BITS Pilani

Hyderabad Campus

Chapter 8: Exergy
Prof. Vikranth Kumar Surasani

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Objectives

 Understanding the limitations of the First law of

thermodynamics
 Under standing the usefulness of the second law and
combined statement of second law
 Be able to specify a system and its surroundings for
second law analysis, and combined statement of the first and
second laws for the determination of lost of work or energy.
 Determination of second law efficiency and pinpoint major
areas of efficiency
 Understand the cause of work and how to remedy them

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 Common Industrial Operations

Operation Examples of Equipment Used

Change in chemical species Reactor
Separation of chemicals Distillation, absorption, liquid-
liquid extraction
Separation of phases Settler
Pressure change Pump, compressor, valve,
turbine, expander
Temperature or phase change Heat exchanger, condenser
Mixing Agitated vessel, in-line mixer
Dividing Pipe tee
Size enlargement of solids Pellet mill
Size reduction of solids Jaw crusher
Separation of solids by size Screen

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Introduction

 Chemical process uses physical/chemical operations to

transform feed materials into products of different composition
 The process is conducted batchwise, continuously, or cyclically.
 Example; benzene and mixture of xylene isomers are produced
by disproposination of toluene.
 Fixed bed catalytic reactor is main heart of the process
2C7H8  C6H6+C8H10 isomers (carried in the presence of H2 )
2C7H8+ H2 C6H6+CH4 (Undesirable side reaction)
 For this continuous production, heat integration diagram is
shown in next slide.

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E- exchangers; B- power plant; C- fractionator;
K- compressor; P-pumps; F- furnaces; T- Cooling tower

D- Decanter; R- Reactor;

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Overall Process streams for toluene disproportionation

Ideally, each operation in a process should conduct irreversibly to

minimize energy input or maximum energy output for 100%
thermodynamic efficiency
Second law analysis identifies the inefficient processes and operations
with in the process which are wasteful of energy.

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The system and the surroundings

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The system and the surroundings

Partitioning of the toluene

disproportionation plant
 Division of the process into
system and surrounding is the
choice of how the thermodynamic
analysis is conducting. e. g. heat
integration diagram shown itself
is the system, surroundings are
ambient air and storage tanks

 Commonly utility plants

considered from the rest of the
process. This is shown in the side
figure, where Benzene-mixed
xylene plant, stream power plants
and cooling towers are considered
as 3 systems

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The system and the surroundings
Partitioning of the toluene disproportionation plant
 Benzene-xylene plant itself a complex system and advisable to
divide it into reaction section and separation section.

 Any individual process, and a part of the individual process can be

considered as system

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Energy Transfer

 Heat or Work, or both, can be transferred across the

boundaries of closed or open systems
 Most useful kind of energy transfer is work
 Less useful, more common is heat transfer (between system and
surrounding)
 Number of devices are used to transfer work between system
and surroundings (pumps, compressors, fans convert shaft to
kinetic energy)
 Turbine and expanders take energy from fluid to shaft work.

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Energy Transfer

Example:
Electrical input to the motor to pump water flow 10 kg/s at specific volume
0.001 m3/kg from pressure P1 0.1 Mpa to P2 2.0 Mpa.
How much electricity it required ideally?
W =10 * 0.001* (2-0.1)*106
=19 KN-m/s(KW)

irreversible
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Energy Transfer

Example:
In actual equipment, electrical resistance may permit only 95 %, and
shaft friction may permit 90% transfer of shaft work, and fluid
friction may cause the rise of temperature equivalent to 5 % loss of
shaft of the shaft work; then eletrical input required
= 19/(0.95*0.9*0.95)= 23.39 kW
Energy loss = 4.39kW

irreversible

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Thermodynamic Properties

 Work or Heat is transferred to or from a system, and most common

forms of energy are associated with,
1) Macroscopic motion (Kinetic energy)
2) Gravitational field (potential energy)
3) Internal energy(translational, rotational, vibrational motion of
molecules)
 First two are relative to some arbitrary reference, and in most of
chemical processes, changes due to these forms are ignored.
Exceptions are combustion chambers and nozzle of rocket
 Internal energy (U) is most important in chemical processing, and is
relative to some arbitrary reference condition.
1) State property
2) Value depends on condition of substance (T, P and composition
as well as phase)
3) Change in internal energy is independent of path

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Thermodynamic Properties

 Other closely related to inernal energy is enthalpy (H)

1) Defined by H =U+PV
2) This property is convenient for continuous process
3) The most desirable ref. for U and H for chemical
processes are 0 K or 25 oC, zero pressure and
standard chemical elements such as C, H2, O2, N2,
Cl2 ans S.
4) With these references U and H are automatically take into
the account of Heat of reaction
 Energy transfer from work is more useful than that of from heat.
 If the temperature of the system is decreases, heat transfer of
the system is less useful and less heat can be transfer to work.
 The state property the differentiate between heat and work is
entropy (S).

