2 nd

& 3
Law ofrd

thermodynamic
Dr. Tran Thi Thu Hanh
 Out line
Lecture Textbook
1.  Kelvin–Planck statement.
c. 22
Heat engine.
2. Clausius statement.
c. 22
Heat pump & Refrigerator.
3. Entropy. c. 22

HCMUT – Dr. HanhTTT

 Thermodynamic concepts

Two important thermodynamic concepts:

Equilibrium, and Quasi-static processes

Equilibrium: A condition in which the macroscopic

variables (for example: T, p) are well defined throughout
the system and do not change in time.

Quasi-static process: A thermodynamic process in

which the external variables (e.g., V) change slowly enough
that the system is always very close to equilibrium.

The thermodynamic processes that we will be considering (e.g., in

heat engines) are all quasi-static processes.

HCMUT – Dr. HanhTTT

 REVERSIBLE – IRREVERSIBLE PROCESS
In a reversible process, the system can be returned to its initial
conditions along the same path on a PV diagram, and every point
along this path is an equilibrium state.
A process that does not satisfy these requirements is irreversible.

P P
Quasi–static
1 process 1 irreversible
Quick (sudden)
2 2 - process
reversible irreversible

V V

HCMUT – Dr. HanhTTT

 QUASI-STATIC vs QUICK PROCES

P P
1 Quasi– Quick (sudden)
1
static - process
process2 2
reversible irreversible

V V

HCMUT – Dr. HanhTTT

 1.1. Kelvin–Planck statement.
!  Can it happen?
! Hot coffee cools down, and coffee spins around.

HCMUT – Dr. HanhTTT

 1.1. Kelvin–Planck statement.
!  Can it happen?
! Hot coffee cools down, and coffee spins around.
! E conserved: U changes to W.
! But! It cannot happen.

HCMUT – Dr. HanhTTT

 1.1. Kelvin–Planck statement.
!  Can it happen?
! Hot coffee cools down, and coffee spins around.
! E conserved: U changes to W.
! But! It cannot happen.

!  2nd law: It is impossible to construct a heat engine

that, operating in a cycle, produces no other effect
than the absorption of energy from a reservoir and
the performance of an equal amount of work.

HCMUT – Dr. HanhTTT

 1.2. Heat engine
!  A heat engine is a device that converts
internal energy to other useful forms, such as
electrical or mechanical energy.

!  A heat engine carries some working

substance through a cyclical process.

!  Reservoir is a large body with temperature

fixed.
extract heat do work
dump heat

HCMUT – Dr. HanhTTT https://www.youtube.com/watch?v=73txXT21aZU

 1.2. Heat engine
!  Since it is a cyclical process,
dU = 0
" Qnet = Weng

!  The work done by the engine equals the net

energy absorbed by the engine. | |
!  The work done by the engine is equals the area
enclosed by the curve of the cycle on the PV
diagram.

!  The work is done by the engine if the cycle is The engine does work!
clockwise and done on the engine if counter-
clockwise.

HCMUT – Dr. HanhTTT

 1.3. Thermal Utility of a Heat Engine
Performance is measured by (desired outcome)/(cost)

!  Thermal efficiency of an engine is defined as

the ratio of the work done by the engine to the
energy absorbed at the higher temperature:

W Qh − Qc Qc
e= = = 1−
Qh Qh Qh

! e = 1 (100% efficiency) if Qc = 0 (No energy

expelled to cold reservoir)!
Kelvin states: Qc ≠ 0; e ≠ 100%

HCMUT – Dr. HanhTTT

 Example
An engine transfers 2.00 x 103 J of energy from a hot
reservoir during a cycle and transfers 1.50 x 103 J as exhaust
to a cold reservoir.
(A) Find the efficiency of the engine.
(B) How much work does this engine do in one cycle?

HCMUT – Dr. HanhTTT

 1.4. The Carnot Cycle for heat engine
!  All steps are reversible - no thermal
contact between systems at different
temperatures.

!  No real heat engine operating between

two energy reservoirs can be more
efficient than a Carnot engine operating
between the same two reservoirs.
PV diagram for the Carnot cycle (1824):
The net work done Weng = the net
energy transferred into the Carnot
!  Carnot efficient (maximum efficient): engine in one cycle, |Qh|- |Qc| . Note
that Eint = 0 for the cycle.
Tc
eCarnot = 1−
Th

HCMUT – Dr. HanhTTT

 1.4. The Carnot Cycle
* Using for ideal gas!

HCMUT – Dr. HanhTTT

 Quiz1
!  Show that the efficiency of a heat engine operating in a
Carnot cycle using an ideal gas is given by Equation
above?

