Module-6

2nd law of Thermodynamics, Entropy & Clausius-Clapeyron

Relation.
According to first law of thermodynamics, energy is always conserved. The possibility or impossibility of
putting energy to use is the subject of the second law of thermodynamics. It also describes the directionality
of natural thermodynamic processes. It can be stated in several equivalent forms.

Equivalent Statements Of The Second Law Of Thermodynamics:

The Kelvin statement:

For example, it is easy to convert mechanical work completely into thermal energy, but it is impossible to
remove thermal energy from a system and convert it completely into mechanical work with no other changes.
This experimental fact is one statement of the second law of thermodynamics.

“It is impossible to remove thermal energy from a system at a single temperature and convert it to
mechanical work without changing the system or surroundings in some other way”.

Second Law of Thermodynamics: Kelvin Statement

The Clausius statement:

If we place an ice cube on a hot day, the ice cube will melt. From the point of view of energy, what has
happened is that some of the heat from the surrounding air enters the ice cube, raising its temperature, and
eventually melting it. The surrounding air subsequently cools somewhat. However, nothing from energy
conversion, or Newton’s law in general, would prevent heat from leaving the ice cube, making the ice cube
colder and the surrounding air warmer. Why then doesn’t this later phenomena occur?

A common example of the conversion of mechanical energy into thermal energy is movement with friction.
For example, when a block slides along a rough table, the initial mechanical [kinetic] energy of the block is
converted into thermal energy as the block and the table are heated. The reverse process never occurs- a
block and table that are warm will never spontaneously cool by converting their thermal energy into kinetic
energy that sends the block sliding across the table. Thus there is a lack of symmetry in the roles played by
heat and work. This lack of symmetry is related to the fact that some processes are irreversible. It may be
mentioned that thermodynamic processes that occur in nature are all irreversible.

Let us take the case of heat conduction which is an irreversible process. If we place a hot body in contact
with a cold body, heat will flow from the hot body to the cold body until they are at the same temperature.
The reverse does not occur; heat does not flow from one to the other making one colder and the other
warmer.

The answer lies in the Clausius statement of the 2nd law of thermodynamics, which can be written as:

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“A processs whose only
y final result is to transferr thermal ene
ergy from a cooler object to a hotterr one is
impossible””.

Second
d Law of Therm
modynamics:: Clausius Sta
atement

In other words,
w “Hea
at never flo
ows sponta
aneously frrom low te
emperature
e to high
temperatture”.

The Refri
rigerator sttatement:

Refrigera
ator:

It is imposssible to makee heat flow frrom a body at

a a lower tem mperature to a body at a higher temp perature
without doiing external work on the working sub bstance. Ene ergy will not flow spontan neously from
m a low
temperature e object to a higher
h temperature object.. This preclud
des a perfect refrigerator.
r

“No cycclic process can

c transfer heat
h from a colder
c place to a hotter place with no input of mecchanical
work”.

Second Law of Thermod

dynamics: Re
efrigerator Sta
atement

The Heatt-engine sttatement:

The study of
o the efficien
ncy of heat en
ngines gave rise to the firsst clear state
ements of the second law. A heat
engine is a cyclic device
e whose purpoose is to convvert as much heat input intto work as posssible. Heat engines
e
contain a working
w substance [water in a steam engine, air anda gasoline vapor in an internal-combustion
engine] that absorbs a quantity of hea
at QH, does work
w W and gives off heat QC as it return
ns to its initial state.
When we analyze
a heat engines, it he
elps us to thiink of two bo
odies with which the working substance e of the
engine can n interact. Onne of these, called the hot reservoir, represents thet heat source; it can give
g the
working subbstance large e amounts of heat at a connstant temperrature TH with
hout appreciabbly changing its own
temperature e. The other body,
b called the
t cold reserrvoir, can abssorb large ammounts of disccarded heat frrom the
engine at a constant lowwer temperatuure TC. In a stteam turbine system,
s the fllames and hoot gases in the
e boiler
are the hott reservoir, an
nd the cold water
w and air used to condense and coolc the used steam are th he cold
reservoir.

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We denote the quantitiees of heat tra
ansferred from
m the hot and
d cold reservvoirs as QH and QC, respe ectively.
When an en ngine repeats
s the same cyycle over and over, QH and
d QC represennt the quantitiies of heat ab
bsorbed
and rejected by the engine during one
e cycle.
The useful output of the engine is the
e net work W done
d by the working
w substtance. From the first law,

W  Q  Q H  QC  Q H  QC .

