Lecture 2

Models of Exergy Calculations

 Content

Introduction

The Temperature formula

The Pressure formula

The Composition formula

 Direct exergy calculations
Process streams 𝑇, 𝑃, 𝐶

𝐻 = 𝑓1 𝑇, 𝑃, 𝐶 𝑆 = 𝑓2 𝑇, 𝑃, 𝐶

∆𝐻 ∆𝑆

σ ∆𝐻 = 0 σ 𝐸𝑥 σ ∆𝑆 > 0
Direct exergy calculations

∆𝐸𝑥 = ∆𝐻 − 𝑇𝑜 ∆𝑆

not always
available

to date only constant 𝑇, 𝑃, 𝐶

Develop simplified formulae

Indirect exergy calculations

Process streams 𝑇, 𝑃, 𝐶

∆𝐻 ∆𝑆

σ 𝐸𝑥
 Indirect exergy calculations
𝟐
𝑇2
𝑇2 𝑇2
𝑑𝑇
𝟏
∆𝐻 = න 𝑐𝑝 𝑑𝑇 ∆𝑆 = න 𝑐𝑝
𝑇1 𝑇1 𝑇1 𝑇
𝐻1 𝐻2
𝑇2 𝑑𝑇 𝑇2
𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∆𝑆 ‫𝑇 𝑇׬‬ ln
1 𝑇1
ቊ𝑐 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑇2 =
𝑝 ∆𝐻 ‫𝑇𝑑 𝑇׬‬ 𝑇2 − 𝑇1
1

𝑇2
ln
𝑇1
∆𝑆 = ∆𝐻
𝑇2 − 𝑇1
 Indirect exergy calculations

For 𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑇2
ln 𝑇𝑜
𝑇1
∆𝐸𝑥 = ∆𝐻 1 − 𝑇𝑜 = ∆𝐻 1 −
𝑇2 − 𝑇1 𝑇𝐿𝑀
General approach

Process streams 𝑇, 𝑃, 𝐶

∆𝐻

∆𝐸𝑥
 The Temperature formula
𝑇
𝟐

𝑇𝑜
∆𝐸𝑥 = ∆𝐻 1 −
𝟏 𝑇𝐿𝑀

‒ It’s called temperature formula because of change in

temperature at constant pressure
‒ The formula is derived by assuming 𝑃 and 𝑐𝑝 constant
‒ This is a reasonable assumption for liquids, ideal and
real gases
 The Temperature formula
Don’t apply the formula blindly !

Superheated vapor
𝑇 𝑇1
𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
ቊ𝑐 ≠ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑝
𝟏
𝑇1
Condenser
Condense

𝑇2
𝟐 Phase change 𝑇2 Subcooled liquid

𝐻
The Temperature formula
Don’t apply the formula blindly !
𝑇
𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
ቊ𝑐 ≠ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑝
𝟏
𝑇1

𝑇3
𝑇2
𝟐

𝐻
Linearize in sections
 The Temperature formula
We can use

𝑇𝑜
∆𝐸𝑥 = ∆𝐻 1 −
𝑇𝐿𝑀
𝑇𝑜
or ൞ ∆𝐸𝑥 = ∆𝐻 1 −
𝑇
𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
for above and below ambient
 The Temperature formula
Example 400𝐾, above
∆𝐻1 = −100𝑘𝐽
300 300
∆𝐸𝑥1 = −100 1 − ln 400 = −13.7𝑘𝐽
−100

𝑇𝑜 = 300𝐾
∆𝐻2 = −100𝑘𝐽
300 200
∆𝐸𝑥2 = −100 1 − ln 300 = +21.6𝑘𝐽
−100
200𝐾, below
∆𝐸𝑥𝑡𝑜𝑡 = +7.9𝑘𝐽
300 200
∆𝐸𝑥𝑡𝑜𝑡 = −200 1 − ln = +7.9𝑘𝐽
−200 400
 The Temperature formula
Example
Three different paths from State 1 (BFW) to State 2
(superheated steam) are shown:
Path A: 1 3 4 2
Path B: 1 5 6 2
Path C: 1 7 8 9 2
a) Use the temperature formula to calculate ∆𝐸𝑥 for path A
b) Compare your answer obtained in a) with one calculated
using the entropy data supplied
c) calculate ∆𝐸𝑥 for path C using the appropriate formulae
and compare again
The Temperature formula
Points 𝑷 𝒃𝒂𝒓 𝑻 𝑲 𝒉 𝒌𝑱Τ𝒌𝒈 𝒔 𝒌𝑱Τ𝒌𝒈𝑲
1 1.013 373 419.1 1.307
2 10 573 3052 7.124
3 10 453 763
4 10 453 2778
5 1.013 373 2675.8
6 1.013 561 3052
7 10 584 1408
8 10 584 2725
9 10 957 3829
𝑇𝑜 = 300𝐾
𝑅 = 8.3143 𝑘𝐽 Τ𝑘𝑚𝑜𝑙𝐾
𝑀𝑤𝑎𝑡𝑒𝑟 = 18 𝑘𝑔Τ𝑘𝑚𝑜𝑙
 The Temperature formula
𝟗
𝑇 𝐾

