B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

THE SECOND LAW OF THERMODYNAMICS

Introduction
The First Law of Thermodynamics is essentially a statement of the principle of conservation of energy.
The energy supplied to a cyclic power plant, whether as heat or work, must be equal to the energy
delivered by the power plant, which may also be heat or work, over the same interval. The Second Law
tells us that there are limits to the relative values of the heat and work interactions. We will see that
there are several ways of expressing the Second Law, all of which yield the same results and can be
deduced from the other statements.
There are many natural events which occur or are part of processes whose direction is not determined by
energy conservation principles.

All heat engines so far designed require to reject some of the heat supplied. It has never been
found possible to convert all heat supplied into work. Designs of engines where friction and
other dissipating processes are progressively reduced approach a limiting ideal (reversible) heat
engine in which heat must be rejected to the surroundings. This despite the fact that the 1 st law
places no limit on the entire conversion of heat supplied to work in a heat engine.

If a stone is dropped into a pond a circular pattern of waves will result. The waves proceed to
the bank where eventually they are damped out. Finally the pond will be still again. The
temperature of the stone, water and the bank will be slightly higher than before. According to the
first law of thermodynamics, it should be possible to return this internal energy to the stone in
terms of potential to raise the stone to its original position. It has been found impossible to devise
even an ideal system to do this.

In a mechanical system (eg a pile of bricks) disturbing the system (eg knocking the bricks over)
causes a transfer of potential energy to internal energy of the system (bricks) and their
surroundings. It is impossible to devise a process by which the internal energy of the
surroundings can be returned such that the system returns to its original state (ordered pile).

There are many other examples of such systems and one common feature that links them all: each of the
initial processes results in a loss of order in the universe as a whole. If we could restore the order
entirely then we could be successful in each case in performing the reverse process which we know from
experience is not possible.
From experience then we become aware that natural processes are always accompanied by a loss of
order an increase in disorder in the Universe. These observations are experimental validation of what
is called the 2nd Law of Thermodynamics. There are many ways of stating this law, however we shall see
that it is very convenient to base statements of this law on the flow of heat from a hot source to a cold
source and on the heat engine. Other methods make use of the property Entropy. However as this
property is defined in terms of the 2nd Law, statements using entropy are actually corollaries of this law.
When discussing the 1st Law it is stated that heat and work are equivalent forms of energy in the sense
that conservation of energy principles can be applied to heat transfer just as work transfers across a
system boundary. However heat and work are not equivalent in the sense of order - X kJ of work are
more ordered than X kJ of heat. For example of a SI engine, heat is supplied by burning fuel and air
producing high temperature combustion products. In these products, the order of motion is low as the
gas molecules move randomly. If this gas drives a piston to produce linear and cyclic work, the work
produced is highly ordered. This example is a statement that we cannot change all the heat into work. If
we could do so we would be able to run a process in nature without increasing the disorder of the
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

universe because we would be converting all the disorder (heat) into an equivalent amount of (ordered)
work. This we know from experience that we cannot do.

The KelvinPlanck & Clausius Statements of the 2nd Law

Kelvin-Planck: It is impossible to construct a heat engine to convert the heat supplied from a single
source into an equivalent amount of work.
Clausius: It is impossible to construct a device which in a closed system operating on a cycle which can
raise heat from a cold to a hotter reservoir without receiving work from the surroundings.

Hot Reservoir, T H

Hot Reservoir, T H
Q

Q
TH > TC

W
Q
Cold Reservoir, T C
Not Possible (Kelvin-Planck)

Figure 1.

Not Possible (Clausius)

Second Law Statements

Note that if the Kelvin Plank statement is true, the Clausius is true also and visa versa.

Reversibility
A reversible process is one which takes place with the system always in thermodynamic equilibrium. We
will now argue that a reversible process may be reversed so that no changes in the system or the
surroundings is observed after the process and its reverse are complete. In a real or irreversible process
returning the system to its initial state is accompanied always by a change in the surroundings. For
example, the heat transfers for the process and its reverse may not add to zero algebraically nor will the
net work transfer be zero.
Because the reversible process involves no departure from equilibrium there can be no dissipation. There
is no heat flow down a finite temperature gradient and there is no dissipation of work to heat or of
kinetic energy of a fluids motion to heat. As a result, the process may be reversed and after the process
and its reverse are complete, there is no change in state of the universe. This may be so because any
change would have to be in the direction of an increase in disorder. But because thermodynamic
equilibrium is maintained, no increase in disorder would have occurred.
On the contrary, irreversible processes cannot be reversed without some change occurring in the
surroundings.
Consider the example of the mechanical system comprising bricks which changes from an ordered pile to
a heap of bricks on the ground. This system could be changed form one state to the other and then
returned to its original state using a system of pulleys and counterweights. Each brick could be moved
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

