Atomic model of matter

The ideal gas model

Ideal-gas processes
Specific heat and heat of
transformation
Heat transfer modes
Chapter 12
Thermal Properties of Matter
Topics:
Sample question:
This thermal image of an elephant shows energy that the elephant
radiates. How important is this radiated energy to the elephants
energy balance?
Phases of matter Gas
Phases of matter Liquid
Phases of matter Solid
A mole is the amount of a substance containing as
many elementary entities (basic particles atoms or
molecules) as there are atoms in 12 g of carbon-12.
Avogadros Number
Experimentally, this number is given by the
Avogadros number:
n moles of gas contains N = nN
A
molecules.
Each mole contains ~ a trillion trillion molecules!
N
A
= 6.02 x 10
23
mol
1
The atomic or molecular mass of a substance is the
mass, in grams, of one mole of that substance.
For example,
Helium:
Copper:
Atomic/Molecular Mass
The mass of an individual atom is given by the
atomic mass divided by Avogadros number.
m(
4
He) = 4.00260 (g/mol, u)
m(
63
Cu) = 63.546 (g/mol, u)
What is the atomic mass of carbon-12?
m(
12
C) = 12 u, exact (by definition!)
Checking Understanding
What is the mass, in u, of a molecule of carbon dioxide, CO
2
?
A.12
B.24
C.32
D.36
E.44
What is the mass, in u, of a molecule of carbon dioxide, CO
2
?




44
Answer
Checking Understanding
Rank the following in terms of the number of moles, from
greatest number of moles to least:
A.20 g of He (A = 4)
B.60 g of Ne (A = 20)
C.120 g of O
2
(atomic oxygen, O, has A = 16)
D.160 g of Ar (A = 40)
E.200 g of Pb (A = 207)
Answer: A - D - C - B - E
The Ideal Gas
at the micro-level

K
avg
=
3
2
k
B
T =
1
2
mv
2
rms
|
\

|
.
|

v
rms
=
3k
B
T
m
E
th
= NK
avg
=
3
2
Nk
B
T
The Ideal gas
T = temperature (kelvin, K)
p = pressure (N/m
2
= pascal, Pa)
V = volume (m
3
)
n = number of moles
N = number of particles (atoms or molecules)
Ideal Gas Parameters
The kinetic energy of the particles determines the temperature;
collisions with the walls determines the pressure.
How do the pressures of the
gases inside and outside of a
balloon compare?
A. They are the same.
B. p
inside
> p
outside

p
inside
< p
outside
Checking Understanding
The Definition of Pressure
Pressure
Force per unit area
N/m
2
= pascal, Pa
The net force on a surface depends on the difference
in pressure on the two sides.
The atmospheric pressure
Standard atmosphere = absolute pressure at sea level

= 1 atm = 101,300 Pa = 101.3 kPa
gauge pressure = absolute pressure 1 atm
A mass sits on top of a piston that is free to
slide in a cylinder of gas. The pressure in
the gas in the cylinder is
A.greater than the pressure of the
atmosphere outside the cylinder.
B.equal to the pressure of the atmosphere
outside the cylinder.
C.less than the pressure of the atmosphere
outside the cylinder.
Checking Understanding
A mass sits on top of a piston that is free to
slide in a cylinder of gas. The pressure in
the gas in the cylinder is
A.greater than the pressure of the
atmosphere outside the cylinder.
Answer
The Ideal-Gas Law
Changing the temperature,
volume or number of particles
changes the pressure of the
gas. We can understand this
using our atomic model of the
ideal gas
and a human demo :-)
Kinetic Theory
Microscopic Quantities Macroscopic Quantities
Kinetic Theory
Averaged over large numbers of molecules
Position
Velocity
KE, etc.
Molecules
Temperature (T)
Pressure (p)
Volume (V)
Bulk
Assumptions:
N identical molecules of mass m are inside a container of volume V;
each molecule acts as a point particle.
They move randomly and obey Newtons laws.
Collisions with each other and with the walls are elastic.
(N)
Pressure is a result of
the collisional impact of
molecules on the wall.

