Chapter 12 – Kinetic theory - Ready Reference

12.1 Introduction

➢ Historical Background: Boyle and Newton explained gas behaviour through atomic theory, but the
formal atomic theory was established more than 150 years later
➢ Kinetic Theory Concept: Maxwell and Boltzmann, explains gas behaviour based on the idea that gases
consist of rapidly moving molecules or atoms with negligible inter-atomic forces
➢ Chapter provides a molecular interpretation of gas pressure and temperature, along with established gas
laws and Avogadro's hypothesis
➢ Applications: Kinetic theory explains specific heat capacities and relates measurable gas properties like
viscosity, conduction, and diffusion to molecular sizes and masses

Example: Consider a balloon filled with air. When heated, the molecules inside move faster and exert
more pressure on the walls of the balloon, causing it to expand. This is explained by the kinetic theory,
as the increased kinetic energy of the air molecules results in increased pressure.

12.2 Molecular Nature of Matter

The molecular nature of matter is explained by focusing on the atomic hypothesis and the dynamic
behaviour of molecules, specifically in gases. Let's break down each concept and explain them with examples:

Atomic Hypothesis:
• Concept: All things are made up of tiny atomic particles (atoms). These atoms move constantly in
random motion, attracting each other when they are apart but repels when close together.
• Example: In liquid form, water molecules move past each other due to weaker intermolecular forces. As
water boils, these turn into gas, where the molecules move in random directions with minimal interaction.
Historical Background of Atomic Theory:
• Concept: John Dalton explains that elements are made of identical atoms and that compounds form
through fixed ratios of atoms. This theory was used to explain laws of chemical combination such as the
law of definite proportions and multiple proportions.
• Example: Dalton’s atomic theory explains why water (H₂O) always consists of 2 hydrogen atoms and 1
oxygen atom. No matter how much water you have, the ratio of hydrogen to oxygen by mass remains
the same, following the law of definite proportions.
Molecular Nature and Size of Atoms:
• Concept: Molecules consist of one or more atoms. The size of an atom is about 1 angstrom (1 Å =
10⁻¹⁰ meters).

✓ In solids like diamond, atoms with a separation of about 2 Å (tightly packed)

✓ In liquids like water, atoms are similarly spaced and move, allowing the liquid to flow
✓ In gases like oxygen, atoms are in the mean free path can be thousands of angstroms

Dynamic Equilibrium and Molecular Motion:

Concept: Even though gases may appear static, they are in constant motion with molecules colliding
with each other and the container walls. These collisions are elastic, meaning kinetic energy is
conserved. The equilibrium in gases is dynamic, meaning the average properties (like temperature and
pressure) remain constant, but individual molecules are always in motion.
Example: In a balloon filled with air, the gas molecules are constantly colliding with the balloon’s
walls, exerting pressure.

Modern Understanding of Atoms:

Concept: Atoms are divisible and consist of subatomic particles: protons, neutrons, and electrons.
Protons and neutrons are further made up of quarks. Modern theories even suggest that there might be more
fundamental entities like "strings" in string theory.

Example: Hydrogen – simplest atom, Carbon - heavier atom

12.3 Behaviour of Gases

The molecules in a gas are far apart, and their interactions are negligible except during collisions. At
low pressures and high temperatures, gases follow the ideal gas law, which states:

PV= KT where:
o P is the pressure,
o V is the volume,
o T is the absolute temperature in Kelvin, and
o K is a constant that depends on the amount of gas.

When we introduce the concept of molecules, we modify this

equation to reflect that K is proportional to the number of molecules N
in the gas:

K=N kB

Here, kB is the Boltzmann constant, which applies to all gases and has a value of:

kB=1.38×10−23 J/K

Example: (under experimental conditions)

P1V1/N1T1=P2V2/N2T2= constant=k B

Avogadro’s Hypothesis and the Ideal Gas Equation:

Avogadro's Law: States that equal volumes of gases at the same temperature and pressure contain the
same number of molecules. This leads to the introduction of the Avogadro number NA and its value is
6.02×1023 molecules for a volume of 22.4 litres of any gas at STP
The ideal gas equation combines the concepts of pressure, volume, temperature, and the number of
moles (μ) of the gas:

PV= μ R T
.
Where μ is the number of moles, R is the universal gas constant, R=8.314 J/mol K , T is the absolute
temperature in Kelvin.
Alternatively, we can express the equation in terms of the number of molecules (N):
PV=N kB T
where kB is Boltzmann's constant and N is the number of molecules.

Example: Calculate the pressure of a gas with 1 mole (μ=1) at T=300 K and V=22.4 L
(standard molar volume at STP):
PV=μ R T
P=μ R T/V

Substituting the values:

P=1×8.314×300/22.4=1.11×105 Pa.

