CEB 2023 Chemical Engineering

Thermodynamics

Ch.3 Volumetric Properties of

Pure Fluids – Part 2
Tutorial
1. Calculate Z and V for ethane at 50°C (323.15K) and 15 bar by the
following equations:
(a) The truncated virial equation with the following experimental
values of virial coefficients:
B = -156.7 cm3 mol-1 C = 9650 cm6 mol-2
(b) The truncated virial equation [ Eq. (3.38)], with a value of B from
the generalized Pitzer correlation [Eq. (3.63)].
(c) The Redlich / Kwong equation
(d) The Soave / Redlich/ Kwong equation
(e) The Peng / Robinson equation
(Problem 3-33, Smith-VanNess-Abbott)
Solution
(a) 𝑃𝑉 𝐵 𝐶
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉
Rearranging the equation,
𝑅𝑇 𝐵 𝐶 (83.14)(323.15) 156.7 9650
𝑉= 1+ + 2 = 1− + 2
𝑃 𝑉 𝑉 15 𝑉 𝑉
Using SOLVE function directly or rearranging the equation to:
𝑉 3 − 1791.113𝑉 2 + 2.8 × 105 𝑉 − 1.7 × 107 = 0
Using SOLVE function,
V= 1625.27 cm3 /mol
𝑃𝑉 15 1625.27
𝑍= = = 0.907
𝑅𝑇 83.14 323.15
How to find Tc, Pc and ω for pure substances from Table B.1

Characteristic Properties of Pure Species

Molar 𝜔 𝑇𝐶 /K 𝑃𝐶 /bar 𝑍𝐶 𝑉𝐶 𝑇𝑛 /K
mass cm mol−1
3

Methane 16.043 0.012 190.6 45.99 0.286 98.6 111.4

Ethane 30.070 0.100 305.3 48.72 0.279 145.5 184.6
Propane 44.097 0.152 369.8 42.48 0.276 200.0 231.1
n-Butane 58.123 0.200 425.1 37.96 0.274 255. 272.7
n-Pentane 72.150 0.252 469.7 33.70 0.270 313. 309.2
n-Hexane 86.177 0.301 507.6 30.25 0.266 371. 341.9
n-Heptane 100.204 0.350 540.2 27.40 0.261 428. 371.6
n-Octane 114.231 0.400 268.7 24.90 0.256 486. 398.8
n-Nonane 128.258 0.444 594.6 22.90 0.252 544. 424.0
n-Decane 142.285 0.492 617.7 21.10 0.247 600. 447.3
Isobutane 58.123 0.181 408.1 36.48 0.282 262.7 261.4
Isooctane 114.231 0.302 544.0 25.68 0.266 468. 372.4
Cyclopentane 70.134 0.196 511.8 45.02 0.273 258. 322.4
Cyclohexane 84.161 0.210 553.6 40.73 0.273 308. 353.9
Methylcyclopentane 84.161 0.230 532.8 37.85 0.272 319. 345.0
Methylcyclohexane 98.188 0.235 572.2 34.71 0.269 368. 374.1
Ethylene 28.054 0.087 282.3 50.40 0.281 131. 169.4
Propylene 42.081 0.140 365.6 46.65 0.289 188.4 225.5
1-Butene 56.108 0.191 420.0 40.43 0.277 239.3 266.9
cis-2-Butene 56.108 0.205 435.6 42.23 0.273 233.8 276.9
Solution
(b) 𝑃𝑉
෠
𝑃𝑟 15 323.15
𝑍= =1+𝐵 𝑃𝑟 = = 0.308 𝑇𝑟 = = 1.058
𝑅𝑇 𝑇𝑟 48.72 305.3

