1 atm Exergy (Availability)

1 atm

2 atm 1 atm
What is the efficiency of such a non-cyclic process?

How to evaluate the performance of devices that execute non-cyclic processes or devices for which the work interaction is zero (e.g. Heat
exchanger)?
Carnot efficiency is applicable for engines that operate in a cycle.
Isentropic efficiencies are also of limited use because the exit state of the model (isentropic) process is not the same as the actual exit state
and it is limited to adiabatic processes (as we consider isentropic process as the ideal process to define isentropic efficiency).
Exergy of a system
A system is said to be in the dead state when it is in thermodynamic equilibrium with the
environment it is in.
At the dead state, a system is at the temperature and pressure of its environment (in thermal
and mechanical equilibrium); it has no kinetic or potential energy relative to the environment
(zero velocity and zero elevation above a reference level); and it does not react with the
environment (chemically inert). It is not possible to develop any work from a system that
exists at the dead state.
Unless specified otherwise, the dead-state temperature and pressure are taken to be 𝑇0 = 250C and 𝑃0 = 1 atm (101.325 kPa).
A system delivers the maximum possible work as it undergoes a reversible process from the specified initial state to the state
of its environment, that is, the dead state.
This represents the useful work potential of the system at the specified state and is called exergy.
Exergy represents the upper limit on the amount of work a device can deliver without violating any thermodynamic laws.
A system has zero exergy at the dead state.
The notion that a system must go to the dead state at the end of the process to maximize the work output can be explained as
follows: If the system temperature at the final state is greater than (or less than) the temperature of the environment it is in, we
can always produce additional work by running a heat engine between these two temperature levels. If the final pressure is
greater than (or less than) the pressure of the environment, we can still obtain work by letting the system expand to the
pressure of the environment. If the final velocity of the system is not zero, we can catch that extra kinetic energy by a turbine
and convert it to rotating shaft work, and so on. No work can be produced from a system that is initially at the dead state.

All these systems (+ environment)

can also develop positive work as
they attain the ambient state.
Note that exergy is an attribute of
systems and environment
together,.

Thus exergy of a closed system is either positive or zero. It is never negative. Even a medium at low temperature (𝑇 < 𝑇0 )
and/or low pressure (𝑃 < 𝑃0 ) contains exergy since a cold medium can serve as the heat sink to a heat engine that absorbs heat
from the environment at 𝑇0 , and an evacuated space makes it possible for the atmospheric pressure to move a piston and do
useful work.
 Exergy Change of a System
Consider a closed system at a specified state that undergoes a process to the state of the environment (that is, the final
temperature and pressure of the system should be 𝑇0 and 𝑃0 , respectively). The useful work delivered during this process
is the exergy of the system at its initial state.
Not magnitude. It has sign (can be positive or negative)

first law:
final initial dead state
state state
dead state

𝑃1 → 𝑃0
𝑇1 → 𝑇0

Useful
𝑄ሶ work
(lifting the
weight)
work done by or against the
surroundings during a process
(displacing the atmosphere)

Note that the work done by or against the atmospheric pressure has significance only for systems whose volume changes
during the process (i.e., systems that involve moving boundary work). It has no significance for cyclic devices and systems
whose boundaries remain fixed during a process such as rigid tanks and steady-flow devices (turbines, compressors,
nozzles, heat exchangers, etc.).
 second law: 𝑄𝑠𝑦𝑠
∆𝑆𝑠𝑦𝑠 = 𝑆𝑔𝑒𝑛 +
𝑇0 𝑇0 is not the sysytem boundary temperature.
To include the external reversibilities also we
take the surrounding temperature.

× 𝑇0 𝑄𝑠𝑦𝑠 = 𝑇0 ∆𝑆𝑠𝑦𝑠 − 𝑇0 𝑆𝑔𝑒𝑛

𝑄𝑠𝑦𝑠 = 𝑇0 𝑆0 − 𝑆1 − 𝑇0 𝑆𝑔𝑒𝑛

𝑆𝑔𝑒𝑛

𝑆𝑔𝑒𝑛
It is easy to see that, since 𝑆𝑔𝑒𝑛 is always greater than or equal to zero, 𝑊𝑢 is a maximum when 𝑆𝑔𝑒𝑛 = 0, i.e.,
when there are no internal or external irreversibilities and the process is fully reversible. Thus,
 𝑆𝑔𝑒𝑛

It can be seen that the irreversibilities – both internal and external, contribute to the lost work.

