1

ENTROPY
Prepared by k.c.abraham
Introduction
Clasusius while working on the formulation and application of 2nd law of thermodynamics
introduced the concept of entropy in 1854. The term literally means transformation. It is a very
important thermodynamic quantity and is very useful in the study of the behavior of heat engines.
Entropy of a substance is that physical quantity which remains constant when the substance undergoes a
reversible adiabatic process just as temperature remains constant in an isothermal change.
Entropy and Adiabatic
Consider a number of isothermal AB, CD, EF, etc at temperatures T1, T2, T3, etc on an indicator
diagram. Let L and M be two adiabatics, which intersect these isothermals at A, B, C, D etc. Let
ABCD and DCEF represent ideal Carnot cycles.
Consider the cycle ABCD.
If 𝑄1 is the quantity of heat absorbed at T1K
and 𝑄2 is the quantity of heat rejected at T2K, 𝑇
𝑄1 1
𝑸𝟏 𝑸𝟐
then by Carnot’s theorem, =
𝑻𝟏 𝑻𝟐
Considering the cycle DCEF, if 𝑄2 is the heat 𝑄2 𝑇2
absorbed at T2 and 𝑄3 is the heat liberated at T3,
𝑸𝟐 𝑸𝟑 𝑇3
we have, = 𝑄3
𝑻𝟐 𝑻𝟑
𝑸𝟏 𝑸𝟐 𝑸
= = 𝑻 𝟑 = ⋯ = 𝒂 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕.
𝑻𝟏 𝑻𝟐 𝟑

It is clear that in going from one adiabatic to

the other, heat is either absorbed or liberated.
The amount of heat absorbed or liberated is not constant, but depends on the temperature. Higher
the temperature, larger is the amount of heat absorbed or liberated.
In general if Q is the quantity of heat absorbed or liberated at temperature T K in going from one
𝑸
adiabatic to the other, = S = a constant
𝑻
This constant is known as the change in entropy between the states represented by the two
adiabatics.
i.e Change in entropy = Heat added or subtracted
Absolute temperature

If S1 and S2 are the entropies for the adiabatics L and M respectively,

𝑸
S2 - S1 = = Constant
𝑻
If the adiabatics lie very close to each other and if dQ is the amount of heat absorbed or liberated at
temperature T in going from one adiabatic to the other, the change in entropy,
𝒅𝑸
dS =
𝑻
 2

Therefore, change in entropy in going from the adiabatic L to the adiabatic M is given by
𝑆2 𝑀 𝑑𝑄
∫𝑆1 𝑑𝑆 = S2 - S1 = ∫𝐿 𝑇
During an adiabatic change no heat is absorbed or rejected by the system, i.e, dQ = 0. So the
change in entropy is zero. This means that there is no change in entropy during a reversible
adiabatic process or the entropy remains constant during an adiabatic reversible process.
Therefore entropy of a substance is that physical quantity which remains constant when the
substance undergoes a reversible adiabatic process.
Note:
Unit of entropy
𝒅𝑸
We know, dS =
𝑻
Therefore entropy is measured in joules per Kelvin (JK-1)
Isentropic
If a system absorbs or rejects a quantity of heat dQ at a temperature T during a reversible
adiabatic process, then the change in entropy,
𝒅𝑸
dS =
𝑻
but for an adiabatic change , dQ = 0
or, dS = 0
Thus there is no change of entropy during a reversible adiabatic process. Therefore entropy remains
constant during a reversible adiabatic process, and this process is known as isentropic process. That
is why the adiabatic curves on the P-V diagram are called isentropics- meaning curves of constant
entropy. or, isentropic process is that process during which the entropy of a system remains constant.
Definitions of Entropy
1. According to statistical definition, entropy is the product of Boltzmann’s constant K and
natural log of thermodynamic probability W.
i.e. entropy of the system S = K log W.
2. Entropy is defined as the degree of disorderliness of a system.
3. Entropy may be defined as the thermal property of a body which remains constant, during an
adiabatic process when no heat is given to or removed from it. It is a physical quantity, though
there is nothing physical to represent it. It has therefore been called a ghostly quantity.
4. Entropy is the state function of any thermodynamic process whose change in an infinitesimal
change of states is given by 2nd law of thermodynamics as
𝒅𝑸
dS =
𝑻
Concept of Entropy
Entropy is a property characteristic of the state of the system and is closely related to the
probability of the state. If a state has high statistical probability, then the entropy of that state is
very large. It is found that if a closed system is in a highly ordered state, then it is a state of very
small statistical probability, and the entropy of that state is very low. The system gradually attains
equilibrium when it has reached the most disordered state. That state is statistically the most
probable state and it is characterized by maximum entropy.
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Entropy, like P.E, cannot be given an absolute numerical value. Only changes in entropy can
be defined. If a system absorbs a quantity of heat dQ at a constant temperature T during a reversible
process, then its entropy increases by dS, where,
𝒅𝑸
dS =
𝑻

If the system rejects a heat dQ, its entropy decreases by dS. This definition applies only to
reversible process. Entropy is not defined properly for an irreversible process. For a reversible
process, the change in entropy
𝑆2 𝒅𝑸
∫𝑆1 𝑑𝑆 = S2 - S1 = ∫ 𝑻

Where S1 and S2 are the values of entropy in states 1 and 2 respectively. If the
𝑑𝑄
system is taken from state 1 to state 2 by an irreversible process, the quantity ∫ may be
𝑇
calculated, but it does not give the change in entropy of the system. The change in entropy is again
given by S2 - S1, since entropy is a property of the state of the system only.

