Chemical Engineering Thermodynamics II (CEB 2023)

VOLUMETRIC PROPERTIES
OF PURE FLUIDS
Chapter 3 - 2nd part
CLO2 : Able to estimate the thermodynamics properties of
fluid for pure substance and mixture.

soraya.sambudi@utp.edu.my
Learning Outcome

• By the end of this lecture, you are expected to:

–Explain the volumetric behavior of pure fluids
(P-V-T diagram)
–Conduct analysis for systems of ideal gases
and real gases
–Apply the equations of state, virial equations
and generalized correlations to the
appropriate systems

2
Quick Review
• Pure substances and their phase changes
process
• P-V-T behavior of pure substances
• Ideal gas equations of state
• The ideal gas
Contents
▪ Ideal gas equation of state
▪ Compressibility factor
▪ Different equations of state
(a) Virial equation
(b) Cubic equation of state
▪ van der Waals (vdW)
▪ Redlich/Kwong (RK)
▪ Soave/Redlich/Kwong
▪ Peng/Robinson (PR)

(c) Theorem of corresponding states

(d) Generalized Correlations for Gases
Virial Equation of State

Figure 3.4: (PV)*, the limiting value of PV as P→ 0, is independent

of the gas

17
Two forms of Virial Equation

Virial coefficients are temperature dependent but not on pressure

18
Application of Virial Equations
▪ Virial expansion series are infinite series
▪ Gives good approximation at low to moderate pressure
▪ Actual compressibility factor can be obtained from graph.
𝑃𝑉
𝑍≡ = 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯
𝑅𝑇
𝜕𝑍 2
= 𝐵′ + 2𝐶 ′ 𝑃 + 3𝐷′𝑃 + ⋯
𝜕𝑃 𝑇
𝜕𝑍
= 𝐵′
𝜕𝑃 𝑇;𝑃=0

Tangent line at P = 0:
𝑍 = 1 + 𝐵′ 𝑃
𝑷𝑽 𝑩𝑷
𝒁= =𝟏+ (𝟐 𝐭𝐞𝐫𝐦𝐬)
𝑹𝑻 𝑹𝑻
𝑷𝑽 𝑩 𝑪
𝒁= = 𝟏 + + 𝟐 (𝟑 𝐭𝐞𝐫𝐦𝐬)
Figure 3.9: Compressibility-factor graph for 𝑹𝑻 𝑽 𝑽
methane

What are the limitations of Virial equations?

Application of Virial Equations

Figure 3.10: Virial coefficients B and C for nitrogen

▪ Extended virial equations – Benedict/Webb/Rubin equation

𝑅𝑇 𝐵0 𝑅𝑇 − 𝐴0 − 𝐶0 Τ𝑇 2 𝑏𝑅𝑇 − 𝑎 𝑎𝛼 𝑐 𝛾 −𝛾
𝑃= + + + + 1 + exp
𝑉 𝑉2 𝑉3 𝑉6 𝑉3𝑇2 𝑉2 𝑉2

8
Application of Virial Equations

𝑃𝑉 𝐵 𝐶
𝑍= = 1 + 𝑍+ 2
𝑅𝑇 𝑉 𝑉

▪ If B is given, 2-term virial equation can be used (low pressure)

▪ If B and C are given, 3-term virial equation can be used (solve
iteratively using initial value = value calculated form ideal gas)
▪ If B and/or C are not given:
(a) Calculate 2nd virial coefficient using Lee/Kesler or Pitzer
correlations
(b) Calculate 3rd virial coefficient using generalized correlations
Example 3.8
Reported values for the virial coefficients of isopropanol vapor at 200℃ (473.15
K) are:
𝐵 = −388 cm3 mol−1 𝐶 = −26 000 cm6 mol−2
Calculate V and Z for isopropanol vapor at 200℃ (473.15 K) and 10 bar by
(a) The ideal-gas equation
(b) Truncated virial equation (2 terms)
(c) Truncated virial equation (3 terms)

