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Module 2
Second Law of Thermodynamics and Entropy
Limitations of first law of thermodynamics:
 Heat can flow from hot body to cold body but not from cold body to hot body. (1st law
not discussed about the direction of flow of heat)
 Not discussed about the feasibility of a process or spontaneity.
 The natural spontaneous process is irreversible.(Not discussed about the reversible
process)
 It is possible to produce an engine with 100% efficiency. (It’s not true)

 All heat energy can be converted into work, but all work cannot be converted into
heat.
It has been observed that energy can flow from a system in the form of heat or work. The first
law of thermodynamics sets no limit to the amount of the total energy of a system which can
be caused to flow out as work. A limit is imposed, however, as a result of the principle
enunciated in the second law of thermodynamics which states that heat will flow naturally
from one energy reservoir to another at a lower temperature, but not in opposite direction
without assistance. This is very important because a heat engine operates between two energy
reservoirs at different temperatures.

Further the first law of thermodynamics establishes equivalence between the quantity of heat
used and the mechanical work but does not specify the conditions under which conversion of
heat into work is possible, neither the direction in which heat transfer can take place. This
gap has been bridged by the second law of thermodynamics.

Devices converting heat to work:

(a) In a mechanical cycle

• In the example considered the system undergoes a cycle in which work is first done
on the system by the paddle wheel as the weight is lowered.
• Then let the cycle be completed by transferring heat to the surrounding.
• From experience it has been learnt that we cannot reverse this cycle. i.e., if we
transfer heat to the gas, as shown by the dotted line, the temperature of the gas will
increase, but the paddle wheel will not turn and lift the weight.
• This system can operate in a cycle in which the heat and work transfers are both
negative, but it cannot operate in a cycle when both are positive, even though this
would not violate the first law.

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(b) In a thermodynamic cycle

A heat engine is used to produce the maximum work transfer from a given positive heat
transfer [Fig. 1 (a)]. The measure of success is called the thermal efficiency of the engine and
is defined by the ratio:

For a reversed heat engine [Fig. 1 (b)] acting as a refrigerator when the purpose is to achieve
the maximum heat transfer from the cold reservoir, the measure of success is called the co-
efficient of performance (C.O.P.). It is defined by the ratio:

For a reversed heat engine [Fig. 1 (b)] acting as a heat pump, the measure of success is again
called the co-efficient of performance. It is defined by the ratio:

Fig. 1

In all the above three cases application of the first law gives the relation Q1 – Q2 = W, and
this can be used to rewrite the expressions for thermal efficiency and co-efficient of
performance solely in terms of the heat transfers.

It may be seen that ηth is always less than unity and (C.O.P.)heat pump is always greater than
unity.

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Kelvin - Planck statement of the Second law of Thermodynamics; PMM I and PMM II:
“It is impossible to construct an engine, which while operating in a cycle produces no other
effect except to extract heat from a single reservoir and do equivalent amount of work”.

Consider a higher temperature reservoir T1 and low temperature reservoir T2. Fig. 2 shows a
heat pump which requires no work and transfers an amount of Q2 from a low temperature to a
higher temperature reservoir (in violation of the Clausius statement). Let an amount of heat
Q1 (greater than Q2) be transferred from high temperature reservoir to heat engine which
develops a net work, W = Q1 – Q2 and rejects Q2 to the low temperature reservoir. Since there
is no heat interaction with the low temperature, it can be eliminated. The combined system of
the heat engine and heat pump acts then like a heat engine exchanging heat with a single
reservoir, which is the violation of the Kelvin-Planck statement.

Fig. 2 Kelvin-Plank statement

Perpetual Motion Machine of the Second Kind:

— A machine which voilates the first law of thermodynamics is called the perpetual motion
machine of the first kind (PMM1). Such a machine creates its own energy from nothing and
does not exist.

Fig. 3. Perpetual motion machine of second kind (PMM2).

— Without violating the first law, a machine can be imagined which would continuously
absorb heat from a single thermal reservoir and would convert this heat completely into work.
The efficiency of such a machine would be 100 per cent. This machine is called the perpetual
motion machine of the second kind (PMM2).

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Clausius Statement of Second law of Thermodynamics:

“It is impossible for a self acting machine working in a cyclic process unaided by any
external agency, to convey heat from a body at a lower temperature to a body at a higher
temperature”.
In other words, heat of, itself, cannot flow from a colder to a hotter body.

