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AVAILABILITY AND IRREVERSIBILITY

There are many forma in which energy can exist. But even under ideal
conditions all these forms cant be converted into work. This indicates that energy
has 2 parts namely available and unavailable part.
Available energy is the maximum portion of energy, which could be converted
into useful work by ideal process, which reduce the system to a dead state (A
state in equilibrium with the earth and its atmosphere).
As the science of thermodynamics developed beyond its industrial roots,
two powerful ideas came to the fore - equilibrium and irreversibility. These
ideas were already implicit in studies of heat. You have already seen that heat
flow from a hot steak to a cold plate is an irreversible process. The effect of this
process is to cool down the hot steak and warm up the cold plate, leading to a
more uniform distribution of temperature. The heat transfer continues until a state
of equilibrium is reached, characterized by a completely uniform temperature.
Understanding the conditions needed for equilibrium, and the irreversible
processes that drive systems towards equilibrium, has deep consequences
throughout the sciences. For example, under normal conditions, the equilibrium
state of carbon is graphite, rather than diamond. Fortunately, the processes that
restore equilibrium are very slow in this case, so diamonds do not perceptibly
turn into graphite. But, under some rather extreme conditions, diamond is the
equilibrium state rather than graphite, and this fact can be used to create new
diamonds from soot. More generally, thermodynamics determines which states of
matter are in equilibrium under any given set of conditions.
Entropy and the second law of thermodynamics provide the key to
understanding equilibrium. An isolated system, free from all other influences,
may undergo various spontaneous changes, some of which will increase its
entropy. If the total entropy increases during a process, as it usually does, the
process is irreversible - it is impossible to return to the starting point, leaving no
other traces, since that would require a decrease in the total entropy, which is
impossible. Once the entropy has increased, it cannot decrease again. An
isolated system therefore approaches a state in which the entropy has the
highest possible value. This is a state of equilibrium. In equilibrium, the entropy of
the system cannot increase (because it is already at a maximum) and it cannot
decrease (because that would violate the second law of thermodynamics). The
only changes allowed are those in which the entropy remains constant.
Reversibility and irreversibility
Previously, we mentioned that on a microscopic level the laws of physics
are invariant under time reversal. In other words, microscopic phenomena look
physically plausible when run in reverse. We usually say that these phenomena
are reversible. What about macroscopic phenomena? Are they reversible? Well,
consider an isolated many particle system which starts off far from equilibrium.
According to the theorem, it will evolve towards equilibrium and, as it does so,
the macroscopic quantity will decrease. But, if we run this process backwards
the system will appear to evolve away from equilibrium, and the quantity will
increase. This type of behavior is not physical because it violates the theorem.
So, if we saw a film of a macroscopic process we could very easily tell if it was
being run backwards. For instance, suppose that by some miracle we were able
to move all of the Oxygen molecules in the air in some classroom to one side of
the room, and all of the Nitrogen molecules to the opposite side. We would not
expect this state to persist for very long. Pretty soon the Oxygen and Nitrogen
molecules would start to intermingle, and this process would continue until they
were thoroughly mixed together throughout the room. This, of course, is the
equilibrium state for air. In reverse, this process looks crazy! We would start off
from perfectly normal air, and suddenly, for no good reason, the Oxygen and
Nitrogen molecules would appear to separate and move to opposite sides of the
room. This scenario is not impossible, but, from everything we know about the
world around us, it is spectacularly unlikely! We conclude, therefore, that
macroscopic phenomena are generally irreversible, because they look wrong
when run in reverse.
How does the irreversibility of macroscopic phenomena arise? It certainly
does not come from the fundamental laws of physics, because these laws are all
reversible. In the previous example, the Oxygen and Nitrogen molecules got
mixed up by continually scattering off one another. Each individual scattering
event would look perfectly reasonable viewed in reverse, but when we add them
all together we obtain a process which would look stupid run backwards. How
can this be? How can we obtain an irreversible process from the combined
effects of very many reversible processes? This is a vitally important question.
Unfortunately, we are not quite at the stage where we can formulate a convincing
answer. Note, however, that the essential irreversibility of macroscopic
phenomena is one of the key results of statistical thermodynamics
Available Energy
The sources of energy can be divided into two groups namely, high-grade energy
and low-grade energy. The conversion of high-grade energy to shaft work is
exempt from the limitations of the second law, while conversion of low grade
energy is subjected to them.
Example: High grade energy:
1) Mechanical work 2) electrical energy 3) water power 4) wind power 5) kinetic
energy of a jet 6) tidal power.
Example: Low grade energy: 1) Heat or thermal energy 2) heat derived from
nuclear fission or fusion. 3) Heat derived from combustion of fossil fuels. 4) Solar
energy.