p=
2
3
N
V
1
2
mv
rms
2
|
\

|
.
|
=
2
3
N
V
K
avg
A quantitative consideration of the physics of
collisions and resulting impact forces leads to the
following main result of the kinetic theory:
[ Carefully read pp. 381-382 of Knight, Jones, and Field. ]
3
2
k
B
T from Chapter 11
Main idea of the kinetic theory:
pV = Nk
B
T
pV = nRT
Absolute pressure in Pa
Volume of the gas in m
3
Number of moles in the gas
Gas constant [ 8.31 J/mol K ]
R = N
A
k
B
Boltzmanns constant
[ 1.38 10
23
J/K ]
Temperature of the gas in K
Number of basic particles in the gas
The Ideal-Gas Law [ equation of state ]
The two identical cylinders shown both
have the same mass on the piston and
the same volume. One contains
hydrogen, the other nitrogen. Both
gases are at the same temperature.
The number of moles of hydrogen is
A.greater than the number of moles of
nitrogen.
B.equal to the number of moles of
nitrogen.
C.less than the number of moles of
nitrogen.
Checking Understanding
The two identical cylinders shown both
have the same mass on the piston and
the same volume. One contains
hydrogen, the other nitrogen. Both
gases are at the same temperature.
The number of moles of hydrogen is


B. equal to the number of moles of
nitrogen.
Answer
The two identical cylinders shown both
have the same mass on the piston and
the same volume. One contains
hydrogen, the other nitrogen. The mass
of gas in each cylinder is the same. The
temperature of the hydrogen gas is
A.greater than the temperature of the
nitrogen.
B.equal to the temperature of the
nitrogen.
C.less than the temperature of the
nitrogen.
Checking Understanding
Answer
The two identical cylinders shown both
have the same mass on the piston and
the same volume. One contains
hydrogen, the other nitrogen. The mass
of gas in each cylinder is the same. The
temperature of the hydrogen gas is




A.less than the temperature of the
nitrogen.
Ideal-Gas Processes
p
i
V
i
T
i
=
p
f
V
f
T
f
Initial and final states of
an ideal gas in a sealed
container (N =constant).
A process of changing
state is then represented
by a path on this diagram.
Each point on a pV diagram
represents a single, unique
state of the gas.
Constant-Volume Process
(Isochoric)
p T
W=0
AE
th
= Q
No change in volume, so
p
i
V
T
i
=
p
f
V
T
f
T
i
T
f
V =constant
Thus,
Constant-Pressure Process
(Isobaric)
V T
W = W
gas
= pAV
AE
th
= Q pAV
Constant pressure, so
pV
i
T
i
=
pV
f
T
f
T
i
T
f
p = constant
Thus,
Constant-Temperature Process
(Isothermal)
p
i
V
i
T
=
p
f
V
f
T
P
1
V
p
f
p
i
T =constant
AE
th
= 0 = QW
gas
Thus,
Q = W
gas
(Heat input = Work output)
W
gas
= area
Work
When a gas expands, it does work on the environment.
When a gas is compressed, it receives work from the
environment.
Work done by gas = W
gas
= Area under the pV graph
Adiabatic process:
so that
AE
th
= W = W
gas
Q= 0
Adiabat
1. System insulation
To achieve no heat flow
2. A rapid volume change
Heat has no time to flow
in or out of the system.
High
A sample of gas is in a cylinder with a
moveable piston. The force on the piston
can be varied, altering the pressure and
volume. A sample of gas is taken from an
initial state to a final state following a
curve on a pV diagram at right. The final
temperature is
A.higher than the initial temperature.
B.the same as the initial temperature.
C.lower than the initial temperature.
Checking Understanding
A sample of gas is in a cylinder with a
moveable piston. The force on the piston
can be varied, altering the pressure and
volume. A sample of gas is taken from an
initial state to a final state following a
curve on a pV diagram at right. The final
temperature is
A.higher than the initial temperature.
Answer
A sample of gas is in a cylinder with a
moveable piston. The force on the
piston can be varied, altering the
pressure and volume. A sample of gas
is taken from an initial state to a final
state following a curve on a pV diagram
at right. The final temperature is
A.higher than the initial temperature.
B.the same as the initial temperature.
C.lower than the initial temperature.
Checking Understanding
A sample of gas is in a cylinder with a
moveable piston. The force on the
piston can be varied, altering the
pressure and volume. A sample of gas
is taken from an initial state to a final
state following a curve on a pV diagram
at right. The final temperature is


