CHAPTER THIRTEEN

KINETIC THEORY

13.1 INTRODUCTION
Boyle discovered the law named after him in 1661. Boyle,
Newton and several others tried to explain the behaviour of
13.1 Introduction gases by considering that gases are made up of tiny atomic
13.2 Molecular nature of matter particles. The actual atomic theory got established more than
13.3 Behaviour of gases 150 years later. Kinetic theory explains the behaviour of gases
13.4 Kinetic theory of an ideal gas based on the idea that the gas consists of rapidly moving
13.5 Law of equipartition of energy atoms or molecules. This is possible as the inter-atomic forces,
13.6 Specific heat capacity which are short range forces that are important for solids
13.7 Mean free path and liquids, can be neglected for gases. The kinetic theory
was developed in the nineteenth century by Maxwell,
Summary Boltzmann and others. It has been remarkably successful. It
Points to ponder gives a molecular interpretation of pressure and temperature
Exercises of a gas, and is consistent with gas laws and Avogadro’s
Additional exercises hypothesis. It correctly explains specific heat capacities of
many gases. It also relates measurable properties of gases
such as viscosity, conduction and diffusion with molecular
parameters, yielding estimates of molecular sizes and masses.
This chapter gives an introduction to kinetic theory.

13.2 MOLECULAR NATURE OF MATTER

Richard Feynman, one of the great physicists of 20th century
considers the discovery that “Matter is made up of atoms” to
be a very significant one. Humanity may suffer annihilation
(due to nuclear catastrophe) or extinction (due to
environmental disasters) if we do not act wisely. If that
happens, and all of scientific knowledge were to be destroyed
then Feynman would like the ‘Atomic Hypothesis’ to be
communicated to the next generation of creatures in the
universe. Atomic Hypothesis: All things are made of atoms -
little particles that move around in perpetual motion,
attracting each other when they are a little distance apart,
but repelling upon being squeezed into one another.
Speculation that matter may not be continuous, existed in
many places and cultures. Kanada in India and Democritus
KINETIC THEORY 319

Atomic Hypothesis in Ancient India and Greece

Though John Dalton is credited with the introduction of atomic viewpoint in modern science, scholars in
ancient India and Greece conjectured long before the existence of atoms and molecules. In the Vaiseshika
school of thought in India founded by Kanada (Sixth century B.C.) the atomic picture was developed in
considerable detail. Atoms were thought to be eternal, indivisible, infinitesimal and ultimate parts of matter.
It was argued that if matter could be subdivided without an end, there would be no difference between a
mustard seed and the Meru mountain. The four kinds of atoms (Paramanu — Sanskrit word for the
smallest particle) postulated were Bhoomi (Earth), Ap (water), Tejas (fire) and Vayu (air) that have characteristic
mass and other attributes, were propounded. Akasa (space) was thought to have no atomic structure and
was continuous and inert. Atoms combine to form different molecules (e.g. two atoms combine to form a
diatomic molecule dvyanuka, three atoms form a tryanuka or a triatomic molecule), their properties depending
upon the nature and ratio of the constituent atoms. The size of the atoms was also estimated, by conjecture
or by methods that are not known to us. The estimates vary. In Lalitavistara, a famous biography of the
Buddha written mainly in the second century B.C., the estimate is close to the modern estimate of atomic
size, of the order of 10 –10 m.
In ancient Greece, Democritus (Fourth century B.C.) is best known for his atomic hypothesis. The
word ‘atom’ means ‘indivisible’ in Greek. According to him, atoms differ from each other physically, in
shape, size and other properties and this resulted in the different properties of the substances formed
by their combination. The atoms of water were smooth and round and unable to ‘hook’ on to each
other, which is why liquid /water flows easily. The atoms of earth were rough and jagged, so they held
together to form hard substances. The atoms of fire were thorny which is why it caused painful burns.
These fascinating ideas, despite their ingenuity, could not evolve much further, perhaps because they
were intuitive conjectures and speculations not tested and modified by quantitative experiments - the
hallmark of modern science.

in Greece had suggested that matter may consist of matter. The theory is now well accepted by
of indivisible constituents. The scientific ‘Atomic scientists. However even at the end of the
Theory’ is usually credited to John Dalton. He nineteenth century there were famous scientists
proposed the atomic theory to explain the laws who did not believe in atomic theory !
of definite and multiple proportions obeyed by From many observations, in recent times we
elements when they combine into compounds. now know that molecules (made up of one or
The first law says that any given compound has, more atoms) constitute matter. Electron
a fixed proportion by mass of its constituents. microscopes and scanning tunnelling
The second law says that when two elements microscopes enable us to even see them. The
form more than one compound, for a fixed mass size of an atom is about an angstrom (10 -10 m).
of one element, the masses of the other elements In solids, which are tightly packed, atoms are
are in ratio of small integers. spaced about a few angstroms (2 Å) apart. In
To explain the laws Dalton suggested, about liquids the separation between atoms is also
200 years ago, that the smallest constituents about the same. In liquids the atoms are not
of an element are atoms. Atoms of one element as rigidly fixed as in solids, and can move
are identical but differ from those of other around. This enables a liquid to flow. In gases
elements. A small number of atoms of each the interatomic distances are in tens of
element combine to form a molecule of the angstroms. The average distance a molecule
compound. Gay Lussac’s law, also given in early can travel without colliding is called the mean
19th century, states: When gases combine free path. The mean free path, in gases, is of
chemically to yield another gas, their volumes the order of thousands of angstroms. The atoms
are in the ratios of small integers. Avogadro’s are much freer in gases and can travel long
law (or hypothesis) says: Equal volumes of all distances without colliding. If they are not
gases at equal temperature and pressure have enclosed, gases disperse away. In solids and
the same number of molecules. Avogadro’s law, liquids the closeness makes the interatomic force
when combined with Dalton’s theory explains important. The force has a long range attraction
Gay Lussac’s law. Since the elements are often and a short range repulsion. The atoms attract
in the form of molecules, Dalton’s atomic theory when they are at a few angstroms but repel when
can also be referred to as the molecular theory they come closer. The static appearance of a gas
320 PHYSICS

