Chemical Engineering Thermodynamics II

CHE-303

INSTRUCTOR: Dr. NAYEF M. ALSAIFI

Chapter 5: The second law of thermodynamics

 First law of thermodynamics

 Law of conservation of energy:

 Energy cannot be created or destroyed but it can only be transformed

 The total amount of energy in any action stays the same. None of the
energy is really “ lost”. It just changes forms.

 Energy forms:
 heat, work, potential, kinetic, chemical, light, electricity, nuclear
energy...etc.

 Energy transforms:

From one form into another form

Kinetic energy Heat

Potential energy Kinetic energy

Chemical energy Work

Heat Work
2
Towards the Second law of thermodynamics and entropy
Direction of processes

3
 Direction of processes

Room temperature 20 oC

95 oC

 If the above cup was left long time in a room, the coffee gets colder because:

(A) Heat transfers from the cup into the room.

(B) Heat transfers from the room into the cup.

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 Direction of processes

 Which process is NOT possible spontaneously?

(A)

(B)

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 Direction of processes

 If you open the stopcock, do you think :

(A) some of the particles will move to the other side

(B) Non of the particles will go to the other side

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 Direction of processes

 Do you think all particles might move from left to right spontaneously?

(A) Not probable process

(B) Very probable process

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 Direction of processes

 If the weight falls, the paddle wheel turns and the temperature of the water rises:

(A) True
(B) False 8
 Direction of processes

 Do you think if you heat up the water, the weight will rise:

(A) Possible
(B) Not possible
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 Second law of thermodynamics

Processes occur in a certain direction and not in the reverse

direction.

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 The Zeroth law of thermodynamics produced a state function called:

(A) Work
(B) Temperature
(C) Heat
(D) Internal energy
(E) Entropy 11
 The first law of thermodynamics produced a state function called:

(A) Work
(B) Temperature
(C) Heat
(D) Internal energy
(E) Entropy 12
 The second law of thermodynamics produced a state function called:

(A) Work
(B) Temperature
(C) Heat
(D) Internal energy
(E) Entropy 13
 What is entropy?

 The heat was gradually transferred to the

molecules in the surrounding air (room).
ROOM ( surrounding air)

293 K
 The heat energy still exists
but it has spread out into the room.
Heat transfer

 Can we collect the spread-out heat energy

from the air and bring it back into the cup
to its original temperature? 373 K
What happened to the energy?

Concentrated Un-concentrated
form in the cup form in the room
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 What is entropy?

Concentrated Un-concentrated
form in the cup form in the room

Low “ spread out” High “ spread out”

energy energy

Difference high “ spread out”

energy - Low “ spread out”
energy > 0
S1 S2

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 What is entropy?

The Greek τροπη (entropy) means TRANSFORMATION

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 The tendency of ENERGY and Matter to spread out

 What makes heat transfer from hot to cold?

 What moves the particles?

ENERGY

MATTER 17
The tendency of ENERGY and Matter to spread out

 The principle driving force for processes are energy spread and
matter spread

 Natural processes occur in the direction that leads to an

increase in the disorder.

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What happens to the energy or matter when it "spreads out" ?

It becomes less useful. (No longer do useful work)

 In any energy transformation some useful energy will be lost

and turned into unrecoverable heat.

 The heat energy in any system has a tendency to “spread

out” until finally everything is the same temperature.

T1 > T2 T2 < T3 < T1

T1 T2 T3 T3

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 What is entropy?

 Entropy measures - with a ratio - the tendency of ENERGY to spread out,

to diffuse, to become less concentrated in one physical location or one
energetic state

 Mathematically, entropy measures the energy dispersion in a system

divided by temperature (dQ/T)

 Entropy is NOT a driving force; it measures the driving force

 Every transfer of energy within a system or with its surroundings involves an

increase in entropy, a decrease in ability to do work, a "spreading out" or
"diffusion" of energy, an increase in "waste heat"

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 Entropy of solid, liquid and gas

Solid Liquid Gas

Minimum entropy
Maximum entropy

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 Entropy Changes

 Entropy is a state function, so its changes in the system are only

dependent upon initial and final states and are independent of the
path

State 1 State 2

S1 S2

Change of entropy = ΔS = S2-S1

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 Change of entropy

 A system and its surroundings form an isolated system.

surroundings Q=0
W=0
system m=0
Isolated
system

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings ≥ 0

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 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings ≥0

∆𝑆𝑡𝑜𝑡𝑎𝑙 > 0 For any real process

(irreversible process)

∆𝑆𝑡𝑜𝑡𝑎𝑙 = 0 For ideal process

(reversible process)

∆𝑆𝑡𝑜𝑡𝑎𝑙 < 0 Impossible process

 Entropy always increases in any real process. There is no violation of

that.

