2021

THERM0 ASSIGNMENT LU 2

MV VILAKATI (220085706)
UNIVERSITY OF JOHANNESBURG
4/17/2021
QUESTION 1
Student no: 220085706
X=6
Y=0
Z=7

(a) Chemical X= methyl acetate

𝐵
𝑙𝑛𝑃 𝑠𝑎𝑡 = 𝐴 −
(𝑇(0 𝐶) + 𝐶)

A=14.2456
B=2662.78
C=219.690
T=50+ (0.7*0) + (0.4*7) = 52.8 0C
Substituting gives;
ln psat=14.2456-(2662.78/(52.8+219.690))
ln psat = 4.473571669
psat = e4.473571669
= 87. 66929015 kPa
Conversion to bar
87. 66929015 kPa 1 bar
100 kPa

= 0.8766929015
= 0.8767bar

(b) Van der Waals EoS alternative equation

𝑍 3 − (1 + 𝐵)𝑍 2 + 𝐴𝑍 − 𝐴𝐵

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a=0.421875 *(R2 (TC) 2/PC
b=0.125*(RTC/PC)
A=aP/ (R2T2)
B= bP/ (RT)
Given Data
T= 52.8+273.15= 325.95 K
TC= 506.6 K
PC= 47.50 bar
P= 0.8767 bar
α= 1

𝑻
𝑻𝒓 =
𝑻𝒄
= 325.95/506.6
= 0.6434070272

Pr=P/Pc
=0.8766929015/47.50

= 0.01845669266

a= [0.421875 *(R2 (TC) 2/PC]*α

= 0.421875*[((83.14)2(506.6)2)/ (47.50)]*1
= 15755804.81 bar. cm6.mol-2

b=0.125*(RTC/PC)
= 0.125*[(83.14*506.6)/47.50]
= 110.8387474 cm3/mole

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A=aP/ (R2T2)

= (15755804.81*0.8766929015)/ [(83.14)2(325.95)2]

= 0.01880901579

B= bP/ (RT)
= (110.8387474 *0.8766929015)/ (83.14*325.95)
= 0.0035857342

(1+B)= 1+0.0035857342
= 1. 0035857342
AB= 0.01880901579*0.0035857342
= 0.00006744413

𝒁𝟑 − 𝟏. 𝟎𝟎𝟑𝟓𝟖𝟓𝟕𝟑𝟒𝟐 𝒁𝟐 + 𝟎. 𝟎𝟏𝟖𝟖𝟎𝟗𝟎𝟏𝟓𝟕𝟗 𝒁 − 𝟎. 𝟎𝟎𝟎𝟎𝟔𝟕𝟒𝟒𝟒𝟏𝟑 = 𝟎

NB: Equation is solved using a solver since the calculator fails saying insufficient memory.

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 Therefore Z1= 0.00407 and Z3= 0.98454
Z2 is discarded. The smaller root correspond to saturated liquid and the larger root correspond to
vapor.
Vsatliquid= Z1 RT/P
= (0.00407*83.14*325.95)/0.8766929015

= 125.8079 cm3/mole

Vsatvapor=Z3RT/P
= (0.98454*83.14*325.95)/0.8766929015
= 30433.1482 cm3/mole

4|Page
(C)
Racket Equation
Given data
Tc= 506.6 K
T= 325.95 K
Zc= 0.257
Vc= 228 cm3/mole
𝑇
𝑇𝑟 =
𝑇𝑐
= 325.95/506.6
= 0.6434070272
Pr=P/Pc
= 0.8766929015/47.50
= 0.01845669266

0.2857
𝑉 = 𝑉𝑐(𝑍𝑐)(1−𝑇𝑟)
= 228*(0.257) ^ (1-0.6434070272) ^0.2857
= 82.8775 cm3/mole

5|Page
 Pitzer Correlation

0.172
𝐵1 = 0.139 −
(𝑇𝑟)4.2
= 0.139- (0.172/ (0.6434070272)4.2)
= - 0.9571956828

0.422
𝐵 0 = 0.083 − (𝑇𝑟)1.6

= 0.083-(0.422/(0.6434070272)1.6)
= -0.7715454598
Pr=P/Pc
= 0.8766929015/47.50
= 0.01845669266

𝑃𝑟
𝑍 0 = 1 + 𝐵 0 ∗ 𝑇𝑟

= 1+ (-0.7715454598)*(0.01845669266/0.6434070272)
= 0.9778675445

𝑃𝑟
𝑍1 = 1 + 𝐵1 ∗ 𝑇𝑟

= 1+ (- 0.9571956828)*(0.01845669266/0.6434070272)
= 0.9725420056
𝑍 = 𝑍 0 + ϣ𝑍1
= 0.9778675445+ (0.9725420056*0.331)
= 1.299778948