lower than the initial temperature.
Answer
A sample of gas is in a cylinder with a
moveable piston. The force on the piston
can be varied, altering the pressure and
volume. A sample of gas is taken from an
initial state to a final state following a
curve on a pV diagram at right. The final
temperature is
A.higher than the initial temperature.
B.the same as the initial temperature.
C.lower than the initial temperature.
Checking Understanding
A sample of gas is in a cylinder with a
moveable piston. The force on the piston
can be varied, altering the pressure and
volume. A sample of gas is taken from an
initial state to a final state following a
curve on a pV diagram at right. The final
temperature is

the same as the initial temperature.
Answer
Suppose you have a sample of gas at 10C that you need to
warm up to 20C. Which will take more heat energy: raising
the temperature while keeping the pressure constant or
raising the temperature while keeping the volume constant?
A.It takes more energy to raise the temperature while keeping
the volume constant.
B.It takes more energy to raise the temperature while keeping
the pressure constant.
C.The heat energy is the same in both cases.
Checking Understanding
Suppose you have a sample of gas at 10C that you need to
warm up to 20C. Which will take more heat energy: raising
the temperature while keeping the pressure constant or
raising the temperature while keeping the volume constant?


It takes more energy to raise the temperature while keeping
the pressure constant.

Answer
When I do work on a gas in an adiabatic process, compressing
it, I add energy to the gas. Where does this energy go?
A.The energy is transferred as heat to the environment.
B.The energy is converted to thermal energy of the gas.
C.The energy converts the phase of the gas.
Checking Understanding
When I do work on a gas in an adiabatic process, compressing
it, I add energy to the gas. Where does this energy go?

The energy is converted to thermal energy of the gas.

Answer
A child has been given a helium balloon. Ignoring repeated
parental suggestions of tying it to his wrist, he lets it go so
that it rapidly rises into the sky. As the balloon rises, it
expands, because the pressure of the atmosphere
decreases. Ignoring heat exchanges with the atmosphere (a
good approximation if it rises quickly) what will happen to the
temperature of the balloon? Will it increase, decrease, or stay
the same? Explain.
Example question
Referring to the pV diagram below, a) What are the initial and
final temperatures?
b) What kind of process is
this likely to be?
c) What are some other ways
to get from the initial to the
final state?
p (kPa)
V (cm
3
)
100 300
600
200
0
0
End
Start
n = 0.02 mol
Isochoric
Isobaric
Example Problem 1
A child attending a carnival in a quaint seaside town has been given
a spherical helium balloon that is 30 cm in diameter.
a)How many moles of helium does the balloon contain?
b)She wants to keep the balloon fresh, so she puts in the freezer,
cooling it down from the hot 28C outside temperature to a frosty
10C. What will be the diameter of the balloon at this lower
temperature?
Example Problem 2
What is the heat Q associated with the process indicated in
the following pV diagram?
Example Problem 3
p (kPa)
V (cm
3
)
100 300
200
0
0
400
n = 0.005 mol, monatomic gas
200
To blow up a rubber balloon, you need to provide a gauge pressure
of about 2000 Pa. Suppose you inflate a spherical balloon from a
diameter of 10 cm to a diameter of 30 cm.
a)What is the change in volume of the balloon?
b)How much work do you do in blowing up the balloon?
Example Problem 4
Question:
System
Heat
What happens to a physical system
when heat is added to it?
Temperature rises
?
?
Q
Answer: specific heat (J/kgK)
Q > 0 and T > 0 (heat is added to a system)
Q < 0 and T < 0 (heat is removed from a system)
By definition, specific heat is always positive.
Q
AT
= McAT
Heat added is negative.
How much heat must be added to raise the
temperature of 1 kg of a substance by 1 K?
Heat added (J) to
raise the
temperature
Rise in
temperature (K)
Question:
Mass of substance (kg)
AT T
f
T
i
Heat absorbed
by water
Measurement of heat transfer
Calorimetry
If the mass of the flask can be ignored, and the
insulation keeps any heat from escaping, then
Q
w
+ Q
b
= 0
Heat absorbed
by object
Total heat to or from
the system is zero
Teq

Calorimetry equation

M
w
c
w
AT
w
+M
b
c
b
AT
b
=0
Heat absorbed
by water
Heat absorbed
by object

M
w
c
w
(T
eq
T
w
)+M
b
c
b
(T
eq
T
b
)=0
1. Write the equation as a statement of conservation of energy.
2. Always:

