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Fugacity coefficient estimation of pure Carbon dioxide and water: Approach

aimed at comparative study through Van der Waals and Soave-Redlich-Kwong
EOS Modelling

Technical Report · November 2017

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Fugacity coefficient estimation of pure Carbon
dioxide and water: Approach aimed at
comparative study through Van der Waals and
Soave-Redlich-Kwong EOS Modelling

Submitted in partial fulfilment of the requirements of

CHE F213-
Chemical Engineering Thermodynamics

By

Arijit Chakraborty Ridhish Kumar

2016A1PS0771G 2015A1PS0584G
Abhishek Kumar Soumalya Barari
2016A1PS0542G 2016A1PS0507G

Under the supervision of:

Prof. Anirban Roy,
Department of Chemical Engineering,
BITS Pilani, K.K Birla Goa Campus
 1. INTRODUCTION
The chemistry of hydrothermal fluids has long been of interest to geochemists, but only
recently has experimental data in the high temperature and pressure range begun to appear. A
knowledge of the fugacity of water is essential to the interpretation of this data. [1] The
values of fugacity coefficients, expressed as functions of state parameters, are necessary for
calculating the equilibria of both chemical and phase processes in the presence of real gases
or vapours (chemical reaction, absorption and distillation processes). There are many
different formulas and methods in chemical thermodynamics for calculating fugacity
coefficients. Very often these methods are too complex or too simple. [2]

In the present report, the authors have written a MATLAB© code to calculate the value of the
fugacity coefficient for pure Carbon dioxide and pure water, from the Van der Waals (VdW)
and Soave-Redlich-Kwong (SRK) Equations of State (EOS) for different temperature and
pressure conditions, and compare the obtained values with the experimentally determined
values which was obtained through a literature search. Then error analysis has been done on
the deviation of the calculated values from the experimental values. Further, the authors
discuss the possible reasons for the same.

2. APPROACH
First, a MATLAB© code was written to calculate the volume roots of the VdW and SRK
EOS. They are cubic equations and were solved by iterative Newton-Raphson Method.
Two general methods are available for the calculation of fugacities: 1) graphical and 2)
analytical. The graphical method can always be used if P-V-T data are available. The
analytical method requires that the P-V-T data be fitted to an analytical expression for the
equation of state in a form which can be integrated. Fortunately, the Van der Waals and
Soave- Redlich- Kwong Equations of State is of such a form and with the proper constants
closely represents the P-V-T data for many gases over a wide range of temperatures and
pressures. [3] The volume roots that were obtained from the previous code, were then
plugged into a MATLAB© code that was written to calculate the value of the fugacity
coefficient through the Van der Waals and Soave- Redlich- Kwong Equations of State
modelling.

The equation used for the Van der Waals EOS is as follows:

𝑃(𝑣 − 𝑏) 𝑎
ln 𝜑 = 𝑍 − 1 − 𝑙𝑛 −
𝑅𝑇 𝑅𝑇𝑣

The equation used for the Soave- Redlich- Kwong EOS is as follows:

𝑎 𝑍+𝐵
ln 𝜑 = 𝑍 − 1 − ln 𝑍 − 𝐵 − ln
𝑏𝑅𝑇 𝐵

The numerical results for both the EOS were compared to the experimental data obtained by
literature search. They’ve been appropriately referenced in the reference section. Statistics
data such as Average Absolute Deviation (AAD %), minimum error and maximum error are
also provided. The accuracy of prediction of fugacity coefficient values is discussed in the
results and discussion section. The experimental data has been obtained from literature search
and has been referenced as [8] and [9].