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Thermodynamic Properties


Q
ΔS reservoir  
Treservoir

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Thermodynamic Properties

Ideal gas at Cont. Temperature

Ideal Gas Mixing

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Thermodynamic Availability

 When matter is taken from state 1, at a given velocity, elevation,

composition, temperature T, and pressure P, to state 2, at a different
velocity, elevation, composition, T, and P, it is of interest to determine
the maximum amount of useful work that can be extracted or the
minimum amount of work that is needed.
first law of thermodynamics can be used to determine the net amount
of energy transferred by heat and/or work in moving from state 1 to
state 2, which is simply the change in enthalpy.
 The first law cannot be used to determine the maximum or minimum
amount of useful work, which depends on the details of the process
used to effect the change in state. The maximum or minimum is
achieved only if the process is reversible.
To determine the maximum rate at which work is performed, max W,
in bringing a stream to equilibrium with its surroundings, a reversible
path can be selected, as illustrated in Figure

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Thermodynamic Availability

 A stream at molar flow rate, m , in state 1, at T1 and elevated

pressure, P1, is fed to turbine I, which operates adiabatically and
reversibly. It is expanded to P2 and the environmental temperature, T0,
while producing shaft work at the rate, WsI. The effluent stream from
turbine I is expanded isothermally (non-adiabatically) and reversibly in
turbine II to the environmental pressure, P0.

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Thermodynamic Availability

 Ignoring Kinetic and potential energy, from 1st law

 from Turbine II
 substituting in 1st law and rearranging

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Thermodynamic Availability

 This reversible work is the maximum work “available” in bringing the

feed stream to the environmental conditions; that is, Ws is the
maximum rate of obtaining work, which can be written mA1→0. The
intensive property, A1→0 , was initially referred to as the
thermodynamic availability and is commonly referred to as the exergy.
The concept of availability was first developed in detail by Keenan
(1951).

 The above equation state that the change in availability of a stream,

when it is converted from state 1 to state 2 in a thermodynamic
process

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Examples of Thermodynamic Availability

Superheating steam

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Examples of Thermodynamic Availability

Liquefying Air

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Examples of Thermodynamic Availability

Isothermal mixing

304. 3 cal/mol of min. work required to separate N2 and O2 from Air mixture

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Examples of Thermodynamic Availability

Thermal mixing

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Examples of Thermodynamic Availability

Thermal mixing

Availability flow diagram for thermal mixing of water

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Equations for Second Law Analysis

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Equations for Second Law Analysis

Energy balance for such system over discrete time Δt

Entropy balance

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Equations for Second Law Analysis

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Equations for Second Law Analysis

And is called availability function, and T0ΔSirr

defined as Lost work . And the above equation
can be written as

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BITS F111, Thermodynamics, BITS, Pilani-Hyderabad Campus P-30
Equations for Second Law Analysis

The availability (A) is referenced to a dead state at T0, P0,

therefore, an absolute quantity. It represents the
maximum amount of work that can be extracted from the
change of state.

The availability function (B), by contrast, can be

referenced to any state and is not an absolute quantity.
however, only the change in availability function appears.
By their definitions, the change in availability function is
exactly equal to the change in availability. The availability
function is used in the second law analysis.

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Equations for Second Law Analysis

For a reversible process, Sirr and, therefore, T0 Sirr and

LW are zero. For an irreversible process, Sirr and LW are
positive. The lost work represents the energy flow
(power) lost because of irreversibilities in the process.
Consider a continuous, steady-state, adiabatic process,
Wi  LW  (m B) | flowstreams
for the decrease in the availability of the streams
 (m B )  0   W  LW  0
i
It means that either work done by the system or lost of work
are positive, or both can be positive. If lost of work LWdot is
greater than decrease in availability, i.e. LW > Δ(mdotB), work
need to be done on the system, i.e. ∑Widot < 0

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Equations for Second Law Analysis

for a reversible process LW

 
 Wi    (m B) | flowstreams if (m B ) is  (ve)
  max
If the process increases the availability function for the
flowing streams, then
for the increase in the availability of the streams
 (m B )  0   W  LW  0
i

That increase will require work to be done by the

surroundings on the process ∑Widot < 0 and for reversible
process  
 Wi   (m B) | flowstreams if (m B ) is  (ve)
  min

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Equations for Second Law Analysis

For a continuous, steady-state process

Energy Balance

Availability Balance

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Equations for Second Law Analysis

Comparison of Energy and Availability balance

1). The left-hand side Eq. is zero. That is, energy is

conserved.
The Right-hand side Eq. is zero only for a reversible
process. Otherwise, is positive and availability is not
conserved.
In an irreversible process, some availability is lost.

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Equations for Second Law Analysis

Comparison of Energy and availability balance

2). In the energy balance, work and heat are counted the same. In the
availability balance, work and heat are not counted the same.
All work input increases the availability of material flowing through the
process. Only a portion of heat transferred into a system is available to
increase the availability of flowing streams.
The heat is degraded by a coefficient equal to 1− (T0 /T ) . This
coefficient is precisely the Carnot cycle efficiency for a heat engine that
takes heat from a source at temperature, T, and converts a portion of it
to useful work, discharging the balance to a sink at a lower
temperature,T0.

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Equations for Second Law Analysis

Comparison of Energy and availability balance

3). The energy balance, which is valid whether the process is reversible
or not, has no terms that take into account irreversibility. Thus, the
energy balance cannot be used to compute the minimum or maximum
energy requirements when taking material from inlet to outlet states.
The availability balance does have a term, LWdot, a measure of
irreversibility. When the lost work is zero, the process is reversible and
Eq. can be used to determine the maximum or minimum energy
requirements to cause a change in availability.

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Causes of Lost work

1. Mixing of two or more streams or batches of material that

differ in temperature, pressure, and/or composition.
2. Finite driving forces for transport processes.
3. Fluid friction and drag.
4. Chemical reactions occurring far from equilibrium.
5. Transferring heat to cooling water, especially when that
heat is available at an elevated temperature.
6. Mechanical friction in machinery such as pumps,
compressors, and turbines.

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