CHAPTER 4 SECOND LAW: ENTROPY

Mr. Getu Seifu

Lesson outcomes
 You will be able to
 Comprehend the existence of entropy as a state function,
related to observable properties of a system, for which
𝒕 𝒅𝑸𝒓𝒆𝒗
changes are computed from: 𝒅𝑺 =
𝑻
 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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Entropy
𝑸𝑯 𝑻𝑯
 Equation = for a Carnot engine may be
𝑸𝑳 𝑻𝑳
written:
𝑄𝐻 𝑄𝐿
=
𝑇𝐻 𝑇𝐿
 If the heat quantities refer to the engine (rather than to the heat
reservoirs), the numerical value of
 QH is positive and Qc is negative.
 The equivalent equation written without absolute-value signs is
therefore 𝑄𝐻 𝑄𝐿 𝑄𝐻 𝑄𝐿
= −𝑇 or +𝑇 =0
𝑇𝐻 𝐿 𝑇𝐻 𝐿

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Entropy

 Thus for a complete cycle of a Carnot engine,

 the two quantities Q/T associated with the absorption
and rejection of heat by the working fluid of the
engine sum to zero.
 The working fluid of a cyclic engine returns to its
initial state, and its properties return to their initial
values.
 A primary characteristic of a property is that the sum
of its changes is zero for any complete cycle.

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Entropy

 Thus for a Carnot cycle equation:

𝑄𝐻 𝑄𝐿
𝑇𝐻
+ 𝑇𝐿
=0
 Suggests the existence of a property whose
changes are given by the quantities Q/ T.

𝑄𝐻 𝑄𝐿 is applicable to Carnot cycle,

+ =0 also applies to other
𝑇𝐻 𝑇𝐿
reversible cycles.
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Entropy
 Thus, for any reversible cycle, Summation of all
quantities 𝒅 𝑸/ 𝑻 for the Carnot engines leads to
the integral:
𝒅𝑸𝒓𝒆𝒗
‫𝑻 ׯ‬ = 𝟎 𝐚𝐧𝐝 ‫𝟎 = 𝒕𝑺𝒅 ׯ‬,
𝐽
• 𝑆 𝑡 𝑖𝑠 𝑎 𝑠𝑡𝑎𝑡𝑒 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 , ,
𝐾
𝑺𝒕 𝒕𝒐𝒕𝒂𝒍 𝒆𝒏𝒕𝒓𝒐𝒑𝒚
• S= molar entropy = =
𝒏 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔

Where the circle in the integral sign signifies

integration over the arbitrary cycle, and the
subscript "rev" indicates that the cycle is reversible.
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Entropy

 Thus the quantities: d 𝑸𝒓𝒆𝒗/𝑻

 Sum to zero for cycle, exhibiting the characteristic of a
property.
 We therefore infer the existence of a property whose
differential changes for the arbitrary cycle are given by these
quantities.
 The property is called entropy, and its differential changes are:

𝒕
𝒅𝑸𝒓𝒆𝒗 Where, 𝑺𝒕 is the total (rather than molar)
𝒅𝑺 =
𝑻 entropy of the system.

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Entropy
 Alternatively, 𝒅𝑸𝒓𝒆𝒗 = 𝑻𝒅𝑺𝒕
 Points A and B on the PV diagram represent two equilibrium states
of a particular fluid, and
 Paths ACB and ADB show two arbitrary reversible processes
connecting these points.
𝒅𝑸𝒓𝒆𝒗
 Integration of Eq. 𝒅𝑺𝒕 = for each path gives:
𝑻

Figure Two reversible

paths joining equilibrium
states A and B
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Entropy

𝒕 𝒅𝑸𝒓𝒆𝒗 𝒅𝑸𝒓𝒆𝒗
∆𝑺 = ‫𝑩𝑪𝑨׬‬ and =‫𝑩𝑫𝑨׬‬
𝑻 𝑻
𝒅𝑸𝒓𝒆𝒗
Where in view of Eq. ‫ׯ‬ = 𝟎 the two integrals must be equal.
𝑻
𝒕
 We conclude that a ∆𝑺 , is independent of path and is a
property change given by 𝑺𝑩 𝒕 − 𝑺𝑨 𝒕 .

