Introduction to Chemical

Engineering Thermodynamic
(CHE325)
By
Engr. Babatunde D.E.
EXERGY
 Exergy is called available or useful energy.
 Exergy is the work potential of a system in specified
environment.
 It represents the amount of useful work that can be
obtained as the system is brought to equilibrium with the
environment.
 Exergy depends on the state of the environment and that
of the system.
 Mass and energy balances were the only analysis tools in
design.
 Exergy is derived from 1st and 2nd law of thermodynamics.
 1st law of thermodynamics: quantity of energy only.
 2nd law of thermodynamics: gives quality of energy been
considered.
 Control Volume for Setting-up the Material Balance

From conservation law;

Energy in = Energy out + accumulation (5.1)
2
𝑉
𝑚1 𝑈 ′ + 𝑃𝑉 + + 𝑔𝑧 + 𝑄+ 𝑊𝑠
2 1

′
𝑉2 ′
𝑉2
= 𝑚2 𝑈 + 𝑃𝑉 + + 𝑔𝑧 + 𝑑 𝑚 𝑈 + 𝑃𝑉 + + 𝑔𝑧 (5.2)
2 2
2
Accumulation term
 𝑉2
 𝑈′= Internal energy = kinetic energy
2
 PV = flow energy 𝑔𝑧 = potential energy
Assuming:
1) Steady state 2) kinetic and potential energy terms are small

The equation reduces to:

𝑚1 𝑈 ′ + 𝑃𝑉 1 + 𝑄+ 𝑊𝑠 = 𝑚2 𝑈 ′ + 𝑃𝑉 2

Rearranging
𝑄+ 𝑊𝑠 = 𝑚2 𝑈 ′ + 𝑃𝑉 2 − 𝑚1 𝑈 ′ + 𝑃𝑉 1 (5.3)

Recall: h = 𝑈 ′ + PV (5.4)
Enthalpy = Internal energy + PV term

𝑄+ 𝑊𝑠 = 𝑚 2 ℎ2 − 𝑚1 ℎ1 (5.5)
 Mathematical Statement of Second Law of
Thermodynamics
 Entropy accumulation = Entropy inflow due to mass flow
- Entropy outflow due to mass flow+ entropy transfer
across the system through heat transfer + entropy
production (5.6a)
 Entropy Production = Entropy outflow due to mass flow
– Entropy inflow due to mass flow - entropy transfer
across the system through heat transfer + Entropy
accumulation ≥ 0 (5.6b)
 The above is the constraint required for 2nd law of
thermodynamics to be complete.
Reason: Entropy is a state of disorderliness and every
process requires a level of disorderliness for it to occur.
 Entropy production = 0 when a process is reversible.
 Entropy production > 0 when it is a real process.
 All real processes are accompanied with entropy
production.
 Entropy production
𝑄
𝑚2 𝑠2 − 𝑚1 𝑠1 + 𝑇𝑜 + 𝑑 𝑚𝑠 ≥0 (5.7)

 Assume steady state operations and quantify entropy

production by σ

𝑄
𝑚2 𝑠2 − 𝑚1 𝑠1 − 𝑇𝑜 =σ (5.8)
To combine equation (5) and (8)
Make 𝑄 in (8) the subject
𝑄= 𝑇𝑜 𝑚2 𝑠2 − 𝑇𝑜 𝑚1 𝑠1 − 𝑇𝑜 σ (5.9)

Substitute equation (9) into (5)

𝑇𝑜 𝑚2 𝑠2 − 𝑇𝑜 𝑚1 𝑠1 − 𝑇𝑜 σ + 𝑊𝑠 = 𝑚2 ℎ2 − 𝑚1 ℎ1 (5.10)

Rearrange further,
𝑚1 ℎ1 − 𝑇𝑜 𝑠1 + 𝑊𝑠 = 𝑚2 ℎ2 − 𝑇𝑜 𝑠2 + 𝑇𝑜 σ (5.11)

For steady state operation, mass input equals mass output.

