Chapter 5

The second law of thermodynamics

Chapter objectives:

1. Introduce the concept of entropy

2. Present the second law of thermodynamics
3. Apply the second law to familiar processes
4. Relate changes in entropy to T and P for substances in the ideal-gas state
5. Present entropy balances for open systems
6. Demonstrate the calculation of ideal work and lost work for flow processes
7. Discuss entropy from a microscopic perspective
 Second law of thermodynamics

There exists a property called entropy (S), which for systems at

5.1 Axiomatic internal equilibrium is an intrinsic property, functionally related to
statements of the
second law the measurable state variables that characterize the system.
5.2 Heat engines
and heat pumps dQrev
dS =
t
(5.1)
5.3 Carnot engine T
with ideal-gas-state
working fluid

5.4 Entropy
The Second Law of Thermodynamics
5.5 Entropy
changes for the The entropy change of any system and its surroundings, considered
ideal-gas state
together, and resulting from any real process, is positive,
5.6 Entropy balance
for open systems
approaching zero when the process approaches reversibility.
5.7 Calculation of
ideal work
ΔStotal ≥ 0 (5.2)
5.8 Lost work
• Every process proceeds in a direction such that the total entropy
5.9 The third law of
thermodynamics
change associated with it is positive.
• An entropy change of zero is attained only by a reversible process.
5.10 Entropy from
the microscopic • No process is possible for which the total entropy decreases.
view
 Second law of thermodynamics
Direct heat transfer between two heat reservoirs
(bodies imagined capable of absorbing or rejecting unlimited
quantities of heat without temperature change)
5.1 Axiomatic
statements of the Hot reservoirs:
second law
furnaces fueled by combustion TH TC Cold reservoirs:
5.2 Heat engines of fossil fuels or by fission of QH QC lakes, rivers, and oceans
and heat pumps radioactive elements (nuclear)
5.3 Carnot engine
with ideal-gas-state
working fluid

dQH dQC
5.4 Entropy
dS =t dS =
t
C
H
TH TC
5.5 Entropy dQrev
changes for the
ideal-gas state
dS =
t
(5.1)
QH T QC
5.6 Entropy balance ΔS =t
H ΔS =t
C
for open systems TH TC
5.7 Calculation of
ideal work QH = −QC
5.8 Lost work
QC
ΔS = −
t
5.9 The third law of
thermodynamics
H
TH ΔStotal = ΔSHt + ΔSCt =
5.10 Entropy from QC QC ⎛ TH − TC ⎞
− + = QC ⎜
⎝ TH TC ⎟⎠
the microscopic
view TH TC
 Second law of thermodynamics
Direct heat transfer between two heat reservoirs
(bodies imagined capable of absorbing or rejecting unlimited
quantities of heat without temperature change)
5.1 Axiomatic
statements of the Hot reservoirs:
second law
furnaces fueled by combustion TH TC Cold reservoirs:
5.2 Heat engines of fossil fuels or by fission of QH QC lakes, rivers, and oceans
and heat pumps radioactive elements (nuclear)
5.3 Carnot engine
with ideal-gas-state
• As TH - TC
working fluid
ΔStotal = ΔS + ΔS =
t
H
t
C decreases, so does
5.4 Entropy • No process is possible
which consists solely QC QC ⎛ TH − TC ⎞ ΔStotal: when TH is
− + = QC ⎜ infinitesimally
⎝ TH TC ⎟⎠
5.5 Entropy
changes for the of the transfer of heat TH TC
ideal-gas state
from one temperature higher than TC,
5.6 Entropy balance level to a higher one. heat transfer is
for open systems ΔStotal ≥ 0 (5.2) reversible.
5.7 Calculation of
ideal work

⎛ TH − TC ⎞ irreversible process
QC (TH − TC ) > 0
5.8 Lost work
QC ⎜ ⎟ ≥0
5.9 The third law of ⎝ TH TC ⎠
thermodynamics

5.10 Entropy from

the microscopic
view
since TH > TC, then QC > 0 which would mean that heat flows
into reservoir C from reservoir H
 Application of the second law to heat engines

The most common examples are the internal-combustion engines and

5.1 Axiomatic the steam power plant. Collectively known as heat engines.
statements of the
second law All rely on a high-temperature source of heat, and all discard heat to the
5.2 Heat engines
environment.
and heat pumps

5.3 Carnot engine

with ideal-gas-state
working fluid
A steam engine is a heat
5.4 Entropy engine that performs
mechanical work using
5.5 Entropy
changes for the steam as its working fluid.
ideal-gas state The steam engine uses the
force produced by steam
5.6 Entropy balance
for open systems pressure to push a piston
back and forth inside a
5.7 Calculation of cylinder. This pushing
ideal work
force is transformed, by a
5.8 Lost work connecting rod and
flywheel, into rotational
5.9 The third law of
thermodynamics
force for work.

