Entropy
Lecture 20
Can two Reversible Adiabatic Paths Intersect Each Other ?
Assume that two reversible adiabatics AC and BC
intersect each other at point C.
Let a reversible isotherm AB be drawn in such a way that
it intersects the reversible adiabatics at A and B.
The three reversible processes AB, BC, and CA together
A
constitute a reversible cycle, and the area included
represents the net work output in a cycle. B
Such a cycle is impossible, as it violates the Kelvin-Planck
statement of the second law.
Therefore, the assumption of the intersection of the
reversible adiabatics is wrong and through one point, C
there can pass only one reversible adiabatic.
Since two constant property lines can never intersect
each other, it is inferred that a reversible adiabatic path
must represent some property, which is yet to be
identified.
Clausius’ Theorem
Let a system be taken from an equilibrium state i to Reversible
another equilibrium state f by following the reversible path adiabatics
i–f.
Let a reversible adiabatic i–a be drawn through i and i
another reversible adiabatic b–f be drawn through f.
Then a reversible isotherm a–b is drawn in such a way that
the area under i–a–b–f is equal to the area under i–f.
Reversible
1 f
From Equation 1 and 2 isotherm
As,
Note: Any reversible path may be substituted by a reversible zigzag path, between the same end
states, consisting of a reversible adiabatic followed by a reversible isotherm and then by a
reversible adiabatic, such that the heat transferred during the isothermal process is the same as
that transferred during the original process.
Clausius’ Theorem…continued
Let a smooth closed curve representing a reversible
cycle be considered. Reversible
Let the closed cycle be divided into a large number adiabatics
đQ3
of strips by means of reversible adiabatics. e Reversible
đQ1
Each strip may be closed at the top and bottom by f isotherms
reversible isotherms. a
b
The original closed cycle is thus replaced by a zigzag
closed path consisting of alternate adiabatic and đQ2
đQ4
isothermal processes, such that the heat transferred c
d g
during all the isothermal processes is equal to the h
heat transferred in the original cycle.
Thus the original cycle is replaced by a large number
of Carnot cycles.
If the adiabatics are close to one another and the
number of Carnot cycles is large, the saw-toothed
zigzag line will coincide with the original cycle.
Clausius’ Theorem…continued
For the elemental cycle abcd If similar equations are written for all the
elemental Carnot cycles, then for the whole
original cycle
If heat supplied is taken as positive
and heat rejected as negative
For the elemental cycle efgh
The cyclic integral of đQ/T for a reversible cycle is
equal to zero. This is known as Clausius’ theorem.
The letter R emphasizes the fact that the equation
is valid only for a reversible cycle.
The Property of Entropy
Let a system be taken from an initial equilibrium state i to a
final equilibrium state f by following the reversible path R1.
The system is brought back from f to i by following another i
reversible path R2. R2
Then the two paths R1 and R2 together constitute a reversible
cycle.
R1
From Clausius’ theorem Since R2 is a reversible path
f
Integral đQ/T is independent of the reversible path connecting i and f.
Therefore, there exists a property of a system whose value at the final state
f minus its value at the initial state i is equal to Integral đQ/T. This property
is called entropy, and is denoted by S.
The Property of Entropy…continued
If Si is the entropy at the initial state i, and If the system is taken from an initial equilibrium
Sf is the entropy at the final state f, then state i to a final equilibrium state f by an irreversible
path, since entropy is a point or state function, and
the entropy change is independent of the path
followed, the non-reversible path is to be replaced
by a reversible path to integrate for the evaluation of
When the two equilibrium states are entropy change in the irreversible process.
infinitesimally near
Reversible
4 T i path
dS is an exact differential because S is a point T
function and a property. The subscript R in đQ
indicates that heat đQ is transferred reversibly. Actual f
It is an extensive property, and has the unit J/K. irreversible
path
dS
Si S Sf
Entropy
Lecture 21
Temperature-Entropy Plot
The infinitesimal change in entropy dS due to reversible heat transfer đQ at temperature T is
If đQrev = 0, i.e., the process is reversible and adiabatic.
i
i f
T
T
R
Qrev =T(Sf - Si)
𝒇 f
Qrev = 𝒊TdS
Si Sf Si Sf
dS S
Area under a reversible path on the Reversible isothermal heat transfer
T-S plot represents heat transfer
Carnot Cycle on T-S Plane
Q1
T
WC WE
Q2
S
The Inequality of Clausius
Consider a cycle ABCD, AB be a general Reversible
process, either reversible or irreversible, while adiabatics
the other processes in the cycle are reversible.
