Thermodynamics

Performance of thermodynamic processes

Module 3
Prof. Anand Veeraragavan
[email protected]
Co-Director, Centre for Hypersonics
School of Mechanical and Mining Engineering

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 MECH3400 Thermodynamics and Heat Transfer

Structure of the “Thermodynamics”

1. Introduction, 1st Law & Thermodynamic properties

2. Entropy
3. Performance of thermodynamic processes
4. Refrigeration and heat pumps
5. Psychrometry
6. Thermodynamic cycles
7. Thermodynamics of Combustion

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Content outline in Module 3

Reversible work and Irreversibilities
Efficiencies
••• Chapter 7
Exergy definition
Exergy change
••• Chapter 8
Balance of exergy

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Reversible processes maximise performance

• Recall that in Module 2, we mentioned that reversible
processes deliver the most work, or consume the least
work.
• This is because irreversible process has 𝑆𝑔𝑒𝑛 greater
than 0, and 𝑆𝑔𝑒𝑛 is the cause of degradation of the
performance of a device.
• Maximum amount of work that can be obtained for a
work-producing device undergoing a reversible process
between an initial and final state.
• Minimum amount of work that can be expended by a
work-consuming device undergoing a reversible
𝑃ത𝑟𝑒𝑣 > 𝑃ത𝑖𝑟𝑟 (𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛) process between an initial and final state (or vice-versa).
𝑃ത𝑟𝑒𝑣 < 𝑃ത𝑖𝑟𝑟 (𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛)
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Reversible work
Work is a function of three factors:
– Initial state
– Final state
– Process path
For work-producing devices, we are often interested in useful work 𝑾𝒖
— The work output of the device that can be used by external users.
Caution: NOT all the “work output” of a device is useful work!

𝑾𝒖 = 𝑃 𝒱2 − 𝒱1 − 𝑃0 𝒱2 − 𝒱1 = 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 − 𝑊𝑠𝑢𝑟𝑟 where 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 is the “work output”

• We define: The useful work output (or input) of a system when it undergoes a reversible
process between specified initial and final states is reversible work, denoted as 𝑾𝒓𝒆𝒗 .
• The difference between reversible work and useful work is called irreversibility, denoted as I.

𝑰 = 𝑊𝑟𝑒𝑣,𝑜𝑢𝑡 − 𝑊𝑢,𝑜𝑢𝑡 or 𝑰 = 𝑊𝑢,𝑖𝑛 − 𝑊𝑟𝑒𝑣,𝑖𝑛

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Reversible work

𝑊𝑟𝑒𝑣,𝑜𝑢𝑡 > 𝑊𝑢,𝑜𝑢𝑡 (𝑖𝑟𝑟𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠) 𝑊𝑟𝑒𝑣,𝑖𝑛 < 𝑊𝑢,𝑖𝑛 (𝑖𝑟𝑟𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)
൝ or ൝
𝑊𝑟𝑒𝑣,𝑜𝑢𝑡 = 𝑊𝑢,𝑜𝑢𝑡 (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠) 𝑊𝑟𝑒𝑣,𝑖𝑛 = 𝑊𝑢,𝑖𝑛 (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)

Obviously, 𝐼 ≥ 0.
When a process is done in a reversible adiabatic manner, entropy of the system or the working fluid
remains constant. This can be proved simply by applying the entropy balance equations for closed
systems or control volumes.
An isentropic process is customarily referred to as an adiabatic reversible process.
Reversible process/work is treated as an idealized model in thermodynamics.
With the first law, we can calculate total energy and energy flows. On its own this is of limited use –
whether that energy can be converted to functional forms depends on our ability to appropriately
design equipment

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Reversible processes in HE & HP

Heat engines are devices consisting at least four components representing four processes of the
working fluid. These processes can be replaced by reversible processes.
Then the cycle becomes Carnot heat engine.

