Module-3: 2nd law of Thermodynamics & Entropy, Clausius-

Clapeyron Relation, and Maxwell’s Thermo dynamical Relation

Introduction:

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:

“A process whose only final result is to transfer thermal energy from a cooler object to a hotter one is
impossible”.

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 Second Law of Thermodynamics: Clausius Statement

In other words, “Heat never flows spontaneously from low temperature to high
temperature”.

The Refrigerator statement:

Refrigerator:

It is impossible to make heat flow from a body at a lower temperature to a body at a higher temperature
without doing external work on the working substance. Energy will not flow spontaneously from a low
temperature object to a higher temperature object. This precludes a perfect refrigerator.

“No cyclic process can transfer heat from a colder place to a hotter place with no input of mechanical
work”.

Second Law of Thermodynamics: Refrigerator Statement

The Heat-engine statement:

The study of the efficiency of heat engines gave rise to the first clear statements of the second law. A heat
engine is a cyclic device whose purpose is to convert as much heat input into work as possible. Heat engines
contain a working substance [water in a steam engine, air and gasoline vapor in an internal-combustion
engine] that absorbs a quantity of heat QH, does work W and gives off heat QC as it returns to its initial state.
When we analyze heat engines, it helps us to think of two bodies with which the working substance of the
engine can interact. One of these, called the hot reservoir, represents the heat source; it can give the
working substance large amounts of heat at a constant temperature T H without appreciably changing its own
temperature. The other body, called the cold reservoir, can absorb large amounts of discarded heat from the
engine at a constant lower temperature TC. In a steam turbine system, the flames and hot gases in the boiler
are the hot reservoir, and the cold water and air used to condense and cool the used steam are the cold
reservoir.
We denote the quantities of heat transferred from the hot and cold reservoirs as Q H and QC, respectively.
When an engine repeats the same cycle over and over, QH and QC represent the quantities of heat absorbed
and rejected by the engine during one cycle.
The useful output of the engine is the net work W done by the working substance. From the first law,

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 W = Q = Q H + QC = Q H − Q C .

We define thermal efficiency of an engine, denoted by e as the quotient

W Q Q
e= = 1+ C = 1− C
QH QH QH

“No cyclic process can convert heat completely into work”.

Second Law of Thermodynamics: Heat-engine Statement

This statement of the Second law in terms of the efficiency of a heat engine (Kelvin-Planck statement) can
also be written as:

“The efficiency of a heat engine can never be 100% or more precisely and technically: The
maximum efficiency of an engine which operates between two temperatures is given by the Carnot
efficiency”:

The Entropy statement:

The second law, is rather different from many familiar physical laws. It is not an equation or a quantitative
relationship but rather a statement of impossibility. However, the second law can be stated as a quantitative
relation with the concept of entropy.

Adding heat to a body increases its disorder because it increases average molecular speeds and therefore
the randomness of molecular motion. Further expansion of a gas increases its disorder because the
molecules have greater randomness of position after the expansion than before.

Thus there are two types of disorder in a substance:

• positional disorder--refers to the distribution of the particles in space.

• thermal disorder--refers to the distribution of the available energy among the particles.

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.

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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 a
dV
larger volume and have more randomness of position. Thus the fractional volume change is a measure
V
dQ
of the increase in disorder, and the above equation shows that it is proportional to the quantity . The
T
dT
term is a measure of thermal disorder which refers to the distribution of the available energy among the
T
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 + nRT
T T V
For simplicity, we will assume that CV is constant. Integrating this equation, we get

dQ T V
∆S = ∫ = C V ln 2 + nRT ln 2
T 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 V 2 and temperature T2. When an ideal
gas undergoes an isothermal expansion, T2 = T1 and its entropy change is

dQ V
∆S = ∫ = nRT ln 2
T 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.
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

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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 is 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 18-10 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”:

ΔSuniv >= 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 1 B dQ
∫
1A
T
+∫
2B T
=0 …………………. (i)

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
∫ T ∫2C T = 0
1A
+ …………………… (ii)

1B
dQ 1C dQ
From equations (i) and (ii) ∫ T ∫2C T
2B
=

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
∫dS = ∫
1 1
T
2
dQ
S 2 − 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
C
dQ
Applying Clausius inequality for the cycle of process A and C ∫ ≤0
T 1 irreversible
2A 1C
dQ dQ
So, ∫
1A
T
+∫
2C
T
≤0 ………………………… V
(ii)
From equations (i) and (ii)
1B 1C
dQ dQ
∫2 B T − 2∫C 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 S 2 – 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

Change in Entropy (Carnot’s Cycle):

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 (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
Q1 Q2
of entropy (here heat is denoted by Q) of the source is T and the gain of entropy of the sink is T
1 2

. The net gain of entropy of the system is

Q1 Q 2
dS = ( - ).
T1 T2
Q1 Q 2
We know, for Carnot cycle =
T1 T2

Q1 Q 2
- =0
T1 T2
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
η′ =
Q1
T1 − T2
Again, the efficiency of a reversible engine is given by η= , working between the same two
T1
temperatures.

According to Carnot theorem, η′ < η

Q1 − Q 2 T1 − T2
Or, <
Q1 T1
Q2 T2
Or, 1- <1-
Q1 T1
Q2 T2
Or, >
Q1 T1
Q 2 Q1
Or, >
T2 T1
Q 2 Q1
Or, - >0
T2 T1
Q2 Q1
is the gain in entropy of the sink and 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.

Q 2 Q1
The net gain in entropy of the system = - = positive.
T2 T1
So the entropy increases in a reversible 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 ΔV 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 D C F
P 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
V1 V2
C by dotted lines.
V
The cycle ABCD represents a complete cycle and Carnot’s
theorem can be applied. Suppose the volume at the point A is V 1 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 Q1 T1
= or =
T1 T2 Q 2 T2
Q1 − Q2 T1 − T2
=
Q2 T2
dL dT
∴ =
L T
The area of the figure

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 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 V 2 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.

Maxwell’s Thermodynamical Relation:

Maxwell making use of the first law and the second law of thermodynamics was able to derive a set of
fundamental relations, know as “thermo dynamical relations”. These relations can be readily used for the
solution of many thermodynamic problems.

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In general, the state of a substance is completely defined by any pair of the quantities P, V, T, and S. In
solving, therefore, any thermodynamic problems, the pair most suitable is chosen as independent variables.
If a body absorbs small amount of heat dQ such that the body performs a small amount of external work dW,
and if dU be the change in internal energy, then the first law of thermodynamics can be written as,

dQ = dU + dW = dU + PdV

or , dU = dQ − PdV - - - - - - - - - - - - - - - - - - - - - - - - - (a)
From the second law of thermodynamics,
dQ = TdS - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (b)
Combining equation (a) and (b), we get,

dU = TdS − PdV - - - - - - - - - - - - - - - - - - - - - - - - (c)

Expressing S and V in terms of the variables x and y, we write

S = f (x , y ) and V = f (x , y )
 ∂S   ∂S 
∴ dS =  dx +  dy
 ∂x   ∂y 

 ∂V   ∂V 
dV =  dx +  dy
 ∂x   ∂y 
Therefore from (c)
 ∂S   ∂S   ∂V   ∂V 
dU = T  dx + T  dy − P  dx − P  dy
 ∂x   ∂y   ∂x   ∂y 

  ∂S   ∂V     ∂S   ∂V 
or dU = T   − P  dx + T   − P   dy
  ∂x   ∂x     ∂y   ∂y 

∂U ∂S ∂V
∴ =T −P
∂x ∂x ∂x

∂U ∂S ∂V
and =T −P
∂y ∂y ∂y

Since dU is a perfect differential, then applying Euler’s condition

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 ∂  ∂U  ∂  ∂U 
ie.  =  , we can write,
∂y  ∂x  ∂x  ∂y 