The exergy change of a closed system during a process is simply the difference between the final and initial
exergies of the system,

Note that exergy is a property (as it is a combination of other properties), and the value of a property does not change unless
the state changes.
This is a closed system since no mass crosses the system boundary during the process.

Air is an ideal gas. = 𝑐𝑉 𝑇1 − 𝑇0

The work potential of the system is 281 MJ, and thus a maximum of 281 MJ of useful work can be obtained from
the compressed air stored in the tank in the specified environment.
 Exergy of a Flow Stream: Flow (or Stream) Exergy
𝑊ሶ
CV
1 0
𝑄ሶ dead state
Steady-State

first law:

second law: 𝑄ሶ
0 = 𝑚ሶ 𝑠1 − 𝑠0 ሶ
+ + 𝑆𝑔𝑒𝑛
𝑇0

𝑇0 is not the CV boundary

× 𝑇0 0 = 𝑚ሶ 𝑇0 𝑠1 − 𝑇0 𝑠0 + 𝑄ሶ + 𝑇0 𝑆𝑔𝑒𝑛
ሶ 𝑄ሶ = 𝑚ሶ 𝑇0 𝑠0 − 𝑇0 𝑠1 − 𝑇0 𝑆𝑔𝑒𝑛
ሶ temperature. To include the
external reversibilities also
𝑉12 we take the surrounding
ሶ
𝑊ሶ = 𝑚ሶ 𝑇0 𝑠0 − 𝑇0 𝑠1 − 𝑇0 𝑆𝑔𝑒𝑛 + 𝑚ሶ ℎ1 + + 𝑔𝑧1 − ℎ0 temperature.
2
𝑉12
𝑊ሶ = 𝑚ሶ ℎ1 + ሶ
+ 𝑔𝑧1 − ℎ0 + 𝑇0 𝑠0 − 𝑇0 𝑠1 − 𝑇0 𝑆𝑔𝑒𝑛
2
𝑉12
𝑊ሶ = 𝑚ሶ ℎ1 − ℎ0 − 𝑇0 𝑠1 − 𝑠0 + ሶ
+ 𝑔𝑧1 − 𝑇0 𝑆𝑔𝑒𝑛
2
𝑉12
𝑊ሶ 𝑚𝑎𝑥 = 𝑊ሶ 𝑟𝑒𝑣 = 𝑚ሶ ℎ1 − ℎ0 − 𝑇0 𝑠1 − 𝑠0 + + 𝑔𝑧1
2
 Specific flow exergy:

Then the exergy change of a fluid stream as it undergoes a process from state 1 to state 2 becomes

The Decrease of Exergy Principle and Exergy Destruction

Recall increase of entropy principle, which can be regarded as one of the statements of the second law, and
indicated that entropy can be created but cannot be destroyed.
Now we are about to establish an alternative statement of the second law of thermodynamics, called the
decrease of exergy principle, which is the counterpart of the increase of entropy principle.
Consider an isolated system. By definition, no heat, work, or mass can cross the boundaries of an
isolated system, and thus there is no energy and entropy transfer.

first law: Total energy of an isolated system remains constant

Entropy change of this system: 𝑆𝑔𝑒𝑛 𝑆𝑔𝑒𝑛

× 𝑇0 𝑇0 𝑆2 − 𝑆1 = 𝑇0 𝑆𝑔𝑒𝑛
since 𝑉2 = 𝑉1 for an isolated system (it cannot
involve any moving boundary and thus any subtract 𝐸2 − 𝐸1 − 𝑇0 𝑆2 − 𝑆1 = −𝑇0 𝑆𝑔𝑒𝑛
boundary work) 𝑃 𝑉 −𝑉 =0
0 2 1 𝐸2 − 𝐸1 + 𝑃0 𝑉2 − 𝑉1 − 𝑇0 𝑆2 − 𝑆1 = −𝑇0 𝑆𝑔𝑒𝑛
 𝐸2 − 𝐸1 + 𝑃0 𝑉2 − 𝑉1 − 𝑇0 𝑆2 − 𝑆1 = −𝑇0 𝑆𝑔𝑒𝑛 𝑋2 − 𝑋1 = −𝑇0 𝑆𝑔𝑒𝑛 ≤ 0
positive
Then we conclude that

