MODULE 3

Energy is a conserved property, and no process is known to have taken place in

violation of the first law of thermodynamics. Therefore, it is reasonable to conclude
that a process must satisfy the first law to occur. However, satisfying the first law
alone does not ensure that the process will actually take place.

It is a common experience that a cup of hot coffee left in a cooler room eventually
cools. This process satisfies the first law of thermodynamics since the amount of
energy lost by the coffee is equal to the amount gained by the surrounding air. Now
consider the reverse process the hot coffee getting even hotter in a cooler room as a
result of heat transfer from the room air. We all know that this process never takes
place. Yet, doing so would not violate the first law as long as the amount of energy
lost by the air is equal to the amount gained by the coffee.

Thus it is clear that the process proceed in a certain direction and not in the reverse
direction. The first law places no restriction on the direction of a process, but
satisfying the first law does not ensure that the process will actually occur. This
inadequacy of the first law to identify whether a process can take place is remedied by
introducing the second law of thermodynamics.

A process will not occur unless it satisfies both the first and second laws of
thermodynamics.

The first law is concerned with the quantity of energy and the transformations of
energy from one form to another with no regard to its quality. The second law asserts
that energy has quality as well as quantity.

THERMAL ENERGY RESERVOIRS

A body with a relatively large thermal energy capacity (mass x specific heat) that can
supply or absorb finite amount of heat without undergoing any change in temperature
is a called a thermal energy reservoir or heat reservoirs. In practice, large bodies of
water such as oceans, lakes, and rivers as well as the atmospheric air can be modeled

1
as thermal reservoirs. A reservoir that supplies energy in the form of heat is called a
source, and one that absorbs energy in the form of heat is called a sink.

KELVIN - PLANCK STATEMENT

It is impossible for any device that operates on a cycle to receive heat from a single
reservoir and produce a net amount of work.

That, is a heat engine must exchange heat with a low temperature sink as well as a
high temperature source to keep operating.

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The Kelvin Plank statement can also be expressed as no heat engine can have a
thermal efficiency of 100 percent.

A heat engine that violates Kelvin Plank statement.

Note that the impossibility of having a 100% efficient heat engine is not due to
friction or other dissipative effects. It is a limitation that applies to both the idealized
and the actual heat engines.

CLAUSIUS STATEMENT

It is impossible to construct a device that operates in a cycle and produce no effect

other than the transfer of heat from a lower-temperature body to a higher temperature
body.

The statement does to imply that a cyclic device that transfers heat from a cold
medium to a warmer one is impossible to construct. It simply states that a refrigerator
will not operate unless the compressor is driven by an external power source such as
an electric motor i.e., the net effect on the surrounding involves the consumption of
some energy in the form of work., in addition to the transfer of heat from a colder
body to a warmer one, it leaves a trace in the surroundings.

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 A refrigerator that violates the Clausius statement

EQUIVALENCE OF THE TWO STATEMENTS

The Kelvin – Plank and the Clausius statements are equivalent in their consequences
and either statement can be used as the expression of these second law of
thermodynamics. Any device that violates the Kelvin-Plank statement also violates the
Clausius statement and vice versa.

Consider the heat engine-refrigerator combination operating between the same two
reservoirs.

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The heat engine is assumed to have in violation of the Kelvin-Planck statement, a
thermal efficiency of 100%, and therefore it converts all the heat Q H it receives to
work w. This work is now supplied to a refrigerator that removes heat in the amount
of QL+ QH to the high temperature reservoir. During this process, the high temperature
receives a net amount of heat Q L. (ie (QL + QH - QH = QL).

Thus the combination of these two devices can be viewed as a refrigerator that
transfers heat in an amount of Q L from a cooler body to a warmer one without
requiring any input from outside. This is clearly a violation of the Clausius statement.
Therefore, a violation of the Kelvin-Planck statement results in the violation of the
Clausius statement.

Again consider a combination of heat pump and heat engine operating between the
same two reservoirs.

In the arrangement the heat pump requires no work and transfers an amount of Q L
from a low temperature to a high temperature reservoir which is a violation of the
Clausius statement.

