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Thermodynamics
Thermodynamics
Thermodynamics
AP Learning Objectives
Kinetic theory and thermodynamics
Ideal gases
Students should know how to apply the ideal gas law and
thermodynamic principles, so they can:
Relate the pressure and volume of a gas during an
isothermal expansion or compression.
Relate the pressure and temperature of a gas during
constant-volume heating or cooling, or the volume and
temperature during constant-pressure heating or
cooling.
Calculate the work performed on or by a gas during an
expansion or compression at constant pressure.
Understand the process of adiabatic expansion or
compression of a gas.
Identify or sketch on a PV diagram the curves that
represent each of the above processes.
AP Learning Objectives
Laws of Thermodynamics
Students should know how to apply the first law of thermodynamics,
so they can:
Relate the heat absorbed by a gas, the work performed by the
gas, and the internal energy change of the gas for any of the
processes above.
Relate the work performed by a gas in a cyclic process to the area
enclosed by a curve on a PV diagram.
Students should understand the second law of thermodynamics, the
concept of entropy, and heat engines and the Carnot cycle, so they
can:
Determine whether entropy will increase, decrease, or remain the
same during a particular situation.
Compute the maximum possible efficiency of a heat engine
operating between two given temperatures.
Compute the actual efficiency of a heat engine.
Relate the heats exchanged at each thermal reservoir in a Carnot
cycle to the temperatures of the reservoirs.
Table of Contents
1. Thermodynamic Systems & Surroundings
2. The Zeroth Law of Thermodynamics
3. The First Law of Thermodynamics
4. Thermal Processes
5. Thermal Processes Using an Ideal Gas
6. Specific Heat Capacities
7. The Second Law of Thermodynamics
8. Heat Engines
9. Carnot’s Principle and the Carnot Engine
10. Refrigerators, Air Conditioners, and Heat Pumps
11. Entropy
12. The Third Law of Thermodynamics
Chapter 15
Thermodynamics
Section 1:
Thermodynamic Systems & Surroundings
Thermodynamic Systems and Their
Surroundings
Thermodynamics is the branch of physics
that is built upon the fundamental laws that
heat and work obey.
The collection of objects on which attention is
being focused is called the system, while
everything else in the environment is called the
surroundings.
Walls that permit heat flow are called
diathermal walls, while walls that do not
permit heat flow are called adiabatic walls.
To understand thermodynamics, it is necessary
to describe the state of a system.
Chapter 15
Thermodynamics
Section 2:
The Zeroth Law of Thermodynamics
Zeroth Law of Thermodynamics
The forgotten Law of Science
Two systems are said to be in thermal equilibrium if there is no
heat flow between them when they are brought into 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
a) An air conditioner transfers heat from the inside of a house to the outside of the
house.
b) A monatomic gas is held within a container that has a moveable piston. The gas
absorbs heat from the surroundings and expands at constant pressure and
temperature.
d) A pot contains oil at 175 C. When frozen sliced potatoes are dropped into the oil,
heat is transferred from the oil to the potatoes.
Section 3:
The First Law of Thermodynamics
Effect of Heat on a System
Suppose that a system gains heat Q and that is the only effect
occurring.
U U f U i Q
U U f U i W
U Q W
Heat is positive when the system gains heat and negative when
(b) U Q W
(a)
U 32 nRTf 32 nRTi
U 3
2
3.0 mol8.31 J mol K 350 K 540 K 7100 J
(b)
W U Q 7100 J 5500 J 12600 J
15.3.1. An insulated container is filled with a mixture of water and
ice at zero C. An electric heating element inside the container
is used to add 1680 J of heat to the system while a paddle does
450 J of work by stirring. What is the increase in the internal
energy of the ice-water system?
a) 450 J
b) 1230 J
c) 1680 J
d) 2130 J
e) zero J
15.3.2. The internal energy of a system increases during some time interval.
Which one of the following statements concerning this situation must be
true?
a) The increase in internal energy indicates that work was done on the system.
b) The increase in internal energy indicates that heat was added to the system.
c) The increase in internal energy indicates that work was done by the system.
d) The increase in internal energy indicates that heat was removed from the
system.
e) The information given is insufficient to indicate the reason for the increase.
15.3.3. A gas is enclosed in a cylinder by a piston. The volume of the gas
is then reduced to one half its original value by applying a force to the
piston. Which one of the following statements concerning the internal
energy of the gas is true?
c) The internal energy of the gas will neither increase nor decrease.
d) The internal energy of the gas will equal the work done in moving the
piston.
e) The internal energy of the gas may increase, decrease, or remain the
same depending on the amount of heat that is gained or lost by the
gas.
15.3.4. Which one of the following statements is not consistent with the
first law of thermodynamics?
b) An engine may be constructed such that the work done by the machine
exceeds the energy input to the engine.
Section 4:
Thermal Processes
Thermal Processes
A quasi-static process is one that occurs slowly enough that a uniform
temperature and pressure exist throughout all regions of the system at all
times.