Reversible isothermal
Heat Addition
Expansion heat addition

Reversible adiabatic Reversible adiabatic

compression expansion
Compression
Reversible isothermal
Heat Rejection heat rejection

Real heat engine Carnot heat engine

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Reversible processes in HE & HP

• Carnot heat engines, or Carnot refrigerators/heat pumps, are idealized cycles to
model the real HEs and HPs.
• Carnot heat engines deliver most work, & Carnot refrigerators/heat pumps consume
least work, under same working conditions.
𝑊 𝑄
• Thermal efficiency for HEs 𝜂𝑡ℎ = , and COPs for HP 𝐶𝑂𝑃 =
𝑄𝐻 𝑊

• For Carnot heat engines, or Carnot refrigerators/heat pumps, we have

𝑊𝑟𝑒𝑣 𝑄𝑟𝑒𝑣
𝜂𝑡ℎ,𝑟𝑒𝑣 = 𝐶𝑂𝑃𝑟𝑒𝑣 =
𝑄𝐻,𝑟𝑒𝑣 𝑊𝑟𝑒𝑣
• By considering thermodynamic temperature scale, these can become
𝑇𝐻 − 𝑇𝐿 𝑇𝐿 𝑇𝐻 𝑇𝐿
𝜂𝑡ℎ,𝑟𝑒𝑣 = =1− 𝐶𝑂𝑃𝑟𝑒𝑣 = 𝐶𝑂𝑃𝑟𝑒𝑣 =
𝑇𝐻 𝑇𝐻 𝑇𝐻 − 𝑇𝐿 𝑇𝐻 − 𝑇𝐿

• These are Carnot efficiency for heat engine, heat pump and refrigerator.
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Example 3.1 – Power Cycle

A power system salesman claims that the Organic Rankine cycle Engine he is selling can recover
40 kW of electricity from 123 kW of waste industrial heat at 110°C. Should you buy his system?

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Efficiencies
Carnot efficiencies represent the theoretical highest efficiencies HEs and HPs could achieve
between two given thermal reservoirs (𝑇𝐻 and 𝑇𝐿 )
Actual efficiencies of these devices are always lower than Carnot efficiencies.
So far, all the efficiencies we discussed are in the general form of
𝜂𝑡ℎ = 𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡𝑝𝑢𝑡Τ𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑝𝑢𝑡
Some examples
𝑚𝑒𝑐ℎ𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
– For mechanical devices: 𝜂𝑚𝑒𝑐ℎ = (e.g. turbines, engines)
𝑚𝑒𝑐ℎ𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛
ℎ𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
– For heat flow: 𝜂ℎ𝑒𝑎𝑡 = (e.g. heat exchangers)
ℎ𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛
𝑚𝑒𝑐ℎ𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
– For power cycles: 𝜂𝑐𝑦𝑐𝑙𝑒 = (e.g. heat engines)
ℎ𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛
All these are first law efficiencies. Carnot efficiency is also a first-law efficiency.

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Efficiencies
• An analysis with the first-law allows us to calculate the first law efficiency (𝜂𝐼 ) of a system
based on total energy inputs and desired energy outputs.
• This is most relevant for the case of engines (power cycles), where we can clearly
calculate heat input and work output. It is less useful for individual thermodynamic
processes, as it provides no reference to possible performance.
• That is where the second-law efficiency is particularly useful.
• Proper efficiency analysis requires careful setting of system
boundaries
• Common forms of expression:
𝑊𝑢 𝜂𝑡ℎ 𝑊𝑟𝑒𝑣 𝐶𝑂𝑃
𝜂𝐼𝐼 = = 𝜂𝐼𝐼 = 𝜂𝐼𝐼 =
𝑊𝑟𝑒𝑣 𝜂𝑡ℎ, 𝑟𝑒𝑣 𝑊𝑢 𝐶𝑂𝑃𝑟𝑒𝑣
Work-producing Work-consuming Refrigerators/
devices devices Heat pumps
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Isentropic efficiency
• Second-law efficiency of various steady-flow devices we have talked about (e.g.
turbines, compressors, nozzles, heat exchangers, etc.) have many different forms
of definitions.
• We can consider a turbine, for example:
– The ratio of actual useful work produced to the ideal, which is what an adiabatic
reversible turbine operating between the same inlet state and exit pressure.
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 𝑊𝑎 ℎ1 − ℎ2,𝑎𝑐𝑡𝑢𝑎𝑙
𝜂𝑇 = = ≅
𝑊𝑟𝑒𝑣 𝑊𝑠 ℎ1 − ℎ2,𝑖𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐

• This second-law efficiency is also

called isentropic efficiency (or an
adiabatic efficiency), as 𝑊𝑟𝑒𝑣 is
isentropic process work.

