IB DP PHYSICS

Thermal properties of matter

Thermal concepts

Atomic model of matter

Ordinary matter can be found in three forms or phases: Solid, liquid and gaseous.

• The solid phase is characterized by high density. Molecules are in fixed positions and
intermolecular forces are substantial.
• In the liquid phase, density is lower and the molecules can move further apart.
Intermolecular forces exist and play an important role, but they are not as substantial as
in the solid phase.
• Gases have molecules that experience little resistance in their motion, and can thus
move freely about. Intermolecular forces are negligible.

Typical arrangement of molecules in solids, liquids and gases.

When bodies change from a phase to another phase (for example, from liquids to solids), we
say that they undergo a phase transition.

Mole: The mole is the SI unit for quantity. One mole of any substance is defined as a quantity of
the substance whose mass in grams is equal to its molar mass μ. Thus, since hydrogen gas H2
has a molar mass μ of 2 g·mol-1, then one mole of H2 has a mass of 2 g.

The Avogadro constant: One mole of any substance contains the same number of molecules as
to be found in 12 grams of Carbon-12. The number is known as the Avogadro constant.

NA = 6.02 · 1023 molecules · mol-1

It follows that, for a number of moles n of a substance with mass m, we have

n= N/NA

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Temperature

Temperature is the concept that shows the ‘hotness’ or ‘coldness’ of a substance.

Microscopically, temperature is associated with the average kinetic energy of the molecules of
a substance.

Temperature is measured by finding a property of a body that changes as its ‘hotness’ changes.
In older thermometers, that was the length of a column of mercury. Electrical resistance,
voltage, luminosity and pressure can also be used.

Temperature and phase transition: In solids, the kinetic energy of each molecule is quite small
compared to the energy required to move molecules apart. Thus, despite the fact that
molecules move about, their average distance does not change. As the temperature increases,
however, the kinetic energy of each molecule increases and in the end becomes comparable
with the energy required for separation. The molecules then abandon their fixed position and
move freely about. The solid begins to melt, turning into a liquid (phase transition). If the
temperature is increased further, the molecules reach a point where they have enough energy
to move so far apart, that intermolecular forces are negligible. The liquid then has turned into a
gas.

Scales of measurement

• The Celsius scale is created by assigning zero to the freezing point of water and 100 to
the boiling point of water (Initially, when Celsius created the scale in 1742, he had
assigned 100 to the freezing point and 0 to the boiling point).
• The Kelvin scale (absolute temperature scale) is the same as Celsius, with 0 K being -273
C. Thus
T (in K) = T(in Celsius) +273.
For reasons we will explain later on, there are no negative K values of temperature. 0 K is the
absolute lowest possible temperature.

Heat

Heat is the type of energy that is transferred from one body into another as a result of
difference in temperature. It is measured in J.

Heat has no meaning without bodies of different temperatures interacting. Thus, the phrase
‘Body A has a heat of 25 J’ is meaningless. The phrase ’25 J of heat was transferred from Body A
to Body B’, on the other hand, is legitimate.

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Internal energy

Internal energy is the energy of a system associated with the random movement of its particles.
It is defined as the sum of the kinetic energies of all the molecules of a substance.

Internal energy can be increased or decreased in a body either by the transfer of heat or by the
result of work performed. Heat, work and internal energy are three different concepts, though
they are all measured in J.

Note: Sometimes the term ‘thermal energy’ is used to imply either heat or internal energy. In
fact, thermal energy is the sum of both kinetic and potential energy of the molecules in a body.
As can be seen, in the case of gases, intermolecular forces can be considered negligible and
thus, no potential energy exists. Thus, internal and thermal energy can be considered identical.

However, in many exercises, you will see a phrase such as ’60 J of thermal energy were
transferred’. In that case, it is assumed that we are talking of heat Q.

One of the great discoveries of the 19th century was to realize that the absolute temperature is
directly proportional to the average kinetic energy of the molecules of a substance.

Systems, states and processes

A system is the complete set of objects under our consideration. It can mean a gas and its
container, the whole of an experimental apparatus or even the Universe. A system is said to be
considered open or closed, depending on whether mass can be exchanged with it or not. A
system is considered isolated if no energy in any form enters or leaves. If all the parameters of a
system are known, then we speak of the system being in a specific state. For an (ideal) gas, a
state is defined by pressure P, volume V and temperature T. And process that changes the state
of a system is called a thermodynamic process.

