Engineering Thermodynamics 43

CHAPTER 2 Second Law Entrophy and Availability

____________________________________________________

In this chapter the idea of cycle efficiency in introduced and the Second Law is then
stated and distinguished from the First Law. Formal definition of a reversible process is
made and its implications both for non-flow and steady-flow processes are discussed.

CYCLE EFFICIENCY

When a closed system undergoes a series of non-flow processes, during which the fluid
passes through a cycle of thermodynamic states, the First Law can be expressed as

∑δQ = ∑δW

If Q1 is the heat supplies, Q2 the heat rejected and W the net work done by the system
during the cycle, the First Law becomes

Q 1 – Q2 = W (6.1)

A system operating in a cycle and producing a net quantity of work from a supply of
heat is called a heat engine. The greater the proportion of the heat supply converted
into work, the better the engine is. Consequently the cycle efficiency of a heat engine is
defined as

workdone W
η= = (6.2)
heat sup plied Q1

Hence, from equations (6.1) and (6.2), we have

Q1 − Q2
η= (6.3)
Q1

The efficiency of any heat engine operating on either a closed system or an open cycle,
consisting of steady-flow processes, can also be expressed by equation (6.3). In this
case Q1 and Q2 must be interpreted either as the heat supplied and rejected per unit
mass flowing round the circuit, or as the rates of heat supplied and rejected.
 Engineering Thermodynamics 44

THE SECOND LAW OF THERMODYNAMICS

Consider the following isolated systems with well-defined initial states:

We have never observed the reverse to occur, but it does not violate the 1st Law. However,
there is a directionality of a process. You can make the reverse happen, but it does not occur
SPONTANEOUSLY.

More observations

The direction of spontaneous change for a ball bouncing on a floor. On each bounce
some of its potential energy is degraded
into the thermal motion of the atoms of the
floor, and that energy disperses into the
atoms of the floor. The reverse has never
been observed to take place.
The reverse, if it occurs, does not violate the
1st Law as long as the energy is conserved.
Recall also that only a small amount of
thermal energy is required to make the ball
jump very high.
 Engineering Thermodynamics 45

Hence, the first Law only states that the net work cannot be produced during a cycle without
some supply of heat. However, First Law never says that some proportions of heat supplied to
an engine must be rejected. Hence, as per the First Law, cycle efficiency can be unity, which is
impossible in practice. All that First Law states that net work cannot be produced during a cycle
without some supply of heat, i.e. that a perpetual motion machine of the first kind is impossible.
So, the 1st Law is not enough. Something is missing! What is missing? A law that can tell us
about the direction of spontaneous change. The Second Law of Thermodynamics tells us about
the directionality of the process. We need it to ensure that systems we design will work. As we
will see later, ENTROPY is a property that we have invented (like internal energy) that will allow
us to apply the 2nd Law quantitatively.

HEAT ENGINE, HEAT PUMP, REFRIGERATOR

Energy reservoirs: Thermal energy reservoirs (TER) is defined as a large body of infinite
heat capacity, which is capable of absorbing or rejecting an
Hot Reservoir
unlimited quantity of heat without suffering appreciable
Q1
changes in its thermodynamic coordinates.
W
Source: TER from which heat is transferred to the system
(Q1-Q2)
Q2 operating in a heat engine cycle.

Cold Reservoir Sink: TER in which heat is rejected from the cycle during a
cycle.
Heat engine
Heat Engine cycle is a thermodynamic cycle in which there is
a net heat transfer to the system and a net work transfer from the system. The system,
which operates in heat engine cycle is called heat engine.

workdone (Energy we want ) W Q1 − Q2 Q

Efficiency , η = = = = 1− 2 ≤ 1
heat sup plied (Energy we pay ) Q1 Q1 Q1

Refrigerator: A device which operating in a cycle maintains a body at a temperature

lower than the temperature of the surroundings.
 Engineering Thermodynamics 46

Atmosphere, T1 Body, T1

Q1 Q1 (=Q2 + W)

W
T2 < T1 W T1 > T2
(Q1-Q2)
Q2 Q2

Body, T2 Atmosphere, T2

Refrigerator Heat pump

Q2 (Energy we want ) Q2
COPRef = =
W (Energy we pay ) Q1 − Q2

Heat Pump: A device which operating in a cycle maintains a body at a temperature

higher than temperature of surroundings

Q1 (Energy we want ) Q1
COPHP = = = COPRef + 1
W (Energy we pay ) Q1 − Q2

Engineering Examples:

A. System (gas) – undergoes a cycle.

 Engineering Thermodynamics 47

From our experience, the reverse cycle does not occur. W < 0 and Q < 0 are possible but W > 0
and Q > 0 are not. However, neither violates the 1st Law.