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Isentropic Efficiency

• The manner in which we formulate the isentropic efficiency depends on whether the
device consumes or produced work.
• If the device consumes work, the formulation is different
• E.g. isentropic efficiency of compressors and pumps
𝑊𝑟𝑒𝑣 𝑊𝑠 ℎ2,𝑖𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐 − ℎ1
𝜂𝐶 = = = Adiabatic compressors
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 𝑊𝑎 ℎ2,𝑎𝑐𝑡𝑢𝑎𝑙 − ℎ1
𝑊𝑠 𝓋(𝑃2 − 𝑃1 )
𝜂𝑃 = = Pumps
𝑊𝑎 ℎ2,𝑎𝑐𝑡𝑢𝑎𝑙 − ℎ1
• The numerator and denominator are reversed to make the meaning of efficiency
realistic.
• Note: often compression will include cooling to reduce work input compared to an
isentropic design. In this case, isentropic efficiency is meaningless.
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Isentropic Efficiency
We can also apply this to devices such as nozzles (which maximise outlet eK):
2
𝐴𝑐𝑡𝑢𝑎𝑙 𝐾𝐸 𝑎𝑡 𝑛𝑜𝑧𝑧𝑙𝑒 𝑒𝑥𝑖𝑡 𝑣2𝑎
𝜂𝑁 = = 2
𝐼𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐 𝐾𝐸 𝑎𝑡 𝑛𝑜𝑧𝑧𝑙𝑒 𝑒𝑥𝑖𝑡 𝑣2𝑠
ℎ1 − ℎ2,𝑎𝑐𝑡𝑢𝑎𝑙
𝜂𝑁 ≅
ℎ1 − ℎ2,𝑖𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐

Or diffusers (which maximise ratio of enthalpy change for the same exit pressure):

ℎ2,𝑖𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐 − ℎ1
𝜂𝐷 ≅
ℎ2,𝑎𝑐𝑡𝑢𝑎𝑙 − ℎ1

Don’t worry too much about the specifics – the point here is that this approach is applied to many
thermodynamic processes. We will return to a more general form of second-law efficiency.

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Example 3.2 – Turbine

In Example 2.6, the gas through the turbine undergoes isentropic process with air entering the inlet at
500°C, and 8 Mpa. It reduces the pressure to 0.5 Mpa at turbine exit. Now, if the turbine process is not
isentropic, instead the air has outlet temperature of 107°C. What is the isentropic efficiency?

𝑃𝑖𝑛 = 8 𝑀𝑃𝑎
𝑇𝑖𝑛 = 500°C
𝜂 𝑇 =?

𝑃𝑜𝑢𝑡 = 0.5 𝑀𝑃𝑎

𝑇𝑜𝑢𝑡 = 107°C

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The Dead State

This is defined as being in equilibrium with the surroundings (environment). This is in
terms of
– Thermal energy
– Mechanical energy (eP and eK)
– Chemical energy
– Magnetic energy
– etc
Maximising work output from a process requires the final state to be the dead state
– That is, no more possible energy can be extracted due to equilibrium, and
consequently no more work
We denote properties of the dead state with a subscript zero, e.g. 𝑇0 , 𝑃0 , ℎ0 , 𝑢0 and 𝑠0 .
Surrounding can be divided into immediate surroundings and the environment

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Exergy
System delivers the maximum useful work 𝑊𝑢 as it undergoes a reversible process from a
specified initial state to its dead state.
This represents the useful work potential of the system at the specified state, is called exergy or
availability.
Unlike energy, exergy of a system depends on state of the system and the state of the environment.
It is a property of system-environment combination.
Exergy is denoted by different letters depending on the object
▪ 𝑋— total exergy (extensive property, kJ)
▪ 𝑥— specific exergy (intensive property, kJ/kg)
▪ 𝜙 — exergy of a fixed mass, or closed system exergy, per mass (intensive property, kJ/kg)
▪ 𝜓 — exergy of a flow stream, or flow exergy, per mass (intensive property, kJ/kg)
Exergies of kinetic and potential energy are themselves.
𝑉2
𝑥𝑘𝑒 = 𝑒𝑘 = 2
and 𝑥𝑝𝑒 = 𝑒𝑝 = 𝑔𝑧 (kJ/kg)

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Exergy of a fixed mass, f

How much exergy does a given mass possess? = How much useful work the mass can
do at the most through any process?
• It depends on the state of the mass, its environment, and the process.
• Let’s start with considering a stationary closed system undergoing a reversible
expansion with heat rejection from state (𝑇, 𝑃, 𝒱, S…) to the state of surroundings
(𝑇0 , 𝑃0 , … ).
• From a 1st Law analysis: −𝛿𝑊 − 𝛿𝑄 = 𝑑𝑈
• The only work 𝛿𝑤 a system can have during a reversible process is the boundary
(piston) work 𝛿𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 = 𝑃𝑑𝒱
• 𝛿𝑊 = 𝑃𝑑𝒱 = 𝑃 − 𝑃0 𝑑𝒱 + 𝑃0 𝑑𝒱 = 𝛿𝑊𝑢,𝑏 + 𝑃0 𝑑𝒱
• Recall that 𝑊𝑢,𝑏 = 𝑃 − 𝑃0 𝒱2 − 𝒱1 , therefore 𝛿𝑊𝑢,𝑏 = 𝑃 − 𝑃0 𝑑𝒱
• The useful work component is that delivered above the atmospheric level

