Ch11/12 .

Thermodynamics
1. Thermodynamics is the branch of physics that is built upon
the fundamental laws that heat and work obey.

In thermodynamics the collection of objects on which

attention is being focused is called the system, while everything
else in the environment is called the surroundings. The system
and its surroundings are separated by walls of some kind.
Walls that permit heat to flow through them, such as those of
the engine block, are called diathermal walls. Perfectly
insulating walls that do not permit heat to flow between the
system and its surroundings are known as adiabatic walls.
1

2. THERMODYMANICS
Thermodynamics is the study
of the motion of heat energy
as it is transferred from the
system to the surrounding or
from the surrounding to the
system.
The transfer of heat could be due to a
physical change or a chemical
change.
There are three laws of chemical
thermodynamics.

CHEMICAL
THERMODYMANICS
3. The first law of thermodynamics:
Energy and matter can be neither created nor destroyed; only
transformed from one form to another. The energy and matter
of the universe is constant.
4. The second law of thermodynamics:
In any spontaneous process there is always an increase in the
entropy of the universe. The entropy is increasing.
5. The third law of thermodynamics:
The entropy of a perfect crystal at 0 K is zero.
There is no molecular motion at absolute 0 K.

6. HEAT

The energy that flows into or out of a

system because of a difference in
temperature between the thermodynamic
system and its surrounding.

Symbolized by "q".
A. When heat is evolved by a system,
energy is lost and "q is negative (-).
B. When heat is absorbed by the system,
the energy is added and "q" is positive (+).

HEAT FLOW
Heat can flow in one of two directions:

a. Exothermic
To give off heat; energy is lost from the
system: (-q)

b. Endothermic
To absorb heat; energy is added to the
system: (+q)

If the heat transfer involves a chemical reaction then q is called:

HEAT OF REACTION
The heat energy (H; enthalpy) required to
return a system to the given temperature at
the completion of the reaction.

q = H at constant pressure
The heat of reaction can be specific to a reaction like:

HEAT OF COMBUSTION
The quantity of heat energy given off when a
specified amount of substance burns in
oxygen.
UNITS: kJ/mol (kilojoules per mole) or kcal/mol (kilocalories per mole)

HEAT CAPACITY &

SPECIFIC HEAT
7. HEAT CAPACITY: The quantity of heat needed
to raise the temperature of a substance one
degree Celsius (or one Kelvin).

q = Cp T
8. SPECIFIC HEAT: The quantity of heat required
to raise the temperature of one gram of a
substance by one degree Celsius (or one
Kelvin).

q = s x m x T

s= c- specific heat

Both Cp & s are chemical specific constants found in the textbook or CRC
Handbook.

UNITS for HEAT ENERGY

9. Heat energy is usually measured in
either Joules, given by the unit (J), and
kilojoules (kJ) or in calories, written
shorthand as (cal), and kilocalories (kcal).

10. 1 cal = 4.184 J

NOTE: This conversion correlates to the specific heat of water which is 1
cal/g oC or 4.184 J/g oC.

SPECIFIC HEAT

11. Determine the energy (in kJ) required

to raise the temperature of 100.0 g of
water from 20.0 oC to 85.0 oC?
m = 100.0 g
q = m x s x T

T = Tf -Ti = 85.0 - 20.0 oC = 65.0 oC

s (H2O) = 4.184 J/ g - oC

q = (100.0 g) x (4.184 J/g-oC) x (65.0oC)

q = 27196 J (1 kJ / 1000J) = 27.2 kJ

12. Determine the specific heat of an

unknown metal that required 2.56 kcal of
heat to raise the temperature of 150.00 g
from 15.0 oC to 200.0 oC?
S = 0.0923 cal /g -oC

13. LAW OF CONSERVATION OF

ENERGY
The law of conservation of energy (the first law
of thermodynamics), when related to heat
transfer between two objects, can be stated
as:
The heat lost by the hot object = the heat gained
by the cold object

-qhot = qcold
-mh x sh x Th = mc x sc x Tc
where T = Tfinal - Tinitial

LAW OF CONSERVATION OF ENERGY

14. Assuming no heat is lost, what mass of cold
water at 0.00oC is needed to cool 100.0 g of
water at 97.6oC to 12.0 oC?

-mh x sh x Th = mc x sc x Tc
- (100.0g) (1 cal/goC) (12.0-97.6oC) = m (1 cal/goC) (12.0 - 0.0 oC)

8560 cal = m (12.0 cal/g)

m = 8560 cal / (12.0 cal/g)

m = 713 g
Calculate the specific heat of an unknown metal if a 92.00 g piece
at 100.0oC is dropped into 175.0 mL of water at 17.8 oC. The final
temperature of the mixture was 39.4 oC.

s (metal) = 0.678 cal/g oC

CW 1: Heat PROBLEMS
1. Iron metal has a specific heat of 0.449 J/g oC. How much heat is
transferred to a 5.00 g piece of iron, initially at 20.0 oC, when it is placed
in a beaker of boiling water at 1 atm?

