Chapter 5:

The Second Law of Thermodynamics

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5.1: Axiomatic Statements of the Second Law

• There exists a property called entropy, S, which for systems at
internal equilibrium is an intrinsic property, functionally
related to the measurable state variables that characterize the
system. Differential changes in this property are given by the
equation:

= (5.1)

Where S t is the total system (not molar) entropy

• The Second Law of Thermodynamics: The entropy change of
any system and its surroundings, considered together, and
resulting from any real process, is positive, approaching zero
when the process approaches reversibility. Mathematically:
∆ ≥0 (5.2)
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 2nd Law: Application to Heat Transfer

• Consider direct heat transfer between two heat reservoirs

(bodies that can absorb or reject unlimited heat without
changing temperature); at constant T, ∆S = Q/T
• Let Q be the quantity of heat transferred from a hot reservoir
at TH to a cold reservoir at TC ; QH is the heat transferred from
the hot reservoir, and QC is the heat received to the cold
reservoir:
=− & = =
• Entropy change from each reservoir:

∆ = & ∆ =

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2nd Law: Application to Heat Transfer (2)

• Combining the two entropy changes:
− −
∆ =∆ +∆ = + =

• By our definition of the problem, QC > 0 and TH > TC , this

means the total entropy change for the process is always > 0
• This conforms with the universal experience that heat flows
from high temperature to low temperature
• More formally: No process is possible which consists solely of
the transfer of heat from one temperature to a higher one
• Note: as ∆T becomes infinitesimal, the heat transfer is
reversible, and ∆S approaches 0

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 2nd Law: Application to Heat Engines
• Heat can not only be used for transfer between temperature
levels – useful work can be produced via engines
• Heat engines operate by absorbing heat at some hot
temperature, producing work, and discarding heat to the
environment
• The 2nd Law imposes restrictions on how much heat intake
can be converted to work
• Heat pumps or refrigerators operate by using work to absorb
heat at some colder temperature and transfer heat to a hotter
one
• The 2nd Law also imposes restrictions on the minimum work
necessary for heat pumps/refrigerators to achieve a given
heat transfer process
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Figure 5.1: Carnot Engine & Heat Pump

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 2nd Law Restrictions on Heat Engines
• A hot reservoir is at TH & a cold reservoir is at TC; QH is the
heat transferred from the hot reservoir, and QC is the heat
absorbed by the cold reservoir; W is the work produced
• For the engine, the 1st Law becomes:
∆U = Q + W = QH + QC + W
• Because engines operate in cycles, the overall ∆U = 0, and
W = − QH − QC
• The entropy change in the system is 0 (a cycle), but for the
surroundings, and hence total:

∆ =− −

Note: with respect to the engine, now QC < 0 & QH > 0

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2nd Law Restrictions on Heat Engines (2)

• Combining with the equation for W to eliminate QH :
−
'= ∆ +

• This gives work output between 2 limits:

1) Totally ineffective engine: W = 0 & only heat transfer occurs
−
∆ =−

*Sign difference due to QC being with respect to engine

2) Reversible process: ∆Stotal = 0, yields a Carnot Engine:

'= −1 (5.3)

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 2nd Law Restrictions on Heat Engines (3)

'= −1 (5.3)

• Check in last case: because QC < 0, then W < 0, meaning

work is produced by the engine
• Obtaining a finite value of W requires a finite value of QC .
That is, some of QH must inevitably be exhausted as QC .
• The larger the ratio TH/TC , the smaller the required QC for a
given W
• More formally: No engine that, operating in a cycle, produces
no effect (in system and surroundings) other than the
extraction of heat from a reservoir and the performance of an
equivalent amount of work is possible
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Carnot’s Equations & Efficiency

• Combining reversibility with W = − QH − QC :
−
= (5.4)

'
= −1 (5.5)

Where QH is the heat transferred into the engine, hence > 0

• Thermal efficiency is defined as the ratio of the work
produced to the heat supplied to the engine (where W < 0):
−' '
-≡ = (5.6)

- 0 =1− (5.7)

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 Carnot Efficiency
- 0 =1− (5.7)

• A Carnot engine operates reversibly in all respects and cannot

be improved – it is the thermodynamic limit, or maximum
possible efficiency of a cycle
• Its efficiency approaches unity only when TH → ∞ or TC → 0,
neither of which is possible
• For real, available cold & hot reservoirs on earth, - → 0.5 is
an approximate realistic limit for the thermal efficiency of a
Carnot engine
• Actual heat engines are irreversible and - is typically < 0.35