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 𝑍𝑅𝑇
𝑉= 𝑃

= (1.299778948*83.14*325.95)/ 0.8766929015
= 40177.5096 cm3/mole

Comparison
Saturated liquid molar volume
% difference= [(125.8079-82.8775)125.8079]*100%
= 34.12 %
Therefore the difference between the saturated molar volume from Van der Waals EoS and Racket
equation is 34.12 %.
Saturated vapor molar volume

% difference= [(40177.5096-30433.1482)/ 40177.5096]*100%

= 24.25%
Therefore the difference between the saturated vapor molar volume from Van der Waals EoS and Pitzer
correlation is 24.25%

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QUESTION 2

COMPONET MOLAR ϣ Tc/ (K) Pc/bar R

MASS(g/mole) (bar.cm3/(mol.K)
Propane 44.097 0.152 369.8 42.48 83.14
n-Butane 58.123 0.200 425.1 37.96 83.14

Mass n-butane
M= 50+ (7*0.3) = 52.1 kg
Mass propane
M = 30+ (0.15*0) =30 kg
Moles n-butane
n=m/MW= (52.1*103/58.123)= 896.374929 moles
Moles propane
n=m/MW= (30*103/44.097)=680.318389 moles
Total number of moles
NT= 896.374929 moles+680.318389 moles= 1576.693318 moles
Mole fraction n-butane
Xi= moles n-butane/total moles
= 896.374929/1576.693318
= 0.568515715
Mole fraction propane
Xj= moles propane/ total moles
= 680.318389/1576.693318
= 0.431484285
n-Butane
Tr= T/Tc=450/425.1
= 1.058574453

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Propane
Tr= T/Tc= 450/369.8
= 1.216873986

n-Butane
𝑎𝑖 = 0.45724((𝑅 2 (𝑇𝑐)2 )/𝑃𝑐)[1 + (0.37464 + 1.54226 ϣ − 0.26992ϣ2 )(1 − (𝑇𝑟)0.5 ]2
= (0.457424*(((83.14)2 (425.1)2)/37.96)[1+ (0.37464 + 1.54226*(0.200)-
0.26992*(0.200)2(1-(1.058574453)0.5]2
= 14467571.66 bar. cm6.mol-2

Propane

𝑎𝑗 = 0.45724(𝑅 2 (𝑇𝑐)2 )/𝑃𝑐[1 + (0.37464 + 1.54226 ϣ − 0.26992ϣ2 ) + (1 − (𝑇𝑟)0.5 ]2

= (0.457424*((83.14)2 (396.8)2)/42.48[1+ (0.37464 + 1.5226*(0.152)-
0.26992*(0.152)2(1-(1.216873986)0.5]2
= 8948860.01 bar. cm6.mol-2

Volume= 2+ (6*0.5) = 5m3

5 m3 (100)3cm3
1m3
= 5 000 000 cm3
Molar volume
V= Vt/NT
= 5 000 000 cm3 /1576.693318
= 3171.193753 cm3 /mole

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n-Butane

𝑅𝑇𝑐
𝑏𝑖 = 0.07780 ∗
𝑃𝑐
= 0.07780 *(83.14*425.1)/37.96
= 72.43600973 cm3 /mole
Propane
𝑅𝑇𝑐
𝑏𝑗 = 0.07780 ∗
𝑃𝑐
= 0.07780*(83.14*369.8)/42.48
= 56.30824815 cm3 /mole

bmix= xi bi + xj bj
= (0.568515715*72.43600973) + (0.431484285*56.30824815)
= 41.18100986 + 24.2961249
=65.47713405 cm3 /mole
𝑅𝑇
𝑎𝑚𝑖𝑥 = [𝑉 2 + 2𝑏𝑚𝑖𝑥𝑉 − 𝑏 2 𝑚𝑖𝑥] [ − 𝑃]
𝑉 − 𝑏𝑚𝑖𝑥
= [(3171.193753)2 +2(65.47713405 *3171.193753)-(65.47713405)2][((83.14*450)/
(3171.193753-65.47713405))-30]
= 10467463.92*(-17.95350491)
= -187927664.90 bar. cm6.mol-2

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amix= x2iai +2 xi xj aij + x2jaj
amix= (0.568515715)2(14467571.66) +2(0.568515715*0.431484285) aij +
(0.431484285)2(8948860.01)
amix= 4676065.546+1666087.018+0.4906111936 aij
amix = 6342152.564+0.4906111936 aij
aij = (-187927664.90-6342152.564)/ 0.4906111936
= -395975102.1 bar. cm6.mol-2

𝑎𝑖𝑗 = (𝑎𝑖𝑎𝑗) 0.5 (1 – 𝑘𝑖𝑗)

= (14467571.66*8948860.01)0.5 (1 – 𝑘𝑖𝑗)
𝑎𝑖𝑗 = 11378412.61(1 – 𝑘𝑖𝑗)

(1 – 𝑘𝑖𝑗)= -395975102.1 /11378412.61

1 – 𝑘𝑖𝑗 = -34.80055748
𝑘𝑖𝑗= 35.8006

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