Carnot cycle:
The cycle was first suggested by a French engineer Sadi Carnot in 1824 which works on
reversible cycle and is known as Carnot cycle.
Any fluid may be used to operate the Carnot cycle (Fig. 4) which is performed in an engine
cylinder the head of which is supposed alternatively to be perfect conductor or a perfect
insulator of a heat. Heat is caused to flow into the cylinder by the application of high
temperature energy source to the cylinder head during expansion, and to flow from the
cylinder by the application of a lower temperature energy source to the head during
compression.

Fig. 4

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The assumptions made for describing the working of the Carnot engine are as follows:
(i) The piston moving in a cylinder does not develop any friction during motion.
(ii) The walls of piston and cylinder are considered as perfect insulators of heat.
(iii) The cylinder head is so arranged that it can be a perfect heat conductor or perfect heat
insulator.
(iv) The transfer of heat does not affect the temperature of source or sink.
(v) Working medium is a perfect gas and has constant specific heat.
(vi) Compression and expansion are reversible.
Following are the four stages of Carnot cycle:
Stage 1. (Process 1-2). Hot energy source is applied. Heat Q1 is taken in whilst the fluid
expands isothermally and reversibly at constant high temperature T1.
Stage 2. (Process 2-3). The cylinder becomes a perfect insulator so that no heat flow takes
place. The fluid expands adiabatically and reversibly whilst temperature falls from T1 to T2.
Stage 3. (Process 3-4). Cold energy source is applied. Heat Q2 flows from the fluid whilst it
is compressed isothermally and reversibly at constant lower temperature T2.
Stage 4. (Process 4-1). Cylinder head becomes a perfect insulator so that no heat flow occurs.
The compression is continued adiabatically and reversibly during which temperature is raised
from T2 to T1.
The work delivered from the system during the cycle is represented by the enclosed area of
the cycle. Again for a closed cycle, according to first law of the thermodynamics the work
obtained is equal to the difference between the heat supplied by the source (Q1) and the heat
rejected to the sink (Q2).

Such an engine since it consists entirely of reversible processes, can operate in the reverse
direction so that it follows the cycle shown in Fig. 4 (b) and operates as a heat pump. Q2 is
being taken in at the lower temperature T2 during the isothermal expansion (process 4-3) and
heat Q1 is being rejected at the upper temperature T1 (process 2-1). Work W will be needed to
drive the pump.
Again, the enclosed area represents this work which is exactly equal to that flowing from it
when used as engine.
The Carnot cycle cannot be performed in practice because of the following reasons:
1. It is imposible to perform a frictionless process.
2. It is impossible to transfer the heat without temperature potential.
3. Isothermal process can be achieved only if the piston moves very slowly to allow heat
transfer so that the temperature remains contant. Adiabatic process can be achieved only if
the piston moves as fast as possible so that the heat transfer is negligible due to very short
time available. The isothermal and adiabatic processes take place during the same stroke
therefore the piston has to move very slowly for part of the stroke and it has to move very fast
during remaining stroke. This variation of motion of the piston during the same stroke is not
possible.

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Clausius Inequality:
đ𝑄
Statement: For any possible cycle the cyclic integral of is less than or equal to zero.
𝑇
Let us consider a cycle ABCD (Fig. 5). Let AB be a general process, either reversible or
irreversible, while the other processes in the cycle are reversible. Let the cycle be divided into
a number of elementary cycles, as shown, for one of these elementary cycles

Fig. 5 Clausius Inequality

Where, dQ is the heat supplied at T, and dQ2 the heat rejected at T2.
Now, the efficiency of a general cycle will be equal to or less than the efficiency of a
reversible cycle.

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For a reversible process

Hence, for any process AB

Then for any cycle

Since entropy is a property and the cyclic integral of any property is zero

This equation is known as Clausius inequality.

It provides the criterion of the reversibility of a cycle.

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Entropy
Definition: “Entropy is a function of a quantity of heat which shows the possibility of
conversion of that heat into work. The increase in entropy is small when heat is added at a
high temperature and is greater when heat addition is made at a lower temperature. Thus for
maximum entropy, there is minimum availability for conversion into work and for minimum
entropy there is maximum availability for conversion into work.”