is misleading. The gas is full of activity and the for a given sample of the gas. Here T is the
equilibrium is a dynamic one. In dynamic temperature in kelvin or (absolute) scale. K is
equilibrium, molecules collide and change their a constant for the given sample but varies with
speeds during the collision. Only the average the volume of the gas. If we now bring in the
properties are constant. idea of atoms or molecules then K is proportional
Atomic theory is not the end of our quest, but to the number of molecules, (say) N in the
the beginning. We now know that atoms are not sample. We can write K = N k . Observation tells
indivisible or elementary. They consist of a us that this k is same for all gases. It is called
nucleus and electrons. The nucleus itself is made Boltzmann constant and is denoted by k .
B
up of protons and neutrons. The protons and
P1V1 P2V2
neutrons are again made up of quarks. Even As = constant = kB (13.2)
N1T1 N 2 T2
quarks may not be the end of the story. There
may be string like elementary entities. Nature if P, V and T are same, then N is also same for
always has surprises for us, but the search for all gases. This is Avogadro’s hypothesis, that the
truth is often enjoyable and the discoveries number of molecules per unit volume is same
beautiful. In this chapter, we shall limit ourselves for all gases at a fixed temperature and pressure.
to understanding the behaviour of gases (and a The number in 22.4 litres of any gas is 6.02 ×
little bit of solids), as a collection of moving 1023. This is known as Avogadro number and
molecules in incessant motion. is denoted by NA. The mass of 22.4 litres of any
gas is equal to its molecular weight in grams at
13.3 BEHAVIOUR OF GASES S.T.P (standard temperature 273 K and pressure
Properties of gases are easier to understand than 1 atm). This amount of substance is called a
those of solids and liquids. This is mainly mole (see Chapter 2 for a more precise definition).
because in a gas, molecules are far from each Avogadro had guessed the equality of numbers
other and their mutual interactions are in equal volumes of gas at a fixed temperature
negligible except when two molecules collide. and pressure from chemical reactions. Kinetic
Gases at low pressures and high temperatures theory justifies this hypothesis.
much above that at which they liquefy (or The perfect gas equation can be written as
solidify) approximately satisfy a simple relation PV = μ RT (13.3)
between their pressure, temperature and volume where μ is the number of moles and R = NA
given by (see Ch. 11) kB is a universal constant. The temperature T is
PV = KT (13.1) absolute temperature. Choosing kelvin scale for

John Dalton (1766- 1844)

He was an English chemist. When different types of atoms combine,
they obey certain simple laws. Dalton’s atomic theory explains these
laws in a simple way. He also gave a theory of colour
blindness.

Amedeo Avogadro (1776 – 1856)

He made a brilliant guess that equal volumes of gases
have equal number of molecules at the same
temperature and pressure. This helped in
understanding the combination of different gases in
a very simple way. It is now called Avogadro’s hypothesis (or law). He also
suggested that the smallest constituent of gases like hydrogen, oxygen and
nitrogen are not atoms but diatomic molecules.
KINETIC THEORY 321

absolute temperature, R = 8.314 J mol–1K–1. i.e., keeping temperature constant, pressure of

Here a given mass of gas varies inversely with volume.
This is the famous Boyle’s law. Fig. 13.2 shows
M N
(13.4) comparison between experimental P-V curves
M0 NA and the theoretical curves predicted by Boyle’s
where M is the mass of the gas containing N law. Once again you see that the agreement is
molecules, M0 is the molar mass and NA the good at high temperatures and low pressures.
Avogadro’s number. Using Eqs. (13.4) and (13.3) Next, if you fix P, Eq. (13.1) shows that V ∝ T
can also be written as i.e., for a fixed pressure, the volume of a gas is
PV = kB NT or P = kB nT proportional to its absolute temperature T
(Charles’ law). See Fig. 13.3.
–1 –1
K
J mol
pV
T

P (atm)
Fig.13.1 Real gases approach ideal gas behaviour
at low pressures and high temperatures.

where n is the number density, i.e. number of

molecules per unit volume. kB is the Boltzmann Fig.13.2 Experimental P-V curves (solid lines) for
constant introduced above. Its value in SI units steam at three temperatures compared
is 1.38 × 10–23 J K–1. with Boyle’s law (dotted lines). P is in units
Another useful form of Eq. (13.3) is of 22 atm and V in units of 0.09 litres.
RT
P (13.5) Finally, consider a mixture of non-interacting
M0
ideal gases: μ moles of gas 1, μ moles of gas
where ρ is the mass density of the gas. 1 2
2, etc. in a vessel of volume V at temperature T
A gas that satisfies Eq. (13.3) exactly at all
and pressure P. It is then found that the
pressures and temperatures is defined to be an
equation of state of the mixture is :
ideal gas. An ideal gas is a simple theoretical
model of a gas. No real gas is truly ideal. PV = ( μ1 + μ2 +… ) RT (13.7)
Fig. 13.1 shows departures from ideal gas
RT RT
behaviour for a real gas at three different i.e. P 1 2 ... (13.8)
temperatures. Notice that all curves approach V V
the ideal gas behaviour for low pressures and = P1 + P2 + … (13.9)
high temperatures. Clearly P1 = μ1 R T/V is the pressure gas 1
At low pressures or high temperatures the would exert at the same conditions of volume
molecules are far apart and molecular and temperature if no other gases were present.
interactions are negligible. Without interactions This is called the partial pressure of the gas.
the gas behaves like an ideal one.
Thus, the total pressure of a mixture of ideal
If we fix μ and T in Eq. (13.3), we get
gases is the sum of partial pressures. This is
PV = constant (13.6) Dalton’s law of partial pressures.
322 PHYSICS