W Fs P As PV
Isobaric process:
W PV P V f Vi
Sign Convention of AP is opposite that of our book!
Isobaric Process
W PV P V f Vi
Work by the system is the area under a PV graph.
Work is path dependent
Example 3 Isobaric Expansion of Water
W PV
W 2.0 105 Pa 1.0 108 m3 0.0020J
U Q W Q
W PV 0
Example 4 Work and the Area Under a
Pressure-Volume Graph
a) GHBD
b) GFBD
c) HABD
d) EDFH
e) CBFG
15.4.2. Consider the pressure-versus-volume plot shown. There are eight
points labeled and the choices below indicate possible multi-step
processes. If the initial state of the system is at A and the final state is
at E, which of the following paths between these two states results in
the largest increase in internal energy of the system?
a) AHDE
b) ABFE
c) AGE
d) ACE
a) A
b) B
c) C
d) D
e) E
15.4.4. An insulated container with rigid walls has two compartments
within. One compartment contains n moles of an ideal gas and the
other compartment has been evacuated. A valve connecting the two
chambers is opened at time t = 0 s. Which one of the following
statements concerning this situation is true?
e) The gas will remain in the first compartment unless heat is added to the
system.
15.4.5. In which of the following cases is a system undergoing an isobaric
process?
b) The system is an ideal gas enclosed in a container with a piston that may
move up or down. A heavy object is placed on top of the piston.
Section 5:
Thermal Processes Using an Ideal Gas
Isothermal Expansion or Compression of an Ideal Gas
Work is the area under
a PV graph integral Vf
W PdV
Calculus Alert! Vi
Vf nRT
Isothermal
expansion or W dV
compression of
Vi V
an ideal gas
V f dV
W nRT
Vi V
xf dx Vf
xi x
ln x f ln xi ln
V
i
Vi
W nRT ln
V
f
Example 5 Isothermal Expansion of an Ideal Gas
(a) Vi
W nRT ln
V
f
0.025 m 3
W 2.0 mol8.31J mol K 298 K ln 3400 J
3
0.050 m
U Q W
3
U nRT
2
W 32 nRT f Ti
PiVi P V o o
b) W1 = W2 = 0
c) W1 > W2
d) W1 < W2
e) It is not possible to compare the work done along each path without
knowing the values of the temperature, pressure, and volume for each
state.
15.5.4. Consider the following pressure-volume graphs. Which of these
graphs represents the behavior of a gas undergoing free expansion?
a) A
b) B
c) C
d) D
e) None of the
graphs represent a
gas undergoing free
expansion.
15.5.5. A gas is enclosed in a cylinder by a piston. The volume of the gas
is then reduced to one half its original value by applying a force to the
piston. Which one of the following statements concerning the internal
energy of the gas is true?
c) The internal energy of the gas will neither increase nor decrease.
d) The internal energy of the gas will equal the work done in moving the
piston.
e) The internal energy of the gas may increase, decrease, or remain the
same depending on the amount of heat that is gained or lost by the gas.
Chapter 15
Thermodynamics
Section 6:
Specific Heat Capacities
Specific Heat Capacities
To relate heat and temperature change in solids and liquids, we
used:
Q mcT
specific heat
capacity
Q nCT
molar specific
heat capacity
Specific Heat Capacities – Constant
P
For gases it is necessary to distinguish between the molar specific heat
capacities which apply to the conditions of constant pressure and constant
volume:
CV , CP
UnR
3
2
T
Qconstant pressure
U W 23
nRT f Ti nR T f Ti 2 nRT
5
first law of
thermodynamics
constant volume
for a monatomic CV 32 R
ideal gas g is the ratio of the
molar specific heat
capacities at constant
monatomic CP 52 R 5 pressure and volume
ideal gas 3
CV 2 R 3
any ideal gas CP CV R
Chapter 15
Thermodynamics
Section 7:
The Second Law of Thermodynamics
Second Law of Thermodynamics
The second law is a statement about the natural tendency of heat to
flow from hot to cold, whereas the first law deals with energy conservation
and focuses on both heat and work.
Section 8:
Heat Engines
Heat Engine
A heat engine is any device that uses heat to
perform work. It has three essential features.
Heat is supplied to the engine at a relatively
high temperature from a place called the hot
reservoir.
Part of the input heat is used to perform work
by the working substance of the engine.
The remainder of the input heat is rejected to a
place called the cold reservoir
W
e
QH
If there are no other losses, then
QH W QC
W QH QC
QH QC QC
e 1
QH QH
Example 6 An Automobile Engine
QH W QC W
e W
QH QH
e
QC QH W
W 1
QC W W 1
e e
1
QC 2510 J 1 8900 J
0.220
15.8.1. An automobile engine that burns gasoline has been
engineered to have a relatively high efficiency of 22 %. While a
car is being driven along a road on a long trip, 14 gallons of
gasoline are consumed by the engine. Of the 14 gallons, how
much gasoline was used in doing the work of propelling the car?
a) 14 gallons
b) about 11 gallons
c) about 8 gallons
d) about 3 gallons
e) about 1 gallon
Chapter 15
Thermodynamics
Section 9:
Carnot’s Principle & the Carnot Engine
Carnot Principle
A reversible process is one in which both the system and the
environment can be returned to exactly the states they were in
before the process occurred.