The high-grade energy in the form of mechanical work or electrical energy is
obtained from sources of low-grade energy. The complete conversion of low-
grade energy, heat in to high-grade energy, shaft work is impossible. That part of
low-grade energy which is available for conversion is refereed to as available
energy, while the part which according to the second law must be rejected is
known as unavailable energy.
Fig 1: Heat transfer from a constant temperature energy source.
In the previous chapter the concept of efficiency of a device such as
turbine, nozzle and compressor are introduced and more correctly termed as first
law efficiency, since it is given as he ratio of two energy terms. This chapter gives
more meaningful definition of efficiency- second law analysis. Our main goal is to
use this analysis to manager our thermal resources and environment better.
Consider the simple situation shown in figure1 in which there is an energy
source Q in the form of heat transfer from a very large source and therefore
constant temperature reservoir at temperature T. what is the ultimate potential for
producing work?
To answer to this question we imagine that a cyclic heat engine is
available as shown in figure (b) to convert the maximum fraction of Q requires
that the engine be completely reversible, i.e. a Carnot cycle, and that the lower
temperature reservoir be at the lowest temperature possible, often but not
necessarily at the ambient temperature. From the first and second laws for the
Carnot cycle and the usual consideration of all the Qs as positive quantities we
find
W
rev HE
= Q Q
o
Q / T = Q
o
/ T
o
W
rev HE
= Q {1-( T
o
/ T ) }
The fraction of Q given by the right side of the equation is the available portion of
the total energy quantity Q.
Consider the situation shown on the T-S Diagram.
The total shaded diagram is Q.
The portion of Q that is below To, the environment temperature, can not be
converted into work by the heat engine and must instead be thrown away. This
portion is therefore the unavailable portion of the energy Q, and the portion lying
between the two temperatures T and To is the available energy.
Fig 2: T-S Diagram for a constant temperature energy source.
Let us consider the same situation except that the heat transfer Q is available
from a constant pressure source, for ex, a simple heat exchanger as shown in
the figure. The Carnot cycle must now be replaced by a sequence of such
engines, with the result shown in the figure B the only difference between the first
and the second example is that the second includes an integral, which
corresponds to S
S = ( Q
rev
/ T ) = Qo /To
W
rev
= Q To * S
Note that this S quantity does not include the standard sign convention. It
corresponds to the change of entropy. The equation specifies the available
portion of the quantity Q. the portion unavailable for producing work in this
circumstance lies below To.
Thus the unavailable energy is the product of lowest temperature of heat
rejection ands the change of entropy of the system during the process of
supplying heat.
Fig 3: Changing temperature energy source.
Decrease in available energy when the heat is transferred
through a finite temperature difference:
Whenever heat id transferred through a finite temperature difference there is a
decrease in the availability of the energy so transferred. let us consider a
reversible heat engine operating between T
1
and To as shown in the figure
Fig 4: Increase in unavailable energy due to heat transfer through a finite
temperature difference.
Then we have Q
1
= T
1
* S
Q
2
= To * S
W = AE = (T
1
To) S
Let us now assume that q
1
is transferred through a finite temperature difference
from the reservoir or source at T
1
to the engine absorbing heat at T
1
lower than
T
1
as shown in the figure
Fig 5: Constant Temperature energy source.
The availability of Q
1
as received by the engine at T
1
and to receiving Q
1
and
rejecting Q
2
.
Q
1
= T
1
S = T
1
S
T
1
> T
1
, Hence S > S
Q
2
= Tc S and Q
2
= To S
Since S > S hence Q
2
> Q
2
And hence W = Q
1
- Q
2
= T
1
S - To S
And W = Q
1
Q
2
= T
1
S To S
Hence W < W since Q
2
> Q
2
.
Available energy lost due to irreversible heat transfer through finite temperature
difference between source and working fluid during heat addition process is
given by
W- W = Q
2
- Q
2
= To (S - S)
or decrease in AE = To (S - S)
Thus the decrease in available energy is the product of the lowest feasible
temperature of heat rejection and the additional entropy change in the system
while receiving heat irreversibly compared to the case of reversible heat transfer
from the same source. The greater is the temperature difference (T
1
T
1
) the
greater is the heat rejection Q
2
and greater will be the unavailable part of the
energy supplied. Energy is said to be degraded each time when it flows through
a finite temperature difference. Thats why the second law is some times called
the law of degradation of energy and the energy is said to run down hill.
Availability:
The availability of a given system is defined as the maximum useful work (total
work pdV work) that is obtainable in a process in which the system comes to
equilibrium with its surroundings. Availability is thus a composite property
depending on the state of the system and surroundings.
