Chemical Engineering Thermodynamics

Spring 2021

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
Mon, 01/02/21
Second Law of Thermodynamics

• The first law suggests that energy is conserved, but it imposes no restriction on the
process direction.

• In an energy balance, both heat and work are included as simple additive terms,
implying that one unit of heat, a joule, is equivalent to the same unit of work.
However, there is a difference between heat and work.

• Work → heat (complete transformation, shown by Joule’s experiment)

Heat → work (complete transformation is not possible, maximum conversion efficiency

is ~40%)

Therefore, heat is a form of energy intrinsically less useful and hence less valuable than
an equal quantity of work or mechanical or electrical energy.
2
 Statements of Second Law

Statement 1: No apparatus can operate in such a way that its only effect (in system and
surroundings) is to convert heat absorbed by a system completely into
work done by the system.

Statement 1a: It is impossible by a cyclic process to convert the heat absorbed by a system
completely into work done by the system.

Statement 2: No process is possible which consists solely in the transfer of heat from one
temperature level to a higher one.

The second law does not prohibit the production of work from heat, but it does place
a limit on how much of the heat directed into a cyclic process can be converted into work
done by the process.

3
 Heat Engines

Device or machine that produce work from heat in a cyclic process. For ex: Steam power plant
in which the working fluid (H2O) periodically returns to its original state.

• Liquid water from a condenser is pumped into a boiler at elevated pressure

• Heat from a fuel is transferred in the boiler to the water, converting it to high-temperature
steam at the boiler pressure.

• Energy is transferred as shaft work from the steam to the surroundings by a device such as
as a turbine, in which the steam expands to reduced pressure and temperature.

• Exhaust steam from the turbine is condensed by transfer of heat to the surroundings,
producing liquid water for return to the boiler, thus completing the cycle. 4
 Heat Engines

• All heat-engine cycles should absorb heat into the system at a high temperature, reject
heat to the surroundings at a lower temperature, and produces work.

• In operation, the working fluid of a heat engine absorbs heat

𝑄𝐻 from a hot reservoir, produces a net amount of work 𝑊 ,
discards heat 𝑄𝐶 to a cold reservoir, and returns
to its initial state. The first law therefore reduces to:

𝑊 = 𝑄𝐻 - 𝑄𝐶 (3.1)

The thermal efficiency of the engine is defined as: η ≡ net work output/heat absorbed.
With equation (3.1) this becomes

𝑊 𝑄𝐻 − 𝑄𝐶 𝑄𝐶
η= 𝑄𝐻
= 𝑄𝐻
= 1- 𝑄𝐻
(3.2)

• For η to be 1, 𝑄𝐶 must be zero. No engine has ever been built that approaches this
result; heat is always rejected to the cold reservoir.

• η of a heat engine depends on the degree of reversibility of its operation.

5
 Carnot Engine
• Carnot engine operates in a completely reversible manner. The four steps that
make up a Carnot cycle are performed in the following order:

Step 1: A system at an initial temperature of a cold reservoir at TC undergoes a

reversible adiabatic process that causes its temperature to rise to that of a hot
reservoir at TH : here, shown by (4).
Step 2: The system maintains contact with the hot reservoir at TH, and undergoes a
reversible isothermal process during which the heat 𝑄𝐻 is absorbed from the hot
reservoir : here, shown by (1).
Step 3: The system undergoes a reversible adiabatic process in the opposite direction of
step 1 that brings in temperature back to that of the cold reservoir at TC : here,
shown by (2).
Step4: The system maintains contact with the reservoir at TC, and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns it to its initial
state with rejection of heat 𝑄𝐶 to the cold reservoir : here, shown by (3). 6
 Carnot’s Theorem
Carnot’s Theorem:

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

All Carnot engines operating between heat reservoirs at the same two temperatures have
the same thermal efficiency. Thus, a corollary to Carnot’s theorem states:

The thermal efficiency of Carnot engine depends only on the temperature levels and not
upon the working substance of the engine.

𝑊 𝑄𝐻 − 𝑄𝐶 𝑄𝐶 𝑇
η= = = 1- = 1 − 𝑇 𝐶 <1 (3.3)
𝑄𝐻 𝑄𝐻 𝑄𝐻 𝐻

7
 Carnot Cycle

D → A: Adiabatic compression until the temperature rises

from TC to TH.

A→ B: Isothermal expansion to arbitrary point c with

absorption of heat 𝑄𝐻

B→ C: Adiabatic expansion until the temperature

decreases to TC .