density of water molecule may therefore, be

regarded as roughly equal to the density of bulk
water = 1000 kg m–3. To estimate the volume of
a water molecule, we need to know the mass of
a single water molecule. We know that 1 mole
of water has a mass approximately equal to
(2 + 16)g = 18 g = 0.018 kg.
Since 1 mole contains about 6 × 1023
molecules (Avogadro’s number), the mass of
a molecule of water is (0.018)/(6 × 1023) kg =
3 × 10–26 kg. Therefore, a rough estimate of the
volume of a water molecule is as follows :
Volume of a water molecule
= (3 × 10–26 kg)/ (1000 kg m–3)
= 3 × 10–29 m3
= (4/3) π (Radius)3
Fig. 13.3 Experimental T-V curves (solid lines) for Hence, Radius ≈ 2 ×10-10 m = 2 Å
CO2 at three pressures compared with
Charles’ law (dotted lines). T is in units of
Example 13.3 What is the average
300 K and V in units of 0.13 litres.
distance between atoms (interatomic
distance) in water? Use the data given in
We next consider some examples which give
Examples 13.1 and 13.2.
us information about the volume occupied by
the molecules and the volume of a single
Answer : A given mass of water in vapour state
molecule.
has 1.67×103 times the volume of the same mass
of water in liquid state (Ex. 13.1). This is also
Example 13.1 The density of water is 1000
the increase in the amount of volume available
kg m–3. The density of water vapour at 100 °C
for each molecule of water. When volume
and 1 atm pressure is 0.6 kg m–3. The
increases by 103 times the radius increases by
volume of a molecule multiplied by the total
V1/3 or 10 times, i.e., 10 × 2 Å = 20 Å. So the
number gives ,what is called, molecular
average distance is 2 × 20 = 40 Å.
volume. Estimate the ratio (or fraction) of
the molecular volume to the total volume
Example 13.4 A vessel contains two non-
occupied by the water vapour under the
reactive gases : neon (monatomic) and
above conditions of temperature and
oxygen (diatomic). The ratio of their partial
pressure.
pressures is 3:2. Estimate the ratio of (i)
number of molecules and (ii) mass density
Answer For a given mass of water molecules,
of neon and oxygen in the vessel. Atomic
the density is less if volume is large. So the
mass of Ne = 20.2 u, molecular mass of O2
volume of the vapour is 1000/0.6 = /(6 ×10 -4 )
= 32.0 u.
times larger. If densities of bulk water and water
molecules are same, then the fraction of Answer Partial pressure of a gas in a mixture is
molecular volume to the total volume in liquid the pressure it would have for the same volume
state is 1. As volume in vapour state has and temperature if it alone occupied the vessel.
increased, the fractional volume is less by the (The total pressure of a mixture of non-reactive
same amount, i.e. 6×10-4. gases is the sum of partial pressures due to its
constituent gases.) Each gas (assumed ideal)
Example 13.2 Estimate the volume of a
obeys the gas law. Since V and T are common to
water molecule using the data in Example
the two gases, we have P1V = μ 1 RT and P2V =
13.1.
μ2 RT, i.e. (P1/P2) = (μ1 / μ2). Here 1 and 2 refer
Answer In the liquid (or solid) phase, the to neon and oxygen respectively. Since (P1/P2) =
molecules of water are quite closely packed. The (3/2) (given), (μ1/ μ2) = 3/2.
KINETIC THEORY 323

(i) By definition μ1 = (N1/NA ) and μ2 = (N2/NA)

where N1 and N2 are the number of molecules
of 1 and 2, and NA is the Avogadro’s number.
Therefore, (N1/N2) = (μ1 / μ2) = 3/2.
(ii) We can also write μ1 = (m1/M1) and μ2 =
(m2/M2) where m1 and m2 are the masses of
1 and 2; and M1 and M2 are their molecular
masses. (Both m1 and M1; as well as m2 and
M2 should be expressed in the same units).
If ρ 1 and ρ 2 are the mass densities of 1 and
2 respectively, we have

1 m1 / V m1 1 M1
Fig. 13.4 Elastic collision of a gas molecule with
2 m2 /V m2 2 M2 the wall of the container.

3 20.2 (vx, vy, vz ) hits the planar wall parallel to yz-

0.947
2 32.0 plane of area A (= l 2). Since the collision is elastic,
the molecule rebounds with the same velocity;
13.4 KINETIC THEORY OF AN IDEAL GAS its y and z components of velocity do not change
in the collision but the x-component reverses
Kinetic theory of gases is based on the molecular
sign. That is, the velocity after collision is
picture of matter. A given amount of gas is a
(-vx, vy, vz ) . The change in momentum of the
collection of a large number of molecules
molecule is : –mvx – (mvx) = – 2mvx . By the
(typically of the order of Avogadro’s number) that
principle of conservation of momentum, the
are in incessant random motion. At ordinary
momentum imparted to the wall in the collision
pressure and temperature, the average distance
= 2mvx .
between molecules is a factor of 10 or more than
To calculate the force (and pressure) on the
the typical size of a molecule (2 Å). Thus the
wall, we need to calculate momentum imparted
interaction between the molecules is negligible
to the wall per unit time. In a small time interval
and we can assume that they move freely in
Δt, a molecule with x-component of velocity vx
straight lines according to Newton’s first law.
will hit the wall if it is within the distance vx Δt
However, occasionally, they come close to each
from the wall. That is, all molecules within the
other, experience intermolecular forces and their
volume Avx Δt only can hit the wall in time Δt.
velocities change. These interactions are called
But, on the average, half of these are moving
collisions. The molecules collide incessantly
towards the wall and the other half away from
against each other or with the walls and change
the wall. Thus the number of molecules with
their velocities. The collisions are considered to
velocity (vx, vy, vz ) hitting the wall in time Δt is
be elastic. We can derive an expression for the
½A vx Δt n where n is the number of molecules
pressure of a gas based on the kinetic theory.
per unit volume. The total momentum
We begin with the idea that molecules of a
gas are in incessant random motion, colliding transferred to the wall by these molecules in
against one another and with the walls of the time Δt is :
container. All collisions between molecules Q = (2mvx) (½ n A vx Δt ) (13.10)
among themselves or between molecules and the The force on the wall is the rate of momentum
walls are elastic. This implies that total kinetic transfer Q/Δt and pressure is force per unit
energy is conserved. The total momentum is area :
conserved as usual. P = Q /(A Δt) = n m vx2 (3.11)
Actually, all molecules in a gas do not have
13.4.1 Pressure of an Ideal Gas the same velocity; there is a distribution in
velocities. The above equation therefore, stands
Consider a gas enclosed in a cube of side l. Take for pressure due to the group of molecules with
the axes to be parallel to the sides of the cube, speed vx in the x-direction and n stands for the
as shown in Fig. 13.4. A molecule with velocity number density of that group of molecules. The
324 PHYSICS

total pressure is obtained by summing over the the gas in equilibrium is the same as anywhere
contribution due to all groups: else. Second, we have ignored any collisions in
P = n m v x2 (13.12) the derivation. Though this assumption is
difficult to justify rigorously, we can qualitatively
where v 2x is the average of vx2 . Now the gas see that it will not lead to erroneous results.
is isotropic, i.e. there is no preferred direction The number of molecules hitting the wall in time
of velocity of the molecules in the vessel. Δt was found to be ½ n Avx Δt. Now the collisions
Therefore, by symmetry, are random and the gas is in a steady state.
2 Thus, if a molecule with velocity (vx, vy, vz )
v 2x = vy = v z2 acquires a different velocity due to collision with
= (1/3) [ v 2x + v y2 + v z2 ] = (1/3) v 2 (13.13) some molecule, there will always be some other
molecule with a different initial velocity which
where v is the speed and v 2 denotes the mean after a collision acquires the velocity (vx, vy, vz ).
If this were not so, the distribution of velocities
of the squared speed. Thus
would not remain steady. In any case we are
P = (1/3) n m v 2 (13.14) finding v x2 . Thus, on the whole, molecular
Some remarks on this derivation. First, collisions (if they are not too frequent and the
though we choose the container to be a cube, time spent in a collision is negligible compared
the shape of the vessel really is immaterial. For to time between collisions) will not affect the
a vessel of arbitrary shape, we can always choose calculation above.
a small infinitesimal (planar) area and carry 13.4.2 Kinetic Interpretation of Temperature
through the steps above. Notice that both A and
Δt do not appear in the final result. By Pascal’s Equation (13.14) can be written as
law, given in Ch. 10, pressure in one portion of PV = (1/3) nV m v 2 (13.15a)

