Thermodynamics

• Thermodynamics Systems and their
Surroundings

• The Laws of Thermodynamics

• Thermal Processes
15.1 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.



15.1 Thermodynamic Systems and Their 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.
15.2 The Zeroth Law of Thermodynamics
Two systems are said to be in thermal equilibrium if there is
no heat flow between then 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.
15.2 The Zeroth Law of Thermodynamics
THE ZEROTH LAW OF
THERMODYNAMICS

Two systems individually in thermal
equilibrium with a third system are in
thermal equilibrium with each other.
15.3 The First Law of Thermodynamics
Suppose that a system gains heat Q and that is the only effect
occurring.

Consistent with the law of conservation of energy, the internal
Energy of the system changes:
Q U U U
i f
= ÷ = A
Heat is positive when the system gains heat and negative when
the system loses heat.
15.3 The First Law of Thermodynamics
If a system does work W on its surroundings and there is no
heat flow, conservation of energy indicates that the internal
energy of the system will decrease:
W U U U
i f
÷ = ÷ = A
Work is positive when it is done by the system and negative
when it is done on the system.
15.3 The First Law of Thermodynamics
THE FIRST LAW OF THERMODYNAMICS

The internal energy of a system changes due to heat and work:


W Q U U U
i f
÷ = ÷ = A
Work is positive when it is done by the system and negative
when it is done on the system.
Heat is positive when the system gains heat and negative when
the system loses heat.
15.3 The First Law of Thermodynamics
Example 1 Positive and Negative Work

In part a of figure, the system gains 1500J of heat
and 2200J of work is done by the system on its
surroundings.

In part b, the system also gains 1500J of heat, but
2200J of work is done on the system.

In each case, determine the change in internal energy
of the system.
15.3 The First Law of Thermodynamics
(a)
(b)
( ) ( ) J 700 J 2200 J 1500 ÷ = + ÷ + =
÷ = A W Q U
( ) ( ) J 3700 J 2200 J 1500 + = ÷ ÷ + =
÷ = A W Q U
15.3 The First Law of Thermodynamics
Example 2 An Ideal Gas

The temperature of three moles of a monatomic ideal gas is reduced
from 540K to 350K as 5500J of heat flows into the gas.

Find (a) the change in internal energy and (b) the work done by the
gas.
nRT U
2
3
=
W Q U U U
i f
÷ = ÷ = A
15.3 The First Law of Thermodynamics
( ) ( ) ( )( ) J 7100 K 540 K 350 K mol J 31 . 8 mol 0 . 3
2
3
2
3
2
3
÷ = ÷ · =
÷ = A
i f
nRT nRT U
( ) J 12600 J 7100 J 5500 = ÷ ÷ = A ÷ = U Q W
(a)
(b)
Exercise 1
When the gas enclosed beneath the piston shown in the
figure receives 2170 J of heat, Q, from its surroundings,
it performs 2840 J of work in raising the piston. What is
the change in the internal energy of the gas?
Ans: ΔU = – 670 J

15.4 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.
isobaric: constant pressure
isochoric: constant volume
isothermal: constant temperature
adiabatic: no transfer of heat
An isothermal process is one in which the temperature
does not change.

An adiabatic process is one in which there is no heat flow
into or out of the system.

The following is a simple summary of the
various thermodynamic processes.
15.4 Thermal Processes: Isobaric Process
An isobaric process is one that occurs at
constant pressure.
( ) V P As P Fs W A = = =
Isobaric process: ( )
i f
V V P V P W ÷ = A =
15.4 Thermal Processes: Isobaric Process
Example 3 Isobaric Expansion of Water

One gram of water is placed in the cylinder and
the pressure is maintained at 2.0x10
5
Pa. The
temperature of the water is raised by 31
o
C. The
water is in the liquid phase and expands by the
small amount of 1.0x10
-8
m
3
.

Find the work done and the change in internal
energy.
15.4 Thermal Processes: Isobaric Process
( )( ) J 0020 . 0 m 10 0 . 1 Pa 10 0 . 2
3 8 5
= × × =
A =
÷
V P W
J 130 J 0020 . 0 J 130 = ÷ = ÷ = A W Q U
( ) ( ) | |( ) J 130 C 31 C kg J 4186 kg 0010 . 0 = · = A =
 
T mc Q
15.4 Thermal Processes: Isobaric Process
( )
i f
V V P V P W ÷ = A =
Exercise 2
A system containing an ideal gas at a constant pressure
of 1.42 x 10
5
Pa gains 2320 J of heat. During the
process, the internal energy of the system increases by
2540 J. What is the change in volume of the gas?