𝟕 𝟖
𝟐 𝟔

𝟑 𝟒
𝟏 𝟓

𝑠 𝑘𝐽Τ𝑘𝑔𝐾
 The Pressure formula
For liquid
Horizontal direction Vertical direction
𝑒𝑥1 = 𝑔ℎ
Work required
No useful work, ∆𝐸𝑥 = 0

ℎ very high
In reality, 𝑒𝑥2 − 𝑒𝑥1 = ∆𝐸𝑥 ≈ 0 ∆𝐸𝑥 = 0
because of pressure drop

Exergy change due to pressure

𝑣2
changes in liquids usually negligible 𝑒𝑥2 = 2
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻
throttling valve processing
𝑇 (isothermal and isenthalpic)

𝟐 𝑃2
𝟏 𝑑𝑃 𝑃2
𝐻 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∆𝑆 = −𝑛𝑅 න = −𝑛𝑅 ln
𝑃1 𝑃 𝑃1

𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃2
ቊ ∆𝐸𝑥 = 𝑛𝑅𝑇𝑜 ln
𝐻 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃1
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻

𝑃2
∆𝐸𝑥 = 𝑛𝑅𝑇𝑜 ln
𝑃1
𝑇𝑜

𝑃1
∆𝐸𝑥 = 𝑛𝑅𝑇𝑜 ln
𝑃2
𝑆
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻
𝑇

𝟏
𝑇1

∆𝐸𝑥 ?
𝑇2
𝟐

𝑆
𝑇1 , 𝑃1 , 𝐻1 𝑇2 , 𝑃2 , 𝐻2
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻
𝑇

𝟏
𝑇1

Construct a
𝟑
convenient path
𝑇2
𝟐

𝑆
𝑇1 , 𝑃1 , 𝐻1 𝑇3 , 𝑃3 , 𝐻3 𝑇2 , 𝑃2 , 𝐻2
CW
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻
𝑇

𝟏 𝟒
𝑇1

Construct a
convenient path
𝑇2
𝟐

𝑆
𝑇1 , 𝑃1 , 𝐻1 𝑇4 , 𝑃4 , 𝐻4 𝑇2 , 𝑃2 , 𝐻2
CW
 The Pressure formula
For ideal gas, 𝒄𝒑 = 𝒇 𝑻
Example

1 𝑘𝑔Τ𝑠 of steam 1𝑏𝑎𝑟

at 5𝑏𝑎𝑟 𝑇 = 500℃
ቊ
𝑇𝑜 = 25℃

∆𝐸𝑥 ?
 The Pressure formula
For real gas, 𝒄𝒑 = 𝒇 𝑻, 𝑷

𝑇1 , 𝑃1 , 𝐻1 𝑇2 , 𝑃2 , 𝐻1

𝑇1 ≠ 𝑇2
The isenthalpic processing

∆𝐸𝑥 ?
 The Pressure formula
For real gas, 𝒄𝒑 = 𝒇 𝑻, 𝑷
𝑇𝑜
∆𝐸𝑥 = ∆𝐻 1 − 𝑃2
𝑇𝑙𝑚 ∆𝐸𝑥 = 𝑛𝑅𝑇𝑜 ln
𝑃1
𝑇
for isenthalpic processes
𝟏
𝑇1
𝟑 𝟐
𝑇2 = 𝑇3 𝐻1 = 𝐻2
𝐻3
𝑇𝑜 𝑃2
∆𝐸𝑥 = ∆𝐻 1 − + 𝑛𝑅𝑇𝑜 ln
𝑇2 𝑃1
𝑆
∆𝑆
 In general

The general formula involved in 𝑻, 𝑷, 𝑯

𝑇𝑜 𝑃2
∆𝐸𝑥 = ∆𝐻 1 − + 𝑛𝑅𝑇𝑜 ln
𝑇𝐿𝑀 𝑃1
0 1
𝑇
𝐻 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
 Example

1 𝑘𝑔Τ𝑠 of 𝑅22 1𝑏𝑎𝑟, 43℃

at 5𝑏𝑎𝑟, 50℃
𝑇𝑜 = 25℃

∆𝐸𝑥 ?
 Example

153 𝑘𝑔Τ𝑠 of
superheated steam 8𝑏𝑎𝑟, 343℃
at 15𝑏𝑎𝑟, 350℃ 𝐻 = 466.2𝑀𝐽
𝐻 = 466.2𝑀𝐽 𝑇𝑜 = 298𝐾