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 Reversible and irreversible processes

 Reversible process is a process that after it is finished can go backwards and

end up where it is started.

 Irreversible process is a process that can not go back and restore itself.

 Examples of irreversible processes:

 Heat transfer
 expansion of a gas or liquid
 Spontaneous chemical reaction
 Spontaneous mixing of matter at different compositions or states
 Friction

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Entropy change problems
(closed and open systems)

ΔS

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Entropy changes in closed system

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 Entropy changes in closed system

Depends only on
states 1 and 2. Must be
𝑠𝑡𝑎𝑡𝑒 2
𝑑𝑄𝑟𝑒𝑣 evaluated
∆𝑆 = along any
DOES NOT depend 𝑠𝑡𝑎𝑡𝑒 1 𝑇𝑠𝑦𝑠𝑡 reversible
on reversibility. pathway

A process between two states does not need to be reversible

to permit calculation of the entropy change.

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 Before starting entropy change calculations

 Always remember

 Heat transfer to the system increases entropy in the system

 Heat transfer out of the system decreases the entropy in the system

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 Entropy changes in closed system

 Three different types of “entropy change” problems:

 Entropy Changes of heat transfer process.

 Such as entropy change associated with heat transfer from a hot

cup of coffee to a room.

 Entropy Changes of a pure substance.

 at constant pressure, constant temperature...etc.

 Entropy Changes of ideal gas

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 Entropy Changes of heat transfer process

 If heat is transferred from a system to surroundings (or from surroundings to

the system), the total entropy of this process is given by:

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings ≥ 0

 If the temperature of system or surroundings remains unchanged,

the change of entropy for the system or surroundings is calculated by :

𝑄𝑟𝑒𝑣
∆𝑆 =
𝑇
 If the temperature of the system or surroundings changes, the change of entropy
is given by:

𝑠𝑡𝑎𝑡𝑒 2
𝑑𝑄𝑟𝑒𝑣
∆𝑆 =
𝑠𝑡𝑎𝑡𝑒 1 𝑇

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 Entropy Changes of heat transfer process

 A heat source at 800 K loses 2000 kJ of heat to a sink at (a) 500 K and (b) 750 K.
 Determine which heat transfer process is more irreversible.
 Solution
 More irreversible means higher entropy generation (higher ∆𝑆𝑡𝑜𝑡𝑎𝑙 )
 We have to study to different cases:
(a) (b)
Sink (surroundings) Sink (surroundings)

800 K Q = 2000 kJ 800 K Q = 2000 kJ

Heat source Heat source

(system)
500 K 750 K
(system)

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings ≥ 0 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings ≥ 0

𝑄𝑟𝑒𝑣 −2000 𝑘𝐽 𝑄𝑟𝑒𝑣 −2000 𝑘𝐽

∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = = = −2.5 𝑘𝐽/𝐾 ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = = = −2.5 𝑘𝐽/𝐾
𝑇 800 𝐾 𝑇 800 𝐾

𝑄𝑟𝑒𝑣 +2000 𝑘𝐽 𝑄𝑟𝑒𝑣 +2000 𝑘𝐽

∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = = = 4 𝑘𝐽/𝐾 ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = = = 2.67 𝑘𝐽/𝐾
𝑇 500 𝐾 𝑇 750 𝐾

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings = −2.5 + 4 = 𝟏. 𝟓 𝒌𝑱/𝑲 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings = −2.5 + 2.67 = 𝟎. 𝟏𝟕 𝒌𝑱/𝑲

(a) has higher total entropy than (b). Therefore, a is more irreversible 32
 Practice

Example 5.4 page 175

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 Entropy Changes of a pure substance.

 A process occurs at constant pressure

 A process occurs at constant volume

 A process occurs at constant Temperature

 A process occurs at adiabatically and reversibly (isentropic)

 Phase transition (vaporization and fusion)