Solution
(a) For an ideal gas, 𝑍 = 1, Formulae:
𝑃𝑉 𝐵𝑃
𝑅𝑇 (83.14 cm3 bar mol−1 K −1 )(473.15 K) 𝑍=
𝑅𝑇
=1+
𝑅𝑇
(2 terms)
𝑉= =
𝑃 10 bar 𝑃𝑉 𝐵 𝐶
𝑍= = 1 + + 2 (3 terms)
= 3934 cm3 mol−1 𝑅𝑇 𝑉 𝑉

(b) For truncated virial equation (2 terms),

𝐵𝑃 (−388 cm3 mol−1 )(10 bar)
𝑍 =1+ =1+ = 0.9014
𝑅𝑇 (83.14 cm3 bar mol−1 K −1 )(473.15 K)
𝑍𝑅𝑇 (0.9014)(83.14 cm3 bar mol−1 K −1 )(473.15 K)
𝑉= = = 3546 cm3 mol−1
𝑃 10 bar

10
Example 3.8
Reported values for the virial coefficients of isopropanol vapor at 200℃ (473.15 K) are:
𝐵 = −388 cm3 mol−1 𝐶 = −26 000 cm6 mol−2
Calculate V and Z for isopropanol vapor at 200℃ (473.15 K) and 10 bar by
(c) Truncated virial equation (3 terms)
i V (cm3/mol)
Solution
𝑃𝑉 𝐵 𝐶 0 3934 → Ideal gas value
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉 1 3539
Rearranging the equation, we get 2 3495
𝑅𝑇 𝐵 𝐶
𝑉= 1+ + 2 3 3489
𝑃 𝑉 𝑉
𝑅𝑇 𝐵 𝐶
4 3488
For iteration, 𝑉𝑖+1 = 1+ +
𝑃 𝑉𝑖 𝑉𝑖 2 5 3488 → V = 3488 cm3 mol-1
(83.14 cm3 bar mol−1 K −1 )(473.15 K)
𝑉𝑖+1 = 𝑃𝑉
10 bar 𝑍=
𝑅𝑇
−388 cm3 mol−1 −26 000 cm6 mol−2 (10 bar)(3488 cm3 mol−1 )
× 1+ + =
𝑉𝑖 𝑉𝑖 2 (83.14 cm3 bar mol−1 K −1 )(473.15 K)
= 0.8866

11
Cubic Equations of State
Simplest equations for both liquid and vapor behavior
Several equation has been proposed to improve the accuracy.
▪ Van der Waals equation of state:
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
▪ Other cubic equations of state are: Redlich/Kwong (RK),
Soave/Redlich/Kwong (SRK), and Peng/Robinson (PR)
equations

14
Cubic equations of state
Example on how to obtain constants for van der Waals
equation of state:
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
▪ Expand the equation: 𝑃𝑉 3 − 𝑅𝑇𝑉 2 + 𝑎𝑉 + 𝑎𝑏 − 𝑃𝑏𝑉 2 = 0
𝑅𝑇𝑐 𝑎 𝑎𝑏
▪ Express at critical point: 𝑉3− 𝑏 + 𝑉2 + 𝑉 − =0
𝑃𝑐 𝑃𝑐 𝑃𝑐
▪ Cubic equation has 3 roots: (𝑉 − 𝑉𝑐 )3 = 0
▪ Expand in polynomial form: 𝑉 3 −3𝑉𝑐 𝑉 2 + 3𝑉𝑐2 𝑉 − 𝑉𝑐3 = 0
1
▪ Compare the terms: 𝑎 = 3𝑃𝑐 𝑉𝑐2 ; 𝑏 = 𝑉𝑐
3