180. J

2. How many calories of energy are given off to lower the temperature of
100.0 g of iron from 150.0 oC to 35.0 oC?

1.23 x 103 cal

3. If 3.47 kJ were absorbed by 75.0 g H 2O at 20.0 oC, what would be the final
temperature of the water?

31.1 oC
4. A 100. g sample of water at 25.3 oC was placed in a calorimeter. 45.0 g of
lead shots (at 100 oC) was added to the calorimeter and the final
temperature of the mixture was 34.4 oC. What is the specific heat of
lead?

1.28 J/g oC
5. A 17.9 g sample of unknown metal was heated to 48.31 oC. It was then
added to 28.05 g of water in an insulted cup. The water temperature rose
from 21.04 oC to 23.98oC. What is the specific heat of the metal in J/g oC?

0.792 J/goC

HW HEAT PROBLEM

_____1. A 250.0 g metal bar requires 5.866 kJ to change its

temperature from 22.0oC to 100.0oC. What is the specific heat of the
metal in J/goC?

_____2. How many joules are required to lower the temperature of

100.0 g of iron from 75.0 oC to 25.0 oC?

_____ 3. If 40.0 kJ were absorbed by 500.0 g H 2O at 10.0 oC, what

would be the final temperature of the water?

_____ 4. A 250 g of water at 376.3 oC is mixed with 350.0 mL of water

at 5.0 oC. Calculate the final temperature of the mixture.

_____5. A 400 g piece of gold at 500.0 oC is dropped into 15.0 L of

water at 22.0oC. The specific heat of gold is 0.131 J/g oC or 0.0312
cal/goC. Calculate the final temperature of the mixture assuming no
heat is lost to the surroundings.

The study of heat and its

transformation into mechanical
energy is called
thermodynamics. The word
thermodynamics stems from
Greek words meaning
movement of heat. The
foundation of thermodynamics is
the conservation of energy and
the fact that heat flows from hot
to cold. It provides the basic
theory of heat engines.

Absolute Zero

As the thermal motion of atoms in a substance

approaches zero, the kinetic energy of the atoms
approaches zero, and the temperature of the
substance approaches a lower limit.

Absolute Zero
15. Absolute zero is the temperature at which no more energy
can be extracted from a substance.
At absolute zero, no further lowering of its temperature is
possible.
This temperature is 273 degrees below zero on the Celsius scale.

Absolute Zero
The absolute temperatures of various
objects and phenomena.

Absolute Zero
think!
A sample of hydrogen gas has a temperature of 0C. If the
gas is heated until its molecules have doubled their average
kinetic energy (the gas has twice the absolute temperature),
what will be its temperature in degrees Celsius?

24.1 Absolute Zero

think!
A sample of hydrogen gas has a temperature of 0C. If the
gas is heated until its molecules have doubled their average
kinetic energy (the gas has twice the absolute temperature),
what will be its temperature in degrees Celsius?
Answer:
At 0C the gas has an absolute temperature of 273 K. Twice
as much average kinetic energy means it has twice the
absolute temperature. This would be 546 K, or 273C.

24.1 Absolute Zero

What happens to a substances temperature as the

motion of its atoms approaches zero?

The Zeroth Law of Thermodynamics

21

Thermal equilibrium: Two systems are said to be in thermal

equilibrium if there is no net flow of heat between them
when they are brought into thermal contact.

Temperature is the indicator of thermal equilibrium in the

sense that there is no net flow of heat between two systems in
thermal contact that have the same temperature.
THE ZEROTH LAW OF THERMODYNAMICS
Two systems individually in thermal equilibrium with a third
system* are in thermal equilibrium with each other.

22

16. First Law of Thermodynamics

The first law of thermodynamics states that

whenever heat is added to a system, it transforms to
an equal amount of some other form of energy.

First Law of Thermodynamics

HISTORY :
In the eighteenth century, heat was thought to be an invisible fluid called
caloric, which flowed like water from hot objects to cold objects.
In the 1840s, James Joule demonstrated that the flow of heat was nothing
more than the flow of energy itself.
The caloric theory of heat was gradually abandoned.

First Law of Thermodynamics

As the weights fall, they give up potential energy and warm the water
accordingly. This was first demonstrated by James Joule, for whom the unit
of energy is named.

First Law of Thermodynamics

Today, we view heat as a form
of energy.
Energy can neither be created
nor destroyed.
16. The first law of thermodynamics is
the law of conservation of energy applied
to thermal systems.

First Law of Thermodynamics

If we add heat energy to a system, the added energy does one or both of two
things:
increases the internal energy of the system if it remains in the system
does external work if it leaves the system
16. So, the first law of thermodynamics states:

Heat added = increase in internal energy + external work done

by the system
Q = U + W
U = Q-W

First Law of Thermodynamics

Work
Adding heat is not the only way to increase the internal energy of a
system.
If we set the heat added part of the first law to zero, changes in internal
energy are equal to the work done on or by the system.

First Law of Thermodynamics

think!
17. a. If 10 J of energy is added to a system that does
no external work, by how much will the internal energy
of that system be raised?

24.2 First Law of Thermodynamics

think!
If 10 J of energy is added to a system that does no
external work, by how much will the internal energy of
that system be raised?
Answer:

U = Q- W = 10J -0 = 10J

The First Law of Thermodynamics

31

THE FIRST LAW OF THERMODYNAMICS

The internal energy of a system changes from an initial
value Ui to a final value of Uf due to heat Q and work.

