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Calculation of Flash Points and Flammability Limits of Substances and Mixtures
Calculation of Flash Points and Flammability Limits of Substances and Mixtures
Hristova,
Journal of the University of Chemical S. Tchaoushev
Technology and Metallurgy, 41, 3, 2006, 291-296
ABSTRACT
Flash point and flammability limits are important factors in the development of safe practices for handling and
storage of pure substances and mixtures. Regulatory authorities use data for flash point in order to classify flammable and
combustible substances.
In the proposed work a critical evaluation of the methods for calculation of flash point and flammability limits of
individual substances and liquid mixtures was made.
Keywords: Flash point, flammability limits, substances, mixtures.
291
Journal of the University of Chemical Technology and Metallurgy, 41, 3, 2006
Pi ,satfp (T f )
where Tf and Tb are in o C. The correlation coefficient LFLi =
is 0.967 and the standard error of estimate is 11.06o C. P (8)
A correlation for organic compounds was de-
veloped using data for 494 compounds. The result is:
sat
where Pi , fp (T ) is the saturated vapor pressure at the
T f = −54.5377 + 0.5883Tb + 0.00022T b
2
(4) flash point temperature and P is the ambient pressure.
Equation (9) shows the relationship between the flam-
where Tf and Tb are in o C. The correlation coefficient mability properties LFL and Tf . Thermodynamically,
is 0.966 and the standard error of estimate is 11.66o C. the relation between an ideal vapor and a non-ideal liq-
292
M. Hristova, S. Tchaoushev
uid is represented by the equilibrium condition pre- considered were ethanol-toluene, hexane-ethanol and
sented in equation (10): ethanol-n-propanol.
White et al [13] reduced Affens and McLarens
model to a simpler equation by ignoring the tempera-
xi γ i Pi sat
y i P = xi γ i Pi or y i =
sat
(9) ture effect upon LFL. They use this equation to esti-
P mate the flash point of jet-fuel mixtures.
Gmehling and Rasmussen [14] have shown that
where xi , y i , γ i and Pi are the liquid mole fraction,
sat
the UNIFAC group contribution method is applicable
vapor mole fraction, activity coefficient of component i for the flash points prediction of binary and multicom-
in the liquid, and its vapor pressure at temperature T, ponent liquid mixtures. The methodology is as follows:
respectively.
The Le Chatelier rule for the flammable va- 1. Determine the flash point temperature by find-
por-air mixture of two components is: ing the temperature which satisfies
y1 y pi
+ 2 =1
LFL1 LFL2 (10) ∑L i
=1 i=1, 2,
.., N, (12)
i
where y1 and y2 refer to the vapor mole fraction of com- where pi is the actual partial pressure of component i in
ponents 1 and 2, and LFL1 and LFL2 refer to the lower a vapor-air mixture which is in equilibrium with the
flammability limit of component 1 and 2. Details on liquid mixture. Li is the partial pressure in a gas-air
the derivation of equation (11) are given by Mashuga mixture with a composition corresponding to the LFL
and Crowl [9]. of pure component i.
The flash point of a binary mixture can be esti-
mated by the model developed by Liaw, et al [10]: 2. Determine the flammability limits at the tem-
perature under study using Zebatekis equation,
point of different binary mixtures using the equations perature T . The pure component vapor pressure may
of Le Chatelier and Walsham. Some of the mixtures be calculated by the Antoine equation:
293
Journal of the University of Chemical Technology and Metallurgy, 41, 3, 2006
where C est is the stoichiometric concentration of the where MLFL is the mixture lower flammability limit
flammable product for complete combustion in air. The (vol. %); Ci is the concentration of component i in the
294
M. Hristova, S. Tchaoushev
gas mixture on an air-free basis (vol. %); and LFLi is However, these methods are valid only at the condi-
the lower flammability limit for compound i in the mix- tions at which the correlations were developed.
ture (vol. %).
Melhem [24] developed a method for the estima- REFERENCES
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