Change of entropy in a Carnot Cycle or change Entropy in a reversible Cycle

Consider a reversible cycle, for e.g,

(𝑃1 , 𝑉1 )
a Carnot cycle. A Carnot’s cycle
consists of two isothermal and two
adiabatic process. During the two (𝑃2 , 𝑉2 )
adiabatic process, represented (𝑇1 , 𝑄1 )
by BC and DA, there is no change (𝑃4 , 𝑉4 )
in entropy. But during the isothermal
expansion represented by AB,
(𝑃3 , 𝑉3 )
the working substance absorbs an (𝑇2 , 𝑄2 )
amount of heat Q1 at constant
temperature T1K.Therefore gain in
entropy of the working substance
during isothermal expansion
𝑸𝟏
from A to B =
𝑻𝟏
During the isothermal compression
represented by CD, the working
substance rejects an amount of heat Q2 at constant temperature T2K.
𝑸𝟐
Therefore loss in entropy during isothermal compression from C to D =
𝑻𝟐
Therefore, net gain in entropy of the working substance during the cycle ABCDA
𝑸𝟏 𝑸𝟐
= − …........(1)
𝑻𝟏 𝑻𝟐
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𝑸𝟏 𝑸𝟐
But for a reversible Carnot’s cycle, = …........... (2)
𝑻𝟏 𝑻𝟐
Put (2) in (1) , we get, net gain in entropy = 0
Therefore net gain in entropy during a Carnot’s cycle is zero, or the entropy of the system remains
constant in all reversible process.
Note:-
Mathematically, the loss in entropy is considered negative
𝑸𝟐
Therefore, loss in entropy = −
𝑻𝟐
𝑸𝟏 𝑸𝟐
i,e equation (2) becomes, = −
𝑻𝟏 𝑻𝟐
𝑸𝟏 𝑸𝟐
Or
𝑻𝟏
+ 𝑻𝟐
=0 for the whole cycle. Or, during a Carnot’s cycle the entropy of the system
remains unchanged.
Change of entropy in any reversible cycle
Consider a reversible cycle, the indicator diagram for which is a closed curve ABCD. This may
be divided into a number of Carnot’s cycles, by drawing a series of adiabatics A1,A2,A3,…… close
together with short isothermal ab, cd, a’b’,c’d’……in between them. Thus any reversible cycle can
be approximated by a number of small Carnot’s cycles like abcd, a’b’c’d’,……Then for each of the
elementary Carnot’s cycle, the net change in entropy is zero.

𝜹𝑸𝟏 𝜹𝑸𝟐
i.e + = 0 , for each one of
𝑻𝟏 𝑻𝟐 B
𝐴4
these cycles. 𝐴3
Where 𝛿𝑄1 is the heat absorbed at temperature T1 𝐴2 𝑏1
and 𝛿𝑄2 is the heat rejected at temperatureT2. 𝐴1 d
a C
Summing up these results for all the
𝑑1 𝑑1
elementary Carnot’s cycles, we have , c
A
Dd
𝜹𝑸𝟏 𝜹𝑸𝟐
∑(
𝑻𝟏
+ 𝑻𝟐
) =0

Or if the elementary Carnot’s cycles be infinitesimally small,

𝜹𝑸
∮ 𝑻
=0

This is known as Clausius theorem. i.e, the change in entropy for a complete reversible
thermodynamic cycle is zero.
𝜹𝑸
𝑪𝒍𝒂𝒖𝒔𝒔𝒊𝒖𝒔 𝒕𝒉𝒆𝒐𝒓𝒆𝒎 𝒊𝒔 ∮ =0
𝑻
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Change of entropy in an Irreversible Process

In an irreversible process like conduction or radiation, heat is lost by a body at higher

temperature T1 and is gained the body at a lower temperature T2. Here T1 > T2. Let the quantity of
heat given out by the body at a temperature T 1 be Q and the heat gained by the body at temperature
T2 be Q. Consider the hot and cold bodies as one system.

Loss in entropy of the hot body = Q/T1

Gain in entropy of the cold body = Q/T2

Total increase in entropy of the system = Q/T2 – Q/T1

This is positive since T2 < T1.Thus the entropy of the system increases in all irreversible process.

Change of Entropy in an Irreversible Cycle

We know, in the case of a reversible cycle

𝛿𝑄
∮ 𝑇
= 0 -------------------- (1)

Where T is the temperature of working substance at which it absorbs or rejects very small amount of
heat 𝛿Q
𝛿𝑄
But in the case of an irreversible cycle, it is found that ∫ assumes a negative value
𝑇

𝛿𝑄
i,e ∫ < 0 ----------------------(2)
𝑇

(If T is the temperature of sources or sink, then the temperature of working will not be equal to T,
since the process is irreversible. Heat is lost by friction, conduction etc.)

Now, let us imagine a body or substance to be taken from state 1 to state 2 by an irreversible process
and then brought back from 2 to 1 by a reversible process. Then the whole cycle remains as an
irreversible cycle.

Therefore for the whole cycle,

2(𝑖𝑟𝑟) 𝛿 𝑄 1(𝑟𝑒𝑣) 𝛿 𝑄
∫1 𝑇
+ ∫2
𝑇
< 0 ----------------------(3)

1 𝛿𝑄
In the case of reversible cycle, we already know, ∫2 = S1-S2
𝑇

Where S1 and S2 are the entropies in states 1 and 2 respectively

Therefore equation (3) becomes,

2(𝑖𝑟𝑟) 𝛿 𝑄
∫1 + S1 – S2 < 0
𝑇
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2(𝑖𝑟𝑟) 𝛿𝑄
Or, S2 – S1 > ∫1 ----------------------- (4)
𝑇

i.e, in an irreversible change from state 1 to state 2, the difference of entropies in the final and initial
2 𝛿𝑄
states is greater than the integral i.e ∫1
𝑇

For closed or self contained system i,e, for systems completely isolated from the surroundings,
obviously, 𝛿Q = 0

S2 - S1 > 0 i.e, the entropy increases in an irreversible cycle.

Claussius Inequality – another way of stating 2nd law of Thermodynamics

𝛿𝑄
For reversible cycle ∮ 𝑇
=0

𝛿𝑄
For an irreversible cycle ∮ 𝑇
<0

Combining the above two, we get,

𝛿𝑄
∮ ≤0
𝑇

This relation is known as Clausius inequality, where, equality sign holds good for reversible process
and inequality (i,e < sign) for irreversible process.
𝛿𝑄
For all closed cycles, Claussius inequality is ∮ ≤ 0
𝑇

This relation is known as Claussius mathematical statement for the 2nd law of thermodynamics.
It is thus clear that the direction of irreversible process in a closed system is always such that the
entropy of the system and the surroundings, or the entropy of the universe, as it is referred to,
always increases.
Mathematical form of Ist law of Thermodynamics in terms of entropy

We know 1st law of Thermodynamics is dQ = dU + dW

And 2nd law of Thermodynamics is dQ = TdS

Combine the above relations, we get, TdS = dU + dW

This is the mathematical from of Ist law of Thermodynamics in terms of entropy.

Principle of increase of Entropy

In a reversible process there is no change in entropy and in an irreversible process there is a net
increase in entropy. But all natural processes in the Universe are irreversible. Thus the total
entropy of the universe increases. This is known as Principle of increase of entropy. Analytically,
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it may be expressed as ds ≥ 0, where the equality sign refers to reversible processes and the
inequality sign to irreversible process. or,
According to the Principle of increase of entropy whenever any physical or chemical process takes place, the
entropy of the Universe increases.