We define thermal
t ency of an engine, denoted
efficie d by e as the quotient

W Q Q
e  1 C  1 C
QH QH QH

“No cyclic process

p can convert
c heat completely
c intto work”.

Second Law dynamics: Heat-engine Sta

w of Thermod atement

This statem
ment of the Se
econd law in terms of the efficiency off a heat engin
ne (Kelvin-Pla
anck stateme
ent) can
also be writtten as:

“Th
he efficiency of
o a heat engiine can neverr be 100% or more preciseely and techniically: The ma
aximum
effiiciency of an engine
e which operates bettween two tem
mperatures iss given by the
e Carnot efficie
ency”:

The Entro
ropy statem
ment:

The second d law, is rather different frrom many fam miliar physica n an equation or a quan
al laws. It is not ntitative
relationship
p but rather a statement off impossibilityy. However, thhe second law w can be statted as a quan
ntitative
relation with
h the conceptt of entropy.

Adding hea
at to a body increases its disorder beca
ause it increaases averagee molecular sppeeds and th
herefore
the random
mness of mo olecular motioon. Further expansion
e off a gas incre
eases its dissorder becau
use the
molecules have
h greater randomness of position affter the expan
nsion than beffore.

Thus there are two types

s of disorder in
i a substancce:

 position
nal disorder---refers to the
e distribution of
o the particle
es in space.
 thermall disorder--re
efers to the distribution of the
t available energy
e amonng the particle
es.

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Entropy and disorder:
Entropy provides a quantitative measure of disorder. To introduce this concept, let us consider an arbitrary
reversible quasi-static process in which a system consisting of an ideal gas absorbs an amount of heat dQ.
According to the first law, dQ is related to the change in the internal energy dU of the gas and the work done
dW = PdV by

dQ  dU  dW  dU  PdV

For an ideal gas, we can write dU in terms of the heat capacity, dU  C V dT , and we can substitute nRT / V
for P from the equation of state. Then

dV
dQ  C V dT  nRT
V
We can write the Equation as

dQ dT dV
 CV  nRT
T T V
The gas is in a more disordered state after the expansion than before because the molecules are moving in
dV
a larger volume and have more randomness of position. Thus the fractional volume change is a
V
dQ
measure of the increase in disorder, and the above equation shows that it is proportional to the quantity
T
dT
. The term is a measure of thermal disorder which refers to the distribution of the available energy among
T
the particles.
We introduce the symbol S for the entropy of the system, and we define the infinitesimal entropy change dS
during an infinitesimal reversible process at absolute temperature T as

dQ dT dV
dS   CV  nR
T T V
For simplicity, we will assume that CV is constant. Integrating this equation, we get

dQ T V
S   T
 CV ln 2  nR ln 2
T1 V1

The above Equation gives the entropy change of an ideal gas that undergoes a reversible expansion from an
initial state of volume V1 and temperature T1 to a final state of volume V2 and temperature T2. When an ideal
gas undergoes an isothermal expansion, T2 = T1 and its entropy change is

dQ V
S   T
 nR ln 2
V1

If a total amount of heat Q is added during a reversible isothermal process at absolute temperature T, the
total entropy change S  S 2  S 1 is given by

Q
S  S 2  S 1 
T
The SI unit of entropy is J/K.

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We can generalize the definition of entropy change to include any reversible process leading from one state
to another, whether it is isothermal or not. We represent the process as a series of infinitesimal reversible
steps. During a typical step, an infinitesimal quantity of heat dQ is added to the system at absolute
dQ
temperature T. Then we sum [integrate] the quotients for the entire process; that is,
T
2
dQ
S  
1
T
The limits 1 and 2 refer to the initial and final states.
Because entropy is a measure of the disorder of a system in any specific state, it must depend only on the
current state of the system, not on its past history. The change in entropy defined by the above equation
does not depend on the path leading from the initial to the final state but it is the same for all possible
processes leading from state 1 to state 2.
Since entropy is a function only of the state of a system, we can also compute entropy changes in
irreversible processes for which above equations are not applicable.