3 𝑅𝑇𝑐 27 𝑅 2 𝑇𝑐 2 1 𝑅𝑇𝑐 𝑃𝑐 𝑉𝑐 3
𝑉𝑐 = 𝑎= 𝑏= 𝑍𝑐 ≡ =
8 𝑃𝑐 64 𝑃𝑐 8 𝑃𝑐 𝑅𝑇𝑐 8
Theorem of Corresponding States
Acentric Factor

▪ The acentric factor for a pure chemical species is defined as the

deviation of reduced saturated pressure from that of simple fluids
at Tr = 0.7.
𝜔 = 1.0 − log(𝑃𝑟 𝑠𝑎𝑡 ) 𝑇𝑟 =0.7

Three-parameter theorem
of corresponding states: All
fluids having the same
value of 𝜔, when compared
at the same Tr and Pr , have
about the same value of Z,
and all deviate from ideal-
gas behavior to about the
same degree.

Figure 3.12: Approximate temperature dependence of

reduced vapor pressure

17
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
Vapor & Vapor-Like Roots

𝜳𝜶 𝑻𝒓
𝒒=
𝜴𝑻𝒓
Liquid & Liquid-Like Roots

▪ From the equation,

𝑅𝑇 𝑎(𝑇) 𝑉−𝑏
𝑉= +𝑏−
𝑃 𝑃 (𝑉 + 𝜖𝑏)(𝑉 + 𝜎𝑏)

▪ Rearrange and solve for 𝑉 in the numerator of the final fraction:

𝑅𝑇 + 𝑏𝑃 − 𝑉𝑃
𝑉 = 𝑏 + (𝑉 + 𝜖𝑏)(𝑉 + 𝜎𝑏)
𝑎(𝑇)

▪ Solve for 𝑍:
1+𝛽−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽

▪ For iteration, start with Z = 𝛽 Initial conditions: 𝑉 = 𝑏 ; 𝑍 = 𝛽

20
Cubic Equations of State
Table 3.1: Parameter assignments for equations of state
Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
vdW 1 0 0 1/8 27/64 3/8
(1873)
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

Formulae for generic cubic equation of state

𝑅𝑇 𝑎 𝑇
𝑃= −
𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝛼(𝑇𝑟 )𝑅 2 𝑇𝑐 2
𝑎 𝑇 =Ψ
𝑃𝑐
𝑅𝑇𝑐
𝑏=Ω
𝑃𝑐
21
Comparative Assessments of RK, SRK and PR EOS

Redlich Kwong EOS:

• Generally good for gas phase properties.
• Poor for liquid phase properties.
• Better when used in conjunction with a correlation for
liquid phase behavior.
• Satisfactory for gas phase fugacity calculation @ Pr < Tr/3.
• Satisfactory for enthalpy departure and entropy departure
calculations.

Soave Redlich Kwong & Peng Robinson EOS

• Serve similar functions as the Redlich Kwong EOS but
require more parameters.
• PR obtains better liquid densities than SRK.
Example 3.9
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar volumes of
(a) Saturated vapor
(b) Saturated liquid
at the above conditions as given by the Redlich/Kwong equation.

Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐

RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

Solution Step-by-step approach:

From Appendix Table B.1, we know that for n-butane, 𝑍𝑅𝑇
𝑉= (Given 𝑅, 𝑇 and 𝑃)
𝑇𝑐 = 425.1 K and 𝑃𝑐 = 37.96 bar 𝑃
• We need to find Z in order to get V
𝑇 350
𝑇𝑟 = = = 0.8233 • To find Z, we need to know 𝑞, 𝛽, 𝜖, 𝜎
𝑇𝑐 425.1
• To get 𝑞 and 𝛽, we need to know
𝑃 9.4573 Ψ, 𝛼 𝑇𝑟 , Ω, 𝑇𝑟 , 𝑃𝑟
𝑃𝑟 = = = 0.2491
𝑃𝑐 37.96
Formulae for vapor-like roots
Ψ𝛼(𝑇𝑟 ) Ψ𝑇𝑟 −1/2 Ψ −3/2
𝑞= = = 𝑇𝑟 𝑍−𝛽
Ω𝑇𝑟 Ω𝑇𝑟 Ω 𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
0.42748 Ψ𝛼(𝑇𝑟 )
= (0.8233)−3/2 = 6.6048 𝑞=
0.08664 Ω𝑇𝑟
𝑃𝑟 0.2491 𝑃𝑟
𝛽 = Ω = 0.08664 = 0.026214 𝛽=Ω
𝑇𝑟 0.8233 𝑇𝑟
23
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
Example 3.9 cont’d
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar
volumes of
(a) Saturated vapor
(b) Saturated liquid
at the above conditions as given by the Redlich/Kwong equation.
Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