This equation can be expressed as the exergy of an isolated system during a process always decreases or, in the limiting case
of a reversible process, remains constant. In other words, it never increases and exergy is destroyed during an actual process.
This is known as the decrease of exergy principle. For an isolated system, the decrease in exergy equals exergy destroyed.
Exergy Destruction
Irreversibilities such as friction, mixing, chemical reactions, heat transfer through a finite
temperature difference, unrestrained expansion, nonquasiequilibrium compression or expansion
always generate entropy, and anything that generates entropy always destroys exergy. The
exergy destroyed is proportional to the entropy generated, and is expressed as

X destroyed = T0 Sgen  0

0 Irreversible process

=0 Reversible process
destroyed 
X
0 Impossible process

Exergy destroyed is a positive quantity for any actual process and becomes zero for a reversible The exergy change of a system
process. can be negative, but the exergy
Exergy destroyed represents the lost work potential and is also called the irreversibility or lost work. destruction cannot.
 Exergy Transfer by Heat, Work, and Mass
Exergy, like energy, can be transferred to or from a system in three forms:
heat, work, and mass flow. The only two forms of exergy interactions associated with a fixed mass or closed system are heat
transfer and work.
Exergy Transfer by Heat, Q
The work potential of the energy transferred from a heat source at temperature 𝑇 is the maximum work that
can be obtained from that energy in an environment at temperature 𝑇0 and is equivalent to the work produced
by a Carnot heat engine operating between the source and the environment.

Heat transfer Q at a location at thermodynamic temperature, T is always

accompanied by exergy transfer

When 𝑇 > 𝑇0 the exergy and heat transfer are in the same direction. That is, both the exergy
and energy content of the medium to which heat is transferred increase. When 𝑇 < 𝑇0 (cold
medium), however, the exergy and heat transfer are in opposite directions. That is, the energy
of the cold medium increases as a result of heat transfer, but its exergy decreases. exergy recovered from the engine must be equal to the
exergy supplied to the engine, since there is no
destruction of exergy as the engines are reversible
Exergy Transfer by Work, W
1 atm 1 atm

W − Wsurr ( for boundary work )

Exergy transfer by work: X work = 2 atm 1 atm
W ( for other forms of work )
𝑋≠0 𝑋=0
Wsurr = P0 (V2 − V1 )
Exergy transfer with work such as shaft work and electrical work is equal to the work W Change in exergy = Work done
itself. When a system does an amount of work, W, its exergy decreases by W. Conversely,
when an amount of work W is done on the system, its exergy increases by W.

Exergy Transfer by Mass

Therefore, the exergy of a system increases by 𝑚𝜓 when mass in the amount

of m enters, and decreases by the same amount when the same amount of
mass at the same state leaves the system.
 Exergy Balance: Control Volumes

It can also be expressed in the rate form as

rate of net exergy by mass flow exergy rate of exergy change

transfer through the by work destruction within the control
control volume volume during a
boundary by heat
process
Exergy Balance for Steady–Flow Systems
Most control volumes encountered in practice such as turbines, compressors, nozzles, diffusers, heat exchangers, pipes, and ducts operate steadily, and thus they
experience no changes in their mass, energy, entropy, and exergy contents as well as their volumes.
For steady-flow devices, dVCV / dt = 0 and dX CV / dt = 0

For a single-stream (one-inlet, one-exit) steady-flow device,

where the subscripts 1 and 2 represent inlet and exit states
Dividing by 𝑚ሶ gives the exergy balance on a unit-mass basis as

Reversible Work
The exergy balance relations presented above can be used to determine the reversible work Wrev by setting the exergy
destroyed equal to zero. The work W in that case becomes the reversible work.

The exergy destroyed is zero only for a reversible process, and reversible work represents the maximum work output for
work–producing devices such as turbines and the minimum work input for work–consuming devices such as
compressors.