C→ D: Isothermal compression to the initial state with PV diagram showing Carnot

rejection of heat 𝑄𝐶 Cycle for an ideal gas
𝑄𝐻 𝑇𝐻
=
For the isothermal steps:
𝑄𝐶 𝑇𝐶

𝑉𝐵 𝑉
𝑄𝐻 = 𝑅𝑇𝐻 𝑙𝑛 (3.4) 𝑄𝐶 = 𝑅𝑇𝐶 𝑙𝑛 𝑉 𝐶 (3.5)
𝑉𝐴 𝐷

Therefore, 𝑉𝑏
𝑄𝐻 𝑇𝐻 ln( ൗ𝑉𝑎 ) (3.6)
=
𝑄𝐶 𝑇𝐶 ln(𝑉𝑐ൗ𝑉 )
𝑑

8
 Carnot Cycle
𝑑𝑉
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑇 𝑉 (3.7)
For an adiabatic process, 𝑑𝑄 = 0

−𝐶𝑉 𝑑𝑇 𝑑𝑉 (3.8)
=
𝑅 𝑇 𝑉

For step D→ A and B→ C, integration gives

𝑇𝐻 𝐶𝑉 𝑑𝑇 𝑉 (3.9)
‫𝑇׬‬ = 𝑙𝑛 𝑉𝑎
𝐶 𝑅 𝑇 𝑑

𝑇𝐻 𝐶𝑉 𝑑𝑇 𝑉 (3.10)
‫𝑇׬‬ = 𝑙𝑛 𝑉𝑐
𝐶 𝑅 𝑇 𝑏

Since the left sides of eqn. (3.9) and (3.10) are the same,

𝑉 𝑉
𝑙𝑛 𝑉𝑎 = 𝑙𝑛 𝑉𝑐 (3.11)
𝑑 𝑏

Or, 𝑉 𝑉
𝑙𝑛 𝑉𝑏 = 𝑙𝑛 𝑉𝑐
𝑑 𝑎
9
 Carnot Cycle

Now, eqn (3.6) becomes

𝑄𝐻 𝑇𝐻 (3.12)
=
𝑄𝐶 𝑇𝐶

Eqn. (3.12) can thus be used to prove eqn. (3.3)

𝑊 𝑄𝐻 − 𝑄𝐶 𝑄𝐶 𝑇
η= = = 1- = 1 − 𝑇𝐶 (3.3)
𝑄𝐻 𝑄𝐻 𝑄𝐻 𝐻

10
 Question

An inventor claims to have devised a cyclic engine which exchanges heat with reservoirs
at 27°C and 327°C, and which produces 0.6 kJ of work for each kJ of heat extracted from
the hot reservoir. Is the claim believable? If instead he claimed that the delivered work
would be 0.25kJ / kJ of extracted heat, would the engine be feasible?

Solution: QH = 1kJ, W = 0.6kJ, TH= 600K, Tc= 300K

𝑊
Efficiency: ηactual = 𝑄𝐻
=0.6

𝑇
ηideal (Carnot) = 1- 𝑇 𝐶 =0.5
𝐻

Since ηactual > ηideal the engine is not possible.

However, for a delivered work of 0.25kJ/kJ of extracted heat the ηactual < ηideal; hence the
engine is feasible.

11
 Question

A central power plant, rated at 800 000 kW, generates steam at 585K and discards heat to
a river at 295K. 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?

Solution: 𝑇
η = 1 − 𝑇𝐶
𝐻 Where, TC = river temperature
TH= steam-generation temperature

295
η=1− = 0.4957 (maximum)
585

Since thermal efficiency = 0.7

η (𝑎𝑐𝑡𝑢𝑎𝑙) = 0.4957*0.7 = 0.3470

1−η 1−0.347
𝑄𝐶 = 𝑊 = 800 000 = 1505500 kW
η 0.347

𝑊 𝑄𝐶 η 𝑄𝐶
η= = 1- = 1- ⇒
𝑄𝐶
=
1−η
𝑄𝐻 𝑄𝐻 𝑊 𝑊 η
12
Tue, 02/02/21
Entropy

For a Carnot engine (eqn. (3.12)) can be written as,

𝑄𝐻 𝑄𝐶 (3.13)
=
𝑇𝐻 𝑇𝐶
The numerical values of QH is positive and that of QC
is negative. Thus, eqn. (3.13) becomes
𝑄𝐻 −𝑄𝐶 (3.14)
=
𝑇𝐻 𝑇𝐶
𝑄𝐻 𝑄 (3.15)
Or, + 𝑇𝐶 = 0 An arbitrary reversible cyclic
𝑇𝐻 𝐶
Process on a PV diagram

• It is interesting to note that the final step of thermodynamic analysis of Carnot cycle
𝑄
leads to the conclusion that there exists a quantity 𝑇 which add up to zero for the
complete cycle.
• Hence, applying eqn. 3.15 to sum up the effects of series of all the infinitesimal
cycles, we arrive at the following relation for the entire original cycle:
δ𝑄𝑟𝑒𝑣 (3.16)
‫ׯ‬ 𝑇
=0

13
 Entropy

Clearly, the relation expressed by eqn. 3.16 suggests the existence of a state variable
δ𝑄
of the form 𝑇𝑟𝑒𝑣 as its sum over a cycle is zero. This state variable is termed as
“Entropy” (S) such that :
δ𝑄𝑟𝑒𝑣 (3.17)
𝑑𝑆 =
𝑇

Thus, ර 𝑑𝑆 = 0

If applied to a perfectly reversible adiabatic process eqn. 3.17 leads to the following
result: dS= 0. Thus, such a process is alternately termed as isentropic.

