Section 3.

Application of the Virial Equations

Figure 3.7 Compressibility-factor
graph for Methane.
All isotherms
originate at Z = 1
for P = 0.
Isotherms are
nearly straight
lines at low P.
Tangent to an
isotherm at P = 0
is a good
approximation.
Application of the Virial Equations
• Differentiation of Eq. (3.33) for a given T:
 Z 
   B '2C ' P  3 D ' P 2

 P T
 Z 
   B'
 P T ; P 0
• Equation of the tangent line:
Z = 1 + B’ P
Application of the Virial Equations
• From Eq. (3.33) & with B’ = B/RT:

• From Eq. (3.34) at low pressure:

• When truncated to 2 terms, Eq. (3.36) is

preferred and applicable at subcritical T up to
a P of about 5 bar.
Application of the Virial Equations
• When P > 5 bar but below the PC, virial
equation is truncated to 3 terms.

• Eq. (3.34) is superior to Eq. (3.33)

Figure 3.8: Density-series virial
coefficients B & C for nitrogen.
Other
gases
have the
same
trends.
B increases
monotonically with T.
Figure 3.8: Density-series virial
coefficients B & C for nitrogen.

C decreases slowly with T.

C passes a max near TC.

C is –ve at low T.
Extended Virial Equations
• Benedict/Webb/Rubin equation:
RT B0 RT  A0  C0 T 2
bRT  a
P  2

V V V3
a c    
 6  3 2 1  2  exp 2
V V T  V  V
• A0, B0, C0, a, b, c,  &  are constant for a
given fluid.
• Used in the petroleum and natural-gas
industries for light hydrocarbons and a few
commonly encountered gases.
Example 3.8
• Reported values for the virial coefficients of
isopropanol vapor at 200 C are:
B= -388 cm3 mol-1 C= -26,000 cm6 mol-2

• Calculate V and Z for isopropanol vapor at

200 C and 10 bar by:
(a) The ideal-gas equation.
(b) Equation (3.36).
(c) Equation (3.38).
Solution 3.8
• T = 200 C = 473.15 K
R = 83.14 cm3 bar mol-1 K-1
a) For an ideal gas, Z =1,
RT 83.14473.15
V   3,934 cm3 mol 1
P 10
b) . RT
V  B  3,934  388  3,546 cm3 mol 1
P
PV V 3,546
Z    0.9014
RT RT P 3,934
Solution 3.8
c) To facilitate iteration, write Eq. (3.38) as:
RT  B C 
Vi 1  1   2 
P  Vi Vi 

With V0 = 3,934 (the ideal gas value)

RT  B C 
V1  1   2 
P  V0 V0 
Iteration continues until Vi+1 – Vi  0
Solution 3.8
V1 = 3539.391 V6 = 3487.980
V2 = 3494.577 V7 = 3487.978
V3 = 3488.836 V8 = 3487.977
V4 = 3488.090 V9 = 3487.977
V5 = 3487.992

V  3488 cm3 mol-1

Z = 0.8866
Solution 3.8
• Conclusion:

The ideal-gas value is 13% too high.

Eq. (3.36) gives a value 1.7% too high.