ENTROPY AND THE SECOND LAW:

The results of Example about the flow of heat from a higher to a lower temperature, or the mixing of
substances at different temperatures, are characteristic of all natural [that is, irreversible] processes. When
we include the entropy changes of all the systems taking part in the process, the increases in entropy are
always greater than the decreases. In the special case of reversible process, the increases and decreases
are equal. Hence we can state the general principle: When all systems taking part in a process are
included, the entropy either remains constant or increases. In other words, no process is possible in
which the total entropy decreases, when all systems taking part in the process are included. This is
an alternative statement of the second law of thermodynamics in terms of entropy. Thus it is equivalent to the
“engine” and “refrigerator” statements discussed earlier.
The increase of entropy in every natural, irreversible process measures the increase of disorder or
randomness in the universe associated with that process. Consider again the example of mixing hot and cold
water. We might have used the hot and cold water as the high- and low-temperature reservoirs of a heat
engine. While removing heat from the hot water and giving heat to the cold water, we could have obtained
some mechanical work. But once the hot and cold water have been mixed and have come to a uniform
temperature, this opportunity to convert heat to mechanical work is lost irretrievably. The lukewarm water will
never unmix itself and separate into hotter and colder portions. No decrease in energy occurs when the hot
and cold water are mixed. What has been lost is not an energy, but opportunity, the opportunity to convert
part of the heat from the hot water into mechanical work. Hence when entropy increases, energy becomes
less available, and the universe becomes more random or ”run down”.

The statement of the second law is in terms of entropy:

“The entropy of a closed system never decreases or equivalently: The change in entropy of the universe is
always greater than or equal to zero”:

∆Suniv  0.

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Change in entropy for different processes:

(1) Entropy changes of a closed system during a reversible process:

A 2

P B
C
1

Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from
state 2 to state 1 along the path B. Since it is a reversible cyclic process

dQ
 T
0

2A
dQ dQ
 
1B
 0 …………………. (i)
1A
T 2B T
Now, consider the reversible cycle from state 1 to 2 along the path A from state 2 to state 1 along path C. For
this reversible cyclic process
2A
dQ 1C dQ
1 A T  2C T
0 …………………… (ii)

1B
dQ 1C dQ
From equations (i) and (ii) 2 B T  2C T

dQ
This shows that  T
has the same value for all the reversible paths from state 2 to state 1. This quantity

is independent of path and is a function of the end states only, therefore it is a property. This property is
dQ
called entropy and defined by the relation dS 
T
The change in entropy is then the inverse of the temperature integrated over the change in heat transfer.
2 2
dQ

1
dS  
1
T
2
dQ
S2  S1   T
1

The quantity S2 – S1 represents the change in entropy of the system when it is changed from state 1 to state
2.

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 (2) Entropy changes of a closed system during an Irreversible process:

Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from
state 2 to state 1 along the path B. For a reversible cyclic process

 dQ  0. 2
2A 1B
dQ dQ
1 A T  2 B T  0 ……………………….. (i) A
B
Now consider an irreversible path C from state 2 to state 1. P
Applying Clausius inequality for the cycle of process A and C C
dQ
 T
0 1 irreversible

2A 1C
dQ dQ
1 A T   0 V
So, …………………………
2C
T
(ii)
From equations (i) and (ii)
1B 1C
dQ dQ
2 B T  
2C
T
0

Since path B is reversible and entropy is a property

1B 1B 1C
dQ
2 B T  2BdS  2CdS
dQ
 dS 
T
2
dQ
or S2 – S1  
1
T
The above equation shows that the effect of irreversibility is always to increase the entropy of a system.

(3) Adiabatic Process: We know that the heat absorbs in a reversible adiabatic process is zero. Hence,
for such a process entropy change is given by

dQ
 dS   T
0

S = Constant
That is Entropy of a system remain constant for a reversible adiabatic process.

(4) Isothermal process: If Q amount of heat absorbed during an isothermal process at constant
temperature T, the change of entropy,
dQ Q
dS   T

T

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Change in Entropy (Carnot’s Cycle):

(1) Reversible process: In a Carnot cycle, the change in entropy of the working substance is zero.
This reversible system consists of a source at T1, the working substance and the sink at T2. The loss
of entropy (here heat is denoted by Q) of the source is Q 1 and the gain of entropy of the sink is Q 2
T1 T2
. The net gain of entropy of the system is
Q1 Q2
dS = ( - ).
T1 T 2
Q1 Q2
We know, for Carnot cycle =
T1 T 2

Q1 Q2
- =0
T1 T 2
That is entropy of the whole system remains constant.

(2) Irreversible process: The efficiency of an irreversible engine absorbing heat Q1 at T1 and
rejecting heat Q2 at temperature T2 is given by
Q1  Q 2
 
Q1
T1  T2
Again, the efficiency of a reversible engine is given by  , working between the same two
T1
temperatures.

