ME 5129 - Principles of Thermal Energy Conversion

Lecture - XXIII

Exergy (second law) analysis of plant cycles

Prof. Sarit Kumar Das

Institute Professor
Heat Transfer &Thermal Power Lab.
Department of Mechanical Engineering
Indian Institute Of Technology Madras

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[email protected]
 Second Law Analysis
 The first law of thermodynamics deals with quantity of energy and asserts that energy cannot be
created or destroyed. This law merely serves as a necessary tool for bookkeeping of energy during a
process.

 The second law, however, deals with the quality of energy. More specially it is concerned with the
degradation of energy during the process, the entropy generation, the lost opportunity to do work.

Availability (Exergy)
 Maximum Work Potential
 A system will deliver maximum possible work as it undergoes
reversible process from the specified initial state to state of its
environment (dead state).
 This represents the useful work potential of the system at the
specified state and is called availability.
 Second Law Analysis
Reversible Work (Wrev) :
 The maximum amount of useful work that can be obtained as a system undergoes a process
between the specified initial and final states.

Irreversibility (I):
 Any difference between the reversible work (Wrev) and the useful work (Wu) is due to the
irreversibilities present during the process.
 Irreversibility rate, 𝐼 = 𝑊𝑟𝑒𝑣 - 𝑊𝑢
Source Source
600K 1000K
Second Law Efficiency (Effectiveness):
 The ratio of actual thermal efficiency to maximum possible
(Reversible) thermal efficiency under the same conditions. A B
30%
 The second law efficiency for heat engines is given as, 30%

th
 II  Sink
threv 300K
 Maximum available work- EXERGY
 Consider heat engine operating between hot source at temperature 𝑻 𝑯
and cold sink at temperature 𝑻𝑳
𝑄 𝐻 = 𝐴.𝐸 +𝑈. 𝐸
𝑊 𝑚𝑎 𝑥 = 𝐴. 𝐸 = 𝑄 𝐻 − 𝑈.𝐸

 As we know maximum attainable efficiency for reversible cycle is,

𝑇𝐻
η𝑟𝑒𝑣 = 1 −
𝑇𝐿
𝑇𝐻
𝑊𝑚𝑎𝑥 = 1 − 𝑄𝐻
𝑇𝐿

1st Law efficiency 2nd Law efficiency

𝑊𝑎𝑐𝑡𝑢𝑎𝑙 𝑊
η𝐼𝐼 = = 𝑎𝑐𝑡𝑢𝑎𝑙
η𝐼 =
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 EXERGY 𝐸𝑥𝑒𝑟𝑔𝑦 (𝑊𝑚𝑥 ) 𝑇
1− 𝑇𝐻 𝑄𝐻
𝐿
𝑄𝐻 𝜼𝑰
𝜼𝑰𝑰 = 𝑻
𝟏− 𝑻𝑯
𝑳
 Introduction : Exergy
 The exergy is the maximum work obtainable as the system comes to
equilibrium with the surroundings.
 The higher the value of exergy, more is the work obtainable from the
system.

 First law of thermodynamics makes only an energy balance of a system or a control volume. It does not
make any distinction of different forms of energy, particularly between work and heat, or heat (internal
energy) available at different temperatures.
 It is the second law which asserts that from engineering viewpoint, all forms of energy are not of the
same quality. Energies of two systems may be quantitatively equal, but qualitatively they may be
different.
-ex., When steam is adiabatically throttles, its energy does not change, but its quality degrades.
 Exergy is a measure of energy quality and exergetic efficiency is a measure of the perfectness of thermal
system.
 While energy of a system in any process remains constant, a part of its exergy is always destroyed.
 Efficiency
 II law efficiency : Evaluates the overall utilization of fuels or energy forms.
 Second law efficiencies will be expressed in terms of a quantity known as available work.
 The quality of an energy form, called available work or availability.
 e.g. Heat capacity of sea surface water and Oil; steam at high pr. &high temp.
 II law efficiency : The available energy/work of a system can be given by:
B  E  POV  TO S  𝑖  ioni
𝑛