Figure Two reversible

paths joining equilibrium
states A and B
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Entropy
 If the fluid is changed from state A to state B by an
irreversible process, the entropy change must still be
Δ𝑆 = 𝑆𝐵 − 𝑆𝐴 ,
 Experiment shows that this result is not given by ‫𝑸 𝒅 ׬‬/ 𝑻
evaluated for the irreversible process,

 Because the calculation of entropy changes by this integral

must in general be along reversible paths.
 The entropy change of a heat reservoir is always given
by 𝑄/ 𝑇,
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Entropy
 Where Q is
 The quantity of heat transferred to or from the
reservoir at temperature T, whether the transfer is
reversible or irreversible.
 The reason is that the effect of heat transfer on a heat
reservoir is the same regardless of the temperature of the
source or sink of the heat.
 If a process is reversible and adiabatic,
d 𝑄𝑟𝑒𝑣 = 0; then, 𝑑𝑆 𝑡 = 0.
 Thus the entropy of a system is constant during a reversible
adiabatic process, and the process is said to be isentropic.
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This discussion of entropy can be summarized as follows:
 This discussion of entropy can be summarized as follows:
Equation
𝒕
𝒅𝑸𝒓𝒆𝒗
𝒅𝑺 =
𝑻
 Is the ultimate source of all equations that relate
the entropy to measurable quantities.
 It does not represent a definition of entropy;
 What it provides is the means for calculating
changes in this property.
 Its essential nature is summarized by the following
axiom:
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This discussion of entropy can be summarized as follows:

 There exists a property called entropy S, which

is an intrinsic property of a system, functionally
related to the measurable coordinates which
characterize the system.
 For a reversible process, changes in this
property are given by Eq.

𝒕
𝒅𝑸𝒓𝒆𝒗
𝒅𝑺 =
𝑻

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This discussion of entropy can be summarized as follows:
 The change in entropy of any system undergoing a finite
reversible process is:
𝒕
𝒅𝑸𝒓𝒆𝒗
∆𝑺 = න
𝑻
 When a system undergoes an irreversible process between two
equilibrium states,
 the entropy change of the system ΔS−is evaluated by application of Eq.
𝒕 𝒅𝑸𝒓𝒆𝒗
∆𝑺 = ‫׬‬
𝑻
 to an arbitrarily chosen reversible process that
accomplishes the same change of state as the actual
process.
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This discussion of entropy can be summarized as follows:
 Integration is not carried out for the
irreversible path.
 Entropy is a state function,
 the entropy changes of the irreversible and reversible processes are
identical.

 In the special case of a mechanically reversible

process,
 the entropy change of the system ‫𝑸 𝒅 ׬‬/ 𝑻
applied to the actual process,
 even though the heat transfer between system and
surroundings is irreversible.
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This discussion of entropy can be summarized as follows:

 The reason is that it is immaterial, as far as the system

is concerned, whether the temperature difference
causing the heat transfer is differential (making the
process reversible) or finite.
 The entropy change of a system caused by the
transfer of heat
 calculated by ‫𝑸 𝒅 ׬‬/ 𝑻 , whether the heat transfer
is accomplished reversibly or irreversibly.

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 ENTROPY CHANGES OF AN IDEAL GAS
 For one mole or a unit mass of fluid undergoing a
mechanically reversible process in a closed system,
 the first law, Equation, 𝒅𝑼 = 𝒅𝑸𝒓𝒆𝒗 – 𝑷𝒅𝑽 becomes:
𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 – 𝑃𝑑𝑉
 Differentiation of the defining equation for enthalpy , H = U + P V, yields:
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑 𝑉 + 𝑉𝑑𝑃
 Eliminating 𝑑𝑈 gives:
𝑑𝐻 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉 + 𝑃𝑑 𝑉 + 𝑉𝑑𝑃 →