5.10 Entropy from

the microscopic
view
 Heat engines and heat pumps

5.1 Axiomatic furnaces fueled by combustion The first law:

statements of the of fossil fuels or by fission of
second law
radioactive elements (nuclear) ΔU t = Q + W (2.3)
5.2 Heat engines
and heat pumps

5.3 Carnot engine

with ideal-gas-state
working fluid
With respect to the engine:
5.4 Entropy ΔU = Q + W = QH + QC + W
5.5 Entropy
changes for the QH is a positive number (transferred to the system)
ideal-gas state QC is a negative number (transferred from the system)
5.6 Entropy balance W is a negative number (transferred from the system)
for open systems

5.7 Calculation of
ideal work Since the engine operates in a cycle:
5.8 Lost work ΔU = 0
5.9 The third law of
thermodynamics W = −QH − QC
lakes, rivers, and oceans
5.10 Entropy from
the microscopic
view
 Heat engines and heat pumps

dQrev
5.1 Axiomatic furnaces fueled by combustion dS =
t
(5.1) ΔStotal ≥ 0 (5.2)
statements of the of fossil fuels or by fission of T
second law
radioactive elements (nuclear)
5.2 Heat engines
and heat pumps

5.3 Carnot engine

with ideal-gas-state QH QC
working fluid
ΔStotal =− −
5.4 Entropy
TH TC
5.5 Entropy
changes for the
ideal-gas state

5.6 Entropy balance

QCTH
for open systems
QH = −TH ΔStotal −
5.7 Calculation of
TC W = −QH − QC
ideal work

5.8 Lost work

5.9 The third law of ⎛ TH − TC ⎞

thermodynamics
lakes, rivers, and oceans W = TH ΔStotal + QC ⎜
5.10 Entropy from ⎝ TC ⎟⎠
the microscopic
view
 Heat engines and heat pumps

⎛ TH − TC ⎞
W = TH ΔStotal + QC ⎜
furnaces fueled by combustion
⎝ TC ⎟⎠
5.1 Axiomatic
statements of the of fossil fuels or by fission of
second law
radioactive elements (nuclear)
5.2 Heat engines
and heat pumps
Limits of work output:
5.3 Carnot engine
with ideal-gas-state
working fluid
a) If the engine is totally ineffective, W = 0
5.4 Entropy
⎛ TH − TC ⎞
ΔStotal = −QC ⎜
⎝ TH TC ⎟⎠
5.5 Entropy
changes for the
ideal-gas state * The difference in sign
5.6 Entropy balance reflects that QC is with
for open systems
TH TC respect to the engine,
5.7 Calculation of
whereas previously it was
ideal work QH QC with respect to the lower-
temperature reservoir.
5.8 Lost work

5.9 The third law of

QC QC ⎛ TH − TC ⎞
thermodynamics
lakes, rivers, and oceans ΔStotal =− + = QC ⎜
TH TC ⎝ TH TC ⎟⎠
*
5.10 Entropy from
the microscopic
view
 Carnot engine

⎛ TH − TC ⎞
W = TH ΔStotal + QC ⎜
furnaces fueled by combustion
⎝ TC ⎟⎠
5.1 Axiomatic
statements of the of fossil fuels or by fission of
second law
radioactive elements (nuclear)
5.2 Heat engines
and heat pumps
Limits of work output:
5.3 Carnot engine
with ideal-gas-state
working fluid
b) If the process is reversible, ΔStotal = 0
5.4 Entropy

⎛ TH − TC ⎞
5.5 Entropy
W = QC ⎜
⎝ TC ⎟⎠
changes for the
ideal-gas state

5.6 Entropy balance

for open systems
⎛ TH ⎞
5.7 Calculation of W = QC ⎜ − 1⎟ (5.3)
ideal work ⎝ TC ⎠
5.8 Lost work

