Temperature, Thermal Expansion & Kinetic Theory

Atomic Theory of Matter

• Atomic and molecular masses are measured in unified atomic mass units (u). This unit is
defined so that the carbon-12 atom has a mass of exactly 12.0000 u. Expressed in
kilograms:
• 1 u = 1.6605 × 10−27 kg
• Brownian motion is the jittery motion of tiny flecks in water; these are the result of
collisions with individual water molecules.

• On a microscopic scale, the arrangements of molecules in solids (a), liquids (b), and
gases (c) are quite different.
Temperature & Thermometers
• Temperature is a measure of how hot or cold something is.
• Most materials expand when heated.
• Thermometers are instruments designed to measure temperature. In order to do this,
they take advantage of some property of matter that changes with temperature.
• Common thermometers used today include the liquid-in-glass type and the bimetallic
strip.
• Temperature is generally measured using either the Fahrenheit or the Celsius scale.
• The freezing point of water is 0°C, or 32°F; the boiling point of water is 100°C, or 212°F.
Thermal Equilibrium & the Zeroth Law of Thermodynamics
• Two objects placed in thermal contact will eventually come to the same temperature.
When they do, we say they are in thermal equilibrium.
• The zeroth law of thermodynamics says that if two objects are each in equilibrium with a
third object, they are also in thermal equilibrium with each other.
Thermal Expansion

• Linear expansion occurs when an object is heated.

• Here, α is the coefficient of linear expansion.
• Volume expansion is similar, except that it is relevant for liquids and gases as well as
solids:
• Here, β is the coefficient of volume expansion.
• For uniform solids, β ≈ 3α.
 • Water behaves differently from most other solids—its minimum volume occurs when its
temperature is 4°C. As it cools further, it expands, as anyone who has left a bottle in the
freezer to cool and then forgets about it can testify.

• A material may be fixed at its ends and therefore be unable to expand when the
temperature changes. It will then experience large compressive or tensile stress—
thermal stress—when its temperature changes.
• The force required to keep the material from
expanding is given by:
• where E is the Young’s modulus of the material.
Therefore, the stress is:

The Gas Laws & Absolute Temperature

• The relationship between the volume, pressure, temperature, and mass of a gas is
called an equation of state.
• We will deal here with gases that are not too dense.
• Boyle’s Law: the volume of a given amount of gas is inversely proportional to the
pressure as long as the temperature is constant.
V ∝ 1/P
• The volume is linearly proportional to the temperature, as long as the temperature is
somewhat above the condensation point and the pressure is constant: V ∝ T.
• Extrapolating, the volume becomes zero at −273.15°C; this temperature is called
absolute zero.
 • The concept of absolute zero allows us to define a third temperature scale—the
absolute, or Kelvin scale.
• This scale starts with 0 K at absolute zero, but otherwise is the same as the Celsius
scale.
• Therefore, the freezing point of water is 273.15 K, and the boiling point is 373.15 K.
• Finally, when the volume is constant, the pressure is directly proportional to the
temperature:
P ∝T.
The Ideal Gas Law
• We can combine the three relations just derived into a single relation:
PV ∝ T
• What about the amount of gas present? If the temperature and pressure are constant,
the volume is proportional to the amount of gas:
PV ∝ mT
• A mole (mol) is defined as the number of grams of a substance that is numerically equal
to the molecular mass of the substance:
• 1 mol H2 has a mass of 2 g
• 1 mol Ne has a mass of 20 g
• 1 mol CO2 has a mass of 44 g
• The number of moles in a certain mass of material:
• We can now write the ideal gas law:
• where n is the number of moles and R is the universal gas constant.

Problem solving with the Ideal Gas Law

• Useful facts and definitions:
 • Standard temperature and pressure (STP)
• T = 273 K (0°C)
• P = 1.00 atm = 1.013 × 105 N/m2 = 101.3 kPa
• Volume of 1 mol of an ideal gas is 22.4 L
• If the amount of gas does not change:

• Always measure T in kelvins

• P must be the absolute pressure

Ideal Gas Law in terms of molecules: Avogadro’s Number

• Since the gas constant is universal, the number of molecules in one mole is the same for
all gases. That number is called the Avogadro’s Number:
• NA = 6.02 × 1023
• The number of molecules in a gas is the number of moles times the Avogadro’s Number:
• N = nNA
• Therefore, we can write:

where k is called Boltzmann’s constant.

