PHYSICAL CHEMISTRY 1

Dr. Ngo Thanh An

 Chapter 3 – Second law of thermodynamics

Transferring heat
to a paddle
wheel will not
cause it to rotate.

A cup of hot coffee does not

get hotter in a cooler room.
These processes cannot
occur even though they
are not in violation of the
first law.
Transferring heat to
a wire will not
generate electricity.
2
 Chapter 3 – Second law of thermodynamics

Processes occur in a certain direction, and not in the reverse

direction.

A process must satisfy both the first

and second laws of thermodynamics
to proceed.
MAJOR USES OF THE SECOND LAW
1. The second law may be used to identify the direction of processes.
2. The second law also asserts that energy has quality as well as quantity. The first law is
concerned with the quantity of energy and the transformations of energy from one form
to another with no regard to its quality. The second law provides the necessary means to
determine the quality as well as the degree of degradation of energy during a process.
3. The second law of thermodynamics is also used in determining the theoretical limits for
the performance of commonly used engineering systems, such as heat engines and
refrigerators, as well as predicting the degree of completion of chemical reactions.
3
 Chapter 3 – Second law of thermodynamics

A source supplies
energy in the
form of heat, and
a sink absorbs it.

Bodies with relatively large thermal

masses can be modeled as thermal
energy reservoirs.
• A hypothetical body with a relatively large thermal energy capacity (mass x specific
heat) that can supply or absorb finite amounts of heat without undergoing any
change in temperature is called a thermal energy reservoir, or just a reservoir.
• In practice, large bodies of water such as oceans, lakes, and rivers as well as the
atmospheric air can be modeled accurately as thermal energy reservoirs because of
their large thermal energy storage capabilities or thermal masses.
4
 Chapter 3 – Second law of thermodynamics

The devices that convert heat to work.

1. They receive heat from a high-
temperature source (solar energy, oil
Work can always be converted to heat furnace, nuclear reactor, etc.).
directly and completely, but the reverse 2. They convert part of this heat to
is not true. work (usually in the form of a
rotating shaft.)
3. They reject the remaining waste
heat to a low-temperature sink (the
atmosphere, rivers, etc.).
Part of the heat received
by a heat engine is 4. They operate on a cycle.
converted to work, while Heat engines and other cyclic devices
the rest is rejected to a usually involve a fluid to and from
sink. which heat is transferred while
undergoing a cycle. This fluid is
called the working fluid.
5
 Chapter 3 – Second law of thermodynamics

Schematic of a
heat engine.

Some heat engines perform better than

others (convert more of the heat they Even the most
receive to work). efficient heat engines
reject almost one-half
of the energy they
receive as waste heat.

6
 Chapter 3 – Second law of thermodynamics

In a steam power plant, the

condenser is the device where
large quantities of waste heat is
rejected to rivers, lakes, or the
atmosphere.
Can we not just take the
condenser out of the plant and
save all that waste energy?
The answer is, unfortunately, a
firm no for the simple reason
that without a heat rejection
process in a condenser, the
A heat-engine cycle cannot be completed without cycle cannot be completed.
rejecting some heat to a low-temperature sink.

Every heat engine must waste some energy by transferring it to a low-

temperature reservoir in order to complete the cycle, even under idealized
conditions.
7
 Chapter 3 – Second law of thermodynamics

It is impossible for any device that

operates on a cycle to receive heat from
a single reservoir and produce a net
amount of work.

No heat engine can have a thermal

efficiency of 100 percent, or as for a power
plant to operate, the working fluid must
exchange heat with the environment as well
as the furnace.
The impossibility of having a 100% efficient
heat engine is not due to friction or other
dissipative effects. It is a limitation that
applies to both the idealized and the actual A heat engine that violates the Kelvin–
heat engines. Planck statement of the second law.

8
 Chapter 3 – Second law of thermodynamics

• The transfer of heat from a low-

temperature medium to a high-temperature
one requires special devices called
refrigerators.
• Refrigerators, like heat engines, are cyclic
devices.
• The working fluid used in the refrigeration
cycle is called a refrigerant.
• The most frequently used refrigeration
cycle is the vapor-compression refrigeration
cycle.