Q is positive when the system gains heat and negative

when it loses heat.
W is positive when work is done by the system and
negative when work is done on the system.

32

CW Internal Energy
Positive and Negative Work

33

17. B The figure illustrates a system and its surroundings. In ist

part , the system gains 1500 J of heat from its surroundings, and
2200 J of work is done by the system on the surroundings.
17. C In the second part , the system also gains 1500 J of heat,
but 2200 J of work is done on the system by the surroundings. In
each case, determine the change in the internal energy of the
system.

34

18. An Ideal Gas

The temperature of three moles of a monatomic ideal gas is
reduced from Ti = 540 K to Tf = 350 K by two different
methods. In the first method 5500 J of heat flows into the gas,
while in the second, 1500 J of heat flows into it. In each case
find (a) the change in the internal energy and (b) the work
done by the gas.
(a)

(b)

35

CW 2: on 1st Law of
Thermodynamics

#1 if 30 Joules is added to the system that

10 Joules of external work is done how
much internal energy of that system be
raised?
#2 If 30 joules is added to the system ,
how much will the internal system be
raised if no external work is done?

Check Your Understanding 1

A gas is enclosed within a chamber that is fitted with a
frictionless piston. The piston is then pushed in, thereby
compressing the gas. Which statement below regarding this
process is consistent with the first law of thermodynamics?
a. The internal energy of the gas will increase.
b. The internal energy of the gas will decrease.
c. The internal energy of the gas will not change.
d. The internal energy of the gas may increase, decrease, or
remain the same, depending on the amount of heat that the gas
gains or loses.
37

Check Your Understanding 1

A gas is enclosed within a chamber that is fitted with a
frictionless piston. The piston is then pushed in, thereby
compressing the gas. Which statement below regarding this
process is consistent with the first law of thermodynamics?
a. The internal energy of the gas will increase.
b. The internal energy of the gas will decrease.
c. The internal energy of the gas will not change.
d. The internal energy of the gas may increase, decrease, or
remain the same, depending on the amount of heat that the gas
gains or loses.
(d)
38

First Law of Thermodynamics

What does the first law of thermodynamics state?

19. Thermal Processes

quasi-static means that it occurs slowly enough that a
uniform pressure and temperature exist throughout all
regions of the system at all times.
a. An isobaric process is one that occurs at constant pressure.

40

The substance in
the chamber is
expanding
isobarically
because the
pressure is held
constant by the
external
atmosphere and
the weight of the
piston and the
block.

41

20.
Isobaric Expansion of Water
One gram of water is placed in the cylinder in above figure, and
the pressure is maintained at 2.0 105 Pa. The temperature of the
water is raised by 31 C. In one case, the water is in the liquid
phase and expands by the small amount of 1.0 108 m3. In
another case, the water is in the gas phase and expands by the
much greater amount of 7.1 105 m3. For the water in each case,
find (a) the work done and (b) the change in the internal energy.

Cliquid water = 4186 J/(kgC)

Cgas water = 2020 J/(kgC).
42

(a)

(b)

43

a. For an isobaric process, a pressure-versus-volume plot is a

horizontal straight line, and the work done [W = P(V f V i)]
is the colored rectangular area under the graph.
44

b. The substance in the

chamber is being heated
isochorically because the
rigid chamber keeps the
volume constant.
c. The pressure-volume plot
for an isochoric process is a
vertical straight line. The
area under the graph is
zero, indicating that no
work is done.
c. isochoric process, one that occurs at constant
volume.
45

d.. isothermal process, one that takes place at constant

temperature. (when the system is an ideal gas.)

e. There is adiabatic process, one that occurs without the transfer

of heat . Since there is no heat transfer, Q equals zero, and the
first law indicates that U = Q W = W. Thus, when work is
done by a system adiabatically, W is positive and the internal
energy of the system decreases by exactly the amount of the
work done. When work is done on a system adiabatically, W is
negative and the internal energy increases correspondingly.

46

21. Adiabatic Processes

When work is done on a gas by adiabatically

compressing it, the gas gains internal energy and
becomes warmer.

Adiabatic Processes
When a gas is compressed or expanded so that no heat enters
or leaves a system, the process is said to be adiabatic.

Adiabatic Processes
Do work on a pump by
pressing down on the
piston and the air is
warmed.

Adiabatic Processes
Blow warm air onto your hand from your wide-open mouth. Now reduce
the opening between your lips so the air expands as you blow. Adiabatic
expansionthe air is cooled.

Adiabatic Processes
A common example of a near-adiabatic process is the compression and
expansion of gases in the cylinders of an automobile engine.
Compression and expansion occur in only a few hundredths of a
second, too fast for heat energy to leave the combustion chamber.
For very high compressions, like those in a diesel engine, the
temperatures are high enough to ignite a fuel mixture without a spark
plug.
Diesel engines have no spark plugs.

CW 3 : Explain the How the

Gasoline engine works.

P 358 Fig 24.4

Flow Chart And
Report 50 points
Use markers and
white paper
Discuss where
Adiabatic process
takes place in the
engines system ?

Discuss where the

1st Law is Applied
in the engines
system ?

Adiabatic Processes

One cycle of a four-stroke internal combustion engine.

