Fuel and Combustion Laboratory (F&C)

Department of Aeronautics and Astronautics

Heat Engine
Ch14 Introduction to Phase and Chemical
Equilibrium

Instructor: Prof. Wei-Cheng Wang

Requirements for equilibrium
 2 subsystems have the same temperature
 No unbalanced mechanical forces between 2 systems for
a s-s process
𝑉𝑖2 𝑉𝑒2
𝑊ሶ 𝑟𝑒𝑣 = 𝑚ሶ 𝑖 ℎ𝑖 + + 𝑔𝑧𝑖 − 𝑇0 𝑠𝑖 − 𝑚ሶ 𝑒 ቀℎ𝑒 + + 𝑔𝑧𝑒 −
2 2
𝑇0 𝑠𝑒 ቁ

Uniform temperature : 𝑇0 = 𝑇𝑖 = 𝑇𝑒 = 𝑐𝑜𝑛𝑠𝑡

and the Gibbs function 𝑔 = ℎ − 𝑇𝑠

2
 𝑣𝑖2
𝑊ሶ 𝑟𝑒𝑣 = 𝑚ሶ 𝑖 𝑔𝑖 + 𝑇𝑠𝑖 + + 𝑔𝑧𝑖 − 𝑇0 𝑠𝑖 − 𝑚ሶ 𝑒 ቀ𝑔𝑒 + 𝑇𝑠𝑒 +
2
𝑣𝑒2 𝑣𝑖2 𝑣𝑒2
+ 𝑔𝑧𝑒 − 𝑇0 𝑠𝑒 ቁ = 𝑚ሶ 𝑖 𝑔𝑖 + + 𝑔𝑧𝑖 − 𝑚ሶ 𝑒 ቀ𝑔𝑒 + +
2 2 2
𝑔𝑍𝑒 ቁ = 0
𝑣𝑖2 𝑣𝑒2
𝑚ሶ 𝑖 = 𝑚ሶ 𝑒 ; =
2 2
∴ 𝑔𝑖 + 𝑔𝑧𝑖 = 𝑔𝑒 + 𝑔𝑧𝑒
⇒ d𝑔𝑇 + 𝑔𝑑𝑍 𝑇 =0
small

∴ At equilibrium d𝐺𝑇,𝑃 = 0

3
Equilibrium between two phases of a pure substance
Consider the changes of state associated with a transfer of
dn moles from 1 to 2 phase. T & P are constant 𝑑𝑛1 = −𝑑𝑛2
Gibbs function G = f(T,P,𝑛1 ,𝑛2 )
𝜕𝐺 𝜕𝐺 𝜕𝐺
𝑑𝐺 = 𝑑𝑇 + 𝑑𝑃 + 𝑑𝑛1 +
𝜕𝑇 𝑃,𝑛1 ,𝑛2 𝜕𝑃 𝑇,𝑛1 ,𝑛2 𝜕𝑛1 𝑇,𝑃,𝑛2
𝜕𝐺 2
𝑑𝑛
𝜕𝑛2 𝑇,𝑃,𝑛1

At the constant T & P

𝑑𝐺 = 0 = 𝑔−1 + 𝑔−2 at equilibrium 𝑔−1 = 𝑔−2

4
From Ch12,
𝑑𝑔 = 𝑣𝑑𝑃 − 𝑠𝑑𝑇
− the phases always have the same value of the Gibbs
function at equilibrium
𝑑𝑔𝑓 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑙𝑖𝑞𝑢𝑖𝑑 = 𝑑𝑔𝑔 𝑣𝑎𝑝𝑜𝑟

𝑣𝑓 𝑑𝑃 − 𝑠𝑓 𝑑𝑇 = 𝑣𝑔 𝑑𝑃 − 𝑠𝑔 𝑑𝑇
⇒ 𝑑𝑃 𝑣𝑔 − 𝑣𝑓 = 𝑑𝑇 𝑠𝑔 − 𝑠𝑓
𝑑𝑃 𝑠𝑓𝑔 ℎ𝑓𝑔
= = (Claperon equation)
𝑑𝑇 𝑣𝑓𝑔 𝑇𝑣𝑓𝑔

5
Example:
A container has liquid water at 20℃, 100 kPa in
equilibrium with a mixture of water vapor and dry air also at
20 ℃, 100 kPa. How much is the water vapor pressure and
what is the saturated water vapor pressure?