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Exergy of a fixed mass, f

• Now we have: −(𝛿𝑊𝑢,𝑏 + 𝑃0 𝑑𝒱) − 𝛿𝑄 = 𝑑𝑈
• For the heat flow out of the system, we can extract the maximum useful work
component if that heat were input into a reversible heat engine operating
between 𝑇 and 𝑇0 as per Carnot efficiency:
𝑇0 𝛿𝑄
• 𝛿𝑊𝑢,𝐻𝐸 = 1 − 𝛿𝑄 = 𝛿𝑄 − 𝑇0 = 𝛿𝑄 + 𝑇0 𝑑𝑆
𝑇 𝑇
𝛿𝑄 −𝛿𝑄
• By the definition of entropy 𝑑𝑆 = (here = , since heat
𝑇 𝑖𝑛𝑡 𝑟𝑒𝑣 𝑇 𝑖𝑛𝑡 𝑟𝑒𝑣
leaves the system)
• 𝛿𝑊𝑢,𝐻𝐸 = 𝛿𝑄 + 𝑇0 𝑑𝑆 From the definition of “reversible”, the
• 𝛿𝑄 = 𝛿𝑊𝑢,𝐻𝐸 − 𝑇0 𝑑𝑆 reversible process of a system cannot have
any heat transfer with environment through a
• −𝛿𝑊𝑢,𝑏 − 𝑃0 𝑑𝒱 − (𝛿𝑊𝑢,𝐻𝐸 − 𝑇0 𝑑𝑆) = 𝑑𝑈 finite temperature difference. Therefore, any
• 𝛿𝑊𝑢,𝐻𝐸 + 𝛿𝑊𝑢,𝑏 = −𝑑𝑈 − 𝑃0 𝑑𝒱 + 𝑇0 𝑑𝑆 heat leaving (or entering) the system must be
achieved through a reversible heat engine
𝛿𝑊𝑢,𝑡𝑜𝑡 between the system and the environment.
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Exergy of a fixed mass, f

0
𝑊𝑢,𝑡𝑜𝑡 = න (−𝑑𝑈 − 𝑃0 𝑑𝒱 + 𝑇0 𝑑𝑆)
𝑖𝑛𝑖𝑡𝑖𝑎𝑙
• So after that involved derivation, we have an expression for the total useful
work delivered for a system if it undergoes a reversible process from a
defined state to the dead state. This is 𝑊𝑢 exergy:
𝑊𝑢 = 𝑈 − 𝑈0 + 𝑃0 𝒱 − 𝒱0 − 𝑇0 (𝑆 − 𝑆0 )
• We can also add kinetic and potential energy into exergy directly, so the
exergy of a closed system of mass m is:
𝑉2
𝑋 = (𝑈 − 𝑈0 ) + 𝑃0 𝒱 − 𝒱0 − 𝑇0 (𝑆 − 𝑆0 ) + 𝑚 + 𝑚𝑔𝑧 (kJ)
2
• Unit-mass form closed system exergy 𝜙:
𝑉2
𝜙 = (𝑢 − 𝑢0 ) + 𝑃0 𝓋 − 𝓋0 − 𝑇0 𝑠 − 𝑠0 + + 𝑔𝑧 (kJ/kg)
2
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Exergy of a flow stream, ψ

