Review of Simple forms of Equations of

State

Ali Kh. Al-matar

(aalmatar@kfupm.edu.sa)
Chemical Engineering Department
King Fahd University of Petroleum and
Minerals
Dhahran, Saudi Arabia
(aalmatar@ju.edu.jo)
Chemical Engineering Department
University of Jordan
Amman, Jordan
Outline
• What is an EOS?
• Simple EOS
– Ideal Gas EOS
– Virial EOS
– Clausius EOS
– Cubic EOS
• vdW
• RK
• SRK
• PR
• What is Next?
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What is an EOS?
• An EOS is a mathematical expression that relates
temperature, pressure and molar volume (PVT).

Pressure explicit (Common)

P  f (T ,V )
EOS

Volume explicit V  f (T , P )

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Simple EOS
Ideal gas

Gas phase Virial

Clausius

EOS Van der Waal

(vdW)

Redlich-Kwong
(RK)
Two phase
Soave-Redlich-
Kwong (SRK)

Peng-Robinson
(PR)

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Ideal Gas EOS
• The simplest of all EOS
• Two basic assumptions
– Molecules are points in space (no
size) RT
P
– Intermolecular forces are not V
present between molecules Z 1
• Limited to low pressure and high
temperature
• Good qualitative predictions
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Ideal Gas (IG) EOS

𝑃𝑉 ∗
= lim 𝑃 𝑉 = 𝑓 𝑇 = 𝑅 𝑇 𝑃 𝑉 ∗𝑡 𝑏𝑎𝑟
𝑃→0
𝑅= = 83.1447 𝑐𝑚3
273.16 𝐾 𝑚𝑜𝑙 𝐾
∗
𝑃𝑉 𝑡 = 22711.8𝑐𝑚3 𝑏𝑎𝑟/𝑚𝑜𝑙
Virial EOS
• Proposed by Kamerlingh Onnes in 1901.
• A series expansion around the ideal gas limit
• Two forms B, C, D …
are called virial coefficients
– Pressure explicit Functions of temperature only

– Volume explicit

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 Virial Coefficients
• To use the virial equation of state, one needs to have
the virial coefficients.
• Second virial coefficients are easily obtained in
compilations or estimated.
• Third virial coefficients and higher are not easily
obtained or estimated.
• Virial EOS is usually truncated to the second term.
J.H. Dymond et al., Virial Coefficients of Pure Gases and Mixtures, Subvolume A: Virial Coefficients of Pure Gases, Springer-Verlag, Berlin, 2002.

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 𝑃𝑉 𝐵𝑃
𝑍= =1+
𝑅𝑇 𝑅𝑇
𝜕𝑍 𝐵
lim = = 𝐵′
𝑃→0 𝜕𝑃 𝑅𝑇
𝑇
Effect of T on Virial Coefficients

Boyle’s temperature (B = 0)
 Pitzer’s Correlations for Second Virial Coefficients

• Applies to nonpolar gases

𝐵𝑃 𝑃𝑟
𝑍 =1+ =1+𝐵
𝑅𝑇 𝑇𝑟
𝐵𝑃𝑐
𝐵= = 𝐵0 +𝜔𝐵1
𝑅𝑇𝑐
0
0.422
𝐵 = 0.083 − 1.6
𝑇𝑟
1
0.172
𝐵 = 0.139 − 4.2
𝑇𝑟
𝑍 = 𝑍 0 + 𝜔𝑍1
0
𝑃
0 𝑟
𝑍 =1+𝐵
𝑇𝑟
1 1
𝑃𝑟
𝑍 =𝐵
𝑇𝑟
Molecules Have a Size: Clausius EOS
• Modification of the ideal gas EOS noting that
molecules do have size.
– Volume available for molecular motion is total
volume minus molecular volumes (covolume b).

𝑉→(𝑉−𝑏) RT
Modify IG-EOS P
V b
𝑃(𝑉−𝑏)=𝑅𝑇

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Intermolecular Interactions Considered: Attractive Forces

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The van der Waals (vdW) EOS
• In 1873, van der waals made two
modifications to the ideal gas law:
– Molecules do have finite size
– Molecules do have intermolecular forces
• Pressure becomes the resultant of
attractive and repulsive pressures
RT
P  P attractive
V b

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• Van der Waals assumed that the attractive pressure is
proportional to the reciprocal of the square of volume
a
P  2
attractive

V
• The constant of proportionality is termed the energy
parameter and is a measure of the strength of attractive
forces. RT a
P  2
V b V

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Evaluating vdW EOS Paramters
• The covolume (b) and
energy parameter (a)
can be determined
using the criticality
condition.
– Mathematically, the
critical point is an
inflection point where
the first and second
derivatives (of pressure
versus volume) are P
   2 P 
zeros.    2  0
 V C  V C 16
Critical Condition

Solve three equations

Substitute

Z C  3 / 8  0.375 17
Cubic EOS (Compressibility Factor)

1873

Complexity in the attractive term

1949

1972

1976

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 SRK and PR EOS
Soave-Redlich-Kwong (SRK) Peng-Robinson (PR)
RT a (T ) RT a (T )
P  P 
v  b v (v  b ) v  b v (v  b )  b (v  b )
( RTc ) 2 ( RTc ) 2
a (T )  0.42748  (T ) a(T )  0.45724  (T )
Pc Pc
 T   T 
 (T )  1   1    (T )  1   1  
 Tc   Tc 

  0.480  1.57  0.176 2   0.37464  1.5422  0.26992 2

RTc RTc
b  0.08664 b  0.07779
Pc Pc
Redlich, Otto; Kwong, J. N. S. (1949). "On The Thermodynamics of Solutions". Chem. Rev. 44 (1): 233–244
Peng, D. Y., and Robinson, D. B. (1976). "A New Two-Constant Equation of State". Industrial and Engineering Chemistry: Fundamentals 15: 59–64

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Cubic EOS Coefficients and Zc
Z 3  Z 2   Z    0

vdW SRK PR
 –1 – B –1 –1 + B

 A A – B – B2 A – 2B – 3B2
 – AB – AB – AB + B2 + B3
Zc 0.3750 0.3333 0.3074

aP bP Initial Guess for solution

A B Vapor (Vapor like): ideal gas (Z = 1).
( RT )2 RT Liquid: Reduced covolume (Z = B).

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Simple EOS
One real root (molar
volume of supercritical
fluid)
T> Tc
Two negative or
conjugate complex
roots with no physical
significance)

Three equal real roots

representing molar
T= Tc
volume of the critical
Roots of cubic EOS fluid.

Maximum positive root

for vapor molar volume

Minimum positive real

T< Tc root for liquid molar
volume if > B

Intermediate real root

for spinodal or
metastable limits.

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Solution of Cubic EOS
Calculate the molar volume of water at the following conditions assuming that water
follows the PR equation of state.
a)
b)
c)

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What is Next?

Ideal gas
Vdw
Virial
RK
Cubic
SRK
EOS

PR

BWR
Multiparameter
MBWR

PHC
Molecular
SAFT
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