Let an amount of heat QH be transferred from high temperature reservoir to heat

engine which develops a net work, W = QH – QL and rejects QL to the low temperature
reservoir.

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Now since there is no heat interaction with the low temperature reservoir, it can be
eliminated. The combined system then acts like a heat engine exchanging heat with a
single reservoir, which is a violation of the Kelvin-Planck statement.

CARNOT CYCLE

The best known reservoir cycle is the Carnot cycle, first proposed by French engineer
Sadi Carnot in 1824.

The Carnot cycle composed of four reversible processes-two isothermal and two
adiabatic.

Consider a closed system that consists of gas contained in an adiabatic piston cylinder
device. The insulation of the cylinder head is such that it may be removed to bring the
cylinder into contact with reservoirs to provide heat transfer. The four reversible
processes that make up the Carnot cycle are;

Reversible isothermal expansion (Process 1-2, TH = const)

Initially (state 1), the temperature of the gas is TH and the cylinder head is in close
contact with source at temperature TH. The gas is allowed to expand slowly, doing
work on its surroundings. As the gas expands, the temperature of the gas tends to
decrease. But as soon as the temperature drops by an infinitesimal amount dT, some
heat flows from the reservoir into the gas, raising the gas temperature to T H. It

6
continues until the piston reaches position 2. The amount of heat transferred to the gas
during this process is QH.

Reversible adiabatic expansion (process 2-3, temperature drops from TH to TL)

At state 2, the reservoir that was in contact with the cylinder head is removed and
replaced by insulation so that the system becomes adiabatic. The gas continues to
expand slowly, doing work on the surroundings until its temperature drops from to T H
to TL (state 3). The piston is assumed to be frictionless and the process be quasi
equilibrium, so that the process is reversible as well as adiabatic.

Reversible isothermal compression (process 3-4, TL = const)

At state 3, the insulation at the cylinder head is removed, and the cylinder is brought
into contact with a sink at temperature TL. Now the piston is pushed inward by an
external force, doing work on the gas. As the gas is compressed, its temperature tends
to rise. But as soon as it rises by an infinitesimal amount dT, heat flows from the gas
to the sink, causing the gas temperature to drop to T L. Thus the gas temperature is
maintained constant at TL. It continues until the piston reaches state 4. The amount of
heat rejected from the gas during this process is Q L.

Reversible adiabatic compression (process 4-1, temperatures rises from TL to TH)

State 4 is such that when the low temperature reservoir removed and the insulation is
put back on the cylinder head. The gas is compressed in a reversible manner so that
the gas returns to its initial state (state 1). The temperature rises from TL to TH during
the reversible adiabatic compression process, which completes the cycle.

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 (Q H) and heat rejected to the sink. (QL).

ie, W = QH – QL

Also, thermal efficiency, th = Work done / Heat supplied by the source

= (QH – QL)/QH

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ie th = 1 – (QL/QH)

But QH = mcpT1 & QL = mcp T2

 th = 1 – (T2/ T1)

Being a reversible cycle, the Carnot cycle is the most efficient cycle operating
between two specified temperature limits. Even though the Carnot cycle cannot be
achieved in reality, the efficiency of actual cycles can be improved by attempting to
approximate the Carnot cycle more closely.

The Carnot cycle cannot be performed in practice because of the following reasons;

1. It is impossible 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 constant. Adiabatic process can be
achieved only if the piston moves as far as possible so that the heat transfers
negligible due to very short time available. The isothermal and adiabatic process take
place during the same stroke therefore the piston has to move very slowly for part of
the stroke and has to move very fast during the remaining stroke. This variation of
motion of the piston during the same stroke is not possible.

COROLLARIES OF THE SECOND LAW (CARNOT PRINCIPLES)

Valuable conclusions can be drawn the two statements of the second law
thermodynamics. Two conclusions pertain to the thermal efficiency of reversible and
irreversible (ie actual) heat engines, and they are known as the Carnot principles.

1. The efficiency of an irreversible heat engine is always less than the

efficiency of a reversible one operating between the same two reservoirs.

