Chapter 6

ENTROPY

By: Dr. Muhammad Ayoub

 Contents

Introduction of Entropy
Calculate Entropy for an ideal gas
Calculate ideal work
Understand The third law of
thermodynamics
Learning Outcome
By the end of this lecture, you are expected to:
 Introduce entropy
 Calculate Entropy for an ideal gas
 Understanding the third law of thermodynamics

2
Review of previous lecture
Statement of 2nd law of thermodynamics
Statement 1:No apparatus can operate in such a way that its only effect (in
system & surroundings) is to convert heat absorbed by a system completely
into work by the system.
Statement 2 (Clausius statement):Heat cannot spontaneously flow from a
cold object to a hot one, whereas the reverse, a spontaneous flow of heat
from a hot object to a cold one, is possible.

Refrigerator |𝑊| 𝑄𝐻 − |𝑄𝐶 | 𝑄𝐶

(Reversed 𝜂= = =1−
|𝑄𝐻 | |𝑄𝐻 | 𝑄𝐻
Carnot
Engine)
Engine
Review of previous lecture
Carnot Engine

• For two given heat reservoirs, no engine can have a thermal efficiency
higher than that of a Carnot engine.

• 𝑎 → 𝑏 Adiabatic compression, 𝑇𝐶 to 𝑇𝐻
• 𝑏 → 𝑐 Isothermal expansion, absorbs heat
|𝑄𝐻 |
• 𝑐 → 𝑑 Adiabatic expansion, 𝑇𝐻 to 𝑇𝐶
• 𝑑 → 𝑎 Isothermal compression, releases
heat |𝑄𝐶 |

|𝑊| 𝑇𝐶
𝜂= =1−
|𝑄𝐻 | 𝑇𝐻
Entropy
“Entropy is a measure of the unavailability of thermal energy
to do work in a closed thermodynamic system”.

The SI units for entropy S, is J/K,

A microscopic (molecular) interpretation of entropy:

Entropy is a measure of the microscopic randomness
associated with a closed system.

Hexagonal crystal structure of Structure of liquid water. Evaporating water molecules.

ice.

Why ice is less dense than liquid water?

 Entropy
Interesting description of entropy:
It is a measure of the disorder and randomness in a closed system or
loss of ability to produce work due to irreversibility

The third law of thermodynamics

The absolute entropy is zero for all perfect

crystalline substances at absolute zero
temperature.

• absolute entropy: represents the entropy change of a substance

taken from absolute zero to a given temperature.

• Based on calorimetric data, the absolute entropy of a gas

at temperature T :
𝑇𝑓 ∆𝐻𝑓 𝑇𝑣 𝑇 (𝐶 )
(𝐶𝑃 )𝑠 (𝐶𝑃 )𝑙 ∆𝐻𝑣 𝑃 𝑔
𝑆= 𝑑𝑇 + + 𝑑𝑇 + + 𝑑𝑇 − (5.40)
0 𝑇 𝑇𝑓 𝑇𝑓 𝑇 𝑇𝑣 𝑇𝑣 𝑇
Entropy
• Entropy S is an intrinsic property of a system, functionally
related to the measurable coordinates that characterize the
system. It is a state function.
• For a reversible cycle:

|𝑄𝐻 | |𝑄𝐶 |
=
Reversible 𝑇𝐻 𝑇𝐶
adiabatic curve Heat quantities refer
𝑄𝐻 −𝑄𝐶 to the working fluid
= of the engine (not
𝑇𝐻 𝑇𝐶 heat reservoirs)

𝑄𝐻 𝑄𝐶
+ =0 − (5.9)
𝑇𝐻 𝑇𝐶
Reversible Adiabatic curves are
𝑑𝑄𝐻 𝑑𝑄𝐶 closely spaced that
isotherm + =0 isothermal steps are
𝑇𝐻 𝑇𝐶
infinitesimal
𝑑𝑄𝑟𝑒𝑣
=0 − (5.10)
𝑇
Summation of all quantities dQ/T
for any arbitary cycle is zero
Entropy
• The differential changes of the total entropy of the system,
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 𝑡 = where 𝑆 𝑡 = total entropy of the system
𝑇