For a control mass we do not have a flow of

mass in or out.

integrating in time from initial state 1 to final state 2 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑

 Second–Law Efficiency
The above equations can be used to define an efficiency for any device, irrespective of whether it
executes a cyclic or non-cyclic process or whether it is adiabatic or not or even when the work
interaction is zero (e.g. heat exchangers).

for a work producing process (turbines, piston–cylinder devices, etc.)

thermal
𝑚(ℎ
ሶ 1 − ℎ2 ) ℎ1 − ℎ2 efficiency
For an adiabatic turbine 𝜂𝐼𝐼,𝑇 = =
𝑚(𝜓
ሶ 1 − 𝜓2 ) 𝜓1 − 𝜓2 At first glance, both engines
changes in kinetic and potential seem to convert to work the
energies are negligible
same fraction of heat that they
receive; thus they are
for a work consuming process performing equally well (as
work-consuming noncyclic (such as compressors) and cyclic (such as
both have 𝜂𝐼 = 30%).
refrigerators) devices

𝜓2 − 𝜓1
For an adiabatic compressor 𝜂𝐼𝐼,𝐶 =
ℎ2 − ℎ1
𝑊 𝑊 𝑊/𝑄 𝜂𝑡ℎ 𝜂𝐼
𝜂 =
For a Heat Engine, 𝐼𝐼 𝑊 = = = =
𝑇 𝑇 𝜂𝑡ℎ,𝑟𝑒𝑣 𝜂𝑐𝑎𝑟𝑛𝑜𝑡
𝑟𝑒𝑣 𝑄 1− 𝐿 1− 𝐿
𝑇𝐻 𝑇𝐻
Now it is becoming apparent that engine B has a
The thermal efficiency and the coefficient of performance is defined on the basis of the first greater work potential available to it (70 percent
law only, and they are sometimes referred to as the first-law efficiencies. The first law of the heat supplied as compared to 50 percent
efficiency, however, makes no reference to the best possible performance, and thus it may for engine A), and thus should do a lot better
be misleading. than engine A.

Because of the way we defined the second-law efficiency, its

value cannot exceed 100 percent.
This is a closed system since no mass crosses the system boundary during the process.

exergy balance to the wall:

exergy destruction in the wall

To determine the rate of total exergy destruction during this heat transfer process, we extend the system to include the regions on both sides of the wall that
experience a temperature change.

The difference between the two exergy destructions is 41.2 W and represents the exergy destroyed in the air layers on both sides of the wall.
This is a closed system since no mass crosses the system boundary during the process.
 integrating in time from initial state 1 to final state 2 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑

The total exergy destroyed during this process can be determined from the exergy balance applied on the extended system (system + immediate surroundings)
whose boundary is at the environment temperature of 𝑇0 (so that there is no exergy transfer accompanying heat transfer to or from the environment as 𝑇𝑘 = 𝑇0 )

energy balance on the system:

The exergy destroyed could also be determined from

−𝑊𝑢,𝑟𝑒𝑣 + 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑 = 𝑋2 − 𝑋1

That is, 44.8 percent of the work potential of the steam is wasted during this process.
 This is a control volume since mass crosses the system boundary during the process.

energy balance

actual power output of

the turbine
 exergy balance applied on the extended system (system + immediate surroundings)
(steady)

𝑇𝑘 = 𝑇0 maximum power output

(reversible power)

That is, 15.1 percent of the work potential is wasted during this process.

exergy destroyed
not counting the kinetic and potential energies

Exergy (maximum work potential) of the steam at

the inlet conditions is simply the stream exergy:
For a device that does not involve the production or the input of work, the definition of second-law efficiency refers to the accomplishment
of the goal of the process relative to the process input in terms of availability changes or transfers. For example, in a heat exchanger,

𝑚ሶ ℎ 𝜓1 − 𝑚ሶ ℎ 𝜓2 + 𝑚ሶ 𝑐 𝜓3 − 𝑚ሶ 𝑐 𝜓4 − 𝑋ሶ 𝑑 = 0

𝑚ሶ ℎ 𝜓1 − 𝜓2 = 𝑚ሶ 𝑐 𝜓4 − 𝜓3 + 𝑋ሶ 𝑑

If no irreversibilites, 𝑋ሶ 𝑑 = 0 ⇒ 𝑚ሶ ℎ 𝜓1 − 𝜓2 = 𝑚ሶ 𝑐 𝜓4 − 𝜓3
 Continuity equation:

First law (a steady-state process):

Products—ideal gas, constant specific heat.

The increase in availability of the water is, per kilogram of water,

The decrease in availability of the products, per kilogram of water, is