Solution i Z
(a) For saturated vapor, 0 1 → Ideal gas value
𝑍𝑖 − 𝛽
𝑍𝑖+1 = 1 + 𝛽 − 𝑞𝛽 1 0.831957
𝑍𝑖 + 𝜖𝛽 𝑍𝑖 + 𝜎𝛽
2 0.837246
𝑍𝑖 − 0.026214
= 1 + 0.026214 − (0.1731) 3 0.832018
𝑍𝑖 𝑍𝑖 + 0.026214
4 0.830875
Perform iteration with 𝑍0 = 1 ; Z converges to 0.8305. 5 0.830623
To find the molar volume of saturated n-butane vapor, 6 0.830568

𝑣
𝑍𝑅𝑇 0.8305 83.14 cm3 bar mol−1 K −1 350 K 7 0.830555
𝑉 = =
𝑃 9.4573 bar 8 0.830553 → Z = 0.8305
= 2555 cm3 mol−1
Example 3.9 cont’d
a) Saturated vapor.
Beside iteration, SOLVE function and transform the equation into polynomial
form can also be used to easily find the value of Z.

𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑍 − 0.026214
= 1 + 0.026214 − (0.1731)
𝑍 𝑍 + 0.026214
𝑍 3 − 𝑍 2 + 0.1462 𝑍 − 4.538 × 10−3 = 0
Using SOLVER, Z = 0.83055, Big root
Example 3.9 cont’d
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar volumes
of
(a) Saturated vapor
(b) Saturated liquid
at the above conditions as given by the Redlich/Kwong equation.
Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐
RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

Solution i Z
(b) For saturated liquid, 0 0.026214 → 𝛽
1+𝛽−𝑍 1 0.034152
𝑍𝑖+1 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
2 0.038027
1.026214 − 𝑍 3 0.040157
= 0.026214 + 𝑍(𝑍 + 0.026214)
0.173138 4 0.041393
Perform iteration with 𝑍0 = 𝛽 ; Z converges to 0.04331. 5 0.042132
To find the molar volume of saturated n-butane vapor, 6 0.042581

𝑙
𝑍𝑅𝑇 0.04331 83.14 cm3 bar mol−1 K −1 350 K ⋮ ⋮
𝑉 = =
𝑃 9.4573 bar 17 0.043310 → Z = 0.04331
= 133.3 cm3 mol−1
Example 3.9 cont’d
b) Saturated liquid.
Beside iteration, SOLVE function and transform the equation into polynomial
form can also be used to easily find the value of Z.

1+𝛽−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
1.026214 − 𝑍
= 0.026214 + 𝑍(𝑍 + 0.026214)
0.173138
𝑍 3 − 𝑍 2 + 0.1462 𝑍 − 4.538 × 10−3 = 0
Using SOLVER, Z = 0.043315, Small root
 Example 3.9 cont’d
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar
volumes of
(a) Saturated vapor
(b) Saturated liquid
at the above conditions as given by the Redlich/Kwong equation.