𝑑𝑄𝑟𝑒𝑣
Δ𝑆 𝑡 = and
𝐴𝐶𝐵 𝑇

𝑑𝑄𝑟𝑒𝑣
Δ𝑆 𝑡 =
𝐴𝐷𝐵 𝑇
𝑑𝑄𝑟𝑒𝑣
∵ =0
𝑇

∴ Δ𝑆 𝑡 = 𝑆𝐵𝑡 − 𝑆𝐴𝑡 = 0
Figure 5.5: Two reversible paths joining equilibrium
states A and B

• If the process from A to B is irreversible:

𝑑𝑄𝑟𝑒𝑣
∴ Δ𝑆 𝑡 = 𝑆𝐵𝑡 − 𝑆𝐴𝑡 Δ𝑆 𝑡 ≠ From experiment
𝑇
Entropy
• For a heat reservoir:
𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑖𝑟𝑟𝑒𝑣
Δ𝑆 𝑡 = =
𝑇 𝑇

• For a reversible and adiabatic process, 𝑑𝑄𝑟𝑒𝑣 = 0:

𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 𝑡 = =0
𝑇
Constant entropy process = isentropic process
Table: Ideal gas Isentropic-process relation ship
Processes in T–s and P–v Space
Processes in T–s and P–v Space

Figure: On a P v diagram, lines of constant temperature (isotherms) and lines of constant

entropy (isentropes) have negative slopes. At a particular state, an isentrope is steeper (has
a greater negative slope) than an isotherm.
Class example :
Sketch the following set of processes on T–s and P–v diagrams:
1–2: isothermal expansion,
2–3: isentropic expansion,
3–4: isothermal compression, and
4–1: isentropic compression.
Class example
The following processes constitute the air-standard Otto cycle.
Plot these processes on P–v and T–s coordinates:

1–2: constant-volume energy addition,

2–3: isentropic expansion,
3–4: constant-volume energy removal, and
4–1: isentropic compression.
Ideal gas temperature and entropy relationship
• For one mole or a unit mass of fluid undergoing a mechanically
reversible process in a closed system, the first law gives
𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊
𝑑𝑄𝑟𝑒𝑣 = 𝑑𝑈 − 𝑑𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉
= 𝑑𝐻 − 𝑃𝑑𝑉 − 𝑉𝑑𝑃 + 𝑃𝑑𝑉 𝐻 ≡ 𝑈 + 𝑃𝑉
= 𝑑𝐻 − 𝑉𝑑𝑃 𝑈 = 𝐻 − 𝑃𝑉
𝑖𝑔
• For ideal gas, 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 and 𝑉 = 𝑅𝑇/𝑃
𝑖𝑔
𝑑𝑄𝑟𝑒𝑣 = 𝐶𝑃 𝑑𝑇 − 𝑅𝑇 𝑃 𝑑𝑃
𝑑𝑄𝑟𝑒𝑣 𝑖𝑔 𝑑𝑇 𝑑𝑃
= 𝐶𝑃 −𝑅 𝑑𝑄𝑟𝑒𝑣
𝑇 𝑇 𝑃 𝑑𝑆 =
S = Molar entropy of an ideal gas 𝑖𝑔
𝑇
𝑖𝑔 𝑑𝑇 𝑑𝑃 𝑑𝑆 𝐶𝑃 𝑑𝑇
𝑑𝑆 = 𝐶𝑃 −𝑅 or = − 𝑑 ln 𝑃
𝑇 𝑃 𝑅 𝑅 𝑇
𝑇 𝑖𝑔
Δ𝑆 𝐶𝑃 𝑑𝑇 𝑃
= − ln − (5.14)
𝑅 𝑇0 𝑅 𝑇 𝑃0
Ideal gas temperature and entropy relationship