Entropy of a Perfect Gas or Entropy of an Ideal Gas:

Consider unit mass ( 1 gm ) of a perfect gas occupying a volume V at pressure P and temperature T.
Let a quantity of heat dQ be given to the gas. By the 1st law of thermodynamics,
dQ = dU + dW
If CV is the specific heat capacity at constant volume, dT is the change in temperature and dV is the
change in volume of the gas
dU = CVdT and
dW = pdV
dQ = CVdT + pdV
Let dS be the change in entropy of the gas, then,
𝑑𝑄 𝐶𝑉 𝑑𝑇+𝑃𝑑𝑉
dS = =
𝑇 𝑇
𝒅𝑻 𝒅𝑽
or, dS = CV +P ----------------(1)
𝑻 𝑻

a). Entropy in terms of Volume V and Temperature T

For unit mass of a gas,
PV = rT r = gas constant for 1 gm of the gas
𝑃 𝑟
=
𝑇 𝑉
𝑑𝑇 𝑑𝑉
Put this in (1), we get, dS = CV +r
𝑇 𝑉
Due to the supply of heat dQ, if the temperature of the gas changes from T 1 to T2 and volume from
V1 to V2 , then, net change in entropy is given by,
𝑆 2 2 𝑇 𝑑𝑇 𝑉 𝑑𝑉
∫𝑆1 𝑑𝑆 = CV ∫𝑇1 + r∫𝑉 2
𝑇 1 𝑉
𝑇 𝑉
S2 – S1 = CV [𝑙𝑜𝑔𝑒 𝑇] 𝑇21 + r [𝑙𝑜𝑔𝑒 𝑉 ]𝑉21
𝑻𝟐 𝑽𝟐
= CV 𝑙𝑜𝑔𝑒 + r 𝑙𝑜𝑔𝑒
𝑻𝟏 𝑽𝟏
𝑻𝟐 𝑽𝟐
S2 – S1 = CV 2.3026 𝑙𝑜𝑔10 + r 2.3026𝑙𝑜𝑔10
𝑻𝟏 𝑽𝟏
Put CP – CV = r

𝑻𝟐 𝑽𝟐
S2 – S1 = 2.3026 Cv 𝒍𝒐𝒈𝟏𝟎 + 2.3026[ Cp – Cv] 𝒍𝒐𝒈𝟏𝟎 -------------(2)
𝑻𝟏 𝑽𝟏

b). Entropy in terms of Pressure and Temperature

𝑉 1
Again, PV = rT or =
𝑟𝑇 𝑃
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Differentiating,
P dV + V dP = r dT
P dV = r dT – V dP
Put these in equation (1)
𝑑𝑇 𝑟 𝑑𝑇−𝑉𝑑𝑃
dS = CV +[ ]
𝑇 𝑇
𝑑𝑇 𝑑𝑇 𝑉𝑑𝑃
= CV + 𝑟[ − ]
𝑇 𝑇 𝑟𝑇
𝑑𝑇 𝑑𝑇 𝑑𝑃
= CV +( CP – CV) [ − ]
𝑇 𝑇 𝑃
𝑑𝑇 𝑑𝑇 𝑑𝑇 𝑑𝑃
= CV + CP – CV - (CP – CV)
𝑇 𝑇 𝑇 𝑃
𝑑𝑇 𝑑𝑃
dS = CP - (CP – CV)
𝑇 𝑃
Due to the supply if heat dQ , if the temperature of the gas changes from T1 to T2 and the pressure
from P1 to P2, the change in entropy is given by,
𝑆 2 2 𝑇 𝑑𝑇 𝑃 𝑑𝑃
∫𝑆1 𝑑𝑆 = CP ∫𝑇1 - (𝐶𝑃 – 𝐶𝑉 ) ∫𝑃 2
𝑇 1 𝑃
𝑇 𝑃
S2 – S1 = CP [𝑙𝑜𝑔𝑒 𝑇] 𝑇21 - (𝐶𝑃 – 𝐶𝑉 ) [𝑙𝑜𝑔𝑒 𝑃]𝑃21

𝑻𝟐 𝑷𝟐
S2 – S1 = 2.3026 CP 𝒍𝒐𝒈𝟏𝟎 - 𝟐. 𝟑𝟎𝟐𝟔(𝑪𝑷 – 𝑪𝑽 ) 𝒍𝒐𝒈𝟏𝟎 …………(3)
𝑻𝟏 𝑷𝟏

c). Entropy in Terms of Pressure and Volume

Once again, we have,

𝐼 𝑟
PV = rT or =
𝑇 𝑃𝑉
Differentiating,
PdV + V dP = r dT
𝑃𝑑𝑉+𝑉𝑑𝑃
dT =
𝑟
Put this in equation (1)
(𝑃𝑑𝑉+𝑉𝑑𝑃) 𝑟 𝑃𝑑𝑉
dS = CV +
𝑟𝑇 𝑃𝑉

(𝑃𝑑𝑉 + 𝑉𝑑𝑃) 𝑑𝑉
dS = CV + r
𝑃𝑉 𝑉
𝑑𝑉 𝑑𝑃 𝑑𝑉
= CV + CV + ( CP – CV)
𝑉 𝑃 𝑉
𝑑𝑃 𝑑𝑉
dS = CV + CP
𝑃 𝑉
Due to the supply of heat dQ, if the volume changes from V1 to V2 and the pressure from P1 to P2 ,
the change in entropy is given by,

𝑆 2 2 𝑃 𝑑𝑃 𝑉 𝑑𝑉
∫𝑆1 𝑑𝑆 = CV ∫𝑃1 + CP ∫𝑉 2
𝑃 1 𝑉

𝑃 𝑉
S2 – S1 = CV [𝑙𝑜𝑔𝑒 𝑃]𝑃21 + CP [𝑙𝑜𝑔𝑒 𝑉 ]𝑉21
 9

𝑃2 𝑉2
= CV 𝑙𝑜𝑔𝑒 + CP 𝑙𝑜𝑔𝑒
𝑃1 𝑉1

𝑷𝟐 𝑽𝟐
S2 – S1 = 2.3026 CV 𝒍𝒐𝒈10 + 2.3026 CP 𝒍𝒐𝒈10 -----------------------(4)
𝑷𝟏 𝑽𝟏

Note:

1) The above relations refer to the change in entropy for 1 gm of the gas; the change for m gm of
the gas can be easily obtained by multiplying the respective relations by m.
2) In case if we take 1 gm – molecule of the gas CP and CV stand for molecular specific heats of the
gas at constant pressure and constant volume respectively and the gas constant r is replaced by
R.
Change in Entropy when ice is converted into steam
Consider unit mass of ice at temperature t0c below the normal melting point of ice, namely (00C or
273K). Let it be gradually heated and converted into steam at temperature t0c above the normal
boiling point of water (i,e 1000C or 373K). The total change in entropy during the process may be
calculated as follows:
Consider unit mass of ice. Let a quantity of heat dQ be supplied to it so that the temperature
rises by dT
dQ = mass x specific heat capacity x rise in temperature
dQ = 1 x c x dT = C dT, where c = specific heat capacity of ice
Let dS be the change in entropy
i,e. dS = dQ/T
Change in entropy when the temperature of the system changes from T1 to T2 is given by
𝑇 𝑑𝑄 𝑇 𝐶 𝑑𝑇
S2 – S1 = ∫𝑇 2 = ∫𝑇 2
1 𝑇 1 𝑇

