Chapter 5

The Second Law of

Thermodynamics
(continued)
 Second Law of Thermodynamics
Alternative statements of the second law,

Clausius Statement
of the Second Law
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.
 Second Law of Thermodynamics
Alternative statements of the second law,
Kelvin-Planck Statement
of the Second Law
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 by heat transfer from a
single thermal reservoir.
NO!
 Aspects of the
Second Law of Thermodynamics
From conservation of mass and energy
principles, (i.e. 1st Law of Thermodynamics)
mass and energy cannot be created or destroyed.
For a process, conservation of mass and
energy principles indicate the disposition of
mass and energy but do not infer whether the
process can actually occur.
The second law of thermodynamics
provides the guiding principle for whether a
process can occur.
Second Law of Thermodynamics
Alternative Statements
There is no simple statement that captures all
aspects of the second law. Several
alternative formulations of the second law are
found in the technical literature. Three
prominent ones are:
Clausius Statement
Kelvin-Planck Statement
Entropy Statement
It is impossible for any system to operate in a way
that entropy is destroyed.
 Irreversible and Reversible
Processes
During a process (i.e. a change from State A
to State B) of a system, irreversibilities
may be present:

within the system, or

with its surroundings (usually the
immediate surroundings), or
both.
Applications to Power Cycles Interacting
with Two Thermal Reservoirs
For a system undergoing a power cycle while
communicating thermally with two thermal
reservoirs, a hot reservoir and a cold reservoir,
the thermal efficiency of any such cycle is

Wcycle QC
= = 1 (Eq. 5.4)
QH QH
By applying the Kelvin-Planck statement of the
second law, Eq. 5.3, three conclusions can be drawn:

Wcycle QC
= = 1 (Eq. 5.4)
QH QH

1. The value of the thermal efficiency must be less than

100%.
2. The thermal efficiency of an irreversible power cycle is
always less than the thermal efficiency of a reversible
power cycle for the same two thermal reservoirs, and
3. All reversible power cycles operating between the same
two thermal reservoirs have the same thermal efficiency.
 Applications to Refrigeration and Heat Pump
Cycles Interacting with Two Thermal Reservoirs
For a system undergoing a refrigeration cycle or heat
pump cycle while communicating thermally with two
thermal reservoirs, a hot reservoir and a cold
reservoir, the coefficient of performance
for the refrigeration cycle is
QC QC
= = (Eq. 5.5)
Wcycle QH QC

and for the heat pump cycle is

QH QH
= = (Eq. 5.6)
Wcycle QH QC
 QC QC
= =
Wcycle QH QC
QH QH
= =
Wcycle QH QC

By applying the Kelvin-Planck statement of the second law,

Eq. 5.3, three conclusions can be drawn:
1. For a refrigeration effect to occur a net work input Wcycle is
required. Accordingly, the coefficient of performance must
be finite in value.
2. The coefficient of performance of an irreversible
refrigeration cycle is always less than the coefficient of
performance of a reversible refrigeration cycle when each
operates between the same two thermal reservoirs.
3. All reversible refrigeration cycles operating between the
same two thermal reservoirs have the same coefficient
of performance.
 Kelvin Temperature Scale
Consider systems undergoing a power cycle and a
refrigeration or heat pump cycle, each while
exchanging energy by heat transfer with hot and cold
reservoirs:

The Kelvin temperature is defined so that

QC TC
= (Eq. 5.7)
QH rev TH
cycle
 Maximum Performance Measures for Cycles
Operating between Two Thermal Reservoirs
It follows that the maximum theoretical thermal efficiency and
coefficients of performance in these cases are achieved only
by reversible cycles. Using Eq. 5.7 in Eqs. 5.4, 5.5, and 5.6,
we get respectively:
TC
Power Cycle: max = 1 (Eq. 5.9)
TH

TC
Refrigeration Cycle: max = (Eq. 5.10)
TH TC

TH
Heat Pump Cycle: max = (Eq. 5.11)
TH TC

where TH and TC must be on the Kelvin or Rankine scale.