2. The efficiencies of all reversible heat engines operating between the same
two reservoirs are the same.

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These two statements can be proved by demonstrating that the violation of either
statement results in the violation of the second law of thermodynamics.

To prove the first statement, consider two heat engines operating between the same
reservoirs. One engine is reversible and the other is irreversible.

Each engine is supplied with the same amount of QH. The amount of work produced
by the reversible heat engine is W rev, and the amount produced by the irreversible one
ie Wirrev.

In violation of the first Carnot principle, we assume that the irreversible heat engine is
more efficient than the reversible one (ie th,irev > th, rev) and thus delivers more work

9
than the reversible one. Now let the reversible heat engine be reversed and operate as
a refrigerator. This refrigerator will receive a work input of Wrev and reject heat to the
high temperature reservoir. Since the refrigerator is rejecting heat in the amount of Q H
to the high temperature reservoir and the irreversible heat engine is receiving the same
amount of heat from this reservoir, the net heat exchange for this reservoir is zero.
Thus, it could be eliminated by having the refrigerator discharge Q H directly into the
irreversible heat engine.

Now considering the refrigerator and the irreversible engine together, we have an
engine that produces a net work in the amount of W irev - Wrev while exchanging heat
with a single reservoir – a violation of the Kelvin- Planck statement of the second law.

Thus we conclude that no heat engine can be more efficient than a reversible heat
engine operating between the same reservoirs.

The second Carnot principle can also be proved in a similar manner. This time we
have to replace the irreversible engine by another reversible engine that is more
efficient and thus delivers more work than the first reversible engine. By following the
same reasoning as above, we will end up having an engine that produces a net amount
of work violation of the second law.

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Thus we conclude that no reversible heat engine can be more efficient than a
reversible one operating between the same tow reservoirs, regardless of how the cycle
is completed or the kind of working fluid is used.

THE THERMODYNAMIC TEMPERATURE SCALE

A temperature scale that is independent of the properties of the substances that are
used to measure temperature is called a thermodynamic temperature scale.

The second Carnot principle states that all reversible heat engines have the same
thermal efficiency when operating between the same two reservoirs, ie, the efficiency
of a reversible engine is independent of the working fluid employed and its properties,
the way the cycle is executed, or the type reversible engine used. Since the energy
reservoirs are characterized by their temperatures, the thermal efficiency of reversible
heat engine is a function of the reservoir temperature only.

For a reversible heat engine operating between two reservoirs

th = (QH – QL)/QH = 1 – (QL/QH)

ie. QH/QL = some function of temperature, ie f (TH, TL)

ie (QH/ QL) = (TH)/ (TL)

This is the only requirement that the second law places on the ratio of heat flows to
and from the reversible heat engines. Several functions  (T) will satisfy this equation,
and the choice is completely arbitrary. Lord Kelvin first proposed taking  (T) = T to
define a thermodynamic temperature scale.

ie. (QH/ QL) rev = TH/ TL

This temperature scale is called the Kelvin scale; the temperature on this scale is
called absolute temperature. On the Kelvin scale, the temperature ratios depend on the
ratios of heat transfer between a reversible heat engine and the reservoirs and are
independent of the physical properties of any substance. On this scale temperature
varies between zero and infinity.

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At the International Conference on Weights and Measures held in 1954, the triple
point of water was assigned the value 273.16 K. The magnitude of a Kelvin is defined
as 1/273.16 of the temperature interval between absolute zero and triple point
temperature of water.

 (QH/ QL) = TH/ 273.16

ie the triple point temperature is taken as reference as absolute zero temperature is

practically not possible.

 T = 273.16 (QH/ QL)

Even though the thermodynamic temperature scale is defined with the help of the
reversible heat engines, it is not possible, nor is it practical, to actually operate such as
engine to determine numerical values on the absolute temperature scale.

Absolute temperatures can be measured accurately by other means, such as the

constant-volume ideal gas thermometer together with exploration techniques.

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CLAUSIUS INEQUALITY (German physicist RJE Clausius)

The second law of thermodynamics often leads to expressions that involve

inequalities. An irreversible (ie actual) heat engine, for example, is less efficient than a
reversible one operating between the same two thermal energy reservoirs.

