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CHEN 310: CHEMICAL

ENGINEERING THERMODYNAMICS

Prof. S. M. Waziri & Prof. M. S. Olakunle

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Entropy
 Learning Outcomes
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At the end of this section, students are expected to be able to:

■ Introduce the concept of entropy, an essential thermodynamic property.
■ Present the second law of thermodynamics, which formalizes the
observed difference between processes that can occur spontaneously and
those that cannot.
■ Apply the second law to some familiar processes.
■ Relate changes in entropy to T and P for substances in the ideal-gas
state.
■ Present entropy balances for open systems.
 Axiomatic Statements

Axiom 1: There exists a form of energy, known as internal energy U, which is an

intrinsic property of a system, functionally related to the measurable coordinates
that characterize the system. For a closed system
∆𝑼𝒕 = 𝑸 + 𝑾

Axiom 2: (The First Law of Thermodynamics) The total energy of any system and its
surroundings is conserved.

Axiom 3: The macroscopic properties of a homogeneous PVT system at internal

equilibrium can be expressed as a function of its temperature, pressure, and
composition.
 Axiomatic Statements
Axiom 4: Entropy S is an intrinsic property of any system at internal equilibrium that is
functionally related to the measurable state variables that characterize the system.
Differential changes in entropy are given by:

𝒅𝑸𝒓𝒆𝒗
𝒅𝑺𝒕 =
𝑻

where St is the system (rather than the molar) entropy.

Axiom 5: (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
 Application of the Second Law to Simple Heat Transfer
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The second-law statement of Rudolf Clausius (1822–1888) is that it is

not possible to construct a device that operates in a cycle and whose
sole effect is to transfer heat from a colder body to a hotter body.
Show from axiom 5 (ΔStotal ≥ 0) that the process below is impossible.
 Application of the Second Law to Simple Heat Transfer
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Energy balance over one complete cycle of the device is

∆𝑼 = 𝑸 + 𝑾

Since the device operates in a cycle, ∆𝑈 = 0 and ∆𝑆𝒅𝒆𝒗𝒊𝒄𝒆 = 0

0
𝟎 = 𝑸𝑯 + 𝑸𝑪 + 𝑾 𝑸𝑯 = −𝑸𝑪

Total entropy change

∆𝑺𝒕𝒐𝒕𝒂𝒍 = ∆𝑆𝒅𝒆𝒗𝒊𝒄𝒆 + ∆𝑺𝑯 + ∆𝑺𝑪

𝑸𝑯 𝑸𝑪 𝑸𝑪 𝑸𝑪
∆𝑺𝒕𝒐𝒕𝒂𝒍 = 0 + + =− +
𝑻𝑯 𝑻𝑪 𝑻𝑯 𝑻𝑪
 Application of the Second Law to Simple Heat Transfer
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𝑻𝑯 − 𝑻𝑪
∆𝑺𝒕𝒐𝒕𝒂𝒍 = 𝑸𝑪
𝑻𝑪 𝑻𝑯

But 𝑻𝑯 − 𝑻𝑪 is positive and Qc is negative. Thus

∆𝑺𝒕𝒐𝒕𝒂𝒍 < 0 (which is a violation of axiom 5)

Consequently, our statement of the second law, ∆𝑺𝒕𝒐𝒕𝒂𝒍 ≥ 0 , is
consistent with the Clausius version, but much more general.
No process is possible which consists solely of the transfer of
heat from one temperature level to a higher one.
 Application of the Second Law to Heat Engines
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Heat engine: A device or machine that

produces work from heat in a cyclic
process
The second law imposes restrictions on
how much of their heat intake can be
converted into work.

Actual heat engines are irreversible, and η rarely

exceeds 0.35.
 Application of the Second Law to Heat Engines
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An alternative statement of the second law, due to Lord Kelvin (William Thomson, 1824–1907) and
Max Planck (1858–1947), is that it is not possible to construct a device operating in a cycle that
results in no effect other than the production of work by transferring heat from a single body. A
schematic diagram of a Kelvin-Planck device is shown below.

