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Chapter 5:
The Second Law of Thermodynamics

Copyright 2022 © McGraw Hill LLC. All rights reserved. No reproduction or distribution without the prior written consent of McGraw Hill LLC.
 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:
𝑡
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 = (5.1)
𝑇
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:
∆𝑆𝑡𝑜𝑡𝑎𝑙 ≥ 0 (5.2)
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 2nd Law: Application to Heat Transfer 1
• 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 transferred to the cold
reservoir:
𝑄𝐻 = −𝑄𝐶 & 𝑄𝐻 = 𝑄𝐶 = 𝑄
• Entropy change from each reservoir:
𝑡
𝑄𝐻 𝑡
𝑄𝐶
∆𝑆𝐻 = & ∆𝑆𝐶 =
𝑇𝐻 𝑇𝐶

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 2nd Law: Application to Heat Transfer 2

• Combining the two entropy changes:

−𝑄𝐶 𝑄𝐶 𝑇𝐻 − 𝑇𝐶
∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝐻𝑡 + ∆𝑆𝐶𝑡 = + = 𝑄𝐶
𝑇𝐻 𝑇𝐶 𝑇𝐻 𝑇𝐶
• 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 1
• 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:
𝑄𝐻 𝑄𝐶
∆𝑆𝑡𝑜𝑡𝑎𝑙 = − −
𝑇𝐻 𝑇𝐶
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 :
𝑇𝐻 − 𝑇𝐶
𝑊 = 𝑇𝐻 ∆𝑆𝑡𝑜𝑡𝑎𝑙 + 𝑄𝐶
𝑇𝐶
• This gives work output between 2 limits:
1) Totally ineffective engine: W = 0 & only heat transfer occurs
𝑇𝐻 − 𝑇𝐶
∆𝑆𝑡𝑜𝑡𝑎𝑙 = −𝑄𝐶
𝑇𝐻 𝑇𝐶
*Sign difference due to QC being with respect to engine
2) Reversible process: ∆Stotal = 0, yields a Carnot Engine:
𝑇𝐻
𝑊 = 𝑄𝐶 −1 (5.3)
𝑇𝐶
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 2nd Law Restrictions on Heat Engines 3
𝑇𝐻
𝑊 = 𝑄𝐶 −1 (5.3)
𝑇𝐶
• 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 :
−𝑄𝐶 𝑄𝐻
= (5.4)
𝑇𝐶 𝑇𝐻
𝑊 𝑇𝐶
= −1 (5.5)
𝑄𝐻 𝑇𝐻
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):
−𝑊 𝑊
𝜂≡ = (5.6)
𝑄𝐻 𝑄𝐻
𝑇𝐶
𝜂𝐶𝑎𝑟𝑛𝑜𝑡 = 1 − (5.7)
𝑇𝐻
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 Carnot Efficiency
𝑇𝐶
𝜂𝐶𝑎𝑟𝑛𝑜𝑡 =1− (5.7)
𝑇𝐻
• 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, 𝜂 → 0.5 is
an approximate realistic limit for the thermal efficiency of a
Carnot engine.
• Actual heat engines are irreversible and 𝜂 is typically < 0.35.

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 Example 5.2

A central power plant, rated at 800,000 kW, generates

steam at 585 K and discards heat to a river at 295 K. If
the thermal efficiency of the plant is 70% of the
maximum possible value, how much heat is discarded
to the river at rated power?

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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 T
reservoir.
• Measure of quality of a heat pump is the coefficient of
performance – the heat extracted at the lower T, divided by W.
𝑄𝐶 𝑇𝐶
𝜔≡ 5.8 & 𝜔𝐶𝑎𝑟𝑛𝑜𝑡 ≡ (5.9)
𝑊 𝑇𝐻 − 𝑇𝐶
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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:
𝑖𝑔 𝑖𝑔
𝑉𝑐 𝑉𝑎
𝑄𝐻 = 𝑅𝑇𝐻 ln 𝑖𝑔
& 𝑄𝐶 = 𝑅𝑇𝐶 ln 𝑖𝑔
𝑉𝑏 𝑉𝑑
• Dividing the two:
𝑖𝑔 𝑖𝑔
𝑄𝐻 𝑇𝐻 ln 𝑉𝑐 ൗ𝑉𝑏
=
𝑄𝐶 𝑇𝐶 ln 𝑉 𝑖𝑔 ൗ𝑉 𝑖𝑔
𝑎 𝑑

