SECOND LAW OF THERMODYNAMICS

Identifies the direction of a process. (e.g.: Heat can only spontaneously transfer from a hot
object to a cold object, not vice versa)

Used to determine the Quality of energy. (e.g.: A high-temperature energy source has a
higher quality since it is easier to extract energy from it to deliver useable work.)

Used to exclude the possibility of constructing 100% efficient heat engine and perpetual-
motion machines. (violates the Kevin-Planck and the Clausius statements of the second
law)

Used to introduce concepts of reversible processes and irreversibilities.

Determines the theoretical performance limits of engineering

systems. (e.g.: A Carnot engine is theoretically the most efficient heat
engine; its performance can be used as a standard for other practical
engines)

Thermal Reservoir

A hypothetical body with a very large thermal capacity (relative to the

system beig examined) to/from which heat can be transferred without
changing its temperature. E.g. the ocean, atmosphere, large lakes.

Kelvin-Planck Statement

It is impossible for any device that operates on a cycle to receive heat from a single reservoir and
produce net work.

This statement is without proof, however it has not been

violated yet.

Consequently, it is impossible to built a heat engine that is

100%.

A heat engine has to reject some energy into a lower

temperature sink in order to complete the cycle.

TH>TL in order to operate the engine. Therefore, the higher the temperature, TH, the higher
the quality of the energy source and more work is produced.

Clausius Statement
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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.

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 Similar to the K-P Statement, it is a negative statement and has no proof, it is based on
experimental observations and has yet to be violated.

Heat can not be transferred from low temperature to higher temperature unless external
work is supplied.

Equivalence of the Two Statements

It can be shown that the violation of one statement leads to a violation of the other statement, i.e.
they are equivalent

Refrigerator and Heat Pumps

The refrigeration cycle is a common method for transferring heat from a low temperature to
a high temperature.

The above figure shows the objectives of

refrigerators and heat pumps. The purpose of a
refrigerator is the removal of heat, called the cooling
load, from a low-temperature medium. The purpose
of a heat pump is the transfer of heat to a high-
temperature medium, called the heating load. When
we are interested in the heat energy removed from a
low-temperature space, the device is called a
refrigerator. When we are interested in the heat
energy supplied to the high-temperature space, the
device is called a heat pump. In general, the term heat
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pump is used to describe the cycle as heat energy is

removed from the low-temperature space and
rejected to the high-temperature space.

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 2 2
[COP]ref =
= = 1 2
(1)

1 1
[COP]HP =
= = 1 2
(2)

From Equations 1 and 2

[COP]HP = [COP]ref + 1

Reversible Processes and Irreversibilities

A reversible process is one that can be executed in the reverse direction with no net change
in the system or the surroundings.

At the end of a forwards and backwards reversible process, both system and the
surroundings are returned to their initial states.

No real processes are reversible.

However, reversible processes are theoretically the most efficient processes.

All real processes are irreversible due to irreversibilities. Hence, real processes are less
efficient than reversible processes.

Common Sources of Irreversibility:

Friction
Sudden Expansion and compression
Heat Transfer between bodies with a finite temperature difference.
A quasi-equilibrium process, e.g. very slow, frictionless expansion or compression is a reversible
process.
A work-producing device which employs quasi-equlibrium or reversible processes produces the
maximum amount of work theoretically possible.

A work-consuming device which employs quasi-equilibrium or reversible processes requires the

minimum amount of work theoretically possible.

One of the most common idealized cycles that employs all reversible processes is called the Carnot
Cycle proposed in 1824 by Sadi Carnot.
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Carnots Principle

No heat engine can be more efficient than a reversible heat engine when both engines work
between the same pair of temperature TH and TC.

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Carnot cycle

Four stage reversible sequence consisting of

1. isothermal expansion at high temperature T2

Q1 = U2-U1+W1-2

2. adiabatic expansion

0 = U3-U2+W2-3

1 1
2 2

3. isothermal compression at low temperature T1

-Q2= U4-U3-W3-4

4. adiabatic compression

0 = U1-U4-W4-1
1
= 1- 1

Therefore, the efficiency of a Carnot cycle is given by,

1 2
=
= 1

2
=1
1

Spontaneous Process and Entropy

Spontaneous Process: A process occurs without outside intervention.

Entropy: In qualitative terms, entropy can be viewed as a measure of randomness or disorder of the
atoms or molecules in a substance.

Introduce the Increase of Entropy Principle which states that

the entropy for an isolated system (or a system plus its surroundings) is always
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increases or, at best, remains the same.

Entropy is a thermodynamic property; it can be viewed as a measure of disorder. i.e. More

disorganized a system the higher its entropy.
Q
Defined using Clausius inequality
T 0
rev
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where Q is the differential heat transfer & T is the absolute temperature at the boundary where
the heat transfer occurs

..

Entropy Generation Example

Qn. Show that heat can not be transferred from the low-temperature sink to the high-temperature
source based on the increase of entropy principle.

S(source) = 2000/800 = 2.5 (kJ/K)

S(sink) = -2000/500 = -4 (kJ/K)

Sgen= S(source)+ S(sink) = -1.5(kJ/K) < 0

It is impossible based on the entropy increase principle

Sgen0, therefore, the heat cannot transfer from low-temp. to high-

temp. without external work input

If the process is reversed, 2000 kJ of heat is transferred from the source to the sink, S gen=1.5
(kJ/K) > 0, and the process can occur according to the second law

If the sink temperature is increased to 700 K, how about the entropy generation? DS(source) =
-2000/800 = -2.5(kJ/K)

S(sink) = 2000/700 = 2.86 (kJ/K)

Sgen= S(source)+ S(sink) = 0.36 (kJ/K) < 1.5 (kJ/K)

Entropy generation is less than when the sink temperature is 500 K, less irreversibility. Heat transfer
between objects having large temperature difference generates higher degree of irreversibilities

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