CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)

Tutorial 01-Solutions

Discussion Question 1

A vapour compression refrigeration system operates on the cycle shown in lecture notes.
The refrigerant is water. Given that the evaporation is at 277.15K and condensation is at
307.15K. The refrigeration rate is 1200 kW, while the compressor efficiency is 76%.
Determine the circulation rate of refrigerant, the coefficient of performance of the cycle,
and the coefficient of performance of a Carnot refrigeration cycle operating between the
same temperature levels.

Comment on the effect of lower evaporator temperatures on the cost of refrigeration.

Solution:

4 Condensation
Compression
Throttling

1 Evaporation 2

Information given (Using the notations in lecture notes):

𝑇𝑇𝑐𝑐 (Evaporator) = 277.15 𝐾𝐾
𝑇𝑇ℎ (condenser) = 307.15 𝐾𝐾
𝑄𝑄𝑐𝑐 = 1200 𝑘𝑘𝑘𝑘
We are asked to find out
(1) Circulation rate of refrigerant 𝑚𝑚̇𝑟𝑟𝑟𝑟𝑟𝑟 :
|𝑄𝑄𝑐𝑐 |
𝑚𝑚̇𝑟𝑟𝑟𝑟𝑟𝑟 =
𝐻𝐻2 − 𝐻𝐻1
(2) COP of refrigeration cycle:
|𝑄𝑄𝑐𝑐 | 𝐻𝐻2 − 𝐻𝐻1
𝐶𝐶𝐶𝐶𝑃𝑃𝑅𝑅𝑅𝑅𝑅𝑅 = =
𝑊𝑊 𝐻𝐻3 − 𝐻𝐻2
Let us first find out the enthalpy values at various states in the refrigeration cycle.
We know the following conditions,

𝑇𝑇2 (Evaporator) = 277.15 𝐾𝐾; 𝑃𝑃2 = 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠@277.15𝐾𝐾 = 0.813 𝑘𝑘𝑘𝑘𝑘𝑘

𝐻𝐻2 = 𝐻𝐻𝑠𝑠𝑠𝑠𝑠𝑠,𝑣𝑣𝑣𝑣𝑣𝑣 @277.15 𝐾𝐾 = 2508.9 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
𝑆𝑆2 = 𝑆𝑆𝑠𝑠𝑠𝑠𝑡𝑡,𝑣𝑣𝑣𝑣𝑣𝑣 @277.15 𝐾𝐾 = 9.0526 𝑘𝑘𝑘𝑘/(𝑘𝑘𝑘𝑘 ∙ 𝐾𝐾)
We also know that,
AY2019-20 | Sem-2 Tutorial 01-Solutions
 𝐻𝐻1 = 𝐻𝐻4
Using the temperature in the condenser, we can find the enthalpy at state “4”
𝑇𝑇4 (Condenser) = 307.15 𝐾𝐾; 𝑃𝑃4 = 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠@307.15 𝐾𝐾 = 5.318 𝑘𝑘𝑘𝑘𝑘𝑘
𝐻𝐻4 = 𝐻𝐻𝑠𝑠𝑠𝑠𝑠𝑠,𝑙𝑙𝑙𝑙𝑙𝑙 @307.15 𝐾𝐾 = 142.4 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘 = 𝐻𝐻1
In order to find the enthalpy, 𝐻𝐻3 , we first assume isentropic compression and find the
enthalpy at the exit of compression for isentropic process (𝐻𝐻3′ ), then using the compressor
efficiency we can find the enthalpy, 𝐻𝐻3 .
We assume,
𝑆𝑆2 = 𝑆𝑆3′ = 9.0526 𝑘𝑘𝑘𝑘/(𝑘𝑘𝑘𝑘 ∙ 𝐾𝐾)
We know that the expected pressure at the exit of compressor is 𝑃𝑃4 = 𝑃𝑃3 = 𝑃𝑃3′ =
𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠@307.15 𝐾𝐾 = 5.318 𝑘𝑘𝑘𝑘𝑘𝑘.
See the following method to find the value of 𝐻𝐻3′
First let us find the superheated steam condition that corresponds to 𝑃𝑃4 = 𝑃𝑃3 = 𝑃𝑃3′ =
5.318 𝑘𝑘𝑘𝑘𝑘𝑘 and 𝑆𝑆3′ = 9.0526 𝑘𝑘𝑘𝑘/(𝑘𝑘𝑘𝑘 ∙ 𝐾𝐾).
Considering steam nearly an ideal gas (low pressure), hence, entropy is linear in
logarithmic pressure. Doing linear interpolation of entropy with ln(𝑃𝑃), while entropy can
be interpolated linearly with temperature. We get a temperature of superheated steam to
be 439.446 K. (Watch the uploaded video for more details on interpolation)
The doing a linear interpolation of enthalpy with pressure and temperature, we get
𝐻𝐻3′ = 2814.73 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
Now using,
𝐻𝐻 ′ −𝐻𝐻 (2814.73−2508.9)
𝜂𝜂𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝐻𝐻3 −𝐻𝐻2 = 0.76 = (𝐻𝐻3 −𝐻𝐻2 )
3 2

We get,
𝐻𝐻3 − 𝐻𝐻2 = 402.37 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘
Let us now calculate the values we are interested in,
(1) Circulation rate of refrigerant 𝑚𝑚̇𝑟𝑟𝑟𝑟𝑟𝑟 :
|𝑄𝑄𝑐𝑐 |
𝑚𝑚̇𝑟𝑟𝑟𝑟𝑟𝑟 =
𝐻𝐻2 − 𝐻𝐻1

|𝑄𝑄𝑐𝑐 | 1200 𝑘𝑘𝑘𝑘

𝑚𝑚̇𝑟𝑟𝑟𝑟𝑟𝑟 = = = 0.507
𝐻𝐻2 − 𝐻𝐻1 (2508.9 − 142.4) 𝑠𝑠
(2) COP of refrigeration cycle:
|𝑄𝑄𝑐𝑐 | 𝐻𝐻2 − 𝐻𝐻1 (2508.9 − 142.4)
𝐶𝐶𝐶𝐶𝑃𝑃𝑅𝑅𝑅𝑅𝑅𝑅 = = = = 5.882
𝑊𝑊 𝐻𝐻3 − 𝐻𝐻2 402.37

AY2019-20 | Sem-2 Tutorial 01-Solutions

(3) Carnot refrigeration cycle operating between the same temperature levels:
277.15
𝐶𝐶𝐶𝐶𝐶𝐶 = = 9.24
307.15 − 277.15

Comment on the effect of lower evaporator temperatures on the cost of refrigeration

𝑄𝑄𝐶𝐶 𝑇𝑇𝑐𝑐
𝐶𝐶𝐶𝐶𝐶𝐶 = =
𝑊𝑊 𝑇𝑇ℎ − 𝑇𝑇𝑐𝑐
Re-writing,
𝑇𝑇ℎ − 𝑇𝑇𝑐𝑐
𝑊𝑊 = 𝑄𝑄𝐶𝐶
𝑇𝑇𝑐𝑐
As the evaporator temperature is lowered, the compressor work required for same cooling
duty increases sharply, hence, the refrigeration cost will increase sharply. A simple
analysis is shown below

𝑇𝑇ℎ 𝑇𝑇𝑐𝑐 𝑄𝑄𝐶𝐶 𝐶𝐶𝐶𝐶𝑃𝑃𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑊𝑊

307.15 277.15 1200 9.24 129.89
307.15 267.15 1200 6.68 179.67
307.15 257.15 1200 5.14 233.33
307.15 247.15 1200 4.12 291.32
307.15 237.15 1200 3.39 354.21
307.15 227.15 1200 2.84 422.63

Discussion Question 2

Estimate the fugacity of ethane at 122.2K and 5 bar using the truncated virial EOS.
For Ethane, Tc = 305.4 K; Pc = 48.84 bar; ω = 0.099
Solution:
This question was just to practice use of truncated virial EOS.
From lecture notes,
𝑃𝑃𝑟𝑟
ln 𝜙𝜙𝑖𝑖 = ln(𝑓𝑓/𝑃𝑃) = 𝐵𝐵�
𝑇𝑇𝑟𝑟
𝑃𝑃 5
𝑃𝑃𝑟𝑟 = = = 0.124
𝑃𝑃𝑐𝑐 48.84
𝑇𝑇 122.2
𝑇𝑇𝑟𝑟 = = = 0.4
𝑇𝑇𝑐𝑐 305.4
𝐵𝐵� = B0 + 𝜔𝜔𝐵𝐵1

AY2019-20 | Sem-2 Tutorial 01-Solutions

 0.422
B0 = 0.083 − = −1.7452
Tr1.6
0.172
B1 = 0.139 − = −7.9311
Tr4.2
Substituting all the numbers we get,
𝑃𝑃𝑟𝑟
ln 𝜙𝜙𝑖𝑖 = ln(𝑓𝑓/𝑃𝑃) = 𝐵𝐵� = −0.6476
𝑇𝑇𝑟𝑟
Substituting pressure value, we get.
𝑓𝑓 = 2.62 𝑏𝑏𝑏𝑏𝑏𝑏
Discussion Question 3

The vapour phase of a pure substance is described by the equation of state:

𝑅𝑅𝑅𝑅 𝑚𝑚3
𝑉𝑉 = + 𝑎𝑎𝑎𝑎𝑃𝑃2 𝑎𝑎 = 0.3 × 10 −16
𝑃𝑃 𝑚𝑚𝑚𝑚𝑚𝑚 𝑃𝑃𝑎𝑎2 𝐾𝐾

The compound has vapour pressure of 50 kPa and 500 kPa at 323 𝐾𝐾 and 373 𝐾𝐾
respectively. Saturated liquid has molar volume of 1.25×10−4 𝑚𝑚3/mol. Estimate the fugacity
of species A at the following conditions.

(a) T = 323 K and P = 10 kPa

(b) T = 323 K and P = 10 MPa
(c) T = 373 K and P = 300 kPa

Solution:
For each combination of temperature and pressure, we will first decide if the species is in a
vapor phase or a liquid phase and then use appropriate equation to find the fugacity.
(a) T = 323 K and P = 10 kPa
At this temperature the vapour pressure is 50 kPa, hence the species will be in a vapour
phase (as 𝑃𝑃 < 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 ).
Fugacity of pure species in vapour phase can be calculated from the mathematical relation
we discussed in the class,
𝑑𝑑𝑑𝑑
𝑑𝑑 ln(𝜙𝜙𝑖𝑖 ) = 𝑑𝑑 ln(𝑓𝑓/𝑃𝑃) = (𝑍𝑍 − 1) (1)
𝑃𝑃
Where,
𝑃𝑃𝑃𝑃
𝑍𝑍 =
𝑅𝑅𝑅𝑅
And,
𝑅𝑅𝑅𝑅
𝑉𝑉 = + 𝑎𝑎𝑎𝑎𝑃𝑃2
𝑃𝑃
Hence,

AY2019-20 | Sem-2 Tutorial 01-Solutions

 𝑃𝑃𝑃𝑃 𝑃𝑃 𝑅𝑅𝑅𝑅 𝑎𝑎𝑃𝑃3
𝑍𝑍 = = � + 𝑎𝑎𝑎𝑎𝑃𝑃2 � = 1 +
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅 𝑃𝑃 𝑅𝑅
Integrating equation (1) from P=0 to P=P
𝑃𝑃
𝑑𝑑𝑑𝑑
� 𝑑𝑑 ln(𝜙𝜙𝑖𝑖 ) = � 𝑑𝑑 ln(𝑓𝑓𝑖𝑖 /𝑃𝑃) = � (𝑍𝑍 − 1)
0 𝑃𝑃
Or,
𝑣𝑣𝑣𝑣𝑣𝑣 𝑃𝑃 𝑃𝑃 𝑃𝑃
𝑓𝑓𝑖𝑖 𝑎𝑎𝑃𝑃3 𝑑𝑑𝑑𝑑 𝑎𝑎𝑃𝑃3 𝑑𝑑𝑑𝑑 𝑎𝑎𝑃𝑃2
ln � � = � �1 + − 1� =� � � =� � � 𝑑𝑑𝑑𝑑
𝑃𝑃 0 𝑅𝑅 𝑃𝑃 0 𝑅𝑅 𝑃𝑃 0 𝑅𝑅
Hence,
𝑣𝑣𝑣𝑣𝑣𝑣 𝑃𝑃
𝑎𝑎 𝑃𝑃3
𝑓𝑓𝑖𝑖 𝑎𝑎𝑃𝑃3
ln � � = � � =
𝑃𝑃 𝑅𝑅 3 0 3𝑅𝑅

Or,

𝑣𝑣𝑣𝑣𝑣𝑣 𝑎𝑎𝑃𝑃3
𝑓𝑓𝑖𝑖 = 𝑃𝑃 exp � �
3𝑅𝑅
Substituting P = 10 kPa, and the appropriate value of “R’
𝑣𝑣𝑣𝑣𝑣𝑣
�𝑓𝑓𝑖𝑖 �@323𝐾𝐾,10𝑘𝑘𝑘𝑘𝑘𝑘 = 10 𝑘𝑘𝑘𝑘𝑘𝑘

(b) T = 323 K and P = 10 MPa

At this temperature the vapour pressure is 50 kPa, hence the species will be in a liquid
phase (as 𝑃𝑃 > 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 ).
Fugacity of pure species in liquid phase can be calculated from the mathematical relation
we discussed in the class,
𝑉𝑉𝑖𝑖𝐿𝐿
𝑓𝑓𝑖𝑖𝐿𝐿 = 𝑓𝑓𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 exp � (𝑃𝑃 − 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 )�
𝑅𝑅𝑅𝑅
We have found in Part (a) that,

𝑣𝑣𝑣𝑣𝑣𝑣 𝑎𝑎𝑃𝑃3
𝑓𝑓𝑖𝑖 = 𝑃𝑃 exp � �
3𝑅𝑅
𝑣𝑣𝑣𝑣𝑣𝑣
Calculating 𝑓𝑓𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 = 𝑓𝑓𝑖𝑖 @323𝐾𝐾, 50𝑘𝑘𝑘𝑘𝑘𝑘
𝑣𝑣𝑣𝑣𝑣𝑣
�𝑓𝑓𝑖𝑖 �@323𝐾𝐾,50𝑘𝑘𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 = 50 𝑘𝑘𝑘𝑘𝑘𝑘

𝑉𝑉𝑖𝑖𝐿𝐿 is provided to us, hence,

𝑉𝑉𝑖𝑖𝐿𝐿
(𝑓𝑓𝑖𝑖𝐿𝐿 )@ 323𝐾𝐾,10 𝑀𝑀𝑀𝑀𝑀𝑀 = 𝑓𝑓𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 exp � (𝑃𝑃 − 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 )�
𝑅𝑅𝑅𝑅
After substituting the know values,
(𝑓𝑓𝑖𝑖𝐿𝐿 )@ 323𝐾𝐾,10 𝑀𝑀𝑀𝑀𝑀𝑀 = 79.45 𝑘𝑘𝑘𝑘𝑘𝑘

AY2019-20 | Sem-2 Tutorial 01-Solutions

(c) T = 373 K and P = 300 kPa
At this temperature the vapour pressure is 500 kPa, hence the species will be in a vapour
phase (as 𝑃𝑃 < 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 ).
Fugacity of pure species in vapour phase can be calculated from the mathematical relation
that we have developed in part (a),

𝑣𝑣𝑣𝑣𝑣𝑣 𝑎𝑎𝑃𝑃3
𝑓𝑓𝑖𝑖 = 𝑃𝑃 exp � �
3𝑅𝑅
Substituting the value of pressure and R, we get,
𝑣𝑣𝑣𝑣𝑣𝑣
�𝑓𝑓𝑖𝑖 �@373𝐾𝐾,300𝑘𝑘𝑘𝑘𝑘𝑘 = 309.9 𝑘𝑘𝑘𝑘𝑘𝑘

Practice Question 01

Calculate the fugacity coefficient of isobutane gas at 88°C and 10 bar by the following
generalized correlations:

a) 2-parameter compressibility factor method

b) Second virial coefficient

Solution:
a) 2-parameter compressibility factor method
𝑑𝑑𝑑𝑑
𝑑𝑑 ln(𝜙𝜙𝑖𝑖 ) = (𝑍𝑍 − 1) … . (1)
𝑃𝑃
2-parameter compressibility factor,
𝑍𝑍 = 𝑍𝑍(𝑇𝑇𝑟𝑟 , 𝑃𝑃𝑟𝑟 )
Rewriting equation (1) in terms of 𝑃𝑃𝑟𝑟 ,
𝑑𝑑𝑃𝑃𝑟𝑟
𝑑𝑑 ln(𝜙𝜙𝑖𝑖 ) = (𝑍𝑍 − 1)
𝑃𝑃𝑟𝑟
Integrating from 𝑃𝑃𝑟𝑟 = 0 to 𝑃𝑃𝑟𝑟 = 𝑃𝑃𝑟𝑟
𝑃𝑃𝑟𝑟
𝑑𝑑𝑃𝑃𝑟𝑟
ln 𝜙𝜙𝑖𝑖 = � (𝑍𝑍 0 − 1) = ln 𝜙𝜙0
0 𝑃𝑃𝑟𝑟
𝑇𝑇𝑟𝑟 = 0.885; 𝑃𝑃𝑟𝑟 = 0.274
We can find the value of 𝜙𝜙0 for the value of 𝑇𝑇𝑟𝑟 , 𝑃𝑃𝑟𝑟 from Table E.13, we get,
𝜙𝜙0 = 0.8662 = 𝜙𝜙𝑖𝑖
b) Second virial coefficient
𝑃𝑃𝑟𝑟
ln 𝜙𝜙𝑖𝑖 = ln(𝑓𝑓/𝑃𝑃) = 𝐵𝐵�
𝑇𝑇𝑟𝑟
0.422 0.172
𝐵𝐵� = B0 + 𝜔𝜔𝐵𝐵1 ; 𝑤𝑤ℎ𝑒𝑒𝑒𝑒𝑒𝑒, B0 = 0.083 − ; B1 = 0.139 −
Tr1.6 Tr4.2
Try yourself, we get,
𝜙𝜙𝑖𝑖 = 0.868
AY2019-20 | Sem-2 Tutorial 01-Solutions
 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Tutorial 02-Solutions

Discussion Question 1

The molar enthalpy of a binary solution is given by:

𝑉𝑉 (𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚) = 500𝑥𝑥1 + 1000𝑥𝑥2 + 𝑥𝑥1 𝑥𝑥2 (50𝑥𝑥1 + 40𝑥𝑥2 )

Find the expressions/values for (1) partial molar volume of species-1; (2) partial molar
volume of species-1 at infinite dilution.

Solution:
Given:
𝑐𝑐𝑚𝑚3
𝑉𝑉 � � = 500𝑥𝑥1 + 1000𝑥𝑥2 + 𝑥𝑥1 𝑥𝑥2 (50𝑥𝑥1 + 40𝑥𝑥2 ) … (1)
𝑚𝑚𝑚𝑚𝑚𝑚

We have discussed the relation between solution property and the partial molar property
before,
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
�1 − 𝑥𝑥2
𝑀𝑀 = 𝑀𝑀 ⇒ �1 = 𝑀𝑀 + 𝑥𝑥2
𝑀𝑀
𝑑𝑑𝑥𝑥1 𝑑𝑑𝑥𝑥1
Writing for molar volume,
𝑑𝑑𝑑𝑑
𝑉𝑉�1 = 𝑉𝑉 + 𝑥𝑥2 … (2)
𝑑𝑑𝑥𝑥1
Replacing 𝑥𝑥2 with 1 − 𝑥𝑥1 in equation (1), we get,
𝑉𝑉 = 500𝑥𝑥1 + 1000(1 − 𝑥𝑥1 ) + 𝑥𝑥1 (1 − 𝑥𝑥1 )�50𝑥𝑥1 + 40(1 − 𝑥𝑥1 )�
After simplifying, we get,
𝑉𝑉 = 1000 − 460𝑥𝑥1 − 30𝑥𝑥12 − 10𝑥𝑥13
𝑑𝑑𝑑𝑑
Finding, 𝑑𝑑𝑥𝑥
1

𝑑𝑑𝑑𝑑 𝑑𝑑
= (1000 − 460𝑥𝑥1 − 30𝑥𝑥12 − 10𝑥𝑥13 )
𝑑𝑑𝑥𝑥1 𝑑𝑑𝑥𝑥1
𝑑𝑑𝑑𝑑
= −460 − 60𝑥𝑥1 − 30𝑥𝑥12
𝑑𝑑𝑥𝑥1
𝑑𝑑𝑑𝑑
Substituting 𝑉𝑉, 𝑥𝑥2 = 1 − 𝑥𝑥1, and 𝑑𝑑𝑥𝑥 in equation (2), we get
1

𝑑𝑑𝑑𝑑
𝑉𝑉�1 = 𝑉𝑉 + 𝑥𝑥2
𝑑𝑑𝑥𝑥1
𝑉𝑉�1 = (1000 − 460𝑥𝑥1 − 30𝑥𝑥12 − 10𝑥𝑥13 ) + (1 − 𝑥𝑥1 )(−460 − 60𝑥𝑥1 − 30𝑥𝑥12 )
After simplification we get,
𝑉𝑉�1 = 540 − 60𝑥𝑥1 + 20𝑥𝑥13

AY2019-20 | Sem-2 Tutorial 02-Solutions

As we know,
𝐽𝐽
𝑉𝑉�1∞ = lim 𝑉𝑉�1 = 540
𝑥𝑥1 →0 𝑚𝑚𝑚𝑚𝑚𝑚
Discussion Question 2

Property relations for a binary mixture comprising of species-1 and Species-2 at 298.15 𝐾𝐾
and 100 𝑘𝑘Pa is given as:

𝑉𝑉 (𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚) = 41.506 𝑥𝑥12 + 5.62𝑥𝑥1 + 18.102

𝑘𝑘𝑘𝑘
𝐻𝐻 � � = −26800𝑥𝑥12 + 18240𝑥𝑥1 + 1850
𝑚𝑚𝑚𝑚𝑚𝑚

a) Evaluate molar density of pure species-1and 2 at 298.15 𝐾𝐾 and 100 𝑘𝑘Pa.

b) It is recommended to prepare 2 𝐿𝐿 of 65% (mol species-1) solution by mixing pure
species 1 and 2 at 298.15 𝐾𝐾 and 100 𝑘𝑘Pa. Estimate the mass of species-1 and 2
required.
c) Evaluate the volume change of mixing for the process described in (b).
d) Evaluate the enthalpy change of mixing for the process described in (b).