5.9 The third law of

Carnot engine
thermodynamics
lakes, rivers, and oceans Engine operating in a reversible manner
5.10 Entropy from
the microscopic
view
 Carnot engine

Carnot engine
5.1 Axiomatic furnaces fueled by combustion
of fossil fuels or by fission of
statements of the
second law ⎛ TH ⎞
radioactive elements (nuclear) W = QC ⎜ − 1⎟ (5.3)
5.2 Heat engines ⎝ TC ⎠
and heat pumps

5.3 Carnot engine

with ideal-gas-state
working fluid
QC < 0 so W < 0
5.4 Entropy work is produced by the engine
5.5 Entropy
changes for the
ideal-gas state For any finite value of W, QC is also finite:
5.6 Entropy balance a portion of the heat transferred from the higher-
for open systems
temperature reservoir must inevitably be
5.7 Calculation of exhausted to the lower-temperature reservoir.
ideal work

5.8 Lost work

It is impossible to construct an engine that,
5.9 The third law of
thermodynamics
operating in a cycle, produces no effect (in
lakes, rivers, and oceans
system and surroundings) other than the
5.10 Entropy from
the microscopic extraction of heat from a reservoir and the
view performance of an equivalent amount of work.
 Carnot engine

Carnot engine
5.1 Axiomatic furnaces fueled by combustion
statements of the of fossil fuels or by fission of
second law ⎛ TH ⎞
radioactive elements (nuclear) W = QC ⎜ − 1⎟ (5.3)
5.2 Heat engines ⎝ TC ⎠
and heat pumps

5.3 Carnot engine

with ideal-gas-state
working fluid
W = −QH − QC
5.4 Entropy

5.5 Entropy QC QH Carnot’s

changes for the − = (5.4)
ideal-gas state TC TH equations
5.6 Entropy balance The smallest possible value of QC is zero;
for open systems
the corresponding value of TC is absolute
5.7 Calculation of zero on the Kelvin scale (-273.15 C)
ideal work

5.8 Lost work

5.9 The third law of W TC Carnot’s

thermodynamics
lakes, rivers, and oceans = − 1 (5.5)
QH TH equations
5.10 Entropy from
the microscopic
view
 Carnot engine

The thermal efficiency of a heat engine is

defined as the ratio of the work produced to
furnaces fueled by combustion
5.1 Axiomatic
statements of the of fossil fuels or by fission of
the heat supplied to the engine.
second law
radioactive elements (nuclear)
−W
5.2 Heat engines
and heat pumps
η= (5.6)
QH
5.3 Carnot engine
with ideal-gas-state
working fluid W TC
= − 1 (5.5)
QH TH
5.4 Entropy

5.5 Entropy TC
changes for the
ideal-gas state
ηCarnot = 1− (5.7) ηCarnot ~ 0.5
TH
5.6 Entropy balance
for open systems TC ≃ 300 K
(cold reservoirs: lakes, rivers, and oceans)
5.7 Calculation of
ideal work TH ≃ 600 K
5.8 Lost work (hot reservoirs: furnaces where the temperature is
maintained by combustion of fossil fuels or by
5.9 The third law of
thermodynamics fission of radioactive elements)
lakes, rivers, and oceans
5.10 Entropy from
the microscopic Actual heat engines are irreversible;
view their efficiency rarely exceeds 0.35
 Carnot engine

The thermal efficiency of a heat engine is

defined as the ratio of the work produced to
5.1 Axiomatic furnaces fueled by combustion the heat supplied to the engine.
statements of the of fossil fuels or by fission of
second law
radioactive elements (nuclear)
−W
5.2 Heat engines
and heat pumps η= (5.6)
QH
5.3 Carnot engine
with ideal-gas-state
working fluid W TC
= − 1 (5.5)
5.4 Entropy
QH TH

5.5 Entropy
TC
changes for the
ideal-gas state ηCarnot = 1− (5.7) ηCarnot ~ 0.5
TH
5.6 Entropy balance
for open systems

5.7 Calculation of
ideal work The second law does not prohibit the continuous
5.8 Lost work
production of work from heat, but it does place a
limit on how much of the heat taken into a
5.9 The third law of
thermodynamics
cyclic process can be converted into work.
lakes, rivers, and oceans
5.10 Entropy from
the microscopic
view