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Carnot Engines
• Steps making up the cycle in a Carnot engine:
1) System at TC undergoes reversible, adiabatic heating up to TH
2) At TH , heat is absorbed in a reversible, isothermal process from a heat
reservoir
3) Starting at TH , system undergoes reversible, adiabatic cooling to TC
4) At TC, heat is rejected to a cold reservoir in a reversible, isothermal
process, reaching the original state and completing the cycle

• For a Carnot engine operating between 2 heat reservoirs,

– Efficiency depends only on the two temperatures, not the working
substance of the engine
– For two given heat reservoirs, no engine can have a thermal efficiency
higher than that of a Carnot engine

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 5.2: Heat Engines and Heat Pumps
• Heat engines operate (as in Figure 5.1) by absorbing heat from a
hot reservoir, using some heat for work, and rejecting remaining
heat to a cold reservoir
• Heat pumps operate in the opposite direction, where work is
required to “pump” heat from low to high temperature reservoirs
• Refrigerators are heat pumps with the “cold box” as the low
temperature reservoir and the environment as the high
temperature reservoir
• Measure of quality of a heat pump is the coefficient of
performance (4) the heat extracted at the lower T, divided by W

4≡ 5.8 & 4 0 ≡ (5.9)

' −
Note that COP of Carnot heat pump only depends on temperature

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5.3: Carnot Engine with Ideal-Gas Working Fluid

• a ➝ b: Adiabatic compression
from TC to TH
• b ➝ c: Isothermal expansion
with absorption of heat QH
• c ➝ d: Adiabatic expansion
from TH to TC
• d ➝ a: Isothermal compression
with rejection of heat QC
• All 4 steps are reversible and in
this analysis, the working fluid
is in the ideal-gas state and has
constant heat capacity

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 Carnot Engine (2)
• For the isothermal steps, Eqn. (3.20) yields:
;< ;<
9: 9
=7 ln ;<
& =7 ln ;<
9= 9>
• Dividing the two:
;< ;<
ln 9: ?9=
= ;< ;<
ln 9 ?9>
• Assuming constant CP , Eqn. (3.23a) gives: TV B-1 = constant:
;< DEF ;< DEF ;< DEF ;< DEF
9 = = 9= → 9 = 9=
;< DEF ;< DEF ;< DEF ;< DEF
> 9> = 9
: : → 9> = 9:

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Carnot Engine (3)

;< DEF ;< DEF ;< DEF ;< DEF
9 = = 9= → 9 = 9=
;< DEF ;< DEF ;< DEF ;< DEF
> 9> = 9
: : → 9> = 9:
• Taking the ratio of the two, and simplifying:
;< DEF ;< DEF ;< ;< ;< ;<
9: 9> 9: 9> 9: 9
= → = → ln = − ln
;< DEF ;< DEF 9=
;<
9
;<
9=
;<
9>
;<
9= 9
• Thus, the following simplifications can be made:
;< ;<
ln 9: ?9= −
= ;< ;<
=− → = (5.4)
ln 9 ?9>

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 5.4: Entropy
• Rearranging Eqn. (5.4):

+ =0=∆ :G:

• If instead of heat being added in 2 steps from 2 reservoirs, it is

added in i steps, but still in a cycle:
;
H =0
;

• As the steps become infinitesimally small:

;
H →I =I =0
;

• This result confirms/reinforces that S is a state function

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Entropy is a State Function

• For 2 independent paths, with
the same endpoints: ADB vs.
ACB:

∆ =J =J
K L KML

• As a state function:
∆ = L − K

• For an irreversible process,

note, ∆S ≠ ∫dQ/T
• If a process is reversible &
adiabatic, dS t = 0, and hence,
it is called isentropic

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 Characteristics of Entropy
• Entropy relates to the 2nd Law in much the same way that internal
energy relates to the 1st Law; Eqn. (5.1) is the ultimate source of all
equations that connect entropy to measurable quantities
• ∆S for a reversible process is given by the integral form of Eqn.
(5.1); for a irreversible process between 2 states, apply Eqn. (5.1)
to an arbitrarily chosen reversible process that accomplishes the
same overall change
• In the special case of a mechanically reversible process (Sec. 2.8),
the entropy change of the system is correctly evaluated from
∫dQ/T applied to the actual process, even though the heat
transfer between system and surroundings represents an external
irreversibility