3. CODE
SRK Code:

% Newton Raphson Method for SRK method water

Tc=647.3; Pc=221.2*10^5; T= 573.15; P=1*10^5; R=8.314;
Tr=T/Tc; w= 0.344;
S=0.48+1.574*w-0.176*w^2;
M=(1+S*(1-Tr^0.5)) ^2;
a=(0.42748*(R^2) *(Tc^2) *M)/Pc;
b=(0.08664*R*Tc)/Pc;
% Change here for different functions
f=@(x) x^3-x^2*((R*T)/P)-x*(b^2+(R*T*b)/P-a/P)-(b*a)/P
%this is the derivative of the above function
df=@(x) 3*x^2-2*x*((R*T)/P) -(b^2+(R*T*b)/P-a/P)
%Temperature and pressure are critical value.
x=(R*T)/P;
for i=1:20
x1=x-(f(x)/df(x));
x=x1;
end
sol=x;
fprintf ('Approximate Root is %.15f’, sol)
final= 1/sol;
fprintf ('Approximate density Root is %.15f’, final)
% SRK CODE FOR FUGACITY %
v=sol;
Z= (P*v)/(R*T);
S=0.48+1.574*w-0.176*w^2;
M=(1+S*(1-Tr^0.5)) ^2;
a=(0.42748*(R^2) *(Tc^2) *M)/Pc;
b=(0.08664*R*Tc)/Pc;
B=(P*b)/(R*T);
sol= Z-1-log(Z-B)- (a/(b*R*T)) *(log((Z+B)/Z));
New sol= exp(sol);
f=New_Sol*P;
fprintf ('Approximate fugacity coefficient is %.15f’, New_Sol);
fprintf ('Approximate fugacity is %.15f’, f);

VDW Code:

%VDW CODE FOR FUGACITY % water

% Newton Raphson Method
%x= specific volume (m^3/kg)
% Change here for different functions
f=@(x) x^3-x^2*(b+(R*T)/P) +(a/P) *x - (a*b)/P
%this is the derivative of the above function
df=@(x) 3*x^2 -2*x*(b-(R*T)/P) +(a/P)
a=0.5537; b=3.049*10^-5; R= 8.314; P=1*10^5; T=573.15;
x=(R*T)/P;
for i=1:1:20
x1=x-(f(x)/df(x));
x=x1;
end
sol=x;
fprintf ('Approximate Root is %.15f’, sol)
final=1/sol;
fprintf ('Approximate Root is %.15f’, final)
v=sol;
Z= (P*v)/(R*T);
sol= Z-1-log((P*(v-b))/(R*T))- a/(R*T*v);
New_Sol= exp(sol);
f=New_Sol*P;
fprintf ('Approximate fugacity coefficient is %.15f’, New_Sol);
fprintf ('Approximate fugacity is %.15f’, f);

4. DERIVATION
Here we attempt to arrive at a suitable expression connecting fugacity with other measurable
quantities.
Using the fundamental relationship,
6
𝑍−1
ln ∅ = 𝑑𝑃
7 𝑃
Where fugacity is defined by 𝑓 = ∅𝑃, ∅ here is called the fugacity coefficient. [2][3][4]
Using elementary transformation of variables, we get a volume explicit form,

: =
ln ∅ = 𝑍 − 1 − >
𝑃𝑑𝑣 … Equation 2
;<

Now for the Van der Waals Equation of state we have the volume explicit form,

? ;< ?
𝑃 + 𝑣 − 𝑏 = 𝑅𝑇 or, 𝑃 = − … Equation 3
=@ =AB =C

Where a is the energy parameter and b is the molecular co-volume and are calculated through
critical temperatures and pressures and are therefore not dependent on temperature for Van
der Waals treatment here.
Using Equation 3, we now have,
= =
𝑅𝑇 𝑎 𝑣−𝑏 𝑎 𝑎
𝑃𝑑𝑣 = − D 𝑑𝑣 = 𝑅𝑇𝑙𝑛 > + − >
> > 𝑣−𝑏 𝑣 𝑣 −𝑏 𝑣 𝑣

? ;<
Since 𝑣 > is large, ≅ 0 and 𝑣 > − 𝑏 = 𝑣 > =
=E 6

Therefore,

𝑃(𝑣 − 𝑏) 𝑎
𝑃𝑑𝑣 = 𝑅𝑇𝑙𝑛 +
𝑅𝑇 𝑣

We then have from Equation 2,

𝑃(𝑣 − 𝑏) 𝑎
ln 𝜑 = 𝑍 − 1 − 𝑙𝑛 −
𝑅𝑇 𝑅𝑇𝑣

We have used similar treatment for the Soave-Redlich-Kwong EOS. [5]

The equation for calculation of fugacity coefficient using the Soave-Redlich-Kwong EOS is

𝑎 𝑍+𝐵
ln 𝜑 = 𝑍 − 1 − ln 𝑍 − 𝐵 − ln
𝑏𝑅𝑇 𝐵

5. RESULTS AND CONCOLUSION

The results, as obtained after running the above MATLAB© scripts have been tabulated
below.