Solution:
a) Evaluate molar density of pure species-1and 2 at 298.15 𝐾𝐾 and 100 𝑘𝑘Pa.
𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 = 𝜌𝜌 = 1/𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
Pure species molar volumes can be found out using the equation provided for molar
volume of a binary mixture.
𝑐𝑐𝑚𝑚3
𝑉𝑉1 = lim 𝑉𝑉 = 41.506 (1)2 + 5.62(1) + 18.102 = 65.23 𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥1 →1

Hence,
1 1 𝑚𝑚𝑚𝑚𝑚𝑚
𝜌𝜌1 = = = 0.0153
𝑉𝑉1 65.23 𝑐𝑐𝑚𝑚3
Similarly,
𝑐𝑐𝑚𝑚3
𝑉𝑉2 = lim 𝑉𝑉 = lim 𝑉𝑉 = 41.506 (0)2 + 5.62(0) + 18.102 = 18.102 𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥2 →1 𝑥𝑥1 →0

Hence,
1 1 𝑚𝑚𝑚𝑚𝑚𝑚
𝜌𝜌2 = = = 0.055
𝑉𝑉2 18.102 𝑐𝑐𝑚𝑚3
b) It is recommended to prepare 2 𝐿𝐿 of 65% (mol species-1) solution by mixing pure
species 1 and 2 at 298.15 𝐾𝐾 and 100 𝑘𝑘Pa. Estimate the mass of species-1 and 2 required.
We have an equation for the solution molar volume, using it, let us first find out the total no
of moles in 2 L (2000 cm3) of solution,
1
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 × 𝜌𝜌 = 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 ×
𝑉𝑉

AY2019-20 | Sem-2 Tutorial 02-Solutions

 𝑐𝑐𝑚𝑚3
𝑉𝑉@𝑥𝑥1=0.65 = 41.506 (0.65)2 + 5.62(0.65) + 18.102 = 39.285 � �
𝑚𝑚𝑚𝑚𝑚𝑚
1
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 2000 × = 50.91 𝑚𝑚𝑚𝑚𝑚𝑚
39.285
Using the mol % provided, we can find the no of moles of each species,
𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 1 = 𝑛𝑛1 = 0.65 × 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 33.09 𝑚𝑚𝑚𝑚𝑚𝑚
𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 2 = 𝑛𝑛2 = (1 − 0.65) × 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 17.818 𝑚𝑚𝑚𝑚𝑚𝑚
Mass of each species needed can be found using molar masses of each species, assuming M1
and M2 to be molar masses of species-1 and 2 respectively,
Mass of species-1 needed (m1),
𝑚𝑚1 = 𝑛𝑛1 𝑀𝑀1 = 33.09𝑀𝑀1
Mass of species-2 needed (m2),
𝑚𝑚2 = 𝑛𝑛2 𝑀𝑀2 = 17.818𝑀𝑀2
c) Evaluate the volume change of mixing for the process described in (b)
∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 − 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉

𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 = � 𝑥𝑥𝑖𝑖 𝑉𝑉𝑖𝑖

𝑖𝑖

∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 = 39.285 − (𝑥𝑥1 𝑉𝑉1 + 𝑥𝑥2 𝑉𝑉2 )

∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 = 39.285 − �(0.65)(65.23) + (1 − 0.65)(18.1)�
𝑐𝑐𝑚𝑚3
∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 = −9.449 < 0 [𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶]
𝑚𝑚𝑚𝑚𝑚𝑚
d) Evaluate the enthalpy change of mixing for the process described in (b)
∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑒𝑒𝑒𝑒𝑒𝑒ℎ𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 − 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑒𝑒𝑒𝑒𝑒𝑒ℎ𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐻𝐻 − � 𝑥𝑥𝑖𝑖 𝐻𝐻𝑖𝑖 = 𝐻𝐻 − (𝑥𝑥1 𝐻𝐻1 + 𝑥𝑥2 𝐻𝐻2 )

𝑖𝑖

Using the equation provided for solution enthalpy,

𝑘𝑘𝑘𝑘
𝐻𝐻 = 𝐻𝐻@𝑥𝑥1 =0.65 = −26800 (0.652 ) + 18240 (0.65) + 1850 = 2383
𝑚𝑚𝑚𝑚𝑚𝑚
As we found pure species molar volume before, we can also find out the pure species
enthalpy values,
𝑘𝑘𝑘𝑘
𝐻𝐻1 = lim 𝐻𝐻 = −26800 (12 ) + 18240 (1) + 1850 = −6710
𝑥𝑥1 →1 𝑚𝑚𝑚𝑚𝑚𝑚
𝑘𝑘𝑘𝑘
𝐻𝐻2 = lim 𝐻𝐻 = lim 𝐻𝐻 = −26800 (02 ) + 18240 (0) + 1850 = 1850
𝑥𝑥2 →1 𝑥𝑥1 →0 𝑚𝑚𝑚𝑚𝑚𝑚
Using the above values,
∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = −2383 − [(0.65)(−6710) + (1 − 0.65)(1850)]
𝑘𝑘𝑘𝑘
∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 6097 >0 [𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒]
𝑚𝑚𝑚𝑚𝑚𝑚
AY2019-20 | Sem-2 Tutorial 02-Solutions
Discussion Question 3

A rigid tank is divided into two compartments via a partition. First compartment (A)
contains a mixture of nitrogen and oxygen in molar ratio, 𝑁𝑁2 : 𝑂𝑂2 = 2: 1. The second
compartment (B) is three times as big in volume as the first compartment and contains
pure oxygen. Both the compartments are at 1 𝑏𝑏ar, 298 𝐾𝐾. The partition is removed and the
system is allowed to reach equilibrium. Assume ideal gas conditions. Assume Molar Gibbs
energy of pure species as ideal gas at standard reference state = 0.

Find the composition and chemical potential before and after the removal of partition.
Solution: First finding composition before and after removal of partition
Species-1: N2; Species-2: O2
As the compartment B is three times as big as compartment A,
𝑉𝑉𝐵𝐵 = 3 𝑉𝑉𝐴𝐴
As we are advised to use ideal gas conditions,
Number of mol in B, 𝑛𝑛𝐵𝐵 = 3 × (number of mol in compartment A, 𝑛𝑛𝐴𝐴 )
Let us take a basis of 1 mol of gas mixture in compartment A
Before removal of partition:
Compartment-A
𝑁𝑁2 : 𝑂𝑂2 = 2: 1
2 1
𝑛𝑛1𝐴𝐴 = 3 𝑚𝑚𝑚𝑚𝑚𝑚 and 𝑛𝑛2𝐴𝐴 = 3 𝑚𝑚𝑚𝑚𝑚𝑚

Composition (mol fraction)

2 1
𝑚𝑚𝑚𝑚𝑚𝑚 2 𝑚𝑚𝑚𝑚𝑚𝑚 1
𝑦𝑦1𝐴𝐴 = 1𝑚𝑚𝑚𝑚𝑚𝑚
3
= 3 and 𝑦𝑦2𝐴𝐴 = 1𝑚𝑚𝑚𝑚𝑚𝑚
3
=3

Compartment-B
It has pure O2, hence,
0 𝑚𝑚𝑚𝑚𝑚𝑚 3 𝑚𝑚𝑚𝑚𝑚𝑚
𝑦𝑦1𝐵𝐵 = 3 𝑚𝑚𝑚𝑚𝑚𝑚 = 0 and 𝑦𝑦2𝐵𝐵 = 3 𝑚𝑚𝑜𝑜𝑜𝑜 = 1

After removal of partition:

𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑛𝑛𝐴𝐴 + 𝑛𝑛𝐵𝐵 = 1 + 3 = 4 𝑚𝑚𝑚𝑚𝑚𝑚
2
𝑀𝑀𝑀𝑀𝑀𝑀 𝑜𝑜𝑜𝑜 𝑁𝑁2 = 3 𝑚𝑚𝑚𝑚𝑚𝑚
1 10
𝑀𝑀𝑀𝑀𝑀𝑀 𝑜𝑜𝑜𝑜 𝑂𝑂2 = 3 + 3 = 3
𝑚𝑚𝑚𝑚𝑚𝑚

Finding the compositions,

2⁄3 2 1
𝑦𝑦1 = 4
= 12 = 6
10⁄3 10 5
𝑦𝑦2 = 4
= 12 = 6

Now Finding out the chemical potential before and after mixing,
𝑖𝑖𝑖𝑖
For ideal gas, 𝐺𝐺𝑖𝑖 → −∞ as 𝑃𝑃 → 0, hence, 𝜇𝜇 → −∞

AY2019-20 | Sem-2 Tutorial 02-Solutions

We also know,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝜇𝜇𝑖𝑖 = 𝐺𝐺𝑖𝑖̅ = 𝐺𝐺𝑖𝑖 + 𝑅𝑅𝑅𝑅 ln 𝑦𝑦𝑖𝑖
As it is mentioned, Molar Gibbs energy of pure species as ideal gas at standard reference
state = 0
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝜇𝜇𝑖𝑖 = 𝐺𝐺𝑖𝑖̅ = 𝑅𝑅𝑅𝑅 ln 𝑦𝑦𝑖𝑖
Before removal of partition:
Compartment-A
2 𝐽𝐽
𝜇𝜇1𝐴𝐴 = 𝑅𝑅𝑅𝑅 ln 𝑦𝑦1𝐴𝐴 = (8.314)(298) �ln �3�� = −1004.9 𝑚𝑚𝑚𝑚𝑚𝑚
1 𝐽𝐽
𝜇𝜇2𝐴𝐴 = 𝑅𝑅𝑅𝑅 ln 𝑦𝑦2𝐴𝐴 = (8.314)(298) �ln �3�� = −2721.9 𝑚𝑚𝑚𝑚𝑚𝑚

Compartment-B
𝜇𝜇2𝐵𝐵 = −∞
After removal of partition:
1 𝐽𝐽
𝜇𝜇1 = 𝑅𝑅𝑅𝑅 ln 𝑦𝑦1 = (8.314)(298) �ln �6�� = −4439.2 𝑚𝑚𝑚𝑚𝑚𝑚
5 𝐽𝐽
𝜇𝜇2 = 𝑅𝑅𝑅𝑅 ln 𝑦𝑦2 = (8.314)(298) �ln �6�� = −451.7 𝑚𝑚𝑚𝑚𝑚𝑚

Discussion Question 4

A rigid insulated tank is divided into two parts, one that contains 50 mol of ethylene at
400K, 1 bar and the other contains 150 mol nitrogen at 300K, 2 bar. The partition is
removed and the contents are allowed to mix and reach equilibrium. Determine the final
pressure, temperature in the tank and the entropy generation, assuming ideal gas state.
The ideal gas heat capacities (𝐶𝐶𝐶𝐶) of ethylene and nitrogen are 43 J/mol-K and 29 J/mol-K,
respectively and may be assumed to be independent of temperature.

Solution:
Species-1: Ethylene; Species-2: Nitrogen
Information provided is listed in the table below:
Compartment # Species Pressure Temperature n, mol
1 1 (ethylene) 1 bar 400 K 𝑛𝑛1 = 50
2 2 (nitrogen) 2 bar 300 K 𝑛𝑛2 = 150

Final temperature
Let us first find out the final temperature,
As the rigid tank is insulated, for adiabatic process, ∆𝑈𝑈 = 0
For an ideal gas, ∆𝑈𝑈 = 𝐶𝐶𝑣𝑣 ∆𝑇𝑇
Hence,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
∆𝑈𝑈 = 𝑛𝑛1 𝐶𝐶𝑣𝑣1 �𝑇𝑇𝑓𝑓 − 𝑇𝑇1 � + 𝑛𝑛2 𝐶𝐶𝑣𝑣2 �𝑇𝑇𝑓𝑓 − 𝑇𝑇2 � = 0 … (1)

AY2019-20 | Sem-2 Tutorial 02-Solutions

Using, 𝐶𝐶𝑣𝑣𝑣𝑣 = 𝐶𝐶𝑝𝑝𝑝𝑝 − 𝑅𝑅
𝐶𝐶𝑣𝑣1 = 43 − 8.314 = 34.686; 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝑣𝑣2 = 29 − 8.314 = 20.686
By substituting the known quantities in equation (1), we get,
𝑇𝑇𝑓𝑓 = 335.85 𝐾𝐾
Final pressure
For a rigid tank,
𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑉𝑉1 + 𝑉𝑉2
Volume of each compartment (Before mixing) can be calculated as,
𝑛𝑛𝑖𝑖 𝑅𝑅𝑇𝑇𝑖𝑖
𝑛𝑛𝑖𝑖 𝑉𝑉𝑖𝑖 = 𝑃𝑃𝑖𝑖

Substituting the values for compartments 1 and 2, we get

(50)(83.14)(400)
𝑛𝑛1 𝑉𝑉1 = (1𝑏𝑏𝑏𝑏𝑏𝑏)
= 1662800 𝑐𝑐𝑚𝑚3
(150)(83.14)(300)
𝑛𝑛2 𝑉𝑉2 = (2𝑏𝑏𝑏𝑏𝑏𝑏)
= 1870650 𝑐𝑐𝑚𝑚3

Volume of tank
𝑛𝑛𝑓𝑓 𝑅𝑅𝑇𝑇𝑓𝑓 (200)(83.14)(335.85)
𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡𝑎𝑎𝑎𝑎 = 𝑉𝑉1 + 𝑉𝑉2 = = = 1662800 + 1870650
𝑃𝑃𝑓𝑓 𝑃𝑃𝑓𝑓

This gives,
𝑃𝑃𝑓𝑓 = 1.58 𝑏𝑏𝑏𝑏𝑏𝑏
Entropy generation:
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑆𝑆𝑔𝑔𝑔𝑔𝑔𝑔 = 𝑆𝑆𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 − 𝑆𝑆𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
Initial entropy = Entropy of pure species
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑆𝑆𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑛𝑛1 𝑆𝑆1 (@𝑇𝑇1 , 𝑃𝑃1 ) + 𝑛𝑛2 𝑆𝑆2 (@𝑇𝑇2 , 𝑃𝑃2 )
Final entropy of mixture is written as,
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑖𝑖𝑖𝑖
𝑆𝑆𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 = �∑𝑖𝑖 𝑥𝑥𝑖𝑖 𝑆𝑆𝑖𝑖 − 𝑅𝑅 ∑𝑖𝑖 𝑦𝑦𝑖𝑖 ln 𝑦𝑦𝑖𝑖 �𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑆𝑆𝑓𝑓𝑓𝑓𝑓𝑓𝑎𝑎𝑎𝑎 = 𝑛𝑛1 𝑆𝑆1 �@𝑇𝑇𝑓𝑓 , 𝑃𝑃𝑓𝑓 � + 𝑛𝑛2 𝑆𝑆2 �@𝑇𝑇𝑓𝑓 , 𝑃𝑃𝑓𝑓 � − 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅 ∑𝑖𝑖 𝑦𝑦𝑖𝑖 ln 𝑦𝑦𝑖𝑖
Combining the equations for initial and final total entropy to find the entropy generation,
we get,
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑆𝑆𝑔𝑔𝑔𝑔𝑔𝑔 = 𝑛𝑛1 ∆𝑆𝑆1 + 𝑛𝑛2 ∆𝑆𝑆2 − 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅 ∑𝑖𝑖 𝑦𝑦𝑖𝑖 ln 𝑦𝑦𝑖𝑖
∆𝑆𝑆𝑖𝑖 = Change in molar entropy of a pure component from initial to final temperature and
pressure conditions, and is given by,
𝑖𝑖𝑖𝑖 𝑇𝑇 𝑃𝑃
∆𝑆𝑆𝑖𝑖 = 𝐶𝐶𝑝𝑝𝑝𝑝 ln � 𝑇𝑇𝑓𝑓 � − 𝑅𝑅 ln � 𝑃𝑃𝑓𝑓 �
𝑖𝑖 𝑖𝑖

Using the above equation and the initial and final T and P values for two species, we get,
𝐽𝐽
∆𝑆𝑆1 = −11.319 𝑚𝑚𝑚𝑚𝑚𝑚.𝐾𝐾
𝐽𝐽
∆𝑆𝑆2 = 5.231 𝑚𝑚𝑚𝑚𝑚𝑚.𝐾𝐾
AY2019-20 | Sem-2 Tutorial 02-Solutions
 𝐽𝐽
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅 ∑𝑖𝑖 𝑦𝑦𝑖𝑖 ln 𝑦𝑦𝑖𝑖 = 935.05 𝑚𝑚𝑚𝑚𝑚𝑚

We get,
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝐽𝐽
𝑆𝑆𝑔𝑔𝑔𝑔𝑔𝑔 = 1153.75 𝐾𝐾

Discussion Question 5

For a ternary solution at constant T and P, the composition dependence of molar property
M is given by:

𝑀𝑀 = 𝑥𝑥1 𝑀𝑀1 + 𝑥𝑥2 𝑀𝑀2 + 𝑥𝑥3 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝑥𝑥3 𝐶𝐶

Where, M1, M2 and M3 are the values of property ‘M’ for pure species 1, 2 and 3 and C is a
parameter independent of composition.

Determine the expressions for 𝑀𝑀 �2, and 𝑀𝑀

�1 , 𝑀𝑀 �3 using the definition of partial molar property
that we have discussed. As a check, verify if the expressions you have derived satisfy the
summability relation. You are also asked to derive expressions for 𝑀𝑀 �𝑖𝑖 at infinite dilution.

Solution:
� 𝟏𝟏 , 𝑴𝑴
Determine the expressions for 𝑴𝑴 � 𝟐𝟐 , and 𝑴𝑴
� 𝟑𝟑
Using the definition of partial molar property,
𝜕𝜕(𝑛𝑛𝑛𝑛)
�𝑖𝑖 ≡ �
𝑀𝑀 �
𝜕𝜕𝑛𝑛𝑖𝑖 𝑃𝑃,𝑇𝑇,𝑛𝑛
𝑗𝑗

We have an expression for , M

𝑀𝑀 = 𝑥𝑥1 𝑀𝑀1 + 𝑥𝑥2 𝑀𝑀2 + 𝑥𝑥3 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝑥𝑥3 𝐶𝐶
Hence,
𝑛𝑛𝑛𝑛 = 𝑛𝑛(𝑥𝑥1 𝑀𝑀1 + 𝑥𝑥2 𝑀𝑀2 + 𝑥𝑥3 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝑥𝑥3 𝐶𝐶)
Or,
𝑛𝑛1 𝑛𝑛2 𝑛𝑛3
𝑛𝑛𝑛𝑛 = 𝑛𝑛1 𝑀𝑀1 + 𝑛𝑛2 𝑀𝑀2 + 𝑛𝑛3 𝑀𝑀3 + 𝑛𝑛 �� � � � � � 𝐶𝐶�
𝑛𝑛 𝑛𝑛 𝑛𝑛
Or,
𝑛𝑛1 𝑛𝑛2 𝑛𝑛3
𝑛𝑛𝑛𝑛 = 𝑛𝑛1 𝑀𝑀1 + 𝑛𝑛2 𝑀𝑀2 + 𝑛𝑛3 𝑀𝑀3 + 𝐶𝐶
𝑛𝑛2
Using the definition of partial molar property to get, 𝑀𝑀 �1,
𝜕𝜕(𝑛𝑛𝑛𝑛)
�1 = �
𝑀𝑀 �
𝜕𝜕𝑛𝑛1 𝑃𝑃,𝑇𝑇,𝑛𝑛
2, 𝑛𝑛3

𝑛𝑛1 𝑛𝑛2 𝑛𝑛3

𝜕𝜕 �𝑛𝑛1 𝑀𝑀1 + 𝑛𝑛2 𝑀𝑀2 + 𝑛𝑛3 𝑀𝑀3 + 𝐶𝐶�
�1 = �
𝑀𝑀 𝑛𝑛2 �
𝜕𝜕𝑛𝑛1
𝑃𝑃,𝑇𝑇,𝑛𝑛2, 𝑛𝑛3

Or,
𝑑𝑑 𝑛𝑛1 𝑛𝑛2 𝑛𝑛3 𝑑𝑑 𝑛𝑛1
�1 = 𝑀𝑀1 +
𝑀𝑀 � 𝐶𝐶� = 𝑀𝑀1 + 𝑛𝑛2 𝑛𝑛3 𝐶𝐶 � �
𝑑𝑑𝑛𝑛1 𝑛𝑛 2 𝑑𝑑𝑛𝑛1 𝑛𝑛2
AY2019-20 | Sem-2 Tutorial 02-Solutions
We get,
1 2𝑛𝑛 𝑛𝑛 𝑛𝑛 𝐶𝐶 2𝑛𝑛
�1 = 𝑀𝑀1 + 𝑛𝑛2 𝑛𝑛3 𝐶𝐶 � − 1 � = 𝑀𝑀1 + 2 3 �1 − 1 �
𝑀𝑀
𝑛𝑛 2 𝑛𝑛 3 𝑛𝑛 2 𝑛𝑛
Or,
𝑛𝑛2 𝑛𝑛3 𝐶𝐶
�1 = 𝑀𝑀1 +
𝑀𝑀 (1 − 2𝑥𝑥1 ) = 𝑀𝑀1 + 𝑥𝑥2 𝑥𝑥3 𝐶𝐶(1 − 2𝑥𝑥1 )
𝑛𝑛2
Similarly, we can get,
𝑛𝑛1 𝑛𝑛3 𝐶𝐶
�2 = 𝑀𝑀2 +
𝑀𝑀 (1 − 2𝑥𝑥2 ) = 𝑀𝑀2 + 𝑥𝑥1 𝑥𝑥3 𝐶𝐶(1 − 2𝑥𝑥2 )
𝑛𝑛2

𝑛𝑛1 𝑛𝑛2 𝐶𝐶
�3 = 𝑀𝑀3 +
𝑀𝑀 (1 − 2𝑥𝑥3 ) = 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝐶𝐶(1 − 2𝑥𝑥3 )
𝑛𝑛2
As a check, verify if the expressions you have derived satisfy the summability
relation.
The solution property, M, can be found out using summability relation, as,
�𝑖𝑖
𝑀𝑀 = � 𝑥𝑥𝑖𝑖 𝑀𝑀
𝑖𝑖
�1 , 𝑀𝑀
Substituting the expression we got for 𝑀𝑀 �2, and 𝑀𝑀
�3 in the above summability relation
and simplifying, we get,
𝑀𝑀 = 𝑥𝑥1 𝑀𝑀1 + 𝑥𝑥2 𝑀𝑀2 + 𝑥𝑥3 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝑥𝑥3 𝐶𝐶

� 𝒊𝒊 at infinite dilution
Derive expressions for 𝑴𝑴
As we have discussed in the lecture notes,
�𝑖𝑖 = 𝑀𝑀
lim 𝑀𝑀 �𝑖𝑖∞
𝑥𝑥𝑖𝑖 →0

Hence,
�1∞ = lim 𝑀𝑀
𝑀𝑀 �1 = lim [𝑀𝑀1 + 𝑥𝑥2 𝑥𝑥3 𝐶𝐶(1 − 2𝑥𝑥1 )]
𝑥𝑥1 →0 𝑥𝑥1 →0

We get,
�1∞ = 𝑀𝑀1 + 𝑥𝑥2 𝑥𝑥3 𝐶𝐶
𝑀𝑀
Similarly,
�2∞ = 𝑀𝑀2 + 𝑥𝑥1 𝑥𝑥3 𝐶𝐶
𝑀𝑀
and
�3∞ = 𝑀𝑀3 + 𝑥𝑥1 𝑥𝑥2 𝐶𝐶
𝑀𝑀

AY2019-20 | Sem-2 Tutorial 02-Solutions

 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Tutorial 03-Solutions

There were typo errors in the equations I used for ln 𝜙𝜙�1 and ln 𝜙𝜙�2 in Questions 1,2 and 4.
Kindly correct those errors. All numbers are correct.