Founders of Kinetic Theory of Gases

James Clerk Maxwell (1831 – 1879), born in Edinburgh,

Scotland, was among the greatest physicists of the nineteenth
century. He derived the thermal velocity distribution of molecules
in a gas and was among the first to obtain reliable estimates of
molecular parameters from measurable quantities like viscosity,
etc. Maxwell’s greatest achievement was the unification of the laws
of electricity and magnetism (discovered by Coulomb, Oersted,
Ampere and Faraday) into a consistent set of equations now called
Maxwell’s equations. From these he arrived at the most important
conclusion that light is an
electromagnetic wave.
Interestingly, Maxwell did not
agree with the idea (strongly
suggested by the Faraday’s
laws of electrolysis) that
electricity was particulate in
nature.

Ludwig Boltzmann
(1844 – 1906) bor n in
Vienna, Austria, worked on the kinetic theory of gases
independently of Maxwell. A firm advocate of atomism, that is
basic to kinetic theory, Boltzmann provided a statistical
interpretation of the Second Law of thermodynamics and the
concept of entropy. He is regarded as one of the founders of classical
statistical mechanics. The proportionality constant connecting
energy and temperature in kinetic theory is known as Boltzmann’s
constant in his honour.
KINETIC THEORY 325

PV = (2/3) N x ½ m v 2 (13.15b) M N2 28
where N (= nV ) is the number of molecules in m 4.65 10 –26 kg.
NA 6.02 1026
the sample.
The quantity in the bracket is the average v 2 = 3 kB T / m = (516)2 m2s-2
translational kinetic energy of the molecules in The square root of v 2 is known as root mean
the gas. Since the internal energy E of an ideal square (rms) speed and is denoted by vrms,
gas is purely kinetic*,
( We can also write v 2 as < v2 >.)
E = N × (1/2) m v 2 (13.16)
vrms = 516 m s-1
Equation (13.15) then gives : The speed is of the order of the speed of sound
PV = (2/3) E (13.17) in air. It follows from Eq. (13.19) that at the same
We are now ready for a kinetic interpretation temperature, lighter molecules have greater rms
of temperature. Combining Eq. (13.17) with the speed.
ideal gas Eq. (13.3), we get Example 13.5 A flask contains argon and
E = (3/2) kB NT (13.18) chlorine in the ratio of 2:1 by mass. The
or E/ N = ½ m v 2 = (3/2) kBT (13.19) temperature of the mixture is 27 °C. Obtain
i.e., the average kinetic energy of a molecule is the ratio of (i) average kinetic energy per
proportional to the absolute temperature of the molecule, and (ii) root mean square speed
gas; it is independent of pressure, volume or vrms of the molecules of the two gases.
the nature of the ideal gas. This is a fundamental Atomic mass of argon = 39.9 u; Molecular
result relating temperature, a macroscopic mass of chlorine = 70.9 u.
measurable parameter of a gas
(a thermodynamic variable as it is called) to a Answer The important point to remember is that
molecular quantity, namely the average kinetic
the average kinetic energy (per molecule) of any
energy of a molecule. The two domains are
(ideal) gas (be it monatomic like argon, diatomic
connected by the Boltzmann constant. We note
in passing that Eq. (13.18) tells us that internal like chlorine or polyatomic) is always equal to
energy of an ideal gas depends only on (3/2) kBT. It depends only on temperature, and
temperature, not on pressure or volume. With is independent of the nature of the gas.
this interpretation of temperature, kinetic theory (i) Since argon and chlorine both have the same
of an ideal gas is completely consistent with the temperature in the flask, the ratio of average
ideal gas equation and the various gas laws kinetic energy (per molecule) of the two gases
based on it. is 1:1.
For a mixture of non-reactive ideal gases, the (ii) Now ½ m vrms2 = average kinetic energy per
total pressure gets contribution from each gas molecule = (3/2) ) kBT where m is the mass
in the mixture. Equation (13.14) becomes of a molecule of the gas. Therefore,
P = (1/3) [n1m1 v12 + n2 m2 v 22 +… ] (13.20) 2
In equilibrium, the average kinetic energy of vrms m M
Ar Cl Cl 70.9
the molecules of different gases will be equal. v 2
m M = =1.77
rms Cl Ar Ar 39.9
That is,
where M denotes the molecular mass of the gas.
½ m1 v12 = ½ m2 v 22 = (3/2) kB T
(For argon, a molecule is just an atom of argon.)
so that Taking square root of both sides,
P = (n1 + n2 +… ) kB T (13.21)
vrms
which is Dalton’s law of partial pressures. Ar
From Eq. (13.19), we can get an idea of the = 1.33
vrms
Cl
typical speed of molecules in a gas. At a
temperature T = 300 K, the mean square speed You should note that the composition of the
of a molecule in nitrogen gas is : mixture by mass is quite irrelevant to the above

* E denotes the translational part of the internal energy U that may include energies due to other degrees of
freedom also. See section 13.5.
326 PHYSICS

Maxwell Distribution Function

In a given mass of gas, the velocities of all molecules are not the same, even when bulk
parameters like pressure, volume and temperature are fixed. Collisions change the direction
and the speed of molecules. However in a state of equilibrium, the distribution of speeds is
constant or fixed.
Distributions are very important and useful when dealing with systems containing large
number of objects. As an example consider the ages of different persons in a city. It is not
feasible to deal with the age of each individual. We can divide the people into groups: children
up to age 20 years, adults between ages of 20 and 60, old people above 60. If we want more
detailed information we can choose smaller intervals, 0-1, 1-2,..., 99-100 of age groups. When
the size of the interval becomes smaller, say half year, the number of persons in the interval
will also reduce, roughly half the original number in the one year interval. The number of
persons dN(x) in the age interval x and x+dx is proportional to dx or dN(x) = nx dx. We have
used nx to denote the number of persons at the value of x.

