Lecture-2

Thermodynamics-II (ME-
221)
Exergy (Definition)
Second Law Efficiency
Exergy of a Fixed Mass
Definition(Exergy)
• Whenever a new source of energy, such as geothermal well, is discovered, people
start estimating how much amount of energy can be taken from it. This
information alone is of little value, for deciding to build a power house on that
site. The main thing is the work potential of that source. The rest amount is
discarded as waste energy.
• Thus it is necessary to have such a property that enables us to determine the
work potential from a source of energy at a given state.
• This property is called Exergy or Availability or Available Energy.
• The work potential of energy in a system at a state is the maximum useful work of
the system
• Work done during a process depends on initial state, final state and process path:

Work = f (initial state, process path, final state)

• Maximum useful work can be obtained between two states when process is
reversible.
• Therefore, all irreversibilities are discarded in finding the work potential.
• System must be in dead state to maximize the work output.
• A system is said to be in dead state if it is in thermodynamic equilibrium with the
environment.
• 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).
• The properties of a system at the dead state are denoted by subscript zero, for
example, P°, T°, h°, u°, and s°
• Unless specified otherwise, the dead-state temperature and pressure are taken
to be T° = 25°C (77°F) and P° =1 atm (101.325 kPa or 14.7 psia).
• A system has zero exergy at the dead state
• Surroundings are everything outside the system boundaries.
• The immediate surroundings refer to the portion of the surroundings that is
affected by the process, and
• Environment refers to the region beyond the immediate surroundings whose
properties are not affected by the process at any point.
• When analyzing the cooling of a hot baked potato in a room at 25°C, for example,
the warm air that surrounds the potato is the immediate surroundings, and the
remaining part of the room air at 25°C is the environment. Note that the
temperature of the immediate surroundings changes from the temperature of
the potato at the boundary to the environment temperature of 25°C
• 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.
• It is important to realize that exergy does not represent the amount of work that
a work-producing device will actually deliver upon installation. Rather, it
represents the upper limit on the amount of work a device can deliver without
violating any thermodynamic laws.
• Note that the exergy of a system at a specified state depends on the conditions of
the environment (the dead state) as well as the properties of the system.
• Therefore, exergy is a property of the system–environment combination and not
of the system alone.
• Kinetic Energy KE= V²/2 Exergy of KE
• Potential Energy PE= gz Exergy of PE
• Reversible Work Wrev= Wu, max Exergy (Useful Work)
• Irreversibility I= Wrev – Wu Exergy Destruction
Second Law Efficiency, ȠII
• The fraction of the heat input that is converted to net work output is a measure
of the performance of a heat engine and is called the thermal efficiency Ƞth
Thermal Efficiency = Net Work output/ Total heat input
• The efficiency of a refrigerator is expressed in terms of the coefficient of
performance (COP), denoted by COPR
COPR = Desired Output/Required Input
• They are defined on the basis of the first law only, and they are sometimes
referred to as the first-law efficiencies. The first law efficiency, however, makes no
reference to the best possible performance, and thus it may be misleading.
• Consider two heat engines, both having a thermal efficiency of 30 percent, as
shown in Fig. One of the engines (engine A) is supplied with heat from a source at
600 K, and the other one (engine B) from a source at 1000 K. Both engines reject
heat to a medium at 300 K. At first glance, both engines seem to convert to work
the same fraction of heat that they receive; thus they are performing equally
well. When we take a second look at these engines in light of the second law of
thermodynamics, however, we see a totally different picture. These engines, at
best, can perform as reversible engines, in which case their efficiencies would be
• Now it is becoming apparent that engine B has a greater work potential available
to it (70 percent of the heat supplied as compared to 50 percent for engine A),
and thus should do a lot better than engine A. Therefore, we can say that engine
B is performing poorly relative to engine A even though both have the same
thermal efficiency. It is obvious from this example that the first-law efficiency
alone is not a realistic measure of performance of engineering devices.

• To overcome this deficiency, we define a second-law efficiency ȠII as the ratio of

the actual thermal efficiency to the maximum possible (reversible) thermal
efficiency under the same conditions
• Second-law efficiency is a measure of the performance of a device relative to its
performance under reversible conditions.
• Based on this definition, the second-law efficiencies of the two heat engines
discussed above are

• That is, engine A is converting 60 percent of the available work potential to useful
work. This ratio is only 43 percent for engine B.

• The second-law efficiency can also be expressed as the ratio of the useful work
output and the maximum possible (reversible) work output:
• This definition is more general since it can be applied to processes (in turbines,
piston–cylinder devices, etc.) as well as to cycles.