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 A process occurs at constant pressure
𝑠𝑡𝑎𝑡𝑒 2 𝑇2 𝑇2 𝑚𝐶
𝑑𝑄𝑟𝑒𝑣 𝑑𝐻 𝑝
∆𝑆 = = = 𝑑𝑇
𝑠𝑡𝑎𝑡𝑒 1 𝑇𝑠𝑦𝑠𝑡 𝑇1 𝑇 𝑇1 𝑇
 Example
 A 500-mL glass of chilled water at 283 K is removed from a refrigerator. It slowly
equilibrates to room temperature at 298 K. The process occurs at one bar. Calculate :
1. the entropy change of the water.
2. the entropy change of surroundings.
3. the entropy change of the universe.
Neglect the heat capacity of the container. For liquid water Cp=4.184 J/g K
1. The entropy change of the water.
𝑇2 𝑚𝐶 𝑇𝑓
𝑝 1𝑔 4.184 𝐽 298
∆𝑆𝑤𝑎𝑡𝑒𝑟 = 𝑑𝑇 = 𝑚𝐶𝑝 ln = 500 𝑚𝑙 ∗ 𝑙𝑛 = 𝟏𝟎𝟖 𝑱/𝑲
𝑇1 𝑇 𝑇𝑖 𝑚𝑙 𝑔 𝐾 283
2. the entropy change of surroundings.
The surroundings temperature doesn’t change significantly. Therefore, this problem is
similar to the heat transfer problems demonstrated in slide 32

𝑄𝑟𝑒𝑣 ∆𝐻 𝑚𝐶𝑝 ∆𝑇 1𝑔 4.184 𝐽 298 − 283 𝐾

∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = = = = −500 𝑚𝑙 ∗ = −𝟏𝟎𝟓. 𝟑 𝑱/𝑲
𝑇 𝑇 𝑇 𝑚𝑙 𝑔 𝐾 298 𝐾
3. The entropy change of the universe.

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆surroundings = 108 − 105.3 = 𝟐. 𝟕 𝑱/𝑲

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 A process occurs at constant volume

𝑠𝑡𝑎𝑡𝑒 2 𝑇2 𝑇2
𝑑𝑄𝑟𝑒𝑣 𝑑𝑈 𝑚𝐶𝑉
∆𝑆 = = = 𝑑𝑇
𝑠𝑡𝑎𝑡𝑒 1 𝑇𝑠𝑦𝑠𝑡 𝑇1 𝑇 𝑇1 𝑇

 Example
 One mole of methane contained in a rigid tank at 300 K is heated
till its temperature rises to 500 K. Calculate the change in the entropy?

 Note that Cv is a function of temperature (not constant).

Answer: 16.61 J/mol K

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 A process occurs at constant Temperature

For now, it is difficult to have general relationships at constant

temperature except for ideal gas case. You will know how to obtain
these equations in Chapter 6.

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 A process occurs adiabatically and reversibly
(isentropic)

 The process that occurs adiabatically and reversibly is called isentropic

𝑠𝑡𝑎𝑡𝑒 2
𝑑𝑄𝑟𝑒𝑣
∆𝑆 = =0
𝑠𝑡𝑎𝑡𝑒 1 𝑇𝑠𝑦𝑠𝑡

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 Phase transition of vaporization and fusion

 Entropy changes of vaporization

𝑣𝑎𝑝
𝑑𝑄𝑟𝑒𝑣 1 𝑄 𝑣𝑎𝑝 ∆𝐻 𝑣𝑎𝑝
∆𝑆 = = 𝑠𝑎𝑡 𝑑𝑄𝑟𝑒𝑣 = 𝑠𝑎𝑡 = 𝑠𝑎𝑡
𝑇 𝑇 𝑇 𝑇

 Entropy changes of fusion

𝑓𝑢𝑠
𝑑𝑄𝑟𝑒𝑣 1 𝑄 𝑓𝑢𝑠 ∆𝐻 𝑓𝑢𝑠
∆𝑆 = = 𝑑𝑄𝑟𝑒𝑣 = =
𝑇 𝑇𝑚 𝑇𝑚 𝑇𝑚

 During phase transition, temperature remains constant in Phase transition.

 A piston-cylinder assembly contains 1 kg saturated liquid water at 100 oC. The

cylinder is brought into contact with a body at 500 C till all the water is converted
into saturated steam at the same pressure. Calculate the change in entropy of
water?

∆𝐻 𝑣𝑎𝑝 2256.94 (@ 373.15 𝐾) 𝐾𝐽

∆𝑆 𝑣𝑎𝑝 = 𝑠𝑎𝑡 = = 6.0483 𝐾
𝑇 373.15 𝑘𝑔

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 Entropy Changes of ideal gas

 The first law of thermodynamics for reversible process in a closed system is given by:

𝑇 𝑖𝑔
Δ𝑆 𝐶𝑃 𝑑𝑇 𝑃
= − ln
𝑅 𝑇0 𝑅 𝑇 𝑃0

𝑇1 𝑖𝑔
∆𝑆 𝐶𝑉 𝑑𝑇 𝑉1
= + ln
𝑅 𝑇0 𝑅 𝑇 𝑉0

 For the derivations of the above equations, please see section 5.5 page 170

 Note that if Cv and Cp are functions of temperature, the above integrals must be
evaluated.