14
 Entropy
Note:

• 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 eqn. (3.17).

• The change in entropy of any system undergoing a finite reversible process is

𝑑𝑄𝑟𝑒𝑣 (3.18)
∆𝑆 𝑡 = ‫׬‬ 𝑇

• When a system undergoes an irreversible process between two equilibrium states,

the entropy change of the system ∆𝑆 𝑡 is evaluated by eqn. (3.18) to an arbitrarily
chosen reversible process that accomplishes the same change of state as the
actual process. Integration is not carried out for the irreversible path. Because entropy
is a state function, the entropy changes of the irreversible and reversible process
are identical.

• Entropy is a state property (just as U and H), even for irreversible process occurring
between two states, the change in entropy would be given by eqn. (3.17).

15
 Entropy calculation for an ideal gas

For one mole or a unit mass of fluid undergoing a mechanically reversible process in a closed
System, the first law becomes

𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉
Differentiation of the defining equation for enthalpy, 𝐻 = 𝑈 + 𝑃𝑉

𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉 𝑑𝑃

Eliminating dU gives: 𝑑𝐻 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉 𝑑𝑃

Or, 𝑑𝑄𝑟𝑒𝑣 = 𝑑𝐻 − 𝑉 𝑑𝑃

For an ideal gas, 𝑑𝐻 = 𝐶𝑝 𝑑𝑇 𝑎𝑛𝑑 𝑉 = 𝑅𝑇Τ

𝑃

With these substitutions and division by T,

𝑑𝑄𝑟𝑒𝑣 𝑑𝑇 𝑑𝑃
= 𝐶𝑝 −𝑅
𝑇 𝑇 𝑃
Eqn (3.17) gives,
𝑑𝑇 𝑑𝑃
𝑑𝑆 = 𝐶𝑝 −𝑅
𝑇 𝑃
16
 Entropy calculation for an ideal gas

𝑑𝑇 𝑑𝑃
𝑑𝑆 = 𝐶𝑝 −𝑅
𝑇 𝑃
𝑑𝑆 𝐶𝑝 𝑑𝑇 𝑑𝑃
= − (3.19)
𝑅 𝑅 𝑇 𝑃
Where, S is the molar entropy of an ideal gas. Integration from an initial state at conditions
T0 and P0 to a final state at conditions T and P gives

𝑇𝐶
∆𝑆 𝑝 𝑑𝑇 𝑃 (3.20)
=න − 𝑙𝑛
𝑅 𝑇0 𝑅 𝑇 𝑃0

Although derived for a mechanically reversible process, this equation (3.20) relates properties
only, and is independent of the process causing the change of state. It is therefore a general
equation for the calculation of entropy changes of an ideal gas.

17
 Question

For an ideal gas with constant heat capacities undergoing a reversible adiabatic (and therefore
Isentropic) process, following eqn can be written
γ−1
𝑇2 𝑃2 γ
=
𝑇1 𝑃1

Show that this same equation results from application of eqn (3.20) with ∆𝑆 = 0

Solution: Because 𝐶𝑝 is constant, eqn (3.20) can be written as

𝑇 𝑅 𝑃
0 = 𝑙𝑛 𝑇2 - 𝐶 ln 𝑃2
1 𝑝 1

𝑅 γ−1
As we know, =
𝐶𝑝 γ

Hence, 𝑇 γ−1 𝑃
𝑙𝑛 𝑇2 = ln 𝑃2
1 γ 1

18
 Irreversibility and Entropy

Consider a system in contact with a heat reservoir during a reversible process. If there is heat
𝑄
absorbed by the reservoir at temperature , the change in entropy of the reservoir is ∆𝑆 = 𝑇 .
In general, reversible processes are accompanied by heat exchanges that occur at different
temperatures. To analyze these, we can visualize a sequence of heat reservoirs at different
temperatures so that during any infinitesimal portion of the cycle there will not be any heat
transferred over a finite temperature difference.
During any infinitesimal portion, heat 𝑑𝑄𝑟𝑒𝑣 will be transferred between the system and one
of the reservoirs which is at T. If dQrev is absorbed by the system, the entropy change of the
system is
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = (3.17)
𝑇
The entropy change of the reservoir is
−𝑑𝑄𝑟𝑒𝑣 (3.21)
𝑑𝑆𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 =
𝑇
The total entropy change of system plus surroundings is
𝑑𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚+ 𝑑𝑆𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 =0 (3.22)

The conclusion is that for a reversible process, no change occurs in the total entropy
produced, i.e., the entropy of the system plus the entropy of the surroundings:
∆𝑆𝑡𝑜𝑡𝑎𝑙 =0 19
 Irreversibility and Entropy

Irreversible and reversible state changes

For an irreversible process, which takes the system between the same specified states
as in the reversible process. This is shown schematically in above figure, with I and R
denoting the irreversible and reversible processes.

