Flash Point Determination of an Ethanol-Water Mixture

Beriña, Robert Lloyd N., Galang, Duane Lemuel Q., Perez, Jose Fernando O.
Department of Chemical Engineering, College of Engineering
University of the Philippines, Diliman, Quezon City, Philippines

Submitted and Received August 17, 2010

Abstract

Flash point is defined as the temperature at which the substance emits sufficient vapor
in order to form a combustible mixture with air, while the fire point is the lowest
temperature at which a substance can sustain a flame for more than five seconds. In
the experiment, the flash points at 20%, 40%, 60%, 80% and 100% ethanol in water
were observed to be 28.9°C, 25°C, 21.75°C, 21.1°C and 17.55°C, respectively. The
theoretical values calculated using the Liaw Model and Wilson Equation were lower
than the experimental values. The percent error ranges from 33.2% to 61.4%, the
highest being exhibited by the pure ethanol solution. It is recommended that the set-up
be improved, i.e. performing in a darker environment as to see the flash point more
clearly and minimize human error.

Keywords: flash point, flame point, open-cup method, Liaw Model, Wilson equation

Introduction the fire point is the lowest temperature at

Flammability is an important factor to
consider in developing safe methods for
storing and handling solids and liquids.
Laboratories and industries commonly use
flammable substances. Corresponding
mixtures are used in order to carry out
certain experiments and processes. With
this in mind, it is important to take note of
the physical properties of the substances in
order to avoid any of the hazards
associated with them. Flash point and fire
point are two of those properties. Flash
point is defined as the temperature at which
the substance emits sufficient vapor in order
to form a combustible mixture with air, while
which a substance can sustain a flame for
more than five seconds. Usually, the fire
point is a few degrees above the flash point.
Different processes handle mixtures at
certain temperatures and pressures so it is
very important to be mindful of the
flammability properties as it can be used to
assess the risk level associated with each
process. It is important to note that
predicted values for these properties are not
accurate and known values may be specific
for certain types or brands. Thus,
experimental values are favored over
theoretical or predicted values.

Page 1 of 6
 There are two basic methods in
determining the flash point of a certain
substance: the open-cup and the closed-
cup method. In the latter, vapors are
prevented from escaping the container thus
resulting in a flash point greater than the
open-cup method. In the experiment,
however, the open-cup method was used.
Mixtures are much more difficult to work
with because their physical attributes are
not as easy to calculate, even with the use
of the mixing rule. Various correlations from
journals may be used to calculate the flash
point of pure hydrocarbons and mixtures of
hydrocarbons. For pure hydrocarbons, the
flash point id calculated using the equation:
(1)
where Tf is the flash point (in °C) and Tb is
the boiling point (in °C). Another correlation,
for estimating the flash points of organic
compounds and petroleum mixtures
(2)
where Tf and Tb are the flash point and
boiling point, respectively, in Kelvin, and a,
b, c are constants evaluated by nonlinear
regression using the Gauss-Jordan iteration
method. This non-linear exponential
correlation was found to be able to predict
the flash point of substances within an error
margin of 1% when tested with over 1220
compounds.
An alternative method, using the boiling
point temperature and chemical structure of
the substance, uses the following equations:
(3)
(4)
(5)
where C, S, H, X and O are the number of
carbon, sulfur, hydrogen, halogen and
oxygen atoms are present in the compound
and temperatures are in Kelvin.
In determining the flash point of a
mixture, what is being calculated in reality is
temperature at which the saturated vapor
pressure is equal to the lower flammability
limit (LFL) composition of the mixture.
(6)
where Pi,satfp(Tf) is the saturated vapor
pressure at the flash point temperature and
P is the ambient pressure. Using Chatelier’s
principle, the relation between the two
components in a mixture is found to be
(7)
Substituting the modified Raoult’s Law
into the equation, we get
(8)
where x is the liquid more fraction, γ is the
activity coefficient, and Pisat is the vapor
pressure. Setting the first component to be
water and the second component ethanol,
all those with a subscript of 1 in equation (8)
can be cancelled out because water is a
non-flammable liquid. The final equation
would then be
Page 2 of 6
 The volume amounts for water and
(9)
ethanol for different molar concentrations
were calculated. The densities of ethanol
Psat can be calculated using Antoine’s and water used were 0.7876 g/mL and 1
equation and the activity coefficients may be g/mL, respectively.
estimated by using equations such as
Margules, van Laar and Wilson. Table 1. Summary of experimental values of
flash point and fire point for different
concentrations of ethanol in water.
Methodology Ethanol Volume of Volume of
(mol %) ethanol (ml) water (ml)
The experiment studied the flash point 20 44.9115 55.0885
property of mixtures of ethanol and water. 40 68.4943 31.5057
The open-cup method was employed for all 60 83.0266 16.9734
80 92.8796 7.1204
mixtures. Materials used in the experiment
100 100 0
include the cup apparatus, Bunsen burner,
taper flame, and a thermocouple.
The flash points and fire points for the
different mixtures of ethanol and water are
Five mixtures of ethanol-water were
tabulated below.
prepared. The molar concentration of
ethanol in water ranged from 20 to 100%,
Table 2. Summary of experimental values of
with 20% increments. A sample calculation flash point and fire point for different
can be found in the appendix. The 5 concentrations of ethanol in water.
mixtures were then maintained in an ice Ethanol Flash Average
bath. (mol %) Point (°C) (°C)
28
20 28.9
The cup was filled with the prepared 29.8
concentration of the mixture. The Bunsen 40 25 25
burner was placed below the cup the same 20.8
60 21.75
time the taper flame was ignited and placed 22.7
directly above the mixture and kept in a 80 21.1 21.1
continuous motion. The flash point of the 17.9
100 17.55
sample is reached when a large blue flame 17.2
appears over the entire sample. The fire
point often soon follows when the entire Ethanol Fire Point Average
(mol %) (°C) (°C)
sample remains ignited after 5-10 seconds.
28.6
After each trial, the cup was thoroughly 20 29.85
31.1
cooled before washing and drying. The
40 25.9 25.9
same procedure was done for each of the 21.5
remaining four concentrations. 60 22.55
23.6
80 22.4 22.4
18.2
Results and Discussion 100 17.85
17.5

