The Second Law of

Thermodynamics

Entropy

Energy of some kind is changing from being

localized (“concentrated”) to becoming
spread out if it is not hindered.
1. R. Clausius (1850)
• “It is impossible to construct a device that operates
in a cycle and produces no effect other than the
removal of heat from a body at one temperature and
the absorption of an equal quantity of heat by a body
at a higher temperature.”
• Led to derive an expression for the maximum
possible energy conversion efficiency taking
losses into account.
2. Max Planck
• “It is impossible to construct an engine that will work
in a complete cycle and produce no other effect
except the raising of a weight and the cooling of a
heat reservoir”
Carnot’s Observation
It is the flow of heat from higher
temperature to a lower temperature
that motivates a steam engine.
Key Insight
Whenever an energy distribution is out
of equilibrium, a potential or
thermodynamic force exists that the
world acts spontaneously to dissipate
or minimize.
Entropy : The dissipated potential.
First Law Second Law
• Expresses that which • Expresses that which
remains the same changes and
• Time-symmetric motivates the change
• No time, the past, • Time asymmetry
present, and future • With its one way flow,
are indistinguishable introduces the basis
for telling the
differences.
The world acts spontaneously to minimize (or
equivalently maximize the entropy) while
energy at the same time is entirely conserved.
S > 0
 Entropy
• A property of matter that measures the degree of
randomization or disorder at the microscopic
level.
– The natural state of affairs is for entropy to be
produced by all processes
– Loss of ability to do useful work
– Decrease in the availability of energy
• Entropy can be produced but never destroyed
– This notion provides the Second Law of
Thermodynamics.
• An extensive property S = ms
At the state of thermodynamic equilibrium
S = 0
Heat flow from glass = heat flow into the room
Whenever energy is out of equilibrium with its
surroundings, a potential exists for producing
change that, following the second law, is
spontaneously minimized.
 Joule’s Experiment
In all real world processes: S >0

“The energy of the world remains the same. The

entropy of the world strives to a maximum.”
 Second Law of Thermodynamics
• The spontaneous flow of heat is unidirectional from
the higher temperature to the lower temperature.
• All naturally occurring processes always tend to
change spontaneously in a direction that will lead to
equilibrium.
• Not all of the heat absorbed by a system can be
converted into work without leaving permanent
changes.
• It is impossible to convert the heat absorbed by a
system completely into work by a cyclic process
(system is restored periodically to its original state).
 Heat Engine
Absorb heat (QH) at a temperature (TH). For a periodic engine,
only a fraction of heat absorbed is converted into work (W)
because heat is rejected (QC) at a lower temperature (TC) to
enable the engine to return to its original state.
• Absorption of heat at a high T
Components • Production of work
• Rejection of heat at a lower T

Cyclic • The working fluid of a heat engine

QH
Operation absorbs heat from a hot reservoir,
• produces a net amount of work, W
• discards heat to a cold reservoir, QC
and returns to its initial state.
 use
Heat Engines
use Engine like the
use ideal
processes Cycles
Heat like
for energy Constant
to do which Carnot
Pressure combine
Work Cycle
and
constrained and the more
Constant practical
by the
Volume Otto
First Law of Heat Engine
Thermodynamics Processes Cycle
Isothermal
and
and the
Adiabatic
Second Law of Other
illustrated by
Thermodynamics Examples
P-V Diagrams
Heat Engine
 TH TH

QH QH

Heat Engine W Heat Engine W

QC QC

TC TC

Forward Heat Engine Reverse Heat Engine

Tc = Low Temperature Energy Reservoir

TH = High Temperature Energy Reservoir
Cycle: W  QH  QC

TH Thermal Efficiency of the

Engine ():
QH
 = net work output / heat input
Heat Engine W W (QH  QC )
 
QH QH
QC
(TH  TC ) TC
TC   1
TH TH
Tc = Low Temperature Energy Reservoir
TH = High Temperature Energy Reservoir
Carnot’s Principle (1824)
1. No engine can be more efficient than a
reversible engine operating between the
same high temperature and low
temperature reservoirs.
2. The efficiencies of all reversible engines
operating between the same constant
temperature reservoirs are the same.
3. The efficiency of a reversible engine
depends only upon the temperatures of
the heat source and heat receiver.
 Carnot’s Principle
1 – 2 : Adiabatic compression from TC to TH
due to work performed on fluid
2 – 3 : Isothermal expansion as fluid expands
when heat is added to the fluid at
temperature TH
3 – 4 : Adiabatic expansion as the fluid
performs work during the expansion and
the temperature drops from TH to TC
4 – 1 : Isothermal compression as fluid
contracts when heat is removed from
the fluid at temperature TC
 Carnot Cycle
2

1 3

4
 Carnot engine equation may be written as:
QH QC QH  QC QH QC
   0
TH TC TH TC TH TC
Suggests the existence of :
Q For a reversible
S  process
T
Where: S = the change in entropy of a system during
some process [cal·K1]
Q = the amount of heat added to the system
during the process [cal]
T = absolute temperature at which the heat
was transferred [K]
Entropy: a measure of the unavailability of
heat to perform work in a cycle.
: a state function that provides one
to predict the natural direction of a
process.
: a measure of the order and
disorder of particles in a system
: an extensive property