6
Solution:
3
Saturated liquid 𝑃𝑔 = 2.339𝑘𝑃𝑎, 𝑣𝑓 = 0.001002 𝑚 ൗ𝑘𝑔
𝑑𝑔 = 𝑣𝑑𝑃 − 𝑠𝑑𝑇
at constant Temp, 𝑑𝑔 = 𝑣𝑑𝑃
‫ 𝑞𝑖𝑙𝑔 ⇒ 𝑃𝑑𝑣 ׬ = 𝑔𝑑 ׬‬− 𝑔𝑓 = ‫ 𝑃 𝑓𝑣 = 𝑃𝑑𝑣 ׬‬− 𝑃𝑔
The vapor in the moisture air is at the partial pressure 𝑃𝜈
𝑃𝑣
𝑔𝑣𝑎𝑝 − 𝑔𝑔 = ‫𝑛𝑙𝑇𝑅 = 𝑃𝑑𝑣 ׬‬
𝑃𝑔
Now at equilibrium, and 2 saturated phases
𝑔𝑙𝑖𝑞 = 𝑔𝑣𝑎𝑝 ; 𝑔𝑓 = 𝑔𝑔
𝑃𝑣
𝑅𝑇𝑙𝑛 + 𝑔𝑔 = 𝑣𝑓 𝑃 − 𝑃𝑔 + 𝑔𝑓
𝑃𝑔
𝑃 0.001002 100−2.339
𝑙𝑛 𝑣 = 𝑣𝑓 (𝑃 − 𝑃𝑔 )/𝑅𝑇 = = 0.000723
𝑃𝑔 0.4615∗293.15
𝑃𝑣 = 2.3407𝑘𝑃𝑎
7
Metastable Equilibrium

8
- Process is reversible & adiabatic
- Point a is expected to have condensation
- If point a is reached in a divergent section of the nozzle ,
no condensation occurs until point b is reached
- Between a and b , temp is below saturation temp for the
given pressure , but steam still exists as vapor
- ⇒ 𝑚𝑒𝑡𝑎𝑠𝑡𝑎𝑏𝑙𝑒 𝑠𝑡𝑎𝑡𝑒

9
Chemical Equilibrium

number of moles :𝑛𝐴 , 𝑛𝐵 , 𝑛𝐶 , 𝑛𝐷

Chemical reaction :𝜈𝐴 𝐴 + 𝜈𝐵 𝐵 ⇌ 𝜈𝐶 𝐶 + 𝜈𝐷 D
Degree of reaction :𝜀

10
 𝑑𝑛𝐴 : −𝜈𝐴 𝑑𝜖
𝑑𝑛𝐵 : −𝜈𝐵 𝑑𝜖
𝑑𝑛𝐶 : +𝜈𝐶 𝑑𝜖
𝑑𝑛𝐷 : +𝜈𝐷 𝑑𝜖

The partial modal Gibbs function

𝑑𝐺𝑇,𝑃 = 𝐺𝐶 𝑑𝑛𝐶 + 𝐺𝐷 𝑑𝑛𝐷 +𝐺𝐴 𝑑𝑛𝐴 +𝐺𝐵 𝑑𝑛𝐵

= (𝜈𝐶 𝐺𝐶 + 𝜈𝐷 𝐺𝐷 -𝜈𝐴 𝐺𝐴 -𝜈𝐵 𝐺𝐵 ) 𝑑𝜀 -------------①

11
𝐺 = 𝐻 − 𝑇𝑆
For a mixture of two components A & B , we differentiate the
above equation with respect to 𝑛𝐴
𝜕𝐺 𝜕𝐻 𝜕𝑆
( ) 𝑇,𝑃,𝑛𝐵 = ( ) 𝑇,𝑃,𝑛𝐵 −𝑇( ) 𝑇,𝑃,𝑛𝐵
𝜕𝑛𝐴 𝜕𝑛𝐴 𝜕𝑛𝐴
Apply the definition of partial modal properties from Ch12
𝐺𝐴 = 𝐻𝐴 − 𝑇𝑆𝐴
0 𝑦𝐴 𝑃
= ℎ𝐴,𝑇𝑃 − 𝑇 𝑠𝐴,𝑇𝑃 − 𝑅 ln 0 ത
𝑃0
0 𝑦𝐴 𝑃
0
= ℎ𝐴,𝑇𝑃 − 𝑇𝑠𝐴,𝑇𝑃 + 𝑅 Tln ത
𝑃0
𝑦𝐴 𝑃
0
= 𝑔𝐴,𝑇𝑃 + 𝑅𝑇 lnത -------------------------②
𝑃0