Maxwell distribution of molecular speeds

In a similar way the molecular speed distribution gives the number of molecules between
2
the speeds v and v+ dv. dN(v) = 4p N a3e–bv v2 dv = nvdv. This is called Maxwell distribution.
The plot of nv against v is shown in the figure. The fraction of the molecules with speeds v and
v+dv is equal to the area of the strip shown. The average of any quantity like v2 is defined by
the integral <v2> = (1/N ) ∫ v2 dN(v) = Å(3kB T/m) which agrees with the result derived from
more elementary considerations.

mass of the molecule, faster will be the speed.

calculation. Any other proportion by mass of
The ratio of speeds is inversely proportional to
argon and chlorine would give the same answers
the square root of the ratio of the masses. The
to (i) and (ii), provided the temperature remains
masses are 349 and 352 units. So
unaltered.
v349 / v352 = ( 352/ 349)1/2 = 1.0044 .
Example 13.6 Uranium has two isotopes
V
of masses 235 and 238 units. If both are Hence difference = 0.44 %.
present in Uranium hexafluoride gas which V
would have the larger average speed ? If [235U is the isotope needed for nuclear fission.
atomic mass of fluorine is 19 units, To separate it from the more abundant isotope
238
estimate the percentage difference in U, the mixture is surrounded by a porous
speeds at any temperature. cylinder. The porous cylinder must be thick and
narrow, so that the molecule wanders through
Answer At a fixed temperature the average individually, colliding with the walls of the long
energy = ½ m <v2 > is constant. So smaller the pore. The faster molecule will leak out more than
KINETIC THEORY 327

the slower one and so there is more of the lighter is V + u towards the bat. When the ball rebounds
molecule (enrichment) outside the porous (after hitting the massive bat) its speed, relative
cylinder (Fig. 13.5). The method is not very to bat, is V + u moving away from the bat. So
efficient and has to be repeated several times relative to the wicket the speed of the rebounding
for sufficient enrichment.]. ball is V + (V + u) = 2V + u, moving away from
When gases diffuse, their rate of diffusion is the wicket. So the ball speeds up after the
inversely proportional to square root of the collision with the bat. The rebound speed will
masses (see Exercise 13.12 ). Can you guess the be less than u if the bat is not massive. For a
explanation from the above answer? molecule this would imply an increase in
temperature.
You should be able to answer (b) (c) and (d)
based on the answer to (a).
(Hint: Note the correspondence, pistonÆ bat,
cylinder Æ wicket, molecule Æ ball.)

13.5 LAW OF EQUIPARTITION OF ENERGY

The kinetic energy of a single molecule is
1 1 1
t mv x2 mvy2 mv z2 (13.22)
2 2 2
For a gas in ther mal equilibrium at
temperature T the average value of energy
denoted by < t > is
1 1 1 3
t mv x2 mvy2 mv z2 kB T (13.23)
2 2 2 2
Fig. 13.5 Molecules going through a porous wall.
Since there is no preferred direction, Eq. (13.23)
Example 13.7 (a) When a molecule (or implies
an elastic ball) hits a ( massive) wall, it 1 1 1 1
rebounds with the same speed. When a ball mv x2 kBT , mvy2 kB T ,
2 2 2 2
hits a massive bat held firmly, the same
thing happens. However, when the bat is 1 1
moving towards the ball, the ball rebounds mv z2 kBT (13.24)
2 2
with a different speed. Does the ball move
faster or slower? (Ch.6 will refresh your A molecule free to move in space needs three
memory on elastic collisions.) coordinates to specify its location. If it is
constrained to move in a plane it needs two;and
(b) When gas in a cylinder is compressed if constrained to move along a line, it needs just
by pushing in a piston, its temperature one coordinate to locate it. This can also be
rises. Guess at an explanation of this in expressed in another way. We say that it has
terms of kinetic theory using (a) above. one degree of freedom for motion in a line, two
(c) What happens when a compressed gas for motion in a plane and three for motion in
pushes a piston out and expands. What space. Motion of a body as a whole from one
would you observe ? point to another is called translation. Thus, a
(d) Sachin Tendulkar uses a heavy cricket molecule free to move in space has three
bat while playing. Does it help him in translational degrees of freedom. Each
anyway ? translational degree of freedom contributes a
term that contains square of some variable of
Answer (a) Let the speed of the ball be u relative motion, e.g., ½ mvx2 and similar terms in
to the wicket behind the bat. If the bat is moving vy and vz. In, Eq. (13.24) we see that in thermal
towards the ball with a speed V relative to the equilibrium, the average of each such term is
wicket, then the relative speed of the ball to bat ½ kBT .
328 PHYSICS

Molecules of a monatomic gas like argon have (13.26)

t r v
only translational degrees of freedom. But what
where k is the force constant of the oscillator
about a diatomic gas such as O2 or N 2? A
and y the vibrational co-ordinate.
molecule of O2 has three translational degrees
Once again the vibrational energy terms in
of freedom. But in addition it can also rotate
Eq. (13.26) contain squared terms of vibrational
about its centre of mass. Figure 13.6 shows the
variables of motion y and dy/dt .
two independent axes of rotation 1 and 2, normal
At this point, notice an important feature in
to the axis joining the two oxygen atoms about
which the molecule can rotate*. The molecule Eq.(13.26). While each translational and
thus has two rotational degrees of freedom, each rotational degree of freedom has contributed only
of which contributes a term to the total energy one ‘squared term’ in Eq.(13.26), one vibrational
consisting of translational energy t and mode contributes two ‘squared terms’ : kinetic
rotational energy r. and potential energies.
Each quadratic term occurring in the
1 1 1 1 1
t r mv x2 mvy2 mv z2 I1 2
1 I2 2
2 (13.25) expression for energy is a mode of absorption of
2 2 2 2 2
energy by the molecule. We have seen that in
thermal equilibrium at absolute temperature T,
for each translational mode of motion, the
average energy is ½ kBT. A most elegant principle
of classical statistical mechanics (first proved
by Maxwell) states that this is so for each mode
of energy: translational, rotational and
vibrational. That is, in equilibrium, the total
energy is equally distributed in all possible
energy modes, with each mode having an average
energy equal to ½ kBT. This is known as the
law of equipartition of energy. Accordingly,
Fig. 13.6 The two independent axes of rotation of a each translational and rotational degree of
diatomic molecule freedom of a molecule contributes ½ kBT to the
energy while each vibrational frequency
where ω1 and ω2 are the angular speeds about contributes 2 × ½ kBT = kBT , since a vibrational
the axes 1 and 2 and I1, I2 are the corresponding mode has both kinetic and potential energy
moments of inertia. Note that each rotational modes.
degree of freedom contributes a term to the The proof of the law of equipartition of energy
energy that contains square of a rotational is beyond the scope of this book. Here we shall
variable of motion.
apply the law to predict the specific heats of
We have assumed above that the O molecule 2
gases theoretically. Later we shall also discuss
is a ‘rigid rotator’, i.e. the molecule does not
vibrate. This assumption, though found to be briefly, the application to specific heat of solids.
true (at moderate temperatures) for O2, is not
always valid. Molecules like CO even at moderate 13.6 SPECIFIC HEAT CAPACITY
temperatures have a mode of vibration, i.e. its 13.6.1 Monatomic Gases
atoms oscillate along the interatomic axis like
a one-dimensional oscillator, and contribute a The molecule of a monatomic gas has only three
vibrational energy term ε v to the total energy: translational degrees of freedom. Thus, the
average energy of a molecule at temperature
2
1 dy 1 2 T is (3/2)kBT . The total internal energy of a
v m ky
2 dt 2 mole of such a gas is