Discussion Question 1 (Textbook Question)

Determine the fugacity coefficients as given by Eqns. (10.63) for nitrogen and methane in a
N2(1)/CH4(2) mixture at 200 K and 30 bar if the mixture contains 40 mol-% N2.
Experimental virial-coefficient data are as follows:

𝐵𝐵11 = −35.2, 𝐵𝐵22 = −105.0, 𝐵𝐵12 = −59.8 cm3·mol-1

Solution:
Species-1: Nitrogen (N2)
Species-2: Methane (CH4)
The equation for fugacity coefficient of a species in a multi-component mixture is,

𝑃𝑃 1
ln 𝜙𝜙�𝑘𝑘 = �𝐵𝐵𝑘𝑘𝑘𝑘 + � � 𝑦𝑦𝑖𝑖 𝑦𝑦𝑗𝑗 �2𝛿𝛿𝑖𝑖𝑖𝑖 − 𝛿𝛿𝑖𝑖𝑖𝑖 ��
𝑅𝑅𝑅𝑅 2
𝑖𝑖 𝑗𝑗

Using the above equation for binary mixture, the equation for fugacity coefficient for
species-1, with 𝑘𝑘 = 1,
2 2
𝑃𝑃 1
ln 𝜙𝜙�1 = �𝐵𝐵11 + � � 𝑦𝑦𝑖𝑖 𝑦𝑦𝑗𝑗 �2𝛿𝛿𝑖𝑖1 − 𝛿𝛿𝑖𝑖𝑖𝑖 ��
𝑅𝑅𝑅𝑅 2
𝑖𝑖=1 𝑗𝑗=1

2 2

� � 𝑦𝑦𝑖𝑖 𝑦𝑦𝑗𝑗 �2𝛿𝛿𝑖𝑖𝑖𝑖 − 𝛿𝛿𝑖𝑖𝑖𝑖 �

𝑖𝑖=1 𝑗𝑗=1

= 𝑦𝑦1 𝑦𝑦1 (2𝛿𝛿11 − 𝛿𝛿11 ) + 𝑦𝑦1 𝑦𝑦2 (2𝛿𝛿11 − 𝛿𝛿12 ) + 𝑦𝑦2 𝑦𝑦1 (2𝛿𝛿21 − 𝛿𝛿21 )
+ 𝑦𝑦2 𝑦𝑦2 (2𝛿𝛿21 − 𝛿𝛿22 )
With 𝛿𝛿𝑖𝑖𝑖𝑖 = 0, 𝛿𝛿𝑘𝑘𝑘𝑘 = 0, and 𝛿𝛿𝑖𝑖𝑖𝑖 = 𝛿𝛿𝑗𝑗𝑗𝑗 , simplifying the above equation we get,
2 2

� � 𝑦𝑦𝑖𝑖 𝑦𝑦𝑗𝑗 �2𝛿𝛿𝑖𝑖𝑖𝑖 − 𝛿𝛿𝑖𝑖𝑖𝑖 � = 2𝑦𝑦22 𝛿𝛿12

𝑖𝑖=1 𝑗𝑗=1

Hence,
𝑃𝑃
ln 𝜙𝜙�1 = [𝐵𝐵 + 2𝑦𝑦22 𝛿𝛿12 ]
𝑅𝑅𝑅𝑅 11
Similarly, we can get an equation for fugacity coefficient for species-2,
𝑃𝑃
ln 𝜙𝜙�2 = [𝐵𝐵 + 2𝑦𝑦12 𝛿𝛿12 ]
𝑅𝑅𝑅𝑅 22

AY2019-20 | Sem-2 Tutorial 03-Solutions

Using the values of virial coefficients provided for pure species and the cross coefficient
values,
𝐵𝐵11 = −35.2, 𝐵𝐵22 = −105.0, 𝐵𝐵12 = −59.8 cm3·mol-1
We get,
𝛿𝛿12 = 2𝐵𝐵12 − 𝐵𝐵11 − 𝐵𝐵22 = 2(−59.8) − (−35.2) − (−105) = 20.6
Substituting the values of virial coefficients and 𝛿𝛿12 , in the fugacity equations for two
species,
For species-1
(30 )
ln 𝜙𝜙�1 = [(−35.2) + 2(0.62 )(20.6)] = −0.05 ⇒ 𝜙𝜙�1 = 0.9511
(83.14 )(200)
For species-2,
(30 )
ln 𝜙𝜙�2 = [(−105) + 2(0.42 )(20.6)] = −0.1835 ⇒ 𝜙𝜙�2 = 0.8324
(83.14 )(200)
Discussion Question 2 (Textbook Question)

Calculate fugacity coefficients of methyl ethyl ketone (MEK) and toluene in an equimolar
mixture at 50°C and 25 kPa. (refer to Table B.1 in the textbook for the data for MEK and
toluene).
Solution:
Species-1: MEK
Species-2: Toluene
This example is similar to question 1, except that we need to calculate the pure species
virial coefficients and the cross coefficient.
Step-1:
Getting the necessary data for MEK and Toluene from Table B.1 in the textbook. The data is
listed in the table below:
Property MEK Toluene
𝑇𝑇𝐶𝐶 (𝐾𝐾) 535.5 591.8
𝑃𝑃𝐶𝐶 (𝑏𝑏𝑏𝑏𝑏𝑏) 41.5 41.06
𝑍𝑍𝐶𝐶 (−) 0.264 0.249
𝑉𝑉𝐶𝐶 (𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚) 267 316
𝜔𝜔 0.323 0.262

Step-2:
Calculating virial coefficient values for pure species, the information is shown in the table
below:

AY2019-20 | Sem-2 Tutorial 03-Solutions

Property MEK Toluene
𝑇𝑇 0.603 0.546
𝑇𝑇𝑟𝑟 =
𝑇𝑇𝑐𝑐
0.422
𝐵𝐵0 = 0.083 − -0.865 -1.028
𝑇𝑇𝑟𝑟1.6
0.172
𝐵𝐵1 = 0.139 − -1.300 -2.045
𝑇𝑇𝑟𝑟4.2

𝐵𝐵𝑖𝑖𝑖𝑖 /𝐵𝐵𝑗𝑗𝑗𝑗 𝐵𝐵11 = −1378.45 𝐵𝐵22 = −1873.89

Step-3:
Similarly, we can find the cross coefficient using the equations provided in the lecture
notes.
Property Mixture
1/2 562.95
𝑇𝑇𝐶𝐶12 (𝐾𝐾) = �𝑇𝑇𝑐𝑐𝑐𝑐 𝑇𝑇𝑐𝑐𝑐𝑐 � �1 − 𝑘𝑘𝑖𝑖𝑖𝑖 �; 𝑤𝑤𝑤𝑤𝑤𝑤ℎ 𝑘𝑘𝑖𝑖𝑖𝑖 = 0
𝜔𝜔1 +𝜔𝜔2
𝜔𝜔12 = 0.293
2
𝑍𝑍𝑐𝑐1 +𝑍𝑍𝑐𝑐2
𝑍𝑍𝑐𝑐12 = 0.257
2
3
1/3
𝑉𝑉𝑐𝑐1 +𝑉𝑉𝑐𝑐2
1/3 290.812
𝑉𝑉𝑐𝑐12 = � � (𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚)
2

𝑍𝑍𝑐𝑐𝑐𝑐𝑐𝑐 𝑅𝑅𝑇𝑇𝑐𝑐𝑐𝑐𝑐𝑐
𝑃𝑃𝐶𝐶12 (𝑏𝑏𝑏𝑏𝑏𝑏) = 41.361
𝑉𝑉𝑐𝑐𝑐𝑐𝑐𝑐

𝑇𝑇
𝑇𝑇𝑟𝑟12 = 0.574
𝑇𝑇 𝑐𝑐12
0.422
𝐵𝐵0 = 0.083 − 1.6
-0.865
𝑇𝑇𝑟𝑟12

0.172
𝐵𝐵1 = 0.139 − 4.2
-1.300
𝑇𝑇𝑟𝑟12

�𝐵𝐵0 +𝜔𝜔12 𝐵𝐵1 �(𝑅𝑅𝑇𝑇𝑐𝑐12 ) 𝐵𝐵12 = −1608.19

𝐵𝐵12 =
𝑃𝑃𝑐𝑐12

Using the values of virial coefficients for pure species and the cross coefficient values that
we just calculated, we get,
𝛿𝛿12 = 2𝐵𝐵12 − 𝐵𝐵11 − 𝐵𝐵22 = 35
Substituting the values of virial coefficients and 𝛿𝛿12 , in the fugacity equations for two
species,
For species-1
(25 𝑘𝑘𝑘𝑘𝑘𝑘 )
ln 𝜙𝜙�1 = [(−1378.45) + 2(0.52 )(35)] ⇒ 𝜙𝜙�1 = 0.9873
(8314 )(323)
For species-2,

AY2019-20 | Sem-2 Tutorial 03-Solutions

 (25 𝑘𝑘𝑘𝑘𝑘𝑘 )
ln 𝜙𝜙�2 = [(−1873.89) + 2(0.52 )(35)] ⇒ 𝜙𝜙�2 = 0.9828
(8314 )(323)

Discussion Question 3

At 542 K, 21.7 bar, the system Ethylbenzene(1)/Benzene(2) is in vapour-liquid

equilibrium.

Available data for this system are given below. Find out the missing information on the
table.

Component 𝑥𝑥𝑖𝑖 𝑦𝑦𝑖𝑖 𝜙𝜙�𝑖𝑖𝐿𝐿 𝜙𝜙�𝑖𝑖𝑉𝑉 𝑓𝑓̂𝑖𝑖𝐿𝐿 (𝑏𝑏𝑏𝑏𝑏𝑏) 𝑓𝑓̂𝑖𝑖𝑉𝑉 (𝑏𝑏𝑏𝑏𝑏𝑏)

Ethylbenzene 0.531 7.150
(1)
Benzene (2) 0.844 9.686

Solution:
Step-1:
The system is in vapor-liquid equilibrium, hence, fugacity values of each species should be
same in both the phases, or,
𝑓𝑓̂𝑖𝑖𝐿𝐿 = 𝑓𝑓̂𝑖𝑖𝑉𝑉
Using this, we complete part of the table:
Component 𝑥𝑥𝑖𝑖 𝑦𝑦𝑖𝑖 𝜙𝜙�𝑖𝑖𝐿𝐿 𝜙𝜙�𝑖𝑖𝑉𝑉 𝑓𝑓̂𝑖𝑖𝐿𝐿 (𝑏𝑏𝑏𝑏𝑏𝑏) 𝑓𝑓̂𝑖𝑖𝑉𝑉 (𝑏𝑏𝑏𝑏𝑏𝑏)
Ethylbenzene 0.531 7.150 7.150
(1)
Benzene (2) 0.844 9.686 9.686

Step-2:
The equations for fugacity coefficient for species in the ideal gas mixture
𝑓𝑓̂𝑖𝑖 𝑓𝑓̂𝑖𝑖
𝜙𝜙�𝑖𝑖 = =
𝑝𝑝𝑖𝑖 𝑦𝑦𝑖𝑖 𝑃𝑃
Also for fugacity coefficient for species in an ideal solution,
𝑓𝑓̂𝑖𝑖𝑖𝑖𝑖𝑖
𝜙𝜙�𝑖𝑖𝑖𝑖𝑖𝑖 =
𝑥𝑥𝑖𝑖 𝑃𝑃
We can first use the fugacity coefficient of Ethylbenzene in liquid phase and calculate the
composition using the fugacity value (highlighted) and the system pressure,
For ethylbenzene in the liquid phase,
𝑓𝑓̂1𝐿𝐿 𝑓𝑓̂1𝐿𝐿 7.150
𝜙𝜙�1𝐿𝐿 = ⇒ 𝑥𝑥1 = 𝐿𝐿 = = 0.6205
𝑥𝑥1 𝑃𝑃 𝜙𝜙�1 𝑃𝑃 (0.531)(21.7)
The composition of ethylbenzene in liquid phase, 𝑥𝑥1 = 0.6205
AY2019-20 | Sem-2 Tutorial 03-Solutions
Hence, composition of toluene in liquid phase, 𝑥𝑥2 = 1 − 𝑥𝑥1 = 1 − 0.6205 = 0.3795
Similarly, using the fugacity coefficient of toluene in vapour phase, we can calculate the
composition using the fugacity value (highlighted) and the system pressure,
For toluene in the vapour phase,
𝑓𝑓̂2𝑉𝑉 𝑓𝑓̂2𝑉𝑉 9.686
𝜙𝜙�2𝑉𝑉 = ⇒ 𝑦𝑦2 = 𝑉𝑉 = = 0.5289
𝑦𝑦2 𝑃𝑃 𝜙𝜙�2 𝑃𝑃 (0.844)(21.7)
The composition of toluene in vapour phase, 𝑦𝑦2 = 0.5289
Hence, composition of ethylbenzene in vapour phase, 𝑦𝑦1 = 1 − 𝑦𝑦2 = 1 − 0.5289 = 0.4711
We can now fill up the first two columns in the table as follows:
Component 𝑥𝑥𝑖𝑖 𝑦𝑦𝑖𝑖 𝜙𝜙�𝑖𝑖𝐿𝐿 𝜙𝜙�𝑖𝑖𝑉𝑉 𝑓𝑓̂𝑖𝑖𝐿𝐿 (𝑏𝑏𝑏𝑏𝑏𝑏) 𝑓𝑓̂𝑖𝑖𝑉𝑉 (𝑏𝑏𝑏𝑏𝑏𝑏)
Ethylbenzene 0.6205 0.4711 0.531 7.150 7.150
(1)
Benzene (2) 0.3795 0.5289 0.844 9.686 9.686

Step-3:
Calculating the unknown fugacity coefficients using the available information,
Fugacity coefficient of ethylbenzene in vapour phase,
𝑓𝑓̂1𝑉𝑉 7.150
𝜙𝜙�1𝑉𝑉 = = = 0.699
𝑦𝑦1 𝑃𝑃 (0.4711)(21.7)
Fugacity coefficient of toluene in liquid phase,
𝑓𝑓̂2𝐿𝐿 9.686
𝜙𝜙�2𝐿𝐿 = = = 1.176
𝑥𝑥2 𝑃𝑃 (0.3795)(21.7)
Completing the table now:
Component 𝑥𝑥𝑖𝑖 𝑦𝑦𝑖𝑖 𝜙𝜙�𝑖𝑖𝐿𝐿 𝜙𝜙�𝑖𝑖𝑉𝑉 𝑓𝑓̂𝑖𝑖𝐿𝐿 (𝑏𝑏𝑏𝑏𝑏𝑏) 𝑓𝑓̂𝑖𝑖𝑉𝑉 (𝑏𝑏𝑏𝑏𝑏𝑏)
Ethylbenzene 0.6205 0.4711 0.531 0.699 7.150 7.150
(1)
Benzene (2) 0.3795 0.5289 1.176 0.844 9.686 9.686

Practice Question 4

For the system ethylene(1)/propylene(2) as a gas, estimate the fugacity and fugacity
coefficient values for both components at 150°C, pressure = 30 bar and 𝑦𝑦1 = 0.35.

Use the appropriate form of

𝑃𝑃 1
ln 𝜙𝜙�𝑘𝑘 = �𝐵𝐵𝑘𝑘𝑘𝑘 + � � 𝑦𝑦𝑖𝑖 𝑦𝑦𝑗𝑗 �2𝛿𝛿𝑖𝑖𝑖𝑖 − 𝛿𝛿𝑖𝑖𝑖𝑖 ��
𝑅𝑅𝑅𝑅 2
𝑖𝑖 𝑗𝑗
Solution:
Species-1: Ethylene
Species-2: Propylene

AY2019-20 | Sem-2 Tutorial 03-Solutions

Similar to Discussion Question-2, collecting the information (properties for pure species)
for ethylene and propylene from Table B.1.
Then using similar method, we can find out the pure species virial coefficients and cross
coefficient, we get,
𝐵𝐵11 = −60; 𝐵𝐵22 = −159; 𝐵𝐵12 = −99
𝛿𝛿12 = 2𝐵𝐵12 − 𝐵𝐵11 − 𝐵𝐵22 = 20.83
Using following equations for fugacity coefficients,
𝑃𝑃
ln 𝜙𝜙�1 = [𝐵𝐵 + 2𝑦𝑦22 𝛿𝛿12 ]
𝑅𝑅𝑅𝑅 11
𝑃𝑃
ln 𝜙𝜙�2 = [𝐵𝐵 + 2𝑦𝑦12 𝛿𝛿12 ]
𝑅𝑅𝑅𝑅 22
we get,
𝜙𝜙�1 = 0.957
𝜙𝜙�2 = 0.875
Calculating the fugacity values,
For ethylene,
𝑓𝑓̂1 = 𝜙𝜙�1 𝑦𝑦1 𝑃𝑃 = (0.957)(0.35)(30) = 10.05 𝑏𝑏𝑏𝑏𝑏𝑏
For propylene,
𝑓𝑓̂2 = 𝜙𝜙�2 𝑦𝑦2 𝑃𝑃 = (0.875)(1 − 0.35)(30) = 17.06 𝑏𝑏𝑏𝑏𝑏𝑏

AY2019-20 | Sem-2 Tutorial 03-Solutions

 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Tutorial 04-Solutions

Discussion Question 1

A gaseous mixture comprising 25% of species-A by mole is formed by mixing pure A and B
at −8 ℃ and 33 𝑏𝑏ar. (a) Check if the mixing is exothermic/endothermic (b) Check if the
mixing is spontaneous.

Information provided:

Property at given T,P Species-A Species-B Mixture

Residual Enthalpy -0.8 -28 -22
(kJ/mol)
Residual Entropy -25 -30 -40
(J/mol)

Solution:
(a) Check if the mixing is exothermic/endothermic:
We need to find the enthalpy of mixing and then conclude if the mixing is
exothermic/endothermic. To start with, we will assume some basis: Let us consider 1 mole
of a binary gaseous mixture of A and B. As the mixture comprises 25% species-A, hence the
mixture will have 0.25 mol of A of Species-A (𝑛𝑛𝐴𝐴 ), and 0.75 mol of Species-B (𝑛𝑛𝐵𝐵 ).
The enthalpy of mixing can be calculated as follows:
∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐻𝐻 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 − 𝐻𝐻 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
Initially we have pure Species-A and Species-B at low temperature and “high” pressure,
hence, the initial enthalpy of each species can be found out using ideal gas state enthalpy
and residual enthalpy of individual species:
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝐻𝐻 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑛𝑛𝐴𝐴 �𝐻𝐻𝐴𝐴 + 𝐻𝐻𝐴𝐴𝑅𝑅 � + 𝑛𝑛𝐵𝐵 (𝐻𝐻𝐵𝐵 + 𝐻𝐻𝐵𝐵𝑅𝑅 )
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝐻𝐻 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = 0.25�𝐻𝐻𝐴𝐴 + 𝐻𝐻𝐴𝐴𝑅𝑅 � + 0.75(𝐻𝐻𝐵𝐵 + 𝐻𝐻𝐵𝐵𝑅𝑅 )
After mixing these species, we get the final gaseous mixture, the enthalpy of which can be
written as (again remember the mixture formed is at high pressure so we need to use real
species properties),
𝐻𝐻 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 = 𝑛𝑛𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 �𝐻𝐻 𝑖𝑖𝑖𝑖 + 𝐻𝐻 𝑅𝑅 � = 1.0�𝐻𝐻 𝑖𝑖𝑖𝑖 + 𝐻𝐻 𝑅𝑅 �
Hence,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = �𝐻𝐻 𝑖𝑖𝑖𝑖 + 𝐻𝐻 𝑅𝑅 � − �0.25�𝐻𝐻𝐴𝐴 + 𝐻𝐻𝐴𝐴𝑅𝑅 � + 0.75(𝐻𝐻𝐵𝐵 + 𝐻𝐻𝐵𝐵𝑅𝑅 )�
Or,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = �𝐻𝐻 𝑖𝑖𝑖𝑖 − 0.25𝐻𝐻𝐴𝐴 − 0.75𝐻𝐻𝐵𝐵 � + (𝐻𝐻 𝑅𝑅 − 0.25𝐻𝐻𝐴𝐴𝑅𝑅 − 0.75𝐻𝐻𝐵𝐵𝑅𝑅 )
As we know for the ideal gas mixture,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝐻𝐻 𝑖𝑖𝑖𝑖 − 0.25𝐻𝐻𝐴𝐴 − 0.75𝐻𝐻𝐵𝐵 = 0
AY2019-20 | Sem-2 Tutorial 04-Solutions
We get,
∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = (𝐻𝐻 𝑅𝑅 − 0.25𝐻𝐻𝐴𝐴𝑅𝑅 − 0.75𝐻𝐻𝐵𝐵𝑅𝑅 )
Using the residual molar enthalpy values, we get,
∆𝐻𝐻 𝑚𝑚𝑖𝑖𝑥𝑥 = �−22 − 0.25(−0.8) − 0.75(−28)� = −0.8 𝑘𝑘𝑘𝑘 = −800 𝐽𝐽
Hence, mixing is exothermic.
(b) Check if the mixing is spontaneous:
We need to find the entropy of mixing and then conclude if the mixing is spontaneous or
not. Again, we will assume some basis of 1 mole of a binary gaseous mixture of A and B. As
the mixture comprises 25% species-A, hence the mixture will have 0.25 mol of A of
Species-A (𝑛𝑛𝐴𝐴 ), and 0.75 mol of Species-B (𝑛𝑛𝐵𝐵 ).
The entropy of mixing can be calculated as follows:
∆𝑆𝑆 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑆𝑆 𝑓𝑓𝑓𝑓𝑛𝑛𝑛𝑛𝑛𝑛 − 𝑆𝑆 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
Initially we have pure Species-A and Species-B at low temperature and “high” pressure,
hence, the initial entropy of each species can be found out using ideal gas state entropy and
residual entropy of individual species:
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝑆𝑆 𝑖𝑖𝑖𝑖𝑖𝑖𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑛𝑛𝐴𝐴 �𝑆𝑆𝐴𝐴 + 𝑆𝑆𝐴𝐴𝑅𝑅 � + 𝑛𝑛𝐵𝐵 (𝑆𝑆𝐵𝐵 + 𝑆𝑆𝐵𝐵𝑅𝑅 )
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝑆𝑆 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = 0.25�𝑆𝑆𝐴𝐴 + 𝑆𝑆𝐴𝐴𝑅𝑅 � + 0.75(𝑆𝑆𝐵𝐵 + 𝑆𝑆𝐵𝐵𝑅𝑅 )
After mixing these species, we get the final gaseous mixture, the entropy of which can be
written as (again remember the mixture formed is at high pressure so we need to use real
species properties),
𝑆𝑆 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 = 𝑛𝑛𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 �𝑆𝑆 𝑖𝑖𝑖𝑖 + 𝑆𝑆 𝑅𝑅 � = 1.0�𝑆𝑆 𝑖𝑖𝑖𝑖 + 𝑆𝑆 𝑅𝑅 �
Hence,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
∆𝑆𝑆 𝑚𝑚𝑚𝑚𝑚𝑚 = �𝑆𝑆 𝑖𝑖𝑖𝑖 + 𝑆𝑆 𝑅𝑅 � − �0.25�𝑆𝑆𝐴𝐴 + 𝑆𝑆𝐴𝐴𝑅𝑅 � + 0.75(𝑆𝑆𝐵𝐵 + 𝑆𝑆𝐵𝐵𝑅𝑅 ))�
Or,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
∆𝑆𝑆 𝑚𝑚𝑚𝑚𝑚𝑚 = �𝑆𝑆 𝑖𝑖𝑖𝑖 − 0.25𝑆𝑆𝐴𝐴 − 0.75𝑆𝑆𝐵𝐵 � + (𝑆𝑆 𝑅𝑅 − 0.25𝑆𝑆𝐴𝐴𝑅𝑅 − 0.75𝑆𝑆𝐵𝐵𝑅𝑅 )
As we know for the ideal gas mixture,
𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖
𝑆𝑆 𝑖𝑖𝑖𝑖 − 0.25𝑆𝑆𝐴𝐴 − 0.75𝑆𝑆𝐵𝐵 = −𝑅𝑅(𝑛𝑛1 ln 𝑦𝑦1 + 𝑛𝑛2 ln 𝑦𝑦2 )
We get,
∆𝑆𝑆 𝑚𝑚𝑚𝑚𝑚𝑚 = −𝑅𝑅(𝑛𝑛1 ln 𝑦𝑦1 + 𝑛𝑛2 ln 𝑦𝑦2 ) + (𝑆𝑆 𝑅𝑅 − 0.25𝑆𝑆𝐴𝐴𝑅𝑅 − 0.75𝑆𝑆𝐵𝐵𝑅𝑅 )
With 𝑛𝑛1 = 0.25, 𝑦𝑦1 = 0.25, 𝑛𝑛2 = 0.75, 𝑦𝑦2 = 0.75 and using the residual entropy values, we
get,
𝐽𝐽
∆𝑆𝑆 𝑚𝑚𝑚𝑚𝑚𝑚 = −6.575 ≠0
𝐾𝐾
Hence, mixing is non-spontaneous.

AY2019-20 | Sem-2 Tutorial 04-Solutions

Discussion Question 2

The partial molar enthalpies (in kJ/mol of mixture) of species 1 and 2 in a binary mixture at
25°C are given by:

�1 = 100(1 + 0.08𝑥𝑥22 );
𝐻𝐻 �2 = 80(1 + 0.1𝑥𝑥12 )
𝐻𝐻

(a) Derive expression for solution enthalpy and calculate the molar enthalpy of an
equimolar solution.
(b) Calculate the molar enthalpies of the pure components.
(c) Calculate the partial molar enthalpies of the two components at infinite dilution.
(d) Derive expression for excess solution enthalpy and calculate excess enthalpy of an
equimolar solution.
(e) Determine the excess partial molar enthalpies of the two components as functions
of the composition and calculate their values at infinite dilution.
(f) Calculate the enthalpy change when the two components are mixed at constant T
and P to produce an equimolar solution. Is this an endothermic/exothermic system?