from its position in the pile to the ground such that all the potential energy is stored in the counterweight.
The counterweight would necessarily be infinitesimally smaller - in limit equal to the weight. The energy
in the counterweight would then be used to move the brick from the heap to its original position. It is
obvious that this process is reversible in that the universe is unchanged as there has been no dissipation
of energy to it. If we were to try to do this by using the internal energy that resulted from the pile being
knocked down then it would be impossible as the Kelvin Planck statement tells us that it is impossible
for heat engines to convert all available energy into work. This would be an irreversible process.
This illustrates a scenario for which we could probably guess intuitively which process is reversible and
which is irreversible. Let us now consider a process which is closer to the normal sphere of interest of
the thermodynamicist: the expansion of a gas.
A gas in a cylinder expands slowly while moving a light, frictionless piston with a weight on top as
shown in Figure 2. Our system boundary comprises the inner walls of the cylinder and the top of the
piston.

p ,V

Q
Figure 2

This is clearly a constant pressure process, hence the work done by the system 1, -W, is given by the
expression:
W pV

and, applying the non-flow energy equation

Q U pV

Now, consider what would happen if the weight was increased very slightly and the heat transfer was
controlled so that the pressure in the gas remained constant. The piston would now slowly fall and work
would be done on the system, as it returned to its original volume would be:
W p ( V )

and, applying the non-flow energy equation

Q U p V

Where the indicates the reversed process. Since the final state involves the gas returning to its original
state U U implying that Q Q . Both the system and the environment have been returned
to their original states. Resisted expansion is therefore a reversible process.
Let us now develop this model further - what would happen if there was friction between the piston and
the cylinder walls? Note that, in the original example, the piston was part of the system but played no
part in the analysis since it was light and frictionless. We may think of the effect of friction on the piston
in two ways. We can take a mechanical approach and say that since there is friction between the piston
and the wall the system would raise a smaller weight than before, and, in order to get the piston to return
a larger weight would be needed. The surroundings would thus do work on the system during the two
processes and would not be returned to its original condition. The second approach draws on the Second
Law- during the expansion the work done by the gas on the piston is partly converted to heat by the
friction of the moving piston (remember this is within the system) and this heat is transferred to the
surroundings. In order to restore the surroundings to their original condition it would be necessary to
1

Work done on the system is positive, but it is often convenient to use the expression
Work out W pdV Wout
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

transform this heat back into work (e.g. to place the extra weight on top of the piston). The Clausius
statement tells us this cannot be done.
No process involving solid or fluid friction can be reversible. We can, however imagine frictionless
processes. We can also repeat the assertion that resisted expansion of a gas is reversible if we consider
the system to comprise only the gas. It is then quite acceptable to imagine that the piston (now part of
the surroundings) to be replace by a frictionless piston.
When we consider our (imaginary) reversed process, providing that we do not have to invoke a machine
that would defy the Second Law, we can assume that the surroundings undergo reversible processes.
So far it has been assumed that the heat transfer to our system can occur. In fact for it to occur reversibly
the surroundings would have to include a series of heat sources and sinks which varied in temperature so
that it was always either infinitesimally above or below the temperature of the system. (we would have
difficulty in achieving this in practice, but it is not inconceivable).
Let us consider what happens when heat passes from a hot system to a cooler system with a finite
temperature difference between the two bodies.
U H U C Q

The sign indicating that the heat interaction is positive for the cold system and negative for the hot
system.
To efface this process we would have to invoke a machine which caused an equivalent amount of heat to
be transferred from the cold to the hot system with no effect on the surroundings. Such a machine would
defy the Clausius statement of the Second Law. Heat transfer through a finite temperature difference
is irreversible.