∂  ∂S ∂V  ∂  ∂S ∂V 
∂y T ∂x − P ∂x  = ∂x T ∂y − P ∂y  , or by transposition,
   

∂T ∂S ∂T ∂S ∂P ∂V ∂P ∂V
. − . = − . - - - - - - - - - - - - - - - - - - - - - -(d)
∂x ∂y ∂y ∂x ∂x ∂y ∂y ∂x

∂T ∂T ∂P ∂P
∂x ∂y ∂x ∂y
or, =
∂S ∂S ∂V ∂V
∂x ∂y ∂x ∂y
Starting from the general equation we shall deduce all the thermodynamic relations.

(1) First Relation: Take T and P as independent variables. Therefore, take T = x and P = y we get,

 ∂T   ∂T 
  =1 ,   = 0
 ∂x  y  ∂y x

 ∂P   ∂P 
  =0 ,   = 1
 ∂x  y  ∂y  x
Substituting these values in equation (d) we get,

 ∂S   ∂V 
  = − 
 ∂y  x  ∂x  y

 ∂S   ∂V 
or,   = −  - - - - - - - - - - - - - - - - - - - - - - - - - - - (1)
 ∂P  T  ∂T  P

Which means that the decrease in entropy per unit increase of pressure during an isothermal process is
equal to the increase of volume per unit increase in temperature when pressure is kept constant.

2. Second Relation: Take S and P as independent variable, i.e. S = x and P = y,

 ∂S   ∂S 
  =1 ,   = 0
 ∂x  y  ∂y  x

 ∂P   ∂P 
  =0 ,   = 1
 ∂x  y  ∂y  x
Substituting these values in equation (d) we get,

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  ∂T   ∂V 
-   = −  
 ∂y x  ∂x  y

 ∂T   ∂V 
or,   =  - - - - - - - - - - - - - - - - - - - - - - - - - - - (2)
 ∂P  S  ∂S  P

Which implies that the increase of temperature per unit increase of pressure, entropy remaining constant is
equal to the increase in volume per unit increase of entropy when pressure is constant.

3. Third Relation: Take S and V as independent variable, i.e. S = x and V = y,

 ∂S   ∂S 
  =1 ,   = 0
 ∂x  y  ∂y  x

 ∂V   ∂V 
  =0 ,   = 1
 ∂x  y  ∂y x
Substituting these values in equation (d) we get,

 ∂T   ∂P 
-   =  
 ∂y  x  ∂x  y

 ∂T   ∂P 
or,   = −  - - - - - - - - - - - - - - - - - - - - - - - - - - - (3)
 ∂V  S  ∂S  V

Which signifies that the increase in temperature per unit increase of volume when entropy is kept constant is
equal to the decrease in pressure per unit increase of entropy when volume is kept constant.

4. Fourth Relation: Take T and V as independent variables, i.e. T = x and V = y,

 ∂T   ∂T 
  =1 ,   = 0
 ∂x  y  ∂y x

 ∂V   ∂V 
  =0 ,   = 1
 ∂x  y  ∂y x
Substituting these values in equation (d) we get,

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  ∂S   ∂P 
  =  
 ∂y  x  ∂x  y

 ∂S   ∂P 
or,   =  - - - - - - - - - - - - - - - - - - - - - - - - - - - (4)
 ∂V T  ∂T  V

Which implies that the increase in entropy per unit increase in volume at constant temperature is equal to the
increase in pressure per unit increase of temperature at constant volume.