𝑇 𝑇2
= C [𝑙𝑜𝑔𝑒 𝑇] 𝑇21 = C 𝑙𝑜𝑔𝑒
𝑇1

𝑻𝟐
∴ S2 – S1 = 2.3026 C 𝒍𝒐𝒈𝟏𝟎 -----------------(1)
𝑻𝟏

a) Change in entropy when the temperature of ice increases from t0 c below the normal M.P to the normal M.P
Here the temperature changes from (273 - t) K to 273K
Change in entropy during this process is given by equation (1)
273
S2 – S1 = 2.3206 C log ------------------ (2)
273−𝑡
Specific heat capacity of ice = C = 2.1x 103 JKg-1K-1
b) Change of entropy when ice at 273K melts to water at 273K:
𝑙𝑖 𝑑𝑄
It is given by S2 - S1 = --------------------------(3 ) dS =
273 𝑇
Where 𝑙i is the specific latent heat of fusion of ice
𝑙i = 3.3x 105 JKg-1
c) Change of entropy when water at 273K is heated to water at 373K:
373
S2 – S1 = 2.3206 C log ------------------------ (4) use eqn (1)
273
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Where specific heat capacity of water c = 4185 JKg -1K-1

d) Change of entropy when water at 373K is converted into steam at 373K:
To convert water at its normal B.P to steam at the same temperature, the quantity of
heat required is called the specific latent heat of vaporization of water or specific latent heat
of steam. Let it be 𝑙 s
Therefore change in entropy during this process,
𝑙𝑠 𝑙𝑠 𝑑𝑄
S2 – S1 = = ----------------------------- (5) dS =
𝑇 373 𝑇

Specific latent heat of steam 𝑙s = 226 x 104 JKg-1

e) Change in entropy when steam at 373K is superheated to steam at t0c or (273+t)K:
373+𝑡
It is given by, S2 – S1 = 2.3206 C log ------------- (6) use eqn (1)
373

Where specific heat capacity of steam, C = 2.02 x 103JKg-1K-1

Note:
1) For total change in entropy during the entire process,
S2 – S1 = (2)+(3)+(4)+(5)+(6)
2) The entire process is represented schematically as

1ce at 1ce at Water at

(273+t)K 273 K 273K
or t0c or 00c or 00c

Water at Steam at Steam at

373 K 373 K or (373+t)K
or 1000c t0 c or t0c

Some Examples of irreversible process

Conduction or radiation of heat, the free expansion of gas into vacuum, the diffusion of gases,
irreversible heat engine etc are some examples of irreversible process.
(1) Irreversible heat engine :
Suppose the working substance in an engine undergoing an irreversible cycle absorbs an amount
of heat Q1 from the source at temperature T1K and rejects an amount of heat Q2 to the sink at T2K
Therefore efficiency of this cycle
𝑸𝟏 −𝑸𝟐 𝑸𝟐
1 = = 𝟏−
𝑸𝟏 𝑸𝟏
The efficiency of a reversible engine working between the same two temperatures

T1K and T2 K is
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𝑻𝟏 −𝑻𝟐 𝑻𝟐
 2= = 𝟏−
𝑻𝟏 𝑻𝟏
But by Carnot’s theorem, the efficiency of the irreversible engine  1 must be less the efficiency
of the reversible engine  2
i.e 1 < 2

𝑸𝟐 𝑻𝟐
or 𝟏 − < 𝟏−
𝑸𝟏 𝑻𝟏

𝑸𝟐 𝑻𝟐
>
𝑸𝟏 𝑻𝟏
𝑸𝟐 𝑸𝟏
or >
𝑻𝟐 𝑻𝟏
𝑸𝟐
But, = increase in entropy of the sink
𝑻𝟐
𝑸𝟏
= decrease in entropy of the source
𝑻𝟏
Therefore change in entropy during this cycle =
𝑸𝟐 𝑸𝟏
–
𝑻𝟐 𝑻𝟏
Clearly this greater than zero
𝑸𝟐 𝑸𝟏
i,e., – >0
𝑻𝟐 𝑻𝟏
ie.., there is an increase in entropy during this irreversible cycle.
Thus, in general, the entropy of a system increases in all irreversible process.

(2) Expansion of perfect gas into Vacuum

Let us consider a perfect gas rushed into vacuum and let the whole system be thermally
insulated. The temperature of the gas does not change during the process as the gas considered is
perfect.

Let the volume of the gas be increased from V1 to V2 during the expansion. The change in
𝑑𝑄
entropy can be found by finding the value of ∫ along reversible path.
𝑇

𝑅𝑇
Considering the isothermal change at the temperature T PV = RT or P =
𝑉

𝑑𝑉
dQ = P dV = RT consider 1 gm –molecule of the
𝑉
If dS is the change in entropy for a small increase in volume dV, gas

𝑑𝑄 𝑅𝑇𝑑𝑉 𝑅𝑑𝑉
dS = = =
𝑇 𝑇𝑉 𝑉

Therefore change in entropy of the gas for the whole expansion from V1 to V2 is
 12

2 𝑆 2 𝑉 𝑑𝑉
∫𝑆 𝑑𝑆 = R ∫𝑉 𝑉
1 1

𝑉 𝑉2
i.e S2 – S1 = R [𝑙𝑜𝑔𝑒 𝑉 ]𝑉21 = R 𝑙𝑜𝑔𝑒
𝑉1

Where, S1 and S2 are the entropies of the gas in the initial and final states.

But V2 > V1

∴ S2 – S1 is always positive.

Thus the entropy of a system increases in an irreversible process.

