Chapter 18 Lecture

In this lecture youll learn

Heat, Work, and the First

L
Law
off Th
Thermodynamics
d
i

Slide 18-1

The First Law of Thermodynamics

To explain the first law of

thermodynamics and how it
extends the principle of
conservation of energy to
thermal phenomena
To describe the basic
thermodynamic processes
applied to ideal gases
Isothermal
Constant volume
Isobaric
Adiabatic
To understand the specific
heats of gases based on
their molecular structure

Slide 18-2

Doing Work

Extension of conservation of energy to include thermodynamic

processes
The change in internal energy of a system is equal to the heat
added to the system plus the work done on the system by its
surroundings:

U = Uf U i = Q + W
Q is positive if energy is transferred to the system and
negative
ti if energy iis ttransferred
f
d outt off the
th system
t

Ap
piston-cylinder
y
system
y
is a useful device for describing
g the
thermodynamic behavior of a gas.
The piston seals the cylinder, allowing the gas volume to
change
h
without
ith t any gas escaping.
i
Work can be done on or by the gas as the piston moves.
If the bottom is uninsulated,
uninsulated heat can flow in or out
out.
The work done on the gas is the negative of the area under
V2
the pV curve:
W pV p dV
V1

W is positive if work is done on the system and negative if

work is done by the system
U is a state function that depends on the thermodynamic state
of the system
y
((P,, V,, T)) and not on how the system
y
arrives at
that state
Slide 18-3

Clicker Question

Reversible and Irreversible Processes

Changing the state of a system can be
done

What is the work done by the gas as it expands from

pressure P1 and volume V1 to pressure P2 and
volume V2 along the indicated straight line?

1.
2.
3.
4.

Slide 18-4

Reversibly, in which case the system

always remains in thermodynamic
equilibrium and follows a well-defined
path in the P-V diagram.

(P1 + P2) (V2 V1) /2

(P1 + P2) (V2 V1)
(P1 - P2) (V2 V1) /2
(P1 - P2) (V2 + V1)

Irreversibly
Irreversibly, in which case the system
goes temporarily out of equilibrium,
without well-defined values for
temperature, pressure, and other
quantities.

Slide 18-5

Slide 18-6

Isothermal Processes and the Ideal Gas

Constant-Volume Processes

An isothermal p
process takes p
place at constant
temperature.
One way to achieve this is to keep the
system in thermal contact with a heat
reservoir a much larger system held at
constant temperature.
The ideal gas law gives P = nRT/V.
Then, with constant T, the work done is

In a constant-volume process (also called isometric

isometric,
isochoric, or isovolumetric), the heat added to the gas and
the resulting temperature change are related by
Q = nCV T
Here CV (J/K
(J/Kmol)
mol) is the molar specific heat at constant
volume.
No work is done in a constant-volume process, so W = 0 and
the first law reads U = Q.
Therefore U = nCV T.
For
F an ideal
id l gas, iinternal
t
l energy d
depends
d on ttemperature
t
alone, so this relationship U = nCV T between U and
T holds for any process.

dV
nRT ln V2 V1
V
Since the temperature
p
doesnt change,
g ,
neither does the internal energy of an ideal
gas. Therefore the first law gives
V2

V2

V1

V1

W p dV nRT

Q W nRT ln V2 V1
Slide 18-7

Isobaric Processes

Slide 18-8

Clicker Question

An isobaric process takes place at constant pressure.

pressure
Then the work done is W = p V.
Adding
g heat to an ideal g
gas results both in a temperature
p
change and in work being done on the surroundings.
Therefore it takes more heat to
create
t a given
i
ttemperature
t
change:
h

Which first-law bar chart describes the

process shown in the pV diagram?

U ii W Q U ff

Ui W Q U f

Ui W Q U f

Q = nCV T + p V
The molar specific heat at
constant pressure, Cp, expresses
this extra work:

Ui W Q U f

Ui W Q U f

nCp T = nCV T + p V
Thus
Th Cp = CV + R.
R
Slide 18-9

Clicker Question

Clicker 18-10

Adiabatic Processes

Containers A and B both have identical gases, and are initially

at the same temperature, pressure, and volume. The two
containers are then placed on a stove. If container A is kept at
a fixed volume and container B is kept at a fixed pressure
(allowing its volume to vary)
vary), in which container will the gas
heat up more quickly?
A. Container A
B. Container B
C Both
C.
B th are h
heated
t d up att the
th same rate.
t

No heat flows into or out of the system.

y
Therefore Q = 0 and the first law reads U = W.
Analysis of the adiabatic process for an ideal gas shows that

pV constant
where = Cp /CV is the ratio of specific heats of the gas.
An adiabatic curve or adiabat is
steeper than an isotherm because
during
g expansion,
p
, the g
gas does
work, it therefore loses internal
energy and its temperature drops.
In
I terms
t
off temperature,
t
t
we have
h

TV 1 constant

Clicker 18-11

The work done on the gas is

P V PV
W 2 2 1 1
1

Slide 18-12

Clicker Question

Ideal-Gas Processes: a Comparison

A gas cylinder and piston are covered with heavy insulation.

insulation
The piston is pushed into the cylinder, compressing the gas. In
this process, the gas temperature

1. doesnt change.
2. decreases.
3 increases
3.
increases.
4. theres not sufficient information to tell.
Slide 18-13

Clicker Question

Clicker Question

During which of the following processes is the work done by the

gas negative?
A.
B.
C.
D.