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 In order to get the theoretical value of Table 3. Percent errors between the
the flash point, the Liaw model, which was experimental and theoretical values.
discussed in the introduction, was used. For mol Flash point
fraction Experimental using the
the calculation of gamma, the Wilson model of flash point Wilson
% diff
was employed. Because of the dependence ethanol equation
of the value of gamma on the temperature, 0.2 28.9 21.68920171 33.24603
several iterations must be made until the 0.4 25 18.30082892 36.60583
value for Psat converges, and the resulting T 0.6 21.75 16.01772103 35.78711
would be the theoretical flash point. A step- 0.8 21.1 13.65114866 54.56575
by-step calculation for the theoretical flash 1 17.55 10.86839252 61.47742
points is included in the appendix.
The e flash point of pure ethanol has a
The theoretical and experimental values literature value of 13°C, still far from the
of the flash points are plotted in Figue 1. As experimental 17.55°C and calculated
seen from the graph, there is a clear 10.87°C. this may be due to the inaccuracy
difference between the two. The in the used model, or non-accordance to
experimental values are well above the certain assumptions of the model.
theoretical values. More models may be
used but due to the lack of constants and One cause of error for this experiment is
coefficients, only one model was used for the method of drying the cup. It is important
comparison in the experiment. Also shown, to wash the cup after each trial and dry it
Table 3 tabulates the percent error between thoroughly. It is possible that some water is
the two values. still present in the cup contributing to
variations in the flash point and fire point
35 measurement. It should also be noted that
Wilson
Mixture flash point, ⁰C

30 the temperature reading in the

25 Experimental thermocouple may not correspond to the
20 appearance of the flash point because of its
15 speed. There is a delay in the
10 measurement. What it measures is the
temperature below the temperature of the
5
fuel bath. Errors in filling the flash point cup
0
are also common problems. Too much
0 0.5 1 1.5
liquids in the cup will result in the test
Mole fraction of ethanol in mixture ignition flame applied too closely to the
Figure 1. Flash point temperature vs. mole surface of the liquid, therefore, obtaining
fraction of ethanol in water. lower observed flash points. This condition
may be possible in the experiment.

