UNIVERSITI MALAYSIA PERLIS

Pusat Pengajian Kejuruteraan Bioproses

ERT 206: Thermodynamics

Assignment -Solutions

1) Estimate the fugacity of isobutylene as a gas at 280 C and 20 bar

Tc = 417.9 K
Pc = 40 bar
= 0.194

Thus,
Tr = T/Tc (since T= TcTr)
= (280+273.15) K/ 417.9 K =1.32364
Pr = P/Pc (since P= PcPr)
= 20 bar / 40 bar = 0.5

For pure gas, using Generalized correlation for fugacity coefficient;

ln i =
Tr
(
Pr
B + B 1 )
0.422
B 0 = 0.083
Tr1.6
0.422
= 0.083
1.323641.6
= 0.18645
0.172
B1 = 0.139
Tr4.2
0.172
= 0.139
1.32364 4.2
= 0.086022

Therefore:
P
(
ln i = r B + B 1
Tr
)
0 .5
= [ 0.18645 + (0.194)(0.086022 )]
1.32364
= 0.06413
i = 0.937886
Fugacity of isobutylene at 280 C and 20 bar is:
f i = i P
= 0.937886(20bar )
= 18.76bar

OR

Fugacity of pure gas can be also estimated using the following equation:

i = 0 ( 1 )

0 and 1 can be obtained in Lee/Kesler Generalized-correlation Table (Appendix E).

By interpolation, find 0 and 1 at Pr = 0.5 and Tr = 1.32364.

Calculation for 1 :

At Tr =1.3
0.6 0.5 1.0399 1
=
0.6 0.4 1.0399 1.0257

1 = 1.0328

At Tr =1.4
0.6 0.5 1.0471 1
=
0.6 0.4 1.0471 1.0304

1 = 1.03875

At Tr =1.32364
1.4 1.32364 1.03875 1
=
1.4 1.3 1.03875 1.0328

1 = 1.0342

Calculation for 0 :
At Tr =1.3
0.6 0.5 0.9141 0
=
0.6 0.4 0.9141 0.9419

0 = 0.928
At Tr =1.4

0.6 0.5 0.9333 0

=
0.6 0.4 0.9333 0.955

0 = 0.94415

At Tr =1.32364
1.4 1.32364 0.94415 0
=
1.4 1.3 0.94415 0.928

0 = 0.931818

i = 0 ( 1 ) = (0.931818)(1.0342 )0.194 = 0.9379

2) For the system ethylene(1)/propylene(2) as a gas, estimate f1 , f2 , 1 and 2 at T =
150C, P = 30 bar, and y1 = 0.35.

Step 1: From Table B1, the data for ethylene and propylene are extracted as follows:

For ethylene,
Pc11 = 50.4 bar
Tc11 = 282.3 K
Vc = 131 cm3/mol
11

Zc11 = 0.281
11 = 0.087

For propylene,
Pc22 = 46.65 bar
Tc22 = 365.6 K
Vc22 = 188.4 cm3/mol
Zc22 = 0.289
22 = 0.140

Step 2: Find Pc12, Tc12, Vc , Zc and 12 using the following equations:

12 12

Vci1/ 3 + Vcj1/ 3
3
ci + cj Zci + Zcj
Vcij = cij = Zcij =
2 2 2

Tcij = (TciTcj ) (1 k )
1/ 2 Zcij RTcij
ij Pcij =
Vcij

For chemically similar species, kij=0

ij Tcij /K Pcij/bar Vcij/cm3mol- Zcij ij

1

11 282.3 50.4 131 0.281 0.087

22 365.6 46.65 188.4 0.289 0.140
12 321.26 48.19 157.966 0.285 0.1135

Step 3: Find Tr12, B0, B1, Bij and Bij using the following equations:
T 0.422 0.172 B RT
Trij = B 0 = 0.083 B1 = 0.139 B ij = B 0 + ij B1 Bij = ij cij
Tcij Tr1ij.6 Trij4.2 Pcij
 ij Trij /K B0 B1 Bij Bij /cm3mol-1

11 1.499 -0.137816 0.107583 -0.128456 -59.819

22 1.1574 -0.25099 0.045911 -0.24456 -159.349
12 1.31715 -0.188579 0.084917 -0.178941 -99.181

Step 4: Find 12 ,,1 ,,2 using the following equations:

12 = 2 B12 B11 B22 ln 1 =

P
RT
(
B11 + y 22 12 ) ln 2 =
P
(
B22 + y12 12 )
RT

12 = 2( 99.181) ( 59.819) ( 159.349)

= 20.806

ln 1 =
30bar
83.14 cm bar molK (150 + 273.15 K )
3 1
[
59.819 + (0.65) (20.806 )
2
]
= 0.043514
1 = 0.9574

ln 2 =
30bar
83.14 cm bar molK (150 + 273.15 K )
3 1
[
159.349 + (0.35) (20.806 )
2
]
= 0.1337
2 = 0.8748