24.3 Adiabatic Processes

One cycle of a four-stroke internal combustion engine.

24.3 Adiabatic Processes

One cycle of a four-stroke internal combustion engine.

24.3 Adiabatic Processes

One cycle of a four-stroke internal combustion engine.

24.3 Adiabatic Processes

One cycle of a four-stroke internal combustion engine.

Adiabatic Processes
When a gas adiabatically expands, it does work on its surroundings
and gives up internal energy, and thus becomes cooler.

Adiabatic Processes
Heat and Temperature
Air temperature may be changed by adding or subtracting heat,
by changing the pressure of the air, or by both.
Heat may be added by solar radiation, by long-wave Earth radiation,
by condensation, or by contact with the warm ground.
Heat may be subtracted by radiation to space, by evaporation of rain
falling through dry air, or by contact with cold surfaces.

Adiabatic Processes
For many atmospheric processes, the amount of heat added or
subtracted is small enough that the process is nearly adiabatic.
In this case, an increase in pressure will cause an increase in
temperature, and vice versa.
We then have the adiabatic form of the first law:
Change in air temperature ~ pressure change

Adiabatic Processes
Pressure and Temperature
Adiabatic processes in the atmosphere occur in large masses of air
that have dimensions on the order of kilometers.
Well call these large masses of air blobs.
As a blob of air flows up the side of a mountain, its pressure lessens,
allowing it to expand and cool.
The reduced pressure results in reduced temperature.

Explain : Pressure
1.High Altitude
2. Low Altitude

24.3 Adiabatic Processes

19. The temperature of a blob of dry air
that expands adiabatically changes by
about 10C for each kilometer of
elevation.

24.3 Adiabatic Processes

An example of this adiabatic warming is the chinooka warm, dry wind
that blows from the Rocky Mountains across the Great Plains.
Cold air moving down the slopes of the mountains is compressed into a
smaller volume and is appreciably warmed.
Communities in the paths of chinooks experience relatively warm weather
in midwinter.

24.3 Adiabatic Processes

A thunderhead is the result of the
rapid adiabatic cooling of a rising
mass of moist air. Its energy
comes from condensation and
freezing of water vapor.

24.3 Adiabatic Processes

What is the effect of adiabatic compression on a

gas?

22. Second Law of Thermodynamics

The second law of thermodynamics states

that heat will never of itself flow from a
cold object to a hot object.

Second and Third Laws of Thermodynamics

Examples :
a.If a hot brick is next to a cold brick, heat flows from the hot brick to the
cold brick until both bricks arrive at thermal equilibrium.
b.In winter, heat flows from inside a warm heated home to the cold air
outside.
c.In summer, heat flows from the hot air outside into the homes cooler
interior.
(Heat can be made to flow the other way, but only by imposing external
effortas occurs with heat pumps.)

23. Absolute ZERO Possible 3rd Law

Absolute ZERO Possible?There is also
a third law of thermodynamics: no
system can reach absolute zero.
As investigators attempt to reach this
lowest temperature, it becomes more
difficult to get closer to it.
Physicists have been able to record
temperatures that are less than a millionth
of 1 kelvinbut never as low as 0 K.

Second and Third Laws of Thermodynamics

What does the second law of thermodynamics state

about heat flow?

CW4: HEAT Engine

and Boiler 50pts

Draw the Boiler on

the right -10pts
Draw the Generic
Heat Engine on the
left of the paper.10pts
Connect the Heat
engine Part to the
Boiler Part

Discuss in what part does

adiabatic process takes
place? Explain why. 10pts
Discuss where the 1st,2nd,3rd
Laws of Thermodynamics
apply in these engines.
Explain why ? 10pts

24.5 Heat Engines and the Second Law

According to the second law of

thermodynamics, no heat engine can convert all
heat input to mechanical energy output.

24.5 Heat Engines and the Second Law

Heat Engine Mechanics
24. A heat engine is any device that changes internal energy into
mechanical work.
The basic idea behind a heat engine is that mechanical work can
be obtained as heat flows from high temperature to low
temperature.
Some of the heat can be transformed into work in a heat engine.

24.5 Heat Engines and the Second Law

24 . Every heat engine will
increase its internal energy by absorbing heat from a reservoir of
higher temperature,
convert some of this energy into mechanical work, and
expel the remaining energy as heat to some lower-temperature
reservoir.

24.5 Heat Engines and the Second Law

24.. When heat energy flows in any
heat engine from a high-temperature
place to a low-temperature place, part
of this energy is transformed into
work output.

24.5 Heat Engines and the Second Law

Heat Engine Physics
25. A steam turbine engine demonstrates the role of temperature difference
between heat reservoir and sink.

24.5 Heat Engines and the Second Law

25. The second law states that when work is done by a heat engine running
between two temperatures, Thot and Tcold, only some of the input heat at Thot
can be converted to work.
The rest is expelled as heat at Tcold.

24.5 Heat Engines and the Second Law

There is always heat exhaust, which may be desirable or
undesirable.
Hot steam expelled in a laundry on a cold winter day may be quite
desirable.
. The same steam on a hot summer day is something else. When
expelled heat is undesirable, we call it thermal pollution.