𝑚1 = 𝑚2

For reversible process 𝑇𝑜 σ = 0

𝑊𝑠,𝑟𝑒𝑣 = 𝑚 ℎ2 − 𝑇𝑜 𝑠2 − 𝑚 ℎ1 − 𝑇𝑜 𝑠1

= 𝑚 ℎ2 − ℎ1 − 𝑇𝑜 𝑠2 − 𝑠1 (5.12)

= 𝑚 ∆ℎ − 𝑇𝑜 ∆𝑠 (5.13)
 𝑊𝑠,𝑟𝑒𝑣 = 𝑚 ∆ℎ − 𝑇𝑜 ∆𝑠 = ΔH – 𝑇𝑜 ΔS =Exergy (5.14)

 The quantity ∆ℎ − 𝑇𝑜 ∆𝑠 is a thermodynamic function

called specific exergy (i.e. per kg or per mol)

 Implications
1. Exergy is lower than energy in amount (or quantity)
because ΔH is energy.
2. ΔH – 𝑇𝑜 ∆𝑆 tells us the true quality of the energy.
3. If 𝑇𝑜 ∆𝑆 is low, the exergy is high.
4. If 𝑇𝑜 ∆𝑆 is high, it implies low exergy.
 Exergy is the work associated with a completely reversible process.
 The state of the environment is referred to as the ‘dead state’
because the system is dead (cannot do any work) from a
thermodynamic point of view.
 It is the maximum amount of useful work that can be produced (by
a work - producing process) or
 the minimum work that should be supplied (work - requiring
process) in bringing the system to its dead state (i.e equilibrium
with the environment).
 pump & compressor are examples of unit that requires work supply
of electrical power
W

 turbine or expander are examples of units that produce work

High pressure steam
WS

low pressure steam

 If the overall process requires work, it is a work-requiring
process.
 If the overall process produces work, it is a work-producing
process.
 For process requiring work as shown below, it is of interest
to reduce the actual work required to ‘practical work’. The
‘practical work’ is to be as close as possible to the minimum
theoretical work required.

- - - - - - - - - - - - WS, actual - - - -- - - - - -- - - - - - WS, max

WS,req Ws,prod - - - - - - - - - - - - - - WS, practical

- - - - - - - - - - - - WS, practical

- - - - - - - - - - - - WS, min - - - - - - - - - - - - - - - WS, actual

Work requiring process work producing process

 Irreversibilities and the Exergy Balance
 "σ" entropy production leads to irreversibility
 The reversible work obtained (or expended) equals
exergy when a system undergoes process from an
initial state to a final state if the final state is dead
state. It is the maximum useful work that can be
obtained or (minimum work that can be expended)
 Any difference between the reversible work and
useful work is due to the presence of Irreversibilities
during the process
 Irreversibility represent the amount of energy that
could have been converted to work but was not
 In energy balance, no irreversibility i.e. Energy in =
Energy out
 In exergy balance, exergy is destroyed i.e Exergy in =
Exergy out + Exergy destroyed
 The exergy destroyed in driving a process is called
irreversibility.
 For real process, Wrev = Wu+ 𝑇𝑜 σ
= Wu + I (Irreversibility)
= ∆Ex process + I (5.15)
• Real processes consume exergy
• Irreversibility is the measure of efficiency of a
process.
• Irreversibility should be as low as possible.
• Irreversibility (or 2nd law efficiency) can be used to
improve design.
• High irreversibility implies high amount of exergy is
consumed or destroyed by the process. High
efficiency and low irreversibility are synonymous.
• There are two types of irreversibilities
1. Inherent or unavoidable irreversibility e.g caused
by factors like process route, chemical inefficiency.

2. Non-inherent or avoidable irreversibility caused by

factors like interaction deficiency in units in a
process.
 Exergy Efficiency
 Exergy efficiency cannot be more than 100%.
 Second law efficiency is a measure of performance
relative to the optimal performance permitted by the
energy balance.
 Second law efficiency can be defined generally as:

𝑒𝑥𝑒𝑟𝑔𝑦 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑒𝑑
Ψ= (5.16𝑎)
𝑒𝑥𝑒𝑟𝑔𝑦 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑
 Work requiring process work producing process
𝑊𝑖𝑑𝑒𝑎𝑙 𝑊𝑠,𝑎𝑐𝑡𝑢𝑎𝑙
Ψ= 5.16𝑏 𝑜𝑟 (5.16𝑐)
𝑊𝑠,𝑎𝑐𝑡𝑢𝑎𝑙 𝑊𝑖𝑑𝑒𝑎𝑙