Kinetic Theory and the Molecular Interpretation of Temperature

Assumptions of kinetic theory:
• large number of molecules, moving in random directions with a variety of speeds
• molecules are far apart, on average
• molecules obey laws of classical mechanics and interact only when colliding
• collisions are perfectly elastic
• The force exerted on the wall by the collision of one molecule is

• Then the force due to all molecules colliding with that wall is

• The averages of the squares of the speeds in all three

directions are equal:
• So the pressure is:

• Rewriting,

• So

• The average translational kinetic energy of the molecules in an ideal gas is directly
proportional to the temperature of the gas.
• We can invert this to find the average speed of molecules in a gas as a function of
temperature:
 Distribution of Molecular Speeds
• These two graphs show the distribution of speeds of molecules in a gas, as derived by
Maxwell. The most probable speed, VP, is not quite the same as the rms speed.
• As expected, the curves shift to the right with temperature.

Real Gases and Changes of Phase

• The curves here represent the behavior of the gas at
different temperatures. The cooler it gets, the farther the
gas is from ideal.
• In curve D, the gas becomes liquid; it begins condensing at
(b) and is entirely liquid at (a).
• The point (c) is called the critical point.
• Below the critical temperature, the gas can liquefy if the
pressure is sufficient; above it, no amount of pressure will
suffice.
• A PT diagram is called a phase diagram; it shows all three
phases of matter. The solid-liquid transition is melting or
freezing; the liquid-vapor one is boiling or condensing; and
the solid-vapor one is sublimation.

Phase diagram
of water
• The triple point is the only point where all three phases can coexist in equilibrium.

Phase diagram
of carbon dioxide

Vapor Pressure and Humidity

• An open container of water can evaporate, rather than boil, away.
The fastest molecules are escaping from the water’s surface, so
evaporation is a cooling process as well.
• 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,
and its pressure is the saturated vapor pressure.
• The saturated vapor pressure increases with temperature.
• Liquid boils when its saturated vapor pressure equals the external
pressure.
• Partial pressure is the pressure each component of a mixture of
gases would exert if it were the only gas present. 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.
• Relative humidity is a measure of the saturation of
the air.

• When the humidity is high, it feels muggy; it is hard for any more water to evaporate.
• The dew point is the temperature at which the air would be saturated with water.
• If the temperature goes below
the dew point, dew, fog, or even rain may occur.
Diffusion
• Even without stirring, a few drops of dye in water will gradually spread throughout. This
process is called diffusion.

• Diffusion occurs from a region of high concentration towards a region of lower

concentration.

• The rate of diffusion is given by:

In this equation, D is the diffusion constant.
Sample Problems

1. A bronze plate with the coefficient of linear expansion α = 18 x 106/oC at 0oC has size of
length 0.4 m and width of 0.2 m. If the plate was heated at 80oC, then what is the increase in
area of the plate.

Given:
Length = 0.4 m Width = 0.2 m
Coefficient of linear expansion for bronze (α) = 18 x 10-6/oC
Initial temp. = 0oC Final temp. = 80oC

Initial area of bronze (Ao) = (0.4)(0.2) = 0.08 m2

The coefficient of area expansion for bronze (β) = 2 x coefficient of linear expansion
(2α) = 36 x 10-6/oC

The change in temperature (ΔT) = 80oC – 0oC = 80oC

Required: The increase of area for bronze at 80oC

Solution:
The increase of area for bronze:
ΔA = β Ao ΔT
ΔA = (36 x 10-6)(0.08)(80) = 230.4 x 10-6 = 2.304 x 10-4 m2

2. At 30oC the volume of an aluminum sphere is 30 cm3. The coefficient of linear expansion is
24 x 10-6/oC. If the final volume is 30.5 cm3, what is the final temperature of the aluminum
sphere?