In a household refrigerator, the freezer

compartment where heat is absorbed by the
refrigerant serves as the evaporator, and the
Basic components of a refrigeration coils usually behind the refrigerator where
system and typical operating conditions. heat is dissipated to the kitchen air serve as
the condenser. 9
Chapter 3 – Second law of thermodynamics

The efficiency of a refrigerator is expressed in terms

of the coefficient of performance (COP).
The objective of a refrigerator is to remove heat (QL)
from the refrigerated space.

Can the value of COPR be greater than unity?

The objective of a
refrigerator is to remove QL
from the cooled space. 10
Chapter 3 – Second law of thermodynamics

The objective of a
heat pump is to
supply heat QH
into the warmer
space.
The work supplied
to a heat pump is
used to extract
energy from the
cold outdoors and
carry it into the
warm indoors.

Can the value of COPHP be

lower than unity?
What does COPHP=1
represent? 11
Chapter 3 – Second law of thermodynamics

It is impossible to construct a device that operates in a

cycle and produces no effect other than the transfer of
heat from a lower-temperature body to a higher-
temperature body.

It states that a refrigerator cannot operate unless its

compressor is driven by an external power source, such
as an electric motor.
This way, the net effect on the surroundings involves the
consumption of some energy in the form of work, in
addition to the transfer of heat from a colder body to a
warmer one.
To date, no experiment has been conducted that
A refrigerator that violates
contradicts the second law, and this should be taken as
the Clausius statement of
sufficient proof of its validity.
the second law.
12
 Chapter 3 – Second law of thermodynamics

Reversible process: A process that can be reversed without leaving any trace on the
surroundings.
Irreversible process: A process that is not reversible.
• All the processes occurring in nature are irreversible.
• Why are we interested in reversible processes?
• (1) they are easy to analyze and (2) they serve as idealized
models (theoretical limits) to which actual processes can be
compared.
• Some processes are more irreversible than others.
• We try to approximate reversible processes. Why?

Two familiar reversible

processes. Reversible processes deliver the most and consume the 13
least work.
 Chapter 3 – Second law of thermodynamics

Quá trình thuận nghịch:

Là quá trình mà khi đi từ A đến B và ngược lại từ B đến A thì hệ không
gây ra bất kỳ sự biến đổi nào trong hệ cũng như cho môi trường. Không
gây biến đổi  tức không tiêu hao năng lượng  tức không có entropy
nội sinh  không sinh ra entropy
Điểm chính của quá trình thuận nghịch, đó là quá trình không gây
ra biến đổi entropy!!!!

Quá trình Bất thuận nghịch: quá trình không thỏa mãn các điều kiện trên
--
Đối với quá trình thuận nghịch:
- Công hệ sinh đạt cực đại  Tại sao????? (liên quan hiệu suất
nhiệt cực đại)
- Công hệ nhận đạt cực tiểu  Tại sao???? (liên quan giá trị COP
cực đại)
Chapter 3 – Second law of thermodynamics
 Chapter 3 – Second law of thermodynamics
• The factors that cause a process to be irreversible are called
irreversibilities.
• They include friction, unrestrained expansion, mixing of two
fluids, heat transfer across a finite temperature difference,
electric resistance, inelastic deformation of solids, and
chemical reactions.
• The presence of any of these effects renders a process
irreversible.

(a) Heat transfer

through a temperature
difference is
irreversible, and (b) the Friction renders a Irreversible compression
reverse process is process irreversible. and expansion processes.
impossible. 16
 Chapter 3 – Second law of thermodynamics

►The Carnot cycle provides an example of a

reversible cycle that operates between two
thermal reservoirs.
►In a Carnot cycle, the system executing the cycle
undergoes a series of four internally reversible
processes: two adiabatic processes alternated
with two isothermal processes.
Chapter 3 – Second law of thermodynamics

Execution of the Carnot cycle in a closed system.

Reversible Isothermal Expansion (process 1-2, TH = constant)
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
Reversible Isothermal Compression (process 3-4, TL = constant)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH) 18
Chapter 3 – Second law of thermodynamics

P-V diagram of the Carnot cycle. P-V diagram of the reversed Carnot
cycle.

The Carnot heat-engine cycle is a totally reversible cycle.