Spontaneous Cooling of a body by Conduction or Radiation

Consider a body at temperature TH placed in contact with a cold reservoir at temperature Tc. The
cooling of the body is spontaneous. Heat flows from the body to the cold reservoir until it is in
thermal equilibrium with the reservoir at temperature Tc. This is clearly an irreversible process. In
this process, entropy is lost by the body and gained by the reservoir.
𝑇𝐻 𝑑𝑄
Entropy lost by the body = CV 𝑙𝑜𝑔𝑒 dS =
𝑇𝐶 𝑇
Entropy gained by the reservoir = CV ( TH –TC) dQ = 1x CV x dT
TC
Loss in entropy of the body is less than the gain in entropy by the principle of
by the reservoir increase of entropy

Thus, although the entropy of the body decreases during the process, the total entropy of the body
and the reservoir increases. i.e., entropy of the Universe increases by,
𝑇𝐻 −𝑇𝐶 𝑇𝐻
S = CV ( ) − CV loge
𝑇𝐶 𝑇𝐶
𝑇 −𝑇 𝑇𝐻 −𝑇𝐶 𝑇𝐻 −−𝑇𝐶
= CV ( 𝐻 𝐶 ) − CV loge ( 1 + ) put x=
𝑇𝐶 𝑇𝐶 𝑇𝐶
𝑥2 𝑥3 𝑥4
= CV x – CV loge (1+x) = 𝐶𝑉 𝑥 − 𝐶𝑉 [𝑥 − + − ………..]
2 3 4
𝑥2 𝑥3 𝑥4
𝑆 = 𝐶𝑉 [ − + ………..]
2 3 4
This is clearly positive.
Thus in a spontaneous (irreversible) process, the entropy of the Universe increases.
Note:
A similar result is also obtained in the case of cooling by radiation.
Important Conclusions :
1) In any spontaneously occurring process in nature, there is an increase in entropy of the system
undergoing the change.
2) Only in the case of reversible process, can the change of entropy be zero
3) Entropy change is never negative.
 13

4) Actual changes are never perfectly reversible. Therefore in actual practice, all changes lead to
an increase in the entropy of the Universe
Second law of Thermodynamics in Terms of Entropy
The 2nd law of thermodynamics can be stated in terms of entropy. It states that “every physical or
chemical process in nature takes place in such a manner that the total entropy increases”.

Clausius states that the 2nd law of thermodynamics is equivalent to the statement that the entropy of
the universe tends to be a maximum.
Explanation:
All natural processes are irreversible. But in an irreversible process, there is a net increase in
entropy. So the entropy of the universe tends to a maximum.
Mathematical Formulation of 2nd law of Thermodynamics
Let S1 and S2 be the entropies of a substance in the initial and final states.
2 𝑑𝑄
Therefore change in entropy S2 – S1 = ∫1
𝑇

If the two states 1 and 2 are infinitesimally close to each other, the above equation may be put as,
𝑑𝑄
dS =
𝑇
or, dQ = TdS
This is the mathematical form of 2nd law of thermodynamics or this is the 2nd law of
thermodynamics as stated in terms of entropy.
Entropy and Available Energy
Let a Carnot engine be allowed to work between a source at temperature T 1 and a sink at lower
temperature T0. If Q1 is the heat absorbed at temperature T1 and Q2 is the heat rejected at
temperature T0, then
𝑸𝟏 −𝑸𝟐 𝑻𝟏 −𝑻𝟎
=
𝑸𝟏 𝑻𝟏
Work done or energy available
𝑻𝟏 −𝑻𝟎 𝑻𝟎
W = Q 1 – Q2 = ( ) Q1 = (1 - ) Q1
𝑻𝟏 𝑻𝟏
To operate the engine, heat must be transferred from the source to the cylinder of the engine
and due to conduction and radiation, the temperature falls (say, to T2). Hence the energy
actually available is
𝑻𝟎
W’ = {1 − } Q1
𝑻𝟐

This is less than W, since T1 >T2

Therefore loss of available energy = W –W’
𝑻𝟎 𝑻𝟎
= (1 - ) Q1 – (1 − ) Q1
𝑻𝟏 𝑻𝟐
𝑄1 𝑄
= ⌈ = 1 ⌉ T0
𝑇2 𝑇1
𝑄1
But, = gain in entropy
𝑇2
𝑄1
= loss in entropy of the system
𝑇1
 14

Since T1 > T2 there is a net gain in entropy.

Therefore, loss of available energy = gain in entropy x To
Thus for a given temperature To of the sink, the loss of the available energy is To times
the gain in entropy. As the entropy of the system increases, the available energy decreases or
unavailable energy increases. The entropy of a system is thus a measure of the unavailability of
energy from it. Greater the increase in entropy of a system, smaller is the energy available for
useful work from it.
Principle of degradation of energy
It states that “the available energy of the universe is tending towards zero” .This can
also be stated as “Whenever an irreversible process takes place, certain amount of energy which could have
been utilized for doing useful work changes to a form in which it becomes unavailable.
Explanation.
Entropy of a system is a measure of the unavailability of energy from it. i.e. an increase
of entropy is always followed by a decrease in available energy.
In nature, almost all process are irreversible, so that the entropy of the universe
continually increases, making more and more energy unavailable. When the entropy of the
universe attains a maximum value, there will be no temperature difference possible. If there
is no temperature difference, it will not be possible to convert any amount of heat into useful
work. Thus, though the bodies possess heat energy, it will not be possible to use it for
conversion into work. This is known as Principle of degradation of energy or Law of
dissipation of energy. This is why 2nd law of thermodynamics is sometimes referred to as the law of
dissipation or degradation of energy.
Heat Death
When the entropy of the Universe reaches to a maximum value, there will not be any
energy available for doing work. At this stage, there will be no temperature difference.
Therefore, it will not be possible to convert any amount of heat into useful work. Thus the
energy is running downhill and the universe is marching towards heat death. i.e., the universe
will be less useful to us as time pass on.
The stage when all the heat energy will be at the same temperature and it will not be
possible to convert even a small amount of heat into work is referred to as the “ Heat death” of
the universe.
Entropy and Probability
The validity of 2nd law of thermodynamics depends on the large number of molecules it
has to deal with. The 2nd law is also called a statistical law and is applicable to wherever a
large number of molecules is concerned. Boltzmann showed that entropy represents the
probability in a given system.
According to statistical definition, entropy is the product of Boltzmann’s constant K and
natural logarithm of thermodynamics probability W.
i.e., entropy of the system S = K log W. Thus the concept of entropy is applicable to any macro
state whether most probable or not.
It is found that the more disorderly an arrangement, the more probable it is.
 15

