CHAPTER 5

THE SECOND LAW OF

THERMODYNAMICS
 CONTENTS

5-1 The 2nd law & thermal energy reservoirs

5-2 Heat engines
5-3 Refrigerators & heat pumps
5-4 Perpetual-motion machines
5-5 The carnot cycle
5-6 The thermodynamic temperature scale
5-7 The carnot heat engine
5-8 The carnot refrigerator & heat pump
 5-1 The 2nd law & thermal energy reservoir

2nd law of processes occur in a certain direction, not

thermodynamics in just any direction.

 E.g. a cup of coffee does not get hotter in a cooler room &
transferring of heat to a wire will not generate electricity.
 1st law places no restriction on the direction of process
 A process will not occur until it satisfies both 1st & 2nd law.

Thermal energy hypothetical body that can absorb or

reservoir/Heat reject finite amounts of heat
reservoir isothermally
 E.g. oceans, lakes, rivers, atm. air & industrial furnace
 A high T heat reservoir from which heat is transferred -heat source
 A low T heat reservoir to which……………….. - heat sink

 Heat transfer from industrial sources to env. is of major concern.

 Work reservoir - sufficiently large system in stable equilibrium to
which & from which finite amounts of work can be transferred
adiabatically without any change in its P.
 Thermodynamic cycle - when the system undergoes a series of
processes & then returns to its original state, so that the properties
of the system at the end of the cycle are the same as its beginning.

5-2 Heat engines

 Work can be converted directly & completely, but converting heat to
work requires heat engines.
 Characteristic:
1) Receive heat from high-temperature
source.
2) Convert part of heat to work
(rotation shaft)
3) Reject remaining waste heat to low T
sink
4) Operate in a cycle.
Steam power plant as a heat engine operating in a thermodynamic cycle:

 The net work output of power plant: Wnet,out = Wout - Win (kJ)
 Can be analyzed as a closed system undergoing a cycle, U = 0,
therefore net output of the system:
Wnet,out = Qin - Qout (kJ)
 Thermal efficiency, nth
 index of performance of a work-producing device or a heat engine.
 defined as the ratio of the net work output to the heat input.
nth = Desired result
Required input
 for heat engines, the desired result is the net work done & the input
is the heat supplied to make the cycle operate.
 Thermal efficiency is always less than 1 or less than 100%.
Wnet ,out
th 
Qin
where
Wnet,out = Wout - Win
Qin  Qnet
Applying 1st law to cyclic heat engine: Q  Wnet ,out  U
net ,in

Wnet ,out  Qnet ,in

Wnet ,out  Qin  Qout
 The cycle thermal efficiency may be written as

Q QL
th  1  out or th  1 
Qin QH
Example:
A steam power plant produces 50 MW of net work while burning fuel
to produce 150MW of heat energy at the high temperature.
Determine the cycle thermal efficiency and the heat rejected by the
cycle to the surroundings. W
th  net ,out

QH
50MW
  0.333  33.3%
150MW
Wnet,out = QH - QL
QL = QH - Wnet,out
= 150 MW - 50 MW
= 100 MW
Example 5-17, Cengel

A 600-MW steam power plant, which is cooled by a nearby river, has

a thermal efficiency of 40%. Determine the rate of heat transfer to
the river water.
Will the actual heat transfer rate be higher or lower than this value?
State why?

Solution:
The rate of heat rejection is to be determined & the result is to be
compared to the actual case in practice.

Assumptions: (1) The plant operates steadily (2) The heat losses from
the working fluid at the pipes and other components are negligible.
Example 5-21, Cengel

An automobile engine consumes fuel at a rate of 28 L/h and deliver

60 kW of power to the wheels. If the fuel has a heating value of
44,000 kJ/kg and a density of 0.8 g/cm2, determine the efficiency of
this engine.

Solution:
Thermal efficiency of the engine is to be determined as power output
& fuel consumption rate of a car are given.

Assumptions: The car operates steadily

 Statements of the 2nd Law:
Kevin-Planck Statement:
It is impossible for any system to operate in a thermodynamic cycle &
deliver a net amount of work to its surroundings while receiving
energy by heat transfer from a single thermal reservoir.

