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Lecture 3

THE HEAT ENGINE, 2ND AND 3RD LAWS

OF THERMODYNAMICS
- Heat Engines and the Second Law of Thermodynamics.
- Reversible and Irreversible Processes.
- The Carnot Engine.
- Entropy.
- Entropy Changes in Irreversible Processes.
- Entropy on a Microscopic Scale.
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HEAT ENGINE
• A heat engine is a device that takes in energy
by heat and, operating in a cyclic process, expels
a fraction of that energy by means of work.
• A heat engine carries some working substance
through a cyclic process during which
• (1) the working substance absorbs energy by heat from
a high-temperature energy reservoir,
• (2) work is done by the engine,
• (3) energy is expelled by heat to a lower-temperature
reservoir.

Example of heat
engine cycling
process
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The Efficiency of a Heat Engine

Work _ done _ by _ the _ engine W'
The Efficiency of an Engine e  
Heat _ received_ from_ hot _ reservoir Q h
Engine operates in a cycle process, the change in internal energy is 0:
U  Q h  Qc  W  0
W '   W  Q h  Qc  Q h  Q'c
Work done by the
engine:

W ' Q h  Q 'c Q'c

e   1
Qh Qh Qh
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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?

Q'c 1.5  103

e  1  1 3
 25%
Qh 2  10
' 3 3 3
W'  Q h  Qc  (2  10 )  (1.5  10 )  0.5  10 J
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2ND LAW OF THERMODYNAMICS

The second law of thermodynamics comes in many equivalent forms!

Kelvin’s statement of the second law:

• It is impossible to build a cyclic machine that converts heat into work with 100% efficiency

Clausius statement of the second law:

• Heat cannot spontaneously flow from a cold (low temperature) body to a hot body.
• To make heat flow from a cold body to a hot body, there must be accompanying change
elsewhere (work has to be done to achieve this).

A combined (Kelvin and Clausius) statement of the second law:

• The entropy of a closed system will increase during any spontaneous change/process.
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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
1 Quasi–static 1 irreversible Quick (sudden) -
process process

2 2
reversible irreversible

V V
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QUASI-STATIC vs QUICK PROCES

P P
1 Quasi–static Quick (sudden) -
1 process
process

2 2
reversible irreversible

V V
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CARNOT ENGINE

Carnot's theorem, developed in 1824 by Nicolas Léonard Sadi Carnot, also

called Carnot's rule, is a principle that specifies limits on the maximum efficiency any 
heat engine can obtain.
Carnot's theorem states:
• All heat engines between two heat reservoirs are less efficient than a 
Carnot heat engine operating between the same reservoirs.
• Every Carnot heat engine between a pair of heat reservoirs is equally efficient,
regardless of the working substance employed or the operation details.
Tc
e max  eCarnot  1
Th
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CARNOT ENGINE CLAUSIUS’S INTEGRATION

Two reservoirs, Divide any reversible cycle into a
series of thin Carnot cycles, where
temperature Th, Tc P the isothermal processes are
Qj,
infinitesimally short:
e  e carnot Tj
Q'c T
1  1 c
Qh Th
Q'c T
  c
Qh Th Qi, Ti
Qc Q
 h V
Tc Th Qi   reversible cycle
Qh Q  T   irriversible cycle
 0
 c 0 i i 
Th Tc

Q   reversible cycle
 T  0  irriversible cycle
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Q   reversible cycle
ENTROPY  T  0  irriversible cycle
Consider a reversible cycle 1a2b1
P
1 The Clausius integration has sign “=“

a Q
 T 0
1a 2 b1
2
Q Q
 T  T 0

b 1a 2 2 b1
Q Q
V
 T    T
1a 2 2 b1
Definition: We define a Q Q
state variable S that the  T   T
1a 2 _ rever 1b 2 _ rever.
change in the entropy dS
is equal to the heat
received in a reversible Q
S   T
process divided by the 1 2 _ reversible
absolute temperature of Q rev.
the system dS 
T
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ENTROPY (Cont.) Q   reversible _ cycle

 T   irreversible _ cycle
 0

Consider an irreversible cycle Q

1a2: irreversible
2b1: reversible
 T
0
1a 2 b1 _ irrev.
The Clausius integration has sign “<“
Q Q
P  T   T 0
1 1a 2irrev. 2 b1 _ rev.
Q Q
a
 T    T
2 1a 2irr. 2 b1rev.
Q Q
b  T   T
1a 2 _ irr. 1b 2 _ rev.
V Q
 T  S
Q   reversible _ process 1 2 rev.
S   T   irreversible _ process Q
1 2  S  
1a 2 _ irr .
T
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ENTROPY State _ 2
Q rev.
• Entropy (S) is a state variable S  S2  S1  
State _ 1
T
P Entropy is a state variable
1 => the change in entropy during a
a process depends only on the endpoints
=> the change in entropy is
2 independent of the actual path
followed.
b Consequently, the entropy change for an
irreversible process can be determined by
V calculating the entropy change for a
reversible process that connects the same
S1a 2irrev.  S1b 2 rev.  S12 initial and final states.
Q
S12  
1a 2
T
Q
S12   T
1b 2
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The principle of Increase of Entropy

Q   reversible_ process
S   T   irreversible _ process
Q rev 1 2 
S12  S may be >0; <0 or =0
12
T

 irreversible _ process
For an isolated system dQ=0 => S12  0
 reversible _ process
DS > 0, for irreversible processes
DS = 0, for reversible processes
DS < 0, the process is impossible
The entropy of the Universe increases in all real processes.
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The Change in Entropy of an Ideal Gas

Q rev
dS 
T P2 V2
dU  Q  PdV S  nC v ln  nC p ln
P1 V1
Q  dU  PdV
dU  PdV i nRdT nR
dS    dV
T 2 T V
T2 V
i nRdT 2 nR
S    dV
T
2 T V
V
1 1

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

V2
2 nRT ln
Isothermal Process dQ Q12 V1 V2
S      nR ln
1
T T T V1

2
Isovolumetric Process nC v dT T2
S    nC v ln
1
T T1

2
Isobaric Process nC p dT T2
S    nC p ln
1
T T1

Adiabatic Process S  0 S  const Iso_entropy Process

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Exercise 1. 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.
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Solution for exerc. 1:

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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
S  
1
T
T  Tmelt  Const
Q mLf
S  
T Tmel
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Exercise 2.
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Exercise 2.
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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).
• The microscopic description of a system is the complete description of each particle in
this system. For example, the microscopic description of the gas would be the list of
the states of each molecule: position and velocity in this problem.
• The macroscopic description, which is in terms of a few properties (p, T , V for
example), is thus far more accessible and useable for engineering applications,
although it is restricted to equilibrium states.
• For a given macroscopic system, there are many microscopic states.
• To address the description of entropy on a microscopic level, we need to state some
results concerning microscopic systems.
• The first is that the average of the function over all of the microstates should have an
extensive behavior, in other words the microscopic description of the entropy of a
system C, composed of parts A and B is given by S=SA+SB. The second is that
entropy should increase with randomness and should be largest for a given energy
when all the quantum states are equiprobable. S is defined as:

S=klnW

k – Boltzmann constant; W – number of microscopic states of a system.

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The 3rd law of thermodynamics

• The Third Law of Thermodynamics is concerned 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

https://www.youtube.com/watch?v=mGDJO2M7RBg
https://www.youtube.com/watch?v=YoekFxOizj4