 The integral is evaluated as follows:

𝑇 𝑖𝑔
𝐶𝑃 𝑑𝑇 𝐷 𝜏+1
= A lnτ + 𝐵𝑇0 + 𝐶𝑇02 + 2 2 𝜏−1
𝑇0 𝑅 𝑇 𝜏 𝑇0 2
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 Example

 Calculate the entropy change when 1 mole of air is heated and expanded from
25 oC and 1 bar to to 100 oC and 0.5 bar?

 Solution
𝑇 𝑖𝑔
Δ𝑆 𝐶𝑃 𝑑𝑇 𝑃
= − ln
𝑅 𝑇0 𝑅 𝑇 𝑃0

𝑇 𝑖𝑔
𝐶𝑃 𝑑𝑇 𝐷 𝜏+1
= A lnτ + 𝐵𝑇0 + 𝐶𝑇02 + 2 2 𝜏−1
𝑇0 𝑅 𝑇 𝜏 𝑇0 2

𝐷 𝜏+1 𝑃
Δ𝑆 = R(A lnτ + 𝐵𝑇0 + 𝐶𝑇02 + 𝜏 − 1 − ln )
𝜏 2 𝑇02 2 𝑃0

For air: A=3.355 B=0.575E-3 C=0 D=-0.016E5

𝑇
τ=
𝑇0
𝐷 𝜏+1 𝑃
Δ𝑆 = R ∗ A lnτ + 𝐵𝑇0 + 𝐶𝑇02 + 𝜏 − 1 − ln = 𝟎. 𝟖𝟐𝟕𝟓 J/mol K
𝜏2 𝑇02 2 𝑃0

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 Entropy Changes of ideal gas

 If the process is adiabatic and reversible (isentropic), the following relationships

could be used:
𝛾−1
𝑇2 𝑉1
=
𝑇1 𝑠=𝑐𝑜𝑛𝑠𝑡.
𝑉2

(𝛾−1)/𝛾
𝑇2 𝑝2
=
𝑇1 𝑠=𝑐𝑜𝑛𝑠𝑡.
𝑝1

𝛾
𝑝2 𝑉1
=
𝑝1 𝑠=𝑐𝑜𝑛𝑠𝑡.
𝑉2

𝐶𝑝
𝛾=
𝐶𝑉

 To see the derivations of the above relationships, see example 5.2 page 171
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 Example

 Helium gas is compressed by an adiabatic compressor from an initial state of 14

psia and 50°F to a final temperature of 320°F in a reversible manner.
Determine the exit pressure of helium.

Answer: 40.5 psia

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PROBLEMS

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 Problem 5.8 (a) page 191

 With respect to 1 kg of liquid water:

 Initially at 0 oC, it is heated to 100 oC by contact with a heat reservoir at 100 oC.
What is the entropy change of water? Of the heat reservoir? What is ∆𝑆𝑡𝑜𝑡𝑎𝑙 ?
Cp= 4.184 kJ/kg K
1 kg
 Solution liquid water
0  100 oC

100 oC

 Choose water as a system and the heat reservoir as surroundings.

 Q= m Cp ΔT = 1 *4.184*(373.15-273.15)=418.4 kJ/kg
𝑠𝑡𝑎𝑡𝑒 2 𝑇2 𝑚𝐶
𝑑𝑄𝑟𝑒𝑣 𝑝 𝑇2 373.15 𝒌𝑱
∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = = 𝑑𝑇 = 𝑚𝐶𝑝 ln = 1 ∗ 4.184 ∗ 𝑙𝑛 = 𝟏. 𝟑𝟎𝟓𝟐
𝑠𝑡𝑎𝑡𝑒 1 𝑇 𝑇1 𝑇 𝑇1 273.15 𝒌𝒈𝑲

−𝑄 −418.4 𝑘𝐽/𝑘𝑔
∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = = = −𝟏. 𝟏𝟐𝟏𝟑 kJ/kg K
𝑇 373.15 𝐾

∆𝑆𝑡𝑜𝑡𝑎𝑙 = 1.3052 − 1.1213 = 0.1839 kJ/kg K

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 Practice

 Try to solve the following problems from your book

 Problem 5.8 (b & c ) page 191

 Problem 5.9

 Problem 5.10

 Problem 5.11

 Problem 5.12

 Problem 5.18

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Entropy balance for open systems

 Heat is the least useful form of energy.

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 energy quality

 Heat is the least useful form of energy.

48
 which one has higher energy quality?
(A) 3000 KJ energy of work

(B) 3000 KJ energy of Heat

Note: from the first law of thermodynamics , they are exactly the same.

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 100% transform

 Impossible process (100 % transform)

Heat Process Work

 Possible process (100 % transform)

Work Process Heat

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