CHAPTER

4 Second Law of
Thermodynamics
 Introduction

 A process must satisfy the first law in order to occur.

 Satisfying the first law alone does not ensure that the process will take
place.

 Second law is useful:

 Provide means for predicting the direction of processes,

 Establishing conditions for equilibrium,
 Determining the best theoretical performance of cycles, engines
and other devices.
A cup of hot coffee does
not get hotter in a cooler
room.
Transferring
heat to a paddle
wheel will not
cause it to
rotate.

These processes cannot occur

even though they are not in
Transferring heat to a wire violation of the first law.
will not generate electricity.
Second Law of Thermodynamics

Kelvin-Planck statement
 No heat engine can have a
thermal efficiency 100
percent.

 As for a power plant to

operate, the working fluid
must exchange heat with the
environment as well as the
furnace.
 Heat Engines

 Work can easily be converted to other forms of

energy, but?

 Heat engine differ considerably from one

another, but all can be characterized :

o They receive heat from a high-temperature source

o They convert part of this heat to work

o They reject the remaining waste heat to a low-

temperature sink atmosphere
o They operate on a cycle
The work-producing
device that best fit
into the definition of a
heat engine is the
steam power plant,
which is an external
combustion engine.
 Thermal Efficiency

 Represent the magnitude of the energy wasted in order to

complete the cycle.
 A measure of the performance that is called the thermal
efficiency.
 Can be expressed in terms of the desired output and the
required input
Desired Result
 th 
Required Input
 For a heat engine the desired result is the net work done
and the input is the heat supplied to make the cycle
operate.
The thermal efficiency is always less than 1 or less than 100
percent.

Wnet , out
 th 
Qin
where

Wnet , out  Wout  Win

Qin  Qnet
 Applying the first law to the cyclic heat engine

Qnet , in  Wnet , out  U

Wnet , out  Qnet , in
Wnet , out  Qin  Qout
 The cycle thermal efficiency may be written as

Wnet , out
 th 
Qin
Qin  Qout

Qin
Qout
 1
Qin
 A thermodynamic temperature scale related to the heat transfers
between a reversible device and the high and low-temperature
reservoirs by

QL TL

QH TH

 The heat engine that operates on the reversible Carnot cycle is

called the Carnot Heat Engine in which its efficiency is

TL
 th , rev  1
TH
 Heat Pumps and Refrigerators

 A device that transfers heat from a low temperature

medium to a high temperature one is the heat pump.

 Refrigerator operates exactly like heat pump except that

the desired output is the amount of heat removed out of
the system

 The index of performance of a heat pumps or

refrigerators are expressed in terms of the coefficient of
performance.
 QH QH QL
COPHP   COPR 
Wnet , in QH  QL Wnet , in
 Carnot Cycle

Process Description

1-2 Reversible isothermal heat addition at high

temperature
2-3 Reversible adiabatic expansion from high
temperature to low temperature
3-4 Reversible isothermal heat rejection at low
temperature
4-1 Reversible adiabatic compression from low
temperature to high temperature
Execution of Carnot cycle in a piston cylinder device
 The thermal efficiencies of actual and reversible heat engines
operating between the same temperature limits compare as follows

 The coefficients of performance of actual and reversible refrigerators

operating between the same temperature limits compare as follows
Example 4.1
Solution:
A steam power plant
produces 50 MW of net Wnet , out
 th 
work while burning fuel to QH
produce 150 MW of heat 50 MW
  0.333 or 33.3%
energy at the high 150 MW

temperature. Determine the

Wnet , out  QH  QL
cycle thermal efficiency and
the heat rejected by the QL  QH  Wnet , out
cycle to the surroundings.  150 MW  50 MW
 100 MW
Example 4.2

A Carnot heat engine receives 500 kJ of heat per cycle from a high-
temperature heat reservoir at 652ºC and rejects heat to a low-temperature heat
reservoir at 30ºC. Determine :
(a) The thermal efficiency of this Carnot engine
(b) The amount of heat rejected to the low-temperature heat
reservoir

Solution:

TH = 652oC
TL QL TL
QH
 th , rev  1  
TH QH TH
HE
WOUT
(30  273) K (30  273) K
 1   0.328
QL (652  273) K ( 652  273) K
TL = 30oC  0.672 or 67.2% QL  500 kJ ( 0.328)
 164 kJ
Example 4.3

An inventor claims to have developed a refrigerator that maintains the

refrigerated space at 2ºC while operating in a room where the temperature is
25ºC and has a COP of 13.5. Is there any truth to his claim?