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5.5: Entropy Changes for the Ideal-Gas State

• For 1 mole or a unit mass of fluid undergoing a mechanically
reversible process in a closed system, the 1st Law (Eqn. 2.7)
becomes:
Q= −R 9
• Differentiation of the definition of enthalpy, H = U + PV:
S = Q+R 9+9 R
• Combining: S= −R 9+R 9+9 R
• Or: = S−9 R
;<
• For the ideal-gas state, S ;< = TU & 9 ;< = 7 /R
• Substituting & dividing by T:
;< R
= TU −7
R
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 Entropy Changes for the Ideal-Gas State (2)
;< R
= TU −7
R
• As a result of Eqn. (5.1), this becomes:
;<
;< R ;<
T
;<
= TU −7 → = U − ln R
R 7 7
• Integrating from initial conditions T0, P0:
W ;<
∆ ;< TU R
=J − ln 5.10
7 WX 7 RY
• Eqn. (5.10) is a general equation for calculation of entropy
changes in the ideal-gas state

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Entropy Changes for the Ideal-Gas State (3)

;<
• By use of Eqn. (4.5) for TU , integration of the first term in
Eqn. (5.10) results in the following:
W ;<
T \ + Y
J U = Z ln + [+ T+ − Y
WX 7 2
] ]
Y Y

(5.11)
• Defining a new mean heat capacity can be useful:
W ;<
∫W TU ⁄
;<
TU = X
(5.12)
^ ln ⁄ Y

• Where:
;<
TU
^ \ + Y − Y
=Z+ [+ T+ (5.13)
7 ] ]
Y 2 ln ⁄ Y
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 Entropy Changes for the Ideal-Gas State (4)

• Thus, by rearranging Eqn. (5.12):

W ;<
T ;<
J U = TU ln
WX 7 ^ Y

• And Eqn. (5.10) becomes:

;<
TU
∆ ;<
^ R
= ln − ln (5.14)
7 7 Y RY
• Eqn. (5.14) is often useful in iterative calculations where the
final temperature is unknown

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Iteration Protocol for Entropy Changes

Procedures for finding T, when ∆S is known, along with T0, P0, &
P, using Eqns. (5.13) & (5.14)

1. Guess an initial value for T: T (0)

– Setting T (0) = T0 often (but not always) leads to quick convergence

2. Use Eqn. (5.13) to evaluate TU ^ /7

3. Use this value in Eqn. (5.14) to evaluate a new T: T (1)
4. Use this new T and repeat steps 2 & 3 until T converges to
within some acceptable tolerance

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 5.6: Entropy Balance for Open Systems
• Because entropy is not conserved, an entropy balance must
consider both the system and surroundings, and includes an
entropy-generation term that accounts for irreversibilities:
• The balance in general terms can be written in words as:
{Time rate of change of entropy in control volume}
+ {Net rate of change in entropy of flowing streams}
+ {Time rate of change of entropy in surroundings}
= {Total rate of entropy generation}

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Equation of Entropy Balance

• The equivalent equation of entropy balance:
a
= hd ≥ 0
b fg
+ ∆ ad ef + (5.15)
c c
where hd is the rate of entropy generation
• This is the general rate form of the entropy balance
• The 1st term is the time rate of change of the total entropy of
the fluid contained within the control volume
• The 2nd term is the net rate of gain of entropy of the flowing
streams
• The 3rd term is the time rate of change of the entropy of the
surroundings, resulting from heat transfer

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 Equation of Entropy Balance (2)
• Let d i be the rate of heat transfer across a particular control
surface (j ) associated with k,i , the temperature in the
surroundings, k , at surface (j )
• The rate of entropy change in the surroundings as a result of
this transfer is then: d i / k,i
• A minus sign is used to convert d i with respect to the system
to a rate with respect to the surroundings, making the 3rd
term in Eqn (5.15):
fg
di
= −H and hence:
c k,i
i
a di
= hd ≥ 0
b
+ ∆ ad ef −H (5.16)
c k,i
i
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Rate of Entropy Generation

• The rate of entropy generation term, hd , reflects the 2nd Law
requirement that it be positive for irreversible processes
• There are 2 sources of irreversibility:
a) Those within the control volume, i.e. internal irreversibilities
b) Those resulting from heat transfer across finite temperature
differences between system and surroundings, i.e. external thermal
irreversibilities