QC TC TC
e 1 1 ec 1
QH TH TH
Example 7 A Tropical Ocean as a Heat Engine
Water near the surface of a tropical ocean has a temperature of 298.2 K, whereas
the water 700 meters beneath the surface has a temperature of 280.2 K. 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 and engine.
TC 280.2 K
ec 1 1 0.060
TH 298.2 K
Conceptual Example 8 Natural Limits on the Efficiency of a Heat Engine
b) An engine may be constructed such that the work done by the machine
exceeds the energy input to the engine.
Section 10:
Refrigerators, Air Conditioners, and Heat Pumps
Refrigeration
Refrigerators, air conditioners, and heat pumps are devices that make
heat flow from cold to hot. This is called the refrigeration process.
Refrigeration
Conceptual Example 9 You Can’t Beat the Second Law of Thermodynamics
Refrigerator or
QC
Coefficient of performance
air conditioner W
Heat Pumps
The heat pump uses
work to make heat from
the wintry outdoors flow
into the house or to hot
Summer weather
outside.
heat
pump
QH
Coefficient of performance
W
Example 10 A Heat Pump
An ideal, or Carnot, heat pump is used to heat a house at 294 K. How much
work must the pump do to deliver 3350 J of heat into the house on a day when
the outdoor temperature is 273 K?
QC TC TC
QC QH
W QH QC QH TH TH
TC
W QH QH
TH
TC 273 K
W QH 1 3350 J 1 240 J
TH 294 K
15.10.1. A house that is heated using a heat pump with an ideal coefficient of
performance loses heat to its surroundings at a rate of Z1(Thouse Tsurr.), where
Z1 is a constant, Thouse is the temperature inside the house; and Tsurr. is the
temperature of its surroundings. In this process, heat is taken from the
surroundings and heats the house at a rate of Z2(Tout Thouse) where Tout is the
temperature of the air output from the heat pump, which has a constant value.
Which one of the following expressions is equal to the efficiency of the heat
pump?
Tout Thouse
a) T T d) Tsurr. Thouse
out surr.
Tsurr. Tout
b) Tsurr. Tout e) Tsurr. Thouse
Thouse
c) Tout Tsurr.
15.10.2. An air conditioner pumps heat from a cold room to the hot outdoors in a three step
cyclic process:
(1) Room temperature, low pressure refrigerant gas passes through a compressor and comes
out with increased temperature and increased pressure. The hot gas passes through
piping on the outside, where heat is rejected to the surroundings.
(2) The gas then passes through a narrower pipe before entering a compressor. Work is
done by the compressor to increase the pressure enough for the gas to turn into a liquid.
(3) The liquid then undergoes free expansion into a gas and cools. The cool gas passes
through pipes that are inside the house. The inside air is cooled by coming into contact
with these pipes. The refrigerant gas exits these pipes as a room temperature, low
pressure gas. The cycle is then repeated.
Why doesn’t this system violate the second law of thermodynamics?
a) The internal energy of the gas is constant.
b) Heat is normally taken from a warm place and transported to a warmer place.
Section 11:
Entropy
Entropy
In general, irreversible processes cause us to lose some, but not necessarily
all, of the ability to do work. This partial loss can be expressed in terms of
a concept called entropy.
Carnot QC TC QC QH
engine QH TH TC TH
entropy Q
change S
T R
reversible
Entropy
Entropy, like internal energy, is a function of the state of the system.
Q
S
T R
QC QH
S 0
TC TH
QC QH 1200 J 1200 J
S universe 1.6 J K
TC TH 350 K 650 K
Restating the Second Law
(a) TC 150 K
ecarnot 1 1 0.77
TH 650 K
W
e W ecarnot QH 0.771200 J 920 J
QH
TC 150 K
(b) ecarnot 1 1 0.57
TH 350 K
W ecarnot QH 0.571200 J 680 J
a) Entropy will always be increasing since the work done on the gas in the box is
negative.
b) Entropy will always be increasing since the temperature of the box is always
less than or equal to T2.
d) Entropy will always be increasing since the temperature of the box is always
greater than absolute zero.
a) Yes, but the law does not apply to living things. It only applies to
inanimate objects.
c) No, because the entropy of the Sun has decreased while the entropy of the
leaf increases as it grows.
d) No, because while the entropy of the leaf is decreasing as it grows, there
is a net increase in entropy because of the light emitted from the leaf.
a) conservation of energy
d) time dilation
Section 12:
The Third Law of Thermodynamics
The 3rd Law of Thermodynamics