In the irreversible process, the system receives heat 𝑑𝑄 and does work 𝑑𝑊.The change
in internal energy for the irreversible process is
𝑑𝑈 = 𝑑𝑄- 𝑑𝑊 (𝑎𝑙𝑤𝑎𝑦𝑠 𝑡𝑟𝑢𝑒 − 𝑓𝑖𝑟𝑠𝑡 𝑙𝑎𝑤) (3.23)

For the reversible process,

(3.24)
𝑑𝑈 = 𝑇𝑑𝑆- 𝑑𝑊𝑟𝑒𝑣

Because the state change is the same in the two processes (we specified that it was),
the change in internal energy is the same. Equating the changes in internal energy in
the above two expressions yields
𝑑𝑄actual− 𝑑𝑊actual = 𝑇𝑑𝑆- 𝑑𝑊𝑟𝑒𝑣 (3.25)
20
 Irreversibility and Entropy

The subscript ``actual'' refers to the actual process (which is irreversible). The entropy
change associated with the state change is

(3.26)

If the process is not reversible, we obtain less work than in a reversible process,
𝑑𝑊actual < 𝑑𝑊𝑟𝑒𝑣 , so that for the irreversible process,
𝑑𝑄𝑎𝑐𝑡𝑢𝑎𝑙 (3.27)
𝑑𝑆 >
𝑇
Note, there is no equality between entropy change and the quantity for an irreversible process.
The equality is only possible for a reversible process.

The change in entropy for any process that leads to transformation between an initial state
“a” and a final state “b” is therefore,
𝑏 𝑑𝑄𝑎𝑐𝑡𝑢𝑎𝑙 (3.28)
∆𝑆 = 𝑆𝑏 -𝑆𝑎 ≥ ‫𝑎׬‬ 𝑇
Where, 𝑑𝑄𝑎𝑐𝑡𝑢𝑎𝑙 is the heat exchanged in the actual process.

The equality only applies to a reversible process. No process is possible for which the
21
total entropy decreases.
Wed, 03/02/21
Clausius Theorem

It states that a system exchanging heat with external reservoirs and undergoing a cyclic process,
is one that ultimately returns to its original state.
𝛿𝑄
ර ≤0
𝑇𝑠𝑢𝑟𝑟

Where, 𝛿𝑄 is the infinitesimal amount of heat absorbed by the system from the reservoir
and 𝑇𝑠𝑢𝑟𝑟 is the temperature of external reservoir at a particular instant in time.

For a carnot cycle,

Proof: T𝐻
η𝑟𝑒𝑣 > η𝑖𝑟𝑟𝑒𝑣 𝑄𝐻 𝑄𝐻

provided both are working under same T limits. Wrev WIrrev

𝑄C1 𝑄C2
Due to difference in work values, we have difference in heat TC
rejection.
Carnot cycle
For reversible heat engine,
𝛿𝑄 𝑄𝐻 𝑄𝐶1
ර =න −න
𝑇 𝑇𝐻 𝑇𝐶
𝑄𝐻 𝑄𝐶1
= − =0 [ ref. eqn. (3.13)]
𝑇𝐻 𝑇𝐶 22
 Clausius Theorem

𝑄𝐶2 > 𝑄𝐶1

𝑄𝐶2 = 𝑄𝐶1 + 𝑄𝑑𝑖𝑓𝑓

𝑄𝑑𝑖𝑓𝑓 > 0

Similarly for irreversible heat engine,

𝛿𝑄 𝑄𝐻 𝑄𝐶2
ර =න −න
𝑇 𝑇𝐻 𝑇𝐶
𝑄𝐻 𝑄𝐶2
= −
𝑇𝐻 𝑇𝐶

𝑄 𝑄𝑑𝑖𝑓𝑓+𝑄𝐶1
= 𝑇𝐻 − ( )
𝐻
𝑇𝐶

𝑄𝑑𝑖𝑓𝑓
= −( ) <0
𝑇𝐶

23
 Clausius Theorem

𝛿𝑄
𝑆2 − 𝑆1 = න + 𝑆𝑔𝑒𝑛
𝑇

For irrev., 𝑆𝑔𝑒𝑛 >0 For rev., 𝑆𝑔𝑒𝑛 = 0

24
 Irreversibility and Entropy

T𝐻
A cyclic heat engine takes heat 𝑄𝐻 from a heat reservoir at TH,
and discards heat 𝑄C to another heat reservoir at TC. 𝑄𝐻
𝑊
Because the engine operates in cycles, it undergoes no net changes 𝑄C
in its properties. The total entropy change of the process is therefore TC
the sum of the entropy changes of the heat reservoirs:

−𝑄 𝑄 (3.29)
∆𝑆𝑡𝑜𝑡𝑎𝑙 = T 𝐻 + TC
𝐻 C

The work produced by the engine as given by eqn. (3.1) 𝑊 = 𝑄𝐻 - 𝑄𝐶

Elimination of 𝑄𝐶 between these two equations and solution for 𝑊 gives

𝑇
𝑊 = −𝑇𝐶 ∆𝑆𝑡𝑜𝑡𝑎𝑙 + 𝑄𝐻 1 − 𝑇𝐶 (3.30)
𝐻

General equation for work of a heat engine for temperature levels TC and TH.