Show from axiom 5, ∆𝑺𝒕𝒐𝒕𝒂𝒍 ≥ 𝟎, that this process is indeed impossible.

 Application of the Second Law to Heat Engines
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Energy balance over one complete cycle of the device is

∆𝑼 = 𝑸 + 𝑾

Since the device operates in a cycle, ∆𝑈 = 0 and ∆𝑆𝒅𝒆𝒗𝒊𝒄𝒆 = 0

𝟎=𝑸+𝑾 𝑾 = −𝑸

Total entropy change

𝑸
∆𝑺𝒕𝒐𝒕𝒂𝒍 = ∆𝑆𝒅𝒆𝒗𝒊𝒄𝒆 + ∆𝑺𝑹𝒆𝒔𝒆𝒓𝒗𝒐𝒊𝒓 ∆𝑺𝒕𝒐𝒕𝒂𝒍 =
𝑻
 Application of the Second Law to Heat Engines
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But T is positive and Q is negative

Thus ∆𝑺𝒕𝒐𝒕𝒂𝒍 < 0 (which is a violation of axiom 5)

Consequently, our statement of the second law, ∆𝑺𝒕𝒐𝒕𝒂𝒍 ≥ 0 , is

consistent with the Kelvin-Planck version, but much more
general.

Note: The reverse process, in which the device receives work

and converts all that work to heat, is possible.
 Entropy
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 A quantity whose cyclic integral is zero depends on the state only

and not the process path, and thus it is a property.
𝑑𝑄
 Therefore, the quantity must represent a property in the
𝑇 𝑟𝑒𝑣
differential form.
❑ Clausius realized in 1865 that he had discovered a new
thermodynamic property, and he chose to name this property
entropy. It is designated S and is defined as
𝑑𝑄
𝑑𝑆 =
𝑇 𝑟𝑒𝑣

❑ The entropy change of a system during a process can be The entropy change between two
determined by integrating between the initial and the final specified states is the same whether the
states 2
𝛿𝑄
process is reversible or irreversible.
∆𝑆 = 𝑆2 − 𝑆1 = න
1 𝑇 𝑟𝑒𝑣
 Entropy and Equilibrium
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 The Second Law (ΔStotal ≥ 0) can be written as

∆𝑆𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 ≥ 0
 Similarly, the First Law can be written as
∆𝐸𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑬𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = 0
 For an isolated system the total energy remains constant and the entropy can only
increase or in the limiting case of a reversible process remain constant (Increase of
entropy principle)
∆𝑆𝒔𝒚𝒔𝒕𝒆𝒎 ≥ 0 and ∆𝐸𝒔𝒚𝒔𝒕𝒆𝒎 = 0
NOTE ∆𝑆𝒔𝒚𝒔𝒕𝒆𝒎 = 0 The system is at equilibrium
∆𝑆𝒔𝒚𝒔𝒕𝒆𝒎 > 0 A change toward equilibrium
 The equilibrium state of an isolated system is that state for which the entropy has its
maximum value.
𝑑𝑆𝒔𝒚𝒔𝒕𝒆𝒎 = 0
 ENTROPY BALANCE FOR OPEN SYSTEMS

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Equation of entropy balance

Steady state
 Some Remarks about Entropy
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1. Processes can occur in a certain direction only, not in any direction. A process must
proceed in the direction that complies with the increase of entropy principle, that is, SG ≥
0. A process that violates this principle is impossible. This principle often forces chemical
reactions to come to a halt before reaching completion.
2. Entropy is a nonconserved property, and there is no such thing as the conservation of
entropy principle. Entropy is conserved during the idealized reversible processes only and
increases during all actual processes.
3. The performance of engineering systems is degraded by the presence of irreversibilities,
and entropy generation is a measure of the magnitudes of the irreversibilities present
during that process. The greater the extent of irreversibilities, the greater the entropy
generation. Therefore, entropy generation can be used as a quantitative measure of
irreversibilities associated with a process. It is also used to establish criteria for the
performance of engineering devices.
 Example 1
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Heat is transferred directly from a heat reservoir at 280oC to another heat reservoir at 5oC.
If the amount of heat transferred is 100 kJ, what is the total entropy change as a result of
this process?
Solution
𝑇𝐻 = 280 + 273.15 = 553.15 𝐾
𝑇𝐶 = 5 + 273.15 = 278.15 𝐾
𝑄𝐻 = −100 𝑘𝐽 (Heat out of reservoir H)
𝑄𝐶 = 100 𝑘𝐽 (Heat into reservoir C)