1 Qh adiabats

2
p Th isotherms
4

3 TC
QC
V
Vb Va V c Vd

HCMUT – Dr. HanhTTT

 Quiz1

Qc Vb
ε = 1− Isothermal Qh = NkTh ⋅ ℓn
Qh processes: Vc
Va
For all engines −Qc = NkTc ⋅ ℓn
Vd

Adiabatic processes:
Vb Va
=
ThαVb = TcαVa Vc Vd
T αV = constant
ThαVc = TcαVd Vb Va
ln = ln
Vc Vd
Qc Tc
Therefore: = For Carnot cycle
Qh Th

Tc
ε = 1− Carnot efficiency
Th
HCMUT – Dr. HanhTTT
 Quiz2
!  The highest theoretical efficiency of a certain engine is
30.0%. If this engine uses the atmosphere, which has a
temperature of 300 K, as its cold reservoir, what is the
temperature of its hot reservoir?

HCMUT – Dr. HanhTTT

 2.1. Clausius statement
!  Can it happen?
! Cool part of the stirring coffee spoon suddenly cools, and
the other end, in hot coffee, is hotter.

HCMUT – Dr. HanhTTT

 2.1. Clausius statement
!  Can it happen?
! Cool part of the stirring coffee spoon suddenly cools, and
the other end, in hot coffee, is hotter.
! Temperature transfer from cold to hot part, the 1st law
remains right!
! But! It cannot happen.

HCMUT – Dr. HanhTTT

 2.1. Clausius statement
!  Can it happen?
! Cool part of the stirring coffee spoon suddenly cools, and
the other end, in hot coffee, is hotter.
! Temperature transfer from cold to hot part, the 1st law
remains right!
! But! It cannot happen.

!  2nd law: It is impossible to construct a cyclical machine

whose sole effect is to transfer energy continuously by heat
from one object to another object at a higher temperature
without the input of work.
! Equivalently, heat does not spontaneously go from a cold to
a hot object

HCMUT – Dr. HanhTTT

 2.2. Heat Pumps and Refrigerators
!  the engine takes in energy Qc from a cold
reservoir and expels energy Qh to a hot
reservoir.

!  work is done on the engine.

Schematic diagram
of a heat pump

HCMUT – Dr. HanhTTT

 2.3. Thermal Utility of a Heat pump
!  Coefficient of performance for a
refrigerator is:
Qc Qc
C.O.P.(cooling mod e) = =
W Qh − Qc
!  Coefficient of performance for a heat
pump is:

Qh Qh
C.O.P.(heating mod e) = =
W Qh − Qc
!  Energy does not transfer spontaneously Clausius states: C.O.P. ≠ ∞
by heat from a cold object to a hot object!

HCMUT – Dr. HanhTTT

 2.4. The Carnot Cycle for heat pump

!  All steps are reversible - no thermal contact

between systems at different temperatures. P

!  No real refrigerators operating between two

energy reservoirs can be more efficient
than a Carnot refrigerator operating
between the same two reservoirs.

!  Efficient:

Tc Th
C.O.P.C.C. = C.O.P.C. H . =
Th − Tc Th − Tc

HCMUT – Dr. HanhTTT https://www.youtube.com/watch?v=Wq2_bnhwDfQ

 Helpful Hints
!  Quickly sketch the process. Define Qh and Qc and Wby (or
Won) as positive and show directions of flow.
!  Determine which Q is given.
!  Write the First Law of Thermodynamics (FLT). There are
only 3 configurations of Carnot engines:

Th Th Th Qleak=Qh

Qh Qh Qh
Wby Won Won
QC QC QC

TC TC Qleak=QC TC

Engine (Qh given) Refrigerator (QC given) Heat Pump (Qh or QC given)

FLT: Wby = Qh - QC Won = Qh - Qc Won = Qh - QC

Wby = Qh(1- TC/Th) Won = QC(Th/TC - 1) Won = Qh(1- TC/Th)
HCMUT – Dr. HanhTTT
 Example-1

