Lecture 3: Second Law of
Thermodynamics and Entropy
by
Prof. T. Sundararajan, Thermodynamics &
Combustion Laboratory
Department of Mechanical Engineering,
IIT Madras
Heat Engine
QH = QC + W
QH
Work, W
Wnet Wt W p QC
th 1
QH QH QH QC
Thermal Power Plant
QH Boiler
Turbine
Pump
Wt
Wp
Condenser
3
QC
Heat Pump or Refrigerator
TH
QH
QH QC W QC
COPHP 1
W W W W
HP
QC
COPRe f
W QC
TC
Kelvin- Planck (K-P) Statement of II Law
“It is impossible to construct a heat engine which exchanges
heat with a single reservoir and produces positive work, while
operating on a cycle”.
Or
“It is impossible to construct heat engine with 100% thermal
efficiency”.
TH
QH
W
E
Clausius Statement
“It is impossible to construct a Heat Pump or Refrigerator which
pumps heat from a low temperature body to a high temperature
body, without any work input, while operating on a cycle”.
Or
“It is impossible to construct a Heat Pump or Refrigerator
which has infinite COP”. T
H
QH
HP
QC
TC
Equivalence of K-P & Clausius Statements
TH
TH TH
QC QH QH-QC
W W
HP
+ = E
QC
QC
TC
TC
Reversible Heat Engine
Source TH TH
QH QH
W W
E HP
W 1 1
QC QC th
QH COPHP (QH / W )
Sink TC TC
Properties of Reversible Heat Engine
• Between given temperatures of TH and TC, maximum
thermal efficiency will be obtained for a reversible heat
engine. Any irreversible heat engine will have a lower
thermal efficiency, as compared to the reversible heat
engine.
• All reversible heat engines operating between the same
temperature limits of TH and TC, will have the same
thermal efficiency irrespective of the material of
construction and working fluid employed.
• The efficiency of a reversible heat engine is only a function
of the temperature limits TH and TC. In other words, th =
f(TH,TC).
Reversible engine is most efficient
Source TH Source TH
QH QH
WR WA
ER EA
QC Q’C
W A > WR
Sink TC Sink TC
Operate reversible engine as heat pump and combine with
engine A. It leads to violation of K-P statement.
Efficiency of Reversible Heat Engine
Source TH
QH QC W
TH TC TH TC QH
W
T E
th , R 1 C
TH
QC
Absolute temperature scale
Sink TC
TKelvin T o
Celsius 273.15
Carnot cycle
1
4
p
2 p
3
4 1
3 2
V V
Heat Engine Heat Pump
Irreversibilities
i) lack of equilibrium
ii) presence of a dissipative effect which
dissipates useful work into thermal form.
Heat transfer due to finite temperature difference (lack of thermal equilibrium)
Free expansion of a gas (lack of mechanical equilibrium)
Mass transfer due to finite concentration difference (lack of chemical
equilibrium)
Flash evaporation (lack of mechanical equilibrium)
Spontaneous chemical reaction such as combustion (lack of chemical
equilibrium)
Friction between two solids (dissipative effect)
Fluid friction or viscosity (dissipative effect)
Ohmic Resistance (dissipative effect)
Magnetic hysterisis (dissipative effect)
Plastic work (dissipative effect)
Clausius inequality
For reversible engine
Q QH QC
T T 0 T 0 0
H C
For irreversible engine
Q QH QC'
T T 0 T 0 0
H C
For any cycle
Q
T 0
Entropy
Qrev
2
Define S
1
T 2
p C
Q Q
1 A 2 C 1
T
0
1 B 2 C 1
T
0
1
B
V
Qrev Qrev
1 A 2
T
2 C 1
T
0
Qrev Qrev
1 B 2
T
2 C 1
T
0 Thus, S is a path independent
quantity or thermodynamic property
Qrev Qrev
1 A 2
T
1 B 2
T
0
Entropy calculations
Qrev
ds
T
Qrev du p dV dH V dp T dS
T V T p
For ideal gas S m C v ln 2 R ln 2 m C p ln 2 R ln 2
T1 V1 T1 p1
T2
For solids/ liquids S m C ln
T1
h fg
For phase change S m
T
For isothermal Qrev
S
T
heat transfer
Entropy change
• Entropy is a measure of randomness in a system
• When heat is added, entropy is transferred to
system. But work is an organised energy interaction.
Work transfer does not produce entropy transfer
• In irreversible processes, useful work is dissipated
into thermal form. Entropy is produced in such cases
• Entropy change S = STransfer + SProduction. In a
reversible adiabatic process, both transfer and
production of entropy are absent. So, such a
process is isentropic
Entropy production & work loss
SUniverse S system S surroundings 0
Lost Work Tamb S produced Tamb SUniverse
Thank You