Solution:
(a) Solution enthalpy:
�𝑖𝑖
Using the summability relation, 𝑀𝑀 = ∑𝑖𝑖 𝑥𝑥𝑖𝑖 𝑀𝑀
Hence, solution enthalpy,
�𝑖𝑖 = 𝑥𝑥1 𝐻𝐻
𝐻𝐻 = � 𝑥𝑥𝑖𝑖 𝐻𝐻 �1 + 𝑥𝑥2 𝐻𝐻
�2
𝑖𝑖

Using the expression for partial molar enthalpies provided to us,

𝐻𝐻 = 𝑥𝑥1 {100(1 + 0.08𝑥𝑥22 )} + 𝑥𝑥2 {80(1 + 0.1𝑥𝑥12 )}
After simplification we get,
𝐻𝐻 = 100 𝑥𝑥1 + 8𝑥𝑥1 𝑥𝑥22 + 80𝑥𝑥2 + 8𝑥𝑥12 𝑥𝑥2
Or,
𝐻𝐻 = 100 𝑥𝑥1 + 80𝑥𝑥2 + 8𝑥𝑥1 𝑥𝑥2 (𝑥𝑥1 + 𝑥𝑥2 )
As we know, 𝑥𝑥1 + 𝑥𝑥2 = 1, we get,
𝐻𝐻 = 100 𝑥𝑥1 + 80𝑥𝑥2 + 8𝑥𝑥1 𝑥𝑥2
For equimolar solution, 𝑥𝑥1 = 𝑥𝑥2 = 0.5, we can calculate solution enthalpy,
𝐻𝐻 = 100 (0.5) + 80 (0.5) + 8(0.5)(0.5) = 92 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
(b) Molar enthalpy of pure components:
As we know,
�𝑖𝑖 = 𝑀𝑀𝑖𝑖
lim 𝑀𝑀 = lim 𝑀𝑀
𝑥𝑥𝑖𝑖 →1 𝑥𝑥𝑖𝑖 →1

Hence for a binary system, pure component molar enthalpies can be calculated as,
�1 = lim 𝐻𝐻
𝐻𝐻1 = lim 𝐻𝐻 �1
𝑥𝑥1 →1 𝑥𝑥2 →0

�2 = lim 𝐻𝐻
𝐻𝐻2 = lim 𝐻𝐻 �2
𝑥𝑥2 →1 𝑥𝑥1 →0

Using the expressions for partial molar enthalpies,

AY2019-20 | Sem-2 Tutorial 04-Solutions
 �1 = lim 𝐻𝐻
𝐻𝐻1 = lim 𝐻𝐻 �1 = 100�1 + 0.08 (02 )� = 100 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥1 →1 𝑥𝑥2 →0

�2 = lim 𝐻𝐻
𝐻𝐻2 = lim 𝐻𝐻 �2 = 80(1 + 0.1 (02 )) = 80 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥2 →1 𝑥𝑥1 →0

(c) Partial molar enthalpies at infinite dilution

As we know,
�𝑖𝑖 = 𝑀𝑀
lim 𝑀𝑀 �𝑖𝑖∞
𝑥𝑥𝑖𝑖 →0

Hence,
�1∞ = lim 𝐻𝐻
𝐻𝐻 �1 = lim 𝐻𝐻
�1
𝑥𝑥1 →0 𝑥𝑥2 →1

�1∞ = 100(1 + 0.08(12 )) = 108 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

𝐻𝐻
And,
�2∞ = lim 𝐻𝐻
𝐻𝐻 �2 = lim 𝐻𝐻
�2
𝑥𝑥2 →0 𝑥𝑥1 →1

�2∞ = 80�1 + 0.1(12 )� = 88 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

𝐻𝐻
(d) Expression for excess solution enthalpy, and quantification:
𝐻𝐻 𝐸𝐸 = 𝐻𝐻 − 𝐻𝐻 𝑖𝑖𝑖𝑖
�𝑖𝑖 𝑎𝑎𝑎𝑎𝑎𝑎
𝐻𝐻 = � 𝑥𝑥𝑖𝑖 𝐻𝐻 �𝑖𝑖𝑖𝑖𝑖𝑖
𝐻𝐻 𝑖𝑖𝑖𝑖 = � 𝑥𝑥𝑖𝑖 𝐻𝐻
𝑖𝑖 𝑖𝑖

�𝑖𝑖𝑖𝑖𝑖𝑖 = 𝐻𝐻𝑖𝑖 ,
As, for ideal solution, 𝐻𝐻

�𝑖𝑖 − � 𝑥𝑥𝑖𝑖 𝐻𝐻𝑖𝑖

𝐻𝐻 𝐸𝐸 = � 𝑥𝑥𝑖𝑖 𝐻𝐻
𝑖𝑖 𝑖𝑖

We already had derived and expression for H, and we also have found out the values of
molar enthalpies of pure components, hence,
𝐻𝐻 𝐸𝐸 = (100 𝑥𝑥1 + 80𝑥𝑥2 + 8𝑥𝑥1 𝑥𝑥2 ) − (𝑥𝑥1 𝐻𝐻1 + 𝑥𝑥2 𝐻𝐻2 )
Or,
𝐻𝐻 𝐸𝐸 = 8𝑥𝑥1 𝑥𝑥2
For equimolar solution, 𝑥𝑥1 = 𝑥𝑥2 = 0.5, we get,
𝐻𝐻 𝐸𝐸 = 2 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
(e) Excess partial molar enthalpies:
�𝑖𝑖 𝐸𝐸 = 𝐻𝐻
𝐻𝐻 �𝑖𝑖 𝑖𝑖𝑖𝑖
�𝑖𝑖 − 𝐻𝐻
𝑖𝑖𝑖𝑖
�𝑖𝑖
Since, 𝐻𝐻 = 𝐻𝐻𝑖𝑖 , we can write above equation for 2 species,
�1 𝐸𝐸 = 𝐻𝐻
𝐻𝐻 �1 − 𝐻𝐻1

�2 𝐸𝐸 = 𝐻𝐻
𝐻𝐻 �2 − 𝐻𝐻2
Using the expression for partial molar enthalpy (provided to us) and the calculated pure
species enthalpies,
�1 𝐸𝐸 = 𝐻𝐻
𝐻𝐻 �1 − 𝐻𝐻1 = 100 (1 + 0.08 𝑥𝑥22 ) − 100 = 8𝑥𝑥22

AY2019-20 | Sem-2 Tutorial 04-Solutions

 �2 𝐸𝐸 = 𝐻𝐻
𝐻𝐻 �2 − 𝐻𝐻2 = 80 (1 + 0.1 𝑥𝑥12 ) − 80 = 8𝑥𝑥12
@ infinite dilution,
∞
�1 𝐸𝐸
𝐻𝐻 �1 𝐸𝐸 = lim 𝐻𝐻
= lim 𝐻𝐻 �1 𝐸𝐸 = 8 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥1 →0 𝑥𝑥2 →1

and
∞
�2 𝐸𝐸
𝐻𝐻 �2 𝐸𝐸 = lim 𝐻𝐻
= lim 𝐻𝐻 �2 𝐸𝐸 = 8 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚
𝑥𝑥2 →0 𝑥𝑥1 →1

(f) Enthalpy of mixing

∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐻𝐻 − � 𝑥𝑥𝑖𝑖 𝐻𝐻𝑖𝑖

𝑖𝑖

We have discussed in the “non-ideal solution” chapter that,

∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐻𝐻 𝐸𝐸 = 8𝑥𝑥1 𝑥𝑥2
For equimolar mixture,
∆𝐻𝐻 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐻𝐻 𝐸𝐸 = 2 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

Discussion Question 3

Volume change of mixing (cm3/mol) for a binary mixture of ethanol (1)/methyl butyl ether
(2) at 25 ℃ is given by:

∆𝑉𝑉 = 𝑥𝑥1 𝑥𝑥2 [−10.26 + 2.2(𝑥𝑥1 − 𝑥𝑥2 )]

(a) Calculate the volume change of mixing when 750 cm3 of pure species 1 and 1500
cm3 of species 2 are mixed at 25 ℃.
(b) Is the solution ideal? If not what would be the volume if an ideal solution were
formed?

Date available: @ 25 ℃, 𝑉𝑉1 = 58.63 𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚; 𝑉𝑉2 = 118.46 𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚

Solution:
(a) Calculate the volume change of mixing
∆𝑉𝑉 = 𝑥𝑥1 𝑥𝑥2 [−10.26 + 2.2(𝑥𝑥1 − 𝑥𝑥2 )]
Let us first calculate the unknown compositions 𝑥𝑥1 𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥2
750 cm3 of pure species 1 and 1500 cm3 of species 2 are mixed,
Hence, the number of moles of each species in the mixture,
Species-1: Species-2:
𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
Number of mol, 𝑛𝑛1 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 (𝑉𝑉 ) Number of mol, 𝑛𝑛2 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 (𝑉𝑉 )
1 2

750 1500
𝑛𝑛1 = 58.63 = 12.79 𝑚𝑚𝑚𝑚𝑚𝑚 𝑛𝑛2 = 118.46 = 12.66 𝑚𝑚𝑚𝑚𝑚𝑚
𝑛𝑛1 12.79
Mole faction of species-1, 𝑥𝑥1 = 𝑛𝑛 = 12.79+12.66 = 0.5026
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

AY2019-20 | Sem-2 Tutorial 04-Solutions

 𝑛𝑛2 12.66
Mole fraction for species-2, 𝑥𝑥2 = 𝑛𝑛 = 12.79+12.66 = 0.4975
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

Using these mole fraction values, we can find the volume change of mixing,
𝑐𝑐𝑚𝑚3
∆𝑉𝑉 𝑚𝑚𝑚𝑚𝑚𝑚 = −2.562
𝑚𝑚𝑚𝑚𝑚𝑚
Converting this to volume in cm3, by multiplying with ntotal,
∆𝑉𝑉 𝑚𝑚𝑚𝑚𝑚𝑚 = −2.562 × (12.79 + 12.66) = −65.203 𝑐𝑐𝑚𝑚3
(b) Is the solution ideal? If not what would be the volume if an ideal solution were formed?
For an ideal solution, ∆𝑉𝑉 𝑚𝑚𝑚𝑚𝑚𝑚 = 0, however, we found the ∆𝑉𝑉 𝑚𝑚𝑚𝑚𝑚𝑚 value to be non-zero, hence
the solution is non-ideal.
Molar volume of ideal solution:

𝑉𝑉 𝑖𝑖𝑖𝑖 = � 𝑥𝑥𝑖𝑖 𝑉𝑉𝑖𝑖 = 𝑥𝑥1 𝑉𝑉1 + 𝑥𝑥2 𝑉𝑉2

𝑖𝑖

After substituting all the numbers, we get,

𝑉𝑉 𝑖𝑖𝑖𝑖 = 88.389 𝑐𝑐𝑚𝑚3 /𝑚𝑚𝑚𝑚𝑚𝑚
Volume of idea solution can be calculated by multiplying the above molar volume of ideal
solution with the ntotal, we get,
𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 88.389 × (12.79 + 12.66) = 2249.5
This value is nearly equal to the combined volumes of species-1 and species-2 we are
mixing.
Discussion Question 4

A binary mixture comprising of species A and B exhibits VLE at 313.15 𝐾𝐾. Estimate the
vapour phase composition in equilibrium with liquid phase containing 35% of A at 21 kPa.

Additional information:

Property Species-A Species-B

𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 4.5 kPa 24 kPa
ln 𝛾𝛾𝑖𝑖 𝑥𝑥𝐵𝐵2 [𝑐𝑐1 + 2(𝑐𝑐2 − 𝑐𝑐1 )𝑥𝑥𝐴𝐴 ] 𝑥𝑥𝐴𝐴2 [𝑐𝑐2 + 2(𝑐𝑐1 − 𝑐𝑐2 )𝑥𝑥𝐵𝐵 ]
𝛾𝛾𝑖𝑖∞ 3.7 2.7
𝜙𝜙�𝑖𝑖 1 1
Solution:
Step-1: Choice of VLE model
Vapour phase: ideal gas mixture (low pressure, 𝜙𝜙�𝑖𝑖 = 1)
Liquid phase: (Real) non-ideal solution (𝛾𝛾𝑖𝑖 ≠ 1)
VLE model: Modified Raoult’s law (𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝛾𝛾𝑖𝑖 𝑥𝑥𝑖𝑖 𝑝𝑝𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 )
Step-2: Expression for activity coefficient
The constants in activity coefficient equations can be evaluated using the activity
coefficient values for the case of infinite dilution (as provided in the table above).

AY2019-20 | Sem-2 Tutorial 04-Solutions

For Species-A
𝛾𝛾𝐴𝐴 = 𝛾𝛾𝐴𝐴∞ 𝑤𝑤ℎ𝑒𝑒𝑒𝑒 𝑥𝑥𝐴𝐴 → 0 (𝑜𝑜𝑜𝑜) 𝑥𝑥𝐵𝐵 → 1
Hence,
ln 𝛾𝛾𝐴𝐴∞ = ln 𝛾𝛾𝐴𝐴 (@ 𝑥𝑥𝐴𝐴 → 0, 𝑥𝑥𝐵𝐵 → 1) = (12 )[𝑐𝑐1 + 2(𝑐𝑐2 − 𝑐𝑐1 )(0)]
This gives us,
ln 𝛾𝛾𝐴𝐴∞ = ln(3.7) = 𝑐𝑐1
Hence,
𝑐𝑐1 = 1.308

For Species-B
𝛾𝛾𝐵𝐵 = 𝛾𝛾𝐵𝐵∞ 𝑤𝑤ℎ𝑒𝑒𝑒𝑒 𝑥𝑥𝐵𝐵 → 0 (𝑜𝑜𝑜𝑜) 𝑥𝑥𝐴𝐴 → 1
Hence,
ln 𝛾𝛾𝐵𝐵∞ = ln 𝛾𝛾𝐵𝐵 (@ 𝑥𝑥𝐵𝐵 → 0, 𝑥𝑥𝐴𝐴 → 1) = (12 )[𝑐𝑐2 + 2(𝑐𝑐1 − 𝑐𝑐2 )(0)]
This gives us,
ln 𝛾𝛾𝐵𝐵∞ = ln(2.7) = 𝑐𝑐2
Hence,
𝑐𝑐2 = 0.993
After substituting the values of 𝑐𝑐1 and 𝑐𝑐2 , we get following expression for activity
coefficients:
ln 𝛾𝛾𝐴𝐴 = 𝑥𝑥𝐵𝐵2 [1.308 + 0.63𝑥𝑥𝐴𝐴 ]
ln 𝛾𝛾𝐵𝐵 = 𝑥𝑥𝐴𝐴2 [0.993 + 0.63𝑥𝑥𝐵𝐵 ]
Step-3: Estimate the vapour phase composition in equilibrium with liquid phase
Using modified Raoult’s law for species-A,
𝑦𝑦𝐴𝐴 𝑃𝑃 = 𝛾𝛾𝐴𝐴 𝑥𝑥𝐴𝐴 𝑝𝑝𝐴𝐴𝑠𝑠𝑠𝑠𝑠𝑠
Or,
𝛾𝛾𝐴𝐴 𝑥𝑥𝐴𝐴 𝑝𝑝𝐴𝐴𝑠𝑠𝑠𝑠𝑠𝑠
𝑦𝑦𝐴𝐴 =
𝑃𝑃
For given liquid composition, 𝑥𝑥𝐴𝐴 = 0.35 𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥𝐵𝐵 = 0.65, calculating activity coefficient for
species-A,
ln 𝛾𝛾𝐴𝐴 = (0.652 )[1.308 + 0.63(0.35)]
We get,
𝛾𝛾𝐴𝐴 = 1.583
Substituting, the 𝛾𝛾𝐴𝐴 , 𝑥𝑥𝐴𝐴 , 𝑝𝑝𝐴𝐴𝑠𝑠𝑠𝑠𝑠𝑠 𝑎𝑎𝑎𝑎𝑎𝑎 𝑃𝑃 values, we get,
𝑦𝑦𝐴𝐴 = 0.119
Hence,
𝑦𝑦𝐵𝐵 = 1 − 𝑦𝑦𝐴𝐴 = 1 − 0.119 = 0.881
AY2019-20 | Sem-2 Tutorial 04-Solutions
Discussion Question 5

VLE data for ethanol (1) – n-hexane (2) system at 318.5 𝐾𝐾 is provided in Table Q5:

Table Q5

Pressure (kPa) 𝒙𝒙𝟏𝟏 𝒚𝒚𝟏𝟏

45.8 0.0 0.0
48.3 0.0048 0.0682
25.3 0.9947 0.9107
23.0 1.0 1.0

(a) Choose an appropriate excess Gibbs energy model and obtain expression for excess
Gibbs energy.
(b) At what compositions excess Gibbs energy (𝐺𝐺 𝐸𝐸 ) is zero? Explain.
𝐺𝐺 𝐸𝐸
(c) Does 𝑅𝑅𝑅𝑅 𝑣𝑣𝑣𝑣 𝑥𝑥1 curve reach a local maximum or minimum for this binary system?
Explain.
𝐺𝐺 𝐸𝐸
(d) Calculate the value of 𝑥𝑥1 at which the local maximum/minimum for 𝑅𝑅𝑅𝑅 can be found.
Also find the activity coefficient values for both the species at this composition (𝑥𝑥1 ).

Solution:
(a) Expression for Gibbs energy
Step-1: Analysis VLE data
Vapour phase: ideal gas mixture (low pressure)
Liquid phase: (Real) non-ideal solution (chemically dissimilar species)
VLE model: Modified Raoult’s law (𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝛾𝛾𝑖𝑖 𝑥𝑥𝑖𝑖 𝑝𝑝𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 )
From VLE data:
Saturation pressure of Ethanol (1), 𝑝𝑝1𝑠𝑠𝑠𝑠𝑠𝑠 = 23 𝑘𝑘𝑘𝑘𝑘𝑘
Saturation pressure of n-hexane (2), 𝑝𝑝2𝑠𝑠𝑠𝑠𝑠𝑠 = 45.8 𝑘𝑘𝑘𝑘𝑘𝑘
Liquid phase @ 48.3 kPa = Infinitely diluted by ethanol (this information can be used to
find activity coefficient for ethanol for the case of infinite dilution)
Liquid phase @ 25.3 kPa = Infinitely diluted by n-hexane (this information can be used to
find activity coefficient for n-hexane for the case of infinite dilution)
Step-2: Choice of Gibbs energy model
Excess Gibbs energy model is chosen based on activity coefficients of the species at
infinitely diluted conditions.
𝛾𝛾𝑖𝑖∞ can be evaluated using VLE data and Raoult’s law,
𝑦𝑦𝑖𝑖 𝑃𝑃
𝛾𝛾𝑖𝑖 =
𝑥𝑥𝑖𝑖 𝑝𝑝𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑦𝑦1 𝑃𝑃 (0.0682)(48.3)
𝛾𝛾1∞ = 𝛾𝛾1 |@𝑥𝑥1 →0,𝑃𝑃=48.3 𝑘𝑘𝑘𝑘𝑘𝑘 = 𝑠𝑠𝑠𝑠𝑠𝑠 = (0.0048)(23) = 29.838
𝑥𝑥1 𝑝𝑝1

AY2019-20 | Sem-2 Tutorial 04-Solutions

And
𝑦𝑦2 𝑃𝑃 (1 − 0.9107)(25.3)
𝛾𝛾2∞ = 𝛾𝛾2 |@𝑥𝑥2 →0,𝑃𝑃=25.3 𝑘𝑘𝑘𝑘𝑘𝑘 = = = 9.307
𝑥𝑥2 𝑝𝑝2𝑠𝑠𝑠𝑠𝑠𝑠 (1 − 0.9947)(45.8)
𝛾𝛾1∞ ≠ 𝛾𝛾2∞ , hence, we cannot use one constant Margules equation. However, we can select
either two-factor Margules equation or Van Laar equation to model excess Gibbs energy.
Step-3: Excess Gibbs energy equation
For two-constant Margules equation,
𝐺𝐺 𝐸𝐸
= (𝐴𝐴21 𝑥𝑥1 + 𝐴𝐴12 𝑥𝑥2 )
𝑥𝑥1 𝑥𝑥2 𝑅𝑅𝑅𝑅
Constants can be found out using,
ln 𝛾𝛾1∞ = 𝐴𝐴12 ⇒ 𝐴𝐴12 = 3.395
ln 𝛾𝛾2∞ = 𝐴𝐴21 ⇒ 𝐴𝐴21 = 2.231
Hence we get,
𝐺𝐺 𝐸𝐸 = 𝑅𝑅𝑅𝑅 {2.231𝑥𝑥1 + 3.395𝑥𝑥2 }𝑥𝑥1 𝑥𝑥2
(b) At what compositions excess Gibbs energy (𝐺𝐺 𝐸𝐸 ) is zero? Explain
𝐺𝐺 𝐸𝐸 = 0, for an ideal solution when solution is dominated by one species.
lim 𝐺𝐺 𝐸𝐸 /𝑅𝑅𝑅𝑅 = 0 𝑜𝑜𝑜𝑜 lim 𝐺𝐺 𝐸𝐸 /𝑅𝑅𝑅𝑅 = 0
𝑥𝑥1 →1 𝑥𝑥2 →1

𝐺𝐺 𝐸𝐸
(c) Does 𝑣𝑣𝑣𝑣 𝑥𝑥1 curve reach a local maximum or minimum for this binary system?
𝑅𝑅𝑅𝑅

Explain
𝐺𝐺 𝐸𝐸
As we discussed, 𝑅𝑅𝑅𝑅 = 0 when, 𝑥𝑥1 = 0 and also 𝑥𝑥1 = 1

For 0 ≤ 𝑥𝑥1 ≤ 1,
𝐺𝐺 𝐸𝐸
= {2.231𝑥𝑥1 + 3.395𝑥𝑥2 }𝑥𝑥1 𝑥𝑥2
𝑅𝑅𝑅𝑅
From the above equation we can make out that 𝐺𝐺 𝐸𝐸 /𝑅𝑅𝑅𝑅 will be positive.
𝐺𝐺 𝐸𝐸
Hence, 𝑅𝑅𝑅𝑅 𝑣𝑣𝑣𝑣 𝑥𝑥1 curve reach a local maximum.
𝐺𝐺 𝐸𝐸
(d) Calculate the value of 𝑥𝑥1 at which the local maximum/minimum for can be found.
𝑅𝑅𝑅𝑅

Also find the activity coefficient values for both the species at this composition (𝑥𝑥1 )
As we discussed in part (c), we should see maximum,
𝐺𝐺 𝐸𝐸
To find this maxima, differentiate with respect to 𝑥𝑥1 and set it to zero (we can directly
𝑅𝑅𝑇𝑇
𝐺𝐺 𝐸𝐸
use the expression for that was derived in part (a), however, we will use another
𝑅𝑅𝑅𝑅

method).
From summability relation:
𝐺𝐺 𝐸𝐸
= ∑𝑖𝑖 𝑥𝑥𝑖𝑖 ln 𝛾𝛾𝑖𝑖
𝑅𝑅𝑅𝑅

AY2019-20 | Sem-2 Tutorial 04-Solutions

For a binary mixture,
𝐺𝐺 𝐸𝐸
= 𝑥𝑥1 ln 𝛾𝛾1 + 𝑥𝑥2 ln 𝛾𝛾2
𝑅𝑅𝑅𝑅

Differentiating above equation with 𝑥𝑥1 , (then using Gibbs-Duhem equation we get
following, see slide # 14 in non-ideal solution chapter)
𝐺𝐺𝐸𝐸
𝑑𝑑� �
𝑅𝑅𝑅𝑅
= ln 𝛾𝛾1 − ln 𝛾𝛾2
𝑑𝑑𝑥𝑥1

Using the expressions for ln 𝛾𝛾𝑖𝑖 from two-constant Margules equation,

𝐺𝐺𝐸𝐸
𝑑𝑑� �
𝑅𝑅𝑅𝑅
= {𝑥𝑥22 [𝐴𝐴12 + 2(𝐴𝐴21 − 𝐴𝐴12 )𝑥𝑥1 ]} − {𝑥𝑥12 [𝐴𝐴21 + 2(𝐴𝐴12 − 𝐴𝐴21 )𝑥𝑥2 ]}
𝑑𝑑𝑥𝑥1

We get,
𝐺𝐺𝐸𝐸
𝑑𝑑� �
𝑅𝑅𝑅𝑅
= 3𝑥𝑥12 (𝐴𝐴12 − 𝐴𝐴21 ) + 2𝑥𝑥1 (𝐴𝐴21 − 2𝐴𝐴12 ) + 𝐴𝐴12
𝑑𝑑𝑥𝑥1

𝐺𝐺𝐸𝐸
𝑑𝑑� �
𝑅𝑅𝑅𝑅
Using 𝐴𝐴12 and 𝐴𝐴21 , and setting = 0, we get,
𝑑𝑑𝑥𝑥1

3.492𝑥𝑥12 − 9.19𝑥𝑥1 + 3.395 = 0

Finding the roots, we get, 𝑥𝑥1 = 0.4498 𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥1 = 2.163
The first root will be of our interest as composition cannot be more than “1.0”.
𝐺𝐺 𝐸𝐸
Hence, the local maximum for 𝑅𝑅𝑅𝑅 can be found @ 𝑥𝑥1 = 0.4498.