Likewise, the inequality of Clausius is a corollary or a consequence of the second law

of thermodynamics. It is expressed as;

 dQ/ T ≤ 0

ie the cyclic integral of dQ/T is always less than or equal to zero. This inequality is
valid for all cycles, reversible or irreversible.

a. Consider a reversible Carnot heat engine cycle operating between reservoirs at

temperatures TH and TL.

For this cycle,  dQ = QH – QL > 0

But we know (QH/ QL) = (TH)/ (TL) = TH/TL

 QH/ TH - QL/ TL = 0

ie.  dQ / T = QH/ TH - QL/ TL = 0

If  dQ approaches zero (by making TH approach TL), then again

 dQ/T = 0

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Thus we conclude that for all reversible heat engine cycles

 dQ  0 and  dQ/T = 0 ………..(1)

b. Now consider an irreversible cyclic heat engine operating between the same
TH and TL as the reversible engine and receiving the same quantity of heat QH.

From the second law, Wirrev < Wrev

ie QH – QL irrev < QH – QL rev

 QL irrev > QL rev

We know from equation (1),  (dQ/ Trev) = (QH/ TH) – (QL rev / TL) = 0

  (dQ/ Tirrev ) = (QH/ TH) - (QL irrev/ TL) < 0 (as QL irrev> QL rev)

and  dQ = QH - QL irrev > 0

Suppose we cause the engine to become more and more irreversible (ie Q Lirrev
increasing), but keeping Q H, TH and TL fixed. The  dQ then approaches zero, and
dQ/ T becomes a progressively larger negative value. Thus we conclude that for all
irreversible heat engine cycles.

 dQ  0
2
 dQ/T < 0 r
#
Thus for all cycles, wer can write,

 dQ/T ≤ 0 Clausius inequality.

PROBLEMS

Q. A Carnot heat engine receives 500 kJ of heat per cycle from a high temperature
source at 6520c and rejects heat to a low temperature sink at 30 0C. Determine

a. the thermal efficiency of his Carnot engine

b. the amount of heat rejected to the sink per cycle

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Solution;

a. th = 1 – TL/ TH

ie, th = 1 – {(30 + 273)/ (652 + 273)} = 0.672

ie the Carnot heat engine converts 67.2% of the heat it receives to work.

b. QH/TH = QL/ TL

 QL = TL (QH/ TH)

= (30 + 273) {500/(652 + 273)} = 164 kJ

ie the Carnot heat engine rejects to a low temperature sink 164 kJ of the 500 kJ of heat
it receives during each cycle.

Q. A heat engine receives heat at the rate of 1500 kJ/min and gives an output of
8.2 kW. Determine

a. The thermal efficiency

b. The rate of heat rejection

Solution;

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a.  th = W/ QH

W = 8.2 kW = 8.2 x 103 W or J/S

QH = 1500 kJ/min = 1500 x 103/60 = 25 x 103 J/S

 th = 8.2 x 103/25 x 103 = 0.328 = 32.8 %

b. W = QH - QL

QL = QH - W

= 25 x 103 – 8.2 x 103 = 16.8 x 103 J/s = 16.8 kJ/S

Q. An inventor claims that his engine has the following specifications

Temperature limits - 7500 C and 250C

Power developed - 75 kW

Fuel burned/hr - 3.9 kg

Heating value of fuel - 74500 kJ/kg

State whether his claim is valid or not.

Solution;

For a specified temperature limits carnot cycle has the maximum thermal efficiency.

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a.  carnot = 1 - TL/ TH

= 1 - (25 + 273)/ (750 + 273) = 0.7086 = 70.86%

b. The actual thermal efficiency claimed,

th = Work done/ Heat supplied

W = 75 kW = 75 x 103 W or J/s.

Heat supplied, QH = fuel burned/sec x Heating value

= 3.9/3600 x 74500 x 103

= 80.7018 x 103 J

th = (75 x 103 )/ 80.7018 x 103 = 0.9292 = 92.92%

Since th >  carnot the claim of the inventor is not valid.