0.422
𝐵0 = 0.083 − 1.6
= −0.3026
1.058

0.172
𝐵1 = 0.139 − 4.2
= 0.00327
1.058
0.308
𝑍 = 1 + −0.3026 + 0.1 0.00327 = 0.915
1.058

𝑍𝑅𝑇 0.915 83.14 323.15

𝑉= = = 1639.181 cm3 /mol
𝑃 15
Tc, Pc
Cubic Equations of State

Table 3.1: Parameter assignments for equations of state

Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐

vdW (1873) 1 0 0 1/8 27/64 3/8
RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3
SRK (1972) 𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔)† 1 0 0.086 64 0.427 48 1/3
PR (1976) 𝛼𝑃𝑅 (𝑇𝑟 ; 𝜔)‡ 1+ 2 1− 2 0.077 80 0.457 24 0.307 40
† 2
𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 = 1 + 0.480 + 1.574 𝜔 − 0.176 𝜔2 1 − 𝑇𝑟 1/2
‡ 2
𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 = 1 + 0.374 64 + 1.542 26 𝜔 − 0.269 92 𝜔2 1 − 𝑇𝑟 1/2

7
Solution
(c) Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

𝑃𝑟 0.308 𝛼 𝑇𝑟 1.058 −0.5

𝛽 = Ω = 0.08664 = 0.0252 𝑞=Ψ = 0.42748 = 4.533
𝑇𝑟 1.058 Ω 𝑇𝑟 0.08664 1.058

Vapor and Vapor-like Root

𝑍 − 0.0252 Or rearrange to polynomial
𝑍 = 1 + 0.0252 − 4.533 0.0252 then use SOLVE function
𝑍 𝑍 + 0.0252
Using SOLVE function to get Z
𝑍 3 − 𝑍 2 + 0.088𝑍 − 0.0029 = 0
Z = 0.906
0.906 83.14 323.15
𝑉= = 1622.748 cm3 /mol
15
Solution
(d) Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
SRK (1972) 𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔)† 1 0 0.086 64 0.427 48 1/3
† 2
𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 = 1 + 0.480 + 1.574 𝜔 − 0.176 𝜔2 1 − 𝑇𝑟 1/2

2
𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 = 1 + 0.480 + 1.574 (0.1) − 0.176 (0.1)2 1− 1.0581/2 = 0.964

𝑃𝑟 0.308 𝛼 𝑇𝑟 0.964
𝛽 = Ω = 0.08664 = 0.0252 𝑞=Ψ = 0.42748 = 4.496
𝑇𝑟 1.058 Ω 𝑇𝑟 0.08664 1.058

Vapor and Vapor-like Root

𝑍 − 0.0252
𝑍 = 1 + 0.0252 − 4.496 0.0252
𝑍 𝑍 + 0.0252
Using SOLVE function to get Z
Z = 0.907
0.907 83.14 323.15
𝑉= = 1624.539 cm3 /mol
15
Solution
(e) Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
PR (1976) 𝛼𝑃𝑅 (𝑇𝑟 ; 𝜔)‡ 1+ 2 1− 2 0.077 80 0.457 24 0.307 40
‡ 2
𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 = 1 + 0.374 64 + 1.542 26 𝜔 − 0.269 92 𝜔2 1 − 𝑇𝑟 1/2

2
𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 = 1 + 0.374 64 + 1.542 26 (0.1) − 0.269 92 (0.1)2 1 − 1.0581/2 = 0.97

𝑃𝑟 0.308 𝛼 𝑇𝑟 0.97
𝛽 = Ω = 0.0778 = 0.02265 𝑞=Ψ = 0.45724 = 5.388
𝑇𝑟 1.058 Ω 𝑇𝑟 0.0778 1.058

Vapor and Vapor-like Root

𝑍 − 0.02265
𝑍 = 1 + 0.02265 − 5.388 0.02265
𝑍 − 0.00938 𝑍 + 0.055
Using SOLVE function to get Z
Z = 0.896
0.896 83.14 323.15
𝑉= = 1604.837 cm3 /mol
15
• 2. Calculate the molar volume of saturated liquid and the molar
volume of saturated vapor by the Redlich / Kwong equation for
Propane at 40°C (313.15 K) where Psat = 13.71 bar and compare
results with values found by suitable generalized correlations.
(Problem 3.38, Smith-VanNess-Abbott)
 Solution
Cubic EoS-saturated liquid
Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