Given:
The coefficient of linear expansion (α) = 24 x 10-6/oC
The coefficient of volume expansion (β) = 3α = 3 x 24 x 10-6/oC = 72 x 10-6 oC-1
The initial temperature (T1) = 30oC

The initial volume (V1) = 30 cm3

The final volume (V2) = 30.5 cm3
The change in volume (ΔV) = 30.5 cm3 – 30 cm3 = 0.5 cm3

Required: The final temperature (T2)

Solution:
ΔV = β (V1)( ΔT)
ΔV = β (V1)(T2 – T1)
0.5 cm3 = (72 x 10-6 oC-1)(30 cm3)(T2 – 30oC)
0.5 = (2160 x 10-6)(T2 – 30)
0.5 = (2.160 x 10-3)(T2 – 30)
0.5 = (2.160 x 10-3)(T2 – 30)
0.5 / (2.160 x 10-3) = T2 – 30
231.48 = T2 – 30
231.48 + 30 = T2
T2 = 261.48oC

3. A sheet of steel at 20oC has size 40 cm in length and 20 cm in width. If the coefficient
of linear expansion for steel is 10-5 oC-1 then what is the change in the area at 60oC.

Given:
Length of steel = 40 cm
Width of steel = 20 cm
The coefficient of linear expansion (α) = 10-5 oC-1
Initial temp. = 20oC
Final temp. = 60oC

The initial area of steel (Ao) = (40)(20) = 800 cm2

The coefficient of area expansion (β) = 2 x coefficient of linear expansion (2α) = 2 x 10-5 oC-1
The change in temperature (ΔT) = 60oC – 20oC = 40oC

Required: The change in area of steel at 60oC

Solution:
Equation of area expansion
ΔA = β Ao ΔT
ΔA = the increase in area of steel, β = coefficient of area expansion, Ao = initial area, ΔT = the
change in temperature = final temperature – initial temperature

The increase in area of steel:

ΔA = β Ao ΔT
ΔA = (2 x 10-5)(800)(40) = 0.64 cm2
4. What is the average translational kinetic energy of molecules in an ideal gas at 57oC?

Given:
Temperature of gas (T) = 57oC + 273 = 330 Kelvin
Boltzmann‘s constant (k) = 1.38 x 10-23 Joule/Kelvin

Required: The average translational kinetic energy

Solution:
The relation between kinetic energy (KE) and the temperature of the gas (T) is
KE = 3/2 kT
KE = 3/2 (1.38x10-23 J/oK)(330 oK)
KE = 6.831x10-21 Joule

5. A gas at 27oC in a closed container. If the kinetic energy of the gas increases 2 times the
initial kinetic energy, what is the final temperature of the gas?

Given:
Initial temperature (T1) = 27oC + 273 = 300 oK
Initial kinetic energy = KE
Final kinetic energy = 2 KE

Required: The final temperature (T2)

Solution:
Initial kinetic energy
KE = 3/2 kT
KE = 3/2 k(300oK)

Final kinetic energy

KE final = 2 KE initial
3/2 kT2 = 2 3/2 kT1
T2 = 2(T1) = 2(300oK)
T2 =600oK

6. 4 liters of oxygen gas has a temperature of 27°C and pressure of 2 atm (1 atm = 105 Pa) in a
closed container. Universal gas constant (R) = 8.314 J/mole / K and Avogadro’s number (NA) =
6.02 x 1023 molecules/mole. How much molecules of oxygen gases are in the container?

Given:
Volume of gases (V) = 4 liters = 4 dm3 = 4 x 10-3 m3
Temperature of gases (T) = 27oC = 27 + 273 = 300 Kelvin
Pressure of gases (P) = 2 atm = 2 x 105 Pa
Universal gas constant (R) = 8.314 J/mole / K
Avogadro’s number (NA) = 6.02 x 1023

Required: How much molecules of oxygen gases are in the container (N)

Solution:

In 1 mole oxygen gases, there are 1.93 x 1023 oxygen molecules.

Formulas for temperature conversion

5
℃ = (℉ − 32 )
9

9
℉ = (℃ 𝑥 ) + 32
5

°𝐾 = (℃ = 273.15)

°𝑅 = (℉ + 459.67)