* Rotation along the line joining the atoms has very small moment of inertia and does not come into play for
quantum mechanical reasons. See end of section 13.6.
KINETIC THEORY 329

i.e. Cv = (3 + f ) R, Cp = (4 + f ) R,
3 3
U kB T NA RT (13.27)
2 2 f
(13.36)
f
The molar specific heat at constant volume,
Cv, is Note that Cp – Cv = R is true for any ideal
gas, whether mono, di or polyatomic.
dU 3
Cv (monatomic gas) = = RT (13.28) Table 13.1 summarises the theoretical
dT 2 predictions for specific heats of gases ignoring
For an ideal gas, any vibrational modes of motion. The values are
Cp – Cv = R (13.29) in good agreement with experimental values of
where Cp is the molar specific heat at constant specific heats of several gases given in Table 13.2.
pressure. Thus, Of course, there are discrepancies between
5 predicted and actual values of specific heats of
Cp = R (13.30)
several other gases (not shown in the table), such
2
as Cl2, C2H6 and many other polyatomic gases.
Cp 5 Usually, the experimental values for specific
The ratio of specific heats (13.31)
Cv 3 heats of these gases are greater than the
predicted values given in Table13.1 suggesting
13.6.2 Diatomic Gases that the agreement can be improved by including
vibrational modes of motion in the calculation.
As explained earlier, a diatomic molecule treated
The law of equipartition of energy is thus well
as a rigid rotator like a dumbbell has 5 degrees
of freedom : 3 translational and 2 rotational.
Using the law of equipartition of energy, the total Table 13.1 Predicted values of specific heat
internal energy of a mole of such a gas is capacities of gases (ignoring
5 5 vibrational modes),
U kBT NA RT (13.32)
2 2
Nature of Cv Cp Cp - Cv g
The molar specific heats are then given by Gas
(J mol- 1 K- 1) (J mol- 1 K- 1) (J mol- K- )
1 1

5 7 Monatomic 12.5 20.8 8.31 1.67

Cv (rigid diatomic) = R, Cp = R (13.33)
2 2
Diatomic 20.8 29.1 8.31 1.40
7
γ (rigid diatomic) = (13.34) Triatomic 24.93 33.24 8.31 1.33
5
If the diatomic molecule is not rigid but has
in addition a vibrational mode Table13.2 Measured values of specific heat
⎛5 ⎞ 7 capacities of some gases
U = ⎜ k BT + k B T ⎟⎟ N A = RT
⎜
⎝2 ⎠ 2

7 9 9
Cv R, C p R, R (13.35)
2 2 7
13.6.3 Polyatomic Gases
In general a polyatomic 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
3 3
U = ( kBT + kBT + f kBT ) NA
2 2
330 PHYSICS

verified experimentally at ordinary As Table 13.3 shows the prediction generally

temperatures. agrees with experimental values at ordinary
temperature (Carbon is an exception).
Example 13.8 A cylinder of fixed capacity
44.8 litres contains helium gas at standard 13.6.5 Specific Heat Capacity of Water
temperature and pressure. What is the
amount of heat needed to raise the We treat water like a solid. For each atom average
temperature of the gas in the cylinder by energy is 3kBT. Water molecule has three atoms,
15.0 °C ? (R = 8.31 J mo1–1 K–1). two hydrogen and one oxygen. So it has
Answer Using the gas law PV = μRT, you can U = 3 × 3 kBT × NA = 9 RT
easily show that 1 mol of any (ideal) gas at and C = ΔQ/ ΔT =Δ U / ΔT = 9R .
standard temperature (273 K) and pressure
This is the value observed and the agreement
(1 atm = 1.01 × 105 Pa) occupies a volume of
22.4 litres. This universal volume is called molar is very good. In the calorie, gram, degree units,
volume. Thus the cylinder in this example water is defined to have unit specific heat. As 1
contains 2 mol of helium. Further, since helium calorie = 4.179 joules and one mole of water
is monatomic, its predicted (and observed) molar is 18 grams, the heat capacity per mole is
specific heat at constant volume, Cv = (3/2) R, ~ 75 J mol-1 K-1 ~ 9R . However with more
and molar specific heat at constant pressure, complex molecules like alcohol or acetone the
Cp = (3/2) R + R = (5/2) R . Since the volume of arguments, based on degrees of freedom, become
the cylinder is fixed, the heat required is more complicated.
determined by Cv. Therefore, Lastly, we should note an important aspect
Heat required = no. of moles × molar specific of the predictions of specific heats, based on the
heat × rise in temperature classical law of equipartition of energy. The
= 2 × 1.5 R × 15.0 = 45 R predicted specific heats are independent of
= 45 × 8.31 = 374 J. temperature. As we go to low temperatures,
however, there is a marked departure from this
13.6.4 Specific Heat Capacity of Solids
prediction. Specific heats of all substances
We can use the law of equipartition of energy to approach zero as T Æ0. This is related to the
determine specific heats of solids. Consider a fact that degrees of freedom get frozen and
solid of N atoms, each vibrating about its mean ineffective at low temperatures. According to
position. An oscillation in one dimension has classical physics degrees of freedom must
average energy of 2 × ½ kBT = kBT . In three
remain unchanged at all times. The behaviour
dimensions, the average energy is 3 kBT. For a
of specific heats at low temperatures shows the
mole of solid, N = N A , and the total
inadequacy of classical physics and can be
energy is
explained only by invoking quantum
U = 3 kBT × NA = 3 RT considerations, as was first shown by Einstein.
Now at constant pressure ΔQ = ΔU + PΔV Quantum mechanics requires a minimum,
= ΔU, since for a solid ΔV is negligible. Hence, nonzero amount of energy before a degree of
Q U freedom comes into play. This is also the reason
C 3R (13.37)
T T why vibrational degrees of freedom come into
Table 13.3 Specific Heat Capacity of some play only in some cases.
solids at room temperature and
13.7 MEAN FREE PATH
atmospheric pressure
Molecules in a gas have rather large speeds of
the order of the speed of sound. Yet a gas leaking
from a cylinder in a kitchen takes considerable
time to diffuse to the other corners of the room.
The top of a cloud of smoke holds together for
hours. This happens because molecules in a gas
have a finite though small size, so they are bound
to undergo collisions. As a result, they cannot
KINETIC THEORY 331