Therefore, all the processes that comprise it can be reversed, in which case it
becomes the Carnot refrigeration cycle.
19
 Chapter 3 – Second law of thermodynamics

The Carnot principles.

Proof of the first Carnot principle.
1. The efficiency of an irreversible heat engine is always less than the efficiency of a
reversible one operating between the same two reservoirs.
2. The efficiencies of all reversible heat engines operating between the same two
reservoirs are the same. 20
Chapter 3 – Second law of thermodynamics

21
 Chapter 3 – Second law of thermodynamics

A temperature scale that is independent of the

properties of the substances that are used to
measure temperature is called a thermodynamic
temperature scale.
Such a temperature scale offers great
conveniences in thermodynamic calculations.

The arrangement of heat engines used to

develop the thermodynamic temperature scale.

22
Chapter 3 – Second law of thermodynamics
Chapter 3 – Second law of thermodynamics
 Chapter 3 – Second law of thermodynamics

For a reversible heat engine operating between two reservoirs at temperatures TH and TL,
the above equation can be written as

If we select φ(T) = T, then

 Chapter 3 – Second law of thermodynamics

This temperature scale is

called the Kelvin scale, and
the temperatures on this
scale are called absolute
temperatures.

For reversible cycles, the heat A conceptual experimental setup to

transfer ratio QH /QL can be determine thermodynamic temperatures on
replaced by the absolute the Kelvin scale by measuring heat transfers
temperature ratio TH /TL. QH and QL. 26
 Chapter 3 – Second law of thermodynamics

The Carnot heat

engine is the
most efficient of
all heat engines
operating
between the
same high- and
low-temperature
reservoirs.
No heat engine can have a higher efficiency
than a reversible heat engine operating
between the same high- and low-
temperature reservoirs.
Any heat engine Carnot heat engine

27
Chapter 3 – Second law of thermodynamics

Can we use °C
unit for
temperature
here?
The higher the temperature
of the thermal energy, the
higher its quality.
The fraction of heat that can be
How do you increase the thermal
converted to work as a function
efficiency of a Carnot heat engine?
of source temperature.
How about for actual heat engines?
28
 Chapter 3 – Second law of thermodynamics

Any refrigerator or heat pump

Carnot refrigerator or heat

pump

How do you increase the COP

No refrigerator can have a higher COP than a of a Carnot refrigerator or
reversible refrigerator operating between the same heat pump? How about for
temperature limits. actual ones? 29
 Chapter 3 – Second law of thermodynamics

The COP of a reversible refrigerator or heat pump is the maximum theoretical

value for the specified temperature limits.
Actual refrigerators or heat pumps may approach these values as their designs
are improved, but they can never reach them.
The COPs of both the refrigerators and the heat pumps decrease as TL decreases.
That is, it requires more work to absorb heat from lower-temperature media.

30
 Chapter 3 – Second law of thermodynamics

Ex 1: An automobile engine has an efficiency of 22.0% and produces 2510 J of

work. How much heat is rejected by the engine?
Ans: 8900 J

Ex 2: An ideal or Carnot heat pump is used to heat a house to a temperature of

TH = 294 K (21 °C). How much work must be done by the pump to deliver QH =
3350 J of heat into the house when the outdoor temperature TC is (a) 273 K (0
°C) and (b) 252 K (–21 °C)?

(a)

(b)
 Chapter 3 – Second law of thermodynamics

Ex 3: Each drawing represents a hypothetical heat engine or a hypothetical heat

pump and shows the corresponding heats and work. Only one is allowed in nature.
Which is it?

32
 Chapter 3 – Second law of thermodynamics

Ex 4: The lowest possible temperature is absolute zero, at

a. 0 on the Kelvin scale and 0 degrees on the Celsius scale.
b. 0 on the Kelvin scale and -100 degrees on the Celsius scale.
c. 0 on the Kelvin scale and -273 degrees on the Celsius scale.
d. 373 on the Kelvin scale and -273 degrees on the Celsius scale.
Ex 5: The second law of thermodynamics tells us that heat cannot flow from
a. hot to cold ever.
b. cold to hot ever.
c. hot to cold without external energy.
d. cold to hot without external energy.
Ex 6: Heat engines such as jet engines are more efficient when run at
a. high temperatures.
b. constant temperatures.
c. low temperatures.
d. a constant rate.
Chapter 3 – Second law of thermodynamics