Entropy—a Property of a System

Refer Fig. 6. Let us consider a system undergoing a reversible process from state 1 to state 2
along path L and then from state 2 to the original state 1 along path M. Applying the Clausius
theorem to this reversible cyclic process, we have

(where the subscript designates a reversible cycle)

Hence when the system passes through the cycle 1-L-2-M-1, we have

………1
Now consider another reversible cycle in which the system changes from state 1 to state 2
along path L, but returns from state 2 to the original state 1 along a different path N. For this
reversible cyclic process, we have

……….2

Fig. 6. Reversible cyclic process between two fixed end states.

Subtracting equation (2) from equation (1), we have

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As no restriction is imposed on paths L and M, except that they must be reversible, the
quantity dQ/T is a function of the initial and final states of the system and is independent of
the path of the process. Hence it represents a property of the system. This property is known
as the “entropy”.

Change of Entropy:
Let S1 = Entropy at the initial state 1, and
S2 = Entropy at the final state 2.
Then, the change in entropy of a system, as it undergoes a change from state 1 to 2, becomes

Lastly, if the two equilibrium states 1 and 2 are infinitesimal near to each other, the integral
sign may be omitted and S2 – S1 becomes equal to dS.
Hence equation may be written as

Where, dS is an exact differential.

Thus, from equation, we find that the change of entropy in a reversible process is equal to
dQ/T This is the mathematical formulation of the second law of thermodynamics.
Equation indicates that when an inexact differential δQ is divided by an integrating factor T
during a reversible process, it becomes an exact differential.
The third law of thermodynamics states “When a system is at zero absolute temperature, the
entropy of system is zero”.
It is clear from the above law that the absolute value of entropy corresponding to a given state
of the system could be determined by integrating (dQ/T)R between the state at absolute zero
and the given state. Zero entropy, however, means the absence of all molecular, atomic,
electronic and nuclear disorders.
As it is not practicable to get data at zero absolute temperature, the change in entropy is
calculated either between two known states or by selecting some convenient point at which
the entropy is given an arbitrary value of zero. For steam, the reference point at which the
entropy is given an arbitrary value of zero is 0°C and for refrigerants like ammonia, Freon-
12, carbon dioxide etc. the reference point is – 40°C, at which the entropy it taken as zero.
Thus, in practice we can determine the change in entropy and not the absolute value of
entropy.
Entropy as a Quantitative Test for Irreversibility:
We know that change in entropy in a reversible process is equal to (dQ/T)R.
Let us now find the change in entropy in an irreversible process.

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Fig. 7. Entropy change for an irreversible process.

Consider a closed system undergoing a change from state 1 to state 2 by a reversible process
1-L-2 and returns from state 2 to the initial state 1 by an irreversible process 2-M-1 as shown
in Fig. 7 on the thermodynamic coordinates, pressure and volume.

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AVAILABLE ENERGY AND EXERGY

There are many forms in which energy can exist. But even under ideal conditions all these
forms cannot be converted completely into work. This indicates that energy has two parts:
— Available part.
— Unavailable part.

Available energy:
‘Available energy’ is the maximum portion of energy which could be converted into useful
work by ideal processes which reduce the system to a dead state (a state in equilibrium with
the earth and its atmosphere). Because there can be only one value for maximum work which
the system alone could do while descending to its dead state, it follows immediately that
‘Available energy’ is a property.

Unavailable energy:
A system which has a pressure difference from that of surroundings, work can be obtained
from an expansion process, and if the system has a different temperature, heat can be
transferred to a cycle and work can be obtained. But when the temperature and pressure
becomes equal to that of the earth, transfer of energy ceases, and although the system
contains internal energy, this energy is unavailable.

Availability (Exergy):
The theoretical maximum amount of work which can be obtained from a system at any state
p1 and T1 when operating with a reservoir at the constant pressure and temperature p0 and T0
is called ‘availability’.

Maximum work in a reversible process:

The available energy (A.E.) or the available part of the energy supplied is the maximum work
output obtainable from a certain heat input in a cyclic heat engine (Fig. 6.1). The minimum
energy that has to be rejected to the sink by the second law is called the unavailable energy
(U.E.), or the unavailable part of the energy supplied.

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Thus unavailable energy is the product of the lowest temperature of heat rejection, and the
change of entropy of the system during the process of supplying heat (Fig. 6.3).