∆𝐸𝑥 ?
 The Composition formula
For mixing
Component 1

ideal 𝑾
system
Component 2
𝑇𝑖𝑛 = 𝑇𝑜𝑢𝑡
Mixture
𝑃𝑖𝑛 = 𝑃𝑜𝑢𝑡
𝐻𝑖𝑛 = 𝐻𝑜𝑢𝑡
𝐸𝑥𝑖𝑛 ≠ 𝐸𝑥𝑜𝑢𝑡
 The Composition formula
For mixing
𝐴 𝑇𝑜 , 𝑃𝑜
ideal gases 𝐴 & 𝐵 mixing
at constant 𝑇𝑜 , 𝑃𝑜

𝑃𝐴 = 𝑦𝐴 𝑃𝑜 𝐴 + 𝐵 at 𝑇𝑜 , 𝑃𝑜
ቊ
𝑃𝐵 = 𝑦𝐵 𝑃𝑜

𝐵 𝑇𝑜 , 𝑃𝑜
 The Composition formula
For mixing
𝑦𝐴 𝑃𝑜
• For component 𝐴 ∆𝐸𝑥𝐴 = 𝑛𝐴 𝑅𝑇𝑜 ln
𝑃𝑜

𝑦𝐵 𝑃𝑜
• For component 𝐵 ∆𝐸𝑥𝐵 = 𝑛𝐵 𝑅𝑇𝑜 ln
𝑃𝑜
𝑘

• For all components ∆𝐸𝑥𝑜 = 𝑅𝑇𝑜 ෍ 𝑛𝑖 ln 𝑦𝑖

𝑖=1
 The Composition formula
For mixing

∆𝐸𝑥𝑜 = ∆𝐻𝑜 + 𝑅𝑇𝑜 ෍ 𝑛𝑖 ln 𝑦𝑖

𝑖=1
 The Composition formula
For separation
𝐴 𝑇𝑜 , 𝑃𝑜
ideal gases 𝐴 & 𝐵 mixing
at constant 𝑇𝑜 , 𝑃𝑜

𝑃𝐴 = 𝑦𝐴 𝑃𝑜 𝐴 + 𝐵 at 𝑇𝑜 , 𝑃𝑜
ቊ
𝑃𝐵 = 𝑦𝐵 𝑃𝑜

𝐵 𝑇𝑜 , 𝑃𝑜
∆𝐸𝑥 = −∆𝐻𝑜 − 𝑅𝑇𝑜 ෍ 𝑛𝑖 ln 𝑦𝑖
𝑖=1
 The Composition formula
𝑘

෍ 𝐸𝑥𝑖 > 𝐸𝑥𝑚𝑖𝑥

𝑖=1
For liquid, 𝑦𝑖 is replaced by 𝑥𝑖
𝑘
• Mixing ∆𝐸𝑥𝑜 = ∆𝐻𝑜 + 𝑅𝑇𝑜 ෍ 𝑛𝑖 ln 𝑥𝑖
𝑖=1

• Separation ∆𝐸𝑥 = −∆𝐸𝑥𝑜

 The Composition formula
In general
Mixture 𝐴 Mixture 𝐶

at 𝑇𝑜 , 𝑃𝑜
Mixture 𝐵 Mixture 𝐷

∆𝐸𝑥𝑜 = ∆𝐻𝑜 + ∆𝐸𝑥𝑜 𝐶 + ∆𝐸𝑥𝑜 𝐷

− ∆𝐸𝑥𝑜 𝐴 + ∆𝐸𝑥𝑜 𝐵
𝑘

∆𝐸𝑥𝑜 𝑗 = ∆𝐻𝑜𝑗 + 𝑅𝑇𝑜 ෍ 𝑛𝑖 ln 𝑦𝑖

𝑖=1
 The Composition formula
Example
By calculation ∆𝐸𝑥𝑜𝑐 separately for the feed, tops and
bottoms stream relative to their pure components,
calculate ∆𝐸𝑥𝑜𝑐 for the distillation column shown below
Tops 𝐴&𝐵
Flow
Feed Tops Bottoms
𝒌𝒎𝒐𝒍Τ𝒉
𝑨 12.2 12.2 0.0
𝑩 484.2 99.9 384.3 Feed
Total 496.4 112.1 384.3
𝑅 = 8.314 𝑘𝐽Τ𝑘𝑚𝑜𝑙𝐾
𝑇𝑜 = 298𝐾
Bottoms 𝐵