Ex 7:
 Chapter 3 – Second law of thermodynamics

Ex 8:
Chapter 3 – Second law of thermodynamics

𝑄𝑄𝐿𝐿
For heat engine, we have: 𝜂𝜂𝑡𝑡ℎ =1−
𝑄𝑄𝐻𝐻
𝑇𝑇𝐿𝐿
𝜂𝜂𝑡𝑡ℎ,𝑟𝑟𝑟𝑟𝑟𝑟 =1−
𝑇𝑇𝐻𝐻

Carnot’s principle: 𝜂𝜂𝑡𝑡ℎ ≤ 𝜂𝜂𝑡𝑡ℎ,𝑟𝑟𝑟𝑟𝑟𝑟

𝑄𝑄𝐿𝐿 𝑇𝑇𝐿𝐿
Therefore: 1− ≤1−
𝑄𝑄𝐻𝐻 𝑇𝑇𝐻𝐻

Or: 𝑄𝑄𝐻𝐻 𝑄𝑄𝐿𝐿

− ≤0
𝑇𝑇𝐻𝐻 𝑇𝑇𝐿𝐿
 Chapter 3 – Second law of thermodynamics

• The cyclic integral indicates

that the integral should be
performed over the entire
cycle and over all parts of
the boundary.

2 3 4 1
δQ δQ δQ δQ
= ∫ T +∫ T +∫ T +∫ T
1 2 3 4
37
Chapter 3 – Second law of thermodynamics

2 3 4 1
δQ δQ δQ δQ QH QL
= ∫
1
T
+∫
2
T
+∫
3
T
+∫
4
T
=
TH
+0−
TL
+0

δQ
∫T ≤0

38
 Chapter 3 – Second law of thermodynamics

• Clausius inequality results in two important concepts:

– Entropy (S)

– Generated entropy (Sg)

39
 Chapter 3 – Second law of thermodynamics

• A thermodynamic (energy) function that describes the

degree of randomness or probability of existence.

• The more disordered the system, the larger its entropy.

• As a state function – entropy change depends only on

the initial and final states, but not on how the change
occurs.
 Chapter 3 – Second law of thermodynamics

• Nature spontaneously proceeds toward the state that

has the highest probability of (energy) existence –
highest entropy
• Entropy is used to predict whether a given
process/reaction is thermodynamically possible;
 Chapter 3 – Second law of thermodynamics

For reversible cycle A-B

2 1
 δQ   δQ 
= ∫  ∫
+  =0
1
T A 2  T B

For reversible cycle C-B

2 1
 δQ   δQ 
= ∫  +∫   =0
1
T C 2  T B
2 2
Subtracting gives  δQ   δQ  All paths are arbitrary
∫1  T A ∫1  T C
=

Since paths A and C are arbitrary, it follows that the integral of δQ/T has the
same value for ANY reversible process between the two sates.
δQ
∴ the quantity ∫ is independent of the path and dependent on the end states only
T 42
 Chapter 3 – Second law of thermodynamics

δQ is a thermodynamic property
⇒ ∫T we call it entropy ( S)

 δQ  2  δQ 
dS ≡   integrating S 2 − S1 = ∫  
 T  rev 1
 T  rev

S2 – S1 depends on the end states Entropy (the unit)

only and not on the path, S = entropy (kJ/K); s = specific entropy
∴ it is same for any path reversible (kJ/kg K)
or irreversible

43
 Chapter 3 – Second law of thermodynamics

Giả sử quá trình AB là thuận nghịch, quá trình CB: BTN

Cho quá trình A-B (thuận nghịch)
2 1
𝛿𝛿𝑄𝑄 𝛿𝛿𝑄𝑄 𝛿𝛿𝑄𝑄
� =� +� =0
𝑇𝑇 1 𝑇𝑇 𝐴𝐴 2 𝑇𝑇 𝐵𝐵
2 1
𝛿𝛿𝑄𝑄 𝛿𝛿𝑄𝑄
Cho quá trình C-B (bất thuận nghịch) � ≥�
1 𝑇𝑇 𝐴𝐴 2 𝑇𝑇 𝐶𝐶
2 1
𝛿𝛿𝑄𝑄 𝛿𝛿𝑄𝑄 𝛿𝛿𝑄𝑄
� =� +� ≤0
𝑇𝑇 1 𝑇𝑇 𝐶𝐶 2 𝑇𝑇 𝐵𝐵