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

COROLLARIES OF THE SECOND LAW OF THERMODYNAMICS

Equivalence of statements of the Second Law
It has been stated that the Clausius statement of the Second Law may be regarded as the first corollary
of the Kelvin-Planck statement. In this note the link between the two is established and seven more
corollaries are introduced, all of which have an important place in thermodynamic analysis.
Firstly we shall show that the Clausius statement and the Kelvin-Planck statements are equivalent. To do
this we shall follow a line of argument which is common in this type of analysis. We will assume that the
statement which we wish to prove is untrue, and then examine the implications of this assertion. In this
case the statement under investigation says that it is impossible to construct a cyclic system which
receives heat from a cold reservoir and delivers an equivalent amount of heat to a reservoir at a higher
temperature without work being done on the system by the surroundings. If this is not true then we can
imagine the device A in Fig.3 to exist. We know that we can construct heat engines which receive heat
from a high temperature reservoir, produce work and deliver the remainder of the heat to a low
temperature reservoir; such a machine is shown as B in Figure 3.
High Temp. Reservoir
& Q W
Q
in
out

& Q
Q
out
A

&
W
out

B
& Q
Q
in

& Q
Q
out

Low Temp. Reservoir

Figure 3, Illustration used in proof of Clausius statement.

Now let us redraw our system boundary to include A, B and the low temperature reservoir. This new
system receives heat from the high temperature reservoir and delivers an equivalent amount of work,
thus defying the Kelvin-Planck statement of the Second Law. Since the only part of the system which we
do not know to be possible is the machine A then A must be impossible. Therefore the Clausius
statement, telling us that machine A is cannot exist, must be true. It is left to the student to show that the
converse is true. That is, if the Clausius statement is valid then the Kelvin-Planck statement is must also
hold. Students should satisfy themselves that this is indeed the case.
Efficiency of Reversible Heat Engines
Corollary 2. It is impossible to construct a heat engine operating between two reservoirs which has
a higher efficiency than a reversible engine operating between the same two reservoirs.
This corollary can be proved by considering two heat engines one being reversible, R, and one being
irreversible, X. The reversible engine can be operated in reverse as a refrigerator. Remembering that the
& the efficiencies of the engines X and R are:
& Q
efficiency of a heat engine is defined W
out
in
W
W
x R and X X
Q1
Q1
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

Let us suppose that X R then WX >WR2 hence, as can be seen from Fig. 4, with the reversible engine
reversed a system can be devised such that there is a net work output while the system exchanges heat
with one reservoir only. This is impossible, therefore the WX cannot be larger that WR. The reversible
engine must have the higher efficiency.
Note that if we construct the same system with an engine having efficiency, X, less than the reversible
efficiency, R. then the system will have a net work input. It is quite feasible to have a system with a
work input which rejects an equivalent amount of heat to the surroundings.

H ig h T e m p . R e s e rv o ir
& Q
Q
out
1

& Q
Q
in
1
& W W
W
out
x
R

WR

RR

X
& Q W
Q
in
1
R

& Q W
Q
out
1
x

L o w T e m p . R e s e rv o ir
Figure 4. System to demonstrate corollary 2
Having demonstrated that no heat engine can have a higher efficiency than a reversible engine then it is a
simple step to deduce Corollary 3. All reversible engines operating between the same two reservoirs
have the same efficiency. If this was not the case one reversible engine must be more efficient than the
other, in contravention of corollary 2.
The Thermodynamic Temperature Scale
Consideration of the Second Law allows us to devise a 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.
If we consider a reversible engine operating between two reservoirs, each at constant temperature, then
Corollaries 2 and 3 tells us that its efficiency must be a function only of the temperatures of the
reservoirs. The efficiency is given by3:

&
The value of Q
out

&
&
W
Q
out
&
1 out
&
Qin
Q
in
&
Qin is thus a function only of the temperature of the reservoirs.
& Q
& f T ,T
Q
out
in
out
in

With reference to Figure 5, we can consider A to be a reversible engine operating between a high
temperature reservoir at T1 , and a low temperature reservoir at T2. This engine must have the same
2

For convenience the work output is regarded as positive in this discussion.