Let U,S and V be the initial energy, entropy and volume of a system and Uo So,
Vo their final values when the system has come to equilibrium with its
environment. The system exchanges heat only with the environment. The
process may be either reversible or irreversible. The useful work obtained in the
process in the form of equation
W <= (U ToS + po V) (Uo ToSo _ poVo)
Let = U ToS + p
o
V where is called the availability function and a
composite property of both the system and its environment, with U,S,V being
properties of the system at some equilibrium state and To po are the temperature
and pressure of the environment. The decrease in availability function in a
process in which the system comes to equilibrium with the environment is
- o = (U ToS + po V) (Uo ToSo _ poVo)
Hence W < = - o
Thus the useful work is equal to or less than the decrease in availability function.
The availability A of a given system in a given environment is the maximum
useful work obtainable in reversible process.
A = W max = - o .
This work is obtained in part from a decrease in the internal energy of the system
and in part from the heat withdrawn from the environment.
Let a system be taken from an equilibrium state 1, in which its availability is A
1
to
a second equilibrium state 2 in which its availability is A
2
. The end state 2 is not
in equilibrium with the environment. The maximum useful work that could be
obtained in the process
W max = A
1
A
2
= (
1
- o ) (
2
- o )
W max = (
1
-
2
)
Availability in steady flow:
The steady stet steady flow equation is given by
H1 + (mv
1
2
) + mgz1 + Q = H2 + (mv
2
2
) + mgz
2
+ W
The subscript 1 and 2 refer to the entrance and exit respectively. At the exit let
the system be in equilibrium with the environment at pressure po and
temperature To. Let symbols without subscripts refers to the entrance condition
of the system and changes in KE and PE are negligible. Then useful work is
given by
W = (H-Ho) + Q. the greater the value of Q larger will be the useful work. Thus
W will be maximum when Q is a maximum.
Let S and So be the entropies of the systems at the entrance and exit of the
device then
(S) system = So S. and (S)surr = - (Q / To)
From the entropy principle ( So S ) (Q - To) > = 0.
Therefore Q <= To (So- S) .
The useful work W <= (H-Ho) + To(So-S)
<= (H-ToS) + (Ho - ToSo)
Hence W <= B Bo where B = H-ToS it is called availability function for
steady flow and is also called as Keenan function.
For entrance and exit condition the useful work is maximum when the heat
absorbed is a maximum. I.e when the internal irreversibility is zero.
The maximum work obtainable from a system at the entrance of a device
when the pressure and temperature at the exit are those of the environment is
called the available of the system in steady flow and is given by
A = W max = B- Bo.
The alternative names for availability and for unavailable quantity To S are
Exergy and Anergy respectively.
Reversible work in a non-flow process:
In a non-flow process dm1 = dm2 =0
The entropy equation for flow process reduces to
(dW)
rev
= - d (U
1
- ToS + (mv
1
2
) + mgZ)
Between two equilibrium end states 1 and 2
(W)
rev1-2
= U
1
-U
2
To(S
1
-S
2
) + m( V
1
2
-V
2
2
)/2 + mg(Z
1
-Z
2
)
If the system doesnt possesses any KE and PE
(W)
rev1-2
= U
1
-U
2
To(S
1
-S
2
)
Irreversibility:
For many, one of the most perplexing questions of the last century has been the
origin of irreversibility. The microscopic equations of motion are time-reversal
invariant and solvable, at least in principle, given appropriate microscopic initial
conditions. Not only are these initial conditions never available, but by the very
definition of the problem we never have any control over the microscopic
variables. It should be clear immediately, then, that this microscopic invariance
has little to do with the irreversibility we see on the macroscopic scale, for we
cannot deal with those equations of motion directly in any event.
A great many of the microscopic states and initial conditions will serve to
define the corresponding macroscopic quantities, however, and we certainly
possess initial conditions on the latter if we are studying experimentally
reproducible phenomena, say. In turn, the microscopic equations of motion are
manifested in those for the statistical operator , or phase-space distribution
in the classical case. These are exact and also irreversible, as we have already
noted above. From whence, then, comes the macroscopic irreversibility we
observe in nature?
The operator is essentially a collection of probabilities, through its expectation
values, so that one can already find the difficulties at that level. There is no harm
in contemplating a time-dependent probability and studying , say, but there is
absolutely nothing in probability theory itself to tell us what the equations of
motion for P(t) should be. [Indeed, we wonder how P can change at all in the
absence of any change in the hypotheses upon which it was constructed.] Only
the physical equations of motion can guide us in the present scenario and, as we
have seen, they are time-reversal invariant. The traditional response to this
impasse has been to approximate the equations of motion for or in some
way, thereby immediately and artificially introducing irreversibility into the
description by discarding relevant information. The most common approximation
is to truncate the hierarchy and close the resulting equations for the lower-order
distribution functions by some means. There is simply no way to tell if this
irreversibility is merely mathematical or not, a point that continues to be missed
[13].