(i.e. entering or leaving a control volume)
• Energy and entropy are carried by flowing mass, so does exergy.
• Let us consider unit-mass form this time.
• We introduced flow work (energy) of a fluid 𝑤𝑓𝑙𝑜𝑤 = 𝑃𝓋. The flow work is essentially
a boundary work done by the downstream fluid, therefore the exergy associated is
similar to boundary work, flow exergy 𝑥𝑓𝑙𝑜𝑤 = 𝑃𝓋 − 𝑃0 𝓋 = (𝑃 − 𝑃0 )𝓋
• Exergy of a flow is a sum of 𝑥𝑓𝑙𝑜𝑤 and the fixed-mass exergy 𝜙
• 𝜓 = 𝜙 + 𝑥𝑓𝑙𝑜𝑤
𝑉2
• 𝜓 = (𝑢 − 𝑢0 ) + 𝑃0 𝓋 − 𝓋0 − 𝑇0 𝑠 − 𝑠0 + + 𝑔𝑧 + (𝑃 − 𝑃0 )𝓋
2
𝑉2
= 𝑢 + 𝑃𝓋 − 𝑢0 − 𝑃0 𝓋0 − 𝑇0 𝑠 − 𝑠0 + + 𝑔𝑧
2
𝑉2
Exergy of a flow stream 𝜓 = (ℎ − ℎ0 ) − 𝑇0 𝑠 − 𝑠0 + + 𝑔𝑧 (kJ/kg)
2
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Change in exergy
• Exergy change of a closed system during a process between state 1 and state 2:
𝑉22 − 𝑉12
∆𝑋 = 𝑋2 − 𝑋1 = (𝑈2 − 𝑈1 ) + 𝑃0 𝒱2 − 𝒱1 − 𝑇0 (𝑆2 − 𝑆1 ) + 𝑚 + 𝑚𝑔(𝑧2 − 𝑧1 ) (kJ)
2
𝑉22 − 𝑉12
∆𝜙 = 𝝓𝟐 − 𝝓𝟏 = (𝑢2 − 𝑢1 ) + 𝑃0 𝓋2 − 𝓋1 − 𝑇0 𝑠2 − 𝑠1 + + 𝑔(𝑧2 − 𝑧1 ) (kJ/kg)
2
∆𝑋 = 𝑚 𝜙2 − 𝜙1 = 𝑚∆𝜙

• Exergy change of a fluid stream as it goes from state 1 to state 2:

𝑉22 − 𝑉12
∆𝜓 = 𝜓2 − 𝜓1 = (ℎ2 − ℎ1 ) − 𝑇0 𝑠2 − 𝑠1 + + 𝑔(𝑧2 − 𝑧1 ) (kJ/kg)
2
• Note that the change retains terms that depend on surrounding conditions!
• Exergy change is zero if the system state or the environment does not change.
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Example 3.3 – Compressed Nitrogen

A full high pressure nitrogen cylinder contains 10.4 kg of nitrogen at 20 MPa and 40°C. How
much work could be obtained from expansion of the cylinder contents in the room temperature
of 35°C? assume atmospheric pressure to be 0.1 MPa.
Assumptions: ideal gas; negligible eK, eP; constant specific heat.
𝑐𝑣 for nitrogen is 0.743, 𝑐𝑝 is 1.039 , R is 0.2968 (Table A-2)
Strategy: how much work can do is essentially the exergy of the gas at current state in the
20 MPa
given environment. Therefore:
40°C

10.4 kg

𝑇0 =35 °C
𝑃0 = 0.1 MPa

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Exergy transfer
• Similar to energy and entropy, exergy can be transported in or out of system.
• The mechanism of exergy transfer is same as that of energy transfer:
Exergy transfer by work — Exergy transferred while work done on or by a system:
𝑊 − 𝑊𝑠𝑢𝑟𝑟 (for boundary work)
𝑋𝑏𝑦 𝑤𝑜𝑟𝑘 = ቊ (kJ) where 𝑊𝑠𝑢𝑟𝑟 = 𝑃0 𝒱2 − 𝒱1
𝑊 (for other forms of work)
Exergy transfer by mass flow — Exergy is carried into or out of a system by streams
of matter:
𝑋𝑏𝑦 𝑚𝑎𝑠𝑠 = 𝑚𝜓 (kJ)
Exergy transfer by heat transfer — exergy transported accompanied by heat transfer:
𝑇0 𝑄
𝑋𝑏𝑦 ℎ𝑒𝑎𝑡 = 1 − 𝑄 (kJ) Recall 𝑆𝑏𝑦 ℎ𝑒𝑎𝑡 =
𝑇 𝑇

where 𝑇 is the temperature of the boundary point at which 𝑄 is transferred.