24.5 Heat Engines and the Second Law

26. Heat Engine Efficiency
French engineer Sadi Carnot carefully analyzed the heat engine and
made a fundamental discovery:
The upper fraction of heat that can be converted to useful work,
even under ideal conditions, depends on the temperature difference
between the hot reservoir and the cold sink.

26 . Heat Engines and the Second Law

The Carnot efficiency, or ideal efficiency, of a heat engine is the
ideal maximum percentage of input energy that the engine can
convert to work.

Thot is the temperature of the hot reservoir.

Tcold is the temperature of the cold.

26.. Heat Engines and the Second Law

Ideal efficiency depends only on the temperature difference
between input and exhaust.
When temperature ratios are involved, the absolute temperature
scale must be used, so Thot and Tcold are expressed in kelvins.
The higher the steam temperature driving a motor or
turbogenerator, the higher the efficiency of power production.

24.5 Heat Engines and the Second Law

think!
27. What is the ideal efficiency of an engine if both its hot
reservoir and exhaust are the same temperaturesay, 400 K?
The equation for ideal efficiency is as follows:

24.5 Heat Engines and the Second Law

think!
What is the ideal efficiency of an engine if both its hot reservoir
and exhaust are the same temperaturesay, 400 K? The
equation for ideal efficiency is as follows:

Answer:
Zero efficiency; (400 - 400)/400 = 0. This means no work
output is possible for any heat engine unless a temperature
difference exists between the reservoir and the sink.

24.5 Heat Engines and the Second Law

28. For example, when the heat reservoir in a steam turbine is 400
K (127C) and the sink is 300 K (27C), calculate the ideal
efficiency .

24.5 Heat Engines and the Second Law

28. For example, when the heat reservoir in a steam turbine is 400
K (127C) and the sink is 300 K (27C), the ideal efficiency is

Under ideal conditions, 25% of the internal energy of the steam can
become work, while the remaining 75% is expelled as waste.
Increasing operating temperature to 600 K yields an efficiency of
(600 300)/600 = 1/2, twice the efficiency at 400 K.

CW5 : Carnot Ideal Efficiency

1.Calculate the ideal
efficiency of a heat
engine that takes in
energy at 400K and
expels heat to a
reservoir at 300K . If the
operating temperature
is increased from 400K
to 600K, what will be its
ideal efficiency?

2. Calculate an
ideal efficiency of a
steam turbine that
has a hot reservoir
of 127 C high
pressure steam
and a sink of 27C .

24.5 Heat Engines and the Second Law

23. For example, when the heat reservoir in a steam turbine is 400
K (127C) and the sink is 300 K (27C), the ideal efficiency is

Under ideal conditions, 25% of the internal energy of the steam can
become work, while the remaining 75% is expelled as waste.
Increasing operating temperature to 600 K yields an efficiency of
(600 300)/600 = 1/2, twice the efficiency at 400 K.

24.5 Heat Engines and the Second Law

By condensing the steam, the pressure on the back sides is greatly reduced.
With confined steam, temperature and pressure go hand in handincrease
temperature and you increase pressure.
The pressure difference is directly related to the temperature difference
between the heat source and the exhaust.

24.5 Heat Engines and the Second Law

Carnots equation states the upper
limit of efficiency for all heat
engines.
The higher the operating temperature
(compared with exhaust temperature)
of any heat engine, the higher the
efficiency.
Only some of the heat input can be
converted to workeven without
considering friction.

24.5 Heat Engines and the Second Law

think!
24. What is the ideal efficiency of an engine if both its hot
reservoir and exhaust are the same temperaturesay, 400 K?
The equation for ideal efficiency is as follows:

24.5 Heat Engines and the Second Law

How does the second law of thermodynamics apply to

heat engines?

Read 24.6 -24.7

Order to Disorder
Very Important
Facts that affects
The environment
and peoples lives

Vocabulary :
New words and
definition

24.6 Order Tends to Disorder

Natural systems tend to proceed toward a

state of greater disorder.

24.6 Order Tends to Disorder

The first law of thermodynamics states that energy can be neither created
nor destroyed.
DISORDER
The second law adds that whenever energy transforms, some of it
degenerates into waste heat, unavailable to do work.
DISORDER
Another way to say this is that organized, usable energy degenerates into
disorganized, nonusable energy.
It is then unavailable for doing the same work again.

24.6 Order Tends to Disorder

EXAMPLE of DISORDER or WASTE of ENERGY
Push a heavy crate across a rough floor and all your work will go into
heating the floor and crate. Work against friction turns into disorganized
energy.

24.6 Order Tends to Disorder

EXAMPLE of DISORDER WASTE ENERGY
Organized energy in the form of electricity that goes into electric lights in
homes and office buildings degenerates to heat energy.
The electrical energy in the lamps, even the part that briefly exists in the
form of light, turns into heat energy.
This energy is degenerated and has no further use.

24.6 Order Tends to Disorder

EXAMPLE of PUTTING ORDER TO
DISORDER
The Transamerica Pyramid and some
other buildings are heated by electric
lighting, which is why the lights are on
most of the time.

24.6 Order Tends to Disorder

We see that the quality of energy is lowered with each
transformation.
Organized energy tends to disorganized forms.