Since for heat reservoirs ∆𝑆 = 𝑄/𝑇

𝑄𝐻 −100 𝑄𝐶 100
∆𝑆𝐻 = 𝑇𝐻
= 553.15 = −0.181 𝑘𝐽 𝐾 −1 and ∆𝑆𝐶 = 𝑇𝐶
= 278.15 = 0.360 𝑘𝐽 𝐾 −1

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝐻 + ∆𝑆𝐶 = 0.179 𝑘𝐽 𝐾 −1

 TdS Relations
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Recall that for a reversible process taking place in a closed system

𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆
𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊𝑟𝑒𝑣 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝑊𝑟𝑒𝑣 = −𝑃𝑑𝑉
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
By definition

𝐻 = 𝑈 + 𝑃𝑉 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
The T ds relations are valid for
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
both reversible and irreversible
𝑇𝑑𝑆 = 𝑑𝐻 − 𝑉𝑑𝑃 processes.
 ENTROPY CHANGE OF LIQUIDS AND SOLIDS

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 Liquids and solids can be approximated as incompressible substances since their specific
volumes remain nearly constant during a process (i.e. dV ≅ 0)
0
𝑑𝑈 𝑃 𝑑𝑈 𝐶𝑑𝑇
𝑑𝑆 = + 𝑑𝑉 = 𝑑𝑆 =
𝑇 𝑇 𝑇 𝑇
𝑇2
𝑑𝑇 𝑇2
𝑆2 − 𝑆1 = න 𝐶 ≅ 𝐶𝑎𝑣𝑔 𝑙𝑛
𝑇1 𝑇 𝑇1
 If the process is isentropic (i.e. ∆𝑆 = 0)
𝑇2
0 = 𝐶𝑎𝑣𝑔 𝑙𝑛 𝑇2 = 𝑇1
𝑇1

The isentropic process of an incompressible substance (e.g. liquids and solids) is also isothermal.
 ENTROPY CHANGES FOR THE IDEAL-GAS STATE

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Starting from the following Gibbs equation

𝑑𝐻 𝑉
𝑇𝑑𝑆 = 𝑑𝐻 − 𝑉𝑑𝑃 𝑑𝑆 = − 𝑑𝑃
𝑇 𝑇
For ideal gas

𝑖𝑔
𝑑𝐻𝑖𝑔 = 𝐶𝑃 𝑑𝑇 𝑅𝑇
and 𝑉 𝑖𝑔 =
𝑃
Therefore
𝑑𝐻 𝑖𝑔 𝑉 𝑖𝑔
𝑖𝑔 𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 = − 𝑑𝑃 = 𝐶𝑃 −𝑅 Although derived for a
𝑇 𝑇 𝑇 𝑃 mechanically reversible process,
𝑑𝑇 𝑖𝑔 𝑇 𝑖𝑔
𝑖𝑔 ∆𝑆 𝐶 𝑑𝑇 𝑃 this equation relates properties
𝑑𝑆 𝑖𝑔 = 𝐶𝑃 − 𝑅 𝑑𝑙𝑛𝑃 =න 𝑃 − 𝑙𝑛 only, independent of the process
𝑇 𝑅 𝑇 𝑅 𝑇 𝑃0
0 causing the change of state, and
𝑇 𝑖𝑔 is therefore a general equation
∆𝑆 𝑖𝑔 𝐶𝑉 𝑑𝑇 𝑉 for the calculation of entropy
NOTE: It can be shown that =න + 𝑙𝑛
𝑅 𝑇0 𝑅 𝑇 𝑉0 changes in the ideal-gas state.
 Exercise 1
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The temperature dependence of ideal gas heat capacity