Using this value, we can find the activity coefficients,

ln 𝛾𝛾1 = 𝑥𝑥22 [𝐴𝐴12 + 2(𝐴𝐴21 − 𝐴𝐴12 )𝑥𝑥1 ] ⇒ 𝛾𝛾1 = 2.036
ln 𝛾𝛾2 = 𝑥𝑥12 [𝐴𝐴21 + 2(𝐴𝐴12 − 𝐴𝐴21 )𝑥𝑥2 ] ⇒ 𝛾𝛾2 = 2.036

AY2019-20 | Sem-2 Tutorial 04-Solutions

 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Sample Examples VLE - Solutions
Sample Example-1
Assuming Raoult’s law is applicable to a binary system, acetonitrile (1) / nitromethane (2),
work on the following tasks:
(a) Generate the VLE data (𝑃 − 𝑥1 − 𝑦1 ) and plot it.

(b) Evaluate the bubble point pressure of a binary mixture (with 40% acetonitrile) @ 75C

(c) Evaluate the dew point pressure of a binary mixture (with 40% acetonitrile) @ 75C
(d) Evaluate the dew point temperature of a binary mixture (with 40% acetonitrile) @ 70
kPa
Information: The saturation pressure for the two species can be calculated using Antoine
equation
3412.1 3331.7
ln 𝑃1𝑠𝑎𝑡 = 14.895 − ; ln 𝑃2𝑠𝑎𝑡 = 14.751 −
𝑇 − 22.627 𝑇 − 45.55
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑠 𝑖𝑛 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇 𝑖𝑠 𝑖𝑛 𝐾𝑒𝑙𝑣𝑖𝑛𝑠
Solution:
(a) Generate the VLE data (𝑃 − 𝑥1 − 𝑦1 ) and plot it:
To generate 𝑃 − 𝑥1 − 𝑦1 data, we need to first assume a constant temperature value and
calculate the saturation pressure for the two species at selected temperature (using the Antoine
equations).

Step-1: Let us assume T = 75C, and calculate saturation pressure for both the species,

𝑃1𝑠𝑎𝑡 = 82.127 𝑘𝑃𝑎; 𝑃2𝑠𝑎𝑡 = 41.913 𝑘𝑃𝑎

Step-2: The two end points on 𝑃 − 𝑥1 − 𝑦1 plot

𝑥1 = 0; 𝑦1 = 0; 𝑃 = 𝑃2𝑠𝑎𝑡

𝑥1 = 1; 𝑦1 = 1; 𝑃 = 𝑃1𝑠𝑎𝑡
For remaining data points, we make use of the bubble point pressure calculations, we assume
certain 𝑥1 value (then, 𝑥2 = 1 − 𝑥1 ), we calculate bubble point pressure using,

𝑃 = ∑ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡

𝑖

Doing sample calculations for 𝑥1 = 0.2, then, 𝑥2 = 1 − 𝑥1 = 0.8),

Calculate bubble point pressure using, 𝑃 = (0.2)(82.127) + (0.8)(41.913)
We get, 𝑃 = 49.93 𝑘𝑃𝑎
Step-3: At selected 𝑥1 , and corresponding bubble point 𝑃 value (calculated in step-2), estimating
vapour composition using the Raoult’s law:

𝑦1 𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡
Rearranging,

𝑦1 = 𝑥1 𝑃1𝑠𝑎𝑡 ⁄𝑃 = (0.2)(82.127)⁄49.93 = 0.33

Repeating steps 2 and 3 for other values of 𝑥1 , the collected data is shown below:

𝒙𝟏 𝑷 𝒚𝟏
0 41.90 0.00
0.1 45.92 0.18
0.2 49.95 0.33
0.3 53.97 0.46
0.4 57.99 0.57
0.5 62.01 0.66
0.6 66.04 0.75
0.7 70.06 0.82
0.8 74.08 0.89
0.9 78.10 0.95
1 82.13 1.00

𝑃 − 𝑥1 − 𝑦1 plot is shown below:

90.00

80.00

70.00
Pressure (kPa)

𝑃 − 𝑥1
60.00 𝑃 − 𝑦1

50.00

40.00

30.00
0 0.2 0.4 0.6 0.8 1
x1, y1

(b) Evaluate the bubble point pressure of a binary mixture (with 40% acetonitrile) @ 75C

The saturation pressure for the two species @75C has been calculated in part (a). The
calculation of bubble point pressure for a binary mixture with 40% acetonitrile is the data point
we got in part(a) for 𝑥1 = 0.4
Repeating calculation for bubble point pressure for 𝑥1 = 0.4

𝑃 = ∑ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡

𝑖
 𝑃 = (0.4)(82.127) + (0.6)(41.913)
We get, 𝑃 = 57.99 𝑘𝑃𝑎
The vapour composition can be found using Raoult’s law,
𝑥1 𝑃1𝑠𝑎𝑡 (0.4)(82.127)
𝑦1 = = = 0.57
𝑃 (57.99)
Hence, 𝑦2 = 1 − 𝑦1 = 0.43

(c) Evaluate the dew point pressure of a binary mixture (with 40% acetonitrile) @ 75C

The saturation pressure for the two species @75C has been calculated in part (a). The
calculation of dew point pressure for a binary mixture with 40% acetonitrile can be done using
the following equation,
1
𝑃=
∑𝑖 𝑦𝑖 𝑃𝑖𝑠𝑎𝑡
1 1
𝑃= 𝑦 𝑦2 = 0.4 = 52.12 𝑘𝑃𝑎
1 0.6
𝑠𝑎𝑡 + 𝑠𝑎𝑡 +
𝑃1 𝑃2 82.127 41.913
Dew point pressure 𝑃 = 52.12 𝑘𝑃𝑎
The liquid composition can be found using Raoult’s law,
𝑦1 𝑃 (0.4)(52.12)
𝑥1 = = = 0.254
𝑃1𝑠𝑎𝑡 (82.127)

Hence, 𝑥2 = 1 − 𝑥1 = 0.746
(d) Evaluate the dew point temperature of a binary mixture (with 40% acetonitrile) @ 70 kPa
Given: 𝑃 = 70 𝑘𝑃𝑎; 𝑦1 = 0.4
Find: 𝑇𝑑𝑒𝑤 ; 𝑥1 ; 𝑥2

Raoult’s law: 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 or 𝑥𝑖 = 𝑦𝑖 𝑃/𝑃𝑖𝑠𝑎𝑡

Eliminating unknown 𝑥𝑖 , we get,

∑ 𝑥𝑖 = ∑ 𝑦𝑖 𝑃/𝑃𝑖𝑠𝑎𝑡 = 1

The unknown dew point temperature appears implicitly in the situation pressure. We need
iterative solution to evaluate dew point temperature.
How to decide what temperature to use?

For given pressure, 𝑃 = 70 𝑘𝑃𝑎, find the 𝑇1𝑠𝑎𝑡 and 𝑇2𝑠𝑎𝑡 using the Antoine equations.
3412.1
𝑇1𝑠𝑎𝑡 = + 22.627 = 343.117𝐾
14.895 − ln 𝑃
3331.7
𝑇2𝑠𝑎𝑡 = + 45.55 = 362.81𝐾
14.751 − ln 𝑃
The dew point temperature should be between 𝑇1𝑠𝑎𝑡 and 𝑇2𝑠𝑎𝑡 , stepwise procedure for iterative
solution is:
 1. Guess temperature between 𝑇1𝑠𝑎𝑡 and 𝑇2𝑠𝑎𝑡
2. Calculate, 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡
𝑦𝑃
3. Evaluate, 𝑥𝑖 = 𝑃𝑠𝑎𝑡
𝑖

𝑖
4. Check if ∑ 𝑥𝑖 = ∑ 𝑦𝑖 𝑃/𝑃𝑖𝑠𝑎𝑡 = 1
5. If ∑ 𝑥𝑖 = 1, then the temperature guess is the dew point temperature
6. If ∑ 𝑥𝑖 ≠ 1, then the temperature guess is wrong, make another guess and repeat steps
2-5, until the criterion in step-5 is satisfied.
The data for iterative procedure is as follows:

Iteration Temperature (K) 𝑃1𝑠𝑎𝑡 𝑃2𝑠𝑎𝑡 𝑥1 𝑥2 ∑ 𝑥𝑖

1 350.00 87.56 45.04 0.32 0.93 1.25
2 345.00 74.49 37.52 0.38 1.12 1.50
3 355.00 102.42 53.76 0.27 0.78 1.05
4 356.00 105.63 55.65 0.27 0.75 1.02
5 356.50 107.26 56.62 0.26 0.74 1.00

Hence, the dew pointe temperature = 356.5 K

The corresponding liquid composition values are available in the table above (for iteration # 5),
𝑥1 = 0.26; 𝑥2 = 0.74
Sample Example-2
For the system methanol (1)/methyl acetate (2), the following equations provide a reasonable
correlation for the activity coefficients:

ln 𝛾1 = 𝐴𝑥22 ln 𝛾2 = 𝐴𝑥12 𝑤ℎ𝑒𝑟𝑒, 𝐴 = 2.771 − 0.00523 𝑇

In addition, the following Antoine equations provide vapour pressures:
3643.13 2665.54
ln 𝑃1𝑠𝑎𝑡 = 16.59158 − ; ln 𝑃2𝑠𝑎𝑡 = 14.25326 −
𝑇 − 33.424 𝑇 − 53.424
(a) Assume the mixture has 20% of methanol; find the pressure ranges over which this system
can exist as two phases at T = 318.15 K.
(b) Comment if the azeotrope exists at 318.15 K, if so, find the azeotrope pressure and the
azeotrope composition for the given temperature.
Solution:
(a) Assume the mixture has 20% of methanol; find the pressure ranges over which this system
can exist as two phases at T = 318.15 K.
The pressure range over which the system exist as two phases is the bubble and dew point
pressure.
Finding the bubble point pressure, using the modified Raoult’s law,
𝑃 = ∑ 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝛾1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑃2𝑠𝑎𝑡
𝑖

Replacing the equation given for 𝛾𝑖

𝑃 = ∑ 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 (exp(𝐴𝑥22 ))𝑃1𝑠𝑎𝑡 + 𝑥2 (exp(𝐴𝑥12 ))𝑃2𝑠𝑎𝑡 … (𝐸𝑞. 2.1)

𝑖

𝛾𝑖 values depend on the constant A. Calculating value of A @ given temperature (T=318.15 K):
𝐴 = 2.771 − 0.00523 (318.15) = 1.107
Calculating the 𝛾𝑖 values,

𝛾1 = exp(𝐴𝑥22 ) = exp(1.107 × 0.82 ) = 2.031;

𝛾2 = 1.0452
@ T = 318.15 K, calculating saturation pressure for both the species,

𝑃1𝑠𝑎𝑡 = 44.54 𝑘𝑃𝑎; 𝑃2𝑠𝑎𝑡 = 65.54 𝑘𝑃𝑎

Using the above values in the 𝐸𝑞. 2.1 we have for bubble point pressure (𝑃), we get,
𝑃 = (0.2)(2.031)(44.54) + (1 − 0.20(1.0452)(65.54) = 72.98 𝑘𝑃𝑎
Hence, bubble point pressure = 72.98 kPa
Similarly calculating dew point pressure using the following equation when modified Raoult’s
law is applicable:

Modified Raoult’s law: 𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 or 𝑥𝑖 = 𝑦𝑖 𝑃/𝛾𝑖 𝑃𝑖𝑠𝑎𝑡

Eliminating unknown 𝑥𝑖 , we get, ∑ 𝑥𝑖 = ∑ 𝑦𝑖 𝑃/𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 1

 1 1
𝑃= = 𝑦1 𝑦2 … (𝐸𝑞. 2.2)
∑(𝑦𝑖 /𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 )
𝑠𝑎𝑡 + 𝑠𝑎𝑡
𝛾1 𝑃1 𝛾2 𝑃2

However, 𝛾𝑖 is a function of liquid composition, 𝑥𝑖 . We need to use iterative method, here are the
steps to follow:
1. Guess 𝛾𝑖 values (𝛾𝑖 = 1)
2. Calculate, 𝑃 using 𝐸𝑞. 2.2.
3. Calculate, 𝑥𝑖
4. Evaluate 𝛾𝑖 using the equations given to us, ln 𝛾1 = 𝐴𝑥22 ; ln 𝛾2 = 𝐴𝑥12
5. If the assumed values of 𝛾𝑖 “in step 1” and calculated values of 𝛾𝑖 (in step 4) are same,
then the calculated value of pressure (in step 2) is the required dew point pressure.
The data for iterative procedure is as follows:

Iteration gamma1 gamma2 P x1 x2 gamma1' gamma2'

1 1 1 59.95973 0.269246 0.730754 1.806119 1.083564
2 1.806119 1.083564 72.81322 0.181031 0.818969 2.101239 1.036948
3 2.101239 1.036948 71.99313 0.153853 0.846147 2.209194 1.026552
4 2.209194 1.026552 71.91756 0.146181 0.853819 2.241323 1.023939
5 2.241323 1.023939 71.91158 0.144073 0.855927 2.250281 1.023246
Hence, dew point pressure = 71.91 kPa
The range of pressure over which this system can exist as two phases at T = 318.15 K, is 71.91 to
72.98 kPa.
(b) Comment if the azeotrope exists at 318.15 K, if so, find the azeotrope pressure and the
azeotrope composition for the given temperature.
The criterion for existence of azeotrope is,
𝛼12 |@𝑥1 =0 > 1 𝑎𝑛𝑑 𝛼12 |@𝑥1 =1 < 1

𝑜𝑟 𝛼12 |@𝑥1 =0 < 1 𝑎𝑛𝑑 𝛼12 |@𝑥1 =1 > 1

For this system, we are using a modified Raoult’s law

𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 𝑜𝑟 𝑦𝑖 =
𝑃
Recall,

𝐾1 𝑦1 𝑥2 𝑥1 𝛾1 𝑃1𝑠𝑎𝑡 𝑥2 𝑃 𝛾1 𝑃1𝑠𝑎𝑡
𝛼12 = = = =
𝐾2 𝑥1 𝑦2 𝑥1 𝑃 𝑥2 𝛾2 𝑃2𝑠𝑎𝑡 𝛾2 𝑃2𝑠𝑎𝑡

Since, ln 𝛾1 = 𝐴𝑥22 ; ln 𝛾2 = 𝐴𝑥12 ,

𝛾1 𝑃1𝑠𝑎𝑡 {exp(𝐴𝑥22 )}𝑃1𝑠𝑎𝑡 {exp(𝐴(1 − 𝑥1 )2 )}𝑃1𝑠𝑎𝑡

𝛼12 = = =
𝛾2 𝑃2𝑠𝑎𝑡 {exp(𝐴𝑥12 )}𝑃2𝑠𝑎𝑡 {exp(𝐴𝑥12 )}𝑃2𝑠𝑎𝑡

Substituting the known values (A, 𝑃1𝑠𝑎𝑡 𝑎𝑛𝑑 𝑃2𝑠𝑎𝑡 ) and expressing 𝛼12 in terms of 𝑥1 ,
{exp(1.107(1 − 𝑥1 )2 )}(44.54)
𝛼12 =
{exp(1.107𝑥12 )}(65.64)
Evaluating 𝛼12 @ 𝑥1 = 0 and @ 𝑥1 = 1,
{exp(1.107(1 − 0)2 )}(44.54)
𝛼12 |@𝑥1 =0 = = 2.052 > 1
{exp((1.107)(0)2 )}(65.64)

and
{exp(1.107(1 − 1)2 )}(44.54)
𝛼12 |@𝑥1 =1 = = 0.224 < 1
{exp((1.107)(1)2 )}(65.64)

As, 𝛼12 |@𝑥1 =0 > 1 𝑎𝑛𝑑 𝛼12 |@𝑥1 =1 < 1, we can conclude that the azeotrope exists at 318.15 K.

Next step is to calculate the azeotrope composition and azeotrope pressure,

@ azeotropic point,
𝑥𝑖 = 𝑦𝑖 𝑎𝑛𝑑 𝛼12 = 1
𝑦 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
Using the modified Raoult’s law, 𝑥𝑖 = 𝑃
𝑖

We can write for azeotrope condition,

𝛾1 𝑃1𝑠𝑎𝑡 𝛾2 𝑃2𝑠𝑎𝑡
=
𝑃 𝑃
Hence, we get, 𝛾1 𝑃1𝑠𝑎𝑡 = 𝛾2 𝑃2𝑠𝑎𝑡

Or,
𝛾1 𝑃2𝑠𝑎𝑡 65.64
| = 𝑠𝑎𝑡 = = 1.4737
𝛾2 @𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 𝑃1 44.54

As, ln 𝛾1 = 𝐴𝑥22 ; ln 𝛾2 = 𝐴𝑥12

Therefore,
𝛾1
ln 𝛾1 − ln 𝛾2 = 𝐴𝑥22 − 𝐴𝑥12 ⇒ ln ( ) = 𝐴𝑥22 − 𝐴𝑥12
𝛾2
After modification we get,
𝛾1
ln ( ) = 𝐴(𝑥2 − 𝑥1 )(𝑥2 + 𝑥1 ) = 𝐴(𝑥2 − 𝑥1 ) = 𝐴(1 − 2𝑥1 )
𝛾2
𝛾1
ln ( ) = ln(1.4737) = 0.388 = 𝐴(1 − 2𝑥1 )
𝛾2
Using A=1.107,
𝑥1 |@𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 = 0.325 = 𝑦1 |@𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒

Using this value of 𝑥1 , calculating 𝛾1 ,

𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒
𝛾1 = 1.657

Now,
𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒
𝑃𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 = 𝛾1 𝑃1𝑠𝑎𝑡 = (1.657)(44.54) ≈ 73.8 𝑘𝑃𝑎
Sample Example-3
Calculate mole fraction of oxygen dissolved in water equilibrated with pure oxygen at 1.013 bar,
25°C. Henry’s law constant at 25°C is 42735 bar.
Solution:
Oxygen: Species-1; Water: Species-2
Given: 𝑃 = 1.013 𝑏𝑎𝑟; 𝑇 = 25℃; ℋ1 = 42735 𝑏𝑎𝑟
Find: 𝑥1
Assumption: Ideal gas/Ideal Solution
Equations:
For Oxygen (infinite dilution in liquid phase): 𝑦1 𝑃 = 𝑥1 ℋ1

For water: 𝑦2 𝑃 = 𝑥2 𝑃2𝑠𝑎𝑡

Combining the equations for oxygen and water, we get,

𝑦1 𝑃 + 𝑦2 𝑃 = 𝑥1 ℋ1 + 𝑥2 𝑃2𝑠𝑎𝑡

Or,

𝑃 = 𝑥1 ℋ1 + 𝑥2 𝑃2𝑠𝑎𝑡
With, 𝑥2 = 1 − 𝑥1 ,

𝑃 = 𝑥1 ℋ1 + (1 − 𝑥1 )𝑃2𝑠𝑎𝑡
Rearranging, we get,
(𝑃 − 𝑃2𝑠𝑎𝑡 )
𝑥1 =
(ℋ1 − 𝑃2𝑠𝑎𝑡 )

Using the Antoine equation, we can find the saturation pressure for water, 𝑃2𝑠𝑎𝑡
3885.7
𝑃2𝑠𝑎𝑡 = 𝑒𝑥𝑝 {16.387 − }
𝑇 − 42.98
With 𝑇 = 25 + 273; 𝑤𝑒 𝑔𝑒𝑡, 𝑃2𝑠𝑎𝑡 = 3.16 𝑘𝑃𝑎 = 0.0316 𝑏𝑎𝑟

Hence,
(1.013 − 0.0316)
𝑥1 = = 2.296 × 10−5
(42735 − 0.0316)
Sample Example-4
Calculate dew point pressure and bubble point pressure for a mixture of 10% methane, 20%
ethane, 70% propane at 10°C.
Use K-factor method.
Solution:
(a) Find: dew point pressure and 𝑥𝑖
Given: 𝑇 = 10℃; 𝑦𝑖
Methane: Species-1;
Ethane: Species-2;
Propane: Species-3;
𝑦1 = 0.1; 𝑦2 = 0.2; 𝑦3 = 0.7
Using K-factor method,
𝐾𝑖 = 𝑦𝑖 /𝑥𝑖
Eliminating unknown liquid composition, 𝑥𝑖 , we get the condition which can be used for finding
the dew point pressure,

∑ 𝑥𝑖 = ∑ 𝑦𝑖 /𝐾𝑖 = 1

K factor depends on the temperature and pressure, To find the dew point pressure, we ned to
use iterative procedure, the steps are included here,
1. Assume pressure value (P)
2. Using the DePriester chart, find out the 𝐾𝑖 values for the combination of given
temperature and assumed pressure.
𝑦
3. Evaluate 𝐾𝑖
𝑖
4. Check if, ∑ 𝑦𝑖 /𝐾𝑖 = 1
5. If condition in step-4 is satisfied, assumed Pressure is the dew point pressure, if not,
make appropriate guess of pressure and repeat steps 2-4.