Q. Source A can supply energy at the rate of 12000 kJ/min at 3200C. A second
source B can supply energy at the rate of 120000 kJ/min at 700C. Which (A or B)
would you choose to supply energy to an ideal reversible heat energy that is to
produce large amount of power if the temperature of the surroundings is 35 0 C?

Solution;

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 A = 1 – (TL/ TA)

= 1 - (35 + 273)/ (320 + 273) = 0.4806 = 48.06%

 B = 1 - (TL/ TB)

= 1 - (35 + 273)/(70 + 273) = 0.102 = 10.2%

The work delivered in the two cases is given by:

WA = thA QA

= 0.4806 x 1200 = 5767.2 kJ/min

WB = B QB

= 0.102 x 120000 = 12240 kJ/min

Source B delivers larger output  B is selected.

REFRIGERATOR

The objective of a refrigerator is to maintain the refrigerated space at a low

temperature by removing heat from it. Discharging this heat to a higher temperature
medium is merely a necessary part of the operation, not the purpose.

The efficiency of a refrigerator is expressed in terms of coefficient of performance

(COPR).

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COPR = Desired output/ Work input = QL/ Win

Win = QH - QL

 COPR = QL/ (QH - QL) = 1/( QH/QL - 1) = 1/( TH/TL - 1) = TL/( TH - TL)

The value of COPR can be greater than one. ie, the amount of heat removed from the
refrigerator space can be greater than the amount of work input.

HEAT PUMP

Another device that transfers heat from a low temperature medium to a high
temperature one is the heat pump. The objective of the heat pump, however is to
maintain a heated space at a high temperature.

COPP = Desired output/ Work input = QH/ Win

= QH/ QH - QL = 1/(1- QL/QH) = 1/(1- TL/TH) = TH/( TH - TL)

COPP = COPR + 1 (for fixed values of QL & QH.)

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Q. The food compartment of a refrigerator is maintained at 4 0 C by removing heat
from it at a rate of 360 kJ/min. If the required power input to the refrigerator is 2 kW,
determine,

a. The coefficient of performance of the refrigerator and

b. The rate of heat rejection to the room that houses the refrigerator

Solution;

a. COPR = QL/ Win

QL = (360 x 103)/60 J/s

Win = 2 kW = 2x 103 W or J/s

 COPR = 360 x 103/60x2x103 = 3

ie., 3 kJ of heat is removed from the refrigerator space for each kJ of work supplied.

b. Win = QH - QL

 QH = Win + QL

 QH = 2 x 103 + (360 x 103)/60 = 8 x 103 J/s

Q. A heat pump is used to meet the heating requirement of a house and maintain it
at 200 C. On a day when the outdoor air temperature drops to -20C, the house is

20
estimated to lose heat at a rate of 80,000 kJ/hr. If the heat pump under these conditions
has a COP of 2.5, determine,

a. The power consumed by the heat pump and

b. The rate at which heat is absorbed from the cold outdoor air.

Solution;

a. COP HP = QH/ Win

Win = Q H/ COPHP

QH = (80,000 x 103)/3600

COP = 2.5

Win = (80,000 x 103)/(3600 x 2.5) = 8.9 kW

b. QH- QL= W

Q L = QH - W

= (80,000 x 103)/3600 - 8.9 x 103 = 13.33 kW = 48000 kJ/hr

Q. A reversible heat engine operates between two reservoirs at temperature 700 0 C

and 500 C. The engine drives a reversible refrigerator which operates between

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reservoirs at temperature of 500 C and -250 C. The heat transfer to the engine is 2500
kJ and the net work output of the combined engine refrigerator plant is 400 kJ.

a. Determine the heat transfer to the refrigerator and the net heat transfer to the
reservoir at 500 C.

b. Reconsider (i) Given that the efficiency of the heat engine and the COP of the
refrigerator are each 45% of their maximum possible values.

Solution;

Heat transfer to the refrigerant = Q3 =?

COPR = Heat extracted/ Work in = Q3/ W3 ………..(1)

But W = W1 - W2 = 400 kJ

W1 =?