Thus the inherent tendency of the nature is to proceed from a less probable or an orderly state
to a more probable or disorderly state so that ultimate destiny of the universe is not order but utter
disorder or chaos.
Entropy and disorder
The uncertainty or loss of information about the state of a system is called disorder.
The disorder is proportional to thermodynamic probability W
But we know,
Entropy S = K log W
Therefore, entropy, being proportional to W is also related to the disorder of the system. i.e,
entropy is a measure of the degree of disorderliness or chaos in a given system .The more
disorderly the state of the system, the higher its entropy.
It is seen that as the temperature of a system is lowered, the entropy of the system and
hence its disorder decreases. This is the reason why it is said that entropy is the measure of the degree of
disorder in a substance just as temperature is a measure of degree of hotness of a body. At the Zero of the
thermodynamic scale of temperature, the thermal agitation completely stops. As a result the
disorder and hence the entropy tends to zero.
Inter-relation between Entropy, disorder and Probability
Boltzmann’s relation connecting entropy and probability is
Entropy S = K log W
K = Boltzmann’s constant
W = statistical probability
It shows that every substance has finite positive entropy and hence is disordered. But at absolute
zero, probability of all molecules, being in the ground state, is maximum.
i.e., W = 1
Therefore S = k log 1 = 0.
Therefore at absolute zero temperature, entropy becomes zero or there is perfect order of the
molecules.
Disorder and hence Entropy are most Probable States
It is the law of nature that disorder is always more probable than order. There is probability
for an orderly state to transform to disorderly state but it is highly improbable that a highly
disordered motion of molecules of a single body would by itself be converted into a regular motion
of the engine shaft.
Disordered houses, disorganized groups of men are natural states of affairs while well kept
houses, organized teams of men are unnatural states and require a lot of organizing activity in order
to be maintained.
Thus it is the law of nature that disorder is always more probable than order and since
entropy is a measure of disorder, it is obvious that in a process in which there is an increase in
entropy, disorderly state is most probable.
Principle of Increase of entropy – Manager of the Universe
The entropy of the universe tends towards a maximum. This implies that the ultimate destiny
of the universe is not order but chaos. This shows that, it is entropy which determines the direction
 16

in which a process should proceed, while the principle of conservation of energy only balances the
energy received and distributed. As this being the case we can rightly quote the statement of
Emden, i.e., “the principle of increase of entropy is the manager of the universe, the principle of energy does the
book-keeping”.
Nernst Heat Theorem and the 3rd law of thermodynamics
Nernst heat theorem states,
“The heat capacities of all solids tend to zero as the temperature tends to absolute zero and the internal
energies and entropies of all substances become equal at that temperature, approaching their common value
asymptotically”.
But there is no ‘natural zero’ for internal energy or for entropy; hence their common value at
absolute zero may be taken as the zero for both internal energy and entropy. The above statement
has the nature of a law and hence it is called 3rd law of thermodynamics.
Un attainability statement of 3rd law of thermodynamics
Another important enunciation of the law is as follows:
“It is impossible by any procedure however idealized, to reduce any given system to the absolute zero of
temperature in a finite number of operations.”
In simple language this means that absolute zero is unattainable in actual practice. This is
known as the principle of un attainability of absolute zero. This has been called by Fowler and
Guggenheim as the un attainability statement of 3rd laws of thermodynamics.
Nernst-Simon statement of 3rd law of thermodynamics
The change in entropy associated with any isothermal reversible process of a condensed
system approaches zero as the temperature approaches zero.
Entropy Statement of 3rd law of Thermodynamics
It is impossible by any finite series of process to reduce the entropy of a system to its zero
point value.

Zero point entropy

The entropy of a system at absolute zero may be called the zero point entropy.
Zero point energy
According to kinetic theory, the average kinetic energy of a molecule is 3/2KT. Hence the
kinetic energy of a system will be zero at absolute zero, which means that the molecules of a system
do not move at all. But the development of Quantum Mechanics has showed that even at absolute
zero, the molecules must be in motion and should possess energy. The energy of the molecules at
absolute zero of temperature is called zero – point energy.
Temperature-entropy diagram
The thermodynamic state of a substance can be determined by plotting the entropy S along
the X-axis and temperature T along the Y-axis. The graph obtained is called the temperature-
Entropy diagram. For an isothermal reversible process, since the temperature remains constant, the
T-S diagram is a straight line parallel to the X-axis. For an adiabatic process, since the entropy
remains constant, the T-S diagram is a straight line parallel to Y-axis.
 17

Importance of T-S diagram

The T-S diagram is of practical significance in engineering and metrology. The T-S diagrams
are of great importance to the mechanical engineer
1) for determining the work-value of the fuel used and
2) for detecting any flow in the working of an engine
Note:
Before the year 1934, entropy was denoted by the symbol  and therefore T-S diagrams
were called as tephigrams, particularly in meteorology.
T-S diagram for Carnot cycle:
Consider a Carnot’s cycle represented by the indicator diagram ABCDA

𝑇1
𝐴1 𝑇1
𝑄1 𝑇1 𝐵1

𝑆1 𝑆2

𝑇2 𝐶1
𝐷1 𝑇2
𝑇2 𝑄2
𝑆1 𝑆2

(a) The isothermal expansion AB of the Carnot cycle is represented by the horizontal line A1B1 in
the T-S diagram. Here a quantity of heat Q1 is absorbed by the system at temperature T1 .
𝑄1
Therefore the gain in entropy along A1B1 = S2—S1 = ---------------- (1)
𝑇1
(b) The adiabatic expansion BC of the Carnot’s cycle is represented by the vertical line B1C1 on the
T-S diagram. Here the entropy remains constant at S2 but the temperature falls to T2
(c) The isothermal compression represented by CD on the P-V diagram is represented by the
horizontal line C1D1 on the T-S diagram. Here a quantity of heat Q2 is rejected at temperature T2.
𝑄2
Therefore the loss in entropy along C1D1 = S2—S1 = …………… (2)
𝑇2
(d) The adiabatic compression DA of the Carnot’s cycle is represented by the vertical line D 1A1 on
the T-S diagram. Here the temperature increases to T1 and the entropy remains constant at S1
The area of the T-S diagram for the Carnot cycle is a rectangle
Therefore area of T-S diagram = Area A1B1C1D1
= A1D1 x D1C1
= (T1 –T2) x (S2 – S1)
𝑄1 𝑄2 𝑄1 −𝑄2
But S2-S1 = = =
𝑇1 𝑇2 𝑇1 −𝑇2
Therefore area of T-S diagram
𝑄1 −𝑄2
= (T1 –T2) ( )
𝑇1 −𝑇2
= Q1 – Q2 ------------------------ (3)
 18

Q1 - Q2 represents the heat energy converted into work. Thus the area of the T-S diagram
represents the actual amount of heat converted into useful work during the cycle. But the area of the
P-V diagram represents the work done during the cycle.
𝐻𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑖𝑛𝑡𝑜 𝑤𝑜𝑟𝑘
Efficiency of the engine  =
𝑇𝑜𝑡𝑎𝑙 ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑
𝑄1 −𝑄2
=
𝑄1
𝑄2
=1- --------------------(4)
𝑄1
This is the same as that obtained by the usual treatment of Carnot’s cycle.
By -kca
***********
Chapter-3