This expression for the efficiency of a cyclic heat engine is a consequence of the First Law of Thermodynamics, The
Second Law leads us to relate the efficiency to the temperature of the heat source and sink.
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

overall as the combined efficiency of two reversible engines X and Y which operate in series. Engine X
operates between T1 and an intermediate temperature Ti and Y operates between Ti and T2.
H ig h T e m p . R e s e rv o ir
&
Q
in
X

&
Q
in
&
& Q& Q
W
out, X
in
i
& Q
&
& Q
W
out, A
in
out

&, T
Q
i
i
&
W

out,Y

& Q
&
Q
i
out

&
Q
out

&
Q
out
L o w T e m p . R e s e rv o ir
Figure 5 Heat engines operating between two temperature levels
&
Q
out, A
a 1 &
,
Qin,A
&
Q
X 1 & i ,
Qin,X

&
Q
1 out,Y ,
&
Q
i

X Y

&
Q
out, A
f (T1, T2 )
&
Q
in, A

&
Q
i
f (T1, Ti )
&
Q
in, X

&
Q
out,Y
f (Ti , T2 )
&
Q
i

&
&
Q
Q
1 out,Y 1 out,A
&
&
Q
Q
in, X
in, A

&
&
&
&
Q
Q
Q
Q
i
x out,Y out,Y out,A
&
&
&
&
Q
Q
Q
Q
in, X
i
in, X
in,A
f T1, T2 f T1, Ti x f Ti , T2

This tells us that f T1, T2 must be of the form f T1 f T2 but an infinite variety of functions could be
chosen having this property. The simplest function is:
&
Q
T1
in, A

(for the general case)

T2 Qout,A

&
Q
1
&
Q2

Thus, once a specific fixed temperature is defined then, in principle, the temperature of any reservoir
could be measured by determining the efficiency (or heat input and output) of a reversible heat engine
operating between the temperature to be measured and the reference temperature. This is the
Thermodynamic Scale of Temperature. It is a consequence of the Second Law of Thermodynamics and
independent of any fluid property.
The efficiency of any reversible heat engine operating between T1 and T2 (T1>T2) is given by:
T
T
rev 1 2 1 low
T1
Thigh
Since it is not possible to construct a practical reversible heat engine thermometer it is convenient to see
how the thermodynamic scale of temperature compares with other temperature scales.
If we fix the temperature of the hot reservoir at any arbitrary temperature then the relationship:
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

&
T1
Q
1 (for a reversible cycle)
&
T2 Q
2

may be expressed

& T
Q
2
2

This implies that as the temperature of the cold reservoir is reduced the heat rejected tends to zero. If
this was achieved then we would contravene the Second Law. However it does demonstrate that
negative temperatures are not possible on this scale and the zero of the thermodynamic scale is an
absolute zero.
The Carnot Cycle:
Let us consider a perfect gas operating on a Carnot Cycle. This is a fully reversible cycle which operates
between two reservoirs, each at constant temperature. It is represented on the pV diagram as Figure 6.
The Cycle comprises a reversible isothermal compression (during which heat is transferred from the
system) from A to B; an adiabatic compression from B to C; an isothermal expansion (during which heat
is transferred to the system) from C to D; and, finally, an adiabatic expansion from D to A.
For each process we can write an expression for the relationship between the pressure and volume.
p
Thigh

Qin
D

pAVA pBVB Isothermal process

pBVB pC VC Adiabatic process
pC VC pDVD Isothermal process

Tlow
B

pDVD pAVA Adiabatic process

A
Qout
V

Figure 6, The Carnot Cycle

(Note - Processes shown schematically - all process lines should be curves)
Eliminating p:

VD
V
A
VC
VB

The heat interactions occur during the isothermal processes. Since, for each of these processes:
Q W U c v T 0

We can write:

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

& RT ln VB
Q
out
low
VA
& RT ln VD
Q
in
high
VC

Hence:

&
Q
T
out
low
&
Thigh
Qin

Therefore:

Tlow
Thigh
The Carnot Cycle must have the same efficiency as any reversible cycle operating between the two
temperatures Thigh and Tlow. Clearly the expressions for the efficiency are the same whether the ideal gas
temperature scale or the thermodynamic temperature scale is used.
This implies that the
thermodynamic temperature scale and the ideal gas temperature scale are identical.

Carnot 1

The Clausius Inequality

Many cycles which are implemented in practical refrigerators and power plants operate with heat being
received and rejected during processes which involve a change in temperature of the working fluid. The
Rankine Cycle is an example of such a cycle. We may regard these cycles as being equivalent to a
number of cycles each operating between distinct temperature levels. Since Corollary 3 tells us that all
reversible cycles operating between the same two reservoirs must have equal efficiencies it is acceptable
to substitute one reversible cycle for another or a series of reversible cycles for one cycle.
The Rankine Cycle is sketched on a T-s diagram in Figure 7 together with a representation of the
equivalent Carnot Cycles. We can see that the Rankine Cycle receives heat at a temperature ranging
from the exit temperature of the feed pump to the steam saturation temperature, Tmax. Heat is rejected at
the condenser temperature, Tmin.