B. Heat transfer from high T to low T: only one direction is possible, so it is impossible to
complete a cycle. This leads us to heat engines and refrigerators – devices that can do the
opposite. What are the limitations on these devices?

The Second Law states that some heat must be rejected during the cycle and hence,
the cycle efficiency is always less than unity.

Thus the First Law states that net work cannot be greater than heat supplied, while the
Second Law goes further and states that it must be less than heat supplied.

If energy is to be supplied to a system in the form of heat, the system must be in contact
with a reservoir whose temperature is higher than that of the fluid at some point in the
cycle. Similarly, if heat is to be rejected, the system must be at some time be in contact
with a reservoir of lower temperature than the fluid. Thus Second Law implies that if a
system is to undergo a cycle and produce work, it must operate between two reservoirs
of different temperatures. A machine which will work continuously, while exchanging
heat with only a single reservoir, is known as a perpetual motion machine of the second
kind (PMM II); such a machine contradicts Second Law.

Heat source It is now possible to see why a ship could not be driven by
an engine using the ocean as a source of heat, or why a
Q
power station could not be run using the atmosphere as a
source of heat. They are impossible because there is no

W natural sink of heat at a lower temperature than the

atmosphere or ocean, and they would therefore be PMM II.
PMMII It should be noted that Second Law does not restrict that
work cannot be continuously and completely converted to
heat. In fact, a fluid in a closed vessel may have work done on it and the heat thus
generated is allowed to cross the boundary. The rates of work and heat may be made
equal and the internal energy of the system remaining constant. An important
consequence of Second law is work is a more valuable form of energy transfer than
 Engineering Thermodynamics 48

heat as heat can never be transformed continuously and completely to work, whereas
work can always be transformed continuously and completely to heat.

The following statements summarise the obvious consequences of the Second Law:

a) If a system is taken through a cycle and produces work, it must be exchanging heat
with at least two reservoir at different temperatures,

b) If a system is taken through a cycle while exchanging heat with one reservoir, the
work done must be zero or negative,

c) Since heat can never be continuously and completely converted into work whereas
work can always be continuously and completely converted into heat, work is more
valuable form of energy transfer than heat.

THE KEIVIN-PLANK’S STATEMENT OF THE

SECOND LAW

It is impossible to construct a system,

which will operate in a cycle, extract heat
from a reservoir and do an equivalent
amount of work on the surroundings.

THE CLAUSIUS STATEMENT OF THE

SECOND LAW

It is impossible to construct a system, which

will operate in a cycle and transfer heat from
a cooler to a hotter body without work being
done on the system by the
surroundings.(Corollary 1)
 Engineering Thermodynamics 49

EQUIVALENCE OF KELVIN PLANK’S AND CLAUSIUS STATEMENTS.

Proof: Suppose the converse of the Clausius’ proposition is true. The system can be

represented by a heat pump for which W = 0. If it takes Q units of heat from the cold
reservoir, it must deliver Q units to the hot reservoir to satisfy the First Law. A heat
engine could also be operated between the two reservoirs; let it be of such a size that it
delivers Q units of heat to the cold reservoir while performing W units of work. Then the
First Law states that the engine must be supplied with (W + Q) units of heat from the hot
reservoir. In the combined plant, the cold reservoir becomes superfluous because the
heat engine could reject its heat directly to the heat pump. The combined plant
represents a heat engine extracting (W + Q) – Q = W units of heat from a reservoir and
delivering an equivalent amount of work. This is impossible according to Kelvin-Plank’s
statement of Second Law. Hence converse of Clausius’ statement is not true and the
original proposition must be true.
 Engineering Thermodynamics 50

Reversibility and irreversibility

The Second Law of Thermodynamics enables us to divide all processes into two
classes:

a) Reversible or ideal process.

b) Irreversible or natural process.