ENTROPY

University Questions
March-2018
1……. of a system is the unavailability of energy from it.
Ans: Entropy.
2. Draw the T-S diagram of a Carnot cycle.
3. Obtain an expression connecting the first and second laws of thermodynamics.
4. Calculate the change in entropy when .0273 Kg of ice at zero degree Celsius is converted into
water at the same temperature. Given latent heat = 80 cal/g.
𝑑𝑄 𝑚𝐿 .0273𝑥80𝑥103
Ans: dS = = = =8 cal/K
𝑇 𝑇 273
5. Discuss the principle of increase of entropy.
March-2017
1. The change of entropy in a completely reversible thermodynamic cycle is ……
Ans: Zero
2. Entropy change can never be negative.
Ans: True
3. Explain Clausius inequality.
4. What is third law of thermodynamics? Explain its outcome.
5. One mole of oxygen gas expands isothermally to four times of its initial volume. Determine the
change in entropy.
𝑉2
Ans: Change of entropy = 2.3026 𝑅𝑙𝑜𝑔10
𝑉1
= 2.303 𝑥 8.314𝑙𝑜𝑔10 4 =11.527 J/K
March-2016
1. Entropy of the universe can reach a maximum value. This statement is:
Ans: Correct
2. What is Clausius inequality?
3. Calculate the change in entropy when 2 Kg of ice melts into water at the same temperature. Given
specific latent heat of water =335x103Jkg-1
Ans:
𝑑𝑄 𝑚𝐿 2𝑥335𝑥103
ds = = = = 2454.2 J/k
𝑇 𝑇 273
March-2015
1. The total change in entropy of the working substance during a complete reversible process is :
Ans: Zero
 19

2. Calculate the change in entropy when 5Kg of water at 1000c is converted into steam at the same
temperature.
𝑑𝑄 𝑚𝐿 𝑐𝑎𝑙
Ans: ds = = = 7.238𝑥 103 = 30.39𝑥103 𝐽/𝐾
𝑇 𝑇 𝐾𝑒𝑙𝑣𝑖𝑛
3. Define entropy. What is its physical significance? Show that entropy of a perfect as remains
constant in a reversible process but increases in an irreversible process.
March-2014
1. In thermodynamic process change in entropy is……
Ans: ds ≥ 0
2.Shape of T-S diagram for adiabatic process is ….
Ans: straight line
3. State the principle of increase of entropy.
4. Calculate the change in entropy in an irreversible process.
5. Calculate the efficiency of Carnot’s engine from Temp- entropy diagram for Carnot’s cycle.
6. Calculate the change in entropy of a perfect gas in terms of temp and pressure.
March- 2013
1. Which of the following is mathematical formulation of second law of thermodynamics?
Ans: dQ= T dS
2. State the principle of increase of entropy.
3. Prove that entropy is a state function.
4.1 Kg of water at 1000C is dropped into Indian Ocean at 250C. Calculate change in entropy of
universe.
5. What is entropy –temp diagram? Mention its uses. Obtain the expression for efficiency of
Carnot’s engine from Temp- entropy diagram for Carnot’s cycle.
March-2012
1. In all thermodynamic process ,the change in entropy dS is……
Ans: dS > 0
2. When a gas expands isothermally, the entropy of the gas ….
Ans: increases
3. One mole of H2 mixed with one mole of N2 at the same temperature. What would be the change
in entropy?
Ans: positive since it is an irreversible process.
4. When the entropy of the universe tends to a maximum, which is the following
is wrong?
Ans: Unavailable energy decreases.
5. What is the change in entropy in a reversible cycle?
6. State and explain the third law of thermodynamics.
𝑄
7. Prove the Clausius inequality ∑
𝑇
≤ 0
Problems
1. 2 kg of water is heated by an electric heating coil from 500c to 800. Compute the change in
entropy of the universe. (sp head capacity of water = 4.18x103 1kg-1 k-1) (sept99)
Solun
𝑇
ds = 2.303 mc log 2
𝑇1 1
353
= 2.303 x 2 x 4.18 x 103 log
323
= 7.42 x 102 J/k

2. Calculate the change in entropy when 1 kg of water at 700cis mixed with 0.5 kg of water at 400c
sp. Heal capacity of water = 4180 Jkg -1.K-1 (march2000)
 20

Solun
Heat lost = Heat gained
m1c (T1-T) = m2 c (T-T2)
1 x c x (343-T) = 0.5 x c (T-313)
 T = 331k

a. Change in entropy of 0.5 kg of water

𝑇
ds1 = m2c log
𝑇2
331
= 0.5 x 4180 x log
313
= 129.45 Jk-1 ……………………(1)
b. Change in entropy of 1 kg of water
𝑇
ds2 = m, c log
𝑇1
331
= 1 x 4180 x log
343
= - 123.68 J kg …………………(2)
 total change in entropy
= 129.45 – 123.68
= 5.77 J/k

3. Calculate the change entropy when 1 gm of ice at 00c is converted into steam at 1000c. sp. latent
heat of fusion = 3.36 x 10-3 J /kg (sept2001)
Sp: heat capacity of water = 4208 J/kg/k
Sp: heat of vaporization = 2.27 x 106 J/kg
Solun:
𝑑𝑄 𝑚𝑙 3.36𝑥105
a. ds1 = = = 1 x 10-3 x
𝑇 𝑇 273
= 1.23 J/K………………………….(1)
𝑇2
b. ds2 = 2.303 mc log
𝑇1
373
= 2.303 x 1x10-3 x 4200 x log10
273
= 1.311 …………………………………(2)

𝑑𝑄 𝑚𝑙 1𝑥10−3 𝑥2.27𝑥106
c. ds3 = = =
𝑇 𝑇 373
= 6.08579 J/k …………………………….(3)

ds = ds1 + ds2 + ds3

= 8.626
4. Calculate the change in entropy when 10 gm of a liquid at 00c is converted into vapor at 1000c.
Given sp heat capacity of water = 4.2x103 J kg -1 k-1. Sp latent heat = 2.27x106 J kg-1
(march2001)
Solun

a. Change is entropy as the liquid rises in temperature from 00c to 1000c or from 273 K to 373
K.
373
ds1 = 2.3026 x 10x10 -3 x 4200 x log
273
= 13.1 Jk-1 ……………………………(1)
 21

b. Change is entropy as the liquid at 1000c is converted into vapor at the same temperature
𝑑𝑄 𝑚𝑙 10𝑥10−3 𝑥2.27𝑥106
ds2 = = =
𝑇 𝑇 373
= 60.87J/k
 Total change in entropy
ds = 13.1 + 60.87 = 78.97 J/k

