Kimberly Wadelton

Procedure
Sweet Briar College
advisor: Dr. Michael Misovich
Hope College

1. First, we created a Maple 9* program to gather numerical data for a wide range of temperatures and
acentric factors using an iterative regula falsi method.
2. In order to simplify our calculations by eliminating units, we used reduced variables. These are simply
the ratio of the variables value to its value at an identified point; usually this point was the critical point.

3. Simply solving SRK with RT a

SRK : P 1 1
T=0 would not give us the b 2
b

results we wanted because
0 0
0 0
indefinite forms appeared in the vapor : 0 1 1 0
liquid : 0 0
b b
0 2b 2
equations for vapor and 0 0 0 2

liquid.
4. Instead of directly using SRK, we used the fugacity equation for SRK. First, we found that the vapor
fugacity was equal to zero. Then, because we are working with vapor-liquid equilibrium, we could equate liquid
and vapor fugacities. This gave us the useful knowledge that all the indeterminate forms in the liquid fugacity
equation must cancel each other.
0 0 a
ln( )
P
RT
1 ln(
P
RT
) ln(1 b )
a
bR
ln(1 b ) ln( L ) 1 ln( ) ln(0)
0 0 bR
ln(2) 0

5.From this knowledge, we derived equations for P and L which matched our numerical results for
low temperatures very well.

Results lim L
1
L1Tr
The vapor and liquid densities behave differently from each Tr 0 b
other in the low temperature limit. We found that the liquid
Where:
density follows this function
2 RTc
Where: C ao ln( 2)(1 f ( w)) 2 L1
C1 C2 1

bo a (1 f ( w)) 2
lim (ln Pr ) 1 C3 2 ao ln( 2) f ( w)(1 f ( w))
Tr 0 Tr Tr 2 C 2

bo
ao ln(2) f ( w) 2
C 3
ln( L1/ )
bo
ln(bo )

Both the temperature and the vapor pressure approach zero in the low
temperature limit. We found their relationship .

We were able to describe the

behavior of SRK over the entire
temperature range from Tr=0 to the
critical temperature!
The new expansion is much
more accurate in the low T
and uses the same number
of terms!

Another result was this dimensionless form of the

SRK equation. It uses only reduced variables, where
density is reduced not by its critical value but by its Tr r Tr ao ao
Pr ( Pr 2
)
r
2
( 2
)
r
3
0
bo bo bo bo
value in the low T limit. (r). It may be useful in future
work.
 Abstract
We analyzed the behavior of the Soave-
Redlich-Kwong cubic equation of state (SRK) for
vapor-liquid equilibrium in the limit as
temperature approaches zero.
Our objective was to develop relationships for
vapor pressure and for liquid density predicted by
SRK in the low temperature limit. This extended
previous work which determined similar
relationships in the high temperature limit near the
vapor-liquid critical point.
A secondary objective was to combine these
new results with the previous work to describe
phase equilibrium from SRK over the entire
temperature range from zero to the critical point
Conclusions
We have developed a relationship between the
vapor pressure and the liquid density as a
function of temperature in the low temperature
limit. (This relationship is still not completely
understood and further investigation is
recommended.)
We have described the behavior of vapor
pressure as predicted by SRK over the entire
range of temperatures.
We have evaluated the deviation between our
equations results and the expected values from
the SRK program over the range of temperatures
relevant to vapor-liquid equilibrium. This deviation
was found to be at worst within one order of
magnitude.

Background Future Work

What is SRK? Find vapor density and fugacity as Tr0 using a
SRK, or Soave-Redlich-Kwong, is a cubic virial equation expansion of SRK.
equation of state.
Characterize the error in the ln(Pr) equation in
RT a order to add a correction term.
SRK : P 2
V b V Vb

Equations of state (EOS) are equations which

describe the relationship among pressure, volume,
and temperature. The most commonly known Notation
equation of state is the ideal gas law. (PV=RT) To reference chart:
predict phase equilibrium, we need EOS capable of
predicting both liquid and vapor volumes at certain a 0.42747( RTc ) 2
Pc

ao 0.42747
T,P. 0.08664 RTc
b Pc

bo 0.08664
b
A Cubic Equation of State h
2 RTc
L1 a (1 f ( w)) 2

One real root -- Liquid L1 L1 reduced variables

P Vapor Pressure (Pa)
Pressure

Three real roots--
Liquid, Vapor, and
undefined
One real root -- Vapor
Volume
Pc Critical Pressure
R Gas constant
Reduced Variable (ex: A variable divided by its
T r) value at the critical point
T Temperature (K)
Tc Critical Temperature
V Volume per mole
P
Z RT

(1 f ( )(1 Tr )) 2

Fugacity coefficient
A cubic EOS is an equation of state which is in the Density per mole

form of a cubic equation in volume. These are the Acentric factor
f() 0.480 1.574 0.176
type which can predict 3 volumes for a certain T
and P. Another example of a cubic equation of state
besides SRK would be the Van der Waals equation Acknowledgements
Id like to thank the National Science
or the Peng Robinson equation. Foundation for sponsoring me,
Hope College for having me, and all those
who contributed to my work, particularly
What is SRK for? Dr. Michael Misovich, Kurtis Blohm, and Matthew
Goetz
Soave-Redlich-Kwong is most commonly used in
chemical engineering applications, around
temperatures close to the critical temperature,
involving phase equilibrium. *Maple 9 is a registered trademark of Waterloo Maple Inc.