𝑑𝑄𝑟𝑒𝑣 = 𝑑𝐻 − 𝑉𝑑𝑃

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 ENTROPY CHANGES OF AN IDEAL GAS
 For an ideal gas, 𝒅𝑯 = 𝑪𝒊𝒈 𝑷 𝒅𝑻 and 𝑽 = 𝑹𝑻/ 𝑷. With these
substitutions and then division by T,

𝑑𝑄𝑟𝑒𝑣 𝑖𝑔 𝑑𝑇 𝑑𝑃
= 𝐶𝑃 −𝑅
𝑇 𝑇 𝑃
𝒕 𝒅𝑸𝒓𝒆𝒗
 As a result of equation: ∆𝑺 = ‫𝑻 ׬‬ , this becomes:

𝑖𝑔 𝑑𝑇 𝑑𝑃 𝑑𝑆 𝐶𝑃 𝑖𝑔 𝑑𝑇
𝑑𝑆 = 𝐶𝑃 −𝑅 𝑂𝑟 = − 𝑑𝑙𝑛𝑃
𝑇 𝑃 𝑅 𝑅 𝑇
 Where S is the molar entropy of an ideal gas.
 Integration from an initial state at conditions To and Po to a final
state at conditions T and P gives:
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 ENTROPY CHANGES OF AN IDEAL GAS

∆𝑺 𝑻
𝑪𝑷 𝒊𝒈 𝒅𝑻 𝑷
= න − 𝒍𝒏
𝑹 𝑻𝟎 𝑹 𝑻 𝑷𝟎

 Derived for a mechanically reversible process

 This equation relates properties only, and
 So it is independent of the process causing the
change of state.
 A general equation for the calculation of
entropy changes of an ideal gas.
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Example

 For the ideal-gas state and constant heat capacities, Eq.

𝑇𝑃 1−𝛾Τ𝛾 = constant for a reversible adiabatic (and
therefore isentropic) process can be written:

 Show that this same equation results from application of

Eq. (*) with Δ𝑆𝑖𝑔 = 0.

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Solution
 Because CP ig is constant, Eq. (*) becomes:

 Exponentiating both sides of this equation leads to the given equation.

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TEMPERATURE DEPENDENCE OF THE HEAT CAPACITY
𝑻 𝑪𝑷 𝒊𝒈 𝒅𝑻
 Evaluation of ‫𝑻 𝑹 𝑻׬‬ requires knowledge of
𝟎
temperature dependence of the heat capacity.
 Temperature dependence of heat capacity is usually given
by an empirical equation

ig ig ig
CP CV CP
= A + BT + CT 2 + DT -2 and = -1
R R R
 The parameters A, B, C and D are tabulated for number of materials.

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TEMPERATURE DEPENDENCE OF THE HEAT CAPACITY
T
C B 2 C 3 T T 0 
 P dT  A(T  T ) (T  T 0)  (T  T 0)  D 
2 3
0
T R 0
2 3  TT 0 

T
C P dT  ( A  B (  C 2 D
 ) (T  T 0  TT 0)  )(T  T 0)
2

2
T T 0
3
T R 0 TT 0

C s B C 2 D
 A (T  T 0)  (T  T 0  TT 0) 
P 2

R 2 3 TT 0

This form of the equation for entropy changes of an ideal gas may be
useful when iterative calculations are required.
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Example
 Methane gas at 550 K and 5 bar undergoes a reversible
adiabatic expansion to 1bar. Assuming ideal-gas-state
methane at these conditions, find its final temperature.
 A=1.702,
 B=9.081 × 10−3,
 C=−2.164 × 10−6,
 D=0.0

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SOLUTION
 For this process ΔSig = 0