Useful Work:
All of the work W of the system with a flexible boundary would not be available for delivery,
since a certain portion of it would be spent in pushing out the atmosphere (Fig. 8.12). The
useful work is defined as the actual work delivered by a system less the work performed on
the atmosphere. If V1 and V2 are the initial and final volume of the system and p0 is the
atmospheric pressure, then the work done on the atmosphere is p0 (V2 - V1). Therefore, the
useful work Wu becomes

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Maximum Useful Work Obtained when the System Exchanges Heat with a Thermal
Reservoir in Addition to the Atmosphere:

If the open system exchanges heat with a thermal energy reservoir at temperature TR in
addition to the atmosphere, the maximum useful work will be increased by d QR ( l – TO/TR),
where d QR is the heat received by the system. For a steady flow process,

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Dead State:
If the state of a system departs from that of the surroundings, an opportunity exists for
producing work (Fig. 8.13). However, as the system changes its state towards that of the
surroundings, this opportunity diminishes, and it ceases to exist when the two are in
equilibrium with each other. When the system is in equilibrium with the surroundings, it must
be in pressure and temperature equilibrium with the surroundings, i.e., at p0 and T0. It must
also be in chemical equilibrium with the surroundings, i.e., there should not be any chemical
reaction or mass transfer. The system must have zero velocity and minimum potential energy.
This state of the system is known as the dead state, which is designated by affixing subscript
'O' to the properties.
Any change in the state of the system from the dead state is a measure of the available work
that can be extracted from it. Farther the initial point of the system from the dead state in
terms of p, t either above or below it, higher will be the available energy or exergy of the
system (Fig. 8.13). All spontaneous processes terminate at the dead state.

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Availability (Exergy):
Whenever useful work is obtained during a process in which a finite system undergoes a
change of state, the process must terminate when the pressure and temperature of the system
have become equal to the pressure and temperature of the surroundings, p 0 and T0, i.e., when
the system has reached the dead state. An air engine operating with compressed air taken
from a cylinder will continue to deliver work till the pressure of air in the cylinder becomes
equal to that of the surroundings, p0. A certain quantity of exhaust gases from an internal
combustion engine used as the high temperature source of a beat engine will deliver work
until the temperature of the gas becomes equal to that of the surroundings, T0.

The availability (A) of a given system is defined as the maximum useful work (total work
minus 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
both the system and surroundings.

1. Availability in a Steady Flow Process:

The reversible (maximum) work associated with a steady flow process for a single flow is
given by Eq. (8.25)

With a given state for the mass entering the control volume, the maximum useful work
obtainable (i.e., the availability) would be when this mass leaves the control volume in
equilibrium with the surroundings (i.e., at the dead state). Since there is no change in volume,
no work will be done on the atmosphere. Let us designate the initial state of the mass entering
the C.V. with parameters having no subscript and the final dead state of the mass leaving the
C.V. with parameters having subscript 0. The maximum work or availability, A, would be

where φ is called the availability function for a steady flow system and VO= 0. This is the
availability of a system at any state as it enters a C. V. in a steady flow process. The
availability per unit mass would be

If subscripts I and 2 denote the states of a system entering and leaving a C.V., the decrease in
availability or maximum work obtainable for the given system surroundings combination
would be

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2. Availability in a Nonflow Process:

Let us consider a closed system and denote its initial state by parameters without any
subscript and the final dead state with subscript 'O'. The availability of the system A, i.e., the
maximum useful work obtainable as the system reaches the dead state, is given by Eq. (8.40).

Second Law Efficiency:

A common measure on energy use efficiency is the first law efficiency, η I. The first law
efficiency is defined as the ratio of the output energy of a device to the input energy of the
device. The first law is concerned only with the quantities of energy, and disregards the forms

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in which the energy exists. It does not also discriminate between the energies available at
different temperatures. It is the second law of thermodynamics which provides a means of
assigning a quality index to energy. The concept of available energy or exergy provides a
useful measure of energy quality (Sec. 8.3).
With this concept it is possible to analyze means of minimizing the consumption of available
energy to perform a given process, thereby ensuring the most efficient possible conversion of
energy for the required task.
The second law efficiency, ηII, of a process is defined as the ratio of the minimum available
energy (or exergy) which must be consumed to do a task divided by the actual amount of
available energy (or exergy) consumed in performing the task.

