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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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Education
CSIR NET-JRF, GATE, IIT-JAM, JEST, TIFR and GRE for Physics
H.N. 28 A/1, Jia Sarai, Near IIT-Delhi, Hauz Khas, New Delhi-110016
Contact: +91-89207-59559, 8076563184
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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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Education
CSIR NET-JRF, GATE, IIT-JAM, JEST, TIFR and GRE for Physics
H.N. 28 A/1, Jia Sarai, Near IIT-Delhi, Hauz Khas, New Delhi-110016
Contact: +91-89207-59559, 8076563184
Website: www.pravegaa.com | Email: [email protected]
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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Education
CSIR NET-JRF, GATE, IIT-JAM, JEST, TIFR and GRE for Physics
H.N. 28 A/1, Jia Sarai, Near IIT-Delhi, Hauz Khas, New Delhi-110016
Contact: +91-89207-59559, 8076563184
Website: www.pravegaa.com | Email: [email protected]
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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Education
CSIR NET-JRF, GATE, IIT-JAM, JEST, TIFR and GRE for Physics
H.N. 28 A/1, Jia Sarai, Near IIT-Delhi, Hauz Khas, New Delhi-110016
Contact: +91-89207-59559, 8076563184
Website: www.pravegaa.com | Email: [email protected]
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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