The statement does not rule out the possibility of a system

developing a net amount of work from a heat transfer drawn from a
single reservoir. It only denies this possibility if the system
undergoes a thermodynamic cycle.

NO!
System
undergo
thermo.
cycle
 Analysis of Kelvin-Planck statement:
(1) From 1st Law:
Wcycle = Qcycle
 the net work done by the system undergoing a cycle = the net heat
transfer to the system. If Wcycle is -ve, then Qcycle is -ve.
 if a net amount of energy is transferred by work to the system
during the cycle, then an equal amount of energy is transferred by
the heat from the system during the cycle.
(2) From 2nd law:
 direction of energy transfer.
 a system undergoing a cycle from a single reservoir cannot deliver a
net amount of work to its surroundings. Therefore Wnet,cycle cannot be
+ve.
 But the statement not rule out the possibly that the net work is zero.
Therefore Wcycle  0 (single reservoir )

MAXIMUM POSSIBLE EFFICIENCY IS LESS THAN 100 %

th  100%
Clausius Statement:
It is impossible for any system to operate in such a way that the sole
result would be an energy transfer by the heat from a cooler to a
hotter body.
 The statement does not rule out the possibility of transferring
energy by heat from a cooler body to a hotter body.
 ‘Sole result’ - when a heat transfer from cooler to hotter body occur,
there must be some other effect within the system, surrounding or
both. COP  

Q Hot

metal
Yes bar No

Cold Q
 5-3 Refrigerators & pumps
 nature process: heat flows from high T to low T
 reverse process: heat from low T to high T refrigerators
 refrigerators & heat engines are cyclic device. The most frequently
used - vapor compression refrigeration cycle (a compressor, a
condenser, an expansion valve & an evaporator)

• (Fig. 5-25)

Basic components of a refrigeration system & typical operating

conditions
 Refrigerators: How it works

 Refrigerant enters the compressor as a vapor & is compressed to

condenser pressure (800 kPa & 60C). It leaves the compressor at a
relatively high temperature & cools down & as it flows through the
coils of condenser(800 kPa & 30C) by rejecting heat to the
surrounding medium.
 It then enters a capillary tube (expansion valve) where its pressure &
temperature drops drastically due to throttling effect.
 The low-temperature refrigerant(120 kPa & -25C) then enters the
evaporator, where it evaporates by absorbing heat from the
refrigerated space.
 The cycle is completed as the refrigerant( 120 kPa & -20C) leaves
the evaporator & reenters the compressor.
 freezer compartment where heat is picked up by refrigerant serves
as evaporator.
 coils where heat is dissipated serve as condenser.

The objective of a refrigerator is to

remove QL from the cooled space.
 QL is the magnitude of heat removed
from the refrigerated space at TL
 QH is the magnitude of heat rejected
to the warm env. At TH.
 Wnet,in is the net work input to the
refrigerator.
 Coefficient of performance (COP)]

 The efficiency of a refrigerator is expressed in terms of coefficient

of performance (COPR)
COPR = desired output = QL
required input Wnet,in
Apply 1st law of cyclic refrigerator,
QL  QH   0  Win   U cycle  0
Win  Wnet ,in  QH  QL
COP relation can be expressed as
QL 1
COPR  
QH  QL QH / QL  1

value of COPR can be greater than unity, that is the amount of heat
removed from the refrigerated space can be greater than the amount
of work input.
 Heat pumps
 device that transfer heat from low T to high T.
 Objective: to maintain a heated space at
a high T by absorbing heat from low T
source.
 COPHP = desired output = QH
required input Wnet,in
can also be expressed as
QH 1
COPHP  
QH  QL 1  QL / QH

 under the same conditions,

COPHP  COPR  1
Example 5-51, Cengel

An air conditioner removes heat steadily from a house at rate of 750

kJ/min while drawing electric power at a rate of 6 kW. Determine
(a) The COP of this air conditioner (2) The rate of heat transfer to
the outside air.

Solution:
Assumption: The air conditioner operates steadily.
Example 5-58, Cengel

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.