Let the cycle be divided into a number of
T=C
elementary cycles, as shown. T
đQ
D C
T2
đQ2
for any process AB, reversible or irreversible.
The Inequality of Clausius…continued
for any process AB, reversible or Since entropy is a property and the cyclic
irreversible. integral of any property is zero.
For a reversible process This equation is known as the inequality of
Clausius. It provides the criterion of the
reversibility of a cycle.
Hence, for any process AB the cycle is reversible.
the cycle is irreversible and
Then for any cycle possible.
the cycle is impossible, since
it violates the second law.
Entropy Change in an Irreversible Process
For any process undergone by a system, we have
For the reversible cycle consisting of A and B
For the irreversible cycle consisting of A and C
5
Entropy Change in an Irreversible Process…continued
for any irreversible process,
5
Since the path B is reversible,
for a reversible process
6
Since entropy is a property, entropy changes
for the paths B and C would be the same. for the general case, we can write
From equations 5, 6 and 7
The equality sign holds good for a reversible process
and the inequality sign for an irreversible process.
Entropy
Lecture 22
Principle of Increase of Entropy
For any infinitesimal process The principle of increase of entropy: The entropy
undergone by a system, we have of an isolated system can never decrease. It always
increases and remains constant only when the
process is reversible.
for an isolated system
System
For a reversible process,
Q
For an irreversible process
Surroundings isolated
(composite) system
Principle of Increase of Entropy…continued
Entropy may decrease locally at some
region within the isolated system, but it Smax
must be compensated by a greater increase
of entropy somewhere within the system so
that the net effect of an irreversible process
is an entropy increase of the whole system.
The entropy increase of an isolated system Sisol
is a measure of the extent of irreversibility Equilibrium
of the process undergone by the system. state
The entropy of an isolated system always
increases and becomes a maximum at the
state of equilibrium. Xe
When the system is at equilibrium, any X
conceivable change in entropy would be
zero.
Transfer of Heat Through a Finite Temperature Difference
System boundary
Q
T1 T2
Reservoir A Reservoir B
for the isolated system comprising
the reservoirs and the rod,
Note: Since T1 > T2, ΔSuniv is positive, and the process is
irreversible and possible. If T1 = T2, ΔSuniv is zero, and the
process is reversible. If T1 < T2, ΔSuniv is negative and the
process is impossible.
Evaluation of Entropy Change by T-ds Relation
Note: The T-ds relations can be used to find the
entropy change between two states in reversible
as well as irreversible processes.
[P,V,T relations and u=f(T) and/or h=f(T)]
Thermodynamic Property Relationship
For a constant volume process constant
volume line
For a constant pressure process
slope of constant volume
line on T−s diagram.
constant
pressure line
slope of constant pressure line
on h−s diagram is given by
temperature.
slope of constant pressure
line on T−s diagram.
Entropy Relations for Ideal Gas
Note: Its time to derive the expressions for change in entropy of an ideal gas in terms
of p-V -T .
Expression for ∆S in terms of Volume and Temperature
8
Expression for ∆S in terms of Temperature and Pressure
9
Expression for ∆S in terms of Pressure and Volume
10
Note: Any equation out of 8, 9 and 10
may be used to find entropy change in
case of constant pressure, constant
volume and constant temperature
process.
Entropy Change in Polytropic Process
Numerical 6.1
A heat engine operates between source at 600 K and sink at 300 K. Heat supplied by
source is 500 kJ. Evaluate feasibility of engine and nature of cycle for the following
conditions.
(i) Heat rejected being 200 kJ
(ii) Heat rejected being 400 kJ
(iii) Heat rejected being 250 kJ
đ𝑄 500 200
ර = − = 0.1667 > 0, 𝐻𝑒𝑎𝑡 𝐸𝑛𝑔𝑖𝑛𝑒 𝑖𝑠 𝑛𝑜𝑡 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒.