12
Substitute ② into ①
𝑦𝐶 𝑃
𝑑𝐺𝑇,𝑃 = {𝜈𝐶 [𝑔𝐶,𝑇𝑃 0 ത ln
+ 𝑅𝑇 ] + 𝜈𝐷 [𝑔𝐷,𝑇𝑃 0 +
𝑃0
𝑦𝐷 𝑃 𝑦𝐴 𝑃
ത ln
𝑅𝑇 ത ln
] − 𝜈𝐴 𝑔𝐴,𝑇𝑃 0 + 𝑅𝑇 −𝜈𝐵 ቂ𝑔𝐵,𝑇𝑃 0 +
𝑃0 𝑃0
𝑦𝐵 𝑃
ത ln
𝑅𝑇 ቃ} --------------------------------③
𝑃0

13
Define ∆𝐺 𝑜 (standard-state Gibbs function change)
∆𝐺 𝑜 =𝜐𝑐 𝑔𝑐 𝑜 + 𝜐𝐷 𝑔𝐷 𝑜 - 𝜐𝐴 𝑔𝐴 𝑜 - 𝜐𝐵 𝑔𝐵 𝑜 −④ (𝑔ഥ𝑖 𝑜 can be found
in the following Table)
<change in Gibbs function>
Substitute④ into ③ and rearrange
𝑦 𝑣𝑐 𝑦 𝑣𝐷 𝑃 𝜐 +𝜐 −𝜐 −𝜐
𝑜 ത 𝑐 𝐷
d𝐺𝑇,𝑃 ={∆𝐺 +𝑅Tln[ 𝑣𝐴 𝑣𝐵 ( ) 𝐶 𝐷 𝐴 𝐵 ]}d𝜀
𝑦𝐴 𝑦𝐵 𝑃𝑜
At equilibrium, d𝐺𝑇,𝑃 =0, d𝜀 is arbitrary
𝑦𝑐 𝑣𝑐 𝑦𝐷 𝑣𝐷 𝑃 𝜐 +𝜐 −𝜐 −𝜐 ∆𝐺 𝑜
ln[ 𝑣𝐴 𝑣𝐵 ( ) 𝐶 𝐷 𝐴 𝐵 ] =- ത
𝑦𝐴 𝑦𝐵 𝑃𝑜 𝑅𝑇

𝐾𝑃
14
Equilibrium constant 𝐾𝑃
𝑦𝑐 𝑣𝑐 𝑦𝐷 𝑣𝐷 𝑃 𝜐 +𝜐 −𝜐 −𝜐
𝐾𝑃 = ( ) 𝐶 𝐷 𝐴 𝐵
𝑦𝐴 𝑣𝐴 𝑦𝐵 𝑣𝐵 𝑃𝑜
<Chemical Equilibrium Equation>
𝑃𝑐 𝑣𝑐 𝑃𝐷 𝑣𝐷
𝐾𝑃 = for ideal gas mixture
𝑃𝐴 𝑣𝐴 𝑃𝐵 𝑣𝐵
𝑃𝐴 , 𝑃𝐵 , 𝑃𝑐 , 𝑃𝐷 : partial pressure of A,B,C,D
∆𝐺 𝑜
𝐾𝑃 = exp(- ത ) −(5)
𝑅𝑇
◎Table A.11 gives 𝐾𝑃 for a number of reactions

15
Kp
 In terms of partial pressure
𝑃𝑐 𝑣𝑐 𝑃𝐷 𝑣𝐷
𝐾𝑃 =
𝑃𝐴 𝑣𝐴 𝑃𝐵 𝑣𝐵
 In terms of standard-state Gibbs function change
∆𝐺 𝑜
𝐾𝑃 = exp(- ത )
𝑅𝑇
 In terms of the equilibrium composition
𝑛𝑖
𝑃𝑖 = 𝑦𝑖 𝑃 = 𝑃
𝑛𝑡𝑜𝑡𝑎𝑙
𝑃𝑐 𝑣𝑐 𝑃𝐷 𝑣𝐷 𝑁𝑐 𝑣𝑐 𝑁𝐷 𝑣𝐷 𝑃 𝜐𝐶 + 𝜐𝐷 − 𝜐𝐴 − 𝜐𝐵
𝐾𝑃 = = ( )
𝑃𝐴 𝑣𝐴 𝑃𝐵 𝑣𝐵 𝑁𝐴 𝑣𝐴 𝑁𝐵 𝑣𝐵 𝑛𝑡𝑜𝑡𝑎𝑙