• Note that the second law efficiency cannot exceed 100 percent
• Second-law efficiency of all reversible devices is 100 percent.
• We can also define a second-law efficiency for work-consuming noncyclic (such as
compressors) and cyclic (such as refrigerators) devices as the ratio of the
minimum (reversible) work input to the useful work input:

• For cyclic devices such as refrigerators and heat pumps, it can also be expressed
in terms of the coefficients of performance as
• The second-law efficiency is intended to serve as a measure of approximation to
reversible operation, and thus its value should range from zero in the worst case
(complete destruction of exergy) to one in the best case (no destruction of
exergy). With this in mind, we define the second-law efficiency of a system during
a process as

• Therefore, when determining the second-law efficiency, the first thing we need to
do is determine how much exergy or work potential is consumed during a
process. In a reversible operation, we should be able to recover entirely the
exergy supplied during the process, and the irreversibility in this case should be
zero. The second-law efficiency is zero when we recover none of the exergy
supplied to the system. Note that the exergy can be supplied or recovered at
various amounts in various forms such as heat, work, kinetic energy, potential
energy, internal energy, and enthalpy.
• For a heat engine, the exergy supplied is the decrease in the exergy of the heat
transferred to the engine, which is the difference between the exergy of the heat
supplied and the exergy of the heat rejected. (The exergy of the heat rejected at
the temperature of the surroundings is zero.) The net work output is the
recovered exergy.

• For a refrigerator or heat pump, the exergy supplied is the work input since the
work supplied to a cyclic device is entirely available. The recovered exergy is the
exergy of the heat transferred to the high-temperature medium (which is the
reversible work) for a heat pump, and the exergy of the heat transferred from the
low-temperature medium for a refrigerator.

• For a heat exchanger with two unmixed fluid streams, normally the exergy
supplied is the decrease in the exergy of the higher temperature fluid stream, and
the exergy recovered is the increase in the exergy of the lower temperature fluid
stream.
Exergy of a Fixed Mass (Closed System
Exergy)
• Internal energy consists of sensible, latent, chemical, and nuclear energies.
• However, in the absence of any chemical or nuclear reactions, the chemical and
nuclear energies can be disregarded and the internal energy can be considered to
consist of only sensible and latent energies that can be transferred to or from a
system as heat whenever there is a temperature difference across the system
boundary.
• The second law of thermodynamics states that heat cannot be converted to work
entirely, and thus the work potential of internal energy must be less than the
internal energy itself.
• But how much less?
• To answer that question, we need to consider a stationary closed system at a
specified state that undergoes a reversible process to the state of the
environment (that is, the final temperature and pressure of the system should be
T° and P°, respectively). The useful work delivered during this process is the exergy
of the system at its initial state as shown in Fig:
• Consider a piston–cylinder device that contains a fluid of mass m at temperature
T and pressure P. The system (the mass inside the cylinder) has a volume V,
internal energy U, and entropy S. The system is now allowed to undergo a
differential change of state during which the volume changes by a differential
amount dV and heat is transferred in the differential amount of dQ. Taking the
direction of heat and work transfers to be from the system (heat and work
outputs), the energy balance for the system during this differential process can be
expressed as

• Heat by the sytem = -ve

• Work by the system= +ve
• since the only form of energy the system contains is internal energy, and the only
forms of energy transfer a fixed mass can involve are heat and work.
• Also, the only form of work a simple compressible system can involve during a
reversible process is the boundary work, which is given to be dW = P dV
• when the direction of work is taken to be from the system (otherwise it would be
-P dV). The pressure P in the P dV expression is the absolute pressure, which is
measured from absolute zero. Any useful work delivered by a piston–cylinder
device is due to the pressure above the atmospheric level.

• A reversible process cannot involve any heat transfer through a finite temperature
difference, and thus any heat transfer between the system at temperature T and
its surroundings at T° must occur through a reversible heat engine
• Noting that dS = dQ/T for a reversible process, and the thermal efficiency of a
reversible heat engine operating between the temperatures of T and T° is Ƞth = 1-
T° /T the differential work produced by the engine as a result of this heat transfer
is

• Substituting the dW and dQ expressions in above Eqs. into the energy balance
relation, gives after rearranging
• Where Wtotal useful is the total useful work delivered as the system undergoes a reversible
process from the given state to the dead state, which is exergy by definition.
• A closed system, in general, may possess kinetic and potential energies, and the total
energy of a closed system is equal to the sum of its internal, kinetic, and potential
energies. Noting that kinetic and potential energies themselves are forms of exergy, the
exergy of a closed system of mass m is
where V is the volume of the system and r is density.
• Note that exergy is a property, and the value of a property does not change unless the
state changes. Therefore, the exergy change of a system is zero if the state of the
system or the environment does not change during the process. For example, the
exergy change of steady flow devices such as nozzles, compressors, turbines, pumps,
and heat exchangers in a given environment is zero during steady operation.
• The exergy of a closed system is either positive or zero. It is never negative.
• Even a medium at low temperature (T< T°) and/or low pressure (P<P°) contains
exergy since a cold medium can serve as the heat sink to a heat engine that
absorbs heat from the environment at T°, and an evacuated space makes it
possible for the atmospheric pressure to move a piston and do useful work (Fig)