A reversible process is one, which is performed in such a way that at the end of the
process, both the system and the surroundings may be restored to their initial states,
without producing any changes in the rest of the universe. Let the state of a system be
represented by a, and let the system be taken to state b by following the path a-b. In the

Wa-b
b

a b

Wb-a

A reversible process

reverse process, the system is taken from state b to a by following the same path b-a. If
the system and also the surroundings are restored to their initial states (a) and no
change in the universe is produced, then the process a-b will be a reversible process.

A reversible process is carried out infinitely slowly with an infinitesimal gradient, so that
every state passed through by the system is an equilibrium state.

Any natural process carried out with a finite gradient is an irreversible process. A
reversible process, which consists of a succession of equilibrium states, is an idealised
hypothetical process, approached only as a limit. All spontaneous processes are
irreversible.
 Engineering Thermodynamics 51

Causes of Irreversibility:
• Friction

• Unrestrained expansion

• Heat transfer through a finite temperature difference

• Mixing of two different substances

The lack of equilibrium (mechanical, thermal or chemical) between the system and its
surroundings, or between two systems, or two parts of the same system, causes a
spontaneous change, which is irreversible. Heat transfer through a finite temperature
difference, free expansion are some examples.

The irreversibility of a process may be due to the dissipative effects in which work is
done without producing equivalent increase in the kinetic or potential energy of the
system. Friction, transfer of electricity through a resistor are some examples.
Question: If all the heat cannot be converted into work, then what is the maximum possible
efficiency?

Maximum efficiency is achieved by reversible engines, which must

• Always be in equilibrium.
• Avoid friction.
• Avoid heat transfer. If we must have heat transfer it should be through infinitesimal
temperature differences ‘dT’ not finite ‘ΔT’.

CARNOT CYCLE

A Carnot cycle consists of

a) A reversible isothermal process in which heat Q1 enters the system reversibly from
a constant temperature source of T1

Q1 = U2 – U1 + W1-2

b) A reversible adiabatic process (isentropic process) in which work WT is done by

the system adiabatically and reversibly at the expense of its internal energy.

0 = U3 – U2 + W2-3
 Engineering Thermodynamics 52

Q1

Heat Exchanger (A), T1

WT
WP

Heat Exchanger (B), T2

Q2
Carnot Engine

c) A reversible isothermal process in which heat Q2 is rejected from the system

reversibly from a constant temperature source of T2

-Q2 = U4 – U3 – W3-4

d) A reversible adiabatic process (isentropic process) in which work WP is done by

the system adiabatically and reversibly at the expense of its internal energy.

0 = U1 – U4 – W4-1

Net work done = Wnet = WT – WP = Q1 – Q2

REVERSIBLE ENGINES OPERATING BETWEEN ONLY TWO RESERVOIRS

Carnot’s Theorem: It is impossible to construct an engine operating between only two heat

reservoirs, which will have a higher efficiency than a reversible engine operating between the same

two reservoirs. (Corollary 2)

 Engineering Thermodynamics 53

Proof. Assume the converse of this proposition is true. Let X be such an engine having an
efficiency ηX. Let it receive heat Q1 from the source, does work WX, and reject heat (Q1 – WX) to
the sink. Then it is assumed that ηX > ηR, where ηR is the efficiency of a reversible engine R
operating between the same two reservoirs (a). If the reversible engine also receives heat Q1
from the source, it will do work WR such that WR < WX and the heat rejected will be (Q1 – WR)

Q1 Q1 Q1 Q1

Net WR
WX WR

(W W )
(Q1-WX) (Q1-WR) (Q1-WX) (Q1-WR)

(a) (b)
which is greater than (Q1 – WX). Let the reversible engine be reversed and act as heat pump
(b). It now receives heat (Q1 – WR) from the low temperature reservoir, receives work WR from
the surrounding and rejects heat Q1 to the high temperature reservoir. If the engine X is coupled
to the heat pump such that the engine X receives heat Q1 directly from the heat pump, then the
combined plant represents a heat engine receiving heat (Q1 – WR) - (Q1 – WX) = (WX - WR) from
the surroundings and delivering an equivalent amount of work. According to Second Law this is
impossible and the assumption ηX > ηR cannot be true. Consequently the original proposition
must be true.