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Thermal properties

Specific heat capacity c: The amount of thermal energy (heat) needed to raise the temperature
of a mass of one kilogram of a substance by one Kelvin. It is measured in J· Kg-1· K-1 .

Specific heat capacities of various substances.

Heat capacity C: The amount of thermal energy (heat) required to change a body ‘s
temperature by 1 K. It is measured in J· K-1.

Form the definitions, it follows that

C= m·c
Also, the energy required to raise the temperature of a mass m by ΔΤ is

Q = m·c·ΔΤ = C·ΔΤ
Heat capacity is useful for bodies composed of different parts. In a tank, for example, with mass
m and specific heat capacity c, filled with water of mass M with specific heat capacity c’ , the
rise in temperature would be Q= C· ΔΤ, where C = m·c + M c’.

Thermal equilibrium

When two bodies of different temperature come in contact, heat flows from the hotter to the
colder until the temperature of both bodies is the same. This state is called thermal equilibrium.
The energy lost by the hot body is equal to that gained by the cold body.

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Change of state (phase transitions)

All ordinary matter can exist as a solid, liquid or gas, the so called states of matter. We can
change states in a substance by heating it. When a specific for each substance temperature is
reached, the melting point, solid will start to change into liquid. If we continue to supply heat,
eventually the liquid will reach the temperature of its boiling point start and start to convert
into gas.

However, temperature does not rise equivocally in the process. If we assume a substance in
which heat is supplied at a constant rate, the graph of the temperature over time will look
similar to this.

Temperature as a function of time when a substance is heated at a constant rate.

As we can see, heat supplied at the melting point does not initially increase the temperature.
Rather, it is used to overcome the forces between the molecules, thus providing the work
necessary to separate the molecules further and convert the solid into liquid.

The energy required to melt a unit mass of material at its melting point is called the specific
latent heat of fusion Lf, and is measured in J· Kg-1 .

In the same vain, energy provided at the boiling point of a substance does not immediately
result in a temperature rise. It is instead once again used to overcome intermolecular forces,
sending the molecules further apart. The liquid is then turned to gas and only then does
temperature start to rise again.

The energy required to vaporize a unit mass of material at its boiling point is called the specific
latent heat of vaporization Lv, and is measured in J· Kg-1 .

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Specific latent heats of fusions and vaporization together with melting nd boiling points for a
variety of substances.

Measuring specific heat capacity

The measurement of the specific heat capacity of a liquid or a solid of mass m and initial
temperature T requires a calorimeter of known specific heat C and an electric heating element.
The liquid or solid is places inside the calorimeter and heat is provided by the heating element
for a specific amount of time t, until the temperature is increased by a specified ΔΤ, usually 40
or 50 K.

By equating the energy supplied by the battery (E=V·I·t) with the energy absorbed by the
calorimeter and the liquid or solid [Eabs= m·c (Tmax – T) + C ( Tmax – T) ], we can calculate c.

Another method, the method of mixtures, puts a hot solid of known initial temperature T and
mass m inside a liquid, such as water, of known specific heat capacity. After the solid and the
water have reached a common temperature, we equate the heat lost by the solid ( Q = m·c· ΔΤ)
with the energy gained by the calorimeter and the water [Eabs= mw·cw ΔTw) + C ( ΔΤcal) ].

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Kinetic theory of gases

The properties of gases can be simulated in terms of a mechanical model. The basic
assumptions of the kinetic theory of gases are:

1. A gas consists of a large number of molecules.

2. Molecules move with a range of speeds.
3. The volume of the molecules is negligible compared with the volume of the gas itself.
4. The collisions of the molecules with each other and with the container are elastic.
5. Molecules exert no force on each other or on the container except when in contact.
6. The duration of the collisions is very small when compared with the time between
collisions.
7. The molecules obey the laws of Newtonian mechanics.