 Example: Power Cycle Analysis
A system undergoes a power cycle while Hot Reservoir
TH = 500 K
receiving 1000 kJ by heat transfer from a
QH = 1000 kJ
thermal reservoir at a temperature of 500 K Wcycle
Power
and discharging 600 kJ by heat transfer to a Cycle

thermal reservoir at (a) 200 K, (b) 300 K, (c) QC = 600 kJ

400 K. For each case, determine whether

TC = (a) 200 K,
the cycle operates irreversibly, operates (b) 300 K,
reversibly, or is impossible. (c) 400 K
Cold Reservoir

Solution: To determine the nature of the cycle, compare

actual cycle performance () to maximum theoretical cycle
performance (max) calculated from Eq. 5.9
 Example: Power Cycle Analysis
Hot Reservoir

Actual Performance: Calculate using TH = 500 K

QH = 1000 kJ
the heat QC 600 kJ Power Wcycle

transfers: = 1 = 1 = 0.4 Cycle

Q 1000 kJ
H QC = 600 kJ

Maximum Theoretical Performance: TC = (a) 200 K,

(b) 300 K,
(c) 400 K
Calculate max from Eq. 5.9 and compare Cold Reservoir

to : max
TC 200 K
(a) max = 1 = 1 = 0.6 0.4 < 0.6 Irreversibly
TH 500 K
TC 300 K
(b) max = 1 = 1 = 0.4 0.4 = 0.4 Reversibly
TH 500 K
TC 400 K
(c) max = 1 = 1 = 0.2 0.4 > 0.2 Impossible
TH 500 K
 Carnot Cycle
The Carnot cycle provides a specific
example of a reversible cycle that operates
between two thermal reservoirs. Other
examples are provided in Chapter 9: the
Ericsson and Stirling cycles.
In a Carnot cycle, the system executing the
cycle undergoes a series of four internally
reversible processes: two adiabatic
processes alternated with two isothermal
processes.
 Carnot Power Cycles
The p-v diagram and schematic of a gas in a piston-cylinder
assembly executing a Carnot cycle are shown below:
 Carnot Power Cycles
The p-v diagram and schematic of water executing a Carnot
cycle through four interconnected components are shown
below:

In each of these cases the thermal efficiency is given by

TC
max = 1 (Eq. 5.9)
TH
Carnot Refrigeration and Heat Pump Cycles
If a Carnot power cycle is operated in the opposite
direction, the magnitudes of all energy transfers
remain the same but the energy transfers are
oppositely directed.
Such a cycle may be regarded as a Carnot
refrigeration or heat pump cycle for which the
coefficient of performance is given, respectively, by
TC
Carnot Refrigeration Cycle: max = (Eq. 5.10)
TH TC

TH
Carnot Heat Pump Cycle: max = (Eq. 5.11)
TH TC
 Clausius Inequality
The Clausius inequality considered next
provides the basis for developing the
entropy concept in Chapter 6.
The Clausius inequality is applicable to any
cycle without regard for the body, or
bodies, from which the system undergoing
a cycle receives energy by heat transfer or
to which the system rejects energy by heat
transfer. Such bodies need not be thermal
reservoirs.
 Clausius Inequality
The Clausius inequality is developed from
the Kelvin-Planck statement of the second
law and can be expressed as:
Q
= cycle
T b
(Eq. 5.13)

where

indicates integral is to be performed over all parts of the

boundary and over the entire cycle.
b subscript indicates integrand is evaluated at the boundary
of the system executing the cycle.
 Clausius Inequality
The Clausius inequality is developed from
the Kelvin-Planck statement of the second
law and can be expressed as:
Q
= cycle
T b
(Eq. 5.13)

The nature of the cycle executed is indicated by the value

of cycle:
cycle = 0 no irreversibilities present within the system Eq.
cycle > 0 irreversibilities present within the system 5.14
cycle < 0 impossible
 Example: Use of Clausius Inequality
A system undergoes a cycle while receiving 1000
kJ by heat transfer at a temperature of 500 K and
discharging 600 kJ by heat transfer at (a) 200 K, (b)
300 K, (c) 400 K. Using Eqs. 5.13 and 5.14, what
is the nature of the cycle in each of these cases?

Solution: To determine the nature of the cycle,

perform the cyclic integral of Eq. 5.13 to each case
and apply Eq. 5.14 to draw a conclusion about the
nature of each cycle.
 Example: Use of Clausius Inequality
Q Qin Qout
Applying Eq. 5.13 to each cycle:
=
T b TH

TC
= cycle

1000 kJ 600 kJ
(a) cycle = = 1 kJ/K cycle = +1 kJ/K > 0
500 K 200 K

Irreversibilities present within system

1000 kJ 600 kJ
(b) cycle = = 0 kJ/K cycle = 0 kJ/K = 0
500 K 300 K

No irreversibilities present within system

1000 kJ 600 kJ cycle = 0.5 kJ/K < 0

(c) cycle = = 0.5 kJ/K
500 K 400 K
Impossible