Corollary 3: All reversible engines operating between the same two reservoirs have the
same efficiency.

Since all reversible engines operating between the same two reservoirs have the same
efficiency, this efficiency must depend upon the only feature, which is common to them all viz.
the temperature of the reservoirs. It is called Carnot efficiency.
 Engineering Thermodynamics 54

THERMODYNAMIC TEMPERATURE SCALE

Corollary 4. A scale of temperature can be defined which is independent of any particular
thermometric substance, and which provides an absolute zero of temperature.

Let us consider the reversible engine operating

Hot Reservoir
between two reservoirs represented symbolically in
Figure. Corollary 3 implies that its efficiency depends QO
only on the temperature of the reservoirs, and
W
therefore that it is independent of the particular
properties of the working fluid and of the quantity of Q1
heat Q0 supplied to the engine. But
Cold Reservoir
Q0 − Q1 Q
η= = 1− 1
Q0 Q0

and hence it follows that Q1/Q0 is a function only of the temperatures of the reservoirs.

Q1
∴ η = 1− = φ (T1 , T0 )
Q0

Q1
Now = φ (T1 , T2 )
Q2
 Engineering Thermodynamics 55

Q2
= φ (T2 , T3 )
Q3

Q1
= φ (T1 , T3 )
Q3

Q1 Q1 Q2
Since =
Q3 Q 2 Q 3

∴ φ(T1,T3) = φ(T1,T2) x φ(T2,T3)

Since, the left side of the above equation is a function of T1 and T3, the right hand side of the equation will be a function of T1 and T3.

Hence we can conclude that

f (T1 ) f (T2 )
φ (T1 , T2 ) = and φ (T2 , T3 ) =
f (T2 ) f (T3 )

Q1 f (T1 )
∴ = φ (T1 , T3 ) =
Q3 f (T3 )

QL f (TL )
In general =
QH f (TH )

QL TL
Lord Kelvin proposed that =
QH TH

With temperature so defined,

QL T
η = 1− = 1− L
QH TH

If Q is measured for several sinks at

different temperatures and plotted against QO
the relation between Q and T, we obtain a
temperature scale, which is linear in Q. The
temperature scale so defined is called the Q
thermodynamic scale, because it depends
solely on the thermodynamic law and not
T TO
 Engineering Thermodynamics 56

upon the properties of any particular substance.

The thermodynamic scale is an absolute scale because it presents us with the idea of an
absolute zero, i.e. T = 0 when Q = 0. The Second Law states that Q can in fact never be zero,
and we may therefore deduce that absolute zero is a conceptual limit and not a
temperature, which can ever be reached in practice. Thus it appears that a definite zero
point exists on absolute temperature scale but this point cannot be reached without violation of
the Second Law. Hence, the Third Law of Thermodynamics can be stated as: It is
impossible by any procedure to reduce the temperature of any system to absolute zero in
a finite number of operations.

What we have learned so far:

• The 2nd Law tells us the direction of spontaneous change.

• The 2nd Law gives us the maximum possible efficiency (coefficient of performance) of a
heat engine (refrigerator).
• A reversible process is one in which both the system and the surroundings can be
returned to their original state.
• To achieve the maximum possible efficiency, we must have a reversible engine
(frictionless, adiabatic, isothermal heat transfer, quasi-equilibrium)
• One realisation of such an engine is a Carnot engine.
• All reversible engines have the same efficiency.
• This maximum efficiency depends only on the temperature of the reservoirs – this yielded
the thermodynamic temperature scale (K).
 Engineering Thermodynamics 57

Entropy- A Measure of disorder /Irreversibility

The Second Law says that spontaneous change will occur only in a certain direction.

These processes are called irreversible. There are many factors that make the process
irreversible, such as

• Friction

• Unrestrained expansion

• Heat transfer through a finite temperature difference

• Mixing of two different substances

Question: Is there any way to quantify the degree of irreversibility?

CLAUSIUS INEQUALITY
δQ
Whenever a system undergoes a cycle, ∫ T
is zero if the cycle is reversible and

δQ
negative if irreversible, i.e. in general ∫ T
≤ 0.

