Soave-Redlich-Kwong equation of state

Soave-Redlich-Kwong (SRK) equation of state is one of the most commonly used cubic equations of
state. It is expressed as:

RT a
P= − E1
V − b V (V + b )

where

R 2Tc2
a = 0.4278 E2
Pc

RTc
b = 0.0867 E3
Pc

( (
 = 1 + ( 0.48 + 1.574 − 0.176 2 ) 1 − Tr ))
2
E4

The P-V-T relation from SRK for each substance is unique and dependent on the critical properties and
the acentric factor of that substance. Figure 1 shows the P-V relations of hexane at different temperatures
as predicted by SRK. The curves may be divided roughly into two parts: the liquid behaviour at small
molar volumes and the vapour behaviour at large molar volumes. The liquid behaviour shows weak
dependence of the molar volume on the pressure, while the vapour behaviour exhibits the expected
strong dependence of the molar volume on the pressure.

4.0E+06
270 °C
3.5E+06

3.0E+06
234.45 °C
Pressure, P/Pa

2.5E+06 (Tc)
2.0E+06

1.5E+06 200 °C

1.0E+06
100 °C
5.0E+05

0.0E+00
0.000 0.001 0.002 0.003 0.004
Molar volume, V/m3 mol-1

Figure 1 P-V relations of hexane at different temperatures as predicted by SRK. From top to bottom:
270 °C, 234.45 °C (critical temperature), 200 °C, and 100 °C.
As the name suggests, SRK is actually a cubic equation and therefore three roots are expected. At
temperatures above the critical temperature, a P-V relation yields only a single real root; the other two
are imaginary and trivial. At temperatures below the critical temperature, a P-V relation may have three
real roots in a certain range of pressure, in which the vapour-liquid transition also takes place.
Nevertheless, the original phase transition behaviour from SRK is unrealistic; it appears smooth with
local maximum and minimum pressures, while a real phase transition contains only a single value of
vapour pressure at a particular temperature. This vapour pressure has to be determined
thermodynamically and could be drawn on a P-V relation (Figure 2). At this vapour pressure, the
smallest molar volume corresponds to the molar volume of the saturated liquid and the largest molar
volume represents the molar volume of the saturated vapour, while the molar volume between the
previous two has no physical meaning. Figure 2 also shows the behaviour of ideal gas, which predicts
no condensation, at the same temperature for comparison.

4.0E+06

3.5E+06

3.0E+06
Pressure, P/Pa

2.5E+06

2.0E+06

1.5E+06

1.0E+06

5.0E+05

0.0E+00
0.000 0.001 0.002 0.003 0.004
Molar volume, V/m3 mol-1

Figure 2 P-V relations of hexane at 200 °C as predicted by SRK (solid curve) and ideal gas law (dashed
curve). The horizontal dashed line represents the vapour pressure at 200 °C calculated from a
thermodynamic constraint.

Residual enthalpy from SRK equation of state

Residual enthalpy can be calculated from SRK equation of state by the following equation:

 Z  dV Z − 1
V
HR
=   +
RT 2

T V V T E5

which is derived from Maxwell relation based on the Gibbs free energy with T and V as the two
arguments.

Cubic equations of state are often converted into their Z form for easier handling. Equation E1 may be
written in terms of compressibility factor, Z, by multiplying both sides by V/RT:
 PV V a
Z= = − E6
RT V − b RT (V + b )

Using expression E6 in equation E5 yields an equation for the residual enthalpy from SRK:

aT 2   ( / T )  Z
HR = −   ln + RT ( Z − 1) E7
b  T V Z + bP / RT

where

  ( / T )     
  =− (
0.48 + 1.574 − 0.176 2 ) 1
− 2
 T
E8
 T V T  TTc 

Using an appropriate value of Z at a temperature and a pressure in equation E7 yields the residual
enthalpy at those temperature and pressure.

Fugacity coefficient from SRK equation of state

Fugacity coefficient may be determined with SRK equation of state by the following equation:

GR
V
 Z  Z  RT / P
= ln  =    −  dV + ln E9
RT P  
V T V  

which is derived from Maxwell relation based on the Gibbs free energy with T and V as the two
arguments.

Using expression E6 in equation E9 yields an equation for the fugacity coefficient from SRK:

GR a  bP   bP 
= ln  = Z − 1 − ln 1 +  − ln  Z −  E10
RT P
bRT  ZRT   RT 

Using an appropriate value of Z at a temperature and a pressure in equation E10 yields the fugacity
coefficient at those temperature and pressure.

Determination of roots
As expected of a cubic equation, equation E6 can be written as a third-degree polynomial:

 a P  bP 2 bP  a bP 2
Z − Z +  2 2 −
3 2
 −  Z − =0 E11
 R T  RT  RT  R 3T 3

A third-degree polynomial of the form:

x3 + cx 2 + dx + e = 0 E12

may be solved by first determining the following parameters:

 p=
( 3d − c ) 2

E13
3

q=
( 2c 3
− 9cd + 27e )
E14
27

3
 p
r = −  E15
 3

 q 
 = arccos  −  E16
 2r 

Then, the three roots are:

  c
1
x1 = 2r cos   −
3
E17
3 3

  + 2  c
1
x2 = 2r 3 cos  − E18
 3  3

  + 4  c
1
x2 = 2r 3 cos  − E19
 3  3

Nevertheless, Excel may show ‘number error’. If this happens, it means that the specified T and P yields
only one real root; the other two are complex roots, which are not of interest to us. The only real root
in this case is:

1 1
 q q  p  q
2 3 3
q  p  c
2 3 3

x = − +   +   − +   +   − E20
 2  2   3    2  2   3   3


Spreadsheet usage
All calculations should be carried out in Excel. Figure 3 shows the suggested layout of the spreadsheet.
Figure 3 Suggested layout of the spreadsheet

For phase equilibrium calculation, the following constraint should be used.

 L = V E21

Solving the above equation at a constant temperature will yield the corresponding vapour pressure.
Alternatively, doing this at a constant pressure will yield the corresponding boiling temperature. Excel’s
Solver add-on is a powerful tool for carrying out these calculations. The objective function should be
set as follows:
2
L 
objective function=  V − 1 E22
 

Setting Excel’s Solver to minimise this objective function while varying T or P will yield the desired
boiling temperature or the vapour pressure, respectively.