• The limiting case of hd = 0 applies when the process is

completely reversible (internally and externally)
• External reversibility means that either heat reservoirs are
included in the surroundings with temperatures equal to
those of the control surface or Carnot engines are
interposed between the control surface and heat-reservoirs
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 Steady-State Entropy Balance
• For steady-state flow processes, the mass and entropy of the
fluid in the control volume are constant, so d(mS )CV/dt = 0,
thus:
di
∆ ad ef − H = hd ≥ 0 (5.17)
k,i
i

• If there is also only one entrance and exit, then ad is the same
for both streams, allowing for division through by ad:
i
∆ −H = hd ≥ 0 (5.18)
k,i
i

• Eqn. (5.18) is valid per unit mass or per mole

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5.7: Calculation of Ideal Work

• In any steady-state flow process requiring work, an absolute

minimum amount of work is required to produce the desired
state change
• Likewise, in a process producing work, there is an absolute
maximum amount of work that can be realized from a given
state change
• In both cases, the limiting value (ideal work) results when the
process is accomplished reversibly
• For a reversible process, the entropy generation is 0, and the
ideal work can be computed

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 Ideal Work (2)
• From Eqn. (5.17) for a reversible process with uniform
surroundings temperature, k :
d
∆ ad ef − = 0 pq d = k ∆ ad ef
k

• Substituting for d in the energy balance of Eqn. (2.29):

1
∆ S + r] + st ad = k∆ ad ef + 'df (quv)
2 ef

• Here, 'df (quv) is the shaft work of a completely reversible

process, to be renamed: 'd;> , yielding:
1
'd;> =∆ S + r] + st ad − k∆ ad ef (5.19)
2 ef

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Ideal Work (3)

1
'd;> =∆ S + r] + st ad − k∆ ad ef (5.19)
2 ef

• In most applications, the kinetic & potential energy terms are

negligible, yielding:
'd;> = ∆ Sad ef − k ∆ ad ef (5.20)
• For the special case of a single stream flowing through the
control volume:
'd;> = ad ∆S − k∆ (5.21)
';> = ∆S − k∆ (5.22)

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 Thermodynamic Efficiency
• The sole connection between an actual process and an
imagined reversible process for determining ideal work is that
they both apply to the same changes of state
• When 'd;> is positive, it is the minimum work required
(input) to accomplish a given change in state, thus
thermodynamic efficiency is defined as the ratio of ideal work
to actual work:
'd;>
- wpqx quyrzqu = (5.23)
'df
• When 'd;> is negative, 'd;> is the maximum work
obtainable, thus efficiency is the inverse of Eqn (5.23):
'df
- wpqx {qp r|u = (5.24)
d
';>
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5.8: Lost Work

• Lost work – Work that is wasted as a result of irreversibilities;
defined as the difference between actual work & ideal work
' f = 'f − ';> 5.25 or 'd f = 'df − 'd;> (5.26)
• Actual work rate comes from the energy balance in Eqn. (2.29)
and the ideal work rate is obtained using Eqn. (5.19):
1
'df = ∆ S + r] + st ad − d (2.29)
2 ef
1
'd;> =∆ S + r] + st ad − k∆ ad ef (5.19)
2 ef

• Their difference – Lost Work:

'd f = k ∆ ad ef − d (5.27)

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 Lost Work (2)
'd f = k∆ ad ef − d (5.27)
• For the case of a single surroundings temperature , k, Eqn.
(5.17) becomes:
d
d
h = ∆ ad ef − (5.28)
k

• Multiplying by k: k h
d = k∆ ad ef − d
• Comparing to Eqn. (5.27), it is observed:
'd f = k hd (5.29)
• By the 2nd Law, hd ≥ 0, so 'd f ≥ 0: the greater the
irreversibility of a process, the greater the rate of entropy
generation and the greater the amount of energy made
unavailable for work (lost)
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Lost Work (3)

'd f = k∆ ad ef − d (5.27)
d
d
h = ∆ ad ef − (5.28)
k

• For the special case of a single stream through the control

volume, Eqns. (5.27) and (5.28) can be rewritten in any of the
following forms:
'd f = ad k∆ − d 5.30
' f = k∆ − (5.31)
d
d
h = ad∆ − (5.32)
k

h =∆ − (5.33)
k
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5.9: The Third Law of Thermodynamics

