In this lecture youll learn

Chapter 17 Lecture

The ideal-gas
ideal gas law
And the relationship between
macroscopic and
microscopic quantities
quantities,
especially temperature and
molecular energy
To describe the three principle
phases of matter
To calculate the energies
involved in phase transitions
To interpret phase diagrams

The Thermal Behavior

off Matter

To calculate thermal expansion

of solids, liquids, and gases

Slide 17-2

Slide 17-1

The Gas Laws

The Ideal-Gas Law

Boyle
Boyles
s Law:

1
P

An ideal gas of N molecules in a closed container obeys a

simple relation between pressure P, volume V, and
temperature T:

(Constant T)

PV NkT

Here k = 1.381023 J/K is Boltzmanns constant.

P must be the absolution pressure
T must be measured in Kelvin
The behavior of most real gases closely approximates the
ideal gas law
If the amount of g
gas does not change:
g

Charles Law:

V T

(Constant P)

Gay-Lussacs Law:

P T

P1V1 P2V2

T1
T2

(Constant V)

Slide 17-3

The Ideal-Gas Law: Alternative Version

Clicker Question

The ideal gas law can also be expressed in terms of the

number of moles of the gas, n:

Two identical cylinders at the same pressure contain the

same gas. If A contains three times as much gas as B, which

PV nRT
Here n= N/NA, where NA = 6.0221023 is the Avogadros
number
R = NAk = 8.314 J/(molK) = 0.0821 (Latm)/(molK) is the
universal gas constant.
At standard
t d d ttemperature
t
and
d pressure (STP) or 0 C and
d1
atm, the volume of 1 mol of gas is 22.4 L
Since the number of moles is also given by mass of the gas (m)
divided the molar mass (M), n = m/M, the ideal gas law can be
written in terms of the density of the gas :

Slide 17-4

cylinder has the higher temperature?

1) cylinder
li d A
2) cylinder B
3) both the same
4) it depends on the pressure P

RT
Slide 17-5

Clicker 17-6

Clicker Question

Clicker Question

Two cylinders at the same temperature contain the same

gas. If B has twice the volume and half the number of moles
as A,
A how does the pressure in B compare with the pressure
in A?
1) PB = 1/2 PA

Consider an air bubble underwater that has the same pressure

as that of the water. As the air bubble rises to the surface, with
the surrounding temperature kept constant, the volume of the
air bubble
A.
B.
C.
D.

2) PB = 2 PA
3) PB = 1/4 PA
4) PB = 4 PA

increases.
decreases.
remains fixed.
could increase or decrease depending on how fast it
rises.

5) PB = PA

Clicker 17-7

Clicker Question

Clicker 17-8

Clicker Question

Water with air bubbles flows through a pipe that gets narrower.
In the narrow region, the bubbles are:

You have two containers of equal volume. One is full of

helium gas. The other holds an equal mass of nitrogen
gas Both gases have the same pressure
gas.
pressure. How does the
temperature of the helium compare to the temperature of
the nitrogen?
1. Thelium < Tnitrogen
2. Thelium = Tnitrogen
3. Thelium > Tnitrogen

Clicker 17-9

Clicker Question

Clicker 17-10

Clicker Question
An auditorium has a volume of 3 x 103 m3. How many
molecules of air are needed to fill the auditorium at STP?
(NA = 6.022 x 1023 (mol)-11) Select the correct answer.

What is the ratio Tf /Ti for this process?

A. 4
B. 2

1.
2.
3.
4.
5.

C 1 (no change)
C.
D. 1/2
E. 1/4

Clicker 17-11

0.8 x 1029
0.8 x 1034
0.8 x 1021
0.8 x 1026
0.8 x 1033

Clicker 17-12

Clicker Question
Consider two containers that have the same volume and
temperature. Inside one container is "dry" air--a mixture of
nitrogen and oxygen. In the second container there is "moist"
air The "moist"
air.
moist air has the same ratio of nitrogen to oxygen
molecules, but it also has some water vapor in the container.
According to the ideal gas law, if the pressures are equal, the
weight off the gas inside the first
f
container will be
1.
1
2.
3.
4.

lighter than the gas inside the second container

container.
equal to the weight of the gas in the second container.
heavier than the g
gas inside the second container.
all these are incorrect because the pressures cannot be
equal.