Δ𝐸𝑥𝑜𝑢𝑡
Ψ= (5.16d)
Δ𝐸𝑥𝑖𝑛
 various exergies can be combined (work exergy, fuel exergy, heat exergy)
 Exergy Efficiency of a Single Unit
Δ𝐸𝑥𝑠𝑖𝑛𝑘
Ψ𝑢𝑛𝑖𝑡 = (5.16𝑒)
Δ𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒
For example, for a heat exchanger

Δ𝐸𝑥𝑐𝑜𝑙𝑑 𝑠𝑡𝑟𝑒𝑎𝑚
Ψℎ𝑒𝑎𝑡 𝑒𝑥𝑐ℎ𝑎𝑛𝑔𝑒𝑟 = (5.16𝑓)
Δ𝐸𝑥ℎ𝑜𝑡 𝑠𝑡𝑟𝑒𝑎𝑚

2nd law efficiency can apply to any complex system

involving thermal, electrical, material exergies.
 Data Required for Exergy Analysis
 Enthalpy, entropy, free energy of formation, heat of reaction,
heat capacities e.t.c

 Despite the vast amount of thermodynamics data available, there

are few pure substances for which we have thermodynamic data
in the range of temperature of interest.

 It may be necessary, as it is usually the case in design and

simulation studies to calculate thermodynamic properties of
pure component and mixtures from basic data, correlations and
equations of state.

 Exergy analysis of a real chemical process requires detailed

information on the actual process conditions.

 The plant data required include stream composition,

temperature, pressure, process topology, design parameter for
the units, and heat flows, electrical exergy flows and work flows.
 Steps in Analysis of a Process
 Break the overall process into suitable units or sub-systems.
 Calculate any unknown variables such as flow rate,
temperature, pressure and composition for all the streams
crossing the unit or sub-system boundary.
 Identify exergy sources and sinks and utilities associated
with each unit and sub-systems.

 Evaluate the exergy of all the streams entering and

leaving the unit or subsystem boundary, and hence the
2nd law efficiencies of the unit and overall process (this
will be done in excel environment
 Application of Exergy Analysis
 Exergy analysis can be applied to processes in several
ways
1. Evaluation of 2nd law efficiency of a process and its
units.
2. Process design:
Differences in the design alternatives can be
investigated using exergy analysis.
3. Equipment design optimization or operation.

4. Thermo-economic or exergo-economic
analysis.

5. Environment problems and sustainability.

Steam is generated at a pressure of 8600 kPa, temperature of 500oC and is fed
to a turbine. Exhaust steam from the turbine enters a condenser at 10kPa
where it is condensed to saturated liquid. The liquid is then pumped to a boiler
where the steam is generated and the cycle is completed. The rating of the
power cycle is 80, 000kW.
The steam is generated in a furnace/boiler unit where methane is burnt
completely to CO2 and H2O with 25% excess air. The flow rate of methane into
the furnace is 366.30 mol/s. The flue gas leaving the furnace is at temperature
of 460K. The ambient or environmental temperature is 298K.
The rate of steam generated is 84.75kg/s.
𝑜
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = −737.64𝑘𝐽/𝑚𝑜𝑙,
𝑜
∆𝑆𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 0.16855𝑘𝐽/𝑚𝑜𝑙. 𝐾
Properties of working fluid at key points (1, 2, 3, 4) in the cycle are given in
Table 1
Questions
1. Calculate the exergy of fuel burnt
2. Calculate the overall 2nd law efficiency
3. Calculate the exergy of each stream
4. Perform component analysis on the four units to
get ∆𝐸𝑠𝑜𝑢𝑟𝑐𝑒 , ∆𝐸𝑠𝑖𝑛𝑘 , 𝐼, Ψ and 𝜂
 Furnace/Boiler

Flue gas

Steam

1
2

Pump

𝑊𝑠
𝑊𝑠

Turbine

Condenser
4
3

CW

Fig 1: steam power plant

Table 1: Properties of working fluid at key points
in the cycle
Point State of steam T(oC) P (kPa) H (kJ/kg) S (kJ/kg.K)