 1 = 1 – T2 / T1

= 1 - (50 + 273)/ (700 + 273) = 0.668

Again 1 = W1/Q1

W1 = 1 Q1 = 0.668 x 2500 = 1670 kJ

 W2 = W1 - 400 = 1670 – 400 = 1270 kJ

COPR = Q3/Q4 – Q3 = T3/ T2 – T3 = 248/(323 – 248) = 3.306

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Substituting in (1), we get

3.306 = Q3/1270

 Heat transfer to the refrigerant, Q3 = 3.306 x 1270 = 4198.6 kJ

Net heat transfer to the reservoir at 50 0C = Q4 + Q2

Q4 = Q3 + W2 = 4186.6 +1270 = 5468.6 kJ

W1 = Q1 - Q2

ie, Q2 = Q1 - W1

= 2500 – 1670 = 830 kJ

 heat rejection to 500 C reservoir = Q2 + Q4 = 830 + 5468.6 = 6298.6 kJ

2) Efficiency of actual heat engine cycle,

 = 0.45 max = 0.45 x 0.668 = 0.3

W1 =  x Q1 = 0.3 x 2500 = 750 kJ

W1 = W1 – W = 750 – 400 = 350 kJ

COPR actual = 0.45 COPR max = 0.45 x 3.306 = 1.48

COP = Q3/ W2

Q3 = COP x W2 = 350 x 1.48 = 518 kJ, the heat rejection to refrigerant.

Heat rejected to 500 C reservoir, = Q2 + Q4

Q4 = Q3 + W2

= 518 + 350 = 868 kJ

W1 = Q1- Q2

Q2 = Q1 – W1 = 2500 – 750 = 1750 kJ

 Q2 + Q4 = 1750 + 868 = 2618 kJ

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Q) i. A reversible heat pump is used to maintain a temperature of 00 C in a refrigerator
when it rejects the heat to the surroundings at 25 0 C. If the heat removal rate from the
refrigerator is 1440 kJ/min, determine the COP of the machine and work input
required.

ii. If the required input to run the pump is developed by a reversible engine which
receives heat at 3800C and rejects heat to atmosphere, then determine the overall COP
of the system.

Solution;

1) COP of the heat pump

a) COPHP = T1/T2 - T1

= (0 + 273)/ {(25 + 273) - (0 + 273)} = 10.92

b) Work input, W =?

COP = Q1/W (Q1 because the aim is to maintain at T1 00C)

 W = Q1/ COP = 24/10.92 = 2.197 kW or kJ/sec

2) Overall COP

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Over all COP of the combined system = = Q1 / Q 3

For a reversible heat engine,

To find Q3

HE = 1 - T2/T3 = 0.54

HE = W/ Q3

 Q3 = 4.06 kJ/s

 COP combined = Q1/Q3 = 5.89

If the purpose of the system is to supply the heat to the sink at 250C, then

COP = (Q2 +Q4)/ Q3

 Q2 = Q4 + W = 24 + 2.01 = 26.01 kJ/s

 COP = (26.01 + 1.687)/ 3.697 = 7.49

Q) An ice plant working on a reversed Carnot cycle heat pump produces 15 tonnes of
ice per day. The ice is formed from water at 0 0C and the formed ice is maintained at 0 0
C. The heat is rejected to the atmosphere at 25 0 C. The heat pump used to run the ice

25
plant is coupled to a Carnot engine which absorbs heat from a source which is
maintained at 2200 C by burning liquid fuel of 44500 kJ/kg calorific value and rejects
the heat to the atmosphere. Determine

1. Power developed by the engine

2. Fuel consumed per hour

Take enthalpy of fusion of ice = 334.5 kJ/kg

Solution;

1) Amount of ice produced per day = 15 tonnes

Enthalpy of fusion of ice = 334.5 kJ/kg

 Amount of heat removed by the pump = (15 x 1000 x 334.5)/ 24 x 60

= 3484.4 kJ/min

COPHP = Q1/W = T1/ (T2 - T1)

= (273 + 0)/ {(25 + 273) – (273 + 0)} = 10.92

 W = Q1/10.92

= 3484.4/10.92 = 319.08 kJ/min

 Power developed = 319.08/60 = 5.3 kW

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2) carnot HE = W/ Q3 = (Q3 – Q4)/ Q3 = (T3 – T4)/T3 = 1– (T4 / T3)

T4 = T2

HE = 1 – {(25 + 273)/ (220 + 273)} = 0.396

 W1/ Q3 = 0.396

Q3 = W/0.396 = 5.3/0.396 = 13.38 kJ/s

Q3 per hour = 13.38 x 60 x 60 = 48168 kJ

(Total heat produced)/ (Heat by 1 kg of fuel) = Q3/ CV

 Quantity of fuel consumed/hr = 48168/44500 = 1.082 kg/hr

Q) 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. Also find the A and B.