𝑇 600 300
đ𝑄 500 400
ර = − = −0.5 < 0, 𝐻𝑒𝑎𝑡 𝐸𝑛𝑔𝑖𝑛𝑒 𝑖𝑠 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑎𝑛𝑑 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒.
𝑇 600 300
đ𝑄 500 250
ර = − = 0, 𝐻𝑒𝑎𝑡 𝐸𝑛𝑔𝑖𝑛𝑒 𝑖𝑠 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑎𝑛𝑑 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒.
𝑇 600 300
Entropy
Lecture 23
Numerical 6.2
Two kg of water at 800C are mixed adiabatically with 3 kg of water at 300C in a constant
pressure process of 1 atmosphere. Find the increase in the entropy of the total mass of
water due to the mixing process (cp of water = 4.187 kJ/kg K)
Find final equilibrium temperature Tf after mixing
𝑚𝑐𝑝 𝑇1 − 𝑇𝑓 = 𝑚𝑐𝑝 𝑇𝑓 − 𝑇2
2 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 3 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
𝑇𝑓
∆𝑆 2 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 = 𝑚𝑐𝑝 𝑙𝑛 ∆𝑆 𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆 2 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 + ∆𝑆 3 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
𝑇1
𝑇𝑓
∆𝑆 3 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 = 𝑚𝑐𝑝 𝑙𝑛 Ans:
𝑇2
∆𝑆 𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 0.0592 𝑘𝐽/𝐾
Numerical 6.3
Ten grams of water at 200C is converted into ice at –100C at constant atmospheric
pressure. Assuming the specific heat of liquid water to remain constant at 4.2 J/g K and
that of ice to be half of this value, and taking the latent heat of fusion of ice at 0°C to be
335 J/g, calculate the total entropy change of the system.
T1 = 293 K
T2 = 273 K Entropy change when ice forms at 00C
T3 = 263 K
hfusion = 335 J/g −𝑚 × ℎ𝑓𝑢𝑠𝑖𝑜𝑛 ∆𝑆 𝑠𝑦𝑠𝑡𝑒𝑚 =
∆𝑆 𝐼𝐼 =
𝑇2 ∆𝑆 𝐼 + ∆𝑆 𝐼𝐼 + ∆𝑆 𝐼𝐼𝐼
Entropy change from 200C to 00C Entropy change from 00C to -100C
𝑇2 𝑇3
∆𝑆 𝐼 = 𝑚𝑐𝑝𝑤 𝑙𝑛 ∆𝑆 𝐼𝐼𝐼 = 𝑚𝑐𝑝𝑖 𝑙𝑛 Ans:
𝑇1 𝑇2
∆𝑆 𝑠𝑦𝑠𝑡𝑒𝑚 = −16.02 𝐽/𝐾
Numerical 6.5
A closed system contains air at a pressure 1 bar, temperature 300 K and volume 0.018
m3. This system undergoes a thermodynamic cycle consisting of the following three
processes in series :
(i) Constant volume heat addition till pressure becomes 5 bar,
(ii) Constant pressure cooling, and
(iii) Isothermal heating to initial state.
Represent the cycle on T-S and p-V plots and evaluate the change in entropy for each
process.
Take cv = 0.718 kJ/kg K and R = 0.287 kJ/kg K.
Numerical 6.5…solution
Find m 𝑉2 𝑇2
𝑆2 − 𝑆1 = 𝑚𝑅 𝑙𝑛 + 𝑚𝑐𝑣 𝑙𝑛
𝑉1 𝑇1
𝑇3 𝑃3
𝑆3 − 𝑆2 = 𝑚𝑐𝑝 𝑙𝑛 − 𝑚𝑅 𝑙𝑛
𝑇2 𝑃2
Find T2
𝑇1 𝑃1
𝑆1 − 𝑆3 = 𝑚𝑐𝑝 𝑙𝑛 − 𝑚𝑅 𝑙𝑛
𝑇3 𝑃3
Answer:
S2-S1 = 0.0242 kJ/K
S3-S2 = -0.0338 kJ/K
S1-S3 = 0.0096 kJ/K