For a closed system: S  0

1. Adiabatic and reversible process:
(Isentropic) dQrev = 0, dS = 0
2. Reversible process: dQ
dS 
T
3. Irreversible process: Since entropy is a state
function, the entropy changes of the irreversible
and reversible processes are identical for the same
change in state.
4. Constant Pressure Process (solid, liquid, or
gas):
dQP nCP dT
dQP  nCP dT dSP  
T T
S T Cpig dT P
  ln
R To R T Po
dU  dQ  dW
dU  dQrev  PdV but dH  dU  d ( PV )
dH  dU  PdV  VdP
dH  dQrev  PdV  PdV  VdP
dH  dQrev  VdP
dQrev  dH  VdP
RT
For ideal gas : dH  Cp dT and V 
ig

P
 RTdP 1
dQ
 rev  Cp ig
dT   
P  T
dQrev Cpig dT RdP dQrev
  and  dS and divide by R
T T P T
S 2 dS Cpig T dT P
S1 R R To T
  ln
Po
For reversible adiabatic process:  1
T2  P2  
  
T1  P1 
T2   1 P2
ln  ln
T1  P1
For T dependence of the molar heat capacity:
C p ig dT      1 
T0 R T  A ln  BT0   CT0   2T02  2  1
T 2 D
 
C p ig dT
T0 R T  ICPS(T0 , T ; A, B, C, D)
T

ig
T Cp dT
Cp ig 
 0 R T
T
S T
ln
T0
    1    1
ig
Cp   D
S
 A   BT0   CT0  2 2 
2

R    T0  2  ln 
ig
Cp
S
 MCPS(T0 , T ; A, B, C, D)
R
dT T

T
Cp ig
 Cp ig
ln
T0 T S To

S C p ig T P
 S
ln  ln
R R To P0
1. As an engineer, you are requested to evaluate an inventor’s
claim and advise whether the claim is possible or not. The
inventor claims to have invented an engine that can take in 20
kW at a temperature of 300K, rejects 10kW at 200K and delivers
10,000 J/s of mechanical power. What advise will you give the
inventor?
Overall Energy Balance
QH  W  QC
QH 20kW = 10kW + 10 kW ()
QH  QC TH  TC
Using Carnot Factor  
QH TH
20  10 300  TC
C.E. W 
20 300
TC  150 K  200 K

QC Using TH 20  10 TH  200

20 TH
TH  400K  300K
The claim is impossible!
 Example Problem

1. A central power plant, rated at 800,000 kW,

generates steam at 585 K and discards heat to a
river at 295K.
a) What is the maximum possible thermal
efficiency of the plant and what is the minimum
amount of heat that must be discarded to the
river?
b) If the actual thermal efficiency of the plant is
70% of the maximum, how much heat must be
discarded into the river at rated power and what
will be the temperature rise of the river, if it has
a flow rate of 160 m3/s?
Given:

585 K Heat Engine 295 K

QH QC
Reactor 800,000 kW River

W TH  TC 585  295
(a)      0.496
QH TH 585
Meaning: 49.6% is converted into useful work and
the other 50.4% is discarded to the river.
W 800000
QH    1612903.23 kW
 0.496
W Q  QC 1612903.23  QC
  H   0.496
QH QH 1612903.23
QC  812903.23 kW
(b) Actual Thermal Efficiency = (0.7) × (0.496)
= 0.3472
W
800000
QH    2304147.47 kW
 0.3472
W QH  QC 2304147.47  QC
    0.3472
QH QH 2304147.47
QC  1504147.47 kW

 H O  1000 kg / m3
2
m  V
kg m3 kg
m  1000 3 160  160000
m s s
Q  m C p T
kJ
1504147.47
Q s
T    40.44K
m C p 160000  4.184
kg kJ

kmol
s kmol  K 18 kg
2. If 10 mol of ethylene is heated from 200 to
1100C in a steady-flow process at
approximately atmospheric pressure, what
is its entropy change?
ig
dQ nCp dT S Cp T P
dS    S
ln  ln
T T R R To P0
   1    1
ig
Cp   D
S
 A   BT0   CT0  2 2 
2

R    T0  2  ln 
C p ig
S
 MCPS(T0 , T ; A, B, C, D)
R
dT T

T
C p ig  C p ig ln
T0 T S To
 Example Problem
1. A coal fired steam power plant produces
150 MW of electric power with a thermal
efficiency of 35%. If the energetic
efficiency of the boiler is 75%, heating
value of coal is 30 MJ/kg, and the
temperature rise of the cooling water in
the condenser is 10C, determine (a) the
fuel consumption rate in kg/h, and (b)
mass flow rate of cooling water.