WA = WB

W A = Q1 - Q 2

= Q2 (Q1/Q2 – 1)

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ie. WA = Q2 (T1/T2 – 1) = Q2 {(T1 – T2)/ T2} …………. (1)

WB = (Q2 - Q3) = Q2 (1 – Q3/Q2)

ie., WB = Q2 (1 – T3/ T2) = Q2 {(T2 - T3)/ T2} ………… (2)

From (1) and (2), we get

Q2 {(T1 – T2)/ T2} = Q2 {(T2 - T3)/ T2}

ie., T1 – T2 = T2 - T3

2 T2 = T2 + T3 = 550 + 350

Hence the intermediate temperature,  T2 = 450 K

A = 1 - T2/T1 = 1 – 450/550 = 0.18

B = 1 - T3/T2 = 1 – 350/450 = 0.22

ENTROPY

By Clausius inequality dQ/T ≤ 0

ie, cylic integral of dQ/T for any cycle is less than or equal to zero. It is equal to zero
for a reversible cycle and is less than zero for an irreversible cycle.

Here we have a quantity whose cyclic integral is zero for a reversible cycle. A
quantity whose cyclic integral is zero depends on the state only and not the process
path, and thus it is a property. Therefore, for a reversible cycle, the quantity dQ/T
must represent a property in the differential form which Clausius named as entropy.

It is designated as ‘S’ and is defined as, ds = dQ/T

The entropy change of a system during a reversible process from 1 to 2,

Consider a cycle that is made up of two processes, process 1- 2, which is arbitrary

(reversible or irreversible), and process 2- 1 which is internally reversible. From the
Clausius inequality,

28
dQ/T ≤ 0

which can be rearranged as

It can be also expressed in differential form as, ds  dQ/T

where the equality holds for a reversible process and the inequality for an irreversible
process.

ie, when a process is carried out from 1 to 2 reversibly the entropy change of a closed
system is equal to integral of dQ/T. When the process is carried out irreversibly the
change in entropy is greater than integral dQ/T. So when the change in entropy is
more and more greater than integral dQ/T, the process is more and more irreversible.

So entropy can be defined as the measure of irreversibility.

In a microscopic point of view, the entropy of a system increases whenever the

molecular randomness of a system increases. The molecular disorder of an isolated

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system increases anytime it undergoes a process. Thus entropy is a measure of
molecular disorder.

A process will proceed only in the direction of increase in entropy.

DEAD STATE

A system is said to be in the dead state when 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 energy relative
to the environment (zero velocity and or potential zero elevation above a reference
level), and it does not react with the environment (chemically inert). Also there are no
unbalanced magnetic, electrical and surface tension effect between the system and its
surroundings. The properties of a system at the dead state are denoted by subscript
zero, viz, P0, T0, h0, u0 & s0. Unless specified otherwise, the dead state temperature
and pressure are assumed to be T 0 = 250C and P0 = 1 atm. A system has zero
availability at the dead state.

ie no work can be produced from a system that is initially at the dead state. The
atmosphere around us contains tremendous amount of energy. However the
atmosphere is in the dead state, and energy it contains has no work potential.

EXERGY OR WOK POTENTIAL OF ENERGY OR AVAILABILITY OR

AVAILABLE ENERGY

The work potential of energy contained in a system at a specified state is the

maximum work output that can be obtained from the system. The wok output from a
system at a specified state is maximized when the process is executed in a reversible
manner to the dead state as the final state.

ie, a system will deliver 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 maximum work potential of the system at the specified state
and is called exergy or availability. It is important to realize that energy does not

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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. There is always a difference,
between exergy and the actual work delivered by a device. This difference represents
the room engineers have for improvement.