25
 Irreversibility and Entropy

(a) Minimum work output, 𝑊 = 0:

• The engine is completely inefficient and the process degenerates into simple irreversible
heat transfer between the two heat reservoirs.

𝑇𝐻 −𝑇𝐶
• ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑄 𝑇𝐻 𝑇𝐶

(b) Maximum work is obtained when the engine is reversible, ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 0:

𝑇
• 𝑊 = 𝑄𝐻 1 − 𝑇𝐶
𝐻

26
 Question

A 40-kg steel casting (Cp = 0.5kJkg-1K-1) at a temperature of 450°C is quenched in 150kg oil
(Cp = 2.5kJkg-1K-1) at 25°C. If there are no heat losses, what is the change in entropy of
(a) The casting
(b) the oil, and
(c) both considered together

Solution: The final temperature T of the oil and steel casting is found by an energy balance.
Because the change in energy of the oil and steel together must be zero,

40 ∗ 0.5 ∗ 𝑇 − 450 + 150 ∗ 2.5 ∗ 𝑇 − 25 = 0

𝑇 = 46.52𝐶

𝐶𝑝 𝑑𝑇 𝑇
(a) ∆𝑆 𝑡 = 𝑚 ‫׬‬ = m𝐶𝑝 𝑙𝑛 𝑇2
𝑇 1

∆𝑆 𝑡 = -16.33kJK-1

(b) Using same formula for oil, ∆𝑆 𝑡 = 26.13kJK-1

(c) Total entropy Change = (-16.33+26.13) kJK-1 = 9.8kJK-1

27
 Question
Mon, 08/02/21

A rigid vessel of 0.06 m3 volume contains an ideal gas, CV = (5/2)R, at 500 K and 1 bar. (a) If
15 kJ of heat 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 kJ is done
on the gas, what is the entropy change of the gas if the process is adiabatic? What is
ΔStotal?

Solution:
No. of moles = 1.443 mol
∆𝑈 = 𝑄 + 𝑊 = 15000𝐽 = 𝑛𝐶𝑉 (𝑇2 − 𝑇1)

Hence, T2 = 1000.12 K

Usign eqn (3.20), ∆S = n[Cp ln(T2/T1) – R ln(P2/P1)]

But P2/T2 = P1/T1 Hence, ∆S = 20.78J/K

For second case, the change of state of gas is same as ‘a’

∆S (system) = 20.78J/K
∆S (surrounding) = 0 (as there is no heat effect on the surrounding)
∆S (universe) = 20.78 +0 = 20.78 J/K 28
 Question

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. Calculate the
molar entropy changes of the two gas streams for both parallel and countercurrent flow in
the exchanger. What is ΔStotalin each case?

Solution: Temperature drop of stream B in either case of flow is same as temperature rise
in stream A i.e. 120°C
Thus, exit temperature of B = 320-120 = 200°C

Thus, in both cases:

463
∆𝑆𝑎 = 𝐶𝑝 ln(343) = 8.729J/molK

473
∆𝑆𝑏 = 𝐶𝑝 ln(593) = -6.95J/molK

∆𝑆𝑡𝑜𝑡𝑎𝑙 = 8.729 − 6.95 = 1.78J/molK

29
 Entropy balance for open systems

• Entropy is not conserved.

• The second law states that the total entropy change associated with any process must
be positive, with a limiting value of zero for a reversible process.

The statement of balance, expressed as rates, is therefore:

(Net rate of change in entropy of flowing streams) + (Time rate of change of entropy in
Control volume) + (Time rate of change of entropy in surroundings) = (Total rate of entropy
Generation)

The equivalent equation of entropy balance is

𝑑(𝑚𝑆)𝑐𝑣 𝑑𝑆𝑡𝑠𝑢𝑟𝑟 (3.31)

∆(𝑆𝑚)ሶ 𝑓𝑠 + 𝑑𝑡
+ 𝑑𝑡 = 𝑆𝐺 ≥ሶ 0

𝑆𝐺ሶ = rate of entropy generation

30
 Entropy balance for open systems
𝑄𝑗ሶ
𝑄𝑗ሶ is the rate of heat transfer with respect to a particular part of the ሶ
𝑇σ,𝑗
control surface associated with 𝑇σ,𝑗 ሶ where subscripts σ, 𝑗 denotes
a temperature in the surroundings.