Eq. of State 𝛼(𝑇𝑟 ) 𝜎 𝜖 Ω Ψ 𝑍𝑐

RK (1949) 𝑇𝑟 −1Τ2 1 0 0.086 64 0.427 48 1/3

Answer for other EOS

Vv (cm3/mol) Vl (cm3/mol)
Exp vdw RK SRK PR Exp vdW RK SRK PR
2482 2667 2555 2520 2486 115.0 191.0 133.3 127.8 112.6
Example 3.11
What pressure is generated when 1 kmol of methane is stored in a volume
of 0.125m3 at 50°C (323.15K)? Base calculation on each of the following:
(a) The ideal gas equation
(b) The Redlich/Kwong equation
Solution
(a) 𝑅𝑇 0.08314 323.15
𝑃= = = 214.9 bar
𝑉 0.125

𝑇 323.15 𝑅𝑇 𝑎 𝑇
(b) 𝑇𝑟 = = = 1.695 𝑃= −
𝑇𝐶 190.6 𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏

𝛼(𝑇𝑟 )𝑅2 𝑇𝑐 2 1.695 −0.5 (0.08314)2 (190.6)2

𝑎 𝑇 =Ψ = 0.42748 = 1.7922 bar m6
𝑃𝑐 45.99
𝑅𝑇𝑐 (0.08314)(190.6)
𝑏=Ω = 0.08664 = 0.02985 m3
𝑃𝑐 45.99
0.08314 323.15 1.7922
𝑃= − = 189.65 bar
0.125 − 0.02985 0.125 0.125 + 0.02985
30
Generalized Correlations for Gases
▪ Pitzer correlations for the compressibility factor
𝑍 = 𝑍•0 + 𝜔𝑍1 −(3.57)

• 2 parameter correlation (𝑇𝑟 , 𝑃𝑟 ) −

Table D1 or E1 to D4 or E4
• When 𝜔 = 0 → 𝑍 = 𝑍 0 (Simple fluids)

• Lee/Kesler correlation
provides reliable estimates
for gases which are nonpolar
or slightly polar (N2 , O2 , Cl2 ,
Br2 , CH4 with symmetrical
structure)

Figure 3.13: Lee/Kesler correlation

31
Generalized Correlation for Compressibility Factor
(Lee/Kesler) 8th Edition book
Generalized Correlation for Compressibility Factor
(Lee/Kesler) 7th Edition book

33
Generalized Correlations for Gases
▪ Pitzer correlations for the compressibility factor
• Quantum gases do not conform to the same corresponding-
states behavior as do normal fluids
• Examples of quantum gases: H2, He, neon
• Typically use temperature-dependent effective critical
parameters.
• Example for H2 gas with 𝜔 = 0:
43.6
𝑇𝑐 /K =
21.8 − 3.58
1+
2.016 𝑇
20.5
𝑃𝑐 /bar =
1+
44.2 −(3.59)
2.016 𝑇
51.5
𝑉𝑐 /cm3 mol−1 = −(3.60)
9.91
1−
2.016 𝑇

34
Generalized Correlations for Gases
▪ Pitzer correlations for the second virial coefficient
• Give approximate analytical expression to 𝑍 0 and 𝑍1 for a
limited range of pressure
𝐵෠ = 𝐵0 + 𝜔𝐵1 -(3.61) − 3.63
𝐵𝑃 𝐵(𝑃𝑐 𝑃𝑟 ) 𝑃 𝐵𝑃
𝑍 =1+ =1+ = 1 + 𝐵෠ 𝑟 where 𝐵෠ = 𝑐 -(3.62)
𝑅𝑇 𝑅(𝑇𝑐 𝑇𝑟 ) 𝑇𝑟 𝑅𝑇𝑐
𝑃𝑟 𝑃𝑟 𝑃𝑟
=1+ 𝐵0 + 𝜔𝐵1 =1+ 𝐵 0 +𝜔𝐵 1
𝑇𝑟 𝑇𝑟 𝑇𝑟
𝑍0 𝑍1
𝐵0 and 𝐵1 are reasonably well represented by:
0.422
𝐵0 = 0.083 − − 3.65
𝑇𝑟 1.6
0.172
𝐵1 = 0.139 − − 3.66
𝑇𝑟 4.2