5. Fifth Relation: Take P and V as independent variables, ie. P = x and V = y,

 ∂P   ∂P 
∴   =1 ,   = 0
 ∂x  y  ∂y  x

 ∂V   ∂V 
  =0 ,   = 1
 ∂x  y  ∂y x
Substituting these values in equation (d) we get,

 ∂T   ∂S   ∂T   ∂S 
    −     =1
 ∂x  y  ∂y  x  ∂y  x  ∂x  y

 ∂T   ∂S   ∂T   ∂S 
or,     −     =1 - - - - - - - - - - - - - - - -(5)
 ∂P  V  ∂V  P  ∂V  P  ∂P  V

6. Sixth Relation: Take T and S as independent variables, ie. T = x and S = y,

 ∂T   ∂T 
∴   =1 ,   = 0
 ∂x  y  ∂y x

 ∂S   ∂S 
  =0 ,   = 1
 ∂x  y  ∂y  x
Substituting these values in equation (d) we get,

 ∂P   ∂V   ∂P   ∂V 
    −     =1
 ∂x  y  ∂y x  ∂y  x  ∂x  y

 ∂P   ∂V   ∂P   ∂V 
or,     −     =1 - - - - - - - - - - - - - - - -(6)
 ∂T  S  ∂S  T  ∂S  T  ∂T  S

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 SOLVED PROBLEMS
Problem No. 1: One kilogram of ice at 00C is melted and converted to water at 00C. Compute the change in
entropy, assuming that the melting is done reversibly. The heat of fusion of water is Lf = 3.34x105 J/kg.
Solution: The heat needed to melt the ice is Q = mLf = 3.34x105 J

Q 3.34 x10 5 J
∆S = S 2 − S 1 = = = 1.22 x10 3 J / K .
T 273 K
This increase corresponds to the increase in disorder when the water molecules go from the highly ordered
state of a crystalline solid to the much more disordered state of a liquid.
When we refreeze the water, Q has the opposite sign, and the entropy change of water is

∆S = −1.22 x10 3 J / K .
The water molecules rearrange themselves into a crystal to form ice, so disorder and entropy both decrease.
Problem No. 2: One kilogram of water at 00C is heated to 1000C. Compute its change in entropy.
Solution: We know dQ = mcdT.
So,
2 2
dQ dT T 373K
∆S = S 2 − S 1 = ∫ = mc ∫ = mc ln 2 = [1.00kg ][4190 J / kg.K ][ln ] = 1.31x10 3 J / K
1 T 1 T T1 273K
Problem No. 3: A gas expands adiabatically and reversibly. What is the change in entropy?
Solution: In an adiabatic process, no heat enters or leaves the system. Hence dQ = 0, and there is no
change in entropy in this reversible process: ∆S = 0 .
Every reversible adiabatic process is a constant-entropy process. For this reason, reversible adiabatic
processes are also called isentropic processes. The increase in disorder resulting from the gas occupying a
greater volume is exactly balanced by the decrease in disorder associated with the lowered temperature and
reduced molecular speeds.
Problem No. 4: A Carnot engine takes 2000 J of heat from a reservoir at 500 K, does some work, and
discards some heat to a reservoir at 350 K. How much work does it do, how much heat is discarded, and
what is the efficiency?
Solution: Thermal efficiency = 1- T2/T1 = 1- 350/500 = 1- 0.70 = 0.30
Since, Thermal efficiency = W/ Qin , W=Thermal efficiency x Qin=0.30x2000 = 600 J

Again, W = Qin – Qout , Qout = Qin – W =2000 – 600 = 1400 J

Heat rejected must be negative since work is done on the system.

Problem No. 5: For the Carnot engine in Problem No. 4, find the total entropy change in the engine during
one cycle.

Solution: There is no entropy change during the adiabatic expansion or adiabatic compression. In an
adiabatic process, no heat enters or leaves the system. Hence dQ = 0, and there is no change in entropy in
this process: ∆S = 0 .