Tmax

T
Tmin

S
Figure 7, Rankine Cycle and Equivalent Carnot Cycles
The efficiency of a Carnot Cycle operating between these temperatures would be:

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

Tmin
Tmax
Each of the infinitesimal Carnot Cycles operating between Tmin and Tint, where Tint<Tmax has an efficiency:
T
int min 1 min max min
Tint
The resulting efficiency of the cycles which have replaced the Rankine Cycle must be less than the
efficiency of a reversible cycle with all heat reception at Tmax and all heat rejection at Tmin.

max min 1

This argument could be generalised to any arbitrary range of temperatures of heat reception and
rejection, leading to Corollary 5: The efficiency of any reversible engine operating between more
than two reservoirs (i.e. more than two temperature levels) must be less than that of a reversible
engine operating between two reservoirs having the maximum and minimum temperatures of the
fluid in the original engine.
If we consider an engine operating between two temperature levels, T1 and T2 we can write4:
rev 1

Q&
T2
1 2,rev
T1
Q&1,rev

T2 Q&2,rev

T1 Q&1,rev
Q&1,rev
Q&1,rev
T1

T1
Q&

2,rev

T2

Q&2,rev
T2

If we consider some arbitrary, but reversible, cycle operating between several hot and cold reservoirs we
could replace this cycle with a large number of reversible cycles each operating between only two
temperatures. The heat interactions and temperature level for each such cycle can be written:
Q&in,rev
T
in
&
Qout,rev Tout

Q&in,rev
Tin

Q&in,rev Q&out,rev

Tin
Tout
Q&
out,rev 0
Tout

Therefore, for the large number of infinitesimal cycles making up the total cycle, we can write,
remembering the convention that heat in is +ve and heat out of the system is -ve:

and, in the limit:

&
Q
rev
0
T

&
dQ
rev
0
T

Reverting to the consideration of a single infinitesimal cycle and allowing for real (i.e. irreversible)
cycles, if we maintain the same temperature levels then the efficiency must be less than that for a
reversible cycle. For a given heat input the rate of heat rejected for the irreversible cycle must be greater
than that for the reversible cycle. Remembering that:
4

The subscript rev denotes the heat supplied or rejected for a reversible cycle. Since we are going to start comparing
reversible and real or irreversible cycles this distinction has now become necessary.
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

&
&
Q
Q
in,rev
out,rev

0
Tin
Tout

Clearly:

&
&
Q
Q
in,irrev
out,irrev

0
Tin
Tout
Then as for the case of reversible cycles we can look at the total cycle and say:

Q&irrev
T 0

and, in the limit:

&
dQ
irrev
0
T

For the general case we can write:

&
dQ
0
T

Students should satisfy themselves that this argument can be applied to heat pump or refrigeration cycles.
This is known as the Clausius Inequality and may be stated as Corollary 6: Whenever a system
undergoes a cycle, (dQ T ) is zero if the cycle is reversible and negative if the cycle is irreversible.
Examples
1

Work W kJ is done on a system operating in a cycle exchanging heat with only one heat reservoir
at temperature T K

Heat Q (=W) must be dissipated to reservoir T

Q
T

Q Q
W

0
T
T
T
(- Q)

2.

In a closed system 1 kg of air initially at 200oC is raised to 3000C by heat exchange with a
reservoir in the surroundings whose temperature is always 10 K higher than that of the air. The
air is cooled back to 200OC by heat rejection to a reservoir in the surroundings whose
temperature is always 10 K less than the air. The pressure of the air is maintained constant.
Apply the Clausius Inequality to this problem and show how the process could be made
reversible.