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In the case of a heat pump, the task is to add heat Q, to a .reservoir to be maintained at
temperature Ta, and the input shaft work is Wi,

Similarly, expressions of ηI and ηII can be obtained for other thermal tasks.

Numerical:

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Module 2
SECOND LAW OF THERMODYNAMICS
1) A cyclic heat engine operates between a source temperature of 800°C and a sink
temperature of 30°C. What is the least rate of heat rejection per kW net output of the engine?

Solution:

2) A domestic food freezer maintains a temperature of - 15°C. The ambient air temperature is
30°C. If heat leaks into the freezer at the continuous rate of 1.75 kJ/s what is the least power
necessary to pump this heat out continuously?

Solution:
Freezer temperature,
T2 = -15 + 273 = 258 K
Ambient air temperature,
T1 = 30 + 273 = 303 K
The refrigerator cycle removes heat from the freezer at the same rate at which heat leaks into
it.

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3) A reversible heat engine operates between two reservoirs at temperatures of 600°C and
40°C. The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 40°C and - 20°C. The heat transfer to the heat engine is 2000 kJ and the net
work output of the combined engine refrigerator plant is 360 kJ.
(a) Evaluate the heat transfer to the refrigerant and the net heat transfer to the
reservoir at 40°C.
(b) Reconsider (a) given that the efficiency of the heat engine and the COP of the
refrigerator are each 40% of their maximum possible values.
Solution:
(a) Maximum efficiency of the heat engine cycle

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4) It is proposed that solar energy be used to warm a large collector plate. This energy would,
in tum, be transferred as heat to a fluid within a heat engine, and the engine would reject
energy as heat to the atmosphere. Experiments indicate that about 1880 kJ/m h of energy can
be collected when the plate is operating at 90°C. Estimate the minimum collector area that
would be required for a plant producing I kW of useful shaft power. The atmospheric
temperature may be assumed to be 20°C.
Solution:
The maximum efficiency for the heat engine operating between the collector plate
temperature end the atmospheric temperature is

5) A domestic food refrigerator maintains a temperature of – 12°C. The ambient air

temperature is 35°C. If heat leaks into the freezer at the continuous rate of 2 kJ/s. Determine
the least power necessary to pump this heat out continuously.

6) A Carnot cycle operates between source and sink temperatures of 250°C and – 15°C. If the
system receives 90 kJ from the source, find :
(i) Efficiency of the system ; (ii) The net work transfer ;(iii) Heat rejected to sink.

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7) A cyclic heat engine operates between a source temperature of 1000°C and a sink
temperature of 40°C. Find the least rate of heat rejection per kW net output of the engine?

8) A reversible heat engine operates between two reservoirs at temperatures 700°C and 50°C.
The engine drives a reversible refrigerator which operates between reservoirs at temperatures
of 50°C and – 25°C. The heat transfer to the engine is 2500 kJ and the net work output of the
combined engine refrigerator plant is 400 kJ.
(i) Determine the heat transfer to the refrigerant and the net heat transfer to the reservoir at
50°C ;
(ii) Reconsider (i) given that the efficiency of the heat engine and the C.O.P. of the
refrigerator are each 45 per cent of their maximum possible values.

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9) Two Carnot engines work in series between the source and sink temperatures of 550 K and
350 K. If both engines develop equal power determine the intermediate temperature.

10) A fish freezing plant requires 40 tons of refrigeration. The freezing temperature is – 35°C
while the ambient temperature is 30°C. If the performance of the plant is 20% of the
theoretical reversed Carnot cycle working within the same temperature limits, calculate the
power required.
Given : 1 ton of refrigeration = 210 kJ/min.

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11) A Carnot heat engine draws heat from a reservoir at temperature T1 and rejects heat to
another reservoir at temperature T3. The Carnot forward cycle engine drives a Carnot
reversed cycle engine or Carnot refrigerator which absorbs heat from reservoir at temperature
T2 and rejects heat to a reservoir at temperature T3. If the high temperature T1 = 600 K and
low temperature T2 = 300 K, determine : (i) The temperature T3 such that heat supplied to
engine Q1 is equal to the heat absorbed by refrigerator Q2.
(ii) The efficiency of Carnot engine and C.O.P. of Carnot refrigerator.
Solution. Refer Fig. 5.18.
Temperature, T1 = 600 K
Temperature, T2 = 300 K

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CLAUSIUS INEQUALITY
1) 300 kJ/s of heat is supplied at a constant fixed temperature of 290°C to a heat engine. The
heat rejection takes place at 8.5°C. The following results were obtained :
(i) 215 kJ/s are rejected.
(ii) 150 kJ/s are rejected.
(iii) 75 kJ/s are rejected.
Classify which of the result report a reversible cycle or irreversible cycle or impossible
results.