Solution:
Assumption: The heat pump operates steadily.
 5-4 Perpetual-motion machines

 A process cannot take place unless its satisfies both 1st & 2nd law of
thermodynamics.
 Any device that violates either law is called perpetual-motion
machine
 device violates the 1st law, it is a perpetual-motion machine of the 1st
kind (PMM1)
 device violates the 2nd law, it is a ……………..of the 2nd kind (PMM2)

Reversible processes A reversible process is a quasi-

Internally reversible
equilibrium, or quasistatic process with a
more restrictive requirement.
quasiequilibrium process, which once
having taken place, can be reversed & in
doing so leave no change in the system.
This says nothing about what happens to
the surroundings about the system.
Totally or externally quasiequilibrium process, which once
reversible process having taken place, can be reversed and in
the system or surroundings.
Irreversible process process that is not reversible.

 All real processes are irreversible & occur because of:

1. Friction
2. Unrestrained expansion of gasses
3. Heat transfer through a finite T difference
4. Mixing of 2 different substances
5. Hysteresis effects
6. I2R losses in electrical circuits
7. Any deviation from a quasistatic process
 5-5 The carnot cycle
 Heat engines are cyclic devices & the working fluid returns to its
initial state at the end of each cycle.
 Work is done by the working fluid during 1 part of the cycle & on the
working fluid during another part.
 The difference between these two = net work delivered by heat
engine.
 The net work, cyclic efficiency can be max. by require least amount
of work & deliver the most - using reversible processes.

 Carnot cycle, proposed by Sadi Carnot in 1824.

 The theoretical heat engine that operates on Carnot cycle is called
the Carnot heat engine.
 Composed of 4 reversible processes - 2 isothermal & 2 adiabatic &
can be executed either in a closed or a steady-flow system.
 Consider a closed system that consists of a gas contained in an
adiabatic piston-cylinder device.
 The insulation of the cylinder head may be removed to bring the
cylinder into contact with reservoir to provide heat transfer.
P - V diagram of the Carnot cycle
(1) Reversible isothermal expansion (process 1-2, TH = constant)

 At state 1, temperature of gas is TH & cylinder head is in contact

with the source at temperature TH.
 The gas is allowed to expend but T of the gas tends to decrease .
Heat flows from the reservoir into the gas , rising the gas T so that
T is kept constant to TH.
 This is a reversible process as the T difference between the gas &
reservoir never exceeds a differential amount dT.
 The process continuous until reaches position 2.
 Amount of heat transferred to the gas during this process is QH.
(2) Reversible adiabatic expansion (process 2-3, T drops from TH to TL)

 At state 2 the reservoir is removed & replaced by insulation, so the

system becomes adiabatic.
 The gas continuous to expand slowly until temperatures drop from TH
to TL (state 3).
 The piston is assumed frictionless & the process to be quasi-
equilibruim, so that the process is reversible as well as adiabatic.
(3) Reversible isothermal compression (process 3-4, TL = constant)

 At state 3, the insulation at the cylinder head is removed & brought

into contact with a sink at temperature TL.
 Now the piston is pushed inward by an external force, doing work on
the gas. As the gas is compressed, its temperature tends to rise but
once it rises to infinitesimal amount dT, heat flows from the gas to
the sink, causing the T to drop to TL. Thus the gas T is maintained at
T L.
 This is a reversible process as T difference between gas & sink
never exceed dT. It continuous until the piston reaches state 4.
 The amount of heat rejected from the gas is QL.
(4) Reversible adiabatic compression (process 4-1, temperature rises
from TL to TH)

 At state 4, the low temperature reservoir is removed & insulation is

put back on the cylinder head. The gas is compressed in a reversible
manner.
 The gas returns to initial state (state 1)
 The temperature rises from TL to TH during the reversible adiabatic
compression process, which complete the cycle.
 From the P - V diagram:

 area under the process curve = boundary work for quasi-

equilibrium(internally reversible) processes
 area under curve 1-2-3 = work done by the gas during the expansion
 area under curve 3-4-1 = work done on the gas during compression
 area enclosed by path cycle 1-2-3-4-1 = difference between the two
& represents the net work done during the cycle.
 The reversed carnot cycle

 The Carnot heat-engine cycle described is a totally reversible cycle.