24.6 Order Tends to Disorder

Imagine that in a corner of a room sits a
closed jar filled with argon gas atoms.
When the lid is removed, the argon atoms
move in haphazard directions, eventually
mixing with the air molecules in the room.
The system moves from a more ordered
state (argon atoms concentrated in the jar)
to a more disordered state (argon atoms
spread evenly throughout the room).

24.6 Order Tends to Disorder

What happens to the orderly state of any

natural system?

24.7 Entropy

According to the second law of thermodynamics, in

the long run, the entropy of a system always
increases for natural processes.

24.7 Entropy
25. Entropy is the measure of the amount of disorder in a
system.
Disorder increases; entropy increases.

24.7 Entropy
When a physical system can distribute its energy freely, entropy increases
and energy of the system available for work decreases.

24.7 Entropy
This run-down house demonstrates entropy. Without continual
maintenance, the house will eventually fall apart.

24.7 Entropy
For the system life forms plus their
waste products there is still a net
increase in entropy.
Energy must be transformed into the
living system to support life. When it is
not, the organism soon dies and tends
toward disorder.

24.7 Entropy
Even the most improbable states may occur, and entropy spontaneously
decrease:
haphazard motions of air molecules could momentarily become
harmonious in a corner of the room
a barrel of pennies dumped on the floor could
show all heads
a breeze might come into a messy room and
make it organized
The odds of these things occurring are infinitesimally small.

24.7 Entropy
The motto of this contractorIncreasing entropy is our
businessis appropriate because by knocking down the building,
the contractor increases the disorder of the structure.

24.7 Entropy
The laws of thermodynamics are sometimes put this way:
You cant win (because you cant get any more energy out of a
system than you put in).
You cant break even (because you cant even get as much energy
out as you put in).
You cant get out of the game (entropy in the universe is always
increasing).

24.7 Entropy

What always happens to the entropy of

systems?

Experiment :
Heat
I. Purpose :
To determine the total amount of Heat
involved in the process of Mixture using Q=
mcT
Q= mhV or Q= mhf using

II. Materials :
graduated cylinder
10 ml of water
ice cube
plates
beaker
thermometer
Triple beam balance

III. Procedures

IV. Data and Results

V=1
0
mL

Mass,
g
M1
Water

Mass,
g
M2
Ice
cube

Ti initial
temperature.
water

Tf final
temperature,
Mixture when
The ice melted

Q= m1cT
water

Q= m2hf
ice

Q = m2cT
Melted ice

Total Q

V. Calculations
Using equations
Q= mcT
Q= mhf

Analysis and Conclusions

1. Explain and Discuss the whole
experiment .
2. Explain how you calculate the total heat
of the system .

The area under a

pressure-volume graph
is the work for any kind
of process.

The colored area gives

the work done by the
gas for the process
from X to Y.

116

Example 4. Work and the Area Under

a Pressure-Volume Graph
Determine the work for the process in
which the pressure, volume, and
temperature of a gas are changed along
the straight line from X to Y in the
figure.

= +180 J

117

Check Your Understanding 2

The drawing shows a
pressure-versusvolume plot for a
three-step process: A to
B, B to C, and C to A.
For each step, the
work can be positive,
negative, or zero.
Which answer below
correctly describes the
work for the three
steps?
118

a.

Positive

Negative

Negative

b.

Positive

Positive

Negative

c.

Negative

Negative

Positive

d.

Positive

Negative

Zero

e.

Negative

Positive

Zero

(b)
119

Thermal Processes Using an Ideal Gas

120

ISOTHERMAL EXPANSION OR COMPRESSION

P = nRT/V
W = P V = P(Vf Vi)

121

Example 5.
Isothermal Expansion of an Ideal Gas
Two moles of the monatomic gas argon expand isothermally at
298 K, from an initial volume of Vi = 0.025 m3 to a final volume of
Vf = 0.050 m3. Assuming that argon is an ideal gas, find (a) the
work done by the gas, (b) the change in the internal energy of the
gas, and (c) the heat supplied to the. gas.
(a)

(b)
(c)
122

ADIABATIC EXPANSION OR COMPRESSION

123

[Ti = PiVi/(nR)]
[Tf = PfVf/(nR)].

124

Type of Thermal
Process

Work Done

Isobaric (constant
pressure)

W = P(Vf Vi)

Isochoric (constant
volume)

W = 0 J

Isothermal
(constant
temperature)
Adiabatic (no heat
flow)

First Law of
Thermodynamics
(U = Q W)

(for an ideal gas)

(for a monatomic ideal gas)

125

Specific Heat Capacities

where the capital letter C refers to the molar specific heat

capacity in units of J/(molK).

126

127

128

The Second Law of Thermodynamics

THE SECOND LAW OF THERMODYNAMICS:
THE HEAT FLOW STATEMENT
Heat flows spontaneously from a substance at a
higher temperature to a substance at a lower
temperature and does not flow spontaneously in the
reverse direction.

129

130

Heat Engines
A heat engine is any device that uses heat to perform work. It
has three essential features:
1.Heat is supplied to the engine at a relatively high input
temperature from a place called the hot reservoir.
2.Part of the input heat is used to perform work by the working
substance of the engine, which is the material within the engine
that actually does the work (e.g., the gasoline-air mixture in an
automobile engine).
3.The remainder of the input heat is rejected to a place called
the cold reservoir, which has a temperature lower than the
input temperature.
131

These three symbols refer

to magnitudes only,
without reference to
algebraic signs. Therefore,
when these symbols appear
in an equation, they do not
have negative values
assigned to them.