Heat Reservoir
310oC
o

210 C

300oC

200oC

290oC

QC = m cp T

200oC
190oC

QH = m cp T

Heat Reservoir

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

Q
cp
T
cycle

573

473

dT
cp
T 10

473

573

dT
T 10

583
463
c p ln
ln
1.005 0.1882 0.1956 0.007 kJ / K
563
483

The answer is < 0 and therefore the process is irreversible. Clearly as the temperature difference across
the heat exchange is reduced to zero Q/T 0, ie the process becomes reversible.
Entropy
We are now in a position to define the property Entropy, if we now consider a closed system changing
2
dQ
state from 1 - 2 as a consequence of a reversible process we can show that
must be the same for
T
1
any reversible process linking the states 1 and 2.
2
C
Property Y

B
A

Property X
Figure 8 - Proof that entropy is a property
If we consider a cycle made up of the reversible processes A and C we can write:
2
1
dQ
dQ

dQ
T AC 1 T A 2 T 0
C
We can then describe another cycle incorporating the reversible process B
2
1
dQ
dQ

dQ
T BC 1 T B 2 T 0
C

Comparing these expressions we can see that:

2
2
dQ dQ
1 T A 1 T
B
Since we have said nothing about the nature of the processes A and B, other than that they are reversible,
2
dQ

the value of the integral

must be the same for all reversible processes linking state 1 and 2. We
T rev
1
can therefore define a property such that:
2

dQ
T
1

rev

dQ
T

rev

S2 S1
dS

The existence of Entropy is the 7th corollary of the Second Law.

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

The property S is the entropy of the system and is independent of the path from 1 to 2, only upon the
end state. It is therefore possible to determine the entropy change between two states whether the system
moved from 1 to 2 by a reversible or an irreversible process. It is, however, useful to invoke a reversible
process (or series of reversible processes) linking the states in order to carry out the calculation.
Entropy has the units of J/K or, more conveniently, kJ/K, and, for a pure substance may be expressed in
the form of specific entropy, i.e. the entropy per unit mass of the substance. For steam-water substance
entropy is tabulated in the steam tables. For a perfect gas there are techniques for calculating the
changes in entropy between two states.

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

Entropy Changes during reversible and irreversible processes

2
C
Property Y

B
A

Property X
Figure 9, Entropy Change during an Irreversible Process
Consider a reversible cycle made up of processes A and B:
2
1
dQ
dQ

dQ
T AB 1 T A 2 T 0
B
and compare this with a cycle incorporating the irreversible process C, the Clausius Inequality tells us
that:
2
1
dQ
dQ

dQ
T CB 1 T C 2 T 0
B
hence:
2

dQ
1 T

dQ

T
1

Since A is a reversible process,

dQ

T
1
2

S2 S1
A

dQ S S
2
1
T C
1
Nothing has been said about the processes considered except that C is irreversible therefore this solution
is general:
2
dQ
S2 S1

T
1
or
dQ
ds
T

The equals sign pertains to a reversible process and the greater than sign represents an irreversible
process. The 8th Corollary may thus be stated: if a system is thermally isolated from its
surroundings then, during any process, its entropy remains constant (if the process is reversible) or
increases. A slightly different statement of this corollary is given in below.

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

Isentropic Processes and Isentropic Efficiency

We will now revise the special class of processes which involve no heat transfer and, if reversible, occur
at constant entropy. (i.e. dQ=dS=0 throughout). Such processes are called isentropic.5
Turbines, compressors and pumps (and the individual processes within them) are frequently regarded as
adiabatic6. The standard against which these components can be measured is thus the work interaction
which would occur if a given mass of fluid were to expand (or be compressed) isentropically.
Example
A steam turbine is supplied with steam at 350oC,15 bar and the outlet pressure is 1 bar. Calculate the
maximum work output per kg of steam. Kinetic and Potential Energy changes may be neglected.
From Tables
15 bar
1

T
1 bar
2f
2

2g

h1 3148kJ / kg
s1 7.102kJ / kgK
s 2 ' 7.102kJ / kgK
s 2 f 1.303kJ / kgK
s 2 g 7.359kJ / kgK
s 2 fg 6.056kJ / kgK
h2 f 417 kJ / kg
h2 fg 2258kJ / kg

A process can involve heat interactions and remain at constant entropy although it is irreversible. The term isentropic is
limited to adiabatic reversible processes
6
A notable exception is the compression of a gas (e.g. air) which is to be used at ambient temperature. In this situation the
compressor is deliberately cooled and the ideal stasndard is that of a reversible isothermal compression.
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x2'

s2' s2 f
s2 g s2 f

s2s s2 f
s 2 fg

7.102 - 1.303
6.056

0.957
h2 ' h2 f xh2 fg 417 0.957 x 2258
2579kJ / kg
wout , s h1 h2 ' 3148 2579
569kJ / kg