• Assuming constant Cp , Eqn. (3.23a) gives: TV 𝛾-1 = constant:

𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1
𝑇𝑎 𝑉𝑎 = 𝑇𝑏 𝑉𝑏 → 𝑇𝐶 𝑉𝑎 = 𝑇𝐻 𝑉𝑏
𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1
𝑇𝑑 𝑉𝑑 = 𝑇𝑐 𝑉𝑐 → 𝑇𝐶 𝑉𝑑 = 𝑇𝐻 𝑉𝑐

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 Carnot Engine 3

𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1

𝑇𝑎 𝑉𝑎 = 𝑇𝑏 𝑉𝑏 → 𝑇𝐶 𝑉𝑎 = 𝑇𝐻 𝑉𝑏
𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1
𝑇𝑑 𝑉𝑑 = 𝑇𝑐 𝑉𝑐 → 𝑇𝐶 𝑉𝑑 = 𝑇𝐻 𝑉𝑐
• Taking the ratio of the two, and simplifying:
𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
𝑉𝑐 𝑉𝑑 𝑉𝑐 𝑉𝑑 𝑉𝑐 𝑉𝑎
= → = → ln = − ln
𝑖𝑔 𝛾−1 𝑖𝑔 𝛾−1 𝑉𝑏
𝑖𝑔
𝑉𝑎
𝑖𝑔
𝑉𝑏
𝑖𝑔
𝑉𝑑
𝑖𝑔
𝑉𝑏 𝑉𝑎
• Thus, the following simplifications can be made:
𝑖𝑔 𝑖𝑔
𝑄𝐻 𝑇𝐻 ln 𝑉𝑐 ൗ𝑉𝑏 𝑇𝐻 −𝑄𝐶 𝑄𝐻
= 𝑖𝑔 𝑖𝑔
=− → = (5.4)
𝑄𝐶 𝑇𝐶 ln 𝑉 ൗ𝑉 𝑇𝐶 𝑇𝐶 𝑇𝐻
𝑎 𝑑

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 5.4: Entropy
• Rearranging Eqn. (5.4):
𝑄𝐶 𝑄𝐻 𝑟𝑒𝑣
+ = 0 = ∆𝑆𝑐𝑦𝑐𝑙𝑒
𝑇𝐶 𝑇𝐻
• If instead of heat being added in 2 steps from 2 reservoirs, its
added in i steps, but still in a cycle:
𝑄𝑖
෍ =0
𝑇
𝑖

• As the steps become infinitesimally small:

𝑄𝑖 𝑑𝑄𝑟𝑒𝑣
෍ →ර = ර 𝑑𝑆 = 0
𝑇 𝑇
𝑖

• 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:
𝑡
𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑟𝑒𝑣
∆𝑆 = න =න
𝐴𝐶𝐵 𝑇 𝐴𝐷𝐵 𝑇
• As a state function:
∆𝑆 𝑡 = 𝑆𝐵𝑡 − 𝑆𝐴𝑡
• For an irreversible process, note,
∆S ≠ ∫dQ/T.
• If a process is reversible &
adiabatic, dS t = 0, and hence it
is isentropic.
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 Characteristics of Entropy

𝑡
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 = (5.1)
𝑇

• 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.