• Integration of the first term on the right of Eq. (5.14) gives

𝑇 𝑖𝑔
𝐶𝑃 𝑑𝑇 𝐷 𝜏+1
= 𝐴 ln 𝜏 + 𝐵𝑇0 + 𝐶𝑇02 + 2 2 𝜏−1 − (5.15)
𝑇0 𝑅 𝑇 𝜏 𝑇0 2

• Mean heat capacity

𝑇
𝑖𝑔 𝑇 𝑖𝑔 𝑑𝑇
𝐶𝑃 ln = 𝐶𝑃
𝑆 𝑇0 𝑇0 𝑇
𝑇 𝑖𝑔
𝐶 𝑑𝑇
𝑇0 𝑃
𝑇
𝑖𝑔
𝐶𝑃 = − (5.16)
𝑆 ln(𝑇 𝑇0 )
𝐶𝑃 𝑖𝑔 𝑆 𝐷 𝜏+1 𝜏−1
= 𝐴 + 𝐵𝑇0 + 𝐶𝑇02 + 2 2 − (5.17)
𝑅 𝜏 𝑇0 2 ln 𝜏

Δ𝑆 𝐶𝑃 𝑖𝑔 𝑆 𝑇 𝑃
= ln − ln − (5.18)
𝑅 𝑅 𝑇0 𝑃0
Class exercise: ( Prob. 5.18 , Smith)
1. An ideal gas with constant heat capacities undergoes a change of state
from 300K and 1.2 bar to conditions 450 K and 6 bar. Determine ΔH
(J mol-1) and ΔS (J mol-1 K-1) . Given, Cp/R =7/2
Formula
𝑇 𝑖𝑔
Δ𝑆 𝐶𝑃 𝑑𝑇 𝑃
= − ln
𝑅 𝑇0 𝑅 𝑇 𝑃0

To be solved in the class

Class example: (Example 5.3, Smith book)
Methane gas at 550 K and 5 bar undergoes a reversible adiabatic
expansion to 1 bar. Assuming methane to be an ideal gas at these
conditions, find its final temperature.

Solution Formulae:
Δ𝑆 𝐶𝑃 𝑖𝑔 𝑇 𝑃
For reversible adiabatic process, 𝑑𝑄𝑟𝑒𝑣 = 0. = 𝑆
ln − ln
𝑅 𝑅 𝑇0 𝑃0
Thus, Δ𝑆 = 0
𝐶𝑃 𝑖𝑔 𝑆 𝐷 𝜏+1 𝜏−1
𝑖𝑔 = 𝐴 + 𝐵𝑇0 + 𝐶𝑇02 +
𝐶𝑃 𝑆 𝑇2 𝑃2 𝑅 𝜏 2 𝑇02 2 ln 𝜏
ln − ln = 0
𝑅 𝑇1 𝑃1
𝑖𝑔
Steps: i 𝑇𝑖 𝐶𝑃 𝑖𝑔 𝑅
𝐶𝑃 𝑆 𝑇2 𝑃2 1 • Assume T < 550 K
𝑆
ln = ln = ln = −1.6094 0 549.00 6.0386
𝑅 𝑇1 𝑃1 5 • Calculate 𝐶𝑃 𝑖𝑔 𝑆