According to Carnot theorem,   

Q1  Q 2 T  T2
Or, < 1
Q1 T1
Q2 T
Or, 1- <1- 2
Q1 T1
Q 2 T2
Or, >
Q1 T1
Q2 Q1
Or, >
T 2 T1
Q2 Q1
Or, - >0
T 2 T1
Q2 Q
is the gain in entropy of the sink and 1 is the loss of entropy of the source. The change of entropy of
T2 T1
the working substance is zero as it returns to the original state at the end of a complete cycle.
Q2 Q1
The net gain in entropy of the system = - = positive.
T 2 T1
So the entropy increases in a irreversible process.

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Clausius-Clapeyron Relation:
The Clausius-Clapeyron relation, in thermodynamics, is a way of characterising the phase transition
between two states of matter, such as solid and liquid. On a pressure-temperature (P-T) diagram, the line
separating the two phases is known as the coexistence curve. The Clausius-Clapeyron relation gives the
slope of this curve

Mathematically,
dP L

dT TV

dP
where is the slope of the coexistence curve, L is the latent
dT
heat, T is the temperature, and ∆V is the volume.
H E
Consider the isothermals FBAE at temperature T + dT and GCDH
at temperature T. Here EA and HD show the liquid state of the A T+dT B
substance. At A and D the substance is purely in the liquid state dP
(as shown in Fig.). From A to B or D to C the substance is in C F
P D T
transition from the liquid to the gaseous state and vice versa. At B
G
and C the substance is purely in the gaseous state. From B to F or
C to G the substance is in the gaseous state. Join A to D and B to
C by dotted lines. V1 V2
V
The cycle ABCD represents a complete cycle and Carnot’s
theorem can be applied. Suppose the volume at the point A is V1 and temperature T+dT. The presssure is
just below its saturation pressure and the liquid begins to evaporate and at the point B the volume is V2. The
substance is in the vapour state.
Suppose the mass of the liquid at B is one gram. The amount of heat absorbed is Q1.

Here Q1 = L + dL
Where, L + dL is the latent heat of the liquid at temperature (T + dT).

At the point B, the pressure is decreased by dP. The vapour will expand and its temperature T, the gas
begins to condense and is converted into the liquid state. At the point D, the substance is in the liquid state.

From C to D, the amount of heat rejected is Q2.

Here Q2 = L, where L is the latent heat at temperature T.

By increasing the pressure a little, the original point A is restored. The cycle ABCDA is completely reversible.
Applying the principle of the Carnot’s reversible cycle
Q1 Q 2 Q 1 T1
 or 
T1 T2 Q 2 T2
Q 1  Q 2 T1  T 2

Q2 T2
dL dT
 
L T
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The area of the figure
ABCD = Q1 –Q2 = dL Here, Q1 = L + dL, Q2 = L,
= dP (V2 – V1) T1 = T + dT, T2 = T
Q1 – Q2 = L + dL - L = dL
dP (V 2  V1 ) dT
  T1 – T2 = T + dT – T = dT
L T
dP L
                 (1)
dT T (V 2  V1 )

This is called the Clapeyron’s latent heat equation.

Applications:

(1) Effect of change of pressure on the melting point.

When a solid is converted into a liquid, there is change in volume.
dP
(i) If V2 is greater than V1, then is a positive quantity.
dT
It means that the rate of change of pressure with respect to temperature is positive. In such cases, the
melting point of the substance will increase with increase in pressure and vice versa.
dP
(ii) If V2 is less than V1, then is a negative quantity.
dT
It means that the rate of change of pressure with respect to temperature is negative. In such cases, the
melting point of the substance will decrease with increase in pressure and vice versa. In the case of melting
ice, the volume of water formed is less than the volume of ice taken. Hence, V2  V1.
Therefore, the melting point of the ice decreases with increase in pressure. Hence ice will melt at a
temperature lower than zero degree centigrade at a pressure higher than the normal pressure. Ice melts at 0
o
C only at a pressure of 76 cm of Hg.

(2) Effect of change of pressure on the boiling point.

When a liquid is converted into a gaseous state, the volume V2 of the gas is always greater than the
corresponding volume V1 of the liquid i.e. V2 > V1.
dP
Therefore, is a positive quantity.
dT
With increase in pressure, the boiling point of a substance increases and vice versa. The liquid will boil at a
lower temperature under reduced pressure. In the case of water, the boiling point increases with increase in
pressure and vice versa. Water boils at 100 oC only at 76 cm of Hg pressure. In the laboratories, while
preparing steam, the boiling point is less than 100 oC because the atmospheric pressure is less than 76 cm
of Hg. In pressure cookers, the liquid boils at a higher temperature because the pressure inside is more than
the atmospheric pressure.

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