Ngoài ra, ta cũng có:

2
𝛿𝛿𝑄𝑄 2 2 2  δQ 
2
� = � 𝑑𝑑𝑆𝑆𝐴𝐴 = � 𝑑𝑑𝑆𝑆𝐶𝐶 ∴ ∫ dS C > ∫  
 T C
1 𝑇𝑇 𝐴𝐴 1 1 1 1

44
 Chapter 3 – Second law of thermodynamics

δQ 2 δQ equality for reversible

dS ≥ or S 2 − S 1 ≥ ∫
T 1 T inequality for irreversible

This can be written out in a common form as an equality

δQ 2 δQ for any process,

dS ≡
T
+ δ S gen or S 2 − S=
1 ∫
1 T
+ S gen 
 with Sgen ≥ 0
2nd law of thermodynamics for a closed system
Entropy Balance Equation for a closed system
 > 0 for irreversible process
S gen ≡ entropy generation 
= 0 for a reversible process
In any irreversible process always entropy is generated (Sgen > 0) due to
irreversibilities occurring inside the system. 45
 Chapter 3 – Second law of thermodynamics

Example: Entropy change during an isothermal process

 Chapter 3 – Second law of thermodynamics

There is some entropy generated during an irreversible

process such that
2
δQ
S 2 − S1 = ∫T
1
+ S gen

Entropy Entropy transfer Entropy generation

change with heat due to irreversibility

This is the entropy balance for a closed system.

47
 Chapter 3 – Second law of thermodynamics

2
δQ
S 2 − S1 = ∫
1
T
+ S gen

 The entropy change can be evaluated independently of the

process details.
 However, the entropy generation depends on the process, and
thus it is not a property of the system.
 The entropy generation is always a positive quantity or zero and
this generation is due to the presence of irreversibilities.
 The direction of entropy transfer is the same as the direction of
the heat transfer: a positive value means entropy is transferred
into the system and a negative value means entropy is transferred
out of the system. 48
Chapter 3 – Second law of thermodynamics
• Number of particles: N
• Arrangement: 2N
• Each particle has only two possible quantum states ↑ or ↓.
• Distribution: m
• Total number of microstates (Ω): 2N
• Total magnetic moment of all the particles is
M = (N↑-N↓).µ
• M just depends on the relative number of up and down moments and not
on the detail of which are up or down.
• The relative number of ups and downs is constrained by:
N↑ + N↓ = N
Chapter 3 – Second law of thermodynamics

Microstate: a microscopic description would necessitate specifying

the state of each particle
Macrostate (state) including a lot of microstate (don’t care which is
up or down. Just focuses on how much is up and down)
 01 (State) ∝ 01 (m), which m equals N↑-N↓
Number m tell us the distribution of N particles among possible
states:
N↓ = (N-m)/2; N↑ = (N+m)/2
 t(m): total number of microstates responding to a (macro)state:

𝑁𝑁!
𝑡𝑡 𝑚𝑚 =
𝑁𝑁 ↑ ! 𝑁𝑁 ↓ !

𝑁𝑁!
𝑡𝑡 𝑚𝑚 =
𝑁𝑁 − 𝑚𝑚 𝑁𝑁 + 𝑚𝑚
! !
2 2
Chapter 3 – Second law of thermodynamics
Chapter 3 – Second law of thermodynamics
 Chapter 3 – Second law of thermodynamics

• For an isolated (or simply an adiabatic closed system), the heat

transfer is zero, then

δQ
∆S = S 2 − S 1 = ∫
1
2

T
+ Sgen ⇒ ∆S adiabatic =Sgen
 This means that the entropy of an adiabatic system during a
process always increases or, In the limiting case of a
reversible process, remains constant.
 In other words, it never decreases.
 This is called Increase of entropy principle.
 This principle is a quantitative measure of the second law.
53
 Chapter 3 – Second law of thermodynamics

• Now suppose the system is not adiabatic.

• We can make it adiabatic by extending the

surrounding until no heat, mass, or work are
crossing the boundary of the surrounding.