132

Efficiencies are often quoted as percentages obtained by

multiplying the ratio W/QH by a factor of 100.

133

Example 6. An Automobile Engine

An automobile engine has an efficiency of 22.0% and produces
2510 J of work. How much heat is rejected by the engine?

134

Carnot's Principle and the Carnot

Engine
A reversible process is one in which both the system and its
environment can be returned to exactly the states they were in
before the process occurred.
CARNOTS PRINCIPLE: AN ALTERNATIVE
STATEMENT OF THE SECOND LAW OF
THERMODYNAMICS
No irreversible engine operating between two reservoirs at
constant temperatures can have a greater efficiency than a
reversible engine operating between the same temperatures.
Furthermore, all reversible engines operating between the
same temperatures have the same efficiency.
135

A Carnot engine is a
reversible engine in which
all input heat QH originates
from a hot reservoir at a
single temperature TH,
and all rejected heat QC
goes into a cold reservoir
at a single temperature TC.
The work done by the
engine is W.

136

where the temperatures TC and TH must be expressed in

kelvins .

137

Example 7.
A Tropical Ocean as a Heat Engine
Water near the surface of a tropical ocean has a temperature
of 298.2 K (25.0 C), whereas water 700 m beneath the surface
has a temperature of 280.2 K (7.0 C). It has been proposed
that the warm water be used as the hot reservoir and the cool
water as the cold reservoir of a heat engine. Find the maximum
possible efficiency for such an engine.

TH = 298.2 K and TC = 280.2 K

138

Conceptual Example 8. Limits on the

Efficiency of a Heat Engine
Consider a hypothetical engine that receives 1000 J of heat as
input from a hot reservoir and delivers 1000 J of work, rejecting
no heat to a cold reservoir whose temperature is above 0 K. Decide
whether this engine violates the first or the second law of
thermodynamics, or both.

It is the second law, not the first law, that limits the
efficiencies of heat engines to values less than 100%.

139

Refrigerators, Air Conditioners, and

Heat Pumps

In the refrigeration process, work W is used to remove heat QC

from the cold reservoir and deposit heat QH into the hot reservoir.140

In a
refrigerator,
the interior
of the unit is
the cold
reservoir,
while the
warmer
exterior is
the hot
reservoir.

141

A window air
conditioner
removes heat from
a room, which is
the cold reservoir,
and deposits heat
outdoors, which is
the hot reservoir.

142

Conceptual Example 9.
You Cant Beat the Second Law of
Thermodynamics
Is it possible to cool your kitchen by leaving the refrigerator
door open or cool your bedroom by putting a window air
conditioner on the floor by the bed?

Rather than cooling the kitchen, the open

refrigerator warms it up. The air conditioner
actually warms the bedroom.

143

144

In a heat pump the

cold reservoir is the
wintry outdoors, and
the hot reservoir is the
inside of the house.

145

This conventional
electric heating
system is delivering
1000 J of heat to the
living room.

QH = W + QC and QC/QH = TC/TH

146

Example 10. A Heat Pump

An ideal or Carnot heat pump is used to heat a house to a
temperature of TH = 294 K (21 C). How much work must be
done by the pump to deliver QH = 3350 J of heat into the
house when the outdoor temperature TC is (a) 273 K (0 C)
and (b) 252 K (21 C)?

(a)

(b)
147

148

Check Your Understanding 3

Each drawing represents a hypothetical heat engine or a
hypothetical heat pump and shows the corresponding heats and
work. Only one is allowed in nature. Which is it?

(c)

149

Entropy
In general, irreversible processes cause us to lose some, but not
necessarily all, of the ability to perform work. This partial loss
can be expressed in terms of a concept called entropy.

Reversible processes do not alter the total entropy of the

universe.
150

Although the
relation S =
(Q/T)R applies
to reversible
processes, it
can be used as
part of an
indirect
procedure to
find the
entropy change
for an
irreversible
process.
151

Example 11. The Entropy of the

Universe Increases
1200 J of heat flow
spontaneously through a
copper rod from a hot
reservoir at 650 K to a
cold reservoir at 350 K.
Determine the amount by
which this irreversible
process changes the
entropy of the universe,
assuming that no other
changes occur.
152

Any irreversible process increases the entropy of the universe.

153

THE SECOND LAW OF THERMODYNAMICS STATED

IN TERMS OF ENTROPY

The total entropy of the universe does not change when a

reversible process occurs ( Suniverse = 0 J/K) and does
increases when an irreversible process occurs ( Suniverse > 0
J/K).

154

Example 12.
Energy Unavailable for Doing Work

155

Suppose that 1200 J of heat is used as input for an engine under two
different conditions. In Figure part a the heat is supplied by a hot
reservoir whose temperature is 650 K. In part b of the drawing, the heat
flows irreversibly through a copper rod into a second reservoir whose
temperature is 350 K and then enters the engine. In either case, a 150-K
reservoir is used as the cold reservoir. For each case, determine the
maximum amount of work that can be obtained from the 1200 J of heat.

156

where T0 is the Kelvin temperature of the coldest heat

reservoir.