 Where, E = internal energy (including PE, KE, etc.); V= volume, S = entropy, io = chemical potential per
mole of ith component, Po & To – Pr.& Temp. of ambient, ni = No. of moles of ith component.
 Available energy is also known by many other names such as:
 Availability, Exergy, Essergy, Free energy  Gibbs, Helmholtz
 II law efficiency of a Carnot engine: Available energy and unavailable energy
𝑊 𝑇2
 I law efficiency is given as: η1 = =1-
𝑄𝑠 𝑇1

𝑊 The change in available energy of a system

 Second law efficiency is expressed as: η2 = =
𝐵 The change in the available energy in the source
Connections among Essergy, Availability, Exergy and Free Energy
Name Function Comments
Essergy E  P0V  T0S   i0 Ni This function was formulated for the special case
i
of an existing medium in (by Gibbs) and in
general in 1962. Its name was changed from
“available energy” to “exergy” in 1963, and from
“exergy” to “essergy” (i.e., “essence of energy”) in
1968 by Evans
Availability E+P0V-T0S- (E0+P0V0-T0S0) Formulated by Keenan in 1941, this function is a
special case of the essergy function
Exergy E+PV-TOS-(E0+P0V0-T0S0) Introduced by Darrieus(1930) and Keenan
(1932), this function (which Keenan called
“availability in steady flow”) was given the name
“exergy” by Rant in 1956. This function is a
special case of essergy.

Free energy Helmholtz: E-TS The function E-TS and E+PV-TS were introduced
by von Helmholtz and Gibbs (1873).These two
Gibbs: E+PV-TS
functions are Legendre transforms of energy that
was shown by Gibbs to yield useful alternate
criteria of equilibrium. As measure of the
potential work of systems, these two functions
represent special cases of the essergy function.
 Flow Exergy
 The available work or exergy (Ew) delivered by the flow system is equal to the net flow of
exergy into the system (via heat transfer and fluid flow) minus the exergy destroyed
through thermodynamic irreversibility. h2,s2

 To explain flow exergy, we need to understand new property called as flow availability
B; 𝐵 = 𝐻 − 𝑇0𝑆
 Flow exergy Ex , 𝐸𝑥 = B−𝐵0 =𝐻 −𝐻0 −𝑇0(S− 𝑆0)
 Exergy calculations change when the environmental conditions change with time or with
altitude. h1,s1
 Maximum available work from flow stream:
𝑊𝑚𝑎𝑥 = 𝑖𝑛 𝑚 𝑒𝑥 − 𝑜𝑢𝑡 𝑚 𝑒𝑥
𝑊𝑚𝑎𝑥 = 𝑚 ℎ2 − ℎ0 − 𝑇0 (𝑆2 − 𝑆0 ) − 𝑚 ℎ1 − ℎ0 − 𝑇0 (𝑆1 − 𝑆0 )
𝑊𝑚𝑎𝑥 = 𝑚 ℎ2 − 𝑇0 𝑆2 − 𝑚 ℎ1 − 𝑇0 𝑆1
 Where 𝑒𝑥is flow exergy(Ex ) per unit mass.
 Energy to exergy
(Combining 1st and 2nd law of thermodynamics)
 1st law of thermodynamics: Energy balance
𝑑𝐸
 = 𝑖𝑄 −𝑊+ 𝑖𝑛 𝑚 ℎ − 𝑜𝑢𝑡 𝑚 ℎ
𝑑𝑡

 2nd law of thermodynamics: Entropy balance:

𝑑𝑆 𝑄𝑖
 𝑆𝑔𝑒𝑛 = − 𝑖𝑇 −𝑊+ 𝑖𝑛 𝑚 𝑠 − 𝑜𝑢𝑡 𝑚 𝑠≥0
𝑑𝑡 𝑖

 Exergy of the system(𝑊 ) :