There is a 70 W heat leak from a room at temperature 22 °C into

an ideal refrigerator. How much electrical power is needed to
keep the refrigerator at -10 °C?
Hint: For the refrigerator, Qc must exactly compensate the heat
leak. So Qc = 70 J for each second of operation. (Watt = J/s)
Assume Qc/Qh = Tc/Th (Carnot)
 Example-2

Suppose that the heat flow out of your 20°C home in the winter is 7
kW. If the temperature outside is -15° C, how much power P would an
ideal heat pump require to keep your inside temperature at 20° C?
Heat Leak
Home, 293K
“ideal” implies
Hot reservoir at Th
Qc/Qh = Tc/Th (Carnot) Qh

Heat Pump: Won

QC Outdoors, 258K
Cold reservoir at TC
 Quiz-1
Consider a hypothetical device that takes 1000 J of heat from a hot reservoir at
300K, ejects 200 J of heat to a cold reservoir at 100K, and produces 800 J of
work.
What is the efficiency of this engine ?
1. 80 %
2. 20%
3. 25%
 Quiz-2

Consider a hypothetical device that takes 1000 J of heat from a hot reservoir at
300K, ejects 200 J of heat to a cold reservoir at 100K, and produces 800 J of
work.
Does this device violate the second law of thermodynamics ?
1. Yes
2. No
 Problem
An electric power plant that would make use of the tem-
perature gradient in the ocean has been proposed. The system
is to operate between 20.0°C (surface water temperature) and
5.00°C (water temperature at a depth of about 1 km). (a)
What is the maximum efficiency of such a system? (b) If the
useful power output of the plant is 75.0 MW, how much
energy is taken in from the warm reservoir per hour?

HCMUT – Dr. HanhTTT

 3.1. New limitation!
The first law of thermodynamics is the conservation of
Energy.
dQ = dU + PdV
This is a statement about the change of energy which does not
upset the fixed quantity of energy.
Based on a recognition that heat is not energy (rather a
flow of energy)

But…….
Hot objects cool Why?-- there seems to be a
Cool objects do not “hot” direction of energy flow
independent of the quantity of
energy

HCMUT – Dr. HanhTTT

 Why?
Nature seems to be irreversible.
All real thermal processes are irreversible and efficiencies
less than estimated for ideal (Carnot) engines.

All the “laws” of physics we have talked

about are reversible.

Newton’s equations of motion.

Conservation of energy
Conservation of momentum
Conservation of angular momentum

New limitation!

HCMUT – Dr. HanhTTT

 3.2. Entropy

A new state variable to defines reversibility

p pressure
V volume familiar quantities
T temperature

Now… S entropy ΔS = Sf - Si

2nd law: The total entropy of an isolated system

cannot decrease. In a reversible process, it
remains the same. In an irreversible process it
increases.
A combined (Kelvin and Clausius) statement of the second law!

HCMUT – Dr. HanhTTT

 Definition
!  Entropy S is a state variable; State _ 2
δQ rev.
for reversible process: ΔS = S2 − S1 = ∫
P State _ 1
T
1
a ⇒ the change in entropy during a
process depends only on the
2
endpoints
b ⇒ the change in entropy is
independent of the actual path
V followed.
ΔS1a 2irrev. = ΔS1b 2 rev. = ΔS12
⇒ the entropy change for an irreversible
δQ
ΔS12 > ∫ process can be determined by
T
1a 2 calculating the entropy change for a
δQ
ΔS12 = ∫ T reversible process that connects the
1b 2 same initial and final states.

HCMUT – Dr. HanhTTT

 Explanation!
The variable entropy S is used to represent the level of uncertainty, choice, probability, or missing information in the system!

W=2 So if left naturally,

W’=6 particles will disperse
# W’ > W throughout the box!

1.  Entropy is a measure of disorder

2.  Statistical means: S = kbln(W)
3.  A system tends toward higher entropy (more disorder), because that
is the most probable situation

HCMUT – Dr. HanhTTT

 The principle of Increase of Entropy
δQ rev δQ ⎫⎪ = reversible _ process
ΔS12 =∫ ΔS ≥ ∫ ⎬
12
T 1− 2
T ⎪⎭ > irreversible _ process
ΔS may be > 0; < 0 or =0

For an isolated system: > irreversible _ process

dQ=0 => ΔS12 ≥ 0}
= reversible _ process

ΔS > 0, for irreversible processes

ΔS = 0, for reversible processes
ΔS < 0, the process is impossible

The entropy of the Universe increases in all real processes.