The rate of entropy change in the surroundings as a result of this Control volume
−𝑄ሶ 𝑗
transfer is then ሶ
.
𝑇σ,𝑗

𝑑𝑆𝑡𝑠𝑢𝑟𝑟 𝑄𝑗ሶ (3.32)

= − σ𝑗 ሶ
𝑑𝑡 𝑇σ,𝑗

Equation (3.31) can be written as

𝑑(𝑚𝑆)𝑐𝑣 ሶ
𝑄𝑗
∆(𝑆𝑚)ሶ 𝑓𝑠 + − σ𝑗 𝑇 ሶ = 𝑆𝐺 ≥ሶ 0 (3.33)
𝑑𝑡 σ,𝑗

31
 Entropy balance for open systems

(a) Rate of entropy generation,𝑆𝐺ሶ

• This is positive for irreversible process

• and zero only for reversible process.

(b) Two sources of irreversibility:

(i) Internal irreversibility: those within the control volume

(ii) External irreversibility: those resulting from heat transfer across finite temperature
differences between system and surroundings

(c) When the 𝑆𝐺ሶ =0, the process is completely reversible

(i) The process is internally reversible within the control volume

(ii) Heat transfer between the control volume and its surroundings is reversible.

32
 Entropy balance for open systems

For steady-state flow process, the mass and entropy of the fluid in the control volume
𝑑(𝑚𝑆)𝑐𝑣
are constant, and =0. Equation (3.31) then becomes
𝑑𝑡

𝑡
𝑑𝑆 𝑠𝑢𝑟𝑟 (3.34)
∆(𝑆𝑚)ሶ 𝑓𝑠 + 𝑑𝑡 = 𝑆𝐺 ≥ሶ 0

If there is only one entrance and one exit, with 𝑚ሶ the same for both streams, dividing through
by 𝑚ሶ yields

𝑄ሶ𝑗
∆𝑆 − σ𝑗 𝑇 ሶ =𝑆𝐺 ≥ 0 (3.35)
σ,𝑗

Each term in eqn. (3.35) is based on a unit amount of fluid flowing through the control volume.

33
 Ideal and lost work for flow systems

For complete reversible process:

𝑄ሶ
∆(𝑆𝑚)ሶ 𝑓𝑠 − 𝑇 = 0
σ

ሶ 𝑓𝑠
ሶ 𝑇σ ∆(𝑆𝑚)
𝑄=

Substitute this expression for 𝑄ሶ in the energy balance, eqn. from 1st set of lectures,

1
∆[{𝐻 + 2 𝑢2 + 𝑔𝑧}𝑚]ሶ 𝑓𝑠 = 𝑇σ ∆(𝑆𝑚)ሶ 𝑓𝑠 +𝑊ሶ𝑠 (rev)

The shaft work, 𝑊ሶ𝑠 (rev), is the work of a completely reversible process. If 𝑊ሶ𝑠 (rev) is given
the name ideal work, 𝑊𝑖𝑑𝑒𝑎𝑙ሶ , the preceding equation may be rewritten:

ሶ = ∆[{𝐻 + 1 𝑢2 + 𝑔𝑧}𝑚]ሶ 𝑓𝑠 -𝑇σ ∆(𝑆𝑚)

𝑊𝑖𝑑𝑒𝑎𝑙 ሶ 𝑓𝑠 (3.36)
2

Neglecting the kinetic- and potential-energy terms, eqn. (3.36) reduces to

ሶ = ∆(𝐻 𝑚)ሶ 𝑓𝑠 -𝑇σ ∆(𝑆𝑚)

𝑊𝑖𝑑𝑒𝑎𝑙 ሶ 𝑓𝑠 (3.37)
34
 Ideal and lost work for flow systems

For the special case of a single stream flowing through the control volume, the terms of
eqn. (3.37) may be expressed as rates or upon division by 𝑚ሶ on the basis of a unit amount
of fluid flowing through the control volume. Thus,

ሶ = 𝑚[∆𝐻
𝑊𝑖𝑑𝑒𝑎𝑙 ሶ − 𝑇σ ∆𝑆 ] (3.38)

A completely reversible process is hypothetical, devised only for determination of the ideal
work associated with a given change of state.

35
 Ideal and lost work for flow systems

In real process however, actual work involved will depend on the extent of associated
irreversibilities; hence we define lost work as follows:
ሶ = −𝑊𝑎𝑐𝑡𝑢𝑎𝑙
𝑊𝑙𝑜𝑠𝑡 ሶ ሶ
+𝑊𝑖𝑑𝑒𝑎𝑙 (3.39)

1 2
ሶ
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 = ∆[{𝐻 + 𝑢 + 𝑔𝑧}𝑚]ሶ 𝑓𝑠 − 𝑄𝑎𝑐𝑡𝑢𝑎𝑙
ሶ (3.40)
2

1 2 (3.41)
ሶ = ∆[{𝐻 +
𝑊𝑖𝑑𝑒𝑎𝑙 𝑢 + 𝑔𝑧}𝑚]ሶ 𝑓𝑠 − 𝑇σ ∆(𝑆𝑚)
ሶ 𝑓𝑠
2

ሶ
Substituting these expressions for 𝑊𝑎𝑐𝑡𝑢𝑎𝑙 ሶ in eqn. (3.39) yields
𝑎𝑛𝑑𝑊𝑖𝑑𝑒𝑎𝑙

ሶ = 𝑇σ ∆(𝑆𝑚)ሶ 𝑓𝑠 - 𝑄𝑎𝑐𝑡𝑢𝑎𝑙
𝑊𝑙𝑜𝑠𝑡 ሶ (3.42)