16
Table of Gibbs function of formation

17
Example:
Using Equation (5) and the Gibbs function data, determine the
equilibrium constant KP for the dissociation process N2→2N at
25°C. Compare your result to the KP value listed in Table A-11.

18
Solution
𝑁2 →2N at 25℃
∆𝐺 𝑜
𝐾𝑃 = exp (- ത )
𝑅𝑇
∆𝐺 𝑜 = 𝑉N 𝑔N 𝑜 - 𝑉N2 𝑔𝑁2 𝑜
=2*(455510 kJ/kmole)-1*0 = 911020 kJ/kmole
𝐾𝑃 = exp(-911020/8.314*298.15)
≅2*10−160 ⇒this reaction is rarely occurred at this
temperature

19
Example:
Determine the temperature at which 10 percent of diatomic
hydrogen (H2) dissociates into monatomic hydrogen (H) at a
pressure of 10 atm.

20
Solution:
𝐻2 ↔ 2𝐻 (stoichiometric),𝑣𝐻 =2, 𝑣𝐻2 =1
10% H2 →0.9 H2 + 0.2H
𝑣𝐻
𝑃𝐻
𝐾𝑃 = 𝑣𝐻2
𝑃𝐻2
𝑛𝑖
𝑃𝑖 = 𝑦𝑖 𝑃 = 𝑃
𝑛𝑡𝑜𝑡𝑎𝑙
𝑣 𝑣𝐻 −𝑣𝐻2
𝑛𝐻𝐻 𝑃
𝐾𝑃 = 𝑣𝐻2
𝑛𝐻2 𝑛𝑡𝑜𝑡𝑎𝑙
0.2 2 10 2−1
= = 0.404
0.9 0.9+0.2
𝑐𝑜𝑟𝑟𝑒𝑠𝑝𝑜𝑛𝑑 𝑡𝑜 𝑇 = 3535𝐾
21
Example:
A mixture of 2 kmol of CO and 3 kmol of O2 is heated to 2600
K at a pressure of 304 kPa. Determine the equilibrium
composition, assuming the mixture consists of CO2, CO, and
O2 as the following figure.

22
Solution:
1
𝑆𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐: 𝐶𝑂 + 𝑂2 ⇌ 𝐶𝑂2
2
1
𝑣𝐶𝑂2 = 1, 𝑣𝑂2 = , 𝑣𝐶𝑂 = 1
2
𝐴𝑐𝑡𝑢𝑎𝑙: 2𝐶𝑂 + 3𝑂2 → 𝑥𝐶𝑂2 + 𝑦𝐶𝑂 + 𝑧𝑂2
Product Leftover
𝐶: 2 = 𝑥 + 𝑦; 𝑦 = 2 − 𝑥
𝑥
𝑂: 8 = 2𝑥 + 𝑦 + 2𝑧 ; 𝑧 = 3 −
2
𝑃 = 304 𝑘𝑃𝑎 = 3 𝑎𝑡𝑚
𝑥
𝑛𝑡𝑜𝑡𝑎𝑙 = 𝑥 + 𝑦 + 𝑧 = 5 −
2

