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SatterfieM, C. N.; Van Eek, M. w.; Bliss, G. s. AIchE J . 1978,2 4 , 709.
Schwartz, J. G.; Dudukovic, M. P. AICh€ J. 1976,22,953.
Schwartz, J. G.; Roberts, G. W. Ind. Eng. Chem. Process Des. Dev. 1973,
12, 262.
Flash Points of Flammable Liquid Mixtures Using UNIFAC
Flash points are used to classify liquids containing combustible components according to their relative flammability.
Such a classification is important for the safe handling of flammable liquids such as organic solvents and solvent
mixtures. The UNIFAC group-contribution method is shown to be applicable for the prediction of flash points of
binary and multicomponent liquid mixtures. The predictions are reliable for mixtures constituted alone from
combustible substances and for mixtures also containing noncombustibles such as water.
Introduction
Flash points are used to classify combustible liquids
according to their relative flammability. Regulations for
the safe handling, transportation, and storage of such
substances are dependent on this classification, and flash
points are therefore of great importance in the chemical
industry. It is the purpose of this paper to show how the
UNIFAC group-contribution method can be used to pre-
dict flash points of liquid mixtures containing combustible
components.
Flash Point
A flash point is not a fundamental physical property and
its value will to some extent depend on the apparatus and
method used for its measurement. The experimental
procedures have, however, been standardized in many
countries, thus allowing for reproducibility and comparison
between flash points measured in different laboratories.
In principle the measurements are carried out in the fol-
lowing way: a small liquid sample is placed in the bottom
of a cup. The temperature of the cup is slowly increased
and the vapors from the liquid surface will mix with air
in the space above. The flash point temperature is reached
when a flame will propagate from an ignition source
through the whole vapor-air mixture. A flash is observed.
The cup may be open to the atmosphere (Open Cup
Tester) or closed, which will confine a given amount of air
(Closed Cup Tester). The closed cup tester is usually
applied today and all calculations here are based on this
type of tester. Lance et al. (1979) have in a recent review
described in detail the apparatus and the procedures used
for the measurement of flash points.
Theory
A flash point is defined as the lowest temperature for
which vapors above a liquid form a flammable mixture
with air at a pressure of 101.325 kPa. For a pure com-
bustible component i the flash point may thus be esti-
mated as the temperature for which the vapor pressure,
Pi",equals the partial pressure at the lower flammability
limit, Li. This is illustrated in Figure 1. A lower flam-
mability limit Li in a homogeneous gas-air mixture at
temperature T corresponds to such a partial pressure of
the combustible compound in air that a flame will just be
0196-4313/82/1021-0186$01.25/0 0 1982 American Chemical Society
Sicardl, S., et ai, Chem. Eng. Sci. 1981,36, 226.
Van Swaaij, W. P.: Charpentler, J. C.; Villermaux, J. Chem. Eng. Sci. lB6B,
2 4 , 1083.
Weekman, V. W. Ph.D. Thesis, Purdue University, 1963.
Engineering Technology Laboratory G u r a y Tosun
Engineering R&D Division
E . I. d u Pont de Nemours & Co., Inc.
Wilmington, Delaware 19898
Received for review August 17, 1981
Accepted November 25, 1981
able to propagate from an ignition source. The ambient
temperature of the gas-air mixture is T. If the partial
pressure is lower than Li the combustible compound i will
burn around the ignition source. The liberated heat,
however, will not be so large that the combustion of any
one layer will ignite the neighboring layer of unburned gas,
and the mixture will not be capable of self-propagation of
flames.
The flash point for a pure combustible liquid i can thus
be written as the temperature TFfor which
P,"/Li = 1 (1)
Le Chatelier (1891) has presented an analogous equation
for binary and multicomponent mixtures containing N
combustible compounds.
cPi/Li= 1 i = 1, 2, ..., N (2)
i
In this equation Pi is the actual partial pressure of com-
ponent i in a vapor-air mixture which is in equilibrium
with the liquid mixture. Li is the partial pressure in a
gas-air mixture with a composition correspbnding to the
lower flammability limit of pure component i.
The lower flammability limit Li is a function of the
temperature and of the heat of combustion AHci. The
pressure has negligible influence on Li at pressures around
atmospheric pressure (Coward and Jones, 1952). The heat
of combustion is the net A H d since the reactants and the
combustion products all are in the gaseous state. Over
moderate ranges of temperature there are only small
changes in Li. Zabetakis (1965) accounted for the tem-
perature effect for various types of substances by means
of an expression which may be written as
L;(t) = Li(25) - 0.182(t - 25)/AH& (3)
LJt) and Li(25) (in kPa) are the lower flammability limits
at t "C and 25 OC, respectively; AHci is the net heat of
combination in kJ/mol. Equation 3 has also been used
by Wu and Finkelman (1978). Tables with values of Li(25)
may, for example, be found in Coward and Jones (1952)
and Zabetakis (1965). Zabetakis also indicates how Li(25)
values may be estimated when no experimental data are
available. Since Jensen et al. (1981) have described a
method for the prediction of pure component vapor
 Ind. Eng. Chem. Fundam., Vol. 21, No. 2, 1982 187

p'
and Li
I
TF -T

Figure 1. Estimation of flash temperature TFfor a pure substance

i. Pi'is the partial pressure in air correspondingto the vapor pres-
sure. Liis the partial pressure correspondingto the lower flamma-
bility limit. T is the temperature.