Seeing is Believing

Can one see atoms rushing about. Almost but not quite. One can see pollen grains of a flower being
pushed around by molecules of water. The size of the grain is ~ 10-5 m. In 1827, a Scottish botanist
Robert Brown, while examining, under a microscope, pollen grains of a flower suspended in water
noticed that they continuously moved about in a zigzag, random fashion.
Kinetic theory provides a simple explanation of the phenomenon. Any object suspended in water is
continuously bombarded from all sides by the water molecules. Since the motion of molecules is random,
the number of molecules hitting the object in any direction is about the same as the number hitting in
the opposite direction. The small difference between these molecular hits is negligible compared to the
total number of hits for an object of ordinary size, and we do not notice any movement of the object.
When the object is sufficiently small but still visible under a microscope, the difference in molecular
hits from different directions is not altogether negligible, i.e. the impulses and the torques given to the
suspended object through continuous bombardment by the molecules of the medium (water or some
other fluid) do not exactly sum to zero. There is a net impulse and torque in this or that direction. The
suspended object thus, moves about in a zigzag manner and tumbles about randomly. This motion
called now ‘Brownian motion’ is a visible proof of molecular activity. In the last 50 years or so molecules
have been seen by scanning tunneling and other special microscopes.
In 1987 Ahmed Zewail, an Egyptian scientist working in USA was able to observe not only the
molecules but also their detailed interactions. He did this by illuminating them with flashes of laser
light for very short durations, of the order of tens of femtoseconds and photographing them. ( 1 femto-
second = 10-15 s ). One could study even the formation and breaking of chemical bonds. That is really
seeing !

move straight unhindered; their paths keep will collide with it (see Fig. 13.7). If n is the
getting incessantly deflected. number of molecules per unit volume, the
molecule suffers nπd2 <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 ) (13.38)
The average distance between two successive
collisions, called the mean free path l, is :
t
v l = <v> τ = 1/(nπd2) (13.39)
d In this derivation, we imagined the other
molecules to be at rest. But actually all molecules
are moving and the collision rate is determined
d by the average relative velocity of the molecules.
Thus we need to replace <v> by <v > in Eq.
r
(13.38). A more exact treatment gives
l 1/ 2 n d2 (13.40)
Let us estimate l and τ for air molecules with
Fig. 13.7 The volume swept by a molecule in time Δt
average speeds <v> = ( 485m/s). At STP
in which any molecule will collide with it.
0.02 1023
Suppose the molecules of a gas are spheres n=
22.4 10 –3
of diameter d. Focus on a single molecule with
the average speed <v>. It will suffer collision with = 2.7 × 10 25 m -3.
any molecule that comes within a distance d Taking, d = 2 × 10–10 m,
between the centres. In time Δt, it sweeps a τ = 6.1 × 10–10 s
volume πd2 <v> Δt wherein any other molecule and l = 2.9 × 10–7 m ≈ 1500d (13.41)
332 PHYSICS

As expected, the mean free path given by

25 273
Eq. (13.40) depends inversely on the number So n 2.7 10 2 1025 m –3
density and the size of the molecules. In a highly 373
evacuated tube n is rather small and the mean Hence, mean free path l 4 10 –7 m
free path can be as large as the length of the
Note that the mean free path is 100 times the
tube.
interatomic distance ~ 40 Å = 4 ×10-9 m calculated
earlier. It is this large value of mean free path that
Example 13.9 Estimate the mean free path leads to the typical gaseous behaviour. Gases can
for a water molecule in water vapour at 373 K. not be confined without a container.
Use information from Exercises 13.1 and Using, the kinetic theory of gases, the bulk
Eq. (13.41) above. measurable properties like viscosity, heat
conductivity and diffusion can be related to the
Answer The d for water vapour is same as that microscopic parameters like molecular size. It
of air. The number density is inversely is through such relations that the molecular
proportional to absolute temperature. sizes were first estimated.

SUMMARY

1. The ideal gas equation connecting pressure (P ), volume (V ) and absolute temperature
(T ) is
PV = μ RT = kB NT
where μ is the number of moles and N is the number of molecules. R and kB are universal
constants.
R
R = 8.314 J mol–1 K–1, kB = = 1.38 × 10–23 J K–1
NA
Real gases satisfy the ideal gas equation only approximately, more so at low pressures
and high temperatures.
2. Kinetic theory of an ideal gas gives the relation
1
P n m v2
3
where n is number density of molecules, m the mass of the molecule and v 2 is the
mean of squared speed. Combined with the ideal gas equation it yields a kinetic
interpretation of temperature.

1 3 1/ 2 3k B T
m v2 k B T , vrms v2
2 2 m
This tells us that the temperature of a gas is a measure of the average kinetic energy
of a molecule, independent of the nature of the gas or molecule. In a mixture of gases at
a fixed temperature the heavier molecule has the lower average speed.
3. The translational kinetic energy

E=
3 kB NT.
2
This leads to a relation

2
PV = E
3
4. The law of equipartition of energy states that if a system is in equilibrium at absolute
temperature T, the total energy is distributed equally in different energy modes of
KINETIC THEORY 333

absorption, the energy in each mode being equal to ½ kB T. Each translational and
rotational degree of freedom corresponds to one energy mode of absorption and has
energy ½ kB T. Each vibrational frequency has two modes of energy (kinetic and potential)
with corresponding energy equal to
2 × ½ kB T = kB T.
5. Using the law of equipartition of energy, the molar specific heats of gases can be
determined and the values are in agreement with the experimental values of specific
heats of several gases. The agreement can be improved by including vibrational modes
of motion.
6. The mean free path l is the average distance covered by a molecule between two
successive collisions :
1
l
2 n d2
where n is the number density and d the diameter of the molecule.