• ⟨CP ig ⟩s /R is evaluated by
C s B C 2 D
 A (T  T 0)  (T  T 0  TT 0) 
P 2

R 2 3 TT 0

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SOLUTION
 T0 = 550

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Entropy change of liquids and solids
 Solids and liquids are incompressible substances since their
specific volumes remain nearly constant during a process. i.e.
𝒅𝒗 ≅ 𝟎
𝒅𝒖
 Therefore 𝒅𝒔 =
𝑻
 And for incompressible substance; 𝒄𝑷 = 𝒄𝒗 = 𝒄 and the specific
heat is also as a function of temperature;
 For solids and liquids
𝟐
𝒅𝑻 𝑻𝟐
𝒔𝟐−𝒔𝟏 = න 𝒄(𝑻) ≅ 𝒄𝒂𝒗 𝐥𝐧
𝟏 𝑻 𝑻𝟏
 For isentropic process;
𝑻𝟐
𝒔𝟐 −𝒔𝟏 = 𝒄𝒂𝒗 𝐥𝐧 = 𝟎 → 𝑻𝟏 = 𝑻𝟐
𝑻𝟏
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 MATHEMATICAL STATEMENT OF THE SECOND LAW

 Consider two heat reservoirs, one at temperature 𝑇𝐻 and a

second at the lower temperature𝑇𝑐.
 Let a quantity of heat 𝑸 be transferred from the hotter to the cooler
reservoir.
 The entropy changes of the reservoirs at 𝑇𝐻 and at 𝑇𝑐 are:

𝒕
−𝑸 𝒕
−𝑸
∆𝒔 𝑯 = 𝒂𝒏𝒅 ∆𝒔 𝑪 =
𝑻𝑯 𝑻𝑳
• These two entropy changes are added to give:

𝑡 𝑡 −𝑄 𝑄 𝑇𝐻 − 𝑇𝐶
∆𝑆𝑡𝑜𝑡𝑎𝑙 = 𝛥𝑆𝐻 + 𝛥𝑆𝐶 = + = 𝑄
𝑇𝐻 𝑇𝐶 𝑇𝐻 𝑇𝐶
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 MATHEMATICAL STATEMENT OF THE SECOND LAW

 Since TH > TC , the total entropy change as a result of this

irreversible process is positive.
 Also, ∆𝑺𝒕𝒐𝒕𝒂𝒍 becomes smaller as the difference TH - TC gets
smaller.
 When TH is only infinitesimally higher than TC, the heat
transfer is reversible, and ∆𝑺𝒕𝒐𝒕𝒂𝒍 approaches zero.
 Thus for
 The process of irreversible heat transfer, ∆𝑺𝒕𝒐𝒕𝒂𝒍 is always
positive,
 The process of heat transfer becomes reversible,
∆𝑺𝒕𝒐𝒕𝒂𝒍 approaching zero .

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 MATHEMATICAL STATEMENT OF THE SECOND LAW

 For any process, the general equation:

∆𝑺𝒕𝒐𝒕𝒂𝒍 ≥ 𝟎

 This mathematical statement of the second law

affirms that every process proceeds in such a
direction that the total entropy change
associated with it is positive, the limiting value
of zero being attained only by a reversible
process. No process is possible for which the
total entropy decreases.
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 MATHEMATICAL STATEMENT OF THE SECOND LAW
 Heat engine operates in a cycles, undergoes no net changes in
its properties.
 The total entropy change of the process is therefore the sum
of the entropy changes of the heat reservoirs:
− 𝑄𝐻 𝑄𝐶
∆𝑆𝑡𝑜𝑡𝑎𝑙 = +
𝑇𝐻 𝑇𝐶
• The work produced by the engine is
𝑊 = 𝑄𝐻 − 𝑄𝐶
Elimination of 1 Qc 1 between these two equations and solution for I W I gives:
𝑇𝐶
𝑊 = −𝑇𝐶 ∆𝑆𝑡𝑜𝑡𝑎𝑙 + 𝑄𝐻 1−
𝑇𝐻
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 MATHEMATICAL STATEMENT OF THE SECOND LAW
𝑇𝐶 The general equation for work of
𝑊 = −𝑇𝐶 ∆𝑆𝑡𝑜𝑡𝑎𝑙 + 𝑄𝐻 1− a heat engine for temperature
𝑇𝐻
levels TC and TH.

