Chapter 15

The Laws of Thermodynamics

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 Contents of Chapter 15

• The First Law of Thermodynamics

• Thermodynamic Processes and the First Law
• Human Metabolism and the First Law
• The Second Law of Thermodynamics—Introduction
• Heat Engines
• Refrigerators, Air Conditioners, and Heat Pumps

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 Contents of Chapter 15

• Entropy and the Second Law of Thermodynamics

• Order to Disorder
• Unavailability of Energy; Heat Death
• Statistical Interpretation of Entropy and the Second
Law
• Thermal Pollution, Global Warming, and Energy
Resources

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 15-1 The First Law of Thermodynamics

The change in internal energy of a closed system will be

equal to the energy added to the system minus the work
done by the system on its surroundings.
(15-1)

This is the law of conservation of energy, written in a

form useful to systems involving heat transfer.

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 15-2 Thermodynamic Processes and the
First Law

An isothermal process is one

where the temperature does
not change.

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 15-2 Thermodynamic Processes and the
First Law

In order for an isothermal process to take place, we

assume the system is in contact with a heat reservoir.
In general, we assume that the system remains in
equilibrium throughout all processes.

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 15-2 Thermodynamic Processes and the
First Law

An adiabatic process is one where there is no heat flow

into or out of the system.

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 15-2 Thermodynamic Processes and the
First Law

An isobaric process (a) occurs at constant pressure; an

isovolumetric one (b) at constant volume.

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 15-2 Thermodynamic Processes and the
First Law

If the pressure is constant, the work done is the pressure

multiplied by the change in volume:
(15-3)

In an isometric process, the volume does not change, so

the work done is zero.

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 15-2 Thermodynamic Processes and the
First Law

For processes where the pressure varies, the work done

is the area under the P-V curve.

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 15-2 Thermodynamic Processes and the
First Law

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 15-3 Human Metabolism and the First Law

If we apply the first law of thermodynamics to the

human body:
(15-1)

we know that the body can do work. If the internal

energy is not to drop, there must be energy coming in. It
isn’t in the form of heat; the body loses heat rather than
absorbing it. Rather, it is the chemical potential energy
stored in foods.

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 15-3 Human Metabolism and the First Law

The metabolic rate is the rate at which internal energy is

transformed in the body.

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 15-4 The Second Law of
Thermodynamics – Introduction

The absence of the process illustrated above indicates

that conservation of energy is not the whole story. If it
were, movies run backwards would look perfectly normal
to us!
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 15-4 The Second Law of
Thermodynamics – Introduction

The second law of thermodynamics is a statement about

which processes occur and which do not. There are many
ways to state the second law; here is one:

Heat can flow spontaneously from a hot object to a cold

object; it will not flow spontaneously from a cold object
to a hot object.

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 15-5 Heat Engines

It is easy to produce thermal energy using work, but how

does one produce work using thermal energy?
This is a heat engine;
mechanical energy can
be obtained from thermal
energy only when heat
can flow from a higher
temperature to a lower
temperature.

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 15-5 Heat Engines

We will discuss only engines that run in a repeating

cycle; the change in internal energy over a cycle is zero,
as the system returns to its initial state.
The high temperature reservoir transfers an amount of
heat QH to the engine, where part of it is transformed
into work W and the rest, QL, is exhausted to the lower
temperature reservoir. Note that all three of these
quantities are positive.

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 15-5 Heat Engines

A steam engine is one

type of heat engine.

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 15-5 Heat Engines

The internal combustion engine is a type of heat engine

as well.

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 15-5 Heat Engines

Why does a heat engine need a temperature difference?

Otherwise the work done on the system in one part of the
cycle will be equal to the work done by the system in
another part, and the net work will be zero.

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 15-5 Heat Engines

The efficiency of the heat engine is the ratio of the work

done to the heat input:
(15-4a)

Using conservation of energy to eliminate W, we find:

(15-4b)

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 15-5 Heat Engines

The Carnot engine was created to examine the efficiency of a

heat engine. It is idealized, as it has no friction. Each leg of
its cycle is reversible.
The Carnot cycle consists of:
• Isothermal expansion
• Adiabatic expansion
• Isothermal compression
• Adiabatic compression
An example is on the next slide.
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 15-5 Heat Engines

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 15-5 Heat Engines

For an ideal reversible engine, the efficiency can be

written in terms of the temperature:

(15-5)

From this we see that 100% efficiency can be achieved

only if the cold reservoir is at absolute zero, which is
impossible.
Real engines have some frictional losses; the best achieve
60-80% of the Carnot value of efficiency.
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 15-6 Refrigerators, Air Conditioners, and
Heat Pumps

These appliances can be thought of as heat engines

operating in reverse.
By doing work, heat is
extracted from the cold
reservoir and exhausted
to the hot reservoir.

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 15-6 Refrigerators, Air Conditioners, and
Heat Pumps

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 15-6 Refrigerators, Air Conditioners, and
Heat Pumps

Refrigerator performance is measured by the coefficient

of performance (COP):
(15-6a)

Substituting:

(15-6b)

(15-6c)

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 15-6 Refrigerators, Air Conditioners, and
Heat Pumps

A heat pump can heat a house in the winter:

(15-7)

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 15-7 Entropy and the Second Law of
Thermodynamics

Definition of the change in entropy S when an amount of

heat Q is added:

(15-8)

Another statement of the second law of thermodynamics:

The total entropy of an isolated system never decreases.

