhibits minimum flashpoint behavior (Fig. 5). The flash point of octane and
ethanol are 15C and 13C respectively, but the corresponding value for the solution over a range of mix concentrations may lie as low as 5C. The minimum value
of the flash point for a binary solution is not necessarily
equivalent to that of the individual component displaying
the lower value; it may be equivalent to a value for a
specific composition located somewhere between the
composition values for the individual components. This
phenomenon is attributable to the observation that this
particular non-ideal solution reflects a highly-positive
deviation from the behavior of an ideal solution, for
which the activity coefficients are observed to be much
larger than unity (see Fig. 2), that such behavior results
in a substantial reduction of the solutions flash point.
The value of flash point for octane in this work, 15C,
is slightly different to the analogous value reported in
the SFPE handbook, namely 13C (SFPE, 1995),
although the value that we used for ethanol is equivalent
to that reported in this handbook. The difference in flashpoint data for octane between that used for this work
and that reported in the SFPE handbook (SFPE, 1995)
may be attributable to the presence of impurities in the
sample or it may be due to measurement error.
By contrast, another highly non-ideal solution,
methanol+methyl acetate, does not exhibit minimum
flash-point behavior, although it does reveal a minimum
boiling azeotrope at 101.3 kPa (Tu, Wu & Liu, 1997).
The minimum value of the flash point for a solution of
methanol + methyl acetate is equivalent to the flash point
of pure methyl acetate, the flash point of which is lower
than that of the other component (see Fig. 3). The mini-

437

mum flash-point behavior of the other highly non-ideal

solution, octane+1-butanol, is not so remarkable as the
solution of octane+ethanol. The predictive curve based
upon our flash point-prediction model and the experimentally-derived data for octane+1-butanol indicates
that the minimum flash point is 14.5C at x1 0.9, a
value which is slightly lower than that for pure octane,
i.e., 15C (see Fig. 4). Thus, the differing relationship
between flash point and individual component composition for different solutions can be attributed to differences in activity coefficients for the individual components of the solution. From an inspection of Fig. 2 it is
apparent that the larger the activity coefficients of solution components, the greater is the possibility that a
mixture of such components will demonstrate minimum
flash-point behavior.
It must be emphasized here that process safety design
based upon the lower flash-point value of individual solution components cannot necessarily be guaranteed safe
for a binary solution because the resultant solution may
reveal minimum flash-point behavior.
5. Conclusion
Affens and McLarens model (1972) and White et
al.s equation (1997), would appear to be equivalent to
our reduced model for the prediction of a solutions
flash-point value for an assumed ideal solution, although
none can be relied upon to describe the flash-point variation of non-ideal solutions, such models being reserved
for describing the behavior of ideal solutions. By contrast, the flash point-prediction model proposed in this
paper is able accurately to predict the flash point for a
binary solution including both ideal and non-ideal alternatives as revealed by a comparison between predicted
and experimentally-derived data. The prediction results
of this model can thus be applied to incorporate
inherently safer design for chemical processes, such as
the determination of the safe storage conditions for
flammable (or combustible) solutions.
It is important to emphasize here that some highly
non-ideal solutions, such as octane+ethanol, may exhibit
the minimum in the flash point vs composition curve.
Acknowledgements
The authors would like to thank the National Science
Council of the R.O.C. for supporting this study financially under grant #NSC 90-2214-E-039-001.
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