Section 3.

Generalized Correlations for Gases

Pitzer Correlations for the
Compressibility Factor
• Z = Z0 +  Z1 (3.53)
Z0 & Z1 are functions of both Tr & Pr.

• When  = 0 (argon, krypton, & xenon)

Z = Z0 = F 0 ( Tr, Pr)

Two-parameter corresponding-states
correlation for Z
Pitzer Correlations for the
Compressibility Factor
• 2nd term of Eq. (3.53) is relatively small.

• Z0 may be used alone for quick but less

accurate.

• Eq. (3.53) is a simple linear relation between

Z &  for given values of Tr & Pr.

• Plot of experimental data for Z vs  for

nonsimple fluids provide values for Z1 (slope).
Lee/Kesler Correlation
• It is in the form of tables.

• Appendix E (Table E.1 through E.4) present

values of Z0 and Z1 as functions of Tr & Pr.

• It provides reliable results for gases which are

nonpolar or only slightly polar (error <2~3%).
Figure 3.11: The Lee/Kesler
correlation for Z0 = F0(Tr,Pr)
Correlation for Quantum Gases
• Quantum gas (hydrogen, helium, neon etc.)
use temperature-dependent effective critical
parameters:
Correlation for Quantum Gases

• where T is absolute temperature in kelvins.

• Use of these effective critical parameters for

H2 requires that  = 0.
Pitzer Correlations for the Second
Virial Coeffficient
• From Eq. (3.36),

• Second correlation:

• Combining Eqs. (3.57) & (3.59):

Pitzer Correlations for the Second
Virial Coeffficient
• Comparison with Eq. (3.53):

• B0 & B1 are functions of Tr only (as second

virial coefficients are functions of T only).
Figure 3.13: Comparison of
correlations for Z0
Straight lines:
virial-coefficient
correlation

Points:
Lee/Kesler
correlation
Figure 3.13: Comparison of
correlations for Z0
Region above
the dashed line:
the two
correlations
differ by less
than 2%.
Figure 3.14: Region where Z0 lies
between 0.98 and 1.02.
Ideal-gas
equation is a
reasonable
approximation
in this region.
Example 3.10
• Determine the molar volume of n-butane at
510 K and 25 bar by each of the following:

a) The ideal-gas equation.

b) The generalized compressibility-factor
correlation.
c) The generalized virial-coefficient correlation.
Solution 3.10(a)
• By ideal-gas equation,
RT
V
P

83.14 510 
25
 1,696.1 cm3 mol 1
Solution 3.10(b)
• From App. B, TC = 425.1 K & PC = 37.96 bar
510 25
Tr   1.200 Pr   0.659
425.1 37.96
• Interpolation in Table E.1 & E.2:
Z0 = 0.865 Z1 = 0.038

• By Eq. (3.53) with  = 0.200

Z  Z   Z  0.865  0.2000.038  0.873
0 1
Solution 3.10(b)
ZRT 0.87383.14 510
V 
P 25
 1,480.7 cm3 mol 1

• If Z1 is neglected, Z = Z0 = 0.865

• V = 1,467.1 cm3 mol-1

1% lower than value by three-parameter
correlation.
Solution 3.10(c)
• By Eqs. (3.61) & (3.62),
B0 = -0.232 B1 = 0.059
• By Eqs. (3.59) & (3.57),
BPC
 B 0   B1  0.232  0.2000.059   0.220
RTC
0.659
Z  1   0.220  0.879
1.200
• V = 1,489.1 cm3 mol-1 (1 % higher)
• Experimental value = 1,480.7 cm3 mol-1
Example 3.11
• What pressure is generated when 500 mol
of methane is stored in a volume of
0.06(m3) at 50(C)? Base calculations on
each of the following:

a) The ideal-gas equation.

b) The Redlich/Kwong equation.
c) A generalized correlation.
Solution 3.11(a)
• By ideal-gas equation,
Solution 3.11(b)
• By the Redlich/Kwong equation,

• From App. B, TC = 190.6 K & PC = 45.99 bar

• By Eqs. (3.45),
Solution 3.11(b)
• By Eq. (3.44),

• Substitution into Redlich/Kwong equation,

Solution 3.11(c)
• P is high, the generalized compressibility-
factor correlation is proper choice.

• Iterative procedure is based on:

Solution 3.11(c)
• Starting value: Z = 1.
Thus, Pr = 4.68

• With Eq.(3.53) & Table D.3 & D.4,

Tr= 1.695 Pr= 4.68 = 0.012 Z= 0.894

• With this new value of Z, Pr is calculated.

Solution 3.11(c)
• Iteration continues till Zi+1 – Zi  0.

• Final value: Z = 0.894 & Pr = 4.35

• Confirmation:
At Pr = 4.35, Tr = 1.695 &  = 0.012
Z = 0.891 + 0.012 (0.268) = 0.894
Comparison of different equations
• The Redlich/Kwong equation:
P = 198.3 (bar)
• The generalized compressibility-factor
correlation:
P = 200.2 (bar)

• The difference is small as the acentric factor

is small.

• Experimental value: P = 196.5 (bar)

Example 3.12
• A mass of 500 g of gaseous ammonia is
contained in a 30,000-cm3 vessel immersed
in a constant-temperature bath at 65C.
Calculate the pressure of the gas by:

a) The ideal-gas equation

b) A generalized correlation
Solution 3.12(a)
• The molar volume of ammonia is:
Vt Vt 30,000 1
V    1,021.2 cm mol
3

n m M 500 17.02
• By the ideal-gas equation:
RT
P
V

83.1465  273.15
1,012.2
 27.53 bar 
Solution 3.12(b)
• Pr  27.53/112.8 = 0.244 (low), the
generalized virial-coefficient correlation
should suffice.

• By Eqs. (3.61) & (3.62) and

Tr = 338.15/405.7 = 0.834
B0 = -0.482 B1 = -0.232
Solution 3.11(b)
• With  = 0.253 & Eq. (3.59):
BPC
 0.482  0.253 0.232  0.541
RTC
 0.541RTC  0.54183.14405.7 
B 
PC 112.8
 161.8 cm3 mol 1
• By solving Eq. (3.37):

P
RT

83.14 338.15
 23.76 bar
V  B 1,012.2  161.8
Conclusion
• Iterative solution is not necessary here as B is
independent of pressure.

• Actual Pr = 23.76/112.8 = 0.211

• Falls within the applicable region in Fig. 3.13

• Experimental data: P = 23.82 bar

Conclusion
• P of ideal-gas equation is 15% higher

• The virial-coefficient correlation gives

satisfactory answer even though ammonia is
a polar molecule.