1 Subcooled water 45.83 8600 203.3 0.6580

2 Superheated 500.00 8600 3391.6 6.6858

steam

3 Wet steam 45.83 10 2436.0 7.6846

4 Saturated water 45.83 10 191.8 0.6493

Solution
Chemical reaction/fuel combustion in the furnace/boiler
𝐶𝐻4 + 2𝑂2 𝐶𝑂2 + 2𝐻2 𝑂

Exergy of fuel burnt is:

𝑜 𝑜
∆𝐸𝑥𝑓𝑢𝑒𝑙 = 𝑛𝐶𝐻4 (∆𝐻𝑐𝑜𝑚𝑏 − 𝑇𝑜 ∆𝑆𝑐𝑜𝑚𝑏 )

= 366.30 −737.64 − 298 0.16855

= −366.30 787.87 𝑘𝐽/𝑠

= −288.60 × 103 𝑘𝐽/𝑠

= −288.60 × 103 𝑘𝑊
Overall 2nd law efficiency (exergy efficiency)
𝐸𝑥𝑒𝑟𝑔𝑦 𝑜𝑢𝑡𝑝𝑢𝑡
Ψ=
𝐸𝑥𝑒𝑟𝑔𝑦 𝑖𝑛𝑝𝑢𝑡

𝐸𝑥𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑜𝑤𝑒𝑟 𝑐𝑦𝑐𝑙𝑒

=
𝐸𝑥𝑒𝑟𝑔𝑦 𝑜𝑓 𝑓𝑢𝑒𝑙 𝑏𝑢𝑟𝑛𝑡

80𝑀𝑊
= × 100 = 27.7%
288.6𝑀𝑊

Calculation of Exergy of Streams

Example: calculation of exergy for point 1 in the cycle

𝐸𝑥1 = Δ𝐻1 − 𝑇𝑜 Δ𝑆1

= 203.4 − 298.15 (0.6580)

= 7.2173𝑘𝐽/𝑘𝑔
 Do this for points 2, 3 and 4. The results are summarized
below

Point Ex (kJ/kg)
1 7.2173
2 1398.228
3 144.83
4 −1.78

 Calculate 𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒 , ∆𝐸𝑠𝑖𝑛𝑘 , 𝐼, Ψ and 𝜂 (1st efficiency)

for the boiler, turbine, condenser and pump
Example: Boiler
Δ𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒 = Δ𝐸𝑥𝑓𝑢𝑒𝑙 = 288.6𝑀𝑊

Δ𝐸𝑥𝑠𝑖𝑛𝑘 = 𝐸𝑥2 − 𝐸𝑥1

𝑘𝑔 𝑘𝐽
= 84.75[1398.228 − 7.2173] ×
𝑠 𝑘𝑔

= 117.89𝑀𝑊

𝐼𝑏𝑜𝑖𝑙𝑒𝑟 = Δ𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒 − Δ𝐸𝑥𝑠𝑖𝑛𝑘

= 288.6 − 117.89 = 170.71𝑀𝑊

Δ𝐸𝑥𝑠𝑖𝑛𝑘 117.89
Ψ= = × 100 = 40.8%
Δ𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒 288.6
For energy efficiency, use enthalpy
Δ𝐻𝑠𝑖𝑛𝑘 = 𝐻2 − 𝐻1

= 3391.6 − 203.4 84.75

= 270.20𝑀𝑊

𝑜
Δ𝐻𝑠𝑜𝑢𝑟𝑐𝑒 = 𝑛𝐶𝐻4 × ∆𝐻𝑐𝑜𝑚𝑏

= (−737.640𝑘𝐽/𝑚𝑜𝑙) × (366.30 𝑚𝑜𝑙/𝑠)

= −270.20𝑀𝑊

Δ𝐻𝑠𝑖𝑛𝑘 270.2
𝜂= = = 100%
Δ𝐻𝑠𝑜𝑢𝑟𝑐𝑒 270.2
Summary of Results of Exergy Analysis of Components

Component Δ𝐸𝑥𝑠𝑜𝑢𝑟𝑐𝑒 Δ𝐸𝑥𝑠𝑖𝑛𝑘 I Ψ(%) 𝜂(%)

MW MW MW 2nd law 1st law
eff eff
Boiler 288.6 117.89 170.71 40.8 100
Turbine 106.23 80.99 25.24 76.2 91.9
Condenser 12.43 ~0 12.43 0 0
Pump 0.98 0.76 0.22 77.6 100