This brings us to the question of time-dependent entropy, and one can now see
the difficulty with defining . There are no definite criteria for
determining how P(t) itself should develop, other than from the physical
equations of motion. And if S is defined as in Eq.(1) it is a constant of the motion.
It may be possible, of course, to define S(t) in a number of other ways, but there
do not seem to be any criteria available to tell us what is unique and correct.
How, then, are we to understand irreversibility and the second law of
thermodynamics? Because much of the conventional wisdom in this area
appears flawed, as noted, another alternative might be to follow a line advocated
by Prigogine and his collaborators [19], and others [20], who suggest that there is
a heretofore unrecognized time irreversibility in all the microscopic laws of
physics, even at the quantum level. They envision a fundamental irreversibility
throughout the microscopic world, despite the absence of any empirical evidence
to support those beliefs. Rather than move further into this twilight zone of
irrationality, we shall consider a simpler and more logical resolution of these
questions arising from reflection on the above discussion.
The actual work done by a system is always less than the idealized reversible
work, and the difference between the two is called the irreversibility of the
process.
I = W
max
W
This is also some time referred to as degradation or dissipation. For a non flow
process between the equilibrium states, when the system exchanges heat only
with the environment
I = {(U
1
-U
2
) To(S
1
-S
2
) } {(U
1
-U
2
) + Q} = To (S
2
-S
1
) Q
= To (S) system + To (S)surr
= To[ (S)system + (S)surr ] Hence I > 0.
Similarly for the steady flow process I = W
max
W
= To (S
2
-S
1
) Q
= To (S) system + To (S)surr
= To[ (S)system + (S)surr ]
Thus same expression for irreversibility applies to both flow and non-flow
process. The quantity To[ (S)system + (S)surr ] represents an increase in
unavailable energy or Anergy.
Second Law efficiency:
With the increased use of availability analysis in recent years a term called
second law efficiency has come into more common use. This term refers to
comparison of the desired output of a process with the cost or input in terms of
the thermodynamic availability. Thus the isentropic turbine efficiency defined by
the ratio of actual work output to the work for a hypothetical isentropic expansion.
From the same inlet state to the same exit pressure which is called first law
efficiency, in that it is a comparison of two energy quantities. The second law
efficiency as just described would be the actual work output of the turbine divided
by the decrease in availability from the same inlet state to the same exit state.
Thus the second law efficiency is

Second law
= W / (
1
-
2
)
Where (
1
-
2
) is the decrease in availability for a steady state steady flow
process. Which is equal to the reversible work or maximum work obtainable.
In this sense this concept provides a rating or measure of the real process in
terms of the actual change of state and is simply another convenient way of
utilizing the concept of thermodynamic availability. In a similar manner the
second law efficiency of a pump or a compressor is the ratio of the increase in
availability to the work input to the device.
Exergy (Availability) analysis:
This introduces a method that uses the conservation of mass and energy
principles together with the second law of thermodynamics for the design and
analysis of thermal systems. It is also called as availability analysis. The main
importance of developing thermal systems that make effective use of non-
renewable energy resources such as oil, natural gas and coal is apparent. This
analysis is suited for the goal of more efficient energy resource use since it
enables the location, types and true magnitude of waste and loss to be
determined. Finally this information can be used to design thermal systems,
guide efforts to reduce sources of inefficiency in existing systems and evaluate
system economics.
Energy is conserved in every device. It cant be destroyed. Energy
entering with fuel, electricity, flowing streams of matter and so on can be
accounted for the products and byproducts. The basis for the Exergy concept is
present in the introduction to the second law of thermodynamics. An opportunity
exists for doing work whatever to systems at different states are brought into
communication and finally they come to equilibrium. When one of the two
systems is a suitably idealized system called an Exergy reference environment
and the other is some system of interest, Exergy is the maximum theoretical work
obtainable as any interact to equilibrium. The definition of Exergy will not be
complete however, until we define the reference environment and show how
numerical values for Exergy can be determined. These tasks are closely related
because the numerical value of Exergy depends on the state of a system of
interest as well as the condition of the environment.
Dead state: Dead state which is also important in completing our understanding
of the property Exergy. If the state of a fixed quantity of matter, a closed system
departs from that of the environment, an opportunity exists fro developing work.
However as the system changes state towards that of the environment new
opportunity diminishes ceasing to exist when the two are in equilibrium with one
another. This state is called Dead state. At the dead state, the fixed quantity of
matter under considerations is imagined to be sealed in an envelope impervious
to mass flow at rest relative to the environment and internally equilibrium at the
temperature and pressure of the environment.
At the dead state both the system and environment possesses energy, but the
value of Exergy is zero because there is no possibility of a spontaneous changes
within the system or the environment, nor can there be an interaction between
them.
