University Of Karachi

DESIGN AND SIMULATION
(Assignment 4)

Syed Saad Ahmed
Roll no: 37
Seat no.: B-0933040
Enrolment no.: Sci/cht/ku29754/2009
B.E 4th Year
Chemical Engineering

Submitted To:
Sir Zeeshan Zaki
Sir Owais Iqbal

2

DESIGN AND SIMULATION

Assignment #4
UNIQUAC Portion
Q: Calculate the activity coefficients of a mixture of 40 mol% Ethanol 60 mol% Ethane at 2 barg
and 62°C.

Solution:
Activity Coefficient

Combinatorial Activity Coefficient
Estimation for a known component


ETHANE
= 2 x CH3 Groups
So its calculated values are
– ri value from table = 2 x 0.9011 = 1.8022
– qi value from table = 2 x 0.848 = 1.696

ETHANOL
= 1 x CH3 + 1 x CH2 +1 x OH Groups

So its calculated values are
– ri value from table = 1 x 0.9011 + 1 x 0.6744 + 1 x 1.0 = 2.5755
– qi value from table = 1 x 0.848 + 1 x 0.540 + 1 x 1.2 = 2.588

Prepared By: SYED SAAD AHMED (B.E Final Year)

3

DESIGN AND SIMULATION

ETHANE
(

)

(

)

ETHANOL
(

)

Components

qi

(

ri

)

xi

xi q i

xi ri
li

Ethane

1.6958

1.8020

0.6

1.0175

1.0812

0.5120

0.4956

-0.271

Ethanol

2.588

2.5755

0.4

1.0352

1.0302

0.4879

0.5043

-1.638

2.0527

2.1114

Sum

Combination activity coefficient (ln

c

)

ETHANE
(

)

Prepared By: SYED SAAD AHMED (B.E Final Year)

(

)

(

)

(

)

(

)

4

DESIGN AND SIMULATION

ETHANOL
(

Component
s
Ethane
Ethanol

)

(

Q

R

1.695
8
2.588

1.8020
2.5755

l

(

)

)

(

x

-0.271

0.6

0.5120

0.4956

-1.638

0.4

0.4879

0.5043

Sum

Residual activity coefficient (ln

(

)

xj lj

ln C

0.1626
0.6552
0.8178

0.007787
0.014034

)

Structure and group details

Compound

Ethane
Ethanol

c

)

Mol.
Frac.

Group

0.6
0.4

CH3
CH3
CH2
OH

Mai
n
No.
1
1
1
5

Sec
No.

1
1
2
14

Quantit
y ni

Total

2
1
1
1

2
3

Group Values
R

Q

0.9011
0.9011
0.6744
1.000

0.848
0.848
0.540
1.200

Group Fractions
Pure Component

Copmound
Ethane
Ethanol

XCH3
2/2=1
= 1/3

XCH2
0/2=0
= 1/3

Mixture
XOH
0/2=0
= 1/3

Mixture XCH3
= [(0.6 x 2) + (0.4 x 1)]/ [(0.6 x2) + (0.4 x 3)]
= 0.6667
Mixture XCH2
= [(0.6 x 0) + (0.4 x 1)]/ [(0.6 x2) + (0.4 x 3)]
= 0.16667
Prepared By: SYED SAAD AHMED (B.E Final Year)

XCH3

XCH2

XOH

0.6667

0.16667

0.16667

5

DESIGN AND SIMULATION

Mixture XOH
= [(0.6 x 0) + (0.4 x 1)]/ [(0.6 x2) + (0.4 x 3)]
= 0.16667

Group Interaction Parameters

The group interaction parameter “a”
amn
M
1
1
5

n
CH3
CH2
OH

1
CH2
0
0
156.4

5
OH
986.5
986.5
0

Now using a temperature of 311.15K we get

mn

CH3
CH2
OH

1
CH3
0
0
156.4

CH3
1
1
0.605

CH2
1
1
0.605

OH
0.042
0.042
1

Segment Fractions
Pure Component

Copmound (i)

m

qm

Xm

Ethane (1)

CH3

0.848

1

Sum
Ethanol (2)

qm x Xm

(i)

0.848

1

0.848

1

m

CH3

0.848

0.333

0.2824

0.3277

CH2

0.540

0.333

0.1798

0.2086

OH

1.200

0.333

0.3996

0.4637

0.8618

1

Sum

Prepared By: SYED SAAD AHMED (B.E Final Year)

6

DESIGN AND SIMULATION

Mixture
Solution of
Groups

m

qm

Xm

qm x Xm

CH3

0.848

0.6667

0.56536

0.66096

CH2

0.540

0.16667

0.0900

0.10522

OH

1.200

0.16667

0.2000

0.23382

0.85536

1

Sum
m

m

{Ethane)
m

(Ethanol)
m

CH3

1

0.3277

0.66096

CH2

0

0.2086

0.10522

OH

0

0.4637

0.23382

ETHANE
m

ln 

m

ETHANE
CH 3

{Ethane)
m

CH3

1

CH2

0

OH

0

1  ln 1  1  0  1  0  0.605 



 0.848

1  1


0  1
0  0.042
 1  1  0  1  0  0.605  1  1  0  1  0  0.605  1  0.042  0  0.042  0  1 