15
During the isothermal expansion at TH = 500 K, the engine takes in 2000 J of heat and its entropy change is

QH 2000 J
∆S H = = = 4 .0 J / K
TH 500K

During the isothermal compression at TC = 500 K, the engine gives off 1400 J of heat, and its entropy change
is

Qc −1400 J
∆S C = = = − 4 .0 J / K
TC 350K

Therefore, total entropy change in the engine during one cycle is

∆ S H + ∆ S C = 4 .0 J / K − 4 . 0 J / K = 0

Problem No. 6: Suppose 1.00 kg of water at 100 0C is placed in thermal contact with 1.00 kg of water at 0
0
C. What is the change in entropy? Assume that specific heat capacity of water is constant at 4190 J/kg.K
over this temperature range.

Solution: The final temperature = 50 0C = 323 K.

The entropy change of the hot water =

T2 dT 323 K dT 323 K
mc ∫ = [1.00kg ][ 4190 J / kg.K ] ∫ = [ 4190 J][ln ] = −603 J/K
T1 T 373 K T 373 K

The entropy change of the cold water =[4190 J/K][ln(323/273)] = 705 J/K.

Therefore, the total entropy change of the system = -603+705 = 102 J/K

Problem No. 7: Find the entropy change for the isothermal expansion of 0.75 mol of an ideal gas from V1 =
1.5 L to V2 = 3 L.

Solution: The change in entropy can be calculated from

Q V
∆S = = nR ln 2 = [0.75mol][8.31 J / mol.K ][ln 2 ] = 4.32 J/K
T V1

Problem No. 8: 1 kg of water at temperature T 1 = 30 0C is mixed with 2 kg of water at T2 = 90 0C in a

calorimeter of negligible heat capacity at a constant pressure of 1 atm. Find the change in entropy of the
system.
Solution: The change in entropy ∆S 1 of the mass m1 = 1 kg of water going from the state T = T 2 to the state
T = Tf can be written as
T
∆S 1 = m1c p ln f
T1

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The change in entropy ∆S 2 of the mass m2 = 2 kg of water going from the state T = T 2 to the state T = Tf can
be written as
Tf
∆S 2 = m 2 c p ln
T2
Now Tf can be calculated by setting the heat lost equal to the heat gained as follows:
m1c p [ Tf − 30 0 C] = m 2 c p [90 0 C − Tf ]

Or, Tf = 70 0 C = 343 K

Problem No. 9: Imagine a Carnot engine that operates between the temperatures T H = 850 K and TL = 300
K. The engine performs 1200 J of work each cycle, which takes 0.25 s. [a] What is the efficiency of this
engine? [b] What is the average power of this engine? [c] How much energy is extracted as heat from the
high-temperature reservoir every cycle? [d] How much energy is delivered as heat to the low-temperature
reservoir every cycle? [e] What is the entropy change of the working substance for the energy transfer to it
from the high-temperature reservoir? From it to the low-temperature reservoir?
Solution: [a] Efficiency of the engine = η = 1 – TL/TH = 1 – 300/850 = 0.647 ≈ 65%
[b] Average power of this engine = P = W/t = 1200 J/0.25 s = 4800 W = 4.8 kW
[c] Energy extracted as heat from the high temperature reservoir every cycle = Q H = W/η = 1200 J/0.647 =
1855 J
[d] Energy delivered as heat to the low-temperature reservoir every cycle = Q L = QH – W = 1855 – 1200 =
655 J
[e] Entropy change of the working substance for the energy transfer to it from the high-temperature reservoir

Q H 1855 J
= ∆S H = = = 2.18 J / K
TH 850 K
Entropy change of the working substance for the energy transfer from it from the low-temperature reservoir =

Q L − 655 J
∆S L = = = −2.18 J / K
TL 300 K
Since energy Q L is removed from the working substance as heat, there is a decrease in entropy.
Note that the net change in entropy of the working substance for one cycle is zero.

Problem No. 10: An inventor claims to have constructed an engine that has an efficiency of 75% when
operated between the boiling and freezing points of water. Is it possible?