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

In practice, we know that the work output will be less than the ideal due to fluid friction etc. We can
account for this by introducing the concept of isentropic efficiency. For a work producing device, for
which changes in KE and PE are small, this is defined:
isen

w
h1 h2
actual for a work producing device
h1 h2 '
wout , s

Thus, if the turbine in our example has an isentropic efficiency of 80% the work output would be given
by:
w out isen w out ,s 0.8 x 596 476.8kJ / kg
If required, properties at state 2 can then be calculated.
For a work absorbing device (compressor, fan, pump etc) the work required for compression will be
greater than that needed for isentropic compression.
isen

win , s
h1 h2 '

h1 h2
win , actual

for a work absorbing device

(Note that texts differ in the definition of the isentropic point is identified eg. as 2S or 2)
Change in Entropy of the Universe
For any process it has been shown that:
ds

dQ
T

where the equals sign pertains to a reversible process and the greater than sign represents an
irreversible process.
For the surroundings, the heat transfer must be -dQ, and the change in entropy assuming that the heat is
transferred to the surroundings reversibly, is given by:
dssurroundings

Combining these gives:

dQ
Tsurroundings

dsuniverse dssystem dssurroundings 0

The entropy of the Universe thus increases in any real process or remains constant if only reversible
processes are considered. This is essentially a re-statement of corollary 8; the Universe is, by definition,
thermally isolated.
Calculation of the entropy generated can be used to test whether a process is reversible (= 0), irreversible
(> 0) or impossible (< 0).
(For an example of heat loss from a system consider a condenser in a steam power cycle. Cooling water
is used to condense the low pressure steam from the turbine exhaust. For the cycle, the heat is a loss,
but to the cooling water, this heat is a gain. In other words, heat loss from a cycle is always a heat gain
by the environment.)

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Example
Consider heat transfer from a system comprising a piston and cylinder arrangement containing a
saturated mixture of steam and water at a constant pressure of 1.01 bar. The outer walls of the cylinder
are exposed to the atmosphere at 25 oC and, over a period of time 1200kJ of heat is transferred to the
surroundings. Calculate the entropy change of the water steam substance, the entropy change of the
surroundings and the entropy change of the Universe.
Solution
The process occurs at constant pressure and, assuming that all the steam does not condense, the
temperature of the system will remain at 100oC throughout the process. Since and there are no internal
irreversibilities within the system boundary, the entropy change of the system may be calculated:
Ssystem

Qsystem
Tsystem

1200kJ
322
. kJ / K
373K

The entropy change for the surroundings, also at constant temperature may be calculated:
S surroundin gs

Qsurroundin gs
Tssurroundi ngs

1200kJ
4.02kJ/K
298K

The sum of the entropy changes gives us the temperature change for the Universe.
SUniverse S system S surroundin gs
3.22 4.02 0.8 kJ/K

The entropy increase of the Universe increases suggesting the process is possible. It is irreversible.
It is clear that the reverse process (heat transfer from the surroundings at 25oC to the system at 100oC) is
impossible. It would violate the Clausius statement of the Second Law of Thermodynamics.
Examination of the solution above shows that, if the reverse process was suggested, it could easily be
shown to result in a decrease in the Entropy of the Universe, another demonstration of its impossibility.
If we take the example a little further and consider the system to be operating at a lower temperature e.g.
50oC it can easily be shown that the entropy increase of the Universe will be less than it was for the
system at 100oC.
SUniverse S system S surroundings

1200 1200

323
298
3.72 4.02 0.3 kJ/K

In the limit the temperature of the system may be considered to be at a temperature infinitesimally higher
than the surroundings:
SUniverse S system S surroundin gs