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Explanation on “transfer”
• We frequently mention “ XXX transfer”. Here XXX is a thermodynamic property such
as mass, energy, entropy, exergy…
• “Work” is not a typical property thus seldom use “transfer”; “heat” is a representation
of thermal energy (internal energy) and thus uses “transfer”.
• The word “transfer” is a vague idea. It has more precise meanings for different
occasions:
1. For the system alone (excluding the boundary) “transfer” means
“entering” or “leaving”.
2. For surroundings (excluding the boundary) “transfer” also means System
“entering” or “leaving”.
3. For the boundary “transfer” means “crossing”.
Boundary
• Tricky things lie with “boundary”

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Explanation on “transfer”
• We often see questions like “how much entropy generation during the heat
transfer process”
• This actually means “during the heat crossing the boundary”.
• This implies that we have to consider the thickness of the boundary, so that
there are temperature gradient within the boundary.
• Here, Medium 1 could be the system, while Medium 2 is the surroundings.
• It is the temperature gradient within the boundary that generates entropy or
destroys exergy.
• There is NO pure heat transfer occurring across a zero-thickness boundary!
• Mass transfer happens only across an imaginary boundary, which has zero
thickness. Therefore, there is no mass generated/destroyed in boundary.

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Explanation on “transfer”
• In practice, we can consider “boundary” including not only the visible
boundary but the immediate surroundings that has temperature gradient.
• The combination of system + this “boundary” is exactly the extended system.
• In this way, the “surroundings” is reduced to the environment.
For example:

A piston-cylinder device contains a statured liq-v water mixture at 100°C and is maintained at constant
pressure. During a process, 600 kJ heat is transferred to the surroundings air at 25°C. Determine (a)
entropy and exergy change of the water mixture, (b) the total entropy generation and exergy destruction
during this heat transfer process.

For (a)
Select system as the “liq-v mixture” alone: the heat transfer means 600 kJ heat leaving the system
and this “leaving” is an internally reversible process, because it can be reversed without creating
any irreversibilities inside the system by simply “adding” the same amount of heat.
Entropy and exergy changes are merely due to heat “leaving” the system.

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Explanation on “transfer”
A piston-cylinder device contains a statured l-v water mixture at 100°C and is maintained constant pressure in it. During a
process, 600 kJ heat is transferred to the surroundings air at 25°C. Determine (a) entropy and exergy change of the water
mixture, (b) the total entropy generation and exergy destruction during this heat transfer process.

Whereas the system remains constant temperature which means the heat “leaving” is an isothermal
process. Therefore, the entropy and exergy changes are
𝑄 −600 𝑇0 298
Δ𝑆𝑠𝑦𝑠 = 𝑆𝑏𝑦 ℎ𝑒𝑎𝑡 = = = −1.61 kJ/kg Δ𝑋𝑠𝑦𝑠 = 𝑋𝑏𝑦 ℎ𝑒𝑎𝑡 = 1 − 𝑄 = 1− −600
𝑇 100 + 273 𝑇 373
= −120.64 kJ
For (b)
Select the “boundary” as system which has 100°C on inner face and 25°C on the outer face: the heat
transfer means 600 kJ heat is crossing the system. This “crossing” is not a reversible process, because
100℃
it has temperature gradient. Apply entropy balance to the system. The state of the system is steady.
25℃ 600 600
∆𝑆𝑠𝑦𝑠 = 𝑆2 − 𝑆1 = 𝑆𝑖𝑛 − 𝑆𝑜𝑢𝑡 + 𝑆𝑔𝑒𝑛 = 0 ⟹ − + 𝑆𝑔𝑒𝑛 = 0 ⟹ 𝑆𝑔𝑒𝑛 = 0.4048 kJ/kg
373 298
Similarly, we can apply exergy balance on the system
𝑆𝑜𝑢𝑡 298 298
𝑆𝑖𝑛 ∆𝑋𝑠𝑦𝑠 = 𝑋𝑖𝑛 − 𝑋𝑜𝑢𝑡 − 𝑋𝑑𝑒𝑠 = 0 ⟹ 600 1 − − 600(1 − ) − X des = 0 X des = 120.6434 kJ
373 298
28
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Decrease of exergy principle

Consider an isolated system. There is no energy and entropy transfer.

𝑉22 − 𝑉12
∆𝑋𝑖𝑠𝑜 = 𝑋2 − 𝑋1 = (𝑈2 − 𝑈1 ) + 𝑃0 𝒱2 − 𝒱1 − 𝑇0 (𝑆2 − 𝑆1 ) + 𝑚 + 𝑚𝑔(𝑧2 − 𝑧1 )
2
𝑋2 − 𝑋1 = 𝐸2 − 𝐸1 − 𝑇0 (𝑆2 − 𝑆1 )
• From 1st law we know ∆𝐸𝑖𝑠𝑜 = 𝐸2 − 𝐸1 = 0
• From 2nd law we have ∆𝑆𝑖𝑠𝑜 = 𝑆2 − 𝑆1 = 𝑆𝑔𝑒𝑛

𝑋2 − 𝑋1 = −𝑇0 𝑠𝑔𝑒𝑛 ≤ 0 ∆𝑋𝑖𝑠𝑜 = 𝑋2 − 𝑋1 𝑖𝑠𝑜 ≤0

• Decrease of exergy principle: the exergy of an isolated system during a

process always decreases or remains constant.