35
Generalized Correlations for Gases
▪ Pitzer correlations for the second virial coefficient

Legend:
— Virial coefficient
correlation
• Lee/Kesler
correlation

Figure 3.14: Comparison of correlations for Z0 . Error <2% for a limited pressure range

36
Generalized Correlations for Gases

▪ Pitzer correlations for the third virial coefficient

• Less common than second virial coefficients
𝐶መ = 𝐶 0 + 𝜔𝐶 1 − 3.69
𝐵 𝐶
𝑍 =1+ + = 1 + 𝐵𝜌 + 𝐶𝜌2
𝑉 𝑉2
𝑃 𝑃𝑟 2 𝐵𝑃𝑐 𝐶𝑃𝑐 2
=1+ 𝐵෠ 𝑟 + 𝐶መ where 𝐵෠ = and 𝐶መ = -(3.68)
𝑇𝑟 𝑍 𝑇𝑟 𝑍 𝑅𝑇𝑐 𝑅 2 𝑇𝑐 2

𝐶 0 and 𝐶 1 are reasonably well represented by:

0.02432 0.00313
𝐶 0 = 0.01407 + − 10.5 − 3.70
𝑇𝑟 𝑇𝑟
0.05539 0.00242
𝐶 1 = −0.02676 + 2.7 − 10.5 − 3.71
𝑇𝑟 𝑇𝑟

37
Example 3.10
Determine the molar volume of n-butane at 510K and 25 bar by each of
the following:
(a) Ideal-gas equation
(b) The generalized compressibility-factor correlation
(c) Equation (3.61), with the generalized correlation for 𝐵෠
(d) Equation (3.68), with the generalized correlations for 𝐵෠ and 𝐶መ

Solution
(a) 𝑅𝑇 83.14 510
𝑉= = = 1696.1 cm3 mol−1
𝑃 25

(b) TC , PC and ω given in Appendix B

510 25
𝑇𝑟 = = 1.2 𝑃𝑟 = = 0.659
425.1 37.96
Example 3.10 cont’d (b) Interpolation in Table D1/E.1 and D2/E.2

0.8 − 0.659 0.659 − 0.6

𝑍0 = 0.8779 + 0.833 = 0.8647
0.8 − 0.6 0.8 − 0.6

0.8 − 0.659 0.659 − 0.6

𝑍1 = 0.0326 + 0.0499 = 0.038
0.8 − 0.6 0.8 − 0.6
𝑍 = 𝑍 0 + 𝜔𝑍1 = 0.8647 + 0.2 0.038 = 0.873
𝑍𝑅𝑇 0.873 83.14 510
𝑉= = = 1480.7 cm3 mol−1
𝑃 25
Example 3.10 cont’d
(c) Eq. (3.65) and (3.66)
0.422 0.172
𝐵0 = 0.083 − = −0.232 𝐵1 = 0.139 − = 0.059
1.21.6 1.24.2

Eq. (3.63) 𝐵෠ = 𝐵0 + 𝜔𝐵1 = −0.232 + 0.2 0.059 = −0.22

Eq. (3.61)
𝑃𝑟 0.659
𝑍 = 1 + 𝐵෠ = 1 − 0.22 = 0.879
𝑇𝑟 1.2
(0.879)(83.14)(510)
𝑉= = 1489.1 cm3 mol−1
25

(d) Eq. (3.70) and (3.71)

0.02432 0.00313
𝐶0 = 0.01407 + − 10.5
= 0.0339
1.2 1.2
0.05539 0.00242
𝐶 1 = −0.02676 + 2.7
− 10.5
= 0.0067
1.2 1.2
Example 3.10 cont’d
(d) Eq. (3.69)