36
Tue, 09/02/21
Ideal and lost work for flow systems

For the case of a single surrounding temperature 𝑇σ , eqn. (3.34) becomes

𝑄ሶ
∆(𝑆𝑚)ሶ 𝑓𝑠 − 𝑇 = 𝑆𝐺ሶ (3.43)
σ

Multiplication by 𝑇σ gives:
𝑇σ ∆(𝑆𝑚)ሶ 𝑓𝑠 −𝑄=
ሶ 𝑇σ 𝑆ሶ 𝐺 (3.44)

The right sides of this equation (3.44) and (3.42) are identical; therefore,

ሶ = 𝑇σ 𝑆𝐺ሶ
𝑊𝑙𝑜𝑠𝑡 (3.45)

As a consequence of the second law, 𝑆𝐺ሶ ≥ 0; 𝑖𝑡 𝑓𝑜𝑙𝑙𝑜𝑤𝑠 𝑡ℎ𝑎𝑡𝑊𝑙𝑜𝑠𝑡 ሶ ≥ 0.when a process

ሶ = 0.
is completely reversible, the equality holds, and 𝑊𝑙𝑜𝑠𝑡

ሶ , i.e., the energy that becomes

For irreversible processes the inequality holds, and 𝑊𝑙𝑜𝑠𝑡
unavailable for work, is positive.
37
 Ideal and lost work for flow systems

When 𝑾𝒊𝒅𝒆𝒂𝒍ሶ is positive, it is the minimum work required to bring about a given change in the
properties of the flowing streams, and is smaller than 𝑊ሶ𝑠 . In this case, a thermodynamic
efficiency η𝑡 is defined as the ratio of the ideal work to the actual work.

ሶ
𝑊𝑖𝑑𝑒𝑎𝑙 (3.46)
η𝑡 (work required) = 𝑊ሶ 𝑠

When 𝑾𝒊𝒅𝒆𝒂𝒍ሶ ሶ
is negative, 𝑊𝑖𝑑𝑒𝑎𝑙 is the maximum work obtainable from a given change in
the properties of the flowing streams, and is larger than 𝑊ሶ𝑆 . In this case, a thermodynamic
efficiency η𝑡 is defined as the ratio of the actual work to the ideal work.

𝑊ሶ 𝑠
η𝑡 (work produced) = ሶ
(3.47)
𝑊𝑖𝑑𝑒𝑎𝑙

38
 Question

A steady-flow adiabatic turbine (expander) accepts gas at conditions T1= 500 K, P1= 6 bar,
and discharges at conditions T2= 371 K, P2= 1.2 bar. Assuming ideal gases, determine (per
mole of gas) Wactual, Wideal, Wlost, and entropy generation rate. Tsurr= 300 K, Cp/R = 7/2.

Solution ∆𝐻 = 𝑛𝐶𝑝(𝑇2 − 𝑇1)

Wactual = Q + ∆𝐻 = -3753.85J [Q=0]

∆S = n[Cp ln(T2/T1) – R ln(P2/P1)]= 4.698 J/K

Wideal = ∆𝐻 − 𝑇σ ∆S = -5163J

ሶ = 𝑊𝑎𝑐𝑡𝑢𝑎𝑙
𝑊𝑙𝑜𝑠𝑡 ሶ ሶ
- 𝑊𝑖𝑑𝑒𝑎𝑙

ሶ = (-3753.85+5163) J = 1409.15J
𝑊𝑙𝑜𝑠𝑡

ሶ
𝑊𝑙𝑜𝑠𝑡 ሶ
1409.15
𝑆𝐺 = = = 4.697𝐽/𝐾
𝑇σ 300
39
 Question

An ideal gas at 25bar is throttled to 1 bar at a rate of 100mols-1. If the temperature of the
surroundings is 300K, calculate the rate of entropy generation and lost work.

Solution
𝑑(𝑚𝑈)𝑐𝑣 1
+∆ 𝐻 + 𝑢2 + 𝑔𝑍 𝑚ሶ = 𝑄ሶ + 𝑊ሶ𝑠
𝑑𝑡 2

𝑑(𝑚𝑈)𝑐𝑣 1 2
+∆ 𝐻 + 𝑢 + 𝑔𝑍 𝑚ሶ = 𝑄ሶ + 𝑊ሶ𝑠
𝑑𝑡 2

∆ 𝐻 =0⇒∆ 𝑇 =0
With no temperature, change in entropy
𝑃2
∆𝑆 𝑖𝑔 = −𝑅𝑙𝑛
𝑃1
∆𝑆 𝑖𝑔 = 26.76𝐽𝑚𝑜𝑙 −1 𝐾 −1
Entropy balance:
𝑑(𝑚𝑆)𝑐𝑣 𝑄ሶ
∆(𝑚𝑆)
ሶ 𝑓𝑠 + − = 𝑆𝐺ሶ
𝑑𝑡 𝑇𝜎
40
 𝑑(𝑚𝑆)𝑐𝑣 𝑄ሶ
∆(𝑚𝑆)
ሶ 𝑓𝑠 + − = 𝑆𝐺ሶ
𝑑𝑡 𝑇𝜎