pressures, it is possible to predict approximate values of 0-

the flame point temperatures TFfor pure substances. M e t h a n o l 11)-
Methylacetate( 2 )
The partial pressures Pi corresponding to vapor-liquid ,
equilibrium VLE at temperature T may be calculated 0
0

using the following equation in which it is assumed that -10 - 0

0
0'

the vapor-air mixture behaves like an ideal gas

<
Pi = xiyipi" (4)
x i is the mole fraction of component i, yi is the activity -201 1 1 ' 1 ' ' J
0. .1 .2 .3 .4 .5 .6 .7 .8 .9 1.0
coefficient, and Pi" is the vapor pressure of component i x1-

a t temperature T.
The pure component vapor pressures Pi" may be calcu-
lated by means of the Antoine equation
log Pi" = Ai - Bi/(t + Ci)
The constanta Ai, Bj,and Ci may be found for many sub-
stances in Gmehling et al. (1977).
Ellis (1976) used values of the activity coefficients y i
calculated from experimental VLE data. In general, the
activity coefficients may be calculated from a model de-
scribing the liquid phase nonideality. Wu and Finkelman
(1978) used, for example, the van Laar equation for binary
mixtures and the Wilson equation for multicomponent
mixtures, and De Micheli and Delogu (1980) used the
NRTL equation. The use of such models requires a
knowledge of the necessary parameters. Parameters for
some commonly applied models and for many different
types of mixtures can be found in Gmehling et al. (1977).
Quite often one cannot find the parameters for all the pairs
of components in a mixture and one has to rely on a
predictive method for the estimation of the activity
coefficients.
UNIFAC is a fast and reliable method for the prediction
of activity coefficients in nonelectrolyte liquid mixtures.
The method is based on the solution of groups concept.
The groups are structural units such as CH3, OH, and
others which when added form the parent molecules. In-
stead of considering a liquid mixture as a solution of
molecules, the mixture is considered as a solution of
groups. The activity coefficients are then determined by
the properties of the groups rather than by those of the
molecules. The activity coefficients are calculated from
two terms: a combinatorial part essentially due to dif-
ferences in size and shape of the molecules and a residual
part due to energetic interactions between the groups.
The UNIFAC method was developed by Fredenslund
et al. (1975). The method was revised and detailed de-
scriptions of the method have been presented (Fredenslund
et al. 1977a,b). The parameters needed for the use of
W A C are group volumes (RK),group surface areas (Qd,
and group interaction parameters (a, and urn). Extensive
tables with parameters are given by Skjold-Jerrgensen et
al. (1979) and by Gmehling et al. (1982). The method now
comprises 40 groups and it allows for the calculation of
activity coefficients for most of the binary and multicom-
ponent mixtures of interest in chemical technology. For
Figure 2. Experimental and predicted flash points for two binary
mixtures containing only combustible components. Experimental
data: DeMicheli and Delogu (1980): TF, flash point in "C; x l , mole
fraction of component 1; 0,experimental point; -, UNIFAC; - - -,
(5) ideal.
0' I
0. .I .2 .3 .4 .5 .6 .7 .0 9,x; 1.0
Figure 3. Experimental and predicted flash points for water (1)-
alcohol (2) mixtures: TF,flash point in O C ; xl, mole fraction of water.
The symbols represent experimental values, and curves are predicted
from UNIFAC. Methanol: (0) Choe and Schecker (1981),-; eth-
anol: (0) Choe and Schecker (1981),---; 2-propanol: (A) Wu and
Finkelman (1978), - --.
further information about the method, the reader is re-
ferred to the above mentioned references.
Results and Discussion
Solution of eq 2 provides iteratively the desired flash
point temperature. The values of Liare calculated from
eq 3 while Pi values are obtained from eq 4 and 5 with the
activity coefficients predicted by means of UNIFAC.
The agreement between experimental and predicted
flash points is generally very good as can be seen from
Figures 2-4 and from Table I.
Figure 2 shows some typical results for binary mixtures
of combustible compounds. The figure presents the ex-
perimental and the UNIFAC predicted flash points. The
figure also shows the flash points obtained with the as-
sumption that the liquid forms an ideal mixture; Le., the
activity coefficients have values of unity ( y i = 1).
Figures 3 and 4 show results for binary mixtures with
only one combustible component. The water-alcohol
188 Ind. Eng. Chem. Fundam., Vol. 21, No. 2, 1982