𝐶መ = 𝐶 0 + 𝜔𝐶 1 = 0.0339 + 0.2 0.0067 = 0.0352

Eq. (3.68)
2
𝑃𝑟 𝑃𝑟
෠
𝑍 =1+𝐵 መ
+𝐶
𝑇𝑟 𝑍 𝑇𝑟 𝑍
2
0.659 0.659
𝑍 = 1 + (−0.22) + (0.0352)
1.2𝑍 1.2𝑍

0.121 0.0106 Using SOLVE function 𝑍 = 0.876

𝑍 =1− +
𝑍 𝑍2

(0.876)(83.14)(510)
𝑉= = 1485.8 cm3 mol−1
25
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℃ (338.15 K).
Calculate the pressure of the gas by
(a) The ideal-gas equation
(b) A generalized correlation

Solution
The molar volume of ammonia,
𝑉𝑡 𝑉𝑡 30 000 cm3
𝑉= = = = 1021.2 cm3 mol−1
𝑛 𝑚/𝑀 500g
17.02 g mol−1

(a) By the ideal-gas equation, Z = 1

𝑅𝑇 (83.14 cm3 bar mol−1 K −1 )(338.15 K)
𝑃= = = 27.53 bar
𝑉 1021.2 cm3 mol−1
Example 3.12 cont’d
A mass of 500 g of gaseous ammonia is contained in a 30 000 cm3 vessel immersed
in a constant-temperature bath at 65℃ (338.15 K). Calculate the pressure of the gas
by
(a) The ideal-gas equation From Table B.1:
For ammonia,
(b) A generalized correlation
• 𝑃𝑐 = 112.8 bar
• 𝑇𝑐 = 405.7 K
Solution • 𝜔 = 0.253
(b) By the generalized correlation,
27.53 338.15 Formulae:
Guess 𝑃𝑟 ≈ = 0.244 and 𝑇𝑟 ≈ = 0.834 𝑃𝑉 𝐵𝑃
112.8 405.7
0.422 𝑍= =1+ (2 terms)
𝑅𝑇 𝑅𝑇
𝐵0 = 0.083 − = −0.482 𝑅𝑇
0.834 1.6 𝑃=
𝑉−𝐵
0.172 ෠ 𝑐
𝐵1 = 0.139 − = −0.232 ෠
𝐵𝑃𝑐 𝐵𝑅𝑇
0.834 4.2 𝐵=
𝑅𝑇𝑐
Thus, 𝐵 =
𝑃𝑐
𝐵෠ = 𝐵0 + 𝜔𝐵1 = −0.482 + 0.253 −0.232 = −0.541 𝐵෠ = 𝐵0 + 𝜔𝐵1
0.422
෠ 𝑐 −0.541 83.14 cm3 bar mol−1 K −1 405.7 K
𝐵𝑅𝑇 𝐵0 = 0.083 − 1.6
𝐵= = 𝑇𝑟
𝑃𝑐 112.8 bar 0.172
𝐵1 = 0.139 − 4.2
= −161.8 cm3 mol−1 𝑇𝑟

𝑅𝑇 83.14 cm3 bar mol−1 K −1 338.15 K

𝑃= = = 23.76 bar
𝑉−𝐵 [1021.2 − (−161.8)] cm3 mol−1
Generalized correlations for liquids

Rackett equation:
(1−𝑇𝑟 )2/7
𝑉 𝑠𝑎𝑡 =
𝑉𝑐 𝑍𝑐
An alternative form of this equation:
𝑃𝑟 1+ 1−𝑇𝑟 2/7
𝑍 𝑠𝑎𝑡 = 𝑍𝑐
𝑇𝑟
Reduced density,
𝜌 𝑉𝑐
𝜌𝑟 ≡ =
𝜌𝑐 𝑉
Liquid volume,
𝜌𝑟1
𝑉2 = 𝑉1
𝜌𝑟2
V2 = required volume
V1 = known volume
ρr1, ρr2 = reduced densities read from Fig. 3.16
 Tr = 0.7641 at
saturated liquid

Tr = 0.7641 and
Pr = 0.887
𝜌𝑟
Example 3.13

For ammonia at 310 K, estimate the density of the

a) Saturated liquid
b) liquid at 100 bar
For comparison, the experimental value is 29.14 cm3/mol.