Rearrange the equation for 𝑇2 , • Calculate T 1 421.32 5.5789

• Repeat iteration until 2 412.17 5.5433
−1.6094 value of T converges
𝑇2 = 𝑇1 exp
𝐶𝑃 𝑖𝑔 𝑅 3 411.41 5.5403
𝑆
4 411.34 5.5400
𝐶𝑃 𝑖𝑔 𝑆 (𝑇𝑖 550) + 1 (𝑇𝑖 550) − 1
= 1.702 + 4.995 − 0.655 5 411.34 −
𝑅 2 ln(𝑇𝑖 550)
The final temperature, 𝑇2 = 411.34 K
Mathematical Statement of the Second Law
• Consider two heat reservoirs, 𝑇𝐻 and 𝑇𝐶 . Let a quantity of heat
|𝑄| be transferred from the hotter to the cooler reservoir.
The entropy changes of the reservoirs are:
−|𝑄| |𝑄|
Δ𝑆𝐻𝑡 = and Δ𝑆𝐶𝑡 =
𝑇𝐻 𝑇𝐶 𝑇𝐻

• Addition of the two entropy changes gives: |𝑄|

−|𝑄| |𝑄| 𝑇𝐻 − 𝑇𝐶 𝑇𝐶
Δ𝑆total = Δ𝑆𝐻𝑡 + Δ𝑆𝐶𝑡 = + = |𝑄|
𝑇𝐻 𝑇𝐶 𝑇𝐻 𝑇𝐶

• Since 𝑇𝐻 > 𝑇𝐶 , Δ𝑆total > 0 ⇒ For irreversible process

• When (𝑇𝐻 −𝑇𝐶 ) → 0 , Δ𝑆total → 0 ⇒ For reversible heat

transfer
Mathematical Statement of the Second Law
• Consider a closed system with no heat transfer for a mole of
fluid:
• A → B Irreversible adiabatic
expansion
• B → C Reversible adiabatic
compression (constant
C entropy)
• C → A Reversible isobaric
compression
𝐴
𝑑𝑄𝑟𝑒𝑣
𝑡
∴ Δ𝑆 = 𝑆𝐴𝑡 − 𝑆𝐵𝑡 =
𝐵 𝑇
• Since the process is cyclic, ∆𝑈 = 0,
𝐴
−𝑊 = 𝑄𝑟𝑒𝑣 = 𝑑𝑄𝑟𝑒𝑣
𝐵
• If 𝛿𝑄𝑟𝑒𝑣 > 0, the second law is violated (i.e. heat absorbed is
completely converted into work done)
𝐴
𝑑𝑄𝑟𝑒𝑣
∴ Δ𝑆 𝑡 = 𝑆𝐴𝑡 − 𝑆𝐵𝑡 = <0 ∴ Δ𝑆 𝑡 = 𝑆𝐵𝑡 − 𝑆𝐴𝑡 > 0
𝐵 𝑇
Mathematical Statement of the Second Law
• Mathematical statement of the second law states that no
process is possible for which the total entropy decreases:
Δ𝑆total ≥ 0

• Work of a heat engine:

−|𝑄𝐻 | |𝑄𝐶 |
Δ𝑆total = +
𝑇𝐻 𝑇𝐶

• Since the work produced by the engine is 𝑊 = 𝑄𝐻 − |𝑄𝐶 |

𝑇𝐶
𝑊 = −𝑇𝑐 ∆𝑆total + |𝑄𝐻 | 1 −
𝑇𝐻
• 𝑊 → minimum when the engine is completely inefficient
(irreversible)
• 𝑊 → maximum when the engine is reversible, Δ𝑆total → 0 (Carnot
engine)
Class Exercise: (Example 5.4 smith book)

Self exercise : 5.10

Smith Book
Entropy Balance for Open Systems
• Entropy is not conserved (Δ𝑆total ≥ 0)
• An entropy balance can be written for both the system and the
surroundings:
Net rate of Time rate of Time rate of
Total rate
change in change of change of
+ + = of entropy
entropy of entropy in entropy in
generation
flowing streams control volume surroundings

• The equivalent equation of entropy balance is:

𝑑 𝑚𝑆 𝑡
𝑑𝑆𝑠𝑢𝑟𝑟
𝐶𝑉
∆(𝑆𝑚)𝑓𝑠 + + = 𝑆𝐺 ≥ 0 − (5.20)
𝑑𝑡 𝑑𝑡
𝑑 𝑚𝑆 𝐶𝑉 𝑄𝑗
∆(𝑆𝑚)𝑓𝑠 + − = 𝑆𝐺 ≥ 0 − (5.21)
𝑑𝑡 𝑇𝜎,𝑗
𝑗
Entropy Balance for Open Systems
• For steady state flow process, the mass and entropy of the fluid in the
control volume are constant, 𝑑 𝑚𝑆 𝐶𝑉 𝑑𝑡 = 0:
0
𝑑 𝑚𝑆 𝐶𝑉 𝑄𝑗
∆(𝑆𝑚)𝑓𝑠 + − = 𝑆𝐺 ≥ 0
𝑑𝑡 𝑇𝜎,𝑗
𝑗

𝑄𝑗
∆(𝑆𝑚)𝑓𝑠 − = 𝑆𝐺 ≥ 0 − (5.22)
𝑇𝜎,𝑗
𝑗

• For steady state flow process with only one entrance and one exit, with
𝑚 the same for both streams,
𝑄𝑗
∆𝑆 − = 𝑆𝐺 ≥ 0 − (5.23)
𝑇𝜎,𝑗
𝑗
Class Example (Example 5.5)
In a steady-state flow process, 1 mol s−1 of air at 600 K (326.85℃) and 1
atm is continuously mixed with 2 mol s−1 of air at 450 K (176.85℃) and 1
atm. The product stream is at 400 K (126.85℃) and 1 atm. Determine
the rate of heat transfer and the rate of entropy generation for the
process. Assume that air is an ideal gas with 𝐶𝑃 = (7 2) 𝑅, that the
surroundings are at 300 K (26.85℃), and that kinetic and potential-
energy changes are negligible.
Class Example (Example 5.5, Smith book)

Solution
For steady state open system with negligible change in kinetic and potential energy and no
shaft work, first law gives ∆𝐻 = 𝑄
𝑄 = 𝑛𝐻 − 𝑛𝐴 𝐻𝐴 − 𝑛𝐵 𝐻𝐵 = 𝑛𝐴 𝐻 − 𝐻𝐴 + 𝑛𝐵 𝐻 − 𝐻𝐵
= 𝑛𝐴 𝐶𝑃 𝑇 − 𝑇𝐴 + 𝑛𝐵 𝐶𝑃 𝑇 − 𝑇𝐵 = 𝐶𝑃 𝑛𝐴 𝑇 − 𝑇𝐴 + 𝑛𝐵 𝑇 − 𝑇𝐵
= (7 2)(8.314) (1) 400 − 600 + (2) 400 − 450
= −8729.7 J s −1
𝑄 𝑄
𝑆𝐺 = 𝑛𝑆 − 𝑛𝐴 𝑆𝐴 − 𝑛𝐵 𝑆𝐵 − = 𝑛𝐴 (𝑆 − 𝑆𝐴 ) + 𝑛𝐵 (𝑆 − 𝑆𝐵 ) − Formula:
𝑇𝜎 𝑇𝜎
𝑄𝑗
𝑇 𝑇 𝑄 𝑇 𝑇 𝑄 ∆(𝑆𝑚)𝑓𝑠 − = 𝑆𝐺
= 𝑛𝐴 𝐶𝑃 ln + 𝑛𝐵 𝐶𝑃 ln − = 𝐶𝑃 𝑛𝐴 ln + 𝑛𝐵 ln − 𝑇𝜎,𝑗
𝑇𝐴 𝑇𝐵 𝑇𝜎 𝑇𝐴 𝑇𝐵 𝑇𝜎 𝑗
−1 −1
= 10.446 J K s
Ideal Work
• For a steady-state flow process that requires work, there exists a
minimum amount of work that must be expended, to
accomplish the desired change of state in the fluid flowing
through the system.
• For a steady-state flow process that produces work, there exists
a maximum amount of work that can be accomplished as a
result of the change of state in the fluid flowing through the
system.