Energy is said to be degraded each time it flows through a finite temperature
difference. That is why the second law of thermodynamics is some times called
the law of degradation of energy and energy is said to run downhill.
Effectiveness:
Effectiveness is defined as the ratio of actual useful work to the maximum useful
work. The useful output of a system is given by the increase of the availability of
the surroundings. The effectiveness of an actual process is always less than
unity. Thus effectiveness of a process is the measure of the extent to which
advantage has been taken of an opportunity to obtain useful work.
NUMERICAL EXAMPLES:
1) In a certain process a vapor while condensing at 420
O
C transfers heat to
water evaporating at 250
O
C. The resulting steam is used in a power cycle,
which rejects heat at 35
O
C. What is the fraction of the available energy in
the heat transfer from the process vapor at 420
O
C that is lost due to
irreversible heat transfer at 250
O
C.
Fig 6: Increase in unavailable energy
Solution:
ABCD would have been the power cycle if there was no temperature difference
between the vapor condensing and the water evaporating, and the area under
CD would have been the unavailable energy at 35
O
C. EFGD is the power cycle
when the vapor condenses at 420
O
C and the water evaporates at 250
O
C. The
unavailable energy becomes the area under DG. Therefore the increase in
available energy due to irreversible heat transfer is represented by the area
under CG.
Q
1
= T
1
S = T
1
S = S / S = T
1
/T
1
W = work done in cycle ABCD = ( T
1
- To) S
W = work done in cycle EFGD = ( T
1
- To) S
The fraction of energy that becomes unavailable due to irreversible heat transfer
= (W-W) / W = [ To(S-S) ] / [( T
1
- To) S ]
= To [(S/S) - 1 ] / ( T
1
- To) = To( T
1
- T
1
) / T
1
( T
1
- To)
= [308( 693-523) ] / [ 523 (693-308) ] = 0.26 Ans
2) Air expands through a turbine from 500 kPa, 520
O
C to 100 kPa,. 300
O
C.
during expansion 10KJ of heat is lost to the surroundings which is at 98
kPa, 20
O
C. neglecting KE and PE changes determine per kg of air a) the
decrease in availability b) the maximum work c) the irreversibility.
Solution:
For air the change in entropy is given by S
2
-S
1
=[ mC
p
ln (T
2
/T
1
) - mR ln(P
2
/P
1
)]
For 1kg of air s
2
-s
1
= Cp ln (T
2
/T
1
) - R ln(P
2
/P
1
)
The change in availability is given by, (
1
-
2
) = b
1
-b
2
= (h
1
-T
os1
) - (h
2
T
os2
)
= (h
1
-h
2
) To (s
1
-s
2
) = Cp(T
1
-T
2
) To (Cp ln (T
2
/T
1
) - R ln(P
2
/P
1
))
= 1.005 (520-300) 293(1.005 ln(573/793) -0.287 ln (1/5)
= 1.005 (220) 293 (-0.4619 + 0.3267) = 221.1 + 39.6 = 260.7 kJ/kg
W max = Change in availability = (
1
-
2
) = 260.7 kJ/kg
From SSSF equation we have
Q + h
1
= W + h
2
or W = (h
1
-h
2
) + Q = 1.005(520-300) 10 =211.1 kJ/kg
Thus the irreversibility I = Wmax W = 260.7 211.1 = 49.6 kJ/kg Ans.
3) Consider a steam turbine that has throttle governor. The steam in the
pipeline flowing through the turbine has a pressure of 3 MPa and a
temperature of 360 OC. At certain load the steam is throttled in an adiabatic
process to 1.5 MPa. Calculate the availability per kg of steam before and
after the process and the reversible work and irreversibility per kg of steam
for this process. Assume To= 25OC po=1 bar = 0.1MPa
Solution:
The availability at the initial condition
= (h
1
-h
o
) To(s
1
-s
o
) = (3140.9 104.9) 298 (6.7844 0.3664 )
= 3036-1912.38 = 1123.62 kJ/kg Ans.
Similarly availability at 1.5MPa after adiabatic throttling = (h
e
-h
o
) To(s
e
-s
o
)
since in adiabatic throttling h
e
=h
i
=3140 kJ/kg and adiabatic Q = 0.
Therefore se from the steam table corresponding to he = 3140.9 kJ/kg and
1.5MPa = 7.0833 kJ/kg K.
Thus
e
= (3140.9 104.9) 298 (7.0833-0.3664) = 3036.13 2001.46 =
1034.67 kJ/kg
Hence W rev =
i
-
e
= 1123.62 1034.67 = 88.95 kJ/kg
Also irreversibility I= To (s
e
-s
i
) = 298(7.0833-6.7844) = 89.07 as W actual is
zero.