Boyle's Law as shown in figure 12.1 states that the pressure (P) of a given mass of gas is inversely proportional
to its volume (V), provided the temperature (T) remains constant. Mathematically, Boyle’s Law is expressed
as:
P∝1/V or P×V=constant (when temperature is constant).
This relationship means that:
• If the volume of a gas is decreased, the pressure increases.
• If the volume of a gas is increased, the pressure decreases.
 This law can be derived from the ideal gas law, PV=μ R T, where μ is the number of moles of gas, R is
the gas constant, and T is the absolute temperature. When the temperature T and the number of moles μ are kept
constant, the product of pressure and volume PV remains constant.

• Figure 12.2 shows P-V curves (pressure vs. volume) for steam at three
different temperatures (T1, T2, T3)
• The solid lines represent the experimental curves, while the dotted
lines represent the idealized prediction of Boyle's law
• At high temperatures and low pressures, the experimental data
closely follow the dotted line (theoretical prediction). This indicates
that gases behave more ideally under these conditions

Charles's Law relates the volume (V) and temperature (T) of a gas while
keeping the pressure constant. It states:
V∝T (at constant pressure)
or,
V/T=constant
This means that if the pressure and amount of gas are constant, the volume of a
gas is directly proportional to its absolute temperature.

• Figure 12.3 shows the T-V curves (temperature vs. volume) for CO₂ at
three different pressures (P1, P2, P3)
• The solid lines represent the experimental data, while the dotted lines
represent the idealized prediction of Charles's law
• The temperature (T) is plotted in units of 300 K and the volume (V) in
units of 0.13 liters.

Summary of Both Laws in Context:

1. Boyle’s Law (Figure 12.2) shows that at constant temperature, the pressure of a gas is inversely
proportional to its volume.
2. Charles’s Law (Figure 12.3) shows that at constant pressure, the volume of a gas is directly
proportional to its absolute temperature.

12.4 Kinetic Theory of an Ideal Gas

12.4.1 Pressure of an Ideal Gas:
• The change in momentum of the molecule is: –mvx – (mvx) =
– 2mvx.
• By the principle of conservation of momentum, the
momentum imparted to the wall in the collision = 2mvx
• All molecules within the volume Avx ∆t only can hit the wall
in time ∆t.
• On the average, half of these are moving towards the wall and
the other half away from the wall. Thus, the number of molecules
with velocity (vx, vy, vz) hitting the wall in time ∆t is ½A vx ∆t n, where n is the number of
molecules per unit volume.
• The total momentum transferred to the wall by these molecules in time ∆t is:
Q = (2mvx) (½ n A vx ∆t) (12.10)
• The force on the wall is the rate of momentum transfer Q/∆t and pressure is force per unit
area:
P = Q / (A ∆t) = n m vx 2
• The total pressure is obtained by summing over the contribution due to all groups:
P = n m vx2 (12.12)
 Where vx2 is the average of vx 2. Now the gas is isotropic, i.e. there is no preferred direction of
velocity of the molecules in the vessel.
• Therefore, by symmetry, vx 2= vy 2 = vz2
= (1/3) {vx 2= vy 2 = vz2}
= (1/3) v2 (12.13)
= (1/3) n m v2 (12.14)
• Thus from equation 12.14, Molecular collisions (if they are not too frequent and the time spent
in a collision is negligible compared to time between collisions) will not affect the calculation
above

Kinetic Interpretation of Temperature

PV = (1/3) v2 nV m (12.15a)

PV = (2/3) N x ½ m v2 (12.15b)
Where N (= nV) is the number of molecules in
the sample.
• The internal energy E of an ideal gas is
purely kinetic, E = N × (1/2) m v2 (12.16)

Equation (12.15) then gives:

PV = (2/3) E (12.17)
• We are now ready for a kinetic interpretation
of temperature. Combining Eq. (12.17) with the
ideal gas Eq. (12.3), we get

E = (3/2) kB NT (12.18)
Or E/ N = ½ m v2 = (3/2) kB T (12.19)
• This is a fundamental result relating
temperature, a macroscopic measurable parameter of a gas to a molecular quantity, namely the
average kinetic energy of a molecule. The two domains are connected by the Boltzmann
constant.
• Eq. (12.18) tells us that internal energy of an ideal gas depends only on temperature, not on
pressure or volume. With this interpretation of temperature, kinetic theory of an ideal gas is
completely consistent with the ideal gas equation and the various gas laws based on it.
• For a mixture of non-reactive ideal gases, the total pressure gets contribution from each gas in
the mixture. Equation (12.14) becomes

P = (1/3) [n1m1 v12 + n2 m2 v22 +] (12.20)

• In equilibrium, the average kinetic energy of the molecules of different gases will be equal.
That is,