For a Reversible Engine

∫ δQ = Q H − QL > 0, since W = QH - QL

While defining the absolute temperature scale, we

showed that
QH TH Q Q
= or H = L
QL TL TH TL
 Engineering Thermodynamics 58

δQ QH QL
Which gives us ∫ T
= −
TH TL
=0

For Irreversible Engine

Wirr < Wrev since W = QH - QL
Hence, QH - QL,irr < QH - QL,rev
i.e. QL,irr > QL,rev
δQ QH QL,irr
Therefore, ∫ T
=
TH
−
TL
<0

Hence, for any cycle (reversible or irreversible) we get,

δQ
∫ T
≤ 0.

Consequences of the Second Law for non-flow process

ENTROPY – A Property of the System
Corollary: There exists a property of a closed system such that a change in its value is
2
δQ
equal to ∫
1
T
for any reversible process undergone by the system between state 1 and

state2.
Proof.

2
δQ
Let us assume that ∫ 1
T
depends upon the

reversible process as well as upon the states.

Consider two reversible processes A and C by
which the system can change from state 1 to state
2. The assumption is that
2 2
⎛ δQ ⎞ ⎛ δQ ⎞
∫1 ⎜⎝ T ⎟⎠ A ≠ ∫1 ⎜⎝ T ⎟⎠C
In each case, let the system returns to its original state by a third reversible
process B. For each of the complete reversible cycles AB and CB we have
 Engineering Thermodynamics 59

2 1
⎛ δQ ⎞ ⎛ δQ ⎞ ⎛ δQ ⎞
∫ ⎜⎝ T ⎟⎠AB = ∫1 ⎜⎝ T ⎟⎠A + ∫2 ⎜⎝ T ⎟⎠B
2 1
⎛ δQ ⎞ ⎛ δQ ⎞ ⎛ δQ ⎞
and ∫ ⎜⎝ T ⎟⎠CB = ∫1 ⎜⎝ T ⎟⎠C + ∫2 ⎜⎝ T ⎟⎠B
If the assumption is true then it follows that
⎛ δQ ⎞ ⎛ δQ ⎞
∫ ⎜⎝ ⎟ ≠∫⎜
T ⎠ AB
⎟
⎝ T ⎠CB
But this cyclic integral must be equal since they are zero for a reversible cycle
2
δQ
(Claussius inequality). Hence, ∫
1
T
is independent of the path of the reversible process

and represents the change in property of the system.

If the property is denoted by S, this corollary can be expressed mathematically as
2
⎛ δQ ⎞
∫ ⎜⎝
1 T
⎟ = S2 − S1
⎠rev
or in the differential form as
⎛ δQ ⎞
dS = ⎜ ⎟
⎝ T ⎠rev
This property S is called entropy of the system.
Entropy change in a process
Let us assume A and B are reversible processes
and C is an irreversible process. For the reversible
cycle consisting of A and B
2 1
⎛ δQ ⎞ ⎛ δQ ⎞ ⎛ δQ ⎞
∫ ⎜⎝ T ⎟⎠AB = ∫1 ⎜⎝ T ⎟⎠A + ∫2 ⎜⎝ T ⎟⎠B = 0
2 1
⎛ δQ ⎞ ⎛ δQ ⎞
or ∫1 ⎜⎝ T ⎟⎠A = − ∫2 ⎜⎝ T ⎟⎠B
For the irreversible cycle consisting of B and C, by
the inequality of Clausius
2 1
⎛ δQ ⎞ ⎛ δQ ⎞ ⎛ δQ ⎞
∫ ⎜⎝ T ⎟⎠CB = ∫1 ⎜⎝ T ⎟⎠C + ∫2 ⎜⎝ T ⎟⎠B < 0
 Engineering Thermodynamics 60

2 2
⎛ δQ ⎞ ⎛ δQ ⎞
Hence, − ∫ ⎜ ⎟ +∫⎜ ⎟ <0
1⎝
T ⎠ A 1 ⎝ T ⎠C
2 2
⎛ δQ ⎞ ⎛ δQ ⎞
i.e. ∫1 ⎜⎝ T ⎟⎠A > ∫ ⎜⎝
1
⎟
T ⎠C
Since the process A is reversible
2 2
⎛ δQ ⎞
∫1 ⎜⎝ T ⎟⎠A = ∫ (dS)
1
A

Since entropy is a property, changes for the path A and C would be the same.
Therefore,
2 2