• This way, the system and its surroundings can be

viewed again as an isolated system.

• The entropy change of an isolated system is the

sum of the entropy changes of its components (the
system and its surroundings), and is never less
than zero.

• Now, let us apply the entropy balance for an

isolated system:

S gen = ∆Stotal = ∆S sys + ∆S surr ≥ 0

54
 Chapter 3 – Second law of thermodynamics

> 0 irreversible process


S gen = 0 reversible process
< 0 imposible process

Lưu ý: Entropy chỉ được truyền vào hệ theo 2 hình thức: hoặc truyền nhiệt, hoặc
truyền khối. Truyền công vào hệ không gây ra sự truyền entropy!!!!!!

55
 Chapter 3 – Second law of thermodynamics

• 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. A process that
violates this principle is impossible.
• Entropy is a non-conserved property. Entropy is conserved
during the idealized reversible process only and increases
during all actual processes.
• The performance of engineering systems is degraded by the
presence of irreversibilities, and the entropy generation is a
measure of the magnitude of the irreversibilities present
during a process.

56
 Chapter 3 – Second law of thermodynamics

∆S = S 2 − S 1 = ∫  δQ 
2

1  T int rev

a. Heating (cooling) process at constant pressure/constant volume:

δ QTN CP dT
Isobaric process: ∆S =∫ =∫
T T

δ QTN CV dT
Isochoric process: ∆S =∫ T
=∫
T
 Chapter 3 – Second law of thermodynamics

∆S = S 2 − S 1 = ∫  δQ 
2

1  T int rev

a. Heating (cooling) process at constant pressure/constant volume:

δ QTN CP dT
Isobaric process: ∆S =∫ =∫
T T

δ QTN CV dT
Isochoric process: ∆S =∫ T
=∫
T
 Chapter 3 – Second law of thermodynamics

δ QTN
QTN
b. Isothermal process: ∆S =∫ T = T
QT V2 P1
Ideal gas expansion: ∆S= = nR ln = nR ln
T V1 P2
QT λ
Phase transfer ∆S= =
T T

Chemical reaction ΔS°reaction = ΣnpS°products – ΣnrS°reactants

 Chapter 3 – Second law of thermodynamics

S = k lnW
• States, S.
– The microscopic energy levels
available in a system.
• Microstates, W.
– The particular way in which particles are distributed
amongst the states. Number of microstates = W.
• The Boltzmann constant, k = 1.38x10-23 J/K
– Effectively the gas constant per molecule = R/NA.

W2
∆S = S2 − S1 = k ln
W1
 Chapter 3 – Second law of thermodynamics

=So limS
= T 0
T →0

3rd law of thermodynamics: The entropy of a perfect crystal

at 0 K is zero.
Because:
- all molecular motion stops
- all particles are in their place

∆S = ST – So = ST
Ví duï: So298 chính laø entropy tuyeät ñoái cuûa moät
chaát ôû 1 atm, 298K (ñieàu kieän chuaån ).

Xét quá trình biến đổi của 1 chất như sau:

raén 1 raén 2
0(K) 
∆S1
→ Tchuyeån pha 
∆S3
→ Tnoùng chaûy
So ∆S2 ∆S4
loûng hôi
Tnoùng chaûy 
∆S5
→ Thoùa hôi 
∆S7
→ T(K)
∆S4 ∆S6 ST
7 7 T2
Tính ST dT λ
ST = So + ∑ ∆Si = ∑ ∆Si = ∑ ∫ Cp +∑
=i 1 =i 1 T
T T
1
2/14/2021 607010 - Chương 2 62
Ví duï:
Tính bieán thieân entropy cuûa cuûa quaù trình
ñoâng ñaëc benzen döôùi aùp suaát 1 atm trong
caùc tröôøng hôïp sau:
a) Quaù trình ñoâng ñaëc thuaän nghòch ôû 5oC vôùi
nhieät ñoâng ñaëc laø λññ = – 2370 cal/mol
b) Quaù trình ñoâng ñaëc baát thuaän nghòch ôû –
5oC .
Bieát nhieät dung cuûa benzen loûng vaø benzen raén
laàn löôït laø 30,3 vaø 29,3 cal/mol.K

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