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REV LECTURE
Second Law of
Thermodynamics

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 Introduction

• Second law of thermodynamics

• Entropy (S)
• Heat engines

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 The Second Law of Thermodynamics --
Introduction
• The first law of thermodynamics states that energy is
conserved.
• Scientists in the 19th century noticed that many
processes that did not violate the law of conservation
of energy, never-the-less did not occur naturally.
• They formulated the second law of thermodynamics.
• Statement of the second law of thermodynamics by
R.J.E. Clausius (1822 – 1888)
Heat flows naturally from a hot object to a cold
object; heat will not flow spontaneously from a
cold object to a hot object. 4
 20-2 Heat Engines

• Circa 1700, the steam engine, the first practical device

to get work from thermal energy was developed.
• The basic idea behind any engine is that mechanical
energy can be obtained from thermal energy only
when heat is allowed to flow from a high temperature
to a low temperature.
• In that process, heat can be transformed to mechanical
work.

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 Heat Engines

• By conservation of energy:
|QH| = |W| + |QL|.
• The high and low temperatures TH and TL are called
the operating temperatures of the engine.
• We will considering only engines that run in a
repeating cycle, that is, the system returns repeatedly
to its starting point, and thus can run continuously.
• Absolute value signs are used because we are worried
only about the magnitudes.
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Steam Engine

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 Internal Combustion Engine

• The material that is heated and cooled, steam in the

case of a steam engine, is called the working
substance.
• In the steam engine, the high temperature is obtained
by burning one of the four fuels mentioned.
• In an internal combustion engine, the high
temperature is achieved by burning the gasoline-air
mixture in the cylinder itself (ignited by the spark
plug).

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 Efficiency

• The efficiency of any heat engine, e, can be defined

as the ratio of the work it does, |W|, to the heat input
at the high temperature, |QH|:

|W| |
e= Q |
H

• Using conservation of energy this works out to:

|QL| |
e =1 -
QH|
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 Example 20-1

Car efficiency.
An automobile engine has an efficiency of 20 percent
and produces an average of 23,000 J of mechanical
work per second during operation. How much heat is
discharged from this engine per second?

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 Efficiency
• The lower we can make |QL| the more efficient the engine will
be.
• If |QL| could be reduced to zero we would have a 100 percent
efficient engine.
• Experience has shown however, that it impossible to reduce |QL|
to zero.
• That such a perfect engine, running continuously in a cycle (a
perpetual motion machine) is not possible is another way of
expressing the second law of thermodynamics.
No device is possible whose sole effect is to transform a given
amount of heat completely into work.
• This is the Kelvin-Planck statement of the second law of
thermodynamics
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20-3 Reversible and Irreversible Process;
the Carnot Engine
• In the early nineteenth century, the French scientist
N.L. Sadi Carnot (1796 – 1832) studied in detail the
process of transforming heat into mechanical energy.
• Goal to increase inefficiency.
• In 1824 Carnot invented, on paper, the Carnot engine.
This is the ideal engine.

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 Reversible and Irreversible
Processes
• The Carnot engine involves reversible processes.
• A reversible process is one carried out infinitely
slowly, so that the process can be considered as a
series of equilibrium states, and the whole process
could be done in reverse with no change in magnitude
of the work done or heat exchanged.
• Of course this cannot be done since it would take an
infinite time.
• All real processes are irreversible: they cannot be
done infinitely slowly, there can be turbulence in the
gas, friction will be present, and so on.
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 Carnot's Engine

• The Carnot engine makes use of a reversible cycle.

• This cycle is called the Carnot cycle and the working
substance is an ideal gas.

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Carnot Cycle

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Carnot Efficiency and the Second Law of
Thermodynamics

|QL| TL
eideal = 1 - =1-
|QH| TH

Carnot’s Theorem
All reversible engines operating between the same
two constant temperatures TH and TL have the same
efficiency. Any irreversible engine operating
between the same two temperatures will have an
efficiency less than this.
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 Example 20-2

Steam engine efficiency.

A steam engine operates between 500oC and 270oC.
What is the maximum possible efficiency of this
engine?

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 Example 20-3

A phony claim?
An engine manufacturer makes the following claims:
The heat input per second of the engine is 9.0 kJ at
475 K. The heat output per second is 4.0 kJ at 325 K.
Do you believe these claims?

