Generalized Correlations for Gases

A) Lee/Kesler Generalized Correlation

𝑍 = 𝑍 + 𝜔𝑍

B) Correlation for the Second Virial Coefficient

𝑃
𝑍 = 1 + (𝐵 + 𝜔𝐵 )
𝑇
0.422
𝐵 = 0.083 −
𝑇 .
0.172
𝐵 = 0.139 −
𝑇 .
C) Correlations for the Third Virial Coefficient

𝑃 𝑃
𝑍 =1+𝐵 +𝐶
𝑇𝑍 𝑇𝑍
𝐵 = 𝐵 + 𝜔𝐵
𝐶 = 𝐶 + 𝜔𝐶
0.02432 0.00313
𝐶 = 0.01407 + −
𝑇 𝑇 .
0.05539 0.00242
𝐶 = −0.02676 + −
𝑇 . 𝑇 .
Example

Determine the molar volume of n-butane at 510 K and 25 bar by each of the following:
a) Lee/Kesler Correlation
b) Correlation of the Second Virial Coefficient
c) Correlation of the Third Virial Coefficient
Experimental value: 1,480.7 cm3/mol

Values of Tc, Pc, ω, and molar mass for n-butane from Appendix B:
𝑇 = 425.1 𝐾
𝑃 = 37.96 𝑏𝑎𝑟
𝜔 = 0.200
𝑀 = 58.123 𝑔/𝑚𝑜𝑙
Reduced parameters Tr and Pr:
𝑇 510
𝑇 = = = 1.20
𝑇 425.1
𝑃 25
𝑃 = = = 0.6586
𝑃 37.96
The molar volume using ideal gas equation:
𝑏𝑎𝑟 ∙ 𝑐𝑚
𝑅𝑇 83.14 (510 𝐾) 𝑐𝑚
𝑚𝑜𝑙 ∙ 𝐾
𝑉= = = 1,696.1
𝑃 25 𝑏𝑎𝑟 𝑚𝑜𝑙
 |1,696.1 − 1,480.7|
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 14.54 %
1,480.7

a) Lee/Kesler Correlation
Table E.1 Values for Z0
Pr
Tr 0.6000 0.6586 0.8000
1.20 0.8779 0.8647 0.8330

𝑍 = 0.8647

Table E.2 Values for Z1

Pr
Tr 0.6000 0.6586 0.8000
1.20 0.0326 0.0377 0.0499

𝑍 = 0.0377
Solving for Z
𝑍 = 𝑍 + 𝜔𝑍 = 0.8647 + 0.2000(0.0377) = 0.8722
Molar volume
𝑏𝑎𝑟 ∙ 𝑐𝑚
𝑅𝑇 83.14 (510 𝐾) 𝑐𝑚
𝑚𝑜𝑙 ∙ 𝐾
𝑉=𝑍 = 0.8722 = 1,479.4
𝑃 25 𝑏𝑎𝑟 𝑚𝑜𝑙
|1,479.4 − 1,480.7|
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 0.09 %
1,480.7

b) Correlation of the Second Virial Coefficient

0.422 0.422
𝐵 = 0.083 − . = 0.083 − = −0.2323
𝑇 1.20 .
0.172 0.172
𝐵 = 0.139 − . = 0.139 − = 0.0589
𝑇 1.20 .
Solving for Z,
𝑃
𝑍 = 1 + (𝐵 + 𝜔𝐵 )
𝑇
0.6586
𝑍 = 1 + (−0.2323 + 0.2000 ∙ 0.0589) = 0.8789
1.20
Molar volume
𝑏𝑎𝑟 ∙ 𝑐𝑚
𝑅𝑇 83.14 (510 𝐾) 𝑐𝑚
𝑚𝑜𝑙 ∙ 𝐾
𝑉=𝑍 = 0.8789 = 1,490.7
𝑃 25 𝑏𝑎𝑟 𝑚𝑜𝑙
|1,4790.7 − 1,480.7|
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 0.68 %
1,480.7

c) Correlation of the Third Virial Coefficient

𝐵 = 𝐵 + 𝜔𝐵 = −0.2323 + 0.2000(0.0589) = −0.02206
 0.02432 0.00313
𝐶 = 0.01407 + −
𝑇 𝑇 .
0.02432 0.00313
𝐶 = 0.01407 + − = 0.03388
1.20 1.20 .

0.05539 0.00242
𝐶 = −0.02676 + . −
𝑇 𝑇 .
0.05539 0.00242
𝐶 = −0.02676 + − = 0.006760
1.20 . 1.20 .
𝐶 = 𝐶 + 𝜔𝐶 = 0.03388 + 0.2000(0.006760) = 0.03523

Solving for Z,
𝑃 𝑃
𝑍 =1+𝐵 +𝐶
𝑇𝑍 𝑇𝑍
0.6586 0.6586
𝑍 = 1 − 0.02206 + 0.0323
1.20𝑍 1.20𝑍
0.1211 0.1062
𝑍 =1− +
𝑍 𝑍
𝑍 = 0.8756
Molar volume
𝑏𝑎𝑟 ∙ 𝑐𝑚
𝑅𝑇 83.14 (510 𝐾) 𝑐𝑚
𝑚𝑜𝑙 ∙ 𝐾
𝑉=𝑍 = 0.8756 = 1,485.0
𝑃 25 𝑏𝑎𝑟 𝑚𝑜𝑙
|1,485.0 − 1,480.7|
% 𝑒𝑟𝑟𝑜𝑟 = × 100 = 0.29 %
1,480.7