4) Consider an air compressor that receives ambient air at 100 kPa, 25OC. It
compresses the air to a pressure of 1 MPa, where it exits at a temperature
of 540 OK. Since the sir and the compressor housing are hotter than
ambient it looses 50 kJ per kg air flowing through the compressor. Find the
reversible work, reversible heat transfer and irreversibility in the process.
Fig 7
Solution:
It is a non-adiabatic compression with no change in KE and PE. Using SSSF
equation, which has single inlet and exit. From the ideal gas tables h
1
= 298.62
kJ/kg and h
e
= 544.69 kJ/kg, si = 6.8629 kJ/kgK and se = 7.4664 kJ/kgK.
The energy equation for the actual compressor is
W= h
1
-h
2
+ Q = 298.62 544.69 50 = -296.07 kJ/kg
The reversible work for the given change of state is given by
W rev = To (s
2
-s
1
) - (h
2
-h
1
) + Q[1-(To/T
h
)]
= 298.2 (7.4664 - 6.8629) (0.287 ln 10)- (544.69-298.62) +0 = -263.17 kJ/kg
Thus irreversibility I =w rev-w = -263.17 (-296.07) = 32.9 kJ/kg.
5) In a steam boiler, hot gases from a fire transfer heat to water which
vaporizes at constant temperature. In a certain case, the gases are cooled
from 1100
o
C to 550
o
C. The specific heat of gases is 1.005kJ/kg K and the
latent heat of water at 220
o
C is 1858.5kJ/kg. All the heat transferred from
the gases goes to the water. How much does the total entropy of the
combined system of gas and water increase a result of the reversible heat
transfer? Obtain the result on the basis of 1 kg of water evaporated. If the
temperature of the surroundings is 30
o
C, find the increase in unavailable
energy due to irreversible heat transfer.
-W
-Q
i
e
Solution.
Fig 8 : h s diagram
Gas is cooled from state 1 to state 2 (Fig). For reversible heat transfer, the
working fluid in the heat engine would have been heated along 2-1, so that at any
instant, the temperature difference between gas and the working fluid is zero.
Then 1-b would have been the expansion of the working fluid down to the lowest
possible temperature To, and the amount of heat rejection would have been
given by the area abcd.
When water evaporates at 220
.o
C as the gas gets cooled from 1100
o
C to 550
o
C, the resulting power cycle has an unavailable energy represented by the area
aefd. The increase in unavailable energy due to irreversible heat transfer is thus
given by area befc.
(S)
water
= Latent heat absorbed /T = 1858.5/(273+220) = 3.77 kJ/kg-K
Q
1
= Heat transferred from the gas
=Heat absorbed by water during evaporation
=mgCpg (1100-550)=1 X 1858.5 kJ
Hence, m
g
C
pg
= 1858.5/550 =3.38kJ/
o
C
S
gas
= ( dQ /T ) = mg Cpg dT/T
m
g
Cpg ln Tg
2
/Tg
1
= 3.38 ln 823 / 1373 = -3.38 * 0.51 = -1.725 kJ/K
hence S total = (S)
water
+ (S)
gas
= 3.77 1.725 = 2.045 kJ/K
Increase in unavailable energy = To (S) total = 303 * 2.045 = 620 kJ.
6) Calculate the available energy in 40 kg of water at 75
o
C with respect to
the surroundings at 5
o
C, the pressure of water being 1 atm.
Solution
If the water is cooled at a constant pressure of 1 atm from 75
o
Cto 5
o
C the
heat given up may be used as a source for a series of Carnot engines each using
the surroundings as a sink. It is assumed that the amount of energy received by
any engine is small relative to that in the source and the temperature of the
source does not change while heat is being exchanged with the engine.
Let us consider that the source has fallen to temperature T, at which level there
operates a Carnot engine which takes in heat at this temperature and rejects
heat at To = 278 K. If s is the entropy change of water, the work obtainable is
W = - m (T-T
o
) s where s is negative.
W 40 (T-To) Cp T/T = -40Cp (1-To/T) T
With a very great number of engines in the series the total work (Maximum)
obtainable when the water is cooled from 348K to 278 K would be
W (max) = AE = - lim 40 Cp (1- To/T) T
= - 40 Cp (1- To/T) T = 40 Cp [(348-278) 278 ln 348/278]
= 1340 kJ.
Q1 = - 4 0 * 4.2 (348-278) = 11760 kJ.
Unavailable energy = Q
1
W
max
= 11760 1340 = 10420 kJ.
7) A 5 kg copper block at a temperature of 200
o
C is dropped into an
insulated tank containing 100 kg oil at a temperature of 30
o
C. Find the
increase in entropy of the universe due to this process when copper block
and the oil reach thermal equilibrium. Assume that the specific heats of
copper and oil are respectively 0.4 kJ/kgK and 2.1 kJ /kgK.
Solution
Applying energy balance, Energy lost by copper block = Energy gained by the oil.
