14 PHYSICAL CHEMISTRY [I.

Where A, B, C, D, etc... Are called first, second, third, etc., virtual coefficients. These coefficients are
constant at a given temperature. The equation is also some-times expressed in the form:
𝐵` 𝐶` 𝐷`
PV = RT (1 + + + +⋯) … (𝐼. 59)
𝑉 𝑉2 𝑉4

On the other hand, Holborn and others use a virial equation in which the product PV is
expressed in a power series of the pressure, as

PV = A1+B1P+C1P2+D1P3+….. … (I.60)
Evidently, A = A1 = RT. It may be mentioned that the second virial coefficient is of major
importance in these equations. Other virial coefficient of higher powers of (𝑉1 ) become significant
only at high pressures.

The different equations of state mentioned earlier can also be given the virial form. For example,
the van der Waals equation may be written as,
𝑅𝑇 𝑎 𝑅𝑇 𝑏 𝑎
P = 𝑉−𝑏 − 𝑉 2 = (1 − ) −
𝑉 𝑉 𝑉2

𝑎 1 1 𝑏
Or PV = RT[1 + (𝑏 − 𝑅𝑇 ) + ( )+ ⋯]
𝑉 2 𝑉

𝑎 1
≈ 𝑅𝑇 [1 + (𝑏 − 𝑅𝑇 ) ]
𝑉

Comparing with equation (I.58), the second virial coefficient

B = bRT − a … (I.61)
At the Boyle temperature, the second term must vanish, i.e., B = 0
𝑎
bRTB – a = 0, or TB = 𝑏𝑅

a result deduced earlier. Again, the Berthelot equation,

9 𝑅𝑇𝑒 6𝑇𝑒
PV = RT + 128 ∙ 𝑃𝑒
∙ (1 − 𝑇2
)𝑃

9 𝑅𝑇𝑒 6𝑇𝑒
Hence, the virial coefficient, B = 128 ∙ 𝑝𝑒
∙ (1 − 𝑇2
). …
(I.62)

I.28. Virial Theorem and Equation of State. A rigorous deduction of the equation of state is
possible from a consideration of the virial theorem of Clausius, An outline of the theory is first given.
Applying the laws of mechanics to the individual molecules (each of mass m and root mean
square velocity c), let us denote the three positional co-ordinates of a given molecules by x, y and z.
Let X, Y, and Z denote the three components of the net external forces acting on the molecules. Then,
we have,

𝑑2 𝑥 𝑑2 𝑦 𝑑 2𝑧
X = m𝑑𝑡 2 , