Homework #7 – PETE 649 – Advanced Fluid Properties – Fall 2017

Nur Iman Khamidy – 201703210 – Department of Petroleum Engineering, CPG, KFUPM

Q1: Derive equation for the following residual properties based on Virial EOS (2-coefficients, B, C) in
term of density.

a) GR
b) HR
c) SR

Answer:
𝑍𝑅𝑇 𝑑𝑃 𝑑𝜌 𝑑𝑍
Let we start with: 𝑃 = 𝑉
= 𝑍𝜌𝑅𝑇 ⇒ 𝑑𝑃 = 𝑅𝑇(𝑍𝑑𝜌 + 𝜌𝑑𝑍) ⇒ 𝑃
= 𝜌
+ 𝑍

𝐵 𝐶
Virial Equation of State (2-coefficients: B and C): 𝑍 = 1 + + = 1 + 𝐵𝜌 + 𝐶𝜌2
𝑉 𝑉2

Then, since B and C are functions of temperature, we can get the following terms:
𝜕𝑍 𝑑𝐵 𝑑𝐶
𝑍 − 1 = 𝐵𝜌 + 𝐶𝜌2 𝑎𝑛𝑑 ( ) = 𝜌 + 𝜌2
𝜕𝑇 𝜌 𝑑𝑇 𝑑𝑇

a) Now, we start to derive the GR as per following:

𝐺𝑅 𝑃
𝑑𝑃 𝑑𝜌 𝑑𝑍 𝜌
𝑑𝜌 𝑍
1
= ∫ (𝑍 − 1) = ∫(𝑍 − 1) ( + ) = ∫ (𝑍 − 1) + ∫ (1 − ) 𝑑𝑍
𝑅𝑇 0 𝑃 𝜌 𝑍 0 𝜌 1 𝑍

𝐺𝑅 𝜌
𝑑𝜌 𝜌
𝑑𝜌
= ∫ (𝑍 − 1) + (𝑍 − 1) − ln 𝑍 = ∫ (𝐵𝜌 + 𝐶𝜌2 ) + (𝐵𝜌 + 𝐶𝜌2 ) − ln 𝑍
𝑅𝑇 0 𝜌 0 𝜌

𝐺𝑅 3
= 2𝐵𝜌 + 𝐶𝜌2 − ln(1 + 𝐵𝜌 + 𝐶𝜌2 )
𝑅𝑇 2
𝟑
∴ 𝑮𝑹 = 𝑹𝑻 [𝟐𝑩𝝆 + 𝑪𝝆𝟐 − 𝐥𝐧(𝟏 + 𝑩𝝆 + 𝑪𝝆𝟐 )]
𝟐
𝑉𝑅 𝑍−1
b) Since = , we can start with the definition of G to get the relationship with H, so that
𝑅𝑇 𝑃
R
we can derive H as per following:
𝐺 𝑑𝐺 𝐺𝑑𝑇
𝐺 = 𝐻 − 𝑇𝑆; 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇; 𝑎𝑛𝑑 𝑑 ( ) = −
𝑅𝑇 𝑅𝑇 𝑅𝑇 2
𝐺 𝑉𝑑𝑃 − 𝑆𝑑𝑇 (𝐻 − 𝑇𝑆)𝑑𝑇 𝑉𝑑𝑃 𝐻𝑑𝑇
𝑑( ) = − = −
𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇 𝑅𝑇 2
𝑅 𝑅 𝑅 𝑅
𝐺 𝑉 𝑑𝑃 𝐻 𝑑𝑇 𝑑𝑃 𝐻
𝑑( ) = − 2
= (𝑍 − 1) − 𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑃 𝑅𝑇 2
𝑅
𝐻𝑅 (𝑍 − 1) 𝜕𝑃 𝜕 (𝐺 ⁄𝑅𝑇) (𝑍 − 1) 𝜌
𝜕𝑍 𝑑𝜌
2
= ( ) − [ ] = − ∫ ( )
𝑅𝑇 𝑃 𝜕𝑇 𝜌 𝜕𝑇 𝑇 0 𝜕𝑇 𝜌 𝜌
𝜌
𝐻𝑅 𝜌
𝜕𝑍 𝑑𝜌 2)
𝜌
𝑑𝐵 𝑑𝐶 𝑑𝜌
= (𝑍 − 1) − 𝑇 ∫ ( ) = (𝐵𝜌 + 𝐶𝜌 − 𝑇 ∫ (𝜌 + 𝜌2 )
𝑅𝑇 0 𝜕𝑇 𝜌 𝜌 0 𝑑𝑇 𝑑𝑇 𝜌
𝑅
𝐻 𝐵 𝑑𝐵 𝐶 𝑑𝐶
= 𝑇 [𝜌 ( − ) + 𝜌2 ( − 0.5 )]
𝑅𝑇 𝑇 𝑑𝑇 𝑇 𝑑𝑇
𝑩 𝒅𝑩 𝑪 𝒅𝑪
∴ 𝑯𝑹 = 𝑹𝑻𝟐 [𝝆 ( − ) + 𝝆𝟐 ( − 𝟎. 𝟓 )]
𝑻 𝒅𝑻 𝑻 𝒅𝑻
c) Since 𝐺 = 𝐻 − 𝑇𝑆, we can derive from this relationship to find SR as function of B, C, and ρ,
𝐺𝑅 𝐻𝑅 𝑆𝑅 𝑆𝑅 𝐻𝑅 𝐺𝑅
as per following: 𝐺 𝑅 = 𝐻 𝑅 − 𝑇𝑆 𝑅 ⇒ 𝑅𝑇 = 𝑅𝑇
− 𝑅
⇒ 𝑅
= 𝑅𝑇
− 𝑅𝑇

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Homework #7 – PETE 649 – Advanced Fluid Properties – Fall 2017
Nur Iman Khamidy – 201703210 – Department of Petroleum Engineering, CPG, KFUPM

𝑆𝑅 𝐵 𝑑𝐵 𝐶 𝑑𝐶 3
= 𝑇 [𝜌 ( − ) + 𝜌2 ( − 0.5 )] − [2𝐵𝜌 + 𝐶𝜌2 − ln(1 + 𝐵𝜌 + 𝐶𝜌2 )]
𝑅 𝑇 𝑑𝑇 𝑇 𝑑𝑇 2
𝑆𝑅 𝐵 𝑑𝐵 𝐶 𝑑𝐶
= ln(1 + 𝐵𝜌 + 𝐶𝜌2 ) − 𝑇 [𝜌 ( + ) + 0.5𝜌2 ( + )]
𝑅 𝑇 𝑑𝑇 𝑇 𝑑𝑇
𝑩 𝒅𝑩 𝑪 𝒅𝑪
∴ 𝑺𝑹 = 𝑹 𝐥𝐧(𝟏 + 𝑩𝝆 + 𝑪𝝆𝟐 ) − 𝑹𝑻 [𝝆 ( + ) + 𝟎. 𝟓𝝆𝟐 ( + )]
𝑻 𝒅𝑻 𝑻 𝒅𝑻

Q2: Find values for residual enthalpy, HR and residual entropy, SR, for n-butane gas at 500 K and 50 bar
using the following approaches:
a) VdW EOS
b) RK EOS
c) SRK EOS
d) PR EOS
e) Lee/Kesler correlation

Answer:

A. For cubic EOS in this case: VdW, RK, SRK and PR EOS, following the procedure below to estimate
the residual enthalpy, HR and residual entropy, SR, for n-butane gas at T = 500 K and P = 50 bar:
1. Critical Properties and acentric factor of n-butane obtained from Table B.1 at Smith, Van Ness
and Abbott (2004) book: Pc = 37.96 bar, Tc = 425.1 K and ω = 0.2; hence we can get reduced
pressure and reduced temperature, respectively: Pr = P/Pc = 1.3172 and Tr = T/Tc = 1.1762
2. The basic generalized cubic equation of state and the value of constants for each of them:

We can get the Z, as per following below, using Microsoft Excel Solver with the first guess Z=1:

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Homework #7 – PETE 649 – Advanced Fluid Properties – Fall 2017
Nur Iman Khamidy – 201703210 – Department of Petroleum Engineering, CPG, KFUPM

3. From that Z of each EOS’s value, we can predict the HR/RT and SR/R of n-butane for each of
them by using procedure as per following below, then we can get HR and SR of n-butane each
of them by multiplying the value of HR/RT with RT and the value of SR/R with R where R =
8.3144598:

Where:
𝑑𝑞 𝛹 𝑑[𝛼(𝑇𝑟 )] 𝛼(𝑇𝑟 )
𝑇𝑟 = { − }
𝑑𝑇𝑟 𝛺 𝑑𝑇𝑟 𝑇𝑟

𝒅[𝜶(𝑻𝒓 )] f(ω) =
EOS =
𝒅𝑻𝒓
VdW 0 1
RK -0.5Tr-3/2 1
SRK 0.48 + 1.574ω – 0.176ω2
f2(ω) – Tr-1/2[ f(ω) + f2(ω)
PR 0.37464 + 1.54226ω – 0.26992ω2

4. The tabulation results for estimating Z of n-butane for each of them by iterating the value of
Z_old, starting from Z_old = 1, are displayed in the following line below:

EOS α(Tr) σ ϵ Ω Ψ
vdW 1 0 0 0.125 0.421875
RK 0.9221 1 0 0.08664 0.42748
SRK 0.8713 1 0 0.08664 0.42748
PR 0.8896 2.4142 -0.4142 0.0778 0.45724

EOS β q Z_old Z_new Z_Rel_Err

vdW 0.1400 2.8694 0.6610 0.6610 1.02424E-07
RK 0.0970 3.8679 0.6852 0.6852 8.30239E-11
SRK 0.0970 3.6548 0.7224 0.7224 4.75744E-07
PR 0.0871 4.4450 0.6909 0.6909 2.2271E-10

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Homework #7 – PETE 649 – Advanced Fluid Properties – Fall 2017
Nur Iman Khamidy – 201703210 – Department of Petroleum Engineering, CPG, KFUPM

5. The tabulation results for estimating HR and SR of n-butane for each of them as per following
below:

EOS I dα/dTr α/Tr Tr dq/dTr HR, J/mol SR, J/mol/K

vdW 0.2118 0 0.8502 -2.8694 -3935.5082 -5.4208
RK 0.1324 -0.3920 0.7839 -5.8019 -4503.0267 -6.5424
SRK 0.1260 -0.6780 0.7407 -7.0001 -4821.5583 -7.4083
PR 0.1129 -0.5847 0.7563 -7.8812 -4984.9969 -7.4214

B. For Lee-Kesler Generalized Correlation, we estimate HR and SR as per following below, extracted
from Lee-Kesler (1975) paper
1. First, we follow the procedure below for estimating the HR/RTc and SR/R of n-butane:

2. For estimating the Z, we need to do iterative procedure with first guess of Z =1, by using the
following equation for each of fluids, simple fluid: Z(0) and reference fluid: Z(r), respectively:

Where: Vr = (ZTr)/Pr and

After getting convergence, then we can calculate Z of n-butane by using:

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Homework #7 – PETE 649 – Advanced Fluid Properties – Fall 2017
Nur Iman Khamidy – 201703210 – Department of Petroleum Engineering, CPG, KFUPM

3. For estimating the the HR/RTc and SR/R of n-butane for each of fluid, we need the final Z value
of each fluid as input of the equation as per following below, then we can get HR and SR of n-
butane each of them by multiplying the value of HR/RTc with RTc and the value of SR/R with R
where R = 8.3144598:

Where: HR/RT = (H-H0)/RTc ; SR/R = (S-S0)/R + ln(P/P0) ; and

4. The tabulation results of Z, Vr and E of n-butane for each of fluid after convergence:

B C D Z_old Z_new Rel_Err Vr E

Simple (0) -0.2383 0.0078 0.0001 0.6782 0.6782 2.2180E-07 0.6056 0.0242
Reference, r -0.2242 -0.0011 0.0001 0.7248 0.7248 2.2698E-08 0.6472 0.0371

5. The tabulation results of HR/RTc and SR/R of n-butane for each fluid, also HR and SR of n-butane
as per following below:

HR/RTc SR/R
Simple (0) -1.3003 -0.8135
Reference, r -1.4760 -0.9909

HR/RTc SR/R Z HR, J/mol SR, J/mol/K

-1.3886 -0.9027 0.7016 -4908.0886 -7.5055

C. Results Summary

EOS Z HR, J/mol SR, J/mol/K

vdW 0.6610 -3935.5082 -5.4208
RK 0.6852 -4503.0267 -6.5424
SRK 0.7224 -4821.5583 -7.4083
PR 0.6909 -4984.9969 -7.4214
Lee-Kesler 0.7016 -4908.0886 -7.5055