13.71 313.15
𝑃𝑟 = = 0.323 𝑇𝑟 = = 0.847
42.48 369.8
𝑃𝑟 0.323 𝛼 𝑇𝑟 0.847 −0.5
𝛽 = Ω = 0.08664 = 0.033 𝑞=Ψ = 0.42748 = 6.33
𝑇𝑟 0.847 Ω 𝑇𝑟 0.08664 0.847

Liquid & Liquid-like Root

1 + 0.033 − 𝑍
𝑍 = 0.033 + (𝑍)(𝑍 + 0.033)
(6.33)(0.033)
Using SOLVE function to get Z

Z = 0.0545 0.0545 83.14 313.15

𝑉= = 103.5 cm3 /mol
13.71
Solution
Cubic EoS-saturated vapor
Vapor & Vapor-like Root
𝑍 − 0.033
𝑍 = 1 + 0.033 − 6.33 0.033
𝑍 𝑍 + 0.033
Using SOLVE function to get Z

Z = 0.79

0.79 83.14 313.15

𝑉= = 1500.21 cm3 /mol
13.71
Solution
Characteristic Properties of Pure Species
Rackett Equation-saturated liquid
Molar 𝜔 𝑇𝐶 /K 𝑃𝐶 /bar 𝑍𝐶 𝑉𝐶 𝑇𝑛 /K
mass cm mol−1
3

Methane 16.043 0.012 190.6 45.99 0.286 98.6 111.4

Ethane 30.070 0.100 305.3 48.72 0.279 145.5 184.6
Propane 44.097 0.152 369.8 42.48 0.276 200.0 231.1
n-Butane 58.123 0.200 425.1 37.96 0.274 255. 272.7
n-Pentane 72.150 0.252 469.7 33.70 0.270 313. 309.2
n-Hexane 86.177 0.301 507.6 30.25 0.266
2 371. 341.9
2/7
𝑉 𝑠𝑎𝑡 = 𝑉 𝑍 1−𝑇𝑟 100.204
n-Heptane
=
0.350
200
540.2
0.276
27.40 0.261
1−0.847 7 = 428.
94.172
371.6
3 /mol
cm398.8
n-Octane 𝑐 𝑐 114.231 0.400 268.7 24.90 0.256 486.
n-Nonane 128.258 0.444 594.6 22.90 0.252 544. 424.0
n-Decane 142.285 0.492 617.7 21.10 0.247 600. 447.3
Isobutane 58.123 0.181 408.1 36.48 0.282 262.7 261.4
Isooctane 114.231 0.302 544.0 25.68 0.266 468. 372.4
Cyclopentane 70.134 0.196 511.8 45.02 0.273 258. 322.4
Cyclohexane 84.161 0.210 553.6 40.73 0.273 308. 353.9
Methylcyclopentane 84.161 0.230 532.8 37.85 0.272 319. 345.0
Methylcyclohexane 98.188 0.235 572.2 34.71 0.269 368. 374.1
Ethylene 28.054 0.087 282.3 50.40 0.281 131. 169.4
Propylene 42.081 0.140 365.6 46.65 0.289 188.4 225.5
1-Butene 56.108 0.191 420.0 40.43 0.277 239.3 266.9
cis-2-Butene 56.108 0.205 435.6 42.23 0.273 233.8 276.9
Solution
Generalized correlation-saturated vapor
0.422
𝐵0 = 0.083 − = −0.46762
0.8471.6

1
0.172
𝐵 = 0.139 − = −0.20648
0.8474.2
0.323
𝑍 = 1 + −0.46762 − 0.152 0.20648 = 0.81
0.847

𝑍𝑅𝑇 0.81 83.14 313.15

𝑉= = = 1537.839 cm3 /mol
𝑃 13.71