• The 3rd Law of Thermodynamics: absolute entropy is zero for all
perfect crystalline substances at absolute zero temperature
• If S = 0 at T = 0 K, then the absolute entropy of a gas, at any T
is:
W~
TU f ∆Se W•
TU ∆S W
TU
=J + +J + +J
Y e W~ W•

(5.35)
where Tf and Tv are the melting point and boiling point respectively; ∆Hf and ∆Hv
are the heats of fusion and vaporization; and ‘s’, ‘l’, and ‘v’ indicate solid, liquid and
gas

• Eqn. (5.35) assumes no solid-state transitions take place

• Although absolute entropy can be obtained, relative values are
more commonly used
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 5.10: Entropy from the Microscopic Viewpoint
• Because molecules in the ideal-gas state do not interact, their
internal energy resides with individual molecules
• Entropy, on the other hand, is a collective property of a large
number of molecules/entities
• Consider the following thought experiment:
An insulated container is partitioned into 2 equal volumes,
containing Avogadro Constant NA of molecules in one section,
and no molecules in the other.
When the partition is withdrawn, the molecules quickly
distribute themselves uniformly throughout the total volume
• Let’s compare the entropy from a macro- and microscopic
viewpoints
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5.10 Continued: Macroscopic View

• The process is an adiabatic expansion, accomplishing no work,
;<
therefore: ∆U = Tb ∆T = 0 & hence ∆T = 0
• The pressure, however, decreases by half, and the entropy
change by Eqn. (5.10) is:
R]
∆ ;< = −7 ln = 7 ln 2
RF
• Since ∆S ≠ 0, this process is clearly irreversible
• At the instant the partition is removed, the molecules take up
only half the volume and are more “ordered” – at the end of
the process, the molecules are distributed throughout the
volume more randomly, and hence more disordered
• Suggests increasing disorder on the molecular level increases
entropy
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 5.10 Continued: Microscopic View

• Boltzmann and Gibbs developed a means to express disorder

quantitatively, defining the quantity, Ω, as the number of
different ways microscopic particles can be distributed among
accessible states
• It is given by the general formula:
…!
Ω= (5.36)
…F ! …] ! …‡ ! ⋯
where N is the total number of particles and N1, N2, N3, etc.
represent the number of particles in states 1, 2, 3, etc.
• In our example, N = NA, and N1 = N2 = NA/2

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5.10 Continued: Microscopic View (2)

• In our case, location of molecules = “states”

• Initially, all molecules are in only 1 “state”, so:
…‰ !
ΩF = =1
…‰ ! 0!
• Hence, initially the molecules can be distributed in just 1 way
• In the final condition, with the molecules uniformly distributed:
…‰ !
Ω] =
…‰ /2 ! ]
• This gives a very large number for Ω] , indicating molecules can
be distributed uniformly between the two states in many ways

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 5.10 Continued: Microscopic View (3)
• Boltzmann established that: = x ln Ω 5.37
– Where k = Boltzmann constant = R/NA

• The entropy difference between states 1 and 2:

Ω] …‰ !
] − F = x ln = x ln = x ln …‰ ! − 2 ln …‰ ⁄2 !
ΩF …‰ ⁄2 ! ]
• Because NA is large, we use Stirling’s formula: ln Œ! = Œ ln Œ − Œ
…‰ …‰ …‰
] − F = x …‰ ln …‰ − …‰ − 2 ln −
2 2 2
…‰
] − F = x… ‰ ln = x…‰ ln 2 = 7 ln 2
…‰ ⁄2
• The same result as the macroscopic analysis!

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5.11 Synopsis
After studying this chapter, including the end-of-chapter problems, one should be able to:

• Comprehend the existence of entropy as a state function, related to observable

properties of a system, for which changes are computed from:

• State the second law of thermodynamics in words and as an inequality in terms of

entropy.

• Define and distinguish between thermal efficiency and thermodynamic efficiency.

• Compute the thermal efficiency of a reversible heat engine.

• Compute entropy changes for the ideal-gas state with heat capacity expressed as a
polynomial in temperature.

• Construct and apply entropy balances for open systems.

• Determine whether a specified process violates the second law.

• Compute ideal work, lost work, and thermodynamic efficiencies of processes.

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