 The Change in Entropy of an Ideal Gas
δQ rev
dS =
T P2 V2
dU = δQ − PdV ΔS = nC v ln + nC p ln
P1 V1
δQ = dU + PdV
dU + PdV i nRdT nR
dS = = + dV
T 2 T V
T2 V
i nRdT 2 nR
ΔS = ∫ + ∫ dV
T
2 T V
V
1 1

T2 V i
= nC v ln + nR ln 2 U= nRT; PV = nRT
T1 V1 2
P2 V2 V i
= nC v ln + nR ln 2 Cv = R
P1V1 V1 2
i+2
P2 V2 V2 Cp = R = Cv + R
= nC v ln + nC v ln + nR ln 2
P1 V1 V1
 The Change in Entropy of an Ideal Gas

V2
2 nRT ln
dQ Q12 V1 V2
Isothermal Process ΔS = ∫ = = = nR ln
1
T T T V1

2
Isovolumetric Process nC v dT T
ΔS = ∫ = nC v ln 2
1
T T1

2
nC p dT T2
Isobaric Process ΔS = ∫ = nC p ln
1
T T1

Adiabatic Process ΔS = 0 S = const Iso_entropy Process

 Example: Free expansion of a gas
A free expansion occurs when a valve is opened
allowing a gas to expand into a bigger container.

vacuum

System is isolated and no heat is transferred

Such an expansion is?

1.  Reversible, because the gas does no work and

hence loses no energy?

2  Reversible, because there is no heat flow from the outside.

3  Irreversible, because the gas won’t spontaneously go

back into the smaller volume.
 Example: Free expansion of a gas
A free expansion occurs when a valve is opened
allowing a gas to expand into a bigger container.

vacuum

System is isolated and no heat is transferred

Such an expansion is:

1.  Reversible, because the gas does no work and

hence loses no energy?

2  Reversible, because there is no heat flow from the outside.

3  Irreversible, because the gas won’t spontaneously go

back into the smaller volume.
 Example: Free Expansion

In the free expansion process;

Calculate ΔS by reversible process (e.g. isothermal)

 Example: Free Expansion

In the free expansion process;

ΔW = 0 expanding into p = 0
Q=0 thermally insulated
ΔU = 0 by First Law but U =U(T)
ΔT = 0

Calculate ΔS by reversible process (e.g. isothermal)

Qr Vf
ΔS = = nR ln > 0
T Vi
https://www.youtube.com/watch?v=mGDJO2M7RBg
 Example: Change in Entropy: Melting
A solid that has a latent heat of fusion Lf melts at a temperature Tm.
Calculate the change in entropy of this substance when a mass m of
the substance melts?
 Example: Change in Entropy: Melting
A solid that has a latent heat of fusion Lf melts at a temperature Tm.
Calculate the change in entropy of this substance when a mass m of
the substance melts?
2
dQ
ΔS = ∫
1
T
T = Tmelt = Const
Q mLf
ΔS = =
T Tmel
Apply: Calculate the change of entropy
when melting 30g of ice to water?
 Example: Change in Entropy: Heating
Determine the value of the change of S (delta S) while reversibly heating
5 moles of an ideal gas from 25 °C to 73 °C at constant volume?
 3.3. Entropy on a microscopic scale
•  In Boltzmann's definition, entropy is a measure of the number of
possible microscopic states (or microstates) of a system
in thermodynamic equilibrium, consistent with its macroscopic
thermodynamic properties (or macrostate).

•  For a macroscopic system, there are many microscopic states.

•  Entropy should increase with randomness and should be largest for a

given energy when all the quantum states are equiprobable.

S=klnW
k – Boltzmann constant; W – number of microscopic states of a system.
 The 3rd law of thermodynamics
•  Concerning with the limiting behavior of systems as the
temperature approaches absolute zero

•  The 3rd law states: The entropy of a perfect monatomic crystal

is zero when the temperature of the crystal is equal to
absolute zero (0 K)

https://www.youtube.com/watch?v=kuGmsnzjbpE
National University of Hochiminh city
Hochiminh University of Technology