 The minimum work output is zero, resulting when the engine

is completely inefficient and the process degenerates into
simple irreversible heat transfer between the two heat
reservoirs.
 The maximum work is obtained when the engine is reversible,
 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 0, and
 the equation reduces to the second term on the right, the
work of a Carnot engine.

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Internally Reversible Isothermal Heat Transfer Processes
 Recall that isothermal heat transfer processes are internally reversible.
 The entropy change of a system during an internally reversible isothermal
heat transfer process can be determined by performing the integration:

Where T0 is the constant temperature of the system and

Q is the heat transfer for the internally reversible process.
• Is particularly useful for determining the entropy changes of
thermal energy reservoirs that can absorb or supply heat
indefinitely at a constant temperature.
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Internally Reversible Isothermal Heat Transfer Processes
 Notice that the entropy change of a system during an
internally reversible isothermal process can be positive
or negative, depending on the direction of heat
transfer.
 Heat transfer to a system increases the entropy of
a system, whereas
 Heat transfer from a system decreases it.

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ENTROPY BALANCE SYSTEMS

∆𝑆𝑡𝑜𝑡𝑎𝑙 ≥ 0
 Equality for internally reversible process and
 Inequality for an irreversible process.
 The change in entropy of a closed system undergoing an
irreversible process is greater than the entropy transfer by
heat transfer.
 Some entropy is generated or created during an irreversible
process,
 generation is due entirely to the presence of irreversibilities.

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ENTROPY BALANCE CLOSED SYSTEMS
 The entropy generated during a process is called entropy
generation and is denoted by Sgen.
 The difference between the entropy change of a closed
system and the entropy transfer is equal to entropy
generation.
𝟐
𝜹𝑸
∆𝑺𝒔𝒚𝒔 = 𝑺𝟐 − 𝑺𝟏 = න + 𝑺𝒈𝒆𝒏
𝟏 𝑻

 The quantity ∆𝑺𝒔𝒚𝒔 = 𝑺𝟐 − 𝑺𝟏 represents the entropy

change of the system.
𝟐 𝜹𝑸
 For a reversible process, it becomes equal to ‫ 𝑻 𝟏׬‬, which
represents the entropy transfer with heat.
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ENTROPY BALANCE SYSTEMS
 The entropy generation is dependent on the process path,
 In the absence of entropy transfer, the entropy change of a
system is due to the entropy generation.
 For an isolated system (or simply an adiabatic closed
system), the heat transfer is zero;
 The entropy of an isolated system during a process always
increases or, in the limiting case of a reversible process, remains
constant.
 Entropy never decreases. This is known as the increase of
entropy principle.

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ENTROPY BALANCE SYSTEMS
 The entropy change of this isolated system during a process is
 the sum of the entropy changes of the system and its
surroundings, which is equal to the entropy generation since an
isolated system involves no entropy transfer
𝑺𝒈𝒆𝒏 = ∆𝑺𝒕𝒐𝒕 = ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 ≥ 𝟎
 The entropy of the universe is continuously increasing.

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ENTROPY BALANCE SYSTEMS

Figure 2 The entropy change of a system

Figure1 A system and its surroundings
can be negative, but the entropy generation
form an isolated system.
cannot.

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ENTROPY BALANCE SYSTEMS
 The increase of entropy principle does not
imply that the entropy of a system cannot
decrease.
 The entropy change of a system can be
negative during a process, but entropy
generation cannot.

