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Chapter 5: The 2
nd
Law of
Thermodynamics
An Introduction
This 1000 hp engine photo is courtesy of Bugatti automobiles.
Motivating The 2nd Law of
Thermodynamics
The 1
st
law of thermodynamics alone does not
predict the direction of a process, e.g.
Can a hot object naturally cool down to a temperature
below its surrounding?
Can a hot mass return to its initial position by losing
its internal energy?
The first law does not distinguish between
reversible and irreversible processes
The 2
nd
law can be used in conjunction with the
1
st
law to determine the capability (e.g., max
efficiency) of a process.
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Spontaneous Processes
Objects spontaneously tend to cool
Fluids move from higher to lower
pressure environments
spontaneously
Objects spontaneously fall from
elevated positions
Spontaneous processes allows occur in a predictable direction,
and have the potential to produce work
Comments
A spontaneous process takes place on its own
but its inverse would not take place
spontaneously
There is an opportunity to develop work from an
spontaneous process that otherwise would be
lost (e.g., turbine, pulley)
If work is developed from s spontaneous
process
What is the max theoretical limit
What factors would preclude its realization
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The Many Uses of the 2
nd
Law
Predict process direction
Establish equilibrium conditions
Determine theoretical best performance
Evaluate factors limiting best performance
Define a temperature scale independent of
properties
Develop means for property evaluation for
derived properties, such as h and u
Statements of the 2
nd
Law
Kelvin-Planck Statement
It is impossible for any system to
operate in a thermodynamic cycle
and deliver a net amount of energy
by work to its surroundings while
receiving energy from a single
thermal reservoir
Clausius Statement
It is impossible for any system to
operate in such a way that the
sole result would be an energy
transfer by heat from a cooler to a
hotter body
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Proof Illustration
K-PClausius ClausiusK-P
Reversible vs. Irreversible
A process is called irreversible if the system and
all parts of its surroundings cannot be exactly
restored to their initial values
A Process is reversible if both the system and
surroundings can be returned to its initial states.
An irreversible process may be returned to initial
state but not if combined with surroundings
All real-world processes are irreversible
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Irreversibilities
Heat transfer through a finite temperature
difference
Unrestrained expansion of a gas or liquid
Spontaneous chemical reaction
Spontaneous mixing
Friction (sliding and flow)
Electric current flow through a resistance
Magnetization or polarization with hysteresis
Inelastic deformation
And many more
ClipArt courtesy of PowerPoint 2002
ClipArt courtesy of PowerPoint 2002
ClipArt courtesy of PowerPoint 2002
Internal vs. External Irreversibilities
For engineering analyses the internal
irreversibilities may be considered as
opposed to total.
A process is internally reversible if there
are no internal irreversibilities
An internally reversible process can return
to its initial state
It consists of a series equilibrium states,
i.e., quasiequilibriumprcocess
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How to Prove Irreversibility
The proof is typically by contradiction
First suppose the process is reversible
Put together a series of additional
reversible (ideal) processes to form a
thermodynamic cycle
Show that existence of such a cycle would
violate the Kevin-Planck Statement
Example: Heating due to Friction
Example: Irreversibility of Friction
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Examples of Reversible Processes
Frictionless mass-spring or pendulum
Adiabatic expansion or compression in
friction-less piston cylinder
Statble equilibrium states
Power Cycles (Heat Engines)
1
cycle
L
H H
W
Q
Q Q
= =
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Refrigeration and Heat Pump
Cycles
Refrigeration Heat Pumps
C C
cycle H C
Q Q
W Q Q
= =

H H
cycle H C
Q Q
W Q Q
= =

Carnot Corollaries
The thermal efficiency of an irreversible
power cycle is always less than that of a
reversible one when each operates
between the same two reservoirs.
All reversible power cycles between the
same two thermal reservoirs have the
same thermal efficiency.
There are similar corollaries for
refrigeration and heat pump cycles.
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Proof Of Carnot Corollary
Kelvin Scale
Carnot corollaries imply that for a
reversible power cycle Q
c
/Q
H
= (T
c
,T
H
)
Q
c
: Heat from system to cold reservoir
Q
H
: Heat from hot reservoir to system
T
c
,T
H
: cold and hot reservoir temperature
: unspecified function
Kelvin scale: (T
c
,T
H
)=T
c
/T
H
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The Kelvin Temperature Scale
C C
H H
rev
Q T
Q T

=


273.16
rev
H
cycle
Q
T
Q

=


273.16 K is the Triple Point temperature of water
ClipArt courtesy of PowerPoint 2002
Maximum Performance
max
1
C
H
T
T
=
Heat Engines Refrigerators & Heat Pumps
max
C
H C
T
T T
=

max
H
H C
T
T T
=

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Carnot Cycle
Reversible power cycle: Two adiabatic processes
alternated with two isothermal processes
Carnot power cycles operated in reverse may be regarded as a reversible
refrigeration or heat pump cycle, with maximum coefficient of
performance
Example: Problem 5.38
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Problem 5.40
Problem 5.50