Solution
310
a) 𝑇𝑟 = 405.7 = 0.7641
Vc = 72.47 and Zc = 0.242 (from Table B.1)
2
1−𝑇𝑟 2/7
𝑉 𝑠𝑎𝑡 = 𝑉𝑐 𝑍𝑐 = 72.47 0.242 0.2359 7
= 28.33 𝑐𝑚3 𝑚𝑜𝑙 −1

In comparison with experimental value (29.14 cm3/mol), there is 2.7%

difference.
Example 3.13
For ammonia at 310 K, estimate the density of the
b) liquid at 100 bar
For comparison, the experimental value is 29.14 cm3/mol.

Solution
100
b) 𝑇𝑟 = 0.7641, 𝑃𝑟 = = 0.887
112.8
From Fig. 3.16, the 𝜌𝑟 = 2.38
𝑉𝑐 72.47
𝑉= = = 30.45 𝑐𝑚3 𝑚𝑜𝑙 −1
𝜌𝑟 2.38

If we start with experimental value of 29.14 cm3/mol as V1 for saturated

𝜌
liquid at 310 K, then we can use Eq : 𝑉2 = 𝑉1 𝑟1
𝜌𝑟2
For saturated liquid at 𝑇𝑟 = 0.7641 from Fig. 3.16, 𝜌𝑟1 = 2.34.
2.34
Hence, 𝑉2 = 29.14 = 28.65 𝑐𝑚3 𝑚𝑜𝑙 −1
2.38
Check list
✓ Ideal gas equation of state
✓ Compressibility factor
✓ Different equations of state
✓ Virial equation
✓ Cubic equation of state
✓ van der Waals (vdW)
✓ Redlich/Kwong (RK)
✓ Soave/Redlich/Kwong
✓ Peng/Robinson (PR)

✓ Theorem of corresponding states

✓ Generalized Correlations for Gases
Compressibility factor (Z) of Real Fluid

Compressibility factor
(Z)

Cubic EoS
Virial EoS Generalized
(gas/vapor and
(gas/vapor) Correlations
liquid)

Vapor and Vapor-like Root Lee Kesler

2 term VdW (gas/vapor)
𝑍−𝛽
Z= 1 + 𝛽 − 𝑞𝛽 𝑍 = 𝑍 0 + 𝜔𝑍1
𝑃𝑉 𝐵𝑃 𝑍+𝜖𝛽 𝑍+𝜎𝛽
𝑍= =1+
𝑅𝑇 𝑅𝑇 Pitzer 2nd
Liquid and Liquid-like Root (gas/vapor)
RK 𝑃𝑟
1+𝛽−𝑍 𝑍 = 1 + 𝐵0 + 𝜔𝐵1
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽 𝑇𝑟
3 term 𝑞𝛽
Pitzer 3rd
𝑃𝑉 𝐵 𝐶 SRK (gas/vapor)
𝑍= =1+ + 2 2
𝑅𝑇 𝑉 𝑉 𝑃𝑟 𝑃𝑟
𝑍 = 1 + 𝐵෠ + 𝐶መ
𝑇𝑟 𝑍 𝑇𝑟 𝑍
Rackett eq.
PR
(liquid)
𝑃𝑟 1+ 1−𝑇𝑟 2/7
𝑍 𝑠𝑎𝑡 = 𝑍
𝑇𝑟 𝑐