Kinetic Theory of the Ideal Gas:

p
Assumptions
The number of molecules in the gas is large and the
average separation between them is large compared to
their dimensions
The molecules
molec les obe
obey Ne
Newtons
tons la
laws
s of motion
motion, b
butt as a
whole they move randomly
The molecules interact only by short-range
short range forces during
collisions
The molecules make p
perfectly
y elastic collisions with the
walls

Clicker 17-13

Kinetic Theory of the Ideal Gas

Molecular Interpretation of Temperature

Comparing
p
g the kinetic theory
y to the ideal g
gas law, we have:
1 2 3
21 2
KE mv kT
mv kT
2
2
32

The force exerted on the wall byy the

collision of one molecule is
2mv x 2mv x
mv x 2
F1

t
2L vx
L

thus the average translational kinetic energy of the molecules in

an ideal gas is directly proportional to the temperature.
The total kinetic energy of the gas is given by:

The force due to all molecules colliding

with that wall is
mv x2
FN
L
The averages
g of the squares
q
of the
speeds in all three directions are equal:
mv 2
1
v x2 v 2y v z2 v 2 F N
3L
3
So the pressure is:
P

Slide 17-14

3
3
NkT nRT
2
2
In a monoatomic ideal gas, the kinetic energy is the only type of
internal energy that the molecules can have:
3
U nRT
2
In a p
polyatomic
y
g
gas, additional p
possibilities for contributions to
the internal energy are rotational and vibrational motion of the
molecules
KE tot

Pressure arises from collisions of

F
mv 2
mv 2 2 N 1 2 the molecules with the walls
N
N
mv
A
3 AL
3V
3 V 2

Slide 17-15

Molecular Speeds and The MaxwellBoltzmann Distribution

Clicker Question

The thermal speed or the root-meansquare (rms) speed of the molecules

is

vrms

Slide 17-16

Which system has the largest average translational

kinetic energy
gy p
per molecule?

3kT
3RT

m
M

where M is the molar mass. Thus at a

given temperature, lighter molecules
move faster on average
average.
At a given temperature, the molecules
exhibit a distribution of speeds, as
derived by Maxwell and Boltzmann
Boltzmann.
At high temperatures the
distribution is broader and peaks
at a higher speed, but the area
under the curve stays the same

Lighter molecules have a higher probability of

reaching the escape speed from the Earth

Slide 17-17

A.
B.
C
C.
D.
E.

1 mol of He at p = 1 atm, T = 300 K

2 mol of N2 at p = 0.5 atm, T = 450 K
2 mol of He at p = 2 atm,
atm T = 300 K
1 mol of Ar at p = 0.5 atm, T = 450 K
1 mol of N2 at p = 0.5 atm, T = 600 K

Clicker 17-18

Clicker Question

Phase Diagrams

An ideal gas is initially held in a container of volume V at

pressure P, and the thermal speed of the gas molecules under
these conditions is v.
v If both the volume and pressure are
doubled to 2V and 2P, the thermal speed of the gas molecules
becomes
A.
B
B.
C.
D
D.
E.

v
2
2v
4v
v/2
v/4

The p
phases of a substance can be
displayed on a plot of pressure versus
temperature.
The solid-liquid
solid liquid transition is melting or
freezing
The liquid-vapor
q
p transition is boiling
g or
condensing
The solid-vapor transition is sublimation
The triple point is the only point where
all three phases can coexist in
equilibrium.
q
The liquid-gas curve ends at the critical
point, where the sharp distinction
b t
between
liquid
li id and
d gas di
disappears.

Water

http://www.youtube.com/watch?v=pOYgdQp4euc
Carbon Dioxide

Slide 17-19

Vapor Pressure and Humidity

Latent Heat

An open container of water can evaporate, rather than

boil, away. The fastest molecules are escaping from the
waters surface, so evaporation is a cooling process.
The inverse process is called condensation.
When the evaporation and condensation processes are
in equilibrium, the vapor just above the liquid is said to
be saturated
saturated, and its pressure is the saturated vapor
pressure.
A liquid boils when its saturated vapor pressure equals the external
pressure.
The partial pressure of water in the air can be as low as zero, and as
high as the saturated vapor pressure at that temperature. The
relative humidity is defined as the ratio of the partial pressure to the
saturated vapor pressure at a given temperature.
point is the temperature
p
at which the air would be saturated
The dew p
with water. If the temperature goes below the dew point, dew, fog, or
even rain may occur.