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ENTROPY BALANCE FOR OPEN SYSTEMS

 Entropy balance can be written for processes in which

fluid enters, exits, or flows through a control volume,
 Entropy is not conserved.
 The second law states that
 The total entropy change associated with any process must be
Positive, and zero.
 The Entropy Balance for both the system and its surroundings,
 considered together, and
 by including an entropy-generation

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ENTROPY BALANCE FOR OPEN SYSTEMS
 Entropy-generation is the sum of
 The difference in entropy between exit and entrance streams,
 Entropy change within the control volume, and
 Entropy change in the surroundings.
 If the process is reversible,
 Three terms sum to zero, making, ΔS total = 0.
 If the process is irreversible,
 Sum to a positive quantity, the entropy-generation term, ΔS
ሶ
total = 𝑺𝑮

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ENTROPY BALANCE FOR OPEN SYSTEMS
 The statement of balance, expressed as rates:

• The equivalent equation of entropy balance is

𝒅(𝒎𝑺)𝑪𝑽 𝒅𝑺𝒕 𝑺𝒖𝒓𝒓

+ ∆(𝒎𝑺)
ሶ 𝒇𝒔 + = 𝑺ሶ 𝑮 ≥ 𝟎
𝒅𝒕 𝒅𝒕
This equation is the general rate form of the entropy balance,
applicable at any instant.
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ENTROPY BALANCE FOR OPEN SYSTEMS
 where 𝑺ሶ 𝑮 is the rate of entropy generation.
 Each term can vary with time.
 Net rate of change in entropy in control volume:
 the time rate of change of the total entropy of the fluid
contained within the control volume.

 The time rate of change of entropy of flowing streams is

the net rate of gain in entropy of the flowing streams.
 i.e., the difference between the total entropy transported out by
exit streams and the total entropy transported in by entrance
streams.

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ENTROPY BALANCE FOR OPEN SYSTEMS
 Time rate of change of entropy in surroundings is the time
rate of change of the entropy of the surroundings, resulting
from heat transfer between system and surroundings.

 Let rate of heat transfer 𝑸ሶ 𝒋 with respect to a particular

part of the control surface be associated with Tσ,j where
subscript σ,j denotes a temperature in the surroundings.

 The rate of entropy change in the surroundings as a

result of this transfer is then − 𝑸ሶ 𝒋 /Tσ,j.
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ENTROPY BALANCE FOR OPEN SYSTEMS
 The minus sign converts 𝑸ሶ 𝒋 , defined with respect to the system, to
 A heat transfer rate with respect to the surroundings.
 So time rate of change of entropy in surroundings is
therefore the sum of all such quantities (𝑄ሶ j/Tσ,j)
 Time rate of change of entropy in surroundings:
𝑑𝑆 𝑡 𝑆𝑢𝑟𝑟 𝑄ሶ 𝑗
= − σ𝑗
𝑑𝑡 𝑇𝜎,𝑗
 Entropy balance is

𝒅(𝒎𝑺)𝑪𝑽 𝑸ሶ 𝒋
+ ∆(𝒎𝑺)
ሶ 𝒇𝒔 − σ𝒋 = 𝑺ሶ 𝑮 ≥ 𝟎
𝒅𝒕 𝑻𝝈,𝒋
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ENTROPY BALANCE FOR OPEN SYSTEMS
 𝑺ሶ 𝑮 , the rate of entropy generation, reflects the second-law requirement that
it be positive for irreversible processes.
 There are two sources of irreversibility:
a) those within the control volume, i.e., internal irreversibilities, and
b) those resulting from heat transfer across finite temperature differences
between system and surroundings,
i.e., external thermal irreversibilities.
 The limiting case for which 𝑺ሶ 𝑮 = 0 applies when the process is
completely reversible, implying:
 The process is internally reversible within the control volume
 Heat transfer between the control volume and its surroundings is
reversible.

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 The heat reservoirs are included in the surroundings with

temperatures equal to those of the control surface or that work-
producing Carnot engines are interposed in the surroundings
between the control-surface temperatures and the heat-
reservoir temperatures.
 For a steady-state flow process the mass and entropy of the
𝒅(𝒎𝑺)𝑪𝑽
fluid in the control volume are constant, and 𝒅𝒕
is zero.