Slide 18-14

Isothermal expansion
Isobaric expansion
Isometric process
Isothermal compression

A 2 mole ideal gas system is maintained at a

constant
t t volume
l
off 4 liters;
lit
if 100 J off heat
h t is
i added,
dd d
what is the change in internal energy of the system?
1.
2.
3.
4.

zero
50 J
67 J
100 J

Slide 18-15

Clicker Question

Slide 18-16

Clicker Question

In a piston-cylinder system containing an ideal gas, the piston

is exposed
p
to atmospheric
p
p
pressure and is free to move while
the cylinder is cooled by placing it on a block of ice. What kind
of basic thermodynamic process does this represent?

A free expansion occurs when a valve is opened allowing a

gas to expand into a bigger container. Assuming that the
container is thermally insulated,
insulated the temperature of the gas
will:
1) increase
2) decrease

A. Isobaric
B Adiabatic
B.
C. Isothermal

3) stay the same

Clicker 18-17

Slide 18-18

Cyclic Processes

Clicker Question

Cyclic
y
p
processes combine the basic p
processes of other
thermodynamic processes to take a system around a
complete cycle and back to its starting state.

In the closed thermodynamic cycle shown in the P-V

Important in technological systems like engines

engines.
Also occur in natural systems from sound waves to oscillating stars.
The work done in or by the gas in a cyclic process is the area
enclosed
l
db
by the
h process curve iin the
h pV
V diagram.
di
For a cycle that is done in the clockwise (counterclockwise) direction,
the work done on the system is negative (positive)

diagram, the work done by the gas is:

P

1) positive
2) zero
3) negative

Slide 18-19

Clicker 18-20

Clicker 18-21

Recall that the temperature

p
of an ideal g
gas is a measure of the
average translational kinetic energy of the gas molecules
In a monoatomic gas with fixed volume, all the added energy
goes into
i t iincreasing
i th
the ttranslational
l ti
l ki
kinetic
ti energy off th
the
molecules
The total internal energy
gy U of n moles of monatomic g
gas is:
3
U nRT
2
The molar specific heats are then given by:
U 3
CV
R 12.5 J mol K
nT 2
5
CP CV R R 20.8 J mol K
2
C
5
= P 1.67
and adiabatic exponent
CV 3
Slide 18-22

Clicker Question

Specific Heats of an Ideal Monoatomic Gas

For the two processes shown, which of the

f ll i iis ttrue:
following

1. QA < QB.
2. QA = QB.
3. QA > QB.

DOF and Equipartition Theorem

Molar Specific Heats of Various Gases

More complex molecules have more degrees of freedom

freedom,
or ways they can absorb energy.
For example, at room temperature, diatomic gases have 5
degrees of freedom per molecule including three
translational and 2 rotational.
The equipartition theorem states
that when a system is in
thermodynamic equilibrium, the
average energy per molecule is kT/2
/
for each degree of freedom.
Thus for diatomic gases at room
temperature,
CV

At moderately high
temperatures, a triatomic
molecule such as CO2 can
ha e 6 degrees of freedom
have
per molecule (three
translational and 3 rotational),
and has volume specific heat
CV = 3R.

5
7
7
R, CP R, 1.4
14
2
2
5
Slide 18-23

Slide 18-24

Temperature Dependence of Specific Heat

At sufficiently high temperatures,

temperatures a
diatomic molecule such as H2 can
have 7 degrees of freedom per
molecule
l
l including
i l di 3 translational,
l i
l 2
rotational, and 2 vibrational (kinetic
and p
potential energies),
g ), and has
volume specific heat CV = 7R/2.

Clicker Question
How many degrees of freedom does a bead on a wire have?

A. 1
B. 2

Conversely, at low enough

temperatures, the rotational degrees
of freedom are frozen out and do
not contribute to the internal energy
or the specific heat.
To explain
p
the temperature
p
dependence requires some quantum
mechanics.

C. 3
D. 4
E. 5

Slide 18-25

Clicker Question

Slide 18-26

Summary

The reason why a diatomic molecule can have just three degrees of
freedom rather than five degrees of freedom is that:
1. The two degrees of freedom associated with rotation are not likely
to be excited when kBT is much less than the quantum unit of
minimum rotational energy excitation.
2. The two degrees of freedom associated with rotation are not likely
to be excited when kBT is much greater than the quantum unit of
minimum rotational energy excitation
excitation.
3. At low temperature the long range intermolecular attractions
between molecules prevent the rotational degrees of freedom from
being activated.
4. The vibrational degree of freedom interferes with the rotational
degree of freedom,
freedom which limits the number of apparent degrees of
freedom.
Slide 18-27

The first law of thermodynamics

y
states that the change
g in a
systems internal energy is equal to the heat added to the
system plus the work done on the system
Thermodynamic processes take systems between states in
their pV diagrams.
Reversible processes remain in equilibrium and follow a
definite path in the pV diagram.
diagram
Irreversible processes result in temporary loss of
equilibrium and dont follow a definite path.
Important ideal-gas processes include isothermal, constant
volume, isobaric, adiabatic, and cyclic processes that
combine these or other processes to take a system through
a complete
l t cycle
l
The specific heats of an ideal gas depend on the structure of
the g
gas molecules
More complex molecules have more degrees of freedom
for absorbing energy.

Slide 18-28