Step 5: Find f1 and f2

f
For gas mixture, i = i
yi P
Thus,

fi = y ii P

f1 = y11 P
= 0.35(0.9574)(30bar )
= 10.053bar

f2 = y 22 P
= 0.65(0.8748)(30bar )
= 17.059bar
 3) Estimate 1 & 2 for an equimolar mixture of methyl ethyl ketone (1)/toluene(2) at
50C and 25kPa. Set all kij=0

ij Tcij /K Pcij/bar Vcij/cm3mol-1 Zcij ij

11 535.5 41.5 267 0.249 0.323

22 591.8 41.1 316 0.264 0.262

STEP 1: Find Tcij, Vcij, Zcij, Pcij and cij

3
V 1 / 3 + Vc112/ 3
Tc12 = (T11T22 ) (1 k12 ) = c11
1/ 2
Vc12
2
= (535.5 591.8) (1 0)
1/ 2
3
2671 / 3 + 3161 / 3
= 563K =
2
Z c11 + Z c12 = 291cm 3 mol 1
Z c12 =
2
0.249 + 0.264
= = 0.264
2

Z c12 RTc12
Pc12 =
Vc12

=
(
0.256 83.14cm 3 bar / mol K (563K ) )
291cm 3 mol 1
= 41.3bar
c11 + c12
c12 =
2
0.323 + 0.262
= = 0.293
2

STEP 2: Find Trii and Trij

T T T
Tr11 = Tr 22 = Tr12 =
Tc11 Tc 22 Tc12

50 + 273.15 50 + 273.15 50 + 273.15

Tr11 = Tr 22 = Tr12 =
535.5 591.8 563.0
= 0.603 = 0.546 = 0.574

STEP 3: Find B 0 and B 1

0.422 0.422 0.422
B110 = 0.083 1.6
0
B22 = 0.083 1 .6
B120 = 0.083 1 .6
Tr11 Tr 22 Tr12
0.422 0.422 0.422
= 0.083 = 0.083 = 0.083
0.6031.6 0.5461.6 0.5741.6
= 0.865 = 1.028 = 0.943
 0.172 0.172 0.172
B 111 = 0.139 4.2
B 122 = 0.139 4.2
B 112 = 0.139 4 .2
Tr11 Tr 22 Tr12
0.172 0.172 0.172
= 0.139 = 0.139 = 0.139
0.603 4.2 0.546 4.2 0.574 4.2
= 1.3 = 2.045 = 1.632

STEP 4: Calculate Bii , Bij , Bii and Bij

B11 = B110 + 11 B111

= 0.865 + 0.323( 1.3) = 1.2849

B11 RTc11
B11 =
Pc11

=
( )
1.2849 83.14cm 3 bar / mol K (535.5K )
= 1378cm 3 / mol
41.5bar

B 22 = B22
0
+ 22 B22
1

= 1.028 + 0.262( 2.045)

= 1.56379

B 22 RTc 22
B22 =
Pc 22

=
( )
1.56379 83.14cm 3 bar / mol K (591.8K )
= 1872cm 3 / mol
41.1bar

B12 = B120 + 12 B12

1

= 0.943 + 0.293( 1.632)

= 1.421176

B12 RTc12
B12 =
Pc12

=
(
1.421176 83.14cm 3bar / mol K (563K ) )
41.3bar

= 1611cm 3 / mol
STEP 5: Calculate 1 and 2

12 = 2 B12 B11 B22

= 2( 1611) + 1378 + 1872 = 28cm 3 mol 1

ln 1 =
P
(
B11 + y2212 ) =
25
8314(323.15)
[ 2
]
1378 + (0.5) (28) = 0.0128
RT

1 = 0.987

ln 2 =
P
RT
(
B22 + y1212 ) =
25
8314(323.15)
[
1872 + (0.5) (28)
2
] = 0.0173

2 = 0.983
4) A system formed initially of 2 mol CO2, 5 mol H2, and 1 mol CO undergoes the
reactions:
CO2 ( g ) + 3H 2 ( g ) CH 3OH ( g ) + H 2 O( g )

CO2 ( g ) + H 2 ( g ) CO( g ) + H 2 O( g )

Develop expressions for the mole fractions of the reacting species as functions of the
reaction coordinates for the two reactions.

Step 1: List down the stoichiometric number of each species and find the total
stoichiometic number for both reactions:

i CO2 H2 CH3OH H2 O CO
j vj
1 -1 -3 1 1 0 -2
2 -1 -1 0 1 1 0

Step 2: Find the total no of moles initially present;

n0 = 2 + 5 + 1 = 8

Step 3: Express the composition of each species in terms of reaction coordinate

according to the following equation:
ni0 + j vi , j j
yi =
n0 + j v j j

2 1 2 5 3 1 2 1
yCO2 = yH2 = yCH 3OH =
8 2 1 8 2 1 8 2 1

1 2 1+ 2
y H 2O = y CO =
8 2 1 8 2 1