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 15-8 Order to Disorder

Entropy is a measure of the disorder of a system.

This gives us yet another statement of the second law:
Natural processes tend to move toward a state of
greater disorder.
Example: If you put milk and sugar in your coffee and
stir it, you wind up with coffee that is uniformly milky
and sweet. No amount of stirring will get the milk and
sugar to come back out of solution.

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 15-8 Order to Disorder

Another example: when a tornado hits a building, there

is major damage. You never see a tornado approach
a pile of rubble and leave a building behind when
it passes.
Thermal equilibrium is a similar process—the uniform
final state has more disorder than the separate
temperatures in the initial state.

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 15-8 Order to Disorder

Growth of an individual, and evolution of a species, are

both processes of increasing order. Do they violate the
second law of thermodynamics?
No! These are not isolated systems. Energy comes into
them in the form of food, sunlight, and air, and energy
also leaves them.
The second law of thermodynamics is the one that defines
the arrow of time—processes will occur that are not
reversible, and movies that run backward will look silly.

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 15-9 Unavailability of Energy; Heat Death

Another consequence of the second law:

In any natural process, some energy becomes
unavailable to do useful work.
If we look at the universe as a whole, it seems inevitable
that, as more and more energy is converted to
unavailable forms, the ability to do work anywhere
will gradually vanish. This is called the heat death of
the universe.

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 15-10 Statistical Interpretation of Entropy
and the Second Law

A macrostate of a system is specified by giving its

macroscopic properties—temperature, pressure,
and so on.
A microstate of a system describes the position and
velocity of every particle.
For every macrostate, there are one or more microstates.

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 15-10 Statistical Interpretation of Entropy
and the Second Law

A simple example: tossing four coins. The macrostates

describe how many heads and tails there are; the
microstates list the different ways of achieving that
macrostate.

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 15-10 Statistical Interpretation of Entropy
and the Second Law

We assume that each microstate is equally probable; the

probability of each macrostate then depends on how
many microstates are in it.
The number of microstates quickly becomes very large if
we have even 100 coins instead of four; the table on the
next slide lists some macrostates, how many microstates
they have, and the relative probability that each
macrostate will occur. Note that the probability of
getting fewer than 20 heads or tails is extremely small.

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 15-10 Statistical Interpretation of Entropy
and the Second Law

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 15-10 Statistical Interpretation of Entropy
and the Second Law

Now we can say that the second law does not forbid
certain processes; all microstates are equally likely.
However, some of them have an extraordinarily low
probability of occurring—a lake freezing on a hot
summer day, broken crockery re-assembling itself;
all the air in a room moving into a single corner.
Remember how low some probabilities got just in going
from four coins to 100—if we are dealing with many
moles of material, they can become so rare as to be
effectively impossible.
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 15-11 Thermal Pollution, Global Warming,
and Energy Resources

The generation of electricity often involves a form of

heat engine, whether it is powered by biomass (a) or
solar power (b). Cooling towers (c) are a feature of many
power plants.

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 15-11 Thermal Pollution, Global Warming,
and Energy Resources

The heat output of any

heat engine, QL, is
referred to as thermal
pollution, as it must be
absorbed by the
environment.

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 15-11 Thermal Pollution, Global Warming,
and Energy Resources

Air pollution is emitted by power plants, industries, and

consumers. In addition, most forms of combustion result
in a buildup of CO2 in the atmosphere, contributing to
global warming. This can be minimized through careful
choices of fuels and processes.
The thermal pollution, however, is a consequence of the
second law, and is unavoidable; it can be reduced only
by reducing the amount of energy we use.

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 15-11 Thermal Pollution, Global Warming,
and Energy Resources

Problem solving in thermodynamics:

1. Define what is part of the system and what is part of
the surroundings.
2. Be careful of the signs for work and heat when using
the first law of thermodynamics.
3. Be careful about units; be sure that you are using the
same ones throughout the problem.
4. Express temperatures in kelvins.

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 15-11 Thermal Pollution, Global Warming,
and Energy Resources

5. Efficiency is always less than 1.

6. Entropy increases when heat is added, and decreases
when heat is removed.

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 Summary of Chapter 15

• First law of thermodynamics: (15-1)

• Isothermal process: temperature is constant.

• Adiabatic process: no heat is exchanged.
• Work done by gas at constant pressure:
(15-3)

• Heat engine changes heat into (15-4a)

useful work; needs temperature
difference.
• Efficiency of a heat (15-4b)
engine:
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 Summary of Chapter 15

• Upper limit on efficiency:

(15-5)

• Refrigerators and air conditioners do work to extract heat from

a cooler region and send it to a warmer region:

(15-6a)

• A heat pump is similar:

(15-7)

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 Summary of Chapter 15

• Second law of thermodynamics:

• heat flows spontaneously from a hot object to a cold one,
but not the reverse
• a given amount of heat cannot be changed entirely to work
• natural processes tend to increase entropy.
• Change in entropy: (15-8)

• Entropy is a measure of disorder.

• As time goes on, less and less energy is available to do useful
work.

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