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 5.5: Entropy Changes for the Ideal-Gas State 1
• 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:
𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉
• Differentiation of the definition of enthalpy, H = U + PV:
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
• Combining: 𝑑𝐻 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
• Or: 𝑑𝑄𝑟𝑒𝑣 = 𝑑𝐻 − 𝑉𝑑𝑃
𝑖𝑔
• For the ideal-gas state, 𝑑𝐻 𝑖𝑔 = 𝐶𝑃 𝑑𝑇 & 𝑉 𝑖𝑔 = 𝑅𝑇/𝑃
• Substituting & dividing by T:
𝑑𝑄𝑟𝑒𝑣 𝑖𝑔 𝑑𝑇 𝑑𝑃
= 𝐶𝑃 −𝑅
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𝑇 𝑇 𝑃 21
 5.5 Entropy Changes for the Ideal-Gas State 2

𝑑𝑄𝑟𝑒𝑣 𝑖𝑔 𝑑𝑇 𝑑𝑃
= 𝐶𝑃 −𝑅
𝑇 𝑇 𝑃
• As a result of Eqn. (5.1), this becomes:
𝑖𝑔 𝑖𝑔
𝑖𝑔 𝑑𝑇 𝑑𝑃 𝑑𝑆 𝐶𝑃 𝑑𝑇
𝑑𝑆 𝑖𝑔 = 𝐶𝑃 −𝑅 → = − 𝑑 ln 𝑃
𝑇 𝑃 𝑅 𝑅 𝑇
• Integrating from initial conditions T0, P0:
𝑇 𝑖𝑔
∆𝑆 𝑖𝑔 𝐶𝑃 𝑑𝑇 𝑃
=න − ln 5.10
𝑅 𝑇0 𝑅 𝑇 𝑃0
• Eqn. (5.10) is a general equation for calculation of entropy
changes in the ideal-gas state.

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 5.5 Entropy Changes for the Ideal-Gas State 3
𝑖𝑔
• By use of Eqn. (4.5) for 𝐶𝑃 , integration of the first term in Eqn.
(5.10) results in the following:
𝑇 𝑖𝑔
𝐶𝑃 𝑑𝑇 𝑇 𝐷 𝑇 + 𝑇0
න = 𝐴 ln + 𝐵 + 𝐶 + 2 2 𝑇 − 𝑇0
𝑇0 𝑅 𝑇 𝑇0 𝑇0 𝑇 2
(5.11)
• Defining a new mean heat capacity can be useful:
𝑇 𝑖𝑔
𝑖𝑔
∫𝑇 𝐶𝑃 𝑑𝑇Τ𝑇
0
𝐶𝑃 = (5.12)
𝑆 ln 𝑇Τ𝑇0
• Where:
𝑖𝑔
𝐶𝑃
𝑆 𝐷 𝑇 + 𝑇0 𝑇 − 𝑇0
=𝐴+ 𝐵+ 𝐶+ 2 2 (5.13)
𝑅 𝑇0 𝑇 2 ln 𝑇Τ𝑇0
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 5.5 Entropy Changes for the Ideal-Gas State 4

• Thus, by rearranging Eqn. (5.12):

𝑇
𝑖𝑔 𝑑𝑇 𝑖𝑔 𝑇
න 𝐶𝑃 = 𝐶𝑃 ln
𝑇0 𝑇 𝑆 𝑇0
• And Eqn. (5.10) becomes:
𝑖𝑔
𝐶𝑃
∆𝑆 𝑖𝑔 𝑆 𝑇 𝑃
= ln − ln (5.14)
𝑅 𝑅 𝑇0 𝑃0
• Eqn. (5.14) is often useful in iterative calculations where the
final temperature is unknown.

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 Example 5.4

Methane gas at 550 K and 5 bar undergoes a reversible

adiabatic expansion to 1 bar. Assuming ideal-gas-state
methane at these conditions, find its final temperature.

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 Ex. 5.4

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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:
𝑇𝑓 ∆𝐻𝑓 𝑇𝑣 𝑇
𝐶𝑃 𝑠 𝐶𝑃 𝑙 ∆𝐻𝑣 𝐶𝑃 𝑣
𝑆=න 𝑑𝑇 + +න 𝑑𝑇 + +න 𝑑𝑇
0 𝑇 𝑇𝑓 𝑇𝑓 𝑇 𝑇𝑣 𝑇𝑣 𝑇

(5.35)
where Tf and Tv are the melting point and boiling point; ∆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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