5. Calculate the total change in entropy when 100 gm of water 200c is mixed with 120gm of water at
500c. sp. heat capacity of water is 4200 J kg-1 k-1 (march2002)
Solun
Heat lost = Heat gained
120 x c x (50- 𝜃) = 100 x c x (𝜃 -20)
 𝜃 = 36.40c = 309.4 k

a. Change in entropy of 100 gm of water al 200c or 293 k to 309.4 k

𝑇2
ds1 = 2.3026 mc log
𝑇1
309.4
= 2.3026 x 0.1 x 4200 log
293
ds1= 22.87 Jk-1 ……………………….(1)

b. Change in entropy of 120 gm of water at 500c or 323 k to 309.4 k

𝑇2
ds2 = 2.3026 mc log
𝑇1
309.4
2.3026 x 0.12 x 4200 x log
323
ds2 = - 21.68 Jk-1………………………..(2)
 total change in entropy
ds = ds1 + ds2
= 22.87 -21.68
= 1.19 Jk-1
6. Calculate the change in entropy when 5 kg of water at 1000c is converted into steam at the same
temperature. Latent heat of steam = 540 cal/gm. (march2003)
Solun.
Heat absorbed by 5 Kg of water at 1000c when it is converted into steam at 1000c
= dQ = 5000 x 540 = 2700000 cal
𝑑𝑄 2700000
 The gain in entropy ds = =
𝑇 373
= 7240 cal/k
7. 1 kg of water at 273 k is brought in contact with a heat reservoir at 373 k. When the temperature
of water has risen to 373 k, what is the change in entropy of water? What is the change in
entropy of reservoir? (sp capacity of water is 4200 J kg -1 k-1) (march 2003)
Solun
𝑇
For water, ds1 = 2.303 mc log 2
𝑇1
373
= 2.303 x 1 x 4200 x log
273
= 1310 J k -1
𝑑𝑄 −𝑚𝑐 𝑑𝑇 −1𝑥4200𝑥100
For reservoir, ds2 = − = = = -1126 Jk-1
𝑇 𝑇2 373
8. Calculate the change in entropy when 10 gm of ice at 00c is converted into water at the same
temperature. (sept2003)
 22

Solun
𝑑𝑄 10𝑥80
ds = = = 2.93 cal/k
𝑇 273
9. 0.1 kg of lead kept at 873 k is mixed with 0.2 kg of water kept at 293 k . Find the difference in
entropy when the system attains thermal equilibrium (C = 0.1449 kJ/kg/k). (march2004)
Solun
Heat lost by lead = Heat gained by water m1=.1, c1=1449, 𝑇𝑓 = 294.35
m1 c1 (373-𝜃) = m2 c2(𝜃 − 293) 𝑇11 = 373 ,m2=.2,c2=4200
0.1 x 1449 (373-𝜃) = .2 x 4200(𝜃 − 293) 𝑇12 = 293
𝜃 = 294.35 k
Change in entropy = Sf - Si
𝑇𝑓 𝑇𝑓
= m1 c1 log + m2 c2 log = 3.861-3.431
𝑇11 𝑇12
= 0.43 J/kg
10. Calculate the change in entropy when 1 kg of water at 363 k is mixed with 0.5 kg of water kept
at 273 k ( specific heat capacity of water = 4180 (𝐽𝐾𝑔−1 𝐾 −1 ) (March 2005)

Solun
𝑚2+𝑚1𝑇
1
Temperature of the mixture = T =
𝑚1 +𝑚2
1 𝑥 363+0.5 𝑥 273
=
1+0.5
= 333k
𝑇
Change in entropy = m1 C log ( ) + m2 C log 𝑇⁄𝑇
𝑇1 2
333 333
= 0.5 x 4180 log + 1x4180 log
273 363
−1
= 54.6 𝐽𝐾

11. Calculate the change in entropy when 0.08 kg of water at 200 c is mixer with 0.12 kg of water at
500c. (March 2006)
Solun
Let the temperature of the mixture be T
Heat gained = Heat lost T1 = 273+20 = 293 k
m1 c ( 𝑇 − 𝑇1 ) = 𝑚2 c ( 𝑇2 -T) T2 = 273 +50 = 323 k
.080 x 4180 ( T – 293)
= 0.12 x 4180 ( 323 – T)
 T = 311 k
𝑇
Change in entropy of 0.08 kg of water = 2.3026 x m x log xc
𝑇1
311
= 2.3026 x 0.08 x log10 x 4180
293
= 2.3026 x. 08 x .0259 x 4180 = 19.942726 𝐽𝑘 −1
Change in entropy of .12 gm of water
311
= 2.3026x.12xlog 10 x 4180
293
= 2.3026 x.12 x(-0.0164) x 4180
= - 18.94376 − sign for loss in entropy
 net change in entropy
= 19.94 2726 – 18.94376
= .998966 J/k
 23

12. If the volume of 2 moles of an ideal gas is doubled during an isothermal expansion, calculate the
change in entropy of the gas. (March 2007)
Solun
PV = nRT
𝜕𝑃 𝑛𝑅
( ) =
𝜕𝑇 𝑉
𝑣2 𝜕𝑣 𝑉2
s = ∫𝑣 𝑛𝑅 𝑣 = nR log
1 𝑉1
𝑉2
N = 2, R = 8.3143/k/mol, =2
𝑉1
s = 2 x 8.314 x 2.303 log 10 2
s = 11.5 3J/k

13. The temp of one kg of water at 273 k is raised to 373 k. calculate the change in entropy of water.
(March 2007)
Solun
𝑇 𝑑𝑄 𝑇 𝑑𝑇
ds = ∫𝑇 2 = mc ∫𝑇 2 dQ = mc(𝑇2 -𝑇1 ) = mcdT
1 𝑇 1 𝑇
𝑇2
= mc log
𝑇1
373
= 1 x 4200 x 2.303 log
273
= 1311 J/k
14. Calculate the change in entropy when 5 kg of water at 373 k is converted into steam at the same
temperature (March 2008)
Solun
𝑑𝑄
dS =
𝑇
d𝑄 = ml = 5 kg x 2.268 x 106
T = 373 k
𝑑𝑄 5𝑥2.268𝑥106
ds = =
𝑇 373
= 30408 J/k
15. Calculate the change in entropy when 20 gm of water at 800c is adiabatically mixed with 60 gm
of water at 300c. ( 2009 March)
Solun
Let T be the equilibrium temp
Heat lost by hot water = Heat gained by cold water
20xCx( 80- T ) = 60xCx(T- 30)
 T = 315.5 k
𝑇
∆ s of hot water = mc loge = -9.43J/k.
𝑇1
𝑇2
∆ s of hot water = mc loge = 10.19 J/k
𝑇
∴ Total change in entropy = 10.19 – 9.43 = 0.76J/k

By k.c.a