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Irreversibility / Exergy Destruction

• Exergy destroyed, or exergy destruction: In the example before, we get 𝑆𝑔𝑒𝑛 = 0.4048 kJ/K
and 𝑋des = 120.6434 kJ while the dead state
• 𝑿𝒅𝒆𝒔𝒕 = 𝑻𝟎 𝑺𝒈𝒆𝒏 = 𝒎𝑻𝟎 𝒔𝒈𝒆𝒏 temperature T0 = 298 K. Do these numbers comply
with the exergy destruction relation here?
• This is generically useful for all systems.
• 𝑋𝑑𝑒𝑠𝑡 > 0 for irreversible processes
• 𝑋𝑑𝑒𝑠𝑡 = 0 for reversible processes
• 𝑋𝑑𝑒𝑠𝑡 < 0 for impossible processes
• Apparently, irreversibility is equivalent to exergy destruction
• 𝐼 = 𝑊𝑟𝑒𝑣 − 𝑊𝑢 = 𝑋𝑑𝑒𝑠𝑡 = 𝑇0 𝑆𝑔𝑒𝑛
• For a work producing device (e.g. turbine), irreversibility is a lost opportunity to do work.
• For a work consuming device (e.g. refrigeration unit, compressor), irreversibility is
wasted work.
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Exergy balance in systems

Analogous to entropy 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡𝑟𝑜𝑝𝑦
= − +
balance of systems 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
We can have exergy balance in
systems
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑇𝑜𝑡𝑎𝑙 𝒆𝒙𝒆𝒓𝒈𝒚 𝑇𝑜𝑡𝑎𝑙𝒆𝒙𝒆𝒓𝒈𝒚 𝑻𝒐𝒕𝒂𝒍 𝒆𝒙𝒆𝒓𝒈𝒚
= − −
𝑬𝒙𝒆𝒓𝒈𝒚 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝒅𝒆𝒔𝒕𝒓𝒐𝒚𝒆𝒅

• General terms for for any system:

• Total form: ∆𝑋𝑠𝑦𝑠 = 𝑋2 − 𝑋1 = 𝑋𝑖𝑛 − 𝑋𝑜𝑢𝑡 − 𝑋𝑑𝑒𝑠𝑡
• Change in exergy
Net exergy Exergy
transfer destruction

• Rate form: 𝑑𝑋𝑠𝑦𝑠 Τ𝑑𝑡 = 𝑋ሶ 𝑖𝑛 − 𝑋ሶ 𝑜𝑢𝑡 − 𝑋ሶ 𝑑𝑒𝑠𝑡

• Unit-mass form: ∆𝑥𝑠𝑦𝑠 = 𝑥𝑖𝑛 − 𝑥𝑜𝑢𝑡 − 𝑥𝑑𝑒𝑠𝑡
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Exergy Balance for Closed Systems

For a closed system, no mass is transferred, and any useful work (i.e. excluding
work on the surroundings) is a direct exergy transfer.

∆𝑋𝑠𝑦𝑠 = 𝑋2 − 𝑋1 = 𝑋𝑏𝑦 ℎ𝑒𝑎𝑡 − 𝑋𝑏𝑦 𝑤𝑜𝑟𝑘 − 𝑋𝑑𝑒𝑠𝑡

Closed
system 𝑇0
∆𝑋𝑠𝑦𝑠 = 𝑋2 − 𝑋1 = ෍ 1 − 𝑄 − [𝑊 − 𝑃0 𝒱2 − 𝒱1 ] − 𝑇0 𝑆𝑔𝑒𝑛 (kJ)
𝑇
𝑑𝑋𝑠𝑦𝑠 𝑇0 𝑑𝒱𝑠𝑦𝑠
=෍ 1− ሶ ሶ
𝑄 − 𝑊 − 𝑃0 ሶ
− 𝑇0 𝑆𝑔𝑒𝑛 (kJ/s = kW)
𝑑𝑡 𝑇 𝑑𝑡

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Exergy Balance for Open Systems