POINTS TO PONDER
1. Pressure of a fluid is not only exerted on the wall. Pressure exists everywhere in a fluid.
Any layer of gas inside the volume of a container is in equilibrium because the pressure
is the same on both sides of the layer.

2. We should not have an exaggerated idea of the intermolecular distance in a gas. At

ordinary pressures and temperatures, this is only 10 times or so the interatomic distance
in solids and liquids. What is different is the mean free path which in a gas is 100
times the interatomic distance and 1000 times the size of the molecule.

3. The law of equipartition of energy is stated thus: the energy for each degree of freedom
in thermal equilibrium is ½ k T. Each quadratic term in the total energy expression of
B
a molecule is to be counted as a degree of freedom. Thus, each vibrational mode gives
2 (not 1) degrees of freedom (kinetic and potential energy modes), corresponding to the
energy 2 × ½ k T = k T.
B B

4. Molecules of air in a room do not all fall and settle on the ground (due to gravity)
because of their high speeds and incessant collisions. In equilibrium, there is a very
slight increase in density at lower heights (like in the atmosphere). The effect is small
since the potential energy (mgh) for ordinary heights is much less than the average
kinetic energy ½ mv2 of the molecules.
5. < v2 > is not always equal to ( < v >)2. The average of a squared quantity is not necessarily
the square of the average. Can you find examples for this statement.

EXERCISES

13.1 Estimate the fraction of molecular volume to the actual volume occupied by oxygen
gas at STP. Take the diameter of an oxygen molecule to be 3 Å.

13.2 Molar volume is the volume occupied by 1 mol of any (ideal) gas at standard
temperature and pressure (STP : 1 atmospheric pressure, 0 °C). Show that it is 22.4
litres.

13.3 Figure 13.8 shows plot of PV/T versus P for 1.00×10–3 kg of oxygen gas at two
different temperatures.
334 PHYSICS

T1
PV (J K–1) T2
T

P x

Fig. 13.8

(a) What does the dotted plot signify?

(b) Which is true: T1 > T2 or T1 < T2?
(c) What is the value of PV/T where the curves meet on the y-axis?
(d) If we obtained similar plots for 1.00×10–3 kg of hydrogen, would we get the same
value of PV/T at the point where the curves meet on the y-axis? If not, what mass
of hydrogen yields the same value of PV/T (for low pressurehigh temperature
region of the plot) ? (Molecular mass of H 2 = 2.02 u, of O 2 = 32.0 u,
R = 8.31 J mo1–1 K–1.)

13.4 An oxygen cylinder of volume 30 litres has an initial gauge pressure of 15 atm and
a temperature of 27 °C. After some oxygen is withdrawn from the cylinder, the gauge
pressure drops to 11 atm and its temperature drops to 17 °C. Estimate the mass of
oxygen taken out of the cylinder (R = 8.31 J mol–1 K–1, molecular mass of O2 = 32 u).

13.5 An air bubble of volume 1.0 cm3 rises from the bottom of a lake 40 m deep at a
temperature of 12 °C. To what volume does it grow when it reaches the surface,
which is at a temperature of 35 °C ?

13.6 Estimate the total number of air molecules (inclusive of oxygen, nitrogen, water
vapour and other constituents) in a room of capacity 25.0 m3 at a temperature of
27 °C and 1 atm pressure.

13.7 Estimate the average thermal energy of a helium atom at (i) room temperature
(27 °C), (ii) the temperature on the surface of the Sun (6000 K), (iii) the temperature
of 10 million kelvin (the typical core temperature in the case of a star).

13.8 Three vessels of equal capacity have gases at the same temperature and pressure.
The first vessel contains neon (monatomic), the second contains chlorine (diatomic),
and the third contains uranium hexafluoride (polyatomic). Do the vessels contain
equal number of respective molecules ? Is the root mean square speed of molecules
the same in the three cases? If not, in which case is vrms the largest ?

13.9 At what temperature is the root mean square speed of an atom in an argon gas
cylinder equal to the rms speed of a helium gas atom at – 20 °C ? (atomic mass of Ar
= 39.9 u, of He = 4.0 u).

13.10 Estimate the mean free path and collision frequency of a nitrogen molecule in a
cylinder containing nitrogen at 2.0 atm and temperature 17 0C. Take the radius of a
nitrogen molecule to be roughly 1.0 Å. Compare the collision time with the time the
molecule moves freely between two successive collisions (Molecular mass of N2 =
28.0 u).
KINETIC THEORY 335

Additional Exer cises

Exercises

13.11 A metre long narrow bore held horizontally (and closed at one end) contains a 76 cm
long mercury thread, which traps a 15 cm column of air. What happens if the tube
is held vertically with the open end at the bottom ?

13.12 From a certain apparatus, the diffusion rate of hydrogen has an average value of
28.7 cm3 s–1. The diffusion of another gas under the same conditions is measured to
have an average rate of 7.2 cm3 s–1. Identify the gas.
[Hint : Use Graham’s law of diffusion: R1/R2 = ( M2 /M1 )1/2, where R1, R2 are diffusion
rates of gases 1 and 2, and M1 and M2 their respective molecular masses. The law is
a simple consequence of kinetic theory.]

13.13 A gas in equilibrium has uniform density and pressure throughout its volume. This
is strictly true only if there are no external influences. A gas column under gravity,
for example, does not have uniform density (and pressure). As you might expect, its
density decreases with height. The precise dependence is given by the so-called law
of atmospheres

n2 = n1 exp [ -mg (h2 – h1)/ kBT ]

where n2, n1 refer to number density at heights h2 and h1 respectively. Use this
relation to derive the equation for sedimentation equilibrium of a suspension in a
liquid column:
n2 = n1 exp [ -mg NA (ρ - P′ ) (h2 –h1)/ (ρ RT)]

where ρ is the density of the suspended particle, and ρ’ that of surrounding medium.
[NA is Avogadro’s number, and R the universal gas constant.] [Hint : Use Archimedes
principle to find the apparent weight of the suspended particle.]

13.14 Given below are densities of some solids and liquids. Give rough estimates of the
size of their atoms :

Substance Atomic Mass (u) Density (103 Kg m-3)

Carbon (diamond) 12.01 2.22

Gold 197.00 19.32
Nitrogen (liquid) 14.01 1.00
Lithium 6.94 0.53
Fluorine (liquid) 19.00 1.14

[Hint : Assume the atoms to be ‘tightly packed’ in a solid or liquid phase, and use
the known value of Avogadro’s number. You should, however, not take the actual
numbers you obtain for various atomic sizes too literally. Because of the crudeness
of the tight packing approximation, the results only indicate that atomic sizes are in
the range of a few Å].