2) In a power plant cycle, the temperature range is 164°C to 51°C, the upper temperature
being maintained in the boiler where heat is received and the lower temperature being
maintained in the condenser where heat is rejected. All other processes in the steady flow
cycle are adiabatic. The specific enthalpies at various points are given in Fig. 5.20.
Verify the Clausius Inequality.

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ENTROPY
1) Water flows through a turbine in which friction causes the water temperature to rise from
35°C to 37°C. If there is no heat transfer, how much does the entropy of the water change in
passing through the turbine? (Water is incompressible and the process can be taken to be a
constant volume.)

2)
(a) One kg of water at 273 K is brought into contact with a heat reservoir at 373 K. When the
water has reached 373 K. find the entropy change of the water, of the heat reservoir, and of
the universe.
(b) If water is heated from 273 K to 373 K by first bringing it in contact with a reservoir at
323 K and then with a reservoir at 373 K. what will the entropy change of the universe be?
(c) Explain how water might be heated from 273 K to 373 K will almost no change in the
entropy of the universe.
Solu1ion:
(a) Water is being heated through a finite temperature difference (Fig. Ex. 7.2). The entropy
of water would increase and that of the reservoir would decrease so that the net entropy

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change of me water (system) and the reservoir together would be positive definite. Water is
being heated irreversibly, and to find the entropy change of water, we have lo assume a
reversible path between the end states which are at equilibrium.

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3) Three identical finite bodies of constant heat capacity are at temperatures 300, 300 and 100
K. If no work or heat is supplied from outside, what is the highest temperature to which any
one of the bodies can be raised by the operation of heat engines or refrigerators.

Solution:
Let the three identical bodies A, B, and C having the same heat capacity C be respectively at
300 K, 100 Kand 300 K initially, and let us operate a beat engine and a refrigerator, as shown
in Fig. Ex. 7.5. Let Tr be the final temperature of bodies A and B, and r; be the final
temperature of body C. N

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4) An iron cube at a temperature of 400°C is dropped into an insulated bath containing 10 kg

water at 25°C. The water finally reaches a temperature of 50°C at steady state. Given that the
specific heat of water is equal to 4186 J/kg K. Find the entropy changes for the iron cube and
the water. Is the process reversible ? If so why ?

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5) 0.04 kg of carbon dioxide (molecular weight = 44) is compressed from 1 bar, 20°C, until
the pressure is 9 bar, and the volume is then 0.003 m3. Calculate the change of entropy.
Take cp for carbon dioxide as 0.88 kJ/kg K, and assume carbon dioxide to be a perfect gas.

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6) Calculate the change of entropy of 1 kg of air expanding polytropically in a cylinder

behind a piston from 7 bar and 600°C to 1.05 bar. The index of expansion is 1.25.

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7) An insulated cylinder of volume capacity 4 m3 contains 20 kg of nitrogen. Paddle work is

done on the gas by stirring it till the pressure in the vessel gets increased from 4 bar to 8 bar.
Determine :
(i) Change in internal energy,
(ii) Work done,
(iii) Heat transferred, and
(iv) Change in entropy.
Take for nitrogen : Cp = 1.04 kJ/kg K, and Cv = 0.7432 kJ/kg K.

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8) A rigid cylinder containing 0.004 m3 of nitrogen at 1 bar and 300 K is heated reversibly
until temperature becomes 400 K. Determine : (i) The heat supplied. (ii) The entropy change.