157

A block of ice is an example of an ordered system

relative to a puddle of water.

158

Example 13. Order to Disorder

Find the change in entropy that results when a 2.3-kg block of
ice melts slowly (reversibly) at 273 K (0 C).

159

Check Your Understanding 4

Two equal amounts of water are mixed together in an insulated
container. The initial temperatures of the water are different,
but the mixture reaches a uniform temperature. Do the energy
and the entropy of the water increase, decrease, or remain
constant as a result of the mixing process?

(d)

Energy of the
Water

Entropy of the
Water

a.

Increases

Increases

b.

Decreases

Decreases

c.

Remains constant

Decreases

d.

Remains constant

Increases

160

The Third Law of Thermodynamics

THE THIRD LAW OF THERMODYNAMICS

It is not possible to lower the temperature of any system to

absolute zero (T = 0 K) in a finite number of steps.

161

Concepts & Calculations

Example 14. The Sublimation of Zinc
The sublimation of zinc (mass per mole = 0.0654 kg/mol) occurs
at a temperature of 6.00 102 K, and the latent heat of
sublimation is 1.99 106 J/kg. The pressure remains constant
during the sublimation. Assume that the zinc vapor can be
treated as a monatomic ideal gas and that the volume of solid
zinc is negligible compared to the corresponding vapor. What is
the change in the internal energy of the zinc when 1.50 kg of
zinc sublimates?

Q = U + W,
Q = mLs,
W = nRT

162

163

Concepts & Calculations Example 15.

The WorkEnergy Theorem

Each of two Carnot engines

uses the same cold reservoir
at a temperature of 275 K
for its exhaust heat. Each
engine receives 1450 J of
input heat.

164

The work from either of these engines is used to drive a pulley

arrangement that uses a rope to accelerate a 125-kg crate from
rest along a horizontal frictionless surface. With engine 1 the crate
attains a speed of 2.00 m/s, while with engine 2 it attains a speed
of 3.00 m/s. Find the temperature of the hot reservoir for each
engine.

165

166

Conceptual Question 14
REASONING AND SOLUTION The efficiency of a Carnot engine is
given by Equation 15.15 efficiency 1 ( TC / TH ) . Three reversible
engines A, B, and C, use the same cold reservoir for their exhaust
heats. They use different hot reservoirs with the following
temperatures: (A) 1000 K; (B) 1100 K; and (C) 900 K. We can
rank these engines in order of increasing efficiency according to the
following considerations. The ratio TC / THis inversely proportional
to the value of TH. The ratio TC / THwill be smallest for engine B;
therefore, the quantity 1 TC / TH will be largest for engine B. Thus,
engine B has the largest efficiency. Similarly, the ratio TC / THwill be
largest for engine C; therefore, the quantity 1 TC / TH will be
smallest for engine C. Thus, engine C has the smallest efficiency.
Hence, the engines are, in order of increasing efficiency: engine C,
engine A, and engine B.
167

Conceptual Question 15
REASONING AND SOLUTION The efficiency of a Carnot engine
is given by Equation 15.15: efficiency 1 ( TC / TH )
a. Lowering the Kelvin temperature of the cold reservoir by a
factor of four makes the ratio TC / THone-fourth as great.
b. Raising the Kelvin temperature of the hot reservoir by a factor of
four makes the ratio TC / TH one-fourth as great.
c. Cutting the Kelvin temperature of the cold reservoir in half and
doubling the Kelvin temperature of the hot reservoir makes the
ratio TC / TH one-fourth as great.
Therefore, all three possible improvements have the same effect on
the efficiency of a Carnot engine.
168

Problem 51
REASONING AND SOLUTION The efficiency of the engine
is e = 1 - (TC/TH) so
Increase TH by 40 K; e = 1 - [(350 K)/(690 K)] = 0.493
Decrease TC by 40 K; e = 1 - [(310 K)/(650 K)] = 0.523
The greatest improvement is made by lowing the temperature
of the cold reservoir.

169

Problem 63
REASONING AND SOLUTION Let CP denote the coefficient
of performance. By definition (Equation 15.16), CP = QC/W,
so that
QC 7.6 104 J
4

CP

2.0

3.8 10 J

Thus, the amount of heat that is pumped out of the back of

the air conditioner is

QH W QC 3.8 104 J + 7.6 104 J = 1.14 105 J

170

The temperature rise in the room can be found as follows:

QH = CV n T

QH
T

CV n

1.14 105 J
5
1.4 K
5R n
[8.31 J/(mol K)](3800 mol)
2
2
QH

171

Problem 64
REASONING AND SOLUTION The amount of heat removed
from the ice QC is

QC = mLf = (2.0 kg)(33.5 * 104 J/kg) = 6.7 * 105 J

The amount of heat leaving the refrigerator QH is therefore
QH = QC(TH/TC) = (6.7 * 105 J)(300 K)/(258 K) = 7.8 * 105 J
The amount of work done by the refrigerator is therefore,
W = QH - QC = 1.1 * 105 J
At $0.10 per kWh (or $0.10 per 3.6 * 106 J), the cost is

$0.1
5
3
(
1
.
1

10
J
)

$
3
.
0

10
0.3 cents
6
3.6 10 J

172