The exergy of a system at a specified stage 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.
Altering the environment is another way of increasing exergy, but it is definitely not
an easy alternative.

The maximum work done during a reversible process is when the system is brought to
the dead state.

ie; the max available part of the energy for a heat transfer Q is.

Wrev max = Q - (u0 - u1)

= Tds - (u0 - u1)

If the temperature during the process is constant T 1, then

Exergy or Wrev max = T1 (s0 - s1) - (u0 – u1)

= (u1 – T1s1) - (u0 – T1s0)

UNAVAILABLE ENERGY

Unavailable energy is the portion of energy that cannot be converted to work by even
a reversible heat engine.

Considering a system, when it reaches the dead state, the transfer of energy ceases,
and although the system contains internal energy, this energy is unavailable.

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USEFUL WORK & WORK SURROUNDINGS

The work done by a work producing device is not always entirely in a usable form.
For eg, when a gas in a piston – cylinder device expands, part of the work done by the
gas is used to push the atmospheric air out of the way of the piston. This work, which
cannot be recovered and utilized for any useful purpose, is equal to the atmospheric
pressure p0 times the volume change of the system.

Wsurr = P0 (v2 - v1) when 1 2

= P0 (v0 – v1) when 1 0

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Note that the work done by or against the atmospheric pressure has significant only
for systems whose volume changes during the process (ie systems that involves
moving boundary work). It has no significance for cyclic device and system, whose
boundaries remain fixed.

ie for constant volume system Wsurr = 0.

The difference between the max work reversible and work surroundings is the useful
work.

Wuseful = Wmax - Wsurr.

= Wmax - P0 (v0- v1)

ie Wuseful = Wrev max – P0 (v0 – v1)

= (u1 – T1s1) - (u0 - T1s0) - P0(v0 – v1)

= (u1 + P0v1 - Ts1) – (u0 +P0v0 - T1s0)

= (h1 – T1s1) – (h0 – T1s0)

IRREVERSIBILITY

The factors that cause a process to be irreversible are called irrevesibilities. They
include friction, unrestricted expansion, mixing of two fluids, heat transfer across a
finite temperature difference, electric resistance inelastic deformation of solids and
chemical reactions.

So any difference between the max reversible wok and the actual useful work is due to
the irreversibilities present during the process. This difference is called irreversibility
‘I’.

I = Wrev max - Wact useful

The irreversibility is equal to the energy destroyed for totally reversible process
irreversibility is zero. Irreversibility represents the energy that could have been

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converted to work but was not. The smaller the irreversibility associated with a
process, the greater the work that will be produced.

HELMHOLTS & GIBBS FUNCTION

The maximum work done during a non- flow reversible process executed by a system
for a heat transfer Q, when it is brought to the dead state is given by,

Wrev max = Q - (u0 – u1)

= Tds – (u0 - u1)

If the temperature during the process is constant T 1, then

Wnev max = T1 (s0 – s1) - (u0 – u1)

= (u1 – T1s1) – (u0 – T1s0)

Where (u - Ts) is known as Helmholtz function denoted by ‘f’.

A process which performs boundary work (eg: piston & cylinder) during its execution
has to do work against atmosphere which is equal t p0 (v0, v1) when the system reaches
the dead state condition.

Wuseful = Wnevmax - P0(v0 – v1)

= (u1 - Ts1) – (u0 – Ts0) – P0(v0 – v1)

= (u1 + P0v1 - Ts1) - (u0 + P0v0 – Ts0)

ie Wuseful = (h1 – Ts1) - (h0 – Ts0)

Where (h – Ts) is known as Gibbs function or Gibbs free energy denoted by ‘g’

Wuseful = g1 – g0

THIRD LAW OF THERMODYNAMICS

The entropy of a pure crystalline substance at absolute zero temperature is zero. This
statement is known as the third law of thermodynamics. The third law of
thermodynamics provides an absolute reference point for the determination of
entropy. The entropy determined relative to this point is called absolute entropy.

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