9) 1.2 m3 of air is heated reversibly at constant pressure from 300 K to 600 K, and is then
cooled reversibly at constant volume back to initial temperature. If the initial pressure is 1
bar, calculate :
(i) The net heat flow.
(ii) The overall change in entropy.
Represent the processes on T-S plot. Take cp = 1.005 kJ/kg K and R = 0.287 kJ/kg K

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10)
(a) One kg of water at 0°C is brought into contact with a heat reservoir at 90°C. When the
water has reached 90°C, find :
(i) Entropy change of water ;
(ii) Entropy change of the heat reservoir ;
(iii) Entropy change of the universe.
(b) If water is heated from 0°C to 90°C by first bringing it in contact with a reservoir at
40°C and then with a reservoir at 90°C, what will the entropy change of the universe be ?
(c) Explain how water might be heated from 0°C to 90°C with almost no change in the
entropy of the universe.

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11) A closed system contains air at a pressure 1 bar, temperature 300 K and volume 0.018
m3. This system undergoes a thermodynamic cycle consisting of the following three
processes in series :
(i) Constant volume heat addition till pressure becomes 5 bar,
(ii) Constant pressure cooling, and
(iii) Isothermal heating to initial state.
Represent the cycle on T-S and p-V plots and evaluate the change in entropy for each
process. Take cp = 0.718 kJ/kg K and R = 0.287 kJ/kg K.

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AVAILABLE ENERGY AND EXERGY

1) One kg of air is compressed polytropically from 1 bar pressure and temperature of 300 K
to a pressure of 6.8 bar and temperature of 370 K. Determine the irreversibility if the sink
temperature is 293 K. Assume R = 0.287 kJ/kg K, cp = 1.004 kJ/kg K and cv = 0.716 kJ/kg
K.

2) A system at 500 K receives 7200 kJ/min from a source at 1000 K. The temperature of
atmosphere is 300 K. Assuming that the temperatures of system and source remain constant
during heat transfer find out :
(i) The entropy produced during heat transfer ;
(ii) The decrease in available energy after heat transfer.

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3) Calculate the decrease in available energy when 20 kg of water at 90°C mixes with 30 kg
of water at 30°C, the pressure being taken as constant and the temperature of the
surroundings being 10°C.
Take Cp of water as 4.18 kJ/kg K.

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4) In a certain process, a vapour, while condensing at 420°C, transfers heat to water

evaporating at 250°C. The resulting steam is used in a power cycle which rejects heat at
35°C. What is the fraction of the available energy in the heat transferred from the process
vapour at 420°C that is lost due to the irreversible heat transfer at 250°C?

5) The moment of inertia of a flywheel is 0.54 kg-m2 and it rotates at a speed 3000 RPM in a
large heat insulated system, the temperature of which is l5°C. If the kinetic energy of the
flywheel is dissipated as frictional beat at the shall: bearings which have a water equivalent of
2 kg, find the rise in the temperature of the bearings when the flywheel bas come to rest.
Calculate the greatest possible amount of this heat which may be returned to the flywheel as
high-grade energy, showing how much of the original kinetic energy is now unavailable.
What would be the final RPM of the flywheel, if it is set in motion with this available
energy?

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6) Two kg of air at 500 kPa, 80°C expands adiabatically in a closed system until its volume is
doubled and its temperature becomes equal to that of the surroundings which is at 100 kPa,
5°C. For this process, determine (a) the maximum work, (b) the change in availability, and (
c) the irreversibility. For air, take c. = 0.718kJ/kg K, 11 = c.T where cv is constant, and
pV= mRT where p is pressure in kPa, V volume in m3, m mass in kg, Ra constant equal to
0.287 kJ/kg K, and T temperature in K.

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7) Air expands through a turbine from 500 kPa, 520°C to 100 kPa, 300°C. During expansion
l0 kJ/kg of heat is lost to the surroundings which are at 98 kPa, 20°C. Neglecting the K.E.
and P.E. changes, determine per kg of air (a) the decrease in availability, (b) the maximum
work, and (c) the irreversibility
For air, Ice CP = 1.005 kJ/kg K. h= CP T where CP is constant, and the p, V and T
relation as in previous exercise.

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8) A mass of IOOO kg of fish initially at 1 bar, 300K is to be cooled to - 20°C. The freezing
point of fish is - 2.2°C, and the specific beats of fish below and above the freezing point are
1.7 and 3.2 kJ/kg K respectively. The latent heat of fusion for the fish can be taken as 235
kJ/kg. Calculate the exergy produced in the chilling process. Take T0 = 300 K and Po= 1bar.

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9) 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.

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10) 5 kg of air at 550 K and 4 bar is enclosed in a closed system.

(i) Determine 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, determine the
availability and effectiveness.

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