AT = T
final
T
initial
The common final (equilibrium) temperature
One calorie (cal) is the
amount of heat needed
to raise the
temperature of 1 gram
of water from 14.5 C
to 15.5 C.
1 cal = 4.186 J
The original definition
of the calorie:
To three significant figures
Follow-up Question:
What else can happen when heat is added?
Temperature increase
System
Heat
Q
Ice melts,
Water vaporizes,
Dry ice sublimes,
etc.
Phase change
A gas can expand without
a change in temperature
Isothermal expansion
When two phases are present, any additional heat goes into
changing the phase, and not raise the temperature, until one
phase has completely turned into the other, at which point
any remaining heat will raise the temperature.
Phase can change when heat is added
The heat of transformation, L, is the heat energy that
must be added to or removed from 1 kg of a substance to
convert it from one phase to another. During the
conversion, the temperature of the system remains
constant. (Energy is used to break or form molecular bonds.)
Heat of transformation (also called latent heat)
Q
phase
= ML
latent heat [J/kg]
mass [kg]
heat added (+) or
removed () [J]
L
f
= heat of fusion for melting and freezing
L
v
= heat of vaporization for boiling and condensing
TABLE 12.5
Melting/boiling temperatures and heats of transformation at 1 atm
Solid Liquid Liquid Gas
80 kcal/kg 540 kcal/kg
A liquid in a closed container will come to equilibrium with its
vapor. However, an open liquid will not, as its vapor keeps
escaping it will continue to evaporate without reaching
equilibrium with the surrounding gas.
An open liquid
Higher-energy molecules escape,
robbing the liquid of thermal energy.
Why perspiration cools (through evaporation)
If a liquid is put into a sealed container with a vacuum above it, some of the
molecules in the liquid will evaporate, especially the higher-energy ones.
Phase Equilibrium
With many molecules air-borne, some will begin to
return to the liquid.
Equilibrium is reached when the
numbers remain constant equal
numbers joining and leaving the liquid.
Equilibrium
Equilibrium
vapor pressure
Temperature
dependent
Boiling point of water
(at sea level)
Boiling Point
The temperature at which
Vapor pressure = External pressure.
Never insist on a 3-minute egg in Denver!
Vapor pressure
curve
What would it be on Mars?
= 1 atm
A general, schematic phase diagram
On the phase boundary curves, the neighboring phases coexist in equilibrium.
All three phases can
coexist in equilibrium.
Triple point
Densities of
liquid and gas
become equal
at the critical
point.
A simplified phase diagram for water (Fig. 12.23)
Ice, when
compressed,
becomes water!
Water is denser
than ice
Ice floats in water!
Specific Heat and Heat of Transformation
T
phase
Summary:
Solving calorimetry problems:
for the combined system
+

Which needs the most heat to bring to a final temperature
of 50C?
A.100 g of iron at 0C
B.100 g of water at 0C
C.100 g of ice at 0C
Checking Understanding
Which needs the most heat to bring to a final temperature
of 50C?


100 g of ice at 0C
Answer
On a hot summer day, a cup of flavored shaved ice can be a
welcome treat. Suppose you ignore the obvious brain freeze
danger and eat an 8 oz (0.22 kg) cup of ice rather quickly. When
it melts in your stomach, how much will this reduce your body
temperature?
Example Problem 5
Suppose you are bicycling at a good clip, using a total
energy of 400 W. As you exercise, your body will start to
warm upand you will perspire to keep yourself cool.
A.If your body is 25% efficient while cycling, by what rate
would your body temperature rise if you had no means of
exhausting excess thermal energy?
B.Assume that the only means by which your body cools
itself is evaporation. To keep your body temperature
constant, what mass of water must be evaporated during a
1.0 h ride?
C.What volume of water must you drink each hour to keep
from becoming dehydrated? (1.0 kg of water has a volume of
1.0 l.)
Example Problem 6
Example Problem 7
A typical hot tub contains about 1 m
3
of water. Suppose the tub
is filled with tap water at 10C. If the tub has a 5500 W electric
heater, how long must the heater run to heat the water to a final
temperature of 40C, ignoring any thermal losses? If electricity
costs 10 per kilowatt-hour, how much will this energy cost?
Heat Transfer
Heat Transfer
If you get a cup of coffee in a paper cup, you may be given a
corrugated paper sleeve to put around it to make it
comfortable to hold. Explain the purpose of the paper sleeve,
and how it accomplishes this. Why is the paper sleeve
corrugated?
Checking Understanding