Following table shows the data collected for various iterations:

Guess 𝑃 = 800 𝑘𝑃𝑎 𝑃 = 1000 𝑘𝑃𝑎 𝑃 = 850 𝑘𝑃𝑎

Species/Data 𝑦𝑖 𝐾𝑖 𝐾𝑖 𝐾𝑖
Methane (1) 0.1 16.5 13 16
Ethane (2) 0.2 2.8 2.25 2.6
Propane (3) 0.7 0.7 0.675 0.77
∑ 𝑦𝑖 /𝐾𝑖 = 0.9311 ∑ 𝑦𝑖 /𝐾𝑖 = 1.3336 ∑ 𝑦𝑖 /𝐾𝑖 = 0.993

Hence, dew point pressure = 850 kPa

Finding the corresponding values of 𝑥𝑖 using K-factor, 𝑥𝑖 = 𝑦𝑖 /𝐾𝑖
We get, 𝑥1 = 0.00625; 𝑥2 = 0.077; 𝑥3 = 0.909
(b) Find: bubble point pressure and 𝑦𝑖
Given: 𝑇 = 10℃; 𝑥𝑖
𝑥1 = 0.1; 𝑥2 = 0.2; 𝑥3 = 0.7
Using K-factor method,
𝐾𝑖 = 𝑦𝑖 /𝑥𝑖
Eliminating unknown vapour composition, 𝑦𝑖 , we get the condition which can be used for
finding the bubble point pressure,

∑ 𝑦𝑖 = ∑ 𝐾𝑖 𝑥𝑖 = 1

K factor depends on the temperature and pressure, To find the bubble point pressure, we ned to
use iterative procedure, the steps are included here,
1. Assume pressure value (P)
2. Using the DePriester chart, find out the 𝐾𝑖 values for the combination of given
temperature and assumed pressure.
3. Evaluate 𝐾𝑖 𝑥𝑖
4. Check if, ∑ 𝐾𝑖 𝑥𝑖 = 1
5. If condition in step-4 is satisfied, assumed Pressure is the bubble point pressure, if not,
make appropriate guess of pressure and repeat steps 2-4.
Following table shows the data collected for various iterations:

Guess 𝑃 = 2000 𝑘𝑃𝑎 𝑃 = 2500 𝑘𝑃𝑎 𝑃 = 2300 𝑘𝑃𝑎

Species/Data 𝑥𝑖 𝐾𝑖 𝐾𝑖 𝐾𝑖
Methane (1) 0.1 5.9 5 5.3
Ethane (2) 0.2 1.25 1.1 1.2
Propane (3) 0.7 0.4 0.35 0.35
∑ 𝑦𝑖 /𝐾𝑖 = 1.12 ∑ 𝑦𝑖 /𝐾𝑖 = 0.965 ∑ 𝑦𝑖 /𝐾𝑖 = 1.01

Hence, dew point pressure = 2300 kPa

Finding the corresponding values of 𝑦𝑖 using K-factor, 𝑦𝑖 = 𝐾𝑖 𝑥𝑖
We get, 𝑦1 = 0.53; 𝑥2 = 0.24; 𝑥3 = 0.245
Sample Example-5
One mole of acetone (1), acetonitrile (2), nitromethane (3) at 80°C and 110 kPa with overall
composition of 𝑧1=0.45, 𝑧2 =0.35, 𝑧3=0.20 is flashed into a mixture of vapour and liquid. Determine
𝐿, 𝑉, 𝑥𝑖, and 𝑦𝑖, assuming Raoult’s Law is valid.
Solution:
Given: One mole of acetone (1), acetonitrile (2), nitromethane (3) at 80°C and 110 kPa entering
the flash unit with overall composition of 𝑧1=0.45, 𝑧2 =0.35, 𝑧3=0.20.
Find: 𝐿, 𝑉, 𝑥𝑖, and 𝑦𝑖
Assumption: Raoult’s Law is valid
Check if the system is in the 2-phase region:
This can be confirmed by
1. Checking if the pressure given is between the dew point and bubble point pressure
values for the mixture at given temperature,
2. Checking if the given temperature is between the bubble point temperature and dew
point temperature at given pressure.
Let us check the pressure value for given temperature.
First, we need to find the saturation pressures for the 3 species at given temperature,
For acetone (1),
2756.22
ln 𝑃1𝑠𝑎𝑡 (𝑖𝑛 𝑘𝑃𝑎) = 14.3145 − ⟹ 𝑃1𝑠𝑎𝑡 = 213.4 𝑘𝑃𝑎
𝑇 (𝑖𝑛 𝐾) − 45.09
For acetonitrile (2),
3431.1
ln 𝑃2𝑠𝑎𝑡 (𝑖𝑛 𝑘𝑃𝑎) = 14.895 − ⟹ 𝑃2𝑠𝑎𝑡 = 95.96 𝑘𝑃𝑎
𝑇 (𝑖𝑛 𝐾) − 22.627
For nitromethane (3)
3331.7
ln 𝑃3𝑠𝑎𝑡 (𝑖𝑛 𝑘𝑃𝑎) = 14.7513 − ⟹ 𝑃2𝑠𝑎𝑡 = 50.14 𝑘𝑃𝑎
𝑇 (𝑖𝑛 𝐾) − 45.55
Note: Do not get confused with the constants in Antoine Equation used here and the values in
the textbook (appendix). Whatever constants you use, make sure you are using correct units.
For finding the bubble point pressure, 𝑥1 = 0.45, 𝑥2 = 0.35, 𝑥3 = 0.20
The equation for bubble point pressure,

𝑃 = ∑ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡 + 𝑥3 𝑃3𝑠𝑎𝑡 = 1

Substituting the values, we get, bubble point pressure = 139.64 kPa

For finding the dew point pressure, 𝑦1 = 0.45, 𝑦2 = 0.35, 𝑦3 = 0.20
The equation for dew point pressure,
1 1
𝑃= 𝑠𝑎𝑡 = =1
∑ 𝑦𝑖 /𝑃𝑖 𝑦1 /𝑃1 + 𝑦2 /𝑃2𝑠𝑎𝑡 + 𝑦3 /𝑃3𝑠𝑎𝑡
𝑠𝑎𝑡
Substituting the values, we get, dew point pressure = 102.62 kPa
As the given pressure is between the bubble and dew point pressure values, the system is in 2-
phase region,
Calculations for flash unit:
Overall mass balance:
𝐹 = 𝐿 + 𝑉 … . . 𝐸𝑞 (5.1)
Component mass balance:
𝑧𝑖 𝐹 = 𝑥𝑖 𝐿 + 𝑦𝑖 𝑉 … . . 𝐸𝑞 (5.2)
Eliminating “L” from Eq (5.2), using Eq (5.1), we get,
𝑧𝑖 𝐹 = 𝑥𝑖 (𝐹 − 𝑉) + 𝑦𝑖 𝑉

Using the Raoult’s law, 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 to eliminate 𝑥𝑖 , we get,

𝑦𝑖 𝑃
𝑧𝑖 𝐹 = (𝐹 − 𝑉) + 𝑦𝑖 𝑉
𝑃𝑖𝑠𝑎𝑡

Or,
𝑧𝑖 𝐹
𝑦𝑖 =
𝑃
𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉)
𝑃𝑖

In the above equation we have two unknowns, eliminating 𝑦𝑖 , by equating ∑ 𝑦𝑖 = 1, we get,

𝑧𝑖 𝐹
∑ 𝑦𝑖 = ∑ =1
𝑃
𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉)
𝑃𝑖

Or,
𝑧1 𝐹 𝑧2 𝐹 𝑧3 𝐹
+ + =1
𝑃 𝑃 𝑃
𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉) 𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉) 𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉)
𝑃1 𝑃2 𝑃3

We know everything, except, V. After substituting the know parameters, we get,

𝑉 = 0.798 𝑚𝑜𝑙 ≈ 0.8 𝑚𝑜𝑙
Using, Eq (5.1), we can get, L = 0.2 mol
Using,
𝑧𝑖 𝐹
𝑦𝑖 = 𝑃
𝑉+ 𝑠𝑎𝑡 (𝐹−𝑉)
𝑃𝑖

We get, 𝑦1 = 0.499; 𝑦2 = 0.34; 𝑦3 = 0.161

Using Raoult’s law, we get, 𝑥1 = 0.257; 𝑥2 = 0.39; 𝑥3 = 0.353
 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Practice Questions – VLE (Sample Solutions)

Kindly use these solutions only for your reference, make sure your procedure is
correct.

Practice Question 1
Consider the methanol (1) + ethanol (2) system at 101.325 kPa.
(a) Generate the VLE data (𝑇 − 𝑥1 − 𝑦1 ) and plot it.
(b) Evaluate the bubble point temperature of a binary mixture (with 60% methanol) @
101.325 kPa.
(c) Evaluate the dew point temperature of a binary mixture (with 40% methanol) @
101.325 kPa.

Solution:

(a) Generate the VLE data (𝑇 − 𝑥1 − 𝑦1 ) and plot it.

To generate 𝑇 − 𝑥1 − 𝑦1 data, we need to first calculate the saturation temperatures for the
two species at given pressure (using the Antoine equations).

Step-1: For P = 101.325 kPa, and calculating saturation temperatures for both the species,
𝑇1𝑠𝑎𝑡 = 64.7℃; 𝑇2𝑠𝑎𝑡 = 78.2℃
Step-2: The two end points on 𝑇 − 𝑥1 − 𝑦1 plot
𝑥1 = 0; 𝑦1 = 0; 𝑇 = 𝑇2𝑠𝑎𝑡
𝑥1 = 1; 𝑦1 = 1; 𝑇 = 𝑇1𝑠𝑎𝑡

For remaining data points, we make use of the bubble point pressure equation to calculate
the bubble point temperature, we assume certain 𝑥1 value (then, 𝑥2 = 1 − 𝑥1 ), we calculate
bubble point temperature using,

𝑃 = ∑ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡

𝑖

Remember, the temperature appears in 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡 . This will be a trial and error method
for every data point we need.

Doing sample calculations for 𝑥1 = 0.2, then, 𝑥2 = 1 − 𝑥1 = 0.8

• Step a: Assume certain value of a bubble point temperature (Assuming a

temperature value between 𝑇1𝑠𝑎𝑡 and 𝑇2𝑠𝑎𝑡 (for 𝑥1 = 0.2, assuming value closer to
𝑇2𝑠𝑎𝑡 ))
• Step b: Find 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡 as assumed temperature.
• Step c: Check if equation for bubble point pressure is satisfied, 𝑃 = (0.2)(𝑃1𝑠𝑎𝑡 ) +
(0.8)(𝑃2𝑠𝑎𝑡 )

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

 • Step d: If criterion in step c is satisfied then assumed value of bubble point
temperature is correct, if not, assume another temperature value and repeat the
calculations.
• For 𝑥1 = 0.2, the bubble point temperature is, 75C.
• Finding the 𝑦1 using the Raoult’s law

Repeating the trial and error calculations for other values of 𝑥1 between 0 and 1, we get the
following table:

𝒙𝟏 𝑻 𝒚𝟏
0.00 78.20 0.00
0.10 76.57 0.16
0.20 75.01 0.30
0.30 73.52 0.42
0.40 72.10 0.53
0.50 70.73 0.63
0.60 69.43 0.72
0.70 68.17 0.80
0.80 66.97 0.87
0.90 65.81 0.94
1.00 64.70 1.00

85.00

80.00
Temperature (C)

T-x1 T-y1
75.00

70.00

65.00

60.00
0.00 0.20 0.40 0.60 0.80 1.00

x1 / y1

(b) Evaluate the bubble point temperature of a binary mixture (with 60% methanol) @
101.325 kPa.

Repeating the procedure given in part (a) to simply get the data point @ 𝑥1 = 0.6, gives us
the answer.

From the table in Part (a), the bubble point temperature for @ 𝑥1 = 0.6 is 69.43C

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

(c) Evaluate the dew point temperature of a binary mixture (with 40% methanol) @
101.325 kPa

For dew point temperature calculations, we have, 𝑦1 = 0.4; 𝑦2 = 0.6, 𝑎𝑛𝑑 𝑃 = 101.325 𝑘𝑃𝑎

Calculating the dew point temperature using the equation for dew point calculations:

1
𝑃=
∑𝑖 𝑦𝑖 𝑃𝑖𝑠𝑎𝑡
1
𝑃= 𝑦 𝑦2
1
𝑠𝑎𝑡 + 𝑠𝑎𝑡
𝑃1 𝑃2

Again, temperature appears in the equation for 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡 .

Using the iterative procedure to calculate the dew point temperature:

• Step a: Assume certain value of a dew point temperature (Assuming a temperature

value between 𝑇1𝑠𝑎𝑡 and 𝑇2𝑠𝑎𝑡
• Step b: Find 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡 as assumed temperature.
• Step c: Check if equation for dew point pressure is satisfied,
1
𝑃= 𝑦 𝑦2
1
𝑠𝑎𝑡 + 𝑠𝑎𝑡
𝑃1 𝑃2
• Step d: If criterion in step c is satisfied then assumed value of dew point
temperature is correct, if not, assume another temperature value and repeat the
calculations.
• For 𝑦1 = 0.4, the dew point temperature comes out to be, 73.77C. You can also read
this value from the 𝑇 − 𝑥1 − 𝑦1 plot given in Part (a)
• You can also find 𝑥1 using the Raoult’s law

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

Practice Question 2
100 mol/min of an equimolar mixture of 1-propanol (1) and 2-propanol (2) at 75C and 200
kPa is fed to a flash distillation unit operating at 75C and 55 kPa. Find out the composition
and flow rates of the streams exiting the flash unit if the system is assumed to follow Raoult’s
law.

Solution:

Information needed: The saturation pressure for the two species can be calculated using
Antoine equation
3483.67 3640.2
ln 𝑃1𝑠𝑎𝑡 = 16.1154 − ; ln 𝑃2𝑠𝑎𝑡 = 16.6796 −
𝑇 + 205.807 𝑇 + 219.61
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑠 𝑖𝑛 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇 𝑖𝑠 𝑖𝑛 C
At the given operating temperature of flash distillation unit (75C),

𝑃1𝑠𝑎𝑡 = 40.83 𝑘𝑃𝑎; 𝑃2𝑠𝑎𝑡 = 75.46 𝑘𝑃𝑎

Let us assume that for given temperature and pressure the mixture exists in the two-phase
region (you can check this by following the procedure explained in Sample example-5 on
VLE).

We can write down the mass balance equations as given in Sample Example-5 on VLE, and
we arrive at the following equation with only one unknown.

𝑧𝑖 𝐹
∑ 𝑦𝑖 = ∑ =1
𝑃
𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉)
𝑃𝑖
Or,
𝑧1 𝐹 𝑧2 𝐹
+ =1
𝑃 𝑃
𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉) 𝑉 + 𝑠𝑎𝑡 (𝐹 − 𝑉)
𝑃1 𝑃2
We are given all the values,

𝑚𝑜𝑙
𝑧1 = 0.5; 𝑧2 = 0.5; 𝐹 = 100 ; 𝑃 = 55𝑘𝑃𝑎
𝑚𝑖𝑛

We have already calculated, 𝑃1𝑠𝑎𝑡 = 40.83 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑃2𝑠𝑎𝑡 = 75.46 𝑘𝑃𝑎

Solving for V, we get, 𝑉 = 59.66 𝑚𝑜𝑙/𝑚𝑖𝑛

Hence, 𝐿 = 40.34 𝑚𝑜𝑙/𝑚𝑖𝑛

We can also find the compositions, 𝑦1 = 0.4386; 𝑦2 = 0.5614

And, 𝑥1 = 0.696; 𝑥2 = 0.0.304

Do not get confused with the numbers, 2-propanol has lower boiling point than 1-propanol.

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

Practice Question 3
A partial condenser is to be designed for a vapor mixture of the following composition: 50
mol % propane, 35 mol % isobutane, and 15 mol % isopentane. Determine the operating
temperature range of the condenser at 10 bar?

Solution:

We need to condense the mixture of three hydrocarbons; hence, the operating range should
be the bubble point and dew point temperatures for the given mixture.

For given species (light hydrocarbons), we can use K-factor method to find the bubble point
and dew point temperatures, the K values can be obtained using DePriester chart:

Bubble point T:
Given: 𝑃 = 10 𝑏𝑎𝑟; 𝑥𝑖
𝑥1 = 0.5; 𝑥2 = 0.35; 𝑥3 = 0.15
Using K-factor method,
𝐾𝑖 = 𝑦𝑖 /𝑥𝑖
Eliminating unknown vapour composition, 𝑦𝑖 , we get the condition which can be used for
finding the bubble point pressure,
∑ 𝑦𝑖 = ∑ 𝐾𝑖 𝑥𝑖 = 1
K factor depends on the temperature and pressure, To find the bubble point temperature,
we need to use iterative procedure, the steps are included here,
1. Assume bubble point temperature value (T)
2. Using the DePriester chart, find out the 𝐾𝑖 values for the combination of assumed
temperature and given pressure.
3. Evaluate 𝐾𝑖 𝑥𝑖
4. Check if, ∑ 𝐾𝑖 𝑥𝑖 = 1

If condition in step-4 is satisfied, assumed temperature is the bubble point temperature, if

not, make appropriate guess of temperature and repeat steps 2-4.

We get,

Bubble point temperature = 37C

For Dew Point T:

Given: 𝑃 = 10 𝑏𝑎𝑟; 𝑦𝑖
𝑦1 = 0.5; 𝑦2 = 0.35; 𝑦3 = 0.15
Using K-factor method,

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

𝐾𝑖 = 𝑦𝑖 /𝑥𝑖
Eliminating unknown liquid composition, 𝑥𝑖 , we get the condition which can be used for
finding the dew point pressure,
∑ 𝑥𝑖 = ∑ 𝑦𝑖 /𝐾𝑖 = 1
K factor depends on the temperature and pressure, To find the dew point temperature, we
need to use iterative procedure, the steps are included here,
1. Assume temperature value (T)
2. Using the DePriester chart, find out the 𝐾𝑖 values for the combination of selected
temperature and given pressure.
𝑦
3. Evaluate 𝐾𝑖
𝑖

4. Check if, ∑ 𝑦𝑖 /𝐾𝑖 = 1

If condition in step-4 is satisfied, assumed temperature is the dew point temperature, if not,
make appropriate guess of temperature and repeat steps 2-4.

Dew point temperature = 53C

Hence, the condenser should operate between 37-53C. (Your answers may differ and
should be acceptable if it is within the range and if your procedure is correct)

Practice Question 4
For a binary system ethyl ethanoate (1)/n-heptane (2) at 70C,
ln 𝛾1 = 0.95𝑥22
ln 𝛾2 = 0.95𝑥12
(a) Evaluate the bubble point pressure of a binary mixture (with 5% ethanoate) @ 70C.
(b) Evaluate the dew point pressure of a binary mixture (with 5% ethanoate) @ 70C.
(c) What is the azeotrope composition and pressure at T = 70C?

Solution:

This question is like Sample Example-2 on VLE.

Assuming modified Raoult’s law is applicable,

(a) Evaluate the bubble point pressure of a binary mixture (with 5% ethanoate) @ 70C.

First calculating the saturation pressure values, you can go to internet and get the Antoine
constants for ethyl ethanoate and n-heptane, we get,

𝑃1𝑠𝑎𝑡 = 79.8 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑃2𝑠𝑎𝑡 = 40.5 𝑘𝑃𝑎

Finding the bubble point pressure, using the modified Raoult’s law,

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

 𝑃 = ∑ 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 𝛾1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑃2𝑠𝑎𝑡
𝑖
Replacing the equation given for 𝛾𝑖
𝑃 = ∑ 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝑥1 (exp(0.95𝑥22 ))𝑃1𝑠𝑎𝑡 + 𝑥2 (exp(0.95𝑥12 ))𝑃2𝑠𝑎𝑡
𝑖

We get,

𝑃 (𝑏𝑢𝑏𝑏𝑙𝑒 𝑝𝑜𝑖𝑛𝑡 𝑝𝑟𝑒𝑠𝑢𝑟𝑒) = 47.97 𝑘𝑃𝑎

(b) Evaluate the dew point pressure of a binary mixture (with 5% ethanoate) @ 70C.

Calculating dew point pressure using the following equation when modified Raoult’s law is
applicable:
Modified Raoult’s law: 𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 or 𝑥𝑖 = 𝑦𝑖 𝑃/𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
Eliminating unknown 𝑥𝑖 , we get, ∑ 𝑥𝑖 = ∑ 𝑦𝑖 𝑃/𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 1
1 1
𝑃= = 𝑦1 𝑦2
∑(𝑦𝑖 /𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 )
𝑠𝑎𝑡 +
2
(exp(0.95𝑥2 ))𝑃1 (exp(0.95𝑥12 ))𝑃2𝑠𝑎𝑡

This requires trial and error method. Refer to Sample Example 2 on VLE.

After trial and error we get,

𝑃 (𝑑𝑒𝑤 𝑝𝑜𝑖𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒) = 42.2 𝑘𝑃𝑎

(c) What is the azeotrope composition and pressure at T = 70C?

This part is also same as Sample Example-2 on VLE,

@ azeotropic point,
𝑥𝑖 = 𝑦𝑖 𝑎𝑛𝑑 𝛼12 = 1
𝑦𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
Using the modified Raoult’s law, =
𝑥𝑖 𝑃

We can write for azeotrope condition,

𝛾1 𝑃1𝑠𝑎𝑡 𝛾2 𝑃2𝑠𝑎𝑡
=
𝑃 𝑃
Hence, we get, 𝛾1 𝑃1𝑠𝑎𝑡 = 𝛾2 𝑃2𝑠𝑎𝑡

Or,
𝛾1 𝑃2𝑠𝑎𝑡 79.8
| = = = 1.97
𝛾2 @𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 𝑃1𝑠𝑎𝑡 40.5

As, ln 𝛾1 = 0.95𝑥22 ; ln 𝛾2 = 0.95𝑥12

Therefore,

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

 𝛾1
ln 𝛾1 − ln 𝛾2 = 0.95𝑥22 − 0.95𝑥12 ⇒ ln ( ) = 0.95𝑥22 − 0.95𝑥12
𝛾2

After modification we get,

𝛾1
ln ( ) = 0.95(𝑥2 − 𝑥1 )(𝑥2 + 𝑥1 ) = 0.95(𝑥2 − 𝑥1 ) = 0.95(1 − 2𝑥1 )
𝛾2
𝛾
Substituting, 𝛾1 = 1.97 as found before and solving for composition we get,
2

𝑥1 |@𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 = 0.857 = 𝑦1 |@𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒

Hence,
𝑥1 |@𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 = 1 − 0.857

𝑃𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 = 𝛾1𝑎𝑧𝑒𝑜𝑡𝑟𝑜𝑝𝑒 𝑃1𝑠𝑎𝑡 = (exp(0.95𝑥22 ))(79.8) ≈ 81.37 𝑘𝑃𝑎

Practice Question 5
Consider a vapour mixture with 50% (by mol) Acetone (1), 30% (by mol) Acetonitrile (2)
and 20% (by mol) Nitromethane (3). At T= 70C, the pressure is gradually increased. What
is the dew point pressure and the composition of the first liquid that is formed? Assume ideal
liquid mixture and ideal gas (Raoult’s law).
Solution:
First, we need to find the saturation pressures for the 3 species at given temperature,
For acetone (1),
𝑃1𝑠𝑎𝑡 = 158.01 𝑘𝑃𝑎
For acetonitrile (2),
𝑃2𝑠𝑎𝑡 = 65.71 𝑘𝑃𝑎
For nitromethane (3)
𝑃2𝑠𝑎𝑡 = 34.83 𝑘𝑃𝑎
For finding the dew point pressure, 𝑦1 = 0.5, 𝑦2 = 0.3, 𝑦3 = 0.20
The equation for dew point pressure,
1 1
𝑃= 𝑠𝑎𝑡 = =1
∑ 𝑦𝑖 /𝑃𝑖 𝑦1 /𝑃1 + 𝑦2 /𝑃2𝑠𝑎𝑡 + 𝑦3 /𝑃3𝑠𝑎𝑡
𝑠𝑎𝑡

Substituting the values, we get, dew point pressure = 74.23 kPa

AY2019-20 | Sem-2 Practice Questions-VLE (Sample Solutions)

 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Practice Questions – Chemical Reaction Equilibrium (CRE)
Sample Solutions

Kindly use these solutions only for your reference.

Practice Question 1
For the following reactions determine the mole fractions of each species in terms of reaction
co-ordinate, and determine the equilibrium constant at T = 298K for each of the following
reactions:
(a) Formation of ethanol from ethylene and water: 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

(b) Oxidation of sulfur dioxide to sulfur trioxide: 2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔)

(c) Dehydrogenation of n-butane to Butadiene: 𝐶4 𝐻10 (𝑔) ⇌ 𝐻2 𝐶: 𝐶𝐻𝐻𝐶: 𝐶𝐻2 (𝑔) + 2𝐻2 (𝑔)

Note: The above sub-questions are independent questions for your practice. The necessary
information for calculation of equilibrium constant can be found in Appendix C.4.

Solution:

The solution is provided only for (a), you may follow the same procedure for other sub-
questions:

(a) Formation of ethanol from ethylene and water: 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

Initial number of moles is not given, let us assume 1 mol of each reactant present initially,
and no product exists (or we can write general equation by using 𝑛𝐶2𝐻4 0 , 𝑎𝑛𝑑 𝑛𝐻2 𝑂0 as initial
moles of the two reactant species). Let us also assume 𝜀 to be the extent of reaction (reaction
coordinate).

Stoichiometric table:
Species 𝑪 𝟐 𝑯𝟒 𝑯𝟐 𝑶 𝑪𝟐 𝑯𝟓 𝑶𝑯 Total
(𝜐𝑖 ) -1 -1 1
Initial moles (𝑛𝑖0 ) 1 1 0 ∑ 𝑛𝑖0 = 2
Moles generated −𝜀 −𝜀 𝜀
(𝑛𝑖,𝑔𝑒𝑛 ), you can call
this a change in moles
Moles at equilibrium 1−𝜀 1−𝜀 𝜀 ∑ 𝑛𝑖 = 2 − 𝜀
(𝑛𝑖 )
𝑦𝑖 1−𝜀 1−𝜀 𝜀 1.0
2−𝜀 2−𝜀 2−𝜀

Calculation of “K” @ 298 K

Species 𝑪 𝟐 𝑯𝟒 𝑯𝟐 𝑶 𝑪𝟐 𝑯𝟓 𝑶𝑯
Reaction- 𝜐𝑖 -1 -1 1
(a) 𝐺𝑖0 (J/mol) 68460 -228572 -168490
AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)
 ∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0 ∆𝐺𝑟𝑜 = (−1)(68460) + (−1)(−228572)
+ (1)(−168490) = −8378

Using the value of ∆𝐺𝑟𝑜 , let us calculate the equilibrium constant at 298 K
−∆𝐺𝑟𝑜 −(−8378)
𝐾 ≡ exp ( ) = exp ( ) ≈ 29.42
𝑅𝑇 (8.314)(298)
Do similar calculations for sub-questions (b) and (c).
Practice Question 2
If standard enthalpy change of reaction is assumed to be independent of temperature,
estimate the equilibrium constant for each of the reactions practice question 1 @ T = 500 K.
Comment if you are unable to estimate the equilibrium constant values.