Solution: The efficiency of a real engine [with its irreversible processes and wasteful energy transfers] must
be less than the efficiency of a Carnot engine operating between the same two temperatures.
The efficiency of a Carnot engine operating between the boiling and freezing points of water is
TL 273
η = 1− = 1− = 0.268 ≈ 27 %
TH 373
Thus the claimed efficiency of 75% for a real engine operating between the given temperatures is impossible.

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 Problem Sheet - Entropy
1. Calculate the change in entropy when 150 gm of ice at 0 OC is converted into steam at 100 OC. Specific
heat of ice = 0.5 cal/gm K, latent heat of ice = 80 cal/g, latent heat of steam = 540 cal/g.

2. Calculate the change in entropy when 10 gm of water at 50 OC is mixed with 30 g of water at 10 OC.
3. The melting point of lead is 325 OC and latent heat of its fusion at 325 OC is 5.86 cal/gm. Calculate the
change in entropy when 8 gm-molecules of lead are fused. Atomic weight of lead is 207.

4. Two identical copper blocks of mass 2.5 kg; block 1 is at temperature T 1 = 60 oC and block 2 is at
temperature T2 = 20oC. The blocks are in a thermally insulated box and are separated by an insulating
shutter. When we lift the shutter, the blocks eventually come to the equilibrium temperature TF = 40 oC.
What is the net entropy change of the two-block system during this irreversible process? The specific
heat of copper is 386 J/kg.K.

5. A brass rod is in contact thermally with a heat reservoir at 150 OC at one end and a heat reservoir at 35
O
C at the other end. Compute the total change in the entropy arising from the process of conduction of
1500 cal of heat through the rod. Does the entropy of the rod change in the process?

6. Calculate the depression of melting point of ice by one atmosphere increase of pressure, given, latent
heat of ice = 3.35 x 105 J/kg and the specific volumes of 1 kg of ice and water at 0 oC are 1.090 x 10-3 m3
and 10-3 m3 respectively.

7. Calculate the change in the boiling point of water when the pressure of steam on its surface is increased
from 1 atmosphere to 1.10 atmospheres. Latent heat of water at 100 oC = 537 cal/g and volume of one
gram of steam at 100 oC = 1676 cm3.

8. Calculate under what pressure water will boil at 120 oC, if the change in specific volume when 1 gram of
water is converted into steam is 1676 cm3?

9. Five moles of an ideal gas undergo a reversible isothermal expansion from volume V1 to volume V2 = 4
V1 at temperature T = 450 K. Find [i] work done by the gas and [ii] the entropy change of the gas. [iii] If
the expansion is reversible and adiabatic instead of isothermal, what is the entropy change of the gas?

10. In an experiment, 250g of aluminium [with a specific heat of 900 J/kg. K] at 100 0C is mixed with 50.0 g of
water at 25 0C, with the mixture thermally isolated. [i] What is the equilibrium temperature? What are the
entropy changes of [ii] the aluminium, [iii] the water, and [iv] the aluminium-water system?

11. A 50g ice cube at -15 0C is placed in a lake whose temperature is 18 0C. Calculate the change in entropy
of the cube-lake system as the ice cube comes to thermal equilibrium with the lake. The specific heat of
ice is 2220 J/kg. K.

12. A Carnot engine has an efficiency of 45%. It operates between constant-temperature reservoirs differing
in temperature by 85.0 0C. What are the temperatures of the two reservoirs?
13. An inventor claims to have constructed an engine that has an efficiency of 75% when operated between
the boiling and freezing point of water. You have to calculate the credibility of the inventors claim in one
way and that is by comparing the claimed 75% efficiency to that of an ideal engine operating between the
same two temperatures.
14. During each cycle, a Carnot engine removes 100J of energy from a reservoir at 400K , does work, and
exhausts heat to a reservoir at 300K. Compute the entropy change of each reservoir for each cycle, and

18