can be analytically expresses as

Show that
22
 Example 2
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Derive equations relating T and P for the reversible adiabatic (and therefore isentropic)
compression of an ideal-gas with constant heat capacities.
Solution 𝑇 𝑖𝑔
∆𝑆 𝑖𝑔 𝐶 𝑑𝑇 𝑃
Recall that =න 𝑃 − 𝑙𝑛
𝑅 𝑇0 𝑅 𝑇 𝑃0 𝑖𝑔
𝑖𝑔 𝑖𝑔 𝐶𝑃 𝑅 γ−1
For ideal gas 𝐶𝑃 = 𝐶𝑉 + 𝑅 Letting γ = 𝑖𝑔 gives 𝑖𝑔 =
𝐶𝑉 𝐶𝑃 γ

γ−1
𝑇
∆𝑆 𝑖𝑔 γ 𝑑𝑇 𝑃 𝑇 γ−1 𝑃 𝑇 𝑃 γ
=0= න − 𝑙𝑛 0 = 𝑙𝑛 − 𝑙𝑛 =
𝑅 γ − 1 𝑇0 𝑇 𝑃0 𝑇0 γ 𝑃0 𝑇0 𝑃0
The following are also valid for isentropic process of ideal gases with constant heat capacities

γ−1 γ
𝑇 𝑉0 𝑃 𝑉0
= and =
𝑇0 𝑉 𝑃0 𝑉
 CALCULATION OF IDEAL WORK
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 A key question addressed by thermodynamics is that of work requirement or availability.

 Maximum work available (work producing process, e.g. flow through turbines)
 Minimum work required (work requiring process, e.g. flow through pumps and compressors)
 For a steady state process, the limiting value of work results when the change of state
associated with the process is accomplished completely reversibly. (i.e. 𝑆𝐺ሶ = 0)
Tσ is the
surroundings
temperature

 Energy balance
 CALCULATION OF IDEAL WORK
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 If 𝑊ሶ 𝑠(𝑟𝑒𝑣) is given the name ideal work, 𝑊ሶ 𝑖𝑑𝑒𝑎𝑙

 For most chemical processes

 For the special case of a single stream flowing through the control volume

𝑊ሶ 𝑖𝑑𝑒𝑎𝑙 is the minimum work required to bring 𝑊ሶ 𝑖𝑑𝑒𝑎𝑙 is the maximum work obtainable
about a given change in the properties of the from a given change in the properties of the
flowing streams flowing streams
Isentropic Efficiencies of Compressors and Pumps
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Compressors
∆𝑃𝐸 = 0
∆𝐾𝐸 = 0

Pumps
 Isentropic Efficiency for a Turbine
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Negligible changes in kinetic

and potential energies
 LOST WORK
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 Work that is wasted as the result of irreversibilities in a process is

called lost work. It is defined as:

 It can be shown that

The greater the irreversibility of a process, the greater the rate of entropy production and the
greater the amount of energy made unavailable for work. Thus every irreversibility carries
with it a price. Minimizing entropy production is essential for efficient use of finite resources.
 THIRD LAW OF THERMODYNAMICS
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 Third Law of Thermodynamics: The absolute entropy is zero for all

perfect crystalline substances at absolute zero temperature.

 The absolute entropy of a gas at temperature T based on calorimetric

data is (Note: The entropy is zero at T = 0 K)

Alternative Statement of the 3rd Law: It is impossible to obtain a

temperature of absolute zero.
 Equations of Balance
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General Equations of Balance Balance Equations for Balance Equations

Steady-Flow Processes for Single-Stream
Steady-Flow Processes