Solution:

Sample calculations are shown for the reaction in sub-question (a):

(a) Formation of ethanol from ethylene and water: 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

∆𝐻𝑟𝑜 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
We can use the following equation to find out K value at 500 K.
𝐾 ∆𝐻𝑟𝑜 1 1
ln = − ( − ) … (2.1)
𝐾𝑜 𝑅 𝑇 𝑇𝑜
We need to first calculate the value of ∆𝐻𝑟𝑜 , this is done by preparing the following table:
Species 𝑪 𝟐 𝑯𝟒 𝑯𝟐 𝑶 𝑪𝟐 𝑯𝟓 𝑶𝑯
Reaction- 𝜐𝑖 -1 -1 1
(a) 𝐻𝑖0 (J/mol) 52510 -241818 -235100
∆𝐻𝑟𝑜 = ∆𝐻𝑟𝑜 = (−1)(52510) + (−1)(−241818)
∑ 𝜐𝑖 𝐻𝑖0 + (1)(−235100) = −45792

Using Eq (2.1),
𝐾@1473𝐾 ∆𝐻𝑟𝑜 1 1
ln 𝑜 = − ( − )
𝐾@298𝐾 𝑅 𝑇 𝑇𝑜
Or
𝐾@500𝐾 (−45792) 1 1
ln =− ( − )
29.42 (8.314) 500 298
We get,
𝐾@500𝐾 ≈ 0.017
Do similar calculations for reactions in sub-questions (b) and (c).

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

Practice Question 3
For the oxidation of SO2 mentioned in practice question 1 (2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔) ),
prepare a stoichiometric table for the following conditions:
(a) The reactor is a closed system that initially contains 2 moles of SO2 and 6 moles of O2.
(b) The reactor is a closed system that initially contains 2 moles of SO2, 4 moles of O2,
and 2 moles of inert N2. Note: the inert species does not take part in the reaction.

Your table should provide an expression for composition of each species in terms of the
extent of reaction (𝜀).

Solution:

The following table shows the solution for part (a)

Species 𝑺𝑶𝟐 𝑶𝟐 𝑺𝑶𝟑 Total

(𝜐𝑖 ) -2 -1 2
Initial moles (𝑛𝑖0 ) 2 6 0 ∑ 𝑛𝑖0 = 8
Moles generated −2𝜀 −𝜀 2𝜀
(𝑛𝑖,𝑔𝑒𝑛 ), you can call
this a change in moles
Moles at equilibrium 2 − 2𝜀 6−𝜀 2𝜀 ∑ 𝑛𝑖 = 8 − 𝜀
(𝑛𝑖 )
𝑦𝑖 2 − 2𝜀 6−𝜀 2𝜀 1.0
8−𝜀 8−𝜀 8−𝜀

You can prepare similar table for part (b), remember you have inert gas in the reaction
mixture.

Practice Question 4
Acetaldehyde is produced by the dehydrogenation of ethanol according to the following
reaction:

𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑔) → 𝐶𝐻3 𝐶𝐻𝑂(𝑔) + 𝐻2 (𝑔)

(a) If the reaction is conducted at T = 550C, comment if it is reasonable to assume

enthalpy change of reaction to be independent of temperature? (Hint: You need to
calculate equilibrium constant (K) by assuming the enthalpy change of reaction to be
independent/dependent of temperature and compare the K values).
(b) Calculate the equilibrium composition if the reaction is carried out at 550C and 2 bar
using one mole of ethanol.

Solution:

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

Calculation of “K” @ 298 K

Species 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 𝐶𝐻3 𝐶𝐻𝑂 𝑯𝟐

Reaction- 𝜐𝑖 -1 1 1
(a) 𝐺𝑖0 (J/mol) -168490 -128860 0
𝑜
∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0 ∆𝐺𝑟 = (−1)(−168490) + (1)(−128860) + (1)(0)
= 39630

Using the above information, we get,

𝐾@298𝐾 = 1.13 × 10−7

Assuming, ∆𝐻𝑟𝑜 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡

We can use the following equation to find out K value at 550C (823 K).
𝐾 ∆𝐻𝑟𝑜 1 1
ln = − ( − ) … (4.1)
𝐾𝑜 𝑅 𝑇 𝑇𝑜
We need to first calculate the value of ∆𝐻𝑟𝑜 , this is done by preparing the following table:
Species 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 𝐶𝐻3 𝐶𝐻𝑂 𝑯𝟐
Reaction- 𝜐𝑖 -1 1 1
(a) 𝐻𝑖0 (J/mol) -235100 -166190 0
∆𝐻𝑟𝑜 = ∆𝐻𝑟𝑜 = (−1)(−235100) + (1)(−166190) + (1)(0)
∑ 𝜐𝑖 𝐻𝑖0 = 68910

Using Eq (4.1), and solving for K @ 550C (823 K), we get,

𝐾@823𝐾 ≈ 5.74
Now Assuming, ∆𝐻𝑟𝑜 = 𝑓(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒)

−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇
∆Go
While, r
can be calculated using the following equation,
RT
o
∆Gro ∆Gr,0 o
− ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫ … . 𝐸𝑞 (4.2)
RT RT0 RT T T0 R T0 R T

Quantifying each terms in Eq (4.2),

Species 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 𝐶𝐻3 𝐶𝐻𝑂 𝑯𝟐
𝜐𝑖 -1 1 1
𝐻𝑖0 (J/mol) -235100 -166190 0
∆𝐻𝑟𝑜 = ∆𝐻𝑟𝑜 = (−1)(−235100) + (1)(−166190) + (1)(0)
∑ 𝜐𝑖 𝐻𝑖0 = 68910

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 𝐺𝑖0 (J/mol) -168490 -128860 0
∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0 ∆𝐺𝑟𝑜 = (−1)(−168490) + (1)(−128860) + (1)(0)
= 39630

First term:
o o (39630) − (68910)
∆Gr,0 − ∆Hr,0
= = −11.82
RT0 (8.314)(298)
Second term:
∆Hro (68910)
= = 10.071
RT (8.314)(823)
∆Co
To quantify the third and the fourth term, we need to first quantify P
term,
R

We are calculating this term at standard state, hence, we can use the equation for ideal gas
state 𝐶𝑝 values for the species involved in our reaction.
𝑖𝑔
𝐶𝑝 𝐷
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 2
R 𝑇
∆Co
Let us use the following table to quantify P
:
R

Species 𝜐𝑖 A B C D
𝐶𝐻3 𝐶𝐻2 𝑂𝐻 -1 3.518 20.001×10-3 -6.002×10-6 0
𝐶𝐻3 𝐶𝐻𝑂 1 1.693 17.978×10-3 -6.158×10-6 0
𝐻2 1 3.249 0.422×10-3 0 0.083×105
∆Co
𝑖𝑔
𝐶𝑝 ∆𝐷
P
= ∑ 𝜐𝑖 ∆𝐴 + ∆𝐵𝑇 + ∆𝐶𝑇 2 +
R R 𝑇2
0.083 ×105
= (1.424) + (−1.601 × 10−3 )𝑇 + (−0.156 × 10−6 )𝑇 + 𝑇2

Using the information gathered in the table above, we can evaluate the third and fourth
1 T ∆Co
term in Eq (4.2). let us start with, T ∫T P
dT
0 R

1 T ∆CPo 1 T ∆𝐷
∫ dT = ∫ {∆𝐴 + ∆𝐵𝑇 + ∆𝐶𝑇 2 + 2 } dT
T T0 R T T0 𝑇
Or,
1 T ∆CPo 1 𝑇 2 − 𝑇02 𝑇 3 − 𝑇03 1 1
∫ dT = {∆𝐴(𝑇 − 𝑇0 ) + ∆𝐵 ( ) + ∆𝐶 ( ) + ∆𝐷 ( − )}
T T0 R T 2 3 𝑇0 𝑇
Substituting the values of temperatures (𝑇 𝑎𝑛𝑑 𝑇0 ) and constants (∆𝐴, ∆𝐵, ∆𝐶 and ∆𝐷), we
get,

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 1 T ∆CPo
∫ dT = 0.33
T T0 R

T ∆Co
P dT
let us start with, ∫T
0 R T

T
∆CPo dT T
∆𝐷 dT
∫ = ∫ {∆𝐴 + ∆𝐵𝑇 + ∆𝐶𝑇 2 + 2 }
T0 R T T0 𝑇 T
Or,
∆CPo dT
T
𝑇 𝑇 2 − 𝑇02 ∆𝐷 1 1
∫ = {∆𝐴 ln ( ) + ∆𝐵(𝑇 − 𝑇0 ) + ∆𝐶 ( )+ ( 2 − 2 )}
T0 R T 𝑇0 2 2 𝑇0 𝑇
Substituting the values of temperatures (𝑇 𝑎𝑛𝑑 𝑇0 ) and constants (∆𝐴, ∆𝐵, ∆𝐶 and ∆𝐷), we
get,
∆CPo dT
T
∫ = 0.601
T0 R T

Now we can go back to Eq (5.1) and substitute all the terms,

o
∆Gro ∆Gr,0 o
− ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫
RT RT0 RT T T0 R T0 R T

Or,
∆Gro
= −11.82 + 10.071 + (0.33) − (0.601) = −2.02
RT
Now we can calculate K value using,
−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇
Or,
𝐾@823𝐾 = 7.54
This is quite different than the K value we got with assumption of constant ∆𝐻𝑟𝑜 , hence, it is
reasonable to assume enthalpy change of reaction to be independent of temperature
(b)
Stoichiometric table:
Species 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 𝐶𝐻3 𝐶𝐻𝑂 𝑯𝟐 Total
(𝜐𝑖 ) -1 1 1
Initial moles (𝑛𝑖0 ) 1 0 0 ∑ 𝑛𝑖0 = 1
Moles generated −𝜀 𝜀 𝜀
(𝑛𝑖,𝑔𝑒𝑛 ), you can call
this a change in moles
Moles at equilibrium 1−𝜀 𝜀 𝜀 ∑ 𝑛𝑖 = 1 + 𝜀
(𝑛𝑖 )
𝑦𝑖 1−𝜀 𝜀 𝜀 1.0
1_ + 𝜀 1+𝜀 1+𝜀
AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)
Using the equation for gas phase reaction at low pressure,

𝑃 𝜈
𝐾 = ( 𝑜 ) ∏(𝑦𝑖 )𝜈𝑖
𝑃
𝑖

Using the K value we calculated and replacing the compositions in terms of the reaction
coordinate, we can find the reaction coordinate,

𝜀 = 0.66

Using this once can find the compositions,

Note: Your answer may differ depending on the accuracy of data used. The key is to
understand the fundamentals and procedure.

Practice Question 5
For the ammonia synthesis reaction,

1 3
𝑁2 (𝑔) + 𝐻2 (𝑔) ⇌ 𝑁𝐻3 (𝑔)
2 2

The equilibrium conversion to ammonia is large at 300 K, but it decreases rapidly with
increasing temperature. However, reaction rates become appreciable only at higher
temperatures. For a feed mixture of hydrogen and nitrogen in the stoichiometric
proportions,

(a) What is the equilibrium mole fraction of ammonia at 1 bar and 300 K?
(b) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 1 bar?
(c) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal gas?
(d) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal solution of gases?
(this is like the calculations we did for reaction in Sample Example-7).

Solution:

(a) What is the equilibrium mole fraction of ammonia at 1 bar and 300 K?

Calculating the K value with an assumption that ∆𝐻𝑟𝑜 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (using the method
discussed in Practice Example 4),

We can get, K = 673

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

We can also assume temperature dependency of ‘K’ and find out the ‘K’ value (using the
method discussed in Practice Example 4),

𝐴𝑠𝑠𝑢𝑚𝑖𝑛𝑔, ∆𝐻𝑟𝑜 = 𝑓(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒)

We get, K ≈ 679.6

Using the equation for gas phase reaction at low pressure,

𝑃 𝜈
𝐾 = ( 𝑜 ) ∏(𝑦𝑖 )𝜈𝑖 … . 𝐸𝑞 (5.1)
𝑃
𝑖

Using this ‘K=679.6’ value we have found out, and expressing 𝑦𝑖 in terms of the extent of
reaction (𝜀),

1 3
𝑁2 (𝑔) + 𝐻2 (𝑔) ⇌ 𝑁𝐻3 (𝑔)
2 2

For a feed mixture of hydrogen and nitrogen in the stoichiometric proportions

Species 𝑁2 𝐻2 𝑁𝐻3 Total

(𝜐𝑖 ) -1/2 -3/2 1
Initial moles (𝑛𝑖0 ) 1/2 3/2 0 ∑ 𝑛𝑖0 = 2
Moles generated 1 3 𝜀
− 𝜀 − 𝜀
(𝑛𝑖,𝑔𝑒𝑛 ), you can call 2 2
this a change in moles
Moles at equilibrium 1−𝜀 3(1 − 𝜀) 𝜀 ∑ 𝑛𝑖 = 2 − 𝜀
(𝑛𝑖 ) 2 2
𝑦𝑖 1−𝜀 3(1 − 𝜀) 𝜀 1.0
2(2 − 𝜀) 2(2 − 𝜀) (2 − 𝜀)

Once we do that, we can reduce Eq (5.1) only in terms of 𝜀.

𝜀
1 −1 𝑦𝑁𝐻3 (2 − 𝜀 )
679.6 = ( ) 1 3 = 1 3 … . 𝐸𝑞 (5.2)
1
𝑦𝑁2 2 ∙ 𝑦𝐻2 2 1−𝜀 2 3(1 − 𝜀) 2
( ) ∙( )
2(2 − 𝜀) 2(2 − 𝜀)

After solving above equation for 𝜀, we would get,

𝜀 = 0.9664

Using the value of 𝜀, you can calculate the mole fractions (𝑦𝑖 ).

(b) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 1 bar?

The mole fraction of ammonia is given, using that find out the extent of reaction (𝜀),

We should get, 𝜀 = 2/3

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)
Using this value in Eq (5.2), calculate the unknown equilibrium constant ‘K’.

𝐾 ≈ 6.16

As we know, K is a function of temperature.

- Assuming ∆𝐻𝑟0 is independent of temperature, we get.

∆𝐺𝑟0
ln 𝐾 =
𝑅𝑇
T = 402 K
- Assuming ∆𝐻𝑟0 is a function of temperature,
−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇
∆Go
While, r
can be calculated using the following equation,
RT
o
∆Gro ∆Gr,0 o
− ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫
RT RT0 RT T T0 R T0 R T

Using trial and error, we will get T = 399.5 K

(c) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal gas?

Repeating the calculations in part (b), with only a change in pressure, P = 100 bar

𝜀 = 2/3

Using this value in Eq (5.2), calculate the unknown equilibrium constant ‘K’.

𝐾 ≈ 0.0616

As we know, K is a function of temperature.

- Assuming ∆𝐻𝑟0 is independent of temperature, we get.

∆𝐺𝑟0
ln 𝐾 =
𝑅𝑇
T = 604 K
- Assuming ∆𝐻𝑟0 is a function of temperature,
−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇
∆Go
While, r
can be calculated using the following equation,
RT
o
∆Gro ∆Gr,0 o
− ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫
RT RT0 RT T T0 R T0 R T

Using trial and error, we will get T = 579 K

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

(d) At what temperature does the equilibrium mole fraction of ammonia equal 0.5 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal solution of gases? (this is
like the calculations we did for reaction in Sample Example-7).

For ideal solution:

𝜙̂𝑖 = 𝜙𝑖

Hence, the equation for finding the equilibrium composition,

𝑃 −1 (𝜙𝑁𝐻3 ∙ 𝑦𝑁𝐻3 )
𝐾 = ( 𝑜) ∏ { 1 3} … 𝐸𝑞 (5.3)
𝑃
𝑖 (𝜙𝑁2 ∙ 𝑦𝑁2 )2 (𝜙𝐻2 ∙ 𝑦𝐻2 )2

The fugacity coefficient of pure species depends on temperature and pressure. “K” is also a
function of temperature; hence, we need an iterative solution to find the temperature (T),

Step-1: Assume a temperature (good guess would be temperature from Part (C)).

Step-2: Find the fugacity coefficient values

Step-3: Find “K” using Eq (5.3)

Step-4: Find temperature as done in Part (b) and/or (c)

Step-5: Check the temperature value with the assumed value

We get,

𝑇 = 568.5𝐾

Practice Question 6
The interconversion of 𝑜 − 𝑥𝑦𝑙𝑒𝑛𝑒 to its isomers, 𝑃 − 𝑥𝑦𝑙𝑒𝑛𝑒 and 𝑚 − 𝑥𝑦𝑙𝑒𝑛𝑒 is carried out
in a batch reactor at 1 atm and 400K.

𝑜 − 𝑥𝑦𝑙𝑒𝑛𝑒 ⟶ 𝑚 − 𝑥𝑦𝑙𝑒𝑛𝑒

𝑚 − 𝑥𝑦𝑙𝑒𝑛𝑒 ⟶ 𝑝 − 𝑥𝑦𝑙𝑒𝑛𝑒

(a) Determine the equilibrium composition of all the species if the reactor initially
contains 20 moles of 𝑜 − 𝑥𝑦𝑙𝑒𝑛𝑒.
(b) If the reaction is carried out at low pressure such that both the vapor and liquid
phases exist at equilibrium. Provide the workflow to evaluate the composition in both
the phases at equilibrium.

Species 0
∆𝐻𝑓,@298𝐾 0
∆𝐺𝑓,@298𝐾
(J/mol) (J/mol)

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 𝑜 − 𝑥𝑦𝑙𝑒𝑛𝑒 19000 122200
𝑚 − 𝑥𝑦𝑙𝑒𝑛𝑒 17000 118900
𝑝 − 𝑥𝑦𝑙𝑒𝑛𝑒 18000 121200

Make appropriate assumptions (where necessary), Refer to Appendix for additional data.
Solution:
(a) Determine the equilibrium composition of all the species if the reactor initially contains
20 moles of 𝑜 − 𝑥𝑦𝑙𝑒𝑛𝑒.
Liquid phase reaction (one should easily figure this out)
(𝑃𝑜 − 𝑃)
∏(𝛾𝑖 𝑥𝑖 )𝜈𝑖 = 𝐾 exp [ ∑ 𝜈𝑖 𝑉𝑖 ]
𝑅𝑇
𝑖 𝑖

Low pressure and chemically similar species, hence, we can assume ideal solution, hence,
we can use a simplified form (slide 26 from lecture notes),

𝐾 = ∏(𝑥𝑖 )𝜈𝑖 … 𝐸𝑞 (6.1)

𝑖

We have multiple reactions,

Let us use notations for compositions of various species:
o-xylene: 𝑥𝑜
m-xylene: 𝑥𝑚
p-xylene: 𝑥𝑝
For reaction-1:

𝐾1 = ∏(𝑥𝑖 )𝜈1,𝑖
𝑖

𝐾1 = 𝑥𝑚 /𝑥𝑜 … 𝐸𝑞 (6.2)
For reaction-2:

𝐾2 = ∏(𝑥𝑖 )𝜈2,𝑖
𝑖

𝐾2 = 𝑥𝑝 /𝑥𝑚 … 𝐸𝑞 (6.3)
Evaluate equilibrium constants @ 298K,
∆𝐺𝑟0 @298𝐾
ln 𝐾@298𝐾 =
𝑅𝑇
𝐾1@298𝐾 = 3.788; 𝐾2@298𝐾 = 0.395

Assuming Enthalpy of reaction to be independent of T,

Calculate K @ 400 K,

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 𝐾@400𝐾 ∆𝐻𝑟0 @298𝐾 1 1
ln ( )=− ( − )
𝐾@298𝐾 𝑅 400 298
We get,
𝐾1@400𝐾 = 3.08; 𝐾2@400𝐾 = 0.44
Hence, Eqs (6.2) and (6.3) becomes,
𝑥𝑚
𝐾1 = = 3.08 … 𝐸𝑞 (6.2𝑎)
𝑥𝑜
𝑥𝑝
𝐾2 = = 0.44 … 𝐸𝑞 (6.3𝑎)
𝑥𝑚
In addition to this we have mole balance equation for all components in the liquid mixture,

∑ 𝑥𝑖 = 𝑥𝑜 + 𝑥𝑚 + 𝑥𝑝 = 1 … 𝐸𝑞 (6.4)

Solving Eqs (6.2a), (6.3a) and (6.4) simultaneously, we get,

0.325𝑥𝑚 + 𝑥𝑚 + 0.44𝑥𝑚 = 1
Hence,
𝑥𝑚 = 0.567
Then we get,
𝑥𝑚
𝑥𝑜 = = 0.184
3.08
And,
𝑥𝑝 = 0.44𝑥𝑚 = 0.25

(b) If the reaction is carried out at low pressure such that both the vapor and liquid phases
exist at equilibrium. Provide the workflow to evaluate the composition in both the phases at
equilibrium.

Heterogeneous reaction

We will need to use VLE and CRE equations to find the unknowns,

Unknowns: 𝐿𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛: 𝑥𝑜 , 𝑥𝑚 , 𝑥𝑝

𝑉𝑎𝑝𝑜𝑢𝑟 𝑝ℎ𝑎𝑠𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛𝑠: 𝑦𝑜 , 𝑦𝑚 , 𝑦𝑝

𝐿(𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑), 𝑉(𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑔 𝑣𝑎𝑝𝑜𝑢𝑟)

𝜀1 (𝑒𝑥𝑡𝑒𝑛𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 − 1, 𝜀2 (𝑒𝑥𝑡𝑒𝑛𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 − 2)

In total we have 10 unknowns.

Governing equations:

(i) Assuming reaction takes place in liquid phase (CRE)

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 𝑥𝑚 𝑥𝑝
𝐾1 = ; 𝐾2 =
𝑥𝑜 𝑥𝑚
(ii) VLE – for three species
Model: Raoult’s law
o-xylene: 𝑦𝑜 𝑃 = 𝑥𝑜 𝑃𝑜𝑠𝑎𝑡
m-xylene: 𝑦𝑚 𝑃 = 𝑥𝑚 𝑃𝑚𝑠𝑎𝑡
P-xylene: 𝑦𝑝 𝑃 = 𝑥𝑝 𝑃𝑝𝑠𝑎𝑡
(iii) Mole balance in two phases
∑ 𝑥𝑖 = 1
∑ 𝑦𝑖 = 1
(iv) Mole balance for each species at equilibrium,
o-xylene: 20 − 𝜀1 = 𝑦𝑜 𝑉 + 𝑥𝑜 𝐿
m-xylene: 𝜀1 − 𝜀2 = 𝑦𝑚 𝑉 + 𝑥𝑚 𝐿
p-xylene: 𝜀2 = 𝑦𝑝 𝑉 + 𝑥𝑝 𝐿
We have 10 equation as written above which can be solved to find the 10 unknowns.

AY2019-20 | Sem-2 Practice Questions-CRE (sample solutions)

 CN2121 Chemical Engineering Thermodynamics (AY2019-20 | Sem-2)
Sample Examples Chemical Reaction Equilibrium (CRE) - Solutions
Sample Example-1
Ethylene is produced from the dehydration of ethanol at 120℃ and 7 bar according to the
reaction,
𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) ⇌ 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑙)

Is this system well-defined?