30 value for the pure component flash point, which gives

Li(25),will influence the calculation of the flash points for
f the mixture. This phenomenon can be seen from the
TF
chloroform (1)-methylethyl-ketone (2) mixture in Figure
4. A somewhat higher experimental flash point for methyl
20
ethyl ketone would have raised the UNIFAC predicted
/ curve giving rise to a better agreement between experi-
mental and predicted values.
Chloroform(1)- ”/ Table I shows that the UNIFAC method may be used
10 for the prediction of flash points for multicomponent
mixtures. It is seen from Table I that an assumption of
ideality of the liquid mixture leads to flash points which
deviate much more from the experimental values than the
UNIFAC predicted ones.
0 Supplement. A computer program for the calculation
of flash points by means of UNIFAC is available from the
authors.
Acknowledgment
-lC The authors thank Professors U. Onken and Aa. Fre-
denslund for criticism and helpful comments to this work.
The authors further thank “Bundesministerium fur For-
schung und Technoiogie” and “Statens Teknisk-Viden-
-2c
skabelige ForskningsrAd” for economic support. There
3 .2 .3 .4 .5 .6 .7 .6
x1-
.9 have not been published very many experimental flash
points for mixtures. We are most grateful that De Micheli
F i g u r e 4. Experimental and predicted flash points for t w o binary and Delogu (1980) and Choe and Schecker (1981) have
mixtures. Experimental data: Choe and Schecker (1981): Tp, flash
p o i n t in “C;xl, mole fraction of chloroform: 0,experimental point;
made their data available for us.
-, U N I F A C . Literature Cited
Choe, M.; Schecker, H. G., University of Dortmund, private communication,
T a b l e I. P r e d i c t i o n of Flash P o i n t s for t h e T e r n a r y 1981.
System: Ethanol ( 1 ) - T o l u e n e (2)-Ethyl A c e t a t e (3). Coward, H. F.; Jones, G. W. U . S . Bur. Mines Bull. 503, 1952.
DeMichell, S.; Delogu, P. Report from Reaction Technique Department,
E x p e r i m e n t a l Data from Wu and F i n k e l m a n ( 1 9 7 8 ) Montedlson D I E Research Center, Bolbte, Italy, 1980.
f l a s h point, “C Ellis, W. H. J. Coat. Technol. 1976, 48, 44.
Fredensiund. Aa.; Jones, R. L.; Prausnitz, J. M. AIChEJ. 1975, 2 1 , 1086.
calcd Fredenslund, Aa.; Gmehling, J.; Micheisen, M. L.; Rasmussen, P.; Prausnitz, J.
M. Ind. Eng. Chern. ProcessDes. D e v . 1977av 16, 450.
compn, m o l e fraction Fredensiund, Aa.; Gmehiing, J.; Rasmussen, P. “Vapor-Liquid Equilibria Using
ideal
x( 1) x( 2) x( 3) exptl mixture U N I F A C UNIFAC”, Elsevier: 1977b.
.
Gmehling, J.; Rasmussen, P.; Fredensiund, Aa. Ind. fng Ch8m ProcessI

1.000 0.000 0.000 12.8 Des. D e v . 1982, 27, 118.

5.56 Gmehling, J.; Onken, U.; Ark, W. “Vapor-Liquid Equilibrium Data Collection”,
0.000 1.000 0.000 DECHEMA Chemistry Data Series, Vol. I (12 Parts); 1977.
0.000 0.000 1.000 -5.56 .
Jensen, T.; Fredenslund, Aa.; Rasmussen, P. Ind. Eng Ch8rn. Fundarn.
0.328 0.328 0.3 44 -3.33 1.58 -1.80 1981, 20, 239.
0.568 0.284 0.148 -1.67 4.81 -0.17 Lance, R. C.; Barnard. A. J.; Hooyman, J. E. J. Hazard. Mater. 1979, 3 ,
0.564 0.141 0.295 -3.33 0.94 -1.77 107.
-2.78 2.40 -1.29 Le Chatelier, H. Ann. Mines 1891, 8 , 388.
0.494 0.247 0.259 SkJoldJsrgensen, S.; Kolbe, E.; Gmehling, J.; Rasmussen, P. Ind. Eng .
0.887 0.0 55 0.058 2.22 7.08 4.06 Chem. Process Des. D e v . 1979, 18, 714.
0.176 0.088 0.7 36 -5.56 -3.07 -4.56 Wu, D. T.; Finkelman, R. Presented at the 175th National Meeting of the
0.856 0.114 0.030 1.67 9.29 3.63 American Chemical Society, Anaheim, CA, March 1978, Division of Or-
ganic Coatings and Plastics Chemistry.
Zabetakis, M. G. U S . Bur. Mines Bull. 627, 1965.
mixtures have positive deviations (ri> 1)from Raoult’s
law, while the chloroform-containing mixtures in Figure
4 have negative deviations (-yi < 1). Lehrstuhl Technische Chemie B Jurgen Gmehling
University of Dortmund 46
It may be noted from Figure 3 that the flash points are Dortmund-Hombruch, West Germany
much less influenced by the water content at low water
concentrations than at high concentrations. This phe- Instituttet for Kemiteknik P e t e r Rasmussen*
nomenon is more pronounced for 2-propanol than for The Technical University of Denmark
DK-2800 Lyngby, Denmark
methanol. UNIFAC describes this behavior very well.
The values of Li(t)from eq 3 are strongly dependent of Received for review June 23, 1981
the value for Li(25). This means that a small error in the Accepted F e b r u a r y 10, 1982