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 20-4 Refrigerators, Air Conditioners, and
Heat Pumps
• The operating principle of refrigerators, air conditioners,
and heat pumps is just the reverse of the heat engine.
• By doing work |W|, heat is taken from a low-temperature
region, TL (inside the refrigerator), and a greater amount
of heat is exhausted at a high temperature, TH (into the
room).
• The work is usually done by a compressor motor that
compresses a fluid.
• A perfect refrigerator—one where no work is required
to take heat from the low-temperature region to the
high-temperature region—is not possible. 22
 Clausius

Restatement of Clausius statement of the second law

of thermodynamics

No device is possible whose sole effect is to

transfer heat from one system at one temperature
into a second system at a higher temperature.

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 Coefficient of Performance (CP)

The coefficient of performance for a refrigerator is

defined as the heat |QL| removed from the low-
temperature area (inside a refrigerator) divided by the
work |W| done to remove the heat.

|QL| [Refrigerator and air

CP = | conditioner]
W|

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 CP Ideal

Energy is conserved, so we can write:

|QH| = |QL| + |W|
Therefore: |W| = |QH| - |QL|

|QL| | |QL|
and CP = W| = |QH| - |QL|
TL
so CPideal = TH - TL

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 Coefficient of Performance (CP)
• The coefficient of performance for a heat pump
acting as a heater can heat a house in the winter by
taking heat |QL| from the outside at low temperature
and delivering heat |QH| to the warmer inside of the
house, by doing work |W|. Thus for a heat pump:
|QH| |W|
CP = [heat pump]

• Most heat pumps can run in reverse and perform as

an air conditioner.
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 Example 20-5

Heat pump.
A heat pump has a coefficient of performance of 3.0
and is rated to do work at 1500 W. (a) How much
heat can it ass to a room per second? (b) If the heat
pump were turned around to act as an air conditioner
in the summer, what would you expect its coefficient
of performance to be assuming all else stays the
same?

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 20-5 Entropy

• When you open a bottle of perfume you can smell the

aroma as the molecules leave the bottle and reach
your nose.
• Why don’t they spontaneously go back into the
bottle?
• It would not violate the first law of thermodynamics.
• There answer it they can do just that, but they most
probably will not.
• The explanation is entropy.

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 Definitions

Entropy is:
 a measure of the disorder of a system.
 a measure of the energy in a system or process
that is unavailable to do work. In a reversible
thermodynamic process, entropy is expressed as
the heat absorbed or emitted divided by the
absolute temperature.
 dS = dQ/T

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 Entropy

• The general statement of the quantity, S, entropy

was introduced by Clausius in the 1860s.
b b
∆ S = Sb – Sa =
∫ dS =
a
∫ dQ [reversible processes]
aT

• ∆ S is independent of the path between the two

points a and b. This tells us that the difference in
entropy between two equilibrium systems does not
depend on how you get from one state tot the other.
Thus, entropy is a state variable.
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 Example 20-8

Entropy changes in a free expansion.

Consider the adiabatic free expansion of n moles of
an ideal gas from volume V1 to volume V2, where V2 >
V1, as was discussed in Section 19-7, Fig. 19-13.
Calculate the change in entropy (a) of the gas (b) of
the surrounding environment. (c) Evaluate ∆ S for
1.00 mole, with V2 = V1.

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 Total Entropy
• For any reversible process:
∆ S = ∆ Ssyst + ∆ Senv = 0
• For irreversible processes:
∆ S = ∆ Ssyst + ∆ Senv > 0
• The second law: the entropy of an isolated system
never decreases. It either stays constant (reversible
process) or increases (irreversible process).
• Although the entropy in one part of the universe may
decrease in any process, the entropy of some other part
of the universe always increases by a greater amount,
so the total entropy always increases.

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 20-7 Order to Disorder

• The entropy of a system can be considered a measure

of the disorder of the system.
• Then the second law of thermodynamics can be stated
as;
Natural processes tend to move toward a state of
greater disorder.

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 The Second Law

The second law of thermodynamics can be stated

in several equivalent ways:
(a) Heat flows spontaneously from a hot object to a cold
one, but not the reverse.
(b) There cannot be a 100 percent efficient heat engine
—that is, one that can change a given amount of
heat completely into work.
(c) Natural processes tend to move toward a state of
greater disorder or greater entropy.

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