Energy
gy is required
q
for a material to change
g p
phase,, even though
g
its temperature is not changing.
On the molecular level, the heat added during a phase change
from solid to liquid and liquid to gas does not increase the
kinetic energy of individual molecules, but rather goes into
breaking molecular bonds.
During a phase change, the amount of heat involved is given as
Q = m L, where L (J/kg) is the heat of transformation, or the
latent heat of the substance
Choose a positive sign if heat is added to the system and a
negative sign if heat is removed from the system
The solid-liquid transition involves the heat of fusion, Lf.
The liquid-gas transition involves the heat of vaporization, Lv.
The direct transition from solid to gas involves the heat of
sublimation, Ls.

Slide 17-21

Example: 1kg Ice to Water to Steam

cice 2090 J kg
k C

Lf 3.33 10 5 J kg
k

c water 4186 J kg C

Lv 2.26 10 6 J kg

Slide 17-20

Slide 17-22

Clicker Question

csteam 2010 J kg C

As a sample of gas undergoes phase change to liquid, the gas

A. absorbs energy.
B. releases energy.
C. neither absorbs nor releases energy.

Energy added (kJ)

Slide 17-23

Slide 17-24

Clicker Question

Clicker Question

You bring a pot of water to boil for some pasta and then your
friend calls on the telephone. Ten minutes later you come back
to the kitchen to find the water still boiling. Its temperature is

Iced tea is made by

y adding
g ice to 1.8 kg
g of hot tea, initially
y
at 80C. How many kg of ice, initially at 0C, are required
to bring the mixture to 10C? (Lf = 80 kcal/kg)

A. greater than 100 C.

B equal to 100 C.
B.
C
C. less than 100 C.

1.
2.
3.
4.

1.8 kg
g
1.6 kg
1.4 kg
1.2 kg

Clicker 17-25

Thermal Expansion

Clicker Question

Most materials expand when heated.

The coefficient of linear expansion, , is
defined as the fractional change in length
per unit temperature change:

L L
T

Clicker 17-26

A long steel beam has a length of 25 m on a cold day

when the temperature is 0C. What is the length of
th b
the
beam on a h
hott d
day when
h T = 40C? ((steel = 1.1
11x
10 -5 / C)

(Typical ~105)
1.
2
2.
3.
4.

Liquids
q
and g
gases are best characterized by
y
the coefficient of volume expansion,
defined as:
V V

T
For an isotropic solid,

25.00044 m
25.0044
25
0044 m
25.011 m
25.044 m

Slide 17-27

Clicker Question

Slide 17-28

Clicker Question
Y wantt to
You
t take
t k apartt a couple
l off aluminum
l i
parts
t held
h ld

Metals such as brass expand when heated. The thin

brass plate has a circular hole in its center. When the
plate is heated, what will happen to the hole?

together by steel screws, but the screws are stuck.

?
What should you do?
1) heat the thing up

1) gets larger

2) cool the thing down

2) gets smaller

3) blow the thing up

3) stays the same

Quartz

Glass Steel Al

Hg

Air

4) vanishes

Slide 17-29

Coefficient of volume expansion (1/

(1/C
C)
Slide 17-30

Clicker Question

The Anomalous Behavior of Water

A grandfather clock uses a brass pendulum to keep perfect

time at room temperature.
temperature If the air conditioning breaks down
on a very hot summer day, how will the grandfather clock be
affected?
1) clock will run slower than usual

Between 0C and 4C,, water contracts on heating.

g
This is a residual effect of the hydrogen bonds that form
ice crystals.
The open structure of the ice crystal makes ice less dense
than liquid water.
Hence solid water
water, unlike most substances
substances, floats in its
liquid phase.
This fact has enormous consequences for aquatic life.

2) clock will still keep perfect time

3) clock will run faster than usual

Slide 17-31

Summary
The ideal-gas
ideal gas law relates pressure
pressure, temperature
temperature, and
volume: PV = NkT
Derivation of the ideal-gas law from Newtonian mechanics
shows that temperature measures the average kinetic
energy of the gas molecules.
Phase changes take substances between solid and liquid
liquid,
liquid and gas, solid and gas.
Phase changes require energy,
described by the heats of
transformation.
The phase structure of a substance
is described in its phase diagram
diagram.
Thermal expansion occurs as most substances are heated.
An
A exception
ti iis water
t iin th
the range ffrom 0C tto 4C
4C.
Slide 17-33

Slide 17-32