Conclusion

Although the experimental and theoretical

values of the flash points exhibit the same
trend, the difference between two flash

Page 4 of 6
points in one specific molar concentration is
too large. The flash point determination
experiment still accounts for some human
error. The experiment may be improved by
having more accurate thermocouples, or by
performing it in a darker environment.
References
Perry, R.H. (2008) ‘Perry’s Chemical
Engineers’ Handbook 8th Edition’ USA:
McGraw-Hill
Hristova, M., Tchaoushev, S. ‘Calculation of
flash points and flammability limits of
substances and mixtures’ Journal of the
University of Chemical Technology and
Metallurgy, 41, 3 (2006) 291-296.
<http://www.uctm.edu/journal/j2006-3/04-
Hristova-291-296.pdf>
Hristova, M., Tchaoushev, S. ‘Calculation of
flash points and flammability limits of
substances and mixtures’ Journal of the
University of Chemical Technology and
Metallurgy, 41, 3 (2006) 291-296.
<http://www.uctm.edu/journal/j2010-
1/2_Mariana_19-24.pdf>
http://www.ilpi.com/msds/ref/flashpoint.html

Appendix
1. Calculation of volumes for ethanol-water mixture
For 20% ethanol
Let x = volume of ethanol (Assay: 99.5% v/v)
Total volume of mixture = 100 mL

Solving for x, x = 44.91149623 mL ethanol

100-x = 55.08850377 mL water

2. Sample calculation with iteration of flash point temperature using Wilson equation, with
x2 = 0.2

i)
ii)
iii)

iv)

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v)

vi)

vii)
viii) Repeat steps iii-vii, setting as until

3. Table of excel iteration to determine flash point temperature.

x2 P1sat (mmHg) T (⁰C) A12 A21 γ Psatnew (mmHg)
124.575 38.55683 0.696779 0.182191 2.435552 51.14858
51.14858 22.50701 0.640928 0.177073 2.550146 48.85015
48.85015 21.7297 0.638192 0.176815 2.555977 48.7387
48.7387 21.69121 0.638057 0.176802 2.556266 48.73318
0.2 48.73318 21.6893 0.63805 0.176801 2.556281 48.73291
48.73291 21.68921 0.638049 0.176801 2.556281 48.7329
48.7329 21.6892 0.638049 0.176801 2.556281 48.7329
48.7329 21.6892 0.638049 0.176801 2.556281 48.7329
48.7329 21.6892 0.638049 0.176801 2.556281 48.7329
62.2875 25.89279 0.652812 0.178186 1.545691 40.2975
40.2975 18.52674 0.626891 0.175741 1.566457 39.7633
39.7633 18.30766 0.626117 0.175667 1.56709 39.74725
39.74725 18.30104 0.626093 0.175664 1.567109 39.74676
0.4
39.74676 18.30084 0.626093 0.175664 1.567109 39.74675
39.74675 18.30083 0.626093 0.175664 1.567109 39.74675
39.74675 18.30083 0.626093 0.175664 1.567109 39.74675
39.74675 18.30083 0.626093 0.175664 1.567109 39.74675
41.525 19.02075 0.628637 0.175908 1.198837 34.63775
34.63775 16.06447 0.618174 0.174904 1.202267 34.53893
34.53893 16.01846 0.618011 0.174888 1.202321 34.53738
0.6 34.53738 16.01773 0.618008 0.174888 1.202321 34.53735
34.53735 16.01772 0.618008 0.174888 1.202321 34.53735
34.53735 16.01772 0.618008 0.174888 1.202321 34.53735
34.53735 16.01772 0.618008 0.174888 1.202321 34.53735
31.14375 14.36337 0.612136 0.174319 1.045757 29.78106
29.78106 13.65456 0.609617 0.174074 1.045982 29.77466
0.8 29.77466 13.65117 0.609605 0.174073 1.045983 29.77463
29.77463 13.65115 0.609605 0.174073 1.045983 29.77463
29.77463 13.65115 0.609605 0.174073 1.045983 29.77463
1 24.915 10.86839 0.599695 0.173103 1 24.915

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