1200 1200

298
298
4.02 4.02 0 kJ/K

The process of heat transfer through an infinitesimally small temperature difference is reversible, and
according to the Second Law it is possible. It is, however, impractical.
Calculation of Entropy changes for particular fluids
The above example is very contrived - most practical processes involve changes in both temperature and
pressure of the system. Generally when calculating changes in entropy we use the fact that entropy is a
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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

property of state, therefore, the change in entropy for a process depends only upon the initial and final
states, not upon the path of the process. The change in entropy calculated for a reversible process is the
change in entropy between the two states considered, irrespective of the actual process taking the system
between the states.
Consider the case of a system comprising a fixed mass, m, of liquid or solid (i.e a substance which has no
appreciable change in volume with temperature). The change in entropy between state 1 at T1 and state 2
at T2
2
dQrev
S
T
1
and the heat supplied may be calculated from:
mcdT
giving:
2
dT
S mc
T
1
which, for the case of constant specific heat with temperature, may be integrated to give:
T
S mc ln 2 for a substance at constant volume
T1
The limitation of the above to the case of constant volume is excessively restrictive. A more general
derivation of more useful equations for calculating entropy changes it is necessary to consider the First
and Second Laws of Thermodynamics in combination.
The First Law applied to unit mass of any substance may be stated 7:
dQ dW du

Expressions for the reversible work and heat transfer are:

dW pdv
dQ Tds

Thus:

Tds pdv du

Because this equation contains only properties of state it is true for any type of process.
Remembering that specific enthalpy is defined by h=u+pv we can write:
dh =du +pdv +vdp

leading to:

dh Tds vdp

Since these equations relate properties of a substance, they must hold for any process, whether it is
reversible or not.
Application to Perfect Gases
7

The convention that work done by the systen is +ve is applied here. If the convention that work done on the system is +ve
then the derivation is:

dQ dW du

dW pdv
dQ Tds
Tds pdv du
giving the same result.

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Using the above relationships we can determine the dependence of entropy on pressure, temperature and
volume for an ideal gas. For an ideal gas we can say:
pv RT

du cvdT
dh cpdT

Thus:

cvdT Tds pdv

or, rearranging:
ds cv

dT p
dv
T T

ds cv

dT
dv
R
T
v

and, since R v p T , we can write:

Since cv can be regarded as a constant, this equation can be integrated between states 1 and 2 to give:
s 2 s1 c v ln

T2
v
R ln 2
T1
v1

irrespective of the process linking states 1 and 2.

Similarly, expressions may also be derived:
T2
p
R ln 2
T1
p1
v
p
s2 s1 cp ln 2 cv ln 2
v1
p1

s2 s1 cp ln

It has been noted that many processes involving gases can be represented by an equation of the form:
pvn constant

For an isentropic process:

s2 s1 0 cp ln

hence:

v2
p
cv ln 2
v1
p1

cp ln v2 cv ln p2 cp lnv1 cv ln p1

or:

cp lnv cv ln p constant

which, together with the definition cp cv , leads to the expression: pv constant

Example of entropy change of system and surroundings
2.5 kg of hydrogen initially at 10 bar, 20oC is compressed to 50 bar irreversibly poloytropically.
Calculate the entropy change of the gas if the index of compression is n = 1.2. Calculate also the entropy
change of the surroundings of a system containing the gas if the compression work is 5000 kJ and the
heat is exchanged with the surroundings at 10oC ( for hydrogen is 1.4).
Solution
p
State
1

P
10

T
293.15

2
pV1.2 = constant

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B53EO1 Mechanical Engineering Science 7a: The Second Law of Thermodynamics

50
(bar)

(m3)

(K)

R = 8.31/2 = 4.16 kJ/kgK

cp cv = R and = cp/cv
(1.4 1) cv = 4.16 thus cv = 10.4 kJ/kgK

1
V

pV mRT
m R T 2.5 4.16 293.15
V1

3.05 m 3
p
10 100
V2 p1

V1 p 2
T2 p 2

T1 p1

1
n

n 1
n

10
V2 3.05

50

1
1 .2

50
T2 293.15

10

0.797 m 3
0 .2
1.2

T
V
S 2 S1 m c v ln 2 R ln 2
T1
V1

383.3 K

383.3
0.797
2.5 10.4 ln
4.16 ln

293.15
3.05

6.83 kJ / K

(note that entropy decreases due to the system becoming more ordered)
U 2 U 1 m cv T2 T1 2.5 10.4 383.3 293.15 2344 kJ
Q1 2 W U 5000 2344 2656 kJ

(this a heat gain of the surroundings as heat is lost by the system)

Q ( 2656)

9.38 kJ / K
T
283.15
S system S surroundings 6.83 9.38 2.55 kJ / k

S surroundings
S universe

The entropy of the universe has increased.

Loss of Available Work

The loss of available work to the system is
surroundings.

Loss of AE = S x To where To are the temperature of the

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