23
𝐹𝑟𝑜𝑚 𝑇𝑎𝑏𝑙𝑒 𝐴. 11,
2𝐶𝑂2 ⇌ 2𝐶𝑂 + 𝑂2 (chosen from the closest reaction in A.11)
𝑎𝑡 2600𝐾, ln 𝐾𝑃 = −5.594
1 −5.594
𝐶𝑂2 ⇌ 𝐶𝑂 + 𝑂2 ; ln 𝐾𝑃 = = −2.797
2 2
1
𝐴𝑛𝑑 𝑖𝑛 𝑡ℎ𝑖𝑠 𝑝𝑟𝑜𝑏𝑙𝑒𝑚, 𝐶𝑂 + 𝑂2 ⇌ 𝐶𝑂2
2
⇒ 𝑆ℎ𝑜𝑢𝑙𝑑 ℎ𝑎𝑣𝑒 𝑖𝑛𝑣𝑒𝑟𝑠𝑒 𝐾𝑃
ln 𝐾𝑃 = +2.797 ∴ 𝐾𝑃 = 16.395
𝑣𝐶𝑂2 𝑣𝐶𝑂2 −𝑣𝐶𝑂 −𝑣𝑂2
𝑛𝐶𝑂2 𝑃
𝐾𝑃 = 𝑣𝐶𝑂 𝑣𝑂2
𝑛𝐶𝑂 𝑛𝑂 𝑛𝑡𝑜𝑡𝑎𝑙
2
1
−
𝑥 3 2
= 1ൗ 5 − 𝑥ൗ2
2 − 𝑥 3 − 𝑥ൗ2 2

24
∴ 𝑥 = 1.906
𝑦 = 2 − 𝑥 = 0.094
𝑥
𝑧 = 3 − = 2.047
2
𝑆𝑜, 𝑡ℎ𝑒 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑎𝑡 2600𝐾 & 304𝑘𝑃𝑎 𝑖𝑠

1.906𝐶𝑂2 + 0.094𝐶𝑂 + 2.047𝑂2

25
Example:
A mixture of 3 kmol of CO, 2.5 kmol of O2, and 8 kmol of
N2 is heated to 2600 K at a pressure of 5 atm. Determine the
equilibrium composition of the mixture as following figure.

26
Solution
1
𝑆𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐: 𝐶𝑂 + 𝑂2 ⇌ 𝐶𝑂2
2
1
𝑣𝐶𝑂2 = 1, 𝑣𝑂2 = , 𝑣𝐶𝑂 = 1
2
𝐴𝑐𝑡𝑢𝑎𝑙: 3𝐶𝑂 + 2.5𝑂2 + 8𝑁2 → 𝑥𝐶𝑂2 + 𝑦𝐶𝑂 + 𝑧𝑂2 + 8𝑁2
Product Leftover Inert
𝐶: 3 = 𝑥 + 𝑦 ; 𝑦 = 3 − 𝑥
𝑥
𝑂: 8 = 2𝑥 + 𝑦 + 2𝑧 ; 𝑧 = 2.5 −
2
𝑥
𝑛𝑡𝑜𝑡𝑎𝑙 = 𝑥 + 𝑦 + 𝑧 + 8 = 13.5 −
2

27
𝐹𝑟𝑜𝑚 𝑙𝑎𝑠𝑡 𝑒𝑥𝑎𝑚𝑝𝑙𝑒, 𝐾𝑃 = 16.395
𝑣𝐶𝑂2 𝑣𝐶𝑂2 −𝑣𝐶𝑂 −𝑣𝑂2
𝑛𝐶𝑂 𝑃
2
𝐾𝑃 = 𝑣
𝐶𝑂 𝑣𝑂2 𝑛
𝑛𝐶𝑂 𝑛𝑂 𝑡𝑜𝑡𝑎𝑙
2
1
−2
𝑥 5
16.395 = 1ൗ 13.5 − 𝑥ൗ2
3 − 𝑥 2.5 − 𝑥ൗ2 2

∴ 𝑥 = 2.764
𝑦 = 3 − 𝑥 = 0.246
𝑥
𝑧 = 2.5 − = 1.123
2

28
𝑇ℎ𝑒 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑎𝑡 2600𝐾 &3 04𝑘𝑃𝑎 𝑖𝑠
2.754𝐶𝑂2 + 0.246𝐶𝑂 + 1.123𝑂2 + 8𝑁2

※ 𝐼𝑛𝑒𝑟𝑡 𝑔𝑎𝑠 𝑑𝑜𝑒𝑠 𝑛𝑜𝑡 𝑎𝑓𝑓𝑒𝑐𝑡 𝐾𝑃 𝑣𝑎𝑙𝑢𝑒 𝑜𝑟 𝐾𝑃 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛,

𝑏𝑢𝑡 𝑖𝑡 𝑑𝑜𝑒𝑠 𝑎𝑓𝑓𝑒𝑐𝑡 𝑡ℎ𝑒 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛

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Class example 1
1. Hydrogen gas is heated from room temperature to
4000 K, 500 kPa, at which state the diatomic species has
partially dissociated to the monatomic form. Determine the
equilibrium composition at this state