M
cu
X C
p cu
X Temperature difference = m
oil
X C
pw
X Temperature difference.
5 X 0.4 X (200 t ) = 100 X 2.1 (t 30 ) 212t = 6700 , t = 31.6
o
C
Heat lost by Copper = 5 X 0.4 X (473 304.6) = 336 8 kJ, then associated
entropy change is dQ/T 336.8/473 0.7120 kJ/K.
Heat gained by oil = 100 X 2.1 X 1.6 = 1.1089 kJ/K.
Entropy of the universe = S cu +Soil = 0.712 +1.1089 = 1.8209 kJ/kg Ans
8) 0.5 kg of ice block at 10
o
C is brought into contact with 5 kg copper
block at 80
o
C in an insulated container. Determine the change in
entropy of
i) Ice block.
ii) Copper block.
iii) The universe.
Given specific heat of ice=2kJ / kg K, specific heat of water = 4.2 kJ/kg K.
specific heat of copper =0.5 kJ /kg K, enthalpy of fusion of water at 0
o
C= 334
kJ/kg.
Solution
Writing the energy balance equation for the system
Energy lost by the copper block = Energy gained by the ice
5 X 0.5 (80 - t) = 0.5 X 2.0 ( 0+10) + 0.5 X 334 + 0.5 X .4.2 (t - 0)
Therefore the value of t is t = 5
O
C
Entropy change of copper block = dQ/T = 187.5/(273 +80) = 0.53116kJ/K
Entropy change of ice block= dQ/T = (10 +167+10.5)/263 = 0.7129kJ/K
Entropy change of the universe = ( S )Cu + ( S)w = 1.24406 Ans
9) Calculate the availability and unavailability of a system that absorbs
15000kJ of heat from a heat source at 500K temperatures while the
environment is at 290 K temperature.
Solution:
Entropy Change, ds = Q/T=15000/500 =30 kJ/K
Unavailable work =T
o
ds =290 X 30 =8700 kJ
Available work = Q - T
o
ds =15000 290 X 30 =6300 kJ
10) 0.2 kg of air initially at 575 K temperature receives 300 kJ of heart
reversibly at constant pressure. Determine the available and unavailable
energies of the heat added.
Take Cp for air = 1.005 kJ / kg K and temperature of surroundings 300 K.
Solution:
Let T
2
be the temperature of air after the addition of heat at constant pressure.
Then
300 = mC
p
(T
2
-T
1
) = 0.2 X 1.005 (T
2
557)
=0.201 T
2
-115.57
T
2
= (300+115.57)/0.201 =2067.5K
Entropy change, ds = mC
p
log
e
T
2
/T
1
= 0.2 X 1.005 og
e
2067.5/575 =
0.2572 kJ /K
Unavailable work = T
o
dS = 300 X 0.2572 = 77.16 kJ
Available work = Q- T
o
dS = 300-300 X 0.2572 = 222.84 kJ
11) A closed system contains 2 kg of air during an adiabatic expansion
process there occurs a change in its pressure from 500kPa to 100 kPa and
in its temperature from 350 K to 320 K. if the volume doubles during the
process make calculations for maximum work, the change in availability
and irreversibility. Take for air C
v
= 0.718 kJ/kg K and R = 0.287 kJ/kgK. The
surrounding conditions may be assumed to be 100 kPa and 300 K.
Solution:
When the system undergoes a change from state 1 to 2 during a mass flow
process the maximum obtainable work is given by
W max = (U
1
-U
2
) To(S
1
-S
2
). Now (U
1
-U
2
) =
mCv(T
1
-T
2
) = * 0.7185(350-220) = 43.08 kJ.
And S
1
-S
2
= m[Cv ln(T
2
/T
1
) R ln V
2
/V
1
]
= 2*[0.718 l n 320 / 350 0.287 ln 2]
= 0.2693 kJ/K. then W max = 43.08 300 (-0.2693) = 123.87 kJ.
Change in availability is given by A
1
A
2
= (U
1
-U
2
) To(S
1
-S
2
) + Po (V
1
-V
2
)
V
1
= mRT
1
/ P
1
= 2 * 0.287 * 250 / 500. = 0.4018 m
3
.
V
2
= 2 V
1
= 2* 0.4018 + 0.8036 m
3
.
A
1
-A
2
= 123.87 + 100(0.4018 0.8036) = 83.67 kJ
It is the measure of maximum useful work or newt work obtainable from the
system.
Irreversibility = max work actual work
W actual = Q (U
2
-U
1
)
Since the system process is adiabatic Q = 0 and W actual = -(U
2
-U)
1
= U
1
-U
2
= n mCv(T
1
-T
2
) = 2* 0.718 (350-320) = 43.08 kJ.
Irreversibility = 123.87 - 43.08 = 80.79 kJ.