For a open system, exergy transfers into or out of the system are caused by all three
mechanisms.
Open ∆(𝑋2 − 𝑋1 )𝐶𝑉 = 𝑋𝑏𝑦 ℎ𝑒𝑎𝑡 − 𝑋𝑏𝑦 𝑤𝑜𝑟𝑘 + 𝑿𝒎𝒂𝒔𝒔, 𝒊𝒏 − 𝑿𝒎𝒂𝒔𝒔, 𝒐𝒖𝒕 − 𝑋𝑑𝑒𝑠𝑡
system 𝑇0
∆(𝑋2 − 𝑋1 )𝐶𝑉 = ෍ 1 − 𝑄 − 𝑊 − 𝑃0 𝒱2 − 𝒱1 + 𝑚𝜓 𝑖𝑛 − (𝑚𝜓)𝑜𝑢𝑡 −𝑋𝑑𝑒𝑠𝑡 (kJ)
𝑇
𝑑𝑋𝐶𝑉 𝑇0 𝑑𝒱𝑠𝑦𝑠
=෍ 1− ሶ ሶ
𝑄 − 𝑊 − 𝑃0 + 𝑚𝜓
ሶ 𝑖𝑛 ሶ 𝑜𝑢𝑡 −𝑋ሶ 𝑑𝑒𝑠𝑡
− (𝑚𝜓) (kJ/s = kW)
𝑑𝑡 𝑇 𝑑𝑡

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Second-law efficiency
𝐸𝑥𝑒𝑟𝑔𝑦 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑒𝑑 𝐸𝑥𝑒𝑟𝑔𝑦 𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑
𝜂𝐼𝐼 = =1−
𝐸𝑥𝑒𝑟𝑔𝑦 𝑒𝑥𝑝𝑒𝑛𝑑𝑒𝑑 𝐸𝑥𝑒𝑟𝑔𝑦 𝑒𝑥𝑝𝑒𝑛𝑑𝑒𝑑

𝑊𝑎𝑐𝑡𝑢𝑎𝑙 ℎ1 − ℎ2 𝑇0 𝑆𝑔𝑒𝑛
Turbines 𝜂 𝑇,𝐼𝐼 = = 𝜂 𝑇,𝐼𝐼 =1−
𝑊𝑟𝑒𝑣 𝜓1 − 𝜓2 𝜓1 − 𝜓2
𝑊𝑟𝑒𝑣 𝜓2 − 𝜓1 𝑇0 𝑆𝑔𝑒𝑛
Compressors 𝜂𝐶,𝐼𝐼 = = 𝜂𝐶,𝐼𝐼 =1−
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 ℎ2 − ℎ1 ℎ2 − ℎ1

𝑚ሶ 𝑐𝑜𝑙𝑑 (𝜓4 − 𝜓3 )
Heat exchangers 𝜂𝐻𝑋,𝐼𝐼 =
𝑚ሶ ℎ𝑜𝑡 (𝜓1 − 𝜓2 )

Closed system expansion 𝑢2 − 𝑢1 𝜙2 − 𝜙1

𝜂𝐸,𝑐𝑙𝑜𝑠𝑒𝑑 = 𝜂𝐶,𝑐𝑙𝑜𝑠𝑒𝑑 =
and compression 𝜙2 − 𝜙1 𝑢2 − 𝑢1
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Example 3.4 – Steam Turbine Performance

1 kg/s of steam enters a turbine at 10 MPa and 400°C, and exits the turbine at 200°C and 100 kPa.
The turbine is currently generating 222 kW. What is its 2nd law efficiency, given T0 is 30°C?
Turbine is steady-flow device, so starting from the general rate form of exergy balance for CVs in a reversible manner:

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Example 3.5 – Heat exchanger

A heat exchanger used to generate high-pressure steam runs hot oil through tubes, generating
saturated steam in the shell at 5 bar pressure. Given that the input temperature of the oil is
180°C, the outlet temperature is 170°C, the heat capacity of oil is 2 kJ/kg/K, the flow-rate of
generated steam is 1 kg/s, and 20 kW of heat is lost from the steam to the surroundings (303 K),
what is the rate of exergy destruction in the heat exchanger?

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Example 3.5 – Heat exchanger

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Summary
We can define for any system flows of exergy, which is a combined thermodynamic measure which relates
to both 1st and 2nd laws of thermodynamics.
We can use exergy to evaluate the reversible work (i.e. maximum) that can be extracted from any system,
and thereby also assess performance of a defined system.

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Next Up
Refrigeration Cycles & Heat Pumps!

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