Deviation (of
Calculated Fugacity Experimental
Pressure (bar) Temperature (K) calculated values
Coefficient Fugacity Coefficient
from experimental)
1 300 0.998 0.998 0.000
1 400 1.015 0.999 0.016
1 500 1.008 0.999 0.009
1 600 1.03 1 0.030
1 700 1.06 1 0.060
1 800 1.004 1 0.004
1 900 1.003 1 0.003
1 1000 1.003 1 0.003
1000 300 0.231 0.111 0.120
1000 400 0.359 0.279 0.080
1000 500 0.479 0.473 0.006
1000 600 0.588 0.64 0.052
1000 700 0.68 0.759 0.079
1000 800 0.754 0.841 0.087
1000 900 0.813 0.885 0.072
1000 1000 0.859 0.914 0.055

Absolute Average Deviation= 0.042 0.042

Table 1: Fugacity Coefficients for Water calculated from Van der Waals EOS

Deviation (of
Calculated Fugacity Experimental
Pressure (bar) Temperature (K) calculated values
Coefficient Fugacity Coefficient
from experimental)
10.3 299.85 0.962 0.94 0.022
10.3 322.05 0.967 0.95 0.017
10.3 388.75 0.977 0.97 0.007
20.7 299.85 0.917 0.9 0.017
20.7 322.05 1.254 0.92 0.334
20.7 388.75 1.292 0.96 0.332
41.4 299.85 1.112 0.8 0.312
41.4 322.05 0.857 0.84 0.017
41.4 388.75 0.933 0.92 0.013
82.8 299.85 0.663 0.63 0.033
82.8 322.05 0.749 0.7 0.049
82.8 388.75 0.924 0.84 0.084
165.5 299.85 0.401 0.38 0.021
165.5 322.05 0.479 0.48 0.001
165.5 388.75 0.673 0.72 0.047

Absolute Average Deviation= 0.087 0.087

Table 2: Fugacity Coefficients for Carbon dioxide calculated from Van der Waals EOS
 Deviation (of
Calculated Fugacity Experimental
Pressure (bar) Temperature (K) calculated values
Coefficient Fugacity Coefficient
from experimental)
1 300 0.997 0.998 0.001
1 400 0.998 0.999 0.001
1 500 0.9995 0.999 0.001
1 600 0.9996 1 0.000
1 700 0.9997 1 0.000
1 800 0.9998 1 0.000
1 900 0.9999 1 0.000
1 1000 1 1 0.000
1000 300 0.132 0.111 0.021
1000 400 0.321 0.279 0.042
1000 500 0.537 0.473 0.064
1000 600 0.723 0.64 0.083
1000 700 0.856 0.759 0.097
1000 800 0.9504 0.841 0.109
1000 900 1.014 0.885 0.129
1000 1000 1.056 0.914 0.142

Absolute Average Deviation= 0.043 0.043

Table 3: Fugacity Coefficients for Water calculated from Soave- Redlich- Kwong EOS

Deviation (of
Calculated Fugacity Experimental
Pressure (bar) Temperature (K) calculated values
Coefficient Fugacity Coefficient
from experimental)
10.3 299.85 0.95 0.94 0.010
10.3 322.05 0.961 0.95 0.011
10.3 388.75 0.982 0.97 0.012
20.7 299.85 0.901 0.9 0.001
20.7 322.05 0.923 0.92 0.003
20.7 388.75 0.964 0.96 0.004
41.4 299.85 0.804 0.8 0.004
41.4 322.05 0.849 0.84 0.009
41.4 388.75 0.929 0.92 0.009
82.8 299.85 0.575 0.63 0.055
82.8 322.05 0.705 0.7 0.005
82.8 388.75 0.865 0.84 0.025
165.5 299.85 0.352 0.38 0.028
165.5 322.05 0.481 0.48 0.001
165.5 388.75 0.76 0.72 0.040

Absolute Average Deviation= 0.014 0.014

Table 4: Fugacity Coefficients for Carbon dioxide calculated from Soave- Redlich- Kwong EOS

Graph 1: Experimental Values of Fugacity Coefficient for Water

 As was expected of the Van der Waals EOS,
which was obtained through modifications in
the Ideal Gas Equation, the fugacity coefficient
values tend to 1in high temperature and low-
pressure conditions. Whereas, in the states of
high pressure and low temperature, the fugacity
coefficient shows significant deviations. This is
with reasonable accuracy.