𝑑 𝑇0
𝑊=− 𝐸 − 𝑇0 𝑆1 + 𝑖 𝑄𝑖 1 − + 𝑖𝑛 𝑚 (ℎ − 𝑇0 𝑆 ) − 𝑜𝑢𝑡 𝑚(ℎ − 𝑇0 𝑆 ) − 𝑇0 𝑆 𝑔𝑒𝑛
𝑑𝑡 𝑇𝑖

 The exergy of an energy form or a substance or a system is a measure of its usefulness work
potential.
 Exergy for steady flow process becomes:
𝑻𝟎
𝑾= 𝒊 𝑸𝒊 𝟏 − + 𝒊𝒏 𝒎 𝒆𝒙 − 𝒐𝒖𝒕 𝒆𝒙 − 𝑻𝟎 𝑺 𝒈𝒆𝒏
𝑻𝒊
 Significance of Exergy
𝑑 𝑇0
𝑊=− 𝐸 − 𝑇0 𝑆1 + 𝑖 𝑄𝑖 1 − + 𝑖𝑛 𝑚 (ℎ − 𝑇0 𝑆 ) − 𝑜𝑢𝑡 𝑚(ℎ − 𝑇0 𝑆 ) − 𝑇0 𝑆 𝑔𝑒𝑛
𝑑𝑡 𝑇𝑖

Maximum Lost available

available work work(Always positive)

 Therefore, 𝑊 = 𝑊 𝑟𝑒𝑣 − 𝑇0 𝑆𝑔𝑒𝑛 Whenever a system operates irreversibly, it destroys work

at a rate that is proportional to the system’s rate of
 Where Exergy loss, I = 𝑇0 𝑆𝑔𝑒𝑛 entropy generation.

 Energy is always conserved. What is not conserved is the exergy ie the useful work potential of
the energy. Once the exergy is wasted, it can never be recovered.
 Improved energy resource utilization can be realized by reducing exergy destruction within a
system and/or reducing loses.
 An objective in exergy analysis is to identify sites where exergy destructions and losses occur and
rank order them for significance.
 This allows attention to be centered on aspects of system operation that offer the greatest
opportunity for cost-effective improvements.
 Simple Rankine cycle for power plant
 The exergy analysis of each steady-flow component of the power cycle allows us
to determine the distribution of the irreversibility among the cycle components
 Rankine cycle consisting of four steady flow components- pump, heater, turbine
and condenser-operates between temperature TH and T0
 The energy interactions experienced by the components are indicated by
arrows that point in the correct physical direction;
- 𝑊 𝑝, 𝑄 𝐻, 𝑊 𝑡, and 𝑄 0 represent positive numerical values
Exergy analysis: Combustion
Rankine cycle
 For a chemically reactive system,
 The standard Gibbs function change (kJ/k mol) = -∆g0 = ε0, Fuel Ф

 The change in the enthalpy of formation(kJ/k mol) = ∆h = -(NCV)0 Coke 1.05

Coal 1.06-1.10
− ∆G0
and, ∆H0 = −
Wood 1.15-1.30
∅= 𝑚f × 𝑁𝐶𝑉 0 (𝑘𝑊)
− ∆H0 Fuel oils and petrol 1.04-1.08

Where 𝑚 𝑓 is the fuel burning rate (kg/s). Therefore, ∆G0 can be estimated. Now, Natural gas 1.04 ± 0.5%

Coal gas 1.00 ± 1%

∆G0 = ∆H0 – T0 ∆S0, T0 ∆S0 = rate of exergy loss in combustion or reaction Blast furnace gas 0.98 ± 1%

∆G0 = - 𝑚f ×(NCV)0 + ∅[𝑚 𝑓x (NCV)0] = 𝑚f × (NCV)0 (∅-1) Hydrogen 0.985

Carbon monoxide 0.973

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