3 - Entropy

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Second Law of
Thermodynamics
3. Entropy
Entropy is an extensive thermodynamic property that is measure of a system’s thermal energy
per unit temperature that is unavailable for doing useful work. Thermodynamic entropy is a
non-conserved state function. For Isolated systems entropy never decreases. In statistical
mechanics, entropy is a measure of the number of ways in which a system may be arranged,
often taken to be a measure of ‘disorder’ (the higher the entropy the higher the disorder).
The infinitesimal change in the entropy ( dS ) of a system is the infinitesimal transfer of heat
energy (Q) to a closed system driving a reversible process, divides by temperature (T) of the
system.
Q
S  
T
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Q
It has unit Joule/Kelvin or dS  
T
Law of thermodynamics and entropy:
According to first law of thermodynamics
 Q  dU  PdV
From definition of Entropy
Q
S    Q  T S  TdS
T
TdS  dU  pdV
Inequality of Clausius
Consider an irreversible cyclic engine working between T1 and T2. If reversible engine is
operating between same temperature then from Carnot theorem.
Efficiency of irreversible (ir) will always smaller than efficiency of reversible engine(  r ).
 irr .   rev.
Q1irr  Q2irr Q1rev  Q2rev Q2irr Q2rev

  1   1 
Q1irr Q1rev Q1irr Q1rev
Q2irr T2 Q2irr Q1irr

1  1   
Q1irr T1 T2 T1
F0 irreversible cyclic Engine

Q1irr Q2irr
 0
T1 T2
Q
or  T
0
This relation is known as inequality of Clausius.
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Example: Two Carnot Engines A and B are operated in series. The first one A receives heat at
900 K and rejects to a reservoir at temperature T K. The second engine, B, receives the heat
rejected by the first Engine and in then rejects to a heat reservoir at 400 K.
Calculate the temperature T for the situation.
(a) The work outputs of the two engines are equal
(b) The efficiency of the two engines are equal.
For Engine A take in heat Q1 at temperature T1 and rejected heat Q at temperature T; and the
engine B taken in heat Q at temperature T and reject heat Q2 at temperature T2.
Solution: (a) WA  Q1  Q WB  Q  Q2
WA  WB Q1  Q  Q  Q2
Q1  Q2
2
Q
Q1 T1 Q2 T2
 and 
Q T Q T
Q1  Q2 T1  T2 T T
  1 2 2 T  650 K
Q T T
Solution: (b)  A   B
T T
1  1 2
T1 T
1
T  T1  T2  2 T  600 K
Example: Calculate the charge in isothermal expansion from an initial volume Vi to volume V f
Solution: For reversible process

TdS  dU  PdV
For isothermal process dU = 0
PdV
dS 
T
nRT
P
V
Vf
dV Vf
dS  nR   nR ln
Vi
V Vi
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Example: A mass of liquid at a temperature T1 is mined with an equal mass of the same liquid at
a lower temperature T2. the system is thermally insulated.
(a) compute the entropy-change
(b) show that it is necessarily positive.
Solution: Let c be the specific heat of the liquid. On the mining equal mass m of the same liquid
at temperature T1 and T2 let (T1 > T2).
Let T be the equilibrium temperature at minute.
mc T1  T   mc T  T2 
T1  T2
T 
2
T
Q
S1  
T1
T
Entropy change of hotter liquid to cool from T1 to T
T
dT T
S1  mc   mc ln
T1
T T1
S 2  Entropy change of hotter liquid to heat from T2 to T
T
S 2  mc ln
T2
S = Entropy change of the system.

S  S1  S 2
2
  T1  T2
 
T2  T  T2  2
 mc ln  mc ln 1   2mc ln
T1T2 2 T1T2
 
 TT 
 1 2 
(b) we know arithmetic mean is greater than geometric mean.
AM  G.M .
T1  T2
So,  T1T2 So S  0
2
Example: Compute the change in entropy when ice melt into steam. It is given that L1 is latent
heat of fusion, c is specific heat at water and L2 latent heat at vaporization.
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Solution: Assume T1 be the Kelvin temperature at which ice melts into water and T2 the Kelvin
temperature at which water is boiled to steam.
S 1 is entropy change when ice is converted into water
mL1
S1 
T1
S 2 Entropy change when water is heated from T1 to T2

T2
dT
S 2  mc 
T1
T
T2
S 2  mc ln
T1
S 3 Entropy change when water change into vapours
mL2
S 3 
T2
mL1 T mL
Total change in entropy S  S1  S 2  S3   mc ln 2  2
T1 T1 T2
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3 - Entropy

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Q1irr  Q2irr Q1rev  Q2rev Q2irr Q2rev

Q2irr T2 Q2irr Q1irr

F0 irreversible cyclic Engine

This relation is known as inequality of Clausius.

Solution: For reversible process

S 2  Entropy change of hotter liquid to heat from T2 to T

S = Entropy change of the system.

S 2 Entropy change when water is heated from T1 to T2

S 3 Entropy change when water change into vapours

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