Boiler Coal Power Plant Condenser

Given: Wnet=150 MW Req’d.: a) m fuel consumption
 = 0.35
b) m cooling water
Boiler efficiency = 0.75
qH = 30 MJ/kg
t = 10C
Solution:
(a)
Wnet Wnet 150
 QH    428.57 MJ / s
QH  0.35
QH  m  qH
MJ
428
s kg 3600s
m   19.022 
MJ s 1hr
0.75  30
kg
m  68480 kg / hr
(b)
QC  QH  Wnet  428.57  150  278.57 MJ / s
QC  Qcooling water
278.57 MJ / s  m  Cpwater  t
MJ
278.57
s 3600s 1000kJ
m     23,968 Mg / hr
kJ
4.184  10C 1hr 1MJ
kg C
 Rankine Cycle
3
Boiler Turbine

2 4

Pump Condenser
1

12 Reversible adiabatic pumping process

23 Constant pressure transfer of heat in the boiler
34 Reversible adiabatic expansion in the turbine
41 Constant pressure transfer of heat in the condenser
12 Reversible adiabatic pumping process
P1 P2 Wpump = H2  H1 S2 = S1

H 2  H1   VdP
P2
Wp = V(P2  P1)
P1
H2 = H1  Wp

23 Constant pressure transfer of heat in the boiler

P2 = P3 QH = H3  H2

34 Reversible adiabatic expansion in the turbine

Wturbine = H3  H4 S3 = S4

41 Constant pressure transfer of heat in the condenser

P4 P1 QC = H4  H1
 Rankine Cycle

Wnet QH  QC Wturbine  Wpump

  
QH QH QH


 H 3  H 2   H 4  H1  H 3  H 4   H 2  H1 

H 3  H 2  H3  H 2 
 Power Cycles
1. Carnot Cycle TSTS (Exp, Comp)
2. Rankine Cycle SPSP
3. Otto Cycle SVSV
4. Diesel Cycle SPSV
5. Dual Cycle SVPSV

Mean Effective Pressure (for reciprocating engine only)

Wn
MEP  VD = piston displacement
VD
 Internal Combustion Engines
• Gasoline engine using the Otto cycle
• Diesel engine using the Diesel cycle

The diesel engine is similar in operation to

the gasoline engine except that there is no
fuel in the cylinder at the beginning of the
compression stroke.
 Example Problem

2. A steam power plant operates on an ideal

Rankine cycle. Superheated steam flows into
the turbine at 3 MPa and 400C with a flow rate
of 100 kg/s and exits the condenser at 50C as
saturated water. Determine (a) the net power
output, (b) the thermal efficiency, and (c) the
quality of steam at the turbine exit. (d) How
would the efficiency change if the condenser
temperature can be lowered to 30C?

Answers: (a) 108,179 kW, (b) 33.2%, (c) 91.3%, (d) 36.5%
 Thermal Efficiency of a Heat Engine
W QC
  1
QH QH

In Otto cycle
  1 r 1

Where r is the compression ratio depending

on the nature of the working gas
Mathematical Statement of the Second Law

Entropy increase of reservoir at TH

Q
SH  
TH
Entropy decrease of reservoir at TH
Q
SC 
TC
Total entropy change in reservoir

ST  SH  SC Q

TH  TC 
TH TC
Since TH > TC, the total entropy change as a
result of this irreversible process is positive.
ST becomes smaller as the difference
(TH  TC) decreases
TH >>>TC: heat transfer is reversible
and ST  0
For irreversible heat transfer process, ST is
always +, approaching 0 as the process
becomes reversible.

Mathematical Statement of the Second Law:

ST  0
 Additional Problems
1. The combination of gasoline with specific gravity of
0.8 and a heating value of 46.8 kJ/g furnishes heat
to a heat engine. The theoretical maximum work
done by the engine is 2270.9 kJ if it rejects 3345.1
kJ at a temperature of 1200C. Determine:
a. Thermal efficiency of heat engine
b. Temperature at which heat is absorbed
c. Volume (cc) of gasoline required.

2. Two moles of ammonia are heated from 200 to

800C in a steady-flow process at atmospheric
pressure. Using Cp=f(T) of ammonia, determine the
entropy change of the gas.
 The Third Law of
Thermodynamics

The absolute entropy is zero for all

perfect crystalline substances at
absolute zero temperature.

NOTE: 5.8 Study Calculation of Ideal Work

5.9 Lost Work
5.10 Third Law of Thermodynamics
on pp.181 – 188
 Additional Problems
1. A Carnot cycle running on a closed system has 1.5 kg
of air. The temperature limits are 300K and 1000K,
and the pressure limits are 20kPa and 1900kPa.
Determine the (a) efficiency and (b) the net work
output.
2. An air standard Carnot cycle is executed in a closed
system between the temperature limits of 300K and
1000K. The pressure before and after the isothermal
compression are 100 and 300 kPa, respectively. If the
net work output per cycle is 0.22 kJ, determine:
1. The maximum P in the cycle
2. The heat transfer to air; and
3. The mass of air.