Since it is a steady-state process, ሶ ሶ

𝑆𝐺 = 𝑚∆(𝑆) 𝑆𝐺ሶ =100mol/s*26.76J/molK
𝑓𝑠

𝑆𝐺ሶ =2.676kJ/molK
𝑊𝑖𝑑𝑒𝑎𝑙 = 𝑊𝑟𝑒𝑣 = ∆𝐻 − 𝑇𝜎 ∆𝑆 𝑚ሶ = ∆𝐻 − 𝑇𝜎 ∆𝑆 𝑛ሶ

𝑊𝑖𝑑𝑒𝑎𝑙 = ∆𝐻 − 𝑇𝜎 ∆𝑆 𝑛ሶ ⇒ 𝑊𝑖𝑑𝑒𝑎𝑙 = −𝑇𝜎 ∆𝑆 𝑛ሶ

⇒ 𝑊𝑖𝑑𝑒𝑎𝑙 = −802.8𝑘𝐽/𝑠

⇒ 𝑊𝑟𝑒𝑎𝑙 = 0

⇒ 𝑊𝑙𝑜𝑠𝑡 = 802.8𝑘𝐽/𝑠

41
 Entropy- Macro and Micro-scopic approach

Ideal gas expansion into an evacuated chamber

At certain point, the partition is ruptured and the gas contained in the left compartment
allowed to fill the entire system volume.

Eventually the gas would reach a new equilibrium state that is characterized by P1/2
throughout.

For this process, applying first law:

∆𝑈 = 𝑄 + 𝑊
But, 𝑄=𝑊=0

∆𝑈 =0
Hence,
 Entropy- Macro and Micro-scopic approach
The entropy change,

(i) Macroscopic approach:

𝑑𝑇 𝑑𝑃 (3.20)
∆𝑆 = 𝐶𝑝 - 𝑅
𝑇 𝑃

Since, T1=T2, ∆𝑇 = 0

𝑑𝑃
∆𝑆 = − 𝑅
𝑃

𝑃
∆𝑆 = − 𝑅 𝑙𝑛 𝑃2
1

𝑉
∆𝑆 = 𝑅 𝑙𝑛 𝑉2= 𝑅𝑙𝑛2 (3.48)
1
 Entropy- Macro and Micro-scopic approach

(ii) Microscopic approach:

From a microscopic point of view the molecular state variables are: position and
energy.

Since there is no change of temperature during the expansion process, the internal
energy of each molecule does not change.

There, is, however, a possible change in the position occupied a molecule. After the
expansion a molecule may be located either on the left half or in the right half of the
compartment at any point of time. We may say, in a simplified sense, there are two
possible positions that it may have.

Considering one mole of gas as basis, if there are, in general, j such states (either
of position or energy) that a molecule may exist in, the total number of ways
that an Avogadro number of molecules (NA= 6.023x1023)may be distributed over all
the available states is given by (with nj molecules in the jthstate):
 Entropy- Macro and Micro-scopic approach

𝑁𝐴 !
Ω= (3.49)
𝑛1 ! 𝑛2 ! … . . (𝑛𝑗 !)

Thermodynamic probability

However, in the final state as there are two possible positional states, the
corresponding maximum thermodynamic probability is:

𝑁!
Ω=
𝑁/2! 𝑁/2!

Boltzmann developed statistical concept of nature (now known as statistical mechanics),

first proposed the relation between entropy and thermodynamic probability:

𝑆 = 𝑘𝑙𝑛Ω
𝑅 (3.50)
𝑘 = 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡= 𝑁
𝐴
 Entropy- Macro and Micro-scopic approach

∆𝑆 = 𝑆2 − 𝑆1 = 𝑘𝑙𝑛Ω2 − 𝑘𝑙𝑛Ω1

Ω
∆𝑆 = 𝑘𝑙𝑛 Ω2
1

Thus, 𝑁𝐴!
∆𝑆 = 𝑘𝑙𝑛 (3.51)
𝑁𝐴/2 ! 𝑁𝐴/2 !

By Stirling’s formula, lnN!= NlnN-N (3.52)

On applying both equation [(3.51) and (3.52)],

𝑁𝐴 (3.53)
∆𝑆 = 𝑘𝑁𝐴𝑙𝑛 𝑁𝐴/2

∆𝑆 = 𝑘𝑁𝐴𝑙𝑛2

∆𝑆 = R𝑙𝑛2
There is thus a convergence between the macroscopic and microscopic description
of the concept of entropy.