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Solution 1:
𝐻2 ↔ 2𝐻
−𝑥 + 2𝑥
Equil.
𝑛𝐻2 = 1 − 𝑥
𝑛𝐻 = 0 + 2𝑥
𝑛 =1+𝑥
2𝑥 2 𝑃 2−1
𝐾= ( 0) at 4000K : ln 𝐾 = 0.934
1−𝑥 1+𝑥 𝑃
=> 𝐾 = 2.545
2.545 𝑥2
= 0.127 25 =
500 1 − 𝑥 2
4×( )
100
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Class example 2
2. Pure oxygen is heated from 25℃ to 3200 K in an
steady flow process at a constant pressure of 200 kPa. Find
the exit composition and the heat transfer.

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Solution 2:
The only reaction will be the dissociation of the oxygen
𝑂2 ↔ 2𝑂 ;
From A.11 : 𝐾 3200 = exp −3.069 = 0.046467
Look at initially 1 mol Oxygen and shift reaction with x
𝑛𝑂2 = 1 − 𝑥 ; 𝑛𝑂 = 2x ; 𝑛𝑡𝑜𝑡 = 1 + 𝑥 ; 𝑦𝑖 = 𝑛𝑖 /𝑛𝑡𝑜𝑡
2
𝑦𝑂 𝑃 2−1 4𝑥 2 1+𝑥 8𝑥 2
𝐾= ( ) = 2=
𝑦 𝑂 2 𝑃𝑂 (1+𝑥)2 1−𝑥 1−𝑥 2
𝐾/8
𝑥2 = => 𝑥 = 0.07599 ;
1+𝐾/8
1−𝑥
𝑦𝑂2 = = 𝟎. 𝟖𝟓𝟗 ; 𝑦𝑂 = 1 − 𝑦𝑂2 = 𝟎. 𝟏𝟒𝟏
1+𝑥

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 𝑞ത = 𝑛𝑂2𝑒𝑥 ℎത 𝑂2𝑒𝑥 + 𝑛𝑂𝑒𝑥 ℎത 𝑂𝑒𝑥 − ℎത 𝑂2𝑖𝑛
= 1 + 𝑥 𝑦𝑂 ℎത 𝑂 + 𝑦𝑂 ℎത 𝑂 − 0
2 2

ℎത 𝑂2 =106022 kJ/kmol ;
ℎത 𝑂 = 249170 + 60767 = 309937 kJ/kmol

𝑞
ത =145015 kJ/kmol 𝑂2
𝑞ത 𝑘𝐽
𝑞 = = 4532 (= 3316.5 𝑖𝑓 𝑛𝑜 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
32 𝑘𝑔

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Class example 3
3. A mixture of 1 kmol carbon dioxide, 2 kmol carbon
monoxide, and 2 kmol oxygen, at 25℃, 150 kPa, is heated
in a constant pressure steady state process to 3000 K.
Assuming that only these same substances are present in the
exiting chemical equilibrium mixture, determine the
composition of that mixture.

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Solution:
𝑛𝑡𝑜𝑡 = 1 − 2𝑥 + 2 + 2𝑥 + 2 + 𝑥 = 5 + 𝑥 so y = 𝑛/𝑛𝑡𝑜𝑡
From A.11 at 3000 K :
𝐾 = exp −2.217 = 0.108935
1
For each 𝑛 > 0 => −1 < 𝑥 < +
2
2
𝑦𝐶𝑂 𝑦𝑂2 𝑃 1 1+𝑥 2 2+𝑥 150
𝐾= ( 0) = 4 ( ) = 0.108935
𝑦2 𝐶𝑂2 𝑃 1−2𝑥 5+𝑥 100

1+𝑥 2 2+𝑥
or = 0.018156 , Trial & error: 𝑥 =
1−2𝑥 5+𝑥
− 0.521

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 𝑦𝐶𝑂2 = 0.4559
𝑛𝐶𝑂2 = 2.042 𝑛𝑂2 = 1.479
𝑦𝐶𝑂 = 0.2139
𝑛𝐶𝑂 = 0.958 𝑛𝑡𝑜𝑡 = 4.479
𝑦𝑂2 = 0.3302

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