Solution:

TH = 25oC
QL TL
COPR  
QH
QH  QL TH  TL
(2  273) K
R
Win 
(25  2) K
QL  1196
.
TL = 2oC

- this claim is also false!

Supplementary Problem 4.1

1. A 600 MW steam power plant, which is cooled by a river, has a thermal

efficiency of 40 percent. Determine the rate of heat transfer to the river water.
Will the actual heat transfer rate be higher or lower than this value? Why?
[900 MW]

2. A steam power plant receives heat from a furnace at a rate of 280 GJ/h. Heat
losses to the surrounding air from the steam as it passes through the pipes and
other components are estimated to be about 8 GJ/h. If the waste heat is
transferred to the cooling water at a rate of 145 GJ/h, determine (a) net power
output and (b) the thermal efficiency of this power plant.
[ 35.3 MW, 45.4% ]

3. An air conditioner removes heat steadily from a house at a rate of 750 kJ/min
while drawing electric power at a rate of 6 kW. Determine (a) the COP of this air
conditioner and (b) the rate of heat transfer to the outside air.
[ 2.08, 1110 kJ/min ]
4. Determine the COP of a heat pump that supplies energy to a house at a rate of
8000 kJ/h for each kW of electric power it draws. Also, determine the rate of
energy absorption from the outdoor air.
[ 2.22, 4400 kJ/h ]

5. An inventor claims to have developed a heat engine that receives 700 kJ of heat
from a source at 500 K and produces 300 kJ of net work while rejecting the waste
heat to a sink at 290 K. Is this reasonable claim?

6. An air-conditioning system operating on the reversed Carnot cycle is required to

transfer heat from a house at a rate of 750 kJ/min to maintain its temperature at
24oC. If the outdoor air temperature is 35oC, determine the power required to
operate this air-conditioning system.
[ 0.463 kW ]

7. A heat pump is used to heat a house and maintain it at 24 oC. On a winter day
when the outdoor air temperature is -5oC, the house is estimated to lose heat at a
rate of 80,000 kJ/h. Determine the minimum power required to operate this heat
pump.
[ 2.18 kW ]
 Entropy

 The 2nd law states that process occur in a certain direction, not
in any direction.
 It often leads to the definition of a new property called
entropy, which is a quantitative measure of disorder for a
system.

 Entropy can also be explained as a measure of the

unavailability of heat to perform work in a cycle.

 This relates to the 2nd law since the 2nd law predicts that not
all heat provided to a cycle can be transformed into an equal
amount of work, some heat rejection must take place.
 Entropy Change

 The entropy change during a reversible process is defined as

 For a reversible, adiabatic process

dS  0
S2  S1

 The reversible, adiabatic process is called an isentropic process.

 Entropy Change and Isentropic Processes

The entropy-change and isentropic relations for a process can be

summarized as follows:

i. Pure substances:
Any process: Δs = s2 – s1 (kJ/kgK)
Isentropic process: s2 = s1

ii. Incompressible substances (liquids and solids):

Any process: s2 – s1 = cav T2/T1 (kJ/kg
Isentropic process: T2 = T1
iii. Ideal gases:

a) constant specific heats (approximate treatment):

for all process
T2 v2
s2  s1  Cv , av ln  R ln
T1 v1

T2 P2
s2  s1  C p , av ln  R ln
T1 P1
for isentropic process
k
 P2   v1 
   
 P1  s  const .  v2 
Example 4.5

Steam at 1 MPa, 600oC, expands in a turbine to 0.01 MPa. If the process is

isentropic, find the final temperature, the final enthalpy of the steam, and the
turbine work.

Solution:

mass balance : m 1  m 2  m State1

energy balance
sup erheated
E  E P1  1 MPa 
 h1  3698.6 kg
in out kJ
o
m 1h1  m 2 h2  W out T1  600 C 
s1  8.0311 kgkJ. K
W  m  h  h 
out 1 2
 Since that the process is isentropic,
 Work of turbine
s2=s1
Wout  h1  h2
State 2  3698.6  2545.6
P2  0.01 MPa  sat.mixture  1153 kJ
kg

s2  8.0311 kgkJ. K  x2  0.984
h2  191.8  0.984  2392.1
 2545.6 kJ
kg

T2  Tsat @ P2  45.81o C
Isentropic Efficiency for Turbine
Isentropic Efficiency for Compressor
Example 4.6

Steam at 1 MPa, 600°C, Solution:

expands in a turbine to 0.01  Theoretically:
MPa. The isentropic work of
wa h1  h2 a
the turbine is 1152.2 kJ/kg. If isen ,T  
the isentropic efficiency of the ws h1  h2 s
turbine is 90 percent, calculate
wa  isen ,T  ws
the actual work. Find the actual
turbine exit temperature or  0.9 1153
quality of the steam.
 1037.7 kJ
kg
State1
P1  1 MPa  h1  3698.6 kg
kJ


T1  600o C  s1  8.0311 kgkJ. K
State 2 s
sat.mixture
P2  0.01 MPa 

 x2 s  0.984
s2 s  s1  8.0311 kgkJ. K 
 h  2545.6 kJ
2s kg

 Obtain h2a from Wa

wa  h1  h2 a State 2a
h2 a  h1  wa
P2  0.01 MPa  sup erheated
 2660.9 kJ  o
kg h2 a  2660.9 kJ
kg  T
 2a  86.85 C
Example 4.7

Air enters a compressor and is  For isentropic process of IGL

k 1
compressed adiabatically from
 T2 s   P2  k
0.1 MPa, 27°C, to a final state   
of 0.5 MPa. Find the work done  T1   P1 
0.4/1.4
on the air for a compressor  0.5 
T2 s   27  273  
isentropic efficiency of 80  0.1 
percent.  475.4 K
 Then
Solution:
Wc , s  1.005  475.4  300 
 From energy balance
W c , s  m  h2 s  h1   176 kJ
kg

Wc , s
W c , s Wc ,a   220 kJ
Wc , s   h2 s  h1 isen,c kg
m
 CP T2 s  T1 
Supplementary Problems 4.2
1. The radiator of a steam heating system has a volume of 20 L and is filled with
the superheated water vapor at 200 kPa and 150oC. At this moment both inlet
and exit valves to the radiator are closed. After a while the temperature of the
steam drops to 40oC as a result of heat transfer to the room air. Determine the
entropy change of the steam during this process.
[ -0.132 kJ/.K ]

2. A heavily insulated piston-cylinder device contains 0.05 m 3 of steam at 300

kPa and 150oC. Steam is now compressed in a reversible manner to a pressure
of 1 MPa. Determine the work done on the steam during this process.
[ 16 kJ ]

3. A piston –cylinder device contains 1.2 kg of nitrogen gas at 120 kPa and
27oC. The gas is now compressed slowly in a polytropic process during which
PV1.3=constant. The process ends when the volume is reduced by one-half.
Determine the entropy change of nitrogen during this process.
[ -0.0617 kJ/kg.K ]
4. Steam enters an adiabatic turbine at 8 MPa and 500oC with a mass flow rate
of 3 kg/s and leaves at 30 kPa. The isentropic efficiency of the turbine is
0.90. Neglecting the kinetic energy of the steam, determine (a) the
temperature at the turbine exit and (b) the power output of the turbine.
[ 69.09oC,3054 kW ]

5. Refrigerant-R134a enters an adiabatic compressor as saturated vapor at 120

kPa at a rate of 0.3 m3/min and exits at 1 MPa pressure. If the isentropic
efficiency of the compressor is 80 percent, determine (a) the temperature of
the refrigerant at the exit of the compressor and (b) the power input, in kW.
Also, show the process on a T-s diagram with respect to the saturation lines.
[ 58.9oC,1.70 kW ]