Solution:
• Number of components (𝑁) = 3
• Number of phases (𝜋) = 2
• Number of reactions (𝑟) = 1
Degrees of freedom, 𝐹 = 𝑁 − 𝜋 + 2 − 𝑟 = 3 − 2 + 2 − 1 = 2
Two variables, pressure and temperature of the system are given. The system is therefore well-
defined.
Sample Example-2
For the following system of reactions, determine the mole fractions of each species in terms of
reaction co-ordinate, if there were 2 moles of methane and 3 moles of water initially.
𝐶𝐻4 + 𝐻2 𝑂 → 𝐶𝑂 + 3𝐻2
𝐶𝐻4 + 2𝐻2 𝑂 → 𝐶𝑂2 + 4𝐻2
Solution:
We should first prepare a stoichiometric table as shown below which will help us determine the
mole fractions of each species in terms of reaction co-ordinate.
Let us consider, 𝜀1 and 𝜀2 are the reaction co-ordinate values for reaction-1 and reaction-2
respectively.
Stoichiometric table:

Species 𝑪𝑯𝟒 𝑯𝟐 𝑶 𝑪𝑶𝟐 𝑯𝟐 𝑪𝑶 Total

Reaction-1 (𝜐𝑖 ) -1 -1 0 3 1
Reaction-2 (𝜐𝑖 ) -1 -2 1 4 0
Initial moles (𝑛𝑖0 ) 2 3 0 0 0 ∑ 𝑛𝑖0 = 5
Moles generated −𝜀1 −𝜀1 0 3𝜀1 𝜀1
(reaction-1) (𝑛𝑔𝑒𝑛,1)
Moles generated −𝜀2 −2𝜀2 𝜀2 4𝜀2 0
(reaction-2) (𝑛𝑔𝑒𝑛,2)
Moles at equilibrium 2 − 𝜀1 2 − 𝜀1 𝜀2 3𝜀1 𝜀1 ∑ 𝑛𝑖 = 5 + 2𝜀1 + 2𝜀2
(𝑛𝑖 ) − 𝜀2 − 2𝜀2 + 4𝜀2

Finding the mole fractions of each species in terms of reaction co-ordinate:

 𝑛𝑖0 + 𝜐𝑖 𝜀 𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
𝑦𝑖 = =
∑ 𝑛𝑖0 + 𝜐𝜀 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚

We get,
2 − 𝜀1 − 𝜀2
𝑦𝐶𝐻4 =
5 + 2𝜀1 + 2𝜀2
2 − 𝜀1 − 2𝜀2
𝑦𝐻2 𝑂 =
5 + 2𝜀1 + 2𝜀2
𝜀2
𝑦𝐶𝑂2 =
5 + 2𝜀1 + 2𝜀2
3𝜀1 + 4𝜀2
𝑦𝐻2 =
5 + 2𝜀1 + 2𝜀2
𝜀1
𝑦𝐶𝑂 =
5 + 2𝜀1 + 2𝜀2
Sample Example-3
Calculate the equilibrium constant of the following reaction at 25℃.
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

If the reaction stoichiometry is rewritten as,

1
𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 𝑁𝑂2 (𝑔)
2
What would be the value of the equilibrium constant at 25℃?
Solution:
Equilibrium constant can be found out using following equation,
−∆𝐺𝑟𝑜
𝐾 ≡ exp ( )
𝑅𝑇

Where, ∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0

Let us first find, ∆𝐺𝑟𝑜 @ 25℃ (298.15 K), we prepare a table as follows which can help us do the
calculations easily,
Reaction-1: 2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

Species NO O2 NO2
Reaction-1 𝜐𝑖 -2 -1 2
𝐺𝑖0 (J/mol) 86550 0 51310
𝑜
∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0 ∆𝐺𝑟 = (−2)(86550) + (1)(0) + (2)(51310) = −70480

Using the value of ∆𝐺𝑟𝑜 , let us calculate the equilibrium constant at 298.15 K
−∆𝐺𝑟𝑜 −(−70480)
𝐾 ≡ exp ( ) = exp ( ) ≈ 2.23 × 1012
𝑅𝑇 (8.314)(298.15)

For the second reaction stoichiometry (stoichiometry is divided by 2),

 1
𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 𝑁𝑂2 (𝑔)
2
Let us call this a “Reaction-2”, the value of ∆𝐺𝑟𝑜 for this stoichiometry will simply be ½ the value
for the initial stoichiometry,
1
∆𝐺𝑟𝑜 = (−70480) = −35240
2
Hence, equilibrium constant, K will be,
−∆𝐺𝑟𝑜 −(−35249)
𝐾 ≡ exp ( ) = exp ( ) ≈ 1.49 × 106
𝑅𝑇 (8.314)(298.15)

So, if the reaction stoichiometry is multiplied by a certain constant ‘ ’, then we can calculate the
K value for a new reaction stoichiometry using,

𝐾 ′ (𝑓𝑜𝑟 𝑛𝑒𝑤 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑦) = 𝐾 𝜆

Sample Example-4
Calculate the equilibrium constant of the following reaction at 1200℃ assuming enthalpy of
reaction to be constant.
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

Equilibrium constant for the reaction at 25℃: 𝐾@298𝐾 = 2.23 × 1012

Solution:
∆𝐻𝑟𝑜 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡

We can use the following equation to find out K value at 1200C (1473 K).
𝐾 ∆𝐻𝑟𝑜 1 1
ln = − ( − ) … 𝐸𝑞 (4.1)
𝐾𝑜 𝑅 𝑇 𝑇𝑜
We need to first calculate the value of ∆𝐻𝑟𝑜 , this is done by preparing the following table:

Species NO O2 NO2
Reaction-1 𝜐𝑖 -2 -1 2
𝐻𝑖0 (J/mol) 90250 0 33180
∆𝐻𝑟𝑜 = ∑ 𝜐𝑖 𝐻𝑖0 ∆𝐻𝑟𝑜 = (−2)(90250) + (1)(0) + (2)(33180) = −114140

Using Eq (4.1),
𝐾@1473𝐾 ∆𝐻𝑟𝑜 1 1
ln 𝑜 =− ( − )
𝐾@298𝐾 𝑅 𝑇 𝑇𝑜

Or
𝐾@1473𝐾 (−114140) 1 1
ln = − ( − )
2.23 × 1012 (8.314) 1473 298
We get,

𝐾@1473𝐾 = 2.445 × 10−4

Sample Example-5
Calculate the equilibrium constant of the following reaction at 1200℃ assuming enthalpy of
reaction to be temperature dependent.
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

Solution:
∆𝐻𝑟𝑜 = 𝑓(𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒)
−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇
∆Go
While, RT
r
can be calculated using the following equation,
o o
∆Gro ∆Gr,0 − ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫ … . 𝐸𝑞 (5.1)
RT RT0 RT T T0 R T0 R T

Quantifying each terms in Eq (5.1),

Species NO O2 NO2
𝜐𝑖 -2 -1 2
𝐻𝑖0 (J/mol) 90250 0 33180
𝑜
∆𝐻𝑟𝑜 = ∑ 𝜐𝑖 𝐻𝑖0 ∆𝐻𝑟 = (−2)(90250) + (1)(0) + (2)(33180) = −114140
𝐺𝑖0 (J/mol) 86550 0 51310
∆𝐺𝑟𝑜 = ∑ 𝜐𝑖 𝐺𝑖0 ∆𝐺𝑟𝑜 = (−2)(86550) + (1)(0) + (2)(51310) = −70480

First term:
o o (−70480) − (−114140)
∆Gr,0 − ∆Hr,0
= = 17.62
RT0 (8.314)(298)
Second term:
∆Hro (−114140)
= = −9.32
RT (8.314)(1473)
∆Co
To quantify the third and the fourth term, we need to first quantify R
P
term,

We are calculating this term at standard state, hence, we can use the equation for ideal gas state
𝐶𝑝 values for the species involved in our reaction.
𝑖𝑔
𝐶𝑝 𝐷
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 +
R 𝑇2
∆Co
Let us use the following table to quantify R
P
:

Species 𝜐𝑖 A B C D
𝑁𝑂 -2 3.387 0.629×10-3
0 0.014×105
𝑂2 -1 3.639 0.506×10-3
0 -0.227×105
𝑁𝑂2 2 4.982 1.195×10-3
0 -0.792×105
∆Co
𝑖𝑔
𝐶𝑝 ∆𝐷
P
= ∑ 𝜐𝑖 ∆𝐴 + ∆𝐵𝑇 + 2
R R 𝑇
−1.385 ×105
= (−0.449) + (0.626 × 10 − 3)𝑇 + 𝑇2
Using the information gathered in the table above, we can evaluate the third and fourth term in
1 T ∆Co
Eq (5.1). let us start with, T ∫T P
dT
0 R

1 T ∆CPo 1 T ∆𝐷
∫ dT = ∫ {∆𝐴 + ∆𝐵𝑇 + 2 } dT
T T0 R T T0 𝑇

Or,

1 T ∆CPo 1 𝑇 2 − 𝑇02 1 1
∫ dT = {∆𝐴(𝑇 − 𝑇0 ) + ∆𝐵 ( ) + ∆𝐷 ( − )}
T T0 R T 2 𝑇0 𝑇

Substituting the values of temperatures (𝑇 𝑎𝑛𝑑 𝑇0 ) and constants (∆𝐴, ∆𝐵 and ∆𝐷), we get,

1 T ∆CPo
∫ dT = −0.1676
T T0 R

T ∆Co
P dT
let us start with, ∫T
0 R T

T
∆CPo dT T
∆𝐷 dT
∫ = ∫ {∆𝐴 + ∆𝐵𝑇 + 2 }
T0 R T T0 𝑇 T

Or,
T
∆CPo dT 𝑇 ∆𝐷 1 1
∫ = {∆𝐴 ln ( ) + ∆𝐵(𝑇 − 𝑇0 ) + ( 2 − 2 )}
T0 R T 𝑇0 2 𝑇0 𝑇

Substituting the values of temperatures (𝑇 𝑎𝑛𝑑 𝑇0 ) and constants (∆𝐴, ∆𝐵 and ∆𝐷), we get,
T
∆CPo dT
∫ = −0.73
T0 R T

Now we can go back to Eq (5.1) and substitute all the terms,

o o
∆Gro ∆Gr,0 − ∆Hr,0 ∆Hro 1 T ∆CPo T
∆CPo dT
= + + ∫ dT − ∫
RT RT0 RT T T0 R T0 R T

Or,
∆Gro
= 17.62 − 9.32 + (−0.1676) − (−0.73) = 8.8634
RT
Now we can calculate K value using,
−∆𝐺𝑟𝑜
ln(𝐾) ≡ ( )
𝑅𝑇

Or,
−∆𝐺𝑟𝑜
𝐾@1473𝐾 = exp ( ) = exp(−8.8634) = 1.416 × 10−4
𝑅𝑇

You may compare this value with the K value we got in Sample example-3 (@ 298K) and in
Sample example-4 (@ T=1473 K but assuming ∆𝐻𝑟𝑜 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡).
Sample Example-6
Nitric oxide reacts with oxygen to form nitrogen dioxide at 1200℃ and 3 bar, according to the
reaction given below.
1
𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 𝑁𝑂2 (𝑔)
2
Determine equilibrium composition if the reaction mixture contains equal amounts of all three
species initially.
Solution:
This is a gas-phase reaction, hence, the general equation to be used to find the equilibrium
composition is,
𝑃 𝜈 𝜈𝑖
𝐾 = ( 𝑜 ) ∏(𝑦𝑖 𝜙̂𝑖 )
𝑃
𝑖

Based on the pressure value we can assume the reaction mixture to behave as an ideal gas, 𝜙̂𝑖 =
1. Hence, we can use the simplified form of the above equation,
𝑃 𝜈
𝐾=( ) ∏(𝑦𝑖 )𝜈𝑖 … 𝐸𝑞 (6.1)
𝑃𝑜
𝑖

Preparing stoichiometric table (Assuming 𝜀 to be the reaction coordinate (extend of reaction)):

Species NO O2 NO2 Total

𝜐𝑖 -1 -1/2 1 𝜈 = ∑ 𝜈𝑖 = −1/2
Initial moles 1 1 1 3
(𝑛𝑖0 )
Moles generated −𝜀 1
− 𝜀 𝜀
2
(𝑛𝑔𝑒𝑛 )
Moles at 1−𝜀 1 − 2𝜀
1 1+𝜀 1
3− 𝜀
equilibrium 2
(𝑛𝑖 )
Mole fraction 1−𝜀 1
1 − 2𝜀
1+𝜀 1
𝑦𝑁𝑂 = 𝑦𝑁𝑂2 =
(composition) at 1 𝑦𝑂2 = 1
3− 𝜀 1 3− 𝜀
equilibrium (𝑦𝑖 ) 2 3 − 2𝜀 2

With the value of 𝜈 and 𝜈𝑖 , we can re-write, Eq (6.1) as,

𝑃 −1/2 𝑦𝑁𝑂2
𝐾=( ) ∏( 1) … 𝐸𝑞 (6.2)
𝑃𝑜
𝑖 𝑦𝑁𝑂 ∙ 𝑦𝑂2 2

In Solved Example-5, the reaction used was

2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

The ‘K’ value for this reaction stoichiometry was,

𝐾 = 1.415 × 10−4
While for Solved Example-6, the reaction given is,
1
𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 𝑁𝑂2 (𝑔)
2
Hence, calculating the K value for the new stoichiometry using,

𝐾 ′ (𝑓𝑜𝑟 𝑛𝑒𝑤 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑦) = 𝐾 𝜆

1
For this example, the multiplier, 𝜆 = 2, hence,
1
𝐾 ′ (𝑓𝑜𝑟 𝑛𝑒𝑤 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑦) = (1.415 × 10−4 )2
Hence, for Solved Example-6,
𝐾 = 0.0119
Hence, using the values of K, pressure and composition in terms of reaction coordinate, we can
re-write Eq (6.2) as,

1+𝜀
( 1 )
3 −1/2 3− 2𝜀
0.0119 = ( ) ∏ 1
1
𝑖 1 2
1−𝜀 1 −2𝜀
( 1 )∙( 1 )
( 3 − 2 𝜀 3 − 2𝜀 )
We have only one unknown, calculating the unknown, 𝜀, we get,
𝜀 = −0.9734
Then using the expressions for compositions, we get,
1−𝜀
𝑦𝑁𝑂 = = 0.566
1
3 − 2𝜀

1
1 −2𝜀
𝑦𝑂2 = = 0.426
1
3 −2𝜀

1+𝜀
𝑦𝑁𝑂2 = = 0.0076
1
3 − 2𝜀

Sample Example-7
Ethylene reacts with water to form ethanol at 473𝐾 and 34 𝑏ar. The reaction conditions assure
the presence of the both liquid and vapour phases.
𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑙) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

Estimate liquid phase and vapour phase compositions if ethylene and water were initially
present in the ratio 1:5.
Also determine the extent of conversion and relative amount of vapour and liquid phases at
equilibrium
You may assume the following:
(i) Ethylene is very volatile and exists in gas phase only.
(ii) Ethanol has limited solubility in liquid phase.
Additional data:
Henry’s constant for ethanol: 80.58 bar

For gaseous phase reaction at 473𝐾 and 34 bar: ∆𝐺𝑟0 @473𝐾 = 14.61 𝑘𝐽/𝑚𝑜𝑙

Solution:
(a) Estimate liquid phase and vapour phase compositions if ethylene and water were initially
present in the ratio 1:5.
Given: Heterogeneous reaction
𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑙) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

You may assume the following:

(i) Ethylene is very volatile and exists in gas phase only.
(ii) Ethanol has limited solubility in liquid phase.
Based on the above assumptions, we will use a stratey-1 from lecture notes, i.e. “Reaction occurs
in gas phase”
(a) Ethylene is very volatile and exists in gas phase only
(b) Water vapourizes, hence, we need to write vapour-liquid equilibrium for water,
𝐻2 𝑂(𝑙) ⇌ 𝐻2 𝑂(𝑔)

The VLE criterion is,

𝑉 𝐿
𝑓̂𝐻2 𝑂 = 𝑓̂𝐻2 𝑂

(c) Reaction in gas-phase,

𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

the equilibrium composition can be found out using,

𝑃 𝜈 𝜈
𝐾=( ) ∏(𝑦𝑖 𝜙̂𝑖 ) 𝑖 … 𝐸𝑞 (7.1)
𝑃𝑜
𝑖

(d) The product formed (ethanol), partially dissolved in liquid phase,

𝐶2 𝐻5 𝑂𝐻(𝑔) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑙) … 𝐸𝑞 (7.2)

The VLE criterion for ethanol is,

𝑉 𝐿
𝑓̂𝐶2 𝐻5 𝑂𝐻 = 𝑓̂𝐶2 𝐻5 𝑂𝐻 … 𝐸𝑞 (7.3)

Let us assume, 𝑦𝐶2 𝐻4 , 𝑦𝐻2 𝑂 𝑎𝑛𝑑 𝑦𝐶2 𝐻5 𝑂𝐻 to be the vapour compositions, hence,

∑ 𝑦𝑖 = 𝑦𝐶2 𝐻4 + 𝑦𝐻2 𝑂 + 𝑦𝐶2 𝐻5 𝑂𝐻 = 1 … .. … 𝐸𝑞 (7.4)

Let us assume, 𝑥𝐶2 𝐻4 , 𝑥𝐻2 𝑂 𝑎𝑛𝑑 𝑥𝐶2 𝐻5 𝑂𝐻 to be the vapour compositions, hence,

∑ 𝑥𝑖 = 𝑥𝐶2 𝐻4 + 𝑥𝐻2 𝑂 + 𝑥𝐶2 𝐻5 𝑂𝐻 = 1 … 𝐸𝑞 (7.5)

Let us first analyze the chemical reaction equilibrium,

Governing equation as written before is,
𝑃 𝜈 𝜈𝑖
𝐾=( 𝑜
) ∏(𝑦𝑖 𝜙̂𝑖 )
𝑃
𝑖

Pressure given is very high, let us assume ideal solution, then,

𝑃 𝜈
𝐾=( ) ∏(𝑦𝑖 𝜙𝑖 )𝜈𝑖
𝑃𝑜
𝑖

Using, 𝜈𝐶2 𝐻4 = −1, 𝜈𝐻2 𝑂 = −1, 𝑎𝑛𝑑 𝜈𝐶2 𝐻5 𝑂𝐻 = 1

Similarly, 𝜈 = ∑ 𝜈𝑖 = −1

𝑃 −1 (𝜙𝐶2 𝐻5 𝑂𝐻 ∙ 𝑦𝐶2 𝐻5 𝑂𝐻 )
𝐾=( 𝑜
) ∏{ } … 𝐸𝑞 (7.6)
𝑃 (𝜙𝐶2 𝐻4 ∙ 𝑦𝐶2 𝐻4 )(𝜙𝐻2 𝑂 ∙ 𝑦𝐻2 𝑂 )
𝑖

In the above equation, we need to evaluate, K and fugacity coefficient values.

We can first calculate the K value using the information given to us, ∆𝐺𝑟0 @473𝐾 = 14.61 𝑘𝐽/𝑚𝑜𝑙,

∆𝐺𝑟0 @473𝐾 14610

𝐾 = exp ( ) = exp ( ) = 0.0243
𝑅𝑇 (8.314)(473)

The fugacity coefficient values for each species can be evaluated using Pitzer Correlation,
𝑃𝑟
ln(𝜙𝑖 ) = 𝐵̂
𝑇𝑟
Assuming, everyone can do these calculations, we get,
𝜙𝐶2 𝐻4 = 0.97; 𝜙𝐻2 𝑂 = 0.87; 𝜙𝐶2 𝐻5 𝑂𝐻 = 0.75

Hence, we can re-write Eq (7.6) as,

𝑃 −1 (0.75𝑦𝐶2 𝐻5 𝑂𝐻 )
0.0243 = ( 𝑜 ) ∏ { } … 𝐸𝑞 (7.7)
𝑃 (0.97𝑦𝐶2 𝐻4 )(0.87𝑦𝐻2 𝑂 )
𝑖

We will now look at the phase equilibrium criteria,

For Ethylene: It is highly volatile and exists only in gas phase,
Hence, 𝑥𝐶2 𝐻4 = 0 … 𝐸𝑞 (7.8)

For water: As discussed before,

𝑉 𝐿
𝑓̂𝐻2 𝑂 = 𝑓̂𝐻2 𝑂

Or,

𝑦𝐻2 𝑂 ∙ 𝜙̂𝐻2 𝑂 ∙ 𝑃 = 𝑥𝐻2 𝑂 ∙ 𝛾𝐻2 𝑂 ∙ 𝑓𝐻2 𝑂 𝐿

Rewriting for idea solution assumption,

𝑦𝐻2 𝑂 ∙ 𝜙𝐻2 𝑂 ∙ 𝑃 = 𝑥𝐻2 𝑂 ∙ 𝑓𝐻2 𝑂 𝐿 … 𝐸𝑞 (7.9)

Fugacity for pure water in liquid phase can be evaluated using,

𝑉𝑖𝐿
𝑓𝑖𝐿 = 𝜙𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 exp [ (𝑃 − 𝑃𝑖𝑠𝑎𝑡 )]
𝑅𝑇

Rewriting Eq (7.9),

𝑉𝐻𝐿2 𝑂
𝑦𝐻2 𝑂 ∙ 𝜙𝐻2 𝑂 ∙ 𝑃 = 𝑥𝐻2 𝑂 ∙ 𝜙𝐻𝑠𝑎𝑡 𝑃 𝑠𝑎𝑡
2 𝑂 𝐻2 𝑂
exp [ (𝑃 − 𝑃𝐻𝑠𝑎𝑡
2𝑂
)] … 𝐸𝑞 (7.10)
𝑅𝑇

For ethanol: The pressure is high enough, we can assume limited solubility of ethanol in water.
VLE criterion (as written before) is,
𝑉 𝐿
𝑓̂𝐶2 𝐻5 𝑂𝐻 = 𝑓̂𝐶2 𝐻5 𝑂𝐻

Or,

𝑦𝐶2 𝐻5 𝑂𝐻 ∙ 𝜙̂𝐶2 𝐻5 𝑂𝐻 ∙ 𝑃 = 𝑥𝐶2 𝐻5 𝑂𝐻 ∙ ℋ𝐶2 𝐻5 𝑂𝐻 [𝐴𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛: 𝐿𝑖𝑚𝑖𝑡𝑒𝑑 𝑠𝑜𝑙𝑢𝑏𝑢𝑙𝑖𝑡𝑦 𝑜𝑓 𝐶2 𝐻5 𝑂𝐻]

Or,
𝑦𝐶2 𝐻5 𝑂𝐻 ∙ 𝜙𝐶2 𝐻5 𝑂𝐻 ∙ 𝑃 = 𝑥𝐶2 𝐻5 𝑂𝐻 ∙ ℋ𝐶2 𝐻5 𝑂𝐻 [𝐴𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛: 𝐼𝑑𝑒𝑎𝑙 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛]

Or,
𝑥𝐶2 𝐻5 𝑂𝐻 ∙ ℋ𝐶2 𝐻5 𝑂𝐻
𝑦𝐶2 𝐻5 𝑂𝐻 = … 𝐸𝑞 (7.11)
𝜙𝐶2 𝐻5 𝑂𝐻 ∙ 𝑃

Solving the highlighted equations (Eqs (7.4, 7.5, 7.7, 7.8, 7.10 and 7.11)) simultaneously, we get,
𝑉𝑎𝑝𝑜𝑢𝑟 𝑝ℎ𝑎𝑠𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛𝑠: 𝑦𝐶2 𝐻4 = 0.373; 𝑦𝐻2 𝑂 = 0.469; 𝑦𝐶2 𝐻5 𝑂𝐻 = 0.158

𝐿𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛𝑠: 𝑥𝐶2 𝐻4 = 0; 𝑥𝐻2 𝑂 = 0.95; 𝑥𝐶2 𝐻5 𝑂𝐻 = 0.05

(b) Also determine the extent of conversion and relative amount of vapour and liquid phases at
equilibrium
Let us write down the reaction again,
𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑙) ⇌ 𝐶2 𝐻5 𝑂𝐻(𝑔)

Let us assume “V” and “L” be the total moles of vapour and liquid phase respectively,
The mole balances for various components at equilibrium are written as,
For ethylene:
𝑛𝐶2 𝐻4 = 𝑦𝐶2 𝐻4 𝑉 + 𝑥𝐶2 𝐻4 𝐿 … 𝐸𝑞 (7.12)

For water:
𝑛𝐻2 𝑂 = 𝑦𝐻2 𝑂 𝑉 + 𝑥𝐻2 𝑂 𝐿 … 𝐸𝑞 (7.13)

For ethanol:
𝑛𝐶2 𝐻5 𝑂𝐻 = 𝑦𝐶2 𝐻5 𝑂𝐻 𝑉 + 𝑥𝐶2 𝐻5 𝑂𝐻 𝐿 … 𝐸𝑞 (7.14)
Preparing the stoichiometric table now (using 𝜀 as the reaction coordinate):

Species 𝐶2 𝐻4 𝐻2 𝑂 𝐶2 𝐻5 𝑂𝐻 Total
𝜐𝑖 -1 -1 1 𝜈 = ∑ 𝜈𝑖 = −1
Initial moles 1 5 0 6
(𝑛𝑖0 )
Moles generated −𝜀 −𝜀 𝜀
(𝑛𝑔𝑒𝑛 )
Moles at 1−𝜀 5−𝜀 𝜀 6−𝜀
equilibrium
(𝑛𝑖 )

Using the number of moles at equilibrium from the above table, using the compositions we have
found in part (a), we can revise the previous equations (Eqs. 7.12-7.14),
For ethylene:
1 − 𝜀 = 0.373𝑉
For water:
5 − 𝜀 = 0.469𝑉 + 0.95𝐿
For ethanol:
𝜀 = 0.153𝑉 + 0.05𝐿
We have 3 unknowns and 3 equations, solving these three equations, we get,
𝜀 = 0.44
𝑉 = 1.5
𝐿 = 4.06