𝑸ሶ 𝒋
ሶ 𝒇𝒔 − σ𝒋
∆(𝒎𝑺) = 𝑺ሶ 𝑮 ≥ 𝟎
𝑻𝝈,𝒋

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 If in addition there is but one entrance and one exit, 𝒎ሶ is
the same for both streams, and dividing through by

𝑸𝒋
∆𝑺 − σ𝒋 = 𝑺𝑮 ≥ 𝟎
𝑻𝝈,𝒋

• is based on a unit mass of fluid flowing through the control

volume.

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Tutorial
1. In a steady-state flow process carried out at atmospheric
pressure, 1 mol⋅s−1 of air at 600 K is continuously mixed with
2 mol⋅s−1 of air at 450 K. The product stream is at 400 K and
1 atm. A schematic representation of the process is shown in
Fig. below. Determine the rate of heat transfer and the rate
of entropy generation for the process. Assume the ideal-gas
state for air with 𝑐𝑃 𝑖𝑔 = (7/2)𝑅, that the surroundings are
at 300 K, and that kinetic- and potential-energy changes of
the streams are negligible.

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Solution
 We start by applying an energy balance to determine the rate of
heat transfer, which we will need to know in order to compute the
rate of entropy generation.
 Writing the energy balance, Eq.

with 𝒎ሶ replaced by 𝒏ሶ , and then

replacing 𝒏ሶ with 𝒏ሶ 𝑨 + 𝒏ሶ 𝑩 ,

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Solution
• The steady-state entropy balance, Eq.
𝑸ሶ 𝒋
ሶ 𝒇𝒔 − σ𝒋
∆(𝒎𝑺) = 𝑺ሶ 𝑮 ≥ 𝟎 with 𝒎ሶ again
𝑻𝝈,𝒋
replaced by 𝒏ሶ , can similarly be written as

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Tutorial
2. A Carnot engine receives 250 kJ·s−1 of heat from a heat-source reservoir
at 525°C and rejects heat to a heat-sink reservoir at 50°C. What are the
power developed and the heat rejected?

3. The following heat engines produce power of 95,000 kW. Determine in

each case the rates at which heat is absorbed from the hot reservoir and
discarded to the cold reservoir.
a) A Carnot engine operates between heat reservoirs at 750 K and
300 K.

b) A practical engine operates between the same heat reservoirs but

with a thermal efficiency η = 0.35.

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4. A particular power plant operates with a heat-source
reservoir at 350°C and a heat sink reservoir at 30°C. It has
a thermal efficiency equal to 55% of the Carnot-engine
thermal efficiency for the same temperatures.
a) What is the thermal efficiency of the plant?

b) To what temperature must the heat-source reservoir be raised

to increase the thermal efficiency of the plant to 35%? Again
η is 55% of the Carnot-engine value

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5. With respect to 1 kg of liquid water:
a) Initially at 0°C, it is heated to 100°C by contact
with a heat reservoir at 100°C. What is the
entropy change of the water? Of the heat
reservoir? What is ΔS total ?
b) Initially at 0°C, it is first heated to 50°C by contact
with a heat reservoir at 50°C and then to 100°C
by contact with a reservoir at 100°C. What is ΔS
total?
c) Explain how the water might be heated from 0°C
to 100°C so that ΔS total = 0.
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6) A rigid vessel of 0.06 m3 volume contains an ideal
gas, CV = (5/2)R, at 500 K and 1 bar.
a) If heat in the amount of 15,000 J is transferred to the gas,
determine its entropy change.

b) If the vessel is fitted with a stirrer that is rotated by a shaft

so that work in the amount of 15,000 J is done on the gas,
what is the entropy change of the gas if the process is
adiabatic? What is ΔS total? What is the irreversible feature
of the process?

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7. An ideal gas, CP = (7/2)R, is heated in a steady-flow
heat exchanger from 70°C to 190°C by another stream
of the same ideal gas which enters at 320°C. The flow
rates of the two streams are the same, and heat losses
from the exchanger are negligible.
a) Calculate the molar entropy changes of the two gas streams
for both parallel and countercurrent flow in the exchanger.
b) What is ΔS total in each case?
c) Repeat parts (a) and
d) for countercurrent flow if the heating stream enters at 200°C.

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