∫ (dS)
1
A = ∫ (dS)
1
C

2 2
⎛ δQ ⎞
Hence, ∫ (dS)
1
C > ∫ ⎜⎝
1
⎟
T ⎠C
Thus for an irreversible process,
δQ
dS >
T
whereas for a reversible process
⎛ δQ ⎞
dS = ⎜ ⎟
⎝ T ⎠rev
Therefore in general
δQ
dS ≥
T
2
δQ
or S2 − S1 ≥ ∫
1
T
For an isolated system which does not undergo any energy interchange with the
surroundings, δQ = 0.
Therefore for an isolated system dS ≥ 0.
For a reversible system, dS = 0 or S = constant.
 Engineering Thermodynamics 61

Thus the entropy for an isolated system can never decrease. It always increases and
remains constant only when the process is reversible. This is known as entropy
principle.

Change of Entropy for special Reversible processes:

⎛ δQ ⎞ ⎛ δQ ⎞
dS = ⎜ ⎟ or s2 − s1 = ⎜ ⎟
⎝ T ⎠rev ⎝ T ⎠rev
1) Adiabatic
⎛ δQ ⎞
δQ = 0 or dS = ⎜ ⎟ =0
⎝ T ⎠rev
Reversible adiabatic is known as isentropic process.
2) Isothermal
1
2
(Q1−2 )rev
s2 − s1 =
TH ∫ (δQ)
1
rev =
TH
or (Q1−2 )rev = T (s2 − s1 )

Summary
• Since entropy is a property, it does not matter how we get from state 1 to state 2. Thus,
we can choose the most convenient reversible path to compute the integral.
• S2 – S1 is independent of the process – once evaluated, it is the same for all processes.
• Entropy of all pure substances is taken to be zero at T = 0 K.
• In the absence of chemical reactions, an arbitrary reference may be selected as in the
case of internal energy and enthalpy. (e.g. sf = 0 at triple point for water).
 Engineering Thermodynamics 62

ENTROPY OF PURE SUBSTANCE

In the saturated region:

s = (1-x) sf + x sg or s = sf + x sfg
where, s is specific entropy in kJ/kg K = S / m.

ENTROPY CHANGE OF AN IDEAL GAS

From First Law: δQ = du + δW = du + pdv
For a reversible process:
⎛ δQ ⎞
⎜ ⎟ = ds or δQ = T ds (from Second Law)
⎝ T ⎠rev
Hence,
Tds = du + pdv
Again
dh = du + d(pv) = du + pdv + vdp
So
Tds = dh – vdp
Hence, the general property relations are
Tds = du + pdv
 Engineering Thermodynamics 63

Tds = dh – vdp
For ideal gas,
du = Cv dT ; dh = CP dT and pv = RT
The entropy change between two states 1 and 2 can be computed as
du p
ds = + dv
T T
dv
= Cv dT + R
v
Hence,
T2 v
s2 − s1 = Cv ln + R ln 2
T1 v1

Again
p1v1 p2 v 2 v 2 ⎛ p1 T2 ⎞
= or =⎜ ⎟
T1 T2 v1 ⎜⎝ p2 T1 ⎟⎠

T2 ⎛p T ⎞
∴ s2 − s1 = Cv ln + R ln ⎜⎜ 1 2 ⎟⎟
T1 ⎝ p2 T1 ⎠

T2 ⎛p ⎞
or s2 − s1 = (Cv + R ) ln − R ln ⎜⎜ 1 ⎟⎟
T1 ⎝ p2 ⎠

T2 ⎛p ⎞
i.e. s2 − s1 = CP ln − R ln ⎜⎜ 1 ⎟⎟
T1 ⎝ p2 ⎠

T2
Similarly, substituting for we get
T1

p2 v
s2 − s1 = Cv ln + CP ln 2
p1 v1

For Constant Volume Process

p1 p2 T2
= ; Hence s2 − s1 = Cv ln
T1 T2 T1
For Constant Pressure Process
v1 v 2 T2
= ; Hence s2 − s1 = CP ln
T1 T2 T1
 Engineering Thermodynamics 64

For Adiabatic Process

s2 = s1
For Isothermal Process
v2 p
P1v1 = p2v2 ; hence s2 − s1 = R ln = − R ln 2
v1 p1