12) A system at 500 K receives 7200kJ/min from a source at 1000 K. The
temperature of atmosphere is 300 K. assuming that the temperature of the
system and source remain constant during heat transfer find out
The entropy produced during heat transfer.
The decrease in available energy after heat transfer.
Temperature of the source T
1
= 1000 K
Temperature of the system, T
2
= 500 K
Temperature of atmosphere, To = 300 K
Heat received by the system, Q =7200kJ/min
Change in entropy of the source during heat transfer
= -Q/T
1
= -7200/1000 = - 7.2 kJ/min K
Change in entropy of the system during heat transfer
= Q/T2 = -7200/500 =14.4kJ/min K
The net change of entropy, S -7.2 + 14.4 = 7.2kJ/min K
Decrease in available energy with source = (1000-300) 7.2 = 5040kJ/min
Decrease in available energy with the system = (500 300) 14.4 = 2880 kJ/min.
13) 15 kg of water is heated in an insulated tank by a churning process
from 300 K to 340 K. If the surrounding temperature is 300 K, find the loss
in availability for the process
Solution
Work added during churning = increase in enthalpy of water
= 15* 4.187*(340 300) = 2512.2 kJ = Enthalpy in the water
Availability of this energy is given by
m[(u
1
-u
0
) T
0
s]
s= C
p
log
e
(T
1
/T
0
)
s = 4.187 log
e
(340/300 )
s= 0.524 kJ/kgK
Available energy = m [C
v
(T
1
T
0
)- T
0
s]
=15[4.187 (340 300) 300 X0.524]
= 2349.3kJ Ans
Loss of availability 2512.2 158.7
= 2353.5 kJ Ans
This shows that conversion of work into heat is highly irreversible process, since
out of 2512.5 kJ of work energy supplied to increase the temperature, only 158.7
kJ will be available again for conversion into work.
14) 5.0 kg of air at 550 K and 4 bar is enclosed in a closed system.
Determine,
i) The availability of the system if the surrounding pressure and temperature are
1 bar and 290 K respectively.
ii) If the air is cooled at constant pressure to the atmospheric temperature,
find availability and effectiveness.
Availability of the system is
= m[(u
1
u
0
)-T
0
(s
1
-s
2
)] = m[C
v
(T
1
T
0
) - T
0
s]
s = C
p *
log
e
(T
1
/T
0
) R log
e
(p
1
/p
0
)
s = 1.005
*
log
e
(550/290) 0.287
*
log
e
(4/1)
= 0.643 0.397 = 0.246 kJ/kg K
Availability of the system = m[C
v
(T
1
T
0
) - T
0
s]
5[0.718(550 - 290) 290 X0.246] = 576.7 kJ Ans
ii) Heat transferred during cooling
Q = m X C
p
X (T
1
T
0
)
5.0 X1.005 X(550 - 290) = 1306.5 kJ Heat lost by the system
Change of entropy of the system during cooling
S = m X C
p
X log
e
(T
1
/T
0
)
S = 5.0 X1005 X log
e
(550/290) = 3.216 kJ/K
Unavailable portion of this energy = T
0
()S = 290 X 3.216 = 932.64 kJ
Available energy = 1306.5 - 932.64 = 373.86 kJ Ans
Effectiveness, = Available Energy/ Availability of the system
=(373.86/576.7) = 0.648 OR 64.8%
= 64.8% Ans
Problems for practice:
1)
500 kJ of heat from an infinite source at 1000K is supplied to 2 kg of gas
initially at 2 bar and 350K in a closed tank. Find the loss in available
energy due to above heat transfer. Take C
v
as 0.8 kJ/kg and surrounding
temperature as 300K.
2)
1000Kj of heat leaves hot gases at 1673K from a firebox of a boiler and
goes to steam at 523K. Atmospheric temperature is 293K. Divide the
energy into available and unavailable portions (1) as it leaves the hot
gases (ii) as it enters the steam
3)
2 kg of air at 5 bar and 353K expands adiabatically in a closed system
until its volume is doubled and its temperature becomes equal to that of
surroundings, which is at 1 bar and 278K. Calculate (1) the maximum
work (ii) the change in availability (iii) The irreversibility.
4)
In a heat exchanger of parallel flow type, water enters at 323K and leaves
at 353K while oil of specific gravity 0.8 enters at 523K and leaves at 373K.
The specific heat of oil is 2.5 kJ/kgK and surrounding temperature is 300K.
Determine the loss in availability on the basis of 1 kg of oil flow per
second.
5)
A pressure vessel has a volume of 1 m
3
and contains air at 1.4 MPa,
175
0
C. The air is cooled to 25
0
C by heat transfer to the surroundings at
250C. Calculate the availability in the initial and final states and the
irreversibility of the process.

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