Graph 2: Calculated Value of Fugacity Coefficient for Water- VdW EOS

On the other hand, the Soave- Redlich-

Kwong EOS which accounts for many
parameters that earlier Equations of
State fail to account for, has predicted
the fugacity coefficient values with
higher accuracy for the same ranges of
pressure and temperature. However, it
must be noted that at high pressure and
high temperature conditions, the Van
der Waals EOS predicts the fugacity
coefficient values with higher
accuracy. Graph 3: Calculated Value of Fugacity Coefficient for Water-
SRK EOS

Graph 4: Experimental CO2 Fugacity Coefficient Values

 With regards to the calculated fugacity
coefficient values from the Van der Waals
EOS, they should an erratic trend. The
absolute average deviation shown is 0.087,
which is much higher when compared to
that for the predicted values from the Soave-
Redlich- Kwong EOS.

Graph 5: Calculated Value of Fugacity Coefficient for CO2-

VdW EOS

The SRK EOS predicts the values

of fugacity coefficient for CO2
very accurately when compared to
the VdW EOS. The graph shows
the trend that as P->0,
f/P->1. Also, the absolute average
deviation is 0.014, which is much
less than was obtained from the
VdW EOS.

Graph 6: Calculated Value of Fugacity Coefficient for CO2- SRK EOS

6. CONCLUSION
Both the EOS show results with reasonable accuracy however, departure from ideal
conditions is better explained by the Soave-Redlich-Kwong model at high pressures. From
the graphs, it is apparent that the Soave-Redlich-Kwong EOS provides a better result of the
fugacity coefficients when compared to the same given by the Van der Waals EOS. Note that
with increasing temperature, the SRK EOS isotherm of water converges closely to 1, like the
experimental isotherm, whereas the VdW EOS isotherm has a slight deviation at a pressure of
1 bar when compared with the experimental isotherm of water. The VdW EOS isotherm of
carbon-dioxide shows deviation from the experimental values at low pressure, whereas the
SRK EOS isotherm shows more accurate results when compared to the experimental
isotherm.

A possible reason for the better results from the SRK EOS is because it accounts for the
sphericity of molecules whereas the VdW EOS fails to account for it. Several other possible
reasons could be the molecular structure of CO2, which is a linear diatomic molecule,
whereas water molecule is non-linear triatomic polar molecule. Forces that are not considered
in the equations of state such as the London Forces, the dipole interactions et cetera, could be
a few of the many reasons that the EOS are inaccurate at times.
 Given the more accurate results obtained with SRK EOS, although for a relatively small data
set, this model could be further explored for its ability to predict thermodynamic properties of
compounds, as was done in this report for fugacity coefficient.

7. CONFLICT OF INTEREST
None declared.

8. ACKNOWLEDGEMENT
The authors would like to thank Prof. Anirban Roy for guiding us in this endeavour.

9. REFERENCES
[1] Anderson, G. M. (1963). fugacity. Geochimica et Cosmochimica Acta, 28(1), 713- 715.

[2] Szarawara, J., & Gawdzik, A. (1989). Method of calculation of fugacity coefficient from
cubic equations of state. Chemical Engineering Science, 44(7), 1489–1494.
https://doi.org/10.1016/0009-2509(89)80025-9

[3] Holley Jr., C. E., Worlton, W. J., & Zeigler, R. K. (1959). Compressibility Factors and
Fugacity Coefficients Calculated from The Beattie-Bridgeman Equation of State for
Hydrogen, Nitrogen, Oxygen, Carbon Dioxide, Ammonia, Methane, And Helium, 2271,
1–51. https://doi.org/10.2172/6419744

[4] Prausnitz, J.M., Lichtenthaller, R.N., and De Azedevo, E.G., 1986. Molecular
thermodynamics of fluid phase equilibria. Prentice Hall, 353p.

[5] Hala, E., Pick, J., Fried, V. and Vilim, O., 1967. Vapor-Liquid Equilibrium. (English
trans. by G. Standart). Pergamon Press, 599 p.

[6] Denbigh, K., 1983. The Principles of Chemical Equilibrium, 4th. ed., Cambridge
Univ. Press, 494 p.

[7] Redlich O. and Kwong J.N.S., 1949. On the thermodynamics of solutions. V. An equation
of state. Fugacities of Gaseous Solutions. Chem. Rev. 44, 233-244.

[8] ExxonMobil Upstream Research Company (2017). High-pressure separation of a multi-

component gas. WO2003022408 A1.

[9] Anderson, G. M. (1963). fugacity. Geochimica et Cosmochimica Acta, 28(1), 713- 715.

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