Ans: ΔV = –1.55 x 10
–3
m
3
15.4 Thermal Processes: Isochoric
isochoric: constant volume
Q W Q U = ÷ = A
0 = W
15.4 Thermal Processes
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 in the figure.
The area under a pressure-volume graph is
the work for any kind of process.
15.4 Thermal Processes
Since the volume increases, the work
is positive.

Estimate that there are 8.9 colored
squares in the drawing.
( )( )
J 180
m 10 0 . 1 Pa 10 0 . 2 9 . 8
3 4 5
+ =
× × =
÷
W
For an isothermal process, P = nRT/V.
Integrating to find the work done in taking the
gas from point A to point B gives:
15.5 Thermal Processes Using and Ideal Gas
ISOTHERMAL EXPANSION OR COMPRESSION
Isothermal
expansion or
compression of
an ideal gas
|
|
.
|

\
|
=
i
f
V
V
nRT W ln
15.5 Thermal Processes Using and Ideal Gas
Example 5 Isothermal Expansion of an Ideal Gas

Two moles of the monatomic gas argon expand isothermally at 298K
from and initial volume of 0.025m
3
to a final volume of 0.050m
3
. Assuming
that argon is an ideal gas, find (a) the work done by the gas, (b) the
change in internal energy of the gas, and (c) the heat supplied to the
gas.
15.5 Thermal Processes Using and Ideal Gas
(a)
( ) ( ) ( )( ) J 3400
m 25 0 . 0
m 050 . 0
ln K 298 K mol J 31 . 8 mol 0 . 2
ln
3
3
+ =
|
|
.
|

\
|
· =
|
|
.
|

\
|
=
i
f
V
V
nRT W
0
2
3
2
3
= ÷ = A
i f
nRT nRT U
(b)
W Q U ÷ = A
(c)
J 3400 + = =W Q
15.5 Thermal Processes Using and Ideal Gas
ADIABATIC EXPANSION OR COMPRESSION
Adiabatic
expansion or
compression of
a monatomic
ideal gas
( )
f i
T T nR W ÷ =
2
3
Adiabatic
expansion or
compression of
a monatomic
ideal gas
¸ ¸
f f i i
V P V P =
V P
c c = ¸
15.6 Specific Heat Capacities
To relate heat and temperature change in solids and liquids, we
used:
T mc Q A =
specific heat
capacity
The amount of a gas is conveniently expressed in moles, so we write the
following analogous expression:
T Cn Q A =
molar specific
heat capacity
15.6 Specific Heat Capacities
For gases it is necessary to distinguish between the molar specific heat
capacities which apply to the conditions of constant pressure and constant
volume:
P V
C C ,
( ) ( ) T nR T T nR T T nR W U Q
i f i f
A = ÷ + ÷ = + A =
2
5
2
3
pressure constant
  
  
          
first law of
thermodynamics
nRT U
2
3
=
V P W A =
constant pressure
for a monatomic
ideal gas
R C
P 2
5
=
15.6 Specific Heat Capacities
( ) T nR T T nR W U Q
i f
A = + ÷ = + A =
2
3
2
3
olume constant v
0
  
          
first law of
thermodynamics
nRT U
2
3
=
constant pressure
for a monatomic
ideal gas
R C
V 2
3
=
monatomic
ideal gas
3
5
2
3
2
5
= = =
R
R
C
C
V
P
¸
any ideal gas R C C
V P
= ÷
Molar Specific Heats for Gases, and the Equipartition of
Energy
For gases, the specific heat depends on the
process—the isothermal specific heat is
different from the isovolumetric one.
Molar Specific Heats for Gases, and the Equipartition of Energy
In this table, we see that the specific heats for gases with
the same number of molecules are almost the same, and
that the difference C
P
– C
V
is almost exactly equal to 2 in all
cases (R=1.986 cal/mol·K)
Exercise 3
An ideal gas absorbs 750 J of heat as it performs 625 J
of work. What is the resulting change in temperature if
there are 1.3 moles of the gas in the system?

Ans: ΔT = 7.7 K

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