½ m1 v1 2= ½ m2 v22 = (3/2) kB T so that

P = (n1 + n2 +.. ) kB T (12.21)
which is Dalton’s law of partial pressures
Law of Equipartition of energy
✓ A free molecule has three translational degrees of freedom has one degree of freedom for
motion in a line, two for motion in a plane and three for motion in space.
✓ Each translational degree of freedom contributes a term that contains square of some variable
of motion, e.g., ½ mvx 2 and similar terms in vy and vz.
✓ In, Eq. (12.24) we see that in thermal equilibrium, the average of each such term is ½ kB T.
✓ Molecules of a monatomic gas like argon have only translational degrees of freedom.
 ✓ Diatomic gas such as O2 or N2? A molecule
of O2 has three translational degrees of freedom. But
in addition it can also rotate about its centre of mass
✓ Figure 12.6 shows the two independent axes
of rotation 1 and 2 and molecule has two rotational
degrees of freedom, contributes to total energy
consisting of translational energy εt and rotational
energy εr
✓ Where ω1 and ω2 are the angular speeds about
the axes 1 and 2 and I1, I2 are the corresponding
moments of inertia.
✓ We have assumed above that the O2 molecule
is a ‘rigid rotator’, i.e., the molecule does not vibrate.
This assumption, though found to be true (at moderate
temperatures) for O2, is not always valid.
✓ Molecules, like CO, even at moderate temperatures
have a mode of vibration, i.e., its atoms oscillate along the
inter atomic axis like a one-dimensional oscillator, and contribute a vibrational energy term ε v to
the total energy:
Where k is the force constant of the oscillator and y the
vibrational co-ordinate.
✓ At this point, notice an important feature in
Eq.(12.26). While each translational and rotational degree
of freedom has contributed only one ‘squared term’ in
Eq.(12.26), one vibrational mode contributes two ‘squared
terms’ : kinetic and potential energies.
✓ Each quadratic term occurring in the expression for
energy is a mode of absorption of energy by the molecule.
✓ In equilibrium, the total energy is equally distributed
in all possible energy modes, with each mode having an
average energy equal to ½ kB T. This is known as the law
of equipartition of energy.
✓ Accordingly, each translational and rotational degree
of freedom of a molecule contributes ½ kB T to the
energy, while each vibrational frequency contributes 2 ×
½ kB T = kB T, since a vibrational mode has both kinetic
and potential energy modes.

12.6 Specific Heat Capacity

12.6.1 Mono atomic Gases:
The molecule of a monatomic gas has only three
translational degrees of freedom. Thus, the average
energy of a molecule at temperature T is (3/2) kBT. The
total internal energy of a mole of such a gas is (12.27 –
12.31)
12.6.2 Di atomic Gases: has 5 degrees of
freedom: 3 translational and 2 rotational (12.32
-12.35)
12.6.3Polyatomic gases: molecule has 3 translational,
3 rotational degrees of freedom and a certain number (f)
of vibrational modes. According to the law of
equipartition of energy, it is easily seen that one mole of
such a gas has as shown from Eq.12.36
 12.6.4 Specific Heat Capacity of Solids:
Consider a solid of N atoms, each vibrating about its mean position. An oscillation in one
dimension has average energy of 2 × ½ kBT = kBT.
In three dimensions, the average energy is 3 kBT.
For a mole of solid, N = NA, and the total energy is
U = 3 kBT × NA = 3 RT
Now at constant pressure ΔQ = ΔU + PΔV = ΔU, since
for a solid ΔV is negligible. Hence,
∆𝑸 ∆𝑼
𝑪 = ∆𝑻 = ∆𝑻 = 3R

12.7 Mean Free Path:

Molecules in a gas leaking from a cylinder in a kitchen takes
considerable time to diffuse to the other corners of the room.
Suppose the molecules of a gas are spheres of diameter d.
Fig 12.7 Focus on a single molecule with the average speed <v>. It
will suffer collision with any molecule that comes within a
distance d between the centres. In time Δt, it sweeps a volume 𝜋d2 <v> t wherein any other molecule
will collide with it (see Fig. 12.7). If n is the number of molecules per unit volume, the molecule suffers
𝜋nd2 <v> Δt collisions in time Δt. Thus, the rate of collisions is n𝜋d2 <v> or the time between two
successive collisions is on the average
𝜏 = 1/(n𝜋 <v> d2 ) (12.38)
The average distance between two successive collisions, called the mean free path l, is:
l = <v> 𝜏 = 1/(n𝜋d2) (12.39)
In this derivation, we imagined the other molecules to be at rest. But actually, all molecules are moving
and the collision rate is determined by the average relative velocity of the molecules. Thus, we need to
replace <v> by <v > in Eq. (12.38). A more exact treatment gives