These in turn lead to the formulation of the Boltzmann equation

1 ̅̅̅2 3
𝑚𝑣 = 𝑘𝑇
2 2

where k is the Boltzmann constant (k = R/NA= 1.38 · 10-23 J ·K-1) and

̅̅̅
2
𝑣12 + 𝑣22 + ⋯ + 𝑣𝛮2
𝑣 =
𝑁

Thus, the above expression is the average of the squared velocities of all the molecules. The
square root of the above is known as vrms and is close, but nor identical, with the mean velocity
of the molecules.

𝑉𝑟𝑚𝑠 = √̅𝑉̅̅2̅

The Boltzmann equation ties together a microscopic quantity, such as the molecular kinetic
energy, with a macroscopic one, which is absolute temperature.

The behavior of gases in general and ideal gases in particular is explained by utilizing a number
of parameters. Temperature T is one of them and has already been discussed. Others are the
volume V occupied by the gas, pressure P which is exerted by the gas and the number of moles
n.

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Molecular explanation of pressure

Pressure P is defined as the normal force F to an area A per unit area

𝐹 𝑠𝑖𝑛𝜃
𝑃=
𝛢

Pressure is measured in Pa (N·m-2). Another common unit is atm (1.013 ·105 Pa).

Gases exert pressure in container. This is a result of the collisions between the molecules of the
gas with the walls of the container (and not from collisions between molecules). In every
collision, each molecule changes its momentum and exerts a force in the walls of the container.
The total force due to all the colliding molecules divided by the area over which is exerted gives
the pressure of the gas.

This point of view enables to identify and explain two factors that affect the pressure of a gas.
The first is the average molecular speed. Higher speed results in greater momentum change
and thus to greater force exerted. The second is the frequency of collisions. More frequent
collisions result in more force exerted and thus in higher pressure.

Thus, when a gas is heated under a constant volume, molecules move faster and collide more
frequently with the walls. Thus, the pressure of the gas increases. In the same vain, when a gas
is compressed, even if we keep its temperature steady (the so called isothermal compression),
molecules have to travel a smaller distance before they collide with the walls. The frequency of
collisions increases and thus, the pressure of the gas increases.

The equation of state

Ideal gases obey a specific equation, which correlates P, V, T and n. This is known as the
equation of state

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 P·V= n · R· T
In fact, a gas can be said to be ideal when it obeys this equation for temperatures, pressures and
volumes. Real gases obey the state equation only for a specific range of these variables.

Caution: The state equation holds only if temperature is expressed in K

If we keep one of the variables constant and changing the others, a number of gas laws emerge.
They each have their own name, since they were discovered in different time periods.
However, they are usually named by the variable kept fixed.

Isothermal (Boyle-Mariot)

An isothermal process is one where temperature is kept constant. As can be seen in the state
equation, we expect P and V to be inversely proportional. Experiments do indeed confirm the
hypothesis.

When T is constant, P·V = const.

Pressure-volume diagram when temperature is constant (isothermal)

The hyperbola in theP-V diagram is known as an isothermal curve or an isotherm.

Isobaric process ( Gay-Lussac Law)

We can also keep the pressure exerted on the gas a constant. Then, temperature (expressed in
K) and volume are found to be proportional, as the state equation predicts. Historically, this is
known as the Gay-Lussac Law, though it has been found that Guillame Amonton had been the
first to publish it, between 1700 and 1702.

When P is constant, V/T = constant

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If temperature T is measured in C, then the V-T graphs for a range of initial conditions seem to
intersect the T axis in a specific point, which is -273.15 0C.

Volume- temperature graph when pressure is constant

Isochoric process (Charles Law)

In a fixed volume, we can deduce from the state equation, that P and T should be proportional.

When V is constant, P/T = constant

Pressure- temperature graph when volume is constant

Adiabatic process

In an adiabatic process, no heat is exchanged between the gas and the environment (Q= 0).
Adiabatic processes are not to be confused with isothermals, since it not temperature that
remains constant, but rather heat that is not exchanged. Adiabatic processes usually happen
fast, before the system has a chance to reach equilibrium. Isothermals, on the other hand, take
place slowly and the system is in thermal equilibrium with its surrounding.

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 P-V diagrams for all processes

Maxwell- Boltzmann distribution

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NOTES

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NOTES

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NOTES

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