• Either case is achieved when the process is completely

reversible. For such a process, entropy generation 𝑆𝐺 is zero.
Thus,
𝑄
∆(𝑆𝑚)𝑓𝑠 − = 0
𝑇𝜎
Rate of heat transfer

𝑄 = 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠
Ideal Work
• Substitution of 𝑄 = 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠 and 𝑊𝑠 = 𝑊𝑖𝑑𝑒𝑎𝑙 into the first
law energy balance:
1
∆ 𝐻 + 𝑢2 + 𝑧𝑔 𝑚 = 𝑄 + 𝑊𝑠
2 𝑓𝑠
1 2
∆ 𝐻 + 𝑢 + 𝑧𝑔 𝑚 = 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠 + 𝑊𝑖𝑑𝑒𝑎𝑙
2 𝑓𝑠
1
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆ 𝐻 + 𝑢2 + 𝑧𝑔 𝑚 − 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠
2 𝑓𝑠

• When the change in kinetic and potential energy is negligible:

𝑊𝑖𝑑𝑒𝑎𝑙 = ∆ 𝐻𝑚 𝑓𝑠 − 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠 − (5.25)

• For steady state flow process with only one entrance and one
exit, with 𝑚 the same for both streams,
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆𝐻 − 𝑇𝜎 ∆𝑆 − (5.27)
Actual work
• When the same property changes occur in an actual process,
the actual work accomplished can be compared with ideal work
via the thermodynamic efficiency or isentropic efficiency which
indicates the ratio of the actual performance of a device to the
performance under idealized conditions, i.e. isentropic
condition.
𝑊𝑖𝑑𝑒𝑎𝑙
𝜂𝑡 work required = → positive − 5.28
𝑊𝑠
𝑊𝑠
𝜂𝑡 work produced = − (5.29)
𝑊𝑖𝑑𝑒𝑎𝑙
→ negative
• 0 ≤ 𝜂𝑡 ≤ 1
• 𝜂𝑡 → 1 for ideal system
Lost work
• Work that is wasted as the result of irreversibilities in a process is called
lost work.
𝑊𝑙𝑜𝑠𝑡 = 𝑊𝑠 − 𝑊𝑖𝑑𝑒𝑎𝑙 − (5.30)
𝑊𝑙𝑜𝑠𝑡 = 𝑊𝑠 − 𝑊𝑖𝑑𝑒𝑎𝑙 − (5.31)
• The actual and ideal work rate is given by:
1
𝑊𝑠 = ∆ 𝐻 + 𝑢2 + 𝑧𝑔 𝑚 −𝑄
2 𝑓𝑠
1
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆ 𝐻 + 𝑢2 + 𝑧𝑔 𝑚 − 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠
2 𝑓𝑠
Thus, 𝑊𝑙𝑜𝑠𝑡 = 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠 − 𝑄 − (5.32)
• Since:
𝑆𝐺 = ∆(𝑆𝑚)𝑓𝑠 − 𝑄 𝑇𝜎 − (5.33)
𝑇𝜎 𝑆𝐺 = 𝑇𝜎 ∆(𝑆𝑚)𝑓𝑠 − 𝑄
Thus, 𝑊𝑙𝑜𝑠𝑡 = 𝑇𝜎 𝑆𝐺 − (5.34)
As 𝑆𝐺 ≥ 0, 𝑊𝑙𝑜𝑠𝑡 ≥ 0
• The greater the irreversibility of a process, the greater the rate of entropy
production and the greater the amount of energy that becomes
unavailable for work (lost).
 Check List

Introduction of entropy
Calculate Entropy for an ideal gas
Draw T-s and Pv diagram
Understand The third law of
thermodynamics
Quiz 2 will be held on October 21 (Monday)
Syllabus : Chapter 4 & 5