 0.848 1  ln 1  1

0
There is no CH2 and OH in pure ethane so we can ignore it.

Prepared By: SYED SAAD AHMED (B.E Final Year)

7

DESIGN AND SIMULATION

ETHANOL
m

ETHANOL
ln CH
3

(Ethanol)
m

CH3

0.3277

CH2

0.2086

OH

0.4637

1  ln 0.3277  1  0.2086  1  0.4637  0.605 



0.3277  1
0.2086  1





 0.848 0.3277  1  0.2086  1  0.4637  0.605 0.3277  1  0.2086  1  0.4637  0.605  



0.46370.042


 
 0.3277  0.042  0.2086  0.042  0.4637  1


= 0.848 x (1-ln (0.8168) -0.6967) = 0.4288

ETHANOL
ln CH
2

1  ln 0.3277  1  0.2086  1  0.4637  0.605 



0.3277  1

0.2086  1



 
 0.540 0.3277  1  0.2086  1  0.4637  0.605 0.3277  1  0.2086  1  0.4637  0.605  




0.46370.042


 
 0.3277  0.042  0.2086  0.042  0.4637  1


= 0.540 x (1-ln (0.8168) - 0.6967) = 0.273

ETHANOL
ln OH

1  ln 0.3277  1  0.2086  1  0.4637  0.605 



0.3277  1
0.2086  1







 1.2 0.3277  1  0.2086  1  0.4637  0.605 0.3277  1  0.2086  1  0.4637  0.605  



0.46370.042





 0.3277  0.042  0.2086  0.042  0.4637  1

= 1.2 x (1-ln (0.8168) - 0.6967) = 0.5056

Prepared By: SYED SAAD AHMED (B.E Final Year)

8

DESIGN AND SIMULATION

MIXTURE
m

MIXTURE
ln CH
3

m

CH3

0.66096

CH2

0.10522

OH

0.23382

1  ln 0.66096  1  0.10522  1  0.23382  0.605 



0.66096  1

 
 0.66096  1  0.10522  1  0.23382  0.605



 0.848

0.10522  1
 0.66096  1  0.10522  1  0.23382  0.605   



0.23382  0.042

 0.66096  0.042  0.10522  0.042  0.23382  1  



=0.848*(1-ln(0.9076)-0.881064)
=0.183072

MIXTURE
ln CH
2

1  ln 0.66096  1  0.10522  1  0.23382  0.605  



0.66096  1

 
 0.66096  1  0.10522  1  0.23382  0.605



 0.540

0.10522  1
 0.66096  1  0.10522  1  0.23382  0.605   






0
.
23382

0
.
042

 0.66096  0.042  0.10522  0.042  0.23382  1  



=0.540*(1-ln(0.9076)-0.881064)
=0.11657

MIXTURE
ln OH

1  ln 0.66096  1  0.10522  1  0.23382  0.605 



0.66096  1

 
 0.66096  1  0.10522  1  0.23382  0.605



 1.2

0.10522  1
 0.66096  1  0.10522  1  0.23382  0.605   



0.23382  0.042

 0.66096  0.042  0.10522  0.042  0.23382  1  



Prepared By: SYED SAAD AHMED (B.E Final Year)

9

DESIGN AND SIMULATION

=1.2*(1-ln (0.9076)-0.881064)
=0.25906

Group

Mixture

Ethane (1)

k

k

ni

 k(1)

ni(  k- 
(1)
k )

ni

 k(1)

ni(  k-  k(1))

CH3

1.2009

2

1

0.4018

1

1.5354

-0.3345

CH2

1.1236

0

0

0

1

1.3139

-0.1903

OH

1.2957

0

0

0

1

1.6579

-0.3622

Sum

Ethanol (2)

0.4018

-0.887

Adding the combinatorial and the residual values:
Compound

ln

R

ln

C

ln

Ethane

0.4018

-0.007787

0.394013

1.4829

Ethanol

-0.887

-0.014034

-0.901034

0.40614

Prepared By: SYED SAAD AHMED (B.E Final Year)

10

DESIGN AND SIMULATION

Flash Calculations
Operating Data
Compounds= Ethane, Ethanol

62°C
2 barg

Temperature
Pressure

335K
3.01325 bara

Step I: ( To find the vapour pressure)
Using Antoine Equation:

Antoine
Ethane
Ethanol

A
3.954
5.336

B
663.720
1648.220

C
256.681
230.918

These values are taken from “Properties of Gases and Liquids” Appendix A, Sec. D Page A.49

For Ethane

For Ethanol

Prepared By: SYED SAAD AHMED (B.E Final Year)

11

DESIGN AND SIMULATION

Step II(To find the volume)
Since, as we know that,

yi  i Pi SAT
Ki  
xi
i P

For Ethane:

(

)(
( )(

)
)

For Ethanol:
(

)(
( )(

Compound
Ethane
Ethanol

)
)

γi
1.4829
0.40614

Pisat
3.954
0.509

Ki
1.946
0.0686

Step III (For the value of Volume):

yi 
Since

zi  K i
1  V K i  1

Therefore:

zi  Ki
1
i  1

 1  V K
i

(

)(
(

(

)
)

)(
(

)
)

VLE Composition of the Mixture
Compound
Ethane
Ethanol

Yi
0.965
0.034

Prepared By: SYED SAAD AHMED (B.E Final Year)

Xi
0.496
0.504

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