 All processes that can be reversed becomes the ‘Carnot refrigeration
cycle’.
 The cycles remain the same except direction of Q & W is reversed.
 Heat in the amount of QL is absorbed from low T reservoir
 Heat in the amount of QH is rejected to a high T reservoir & work
input of Wnet,in is required to accomplish.
 The carnot principles

 The 2nd law of thermodynamics puts limits on the operation of cyclic

device as expressed by the Kelvin-Planck & Clausius statements.
 Considering heat engines operating between two fixed temperature
reservoir at TH  TL. Two conclusions about the thermal efficiency of
reversible & irreversible heat engines known as Carnot Principles:

(a) The efficiency of an irreversible heat engine is always less than the
efficiency of a reversible one operating between the same two
reservoirs.
th  th, Carnot

(b) The efficiencies of all reversible heat engines operating between

same two constant temperature heat reservoir have the same
efficiency.
 = HE
High-temperature reservoir
at TH

1 2 3
Irrev Rev Rev
th,1th,2 th,2=th,3
Low-temperature reservoir
at TL

Diagram of Carnot principles

 These 2 statements can be proved by demonstrating that the
violation of either statement results in the violation of the 2nd law of
thermodynamics.
 To prove the 1st statement, consider 2 heat exchanges operating
between the same reservoir. By referring to figure (a),1 engine is
reversible & other is reversible.
 Each engine is supplied with same amount of heat QH. Amount of work
produced by reversible heat engine is Wrev & amount produced by
irreversible one is Wirrev.
 In violation of 1st Carnot principle, we assume th, irrev  th,rev
 Now, let the reversible heat engine be reversed & operate as a
refrigerator. It will receive a work input Wrev & reject heat to the
high-temperature reservoir.
 Since the refrigerator is rejecting heat QH to the high-temperature
reservoir & irreversible heat engine is receiving the same amount of
heat from this reservoir. Net heat exchange = 0

 Now consider the refrigerator & irreversible engine together in

figure (b), producing a net work
Wirrev - Wrev exchanging heat
with a single reservoir (violation
Kelvin-Planck statement 2nd law.
 Therefore, our initial assumption
that th, irrev  th,rev is incorrect.
 Conclusion: No heat engine can be
more efficient than a reversible
heat engine operating between
the same reservoir.
 5-6 The thermodynamic temperature scale
Definition: A temperature scale that is independent of the properties of
the substances that are used to measure temperature
 From 2nd Carnot principle:
(a) rev engine is independent of the working
fluid employed & its properties
(b) the way the cycle is executed
(c) or the type of reversible engine used
 Thermal efficiency of reversible heat
engine is a function of reservoir T only
th,rev = g(TH,TL)
or
QH
 f (TH , TL )
QL

since th = 1 - QL/QH

All Reversible heat engines operating between the same two reservoirs have
the same efficiency (the Second Carnot principle)
 Since the thermal efficiency in general is
th = 1 - QL/QH

 For the Carnot Engine, this can be written

as
th  g TL , TH   1  f TL , TH 
 Considering engines A, B, & C:
Q1 Q1 Q2

Q3 Q2 Q3
 This look like
f (T1 , T3 )  f (T1 , T2 ) f (T2 , T3 )
 One way to define the f function is

 (T1 )  (T2 )  (T1 )

f (T1 , T3 )  
 (T2 )  (T3 )  (T3 )
 The simplest form of  is the absolute Temperature itself.
T1
f (T1 , T3 ) 
T3 TL
 The Carnot thermal efficiency becomes th,rev  1 
TH
This is the maximum possible efficiency of a heat engine operating
between two heat reservoirs at temperatures TH & TL. Note that the
temperatures are absolute temperatures.

 These statements form the basis for establishing an absolute

temperature scale, also called the Kelvin scale, related to the heat
transfer between a reversible device & the high and low temperature
heat reservoirs by Q  T
 L   L
 QH  rev TH
where TH/TL are the absolute temperatures of the high & low
temperature heat reservoirs.
 Only valid when heat engine operating between 2 constant
temperature heat reservoir.
 5-7 The carnot heat engine

 Carnot heat engine hypothetical heat engine that operates on

the reversible Carnot cycle
 Thermal efficiency of any heat engine, reversible or irreversible:
QL
th  1 
QH

where QH = heat transferred to the heat engine from a high T

reservoir at TH
QL = heat rejected to a low T reservoir at TL.
 Efficiency of a Carnot engine or any reversible heat engine, becomes
TL
th,rev  1
TH
 The above relation is known as the Carnot efficiency. It is the
highest efficiency a heat engine operating between the 2 thermal
energy reservoirs at temperatures TL & TH can have.
 All irreversible (i.e actual) heat engines operating between these
limits (TL & TH) will have lower efficiencies.
 An actual heat engine cannot reach this maximum theoretical
efficiency value because it is impossible to completely eliminate all
the irreversibilities associated with the actual cycle.

 The thermal efficiencies of actual & reversible heat engines

operating between the same temperature limits compare as follows
 th,rev irreversible heat engine
th = th,rev reversible heat engine
 th,rev impossible heat engine
Example 5-81, Cengel

A Carnot heat engine receives 650 kJ of heat from a source of

unknown temperature and rejects 200 kJ of heat to a sink at 17C.
Determine (a) the temperature of the source (b) the thermal
efficiency of the heat engine.

Solution:
Assumption: The Carnot heat engine operates steadily.
Carnot cycle: 5.61, Moran & Shapiro

One-half kilogram of water executes a Carnot power cycle. During the

isothermal expansion, the water is heated until it is a saturated vapor
from an initial state where the pressure is 15 bar and the quality is
25%. The vapor then expands adiabatically to a pressure of 1 bar
while doing 403.8 kJ/kg of work.

(a) Sketch the cycle on p-v diagrams

(b) Evaluate the heat & work for each process, in kJ
(c) Evaluate the thermal efficiency
 Carnot Steam power cycle
(Process 1-2)
 As water flows through the boiler, a change of phase from liquid to
vapor at constant temperature TH occurs at a result of heat transfer
from hot reservoir.
 As temperature remains constant, pressure also remains constant
during the phase change.
(Process 2-3)
 The steam existing the boiler expands adiabatically through the
turbine & work is developed. In this process temperature decreases
to temperature of the cold reservoir TL & there is an accompanying
decrease in pressure.
(Process 3-4)
 As the steam passes through the condenser, heat transfer to cold
reservoir occurs & some vapor condenses at constant TL.
Temperature & pressure remains constant as water passes through
the condenser.
(Process 4-1)
 Pump - receives two-phase liquid-vapor mixture from the condenser &
returns it adiabatically to the state of boiler entrance.
 During this process, work input is required to increase the pressure
& temperature increases from TL to TH.
 The thermal efficiency of actual heat engines can be maximized by
supplying heat to the engine at the highest possible temperature
(limited by material strength) & rejecting heat from the engine at
the lowest possible temperature.

5 - 8 The carnot refrigerator & heat pump

 A refrigerator or a heat pump that operates on the reversed Carnot

cycle is called Carnot refrigerator or a Carnot heat pump.
 The COP reversible or irreversible is given by:
1 1
COPR  COPHP 
QH and Q
1 1 L
QL QH
 where QL = amount of heat absorbed from the low-temperature
medium
 QH = amount of heat rejected to the high-temperature medium
 The COPs of all reversible refrigerators or heat pumps: replace heat
transfer ratio by ratio of the absolute temperature of the high and
low temperature reservoirs:
1 1
COPR ,rev  and COPHP,rev 
TH T
1 1 L
TL TH
 these are the maximum possible COPs for a refrigerator or a heat
pump operating between the temperature limits of TH & TL.
 The COP of actual & reversible (such as Carnot) refrigerators
operating between the same temperature limits compare as follows:

 COPR,rev irreversible refrigerator

COPR = COPR,rev reversible refrigerator
 COPR,rev impossible refrigerator

 A similar relation can be obtained for heat pumps by replacing all

values of COPR by COPHP in the above relation.
Example 5-98, Cengel

A Carnot refrigerator operates in a room in which the temperature is

25C. The refrigerator consumes 500 W of power when operating and
has a COP of 4.5. Determine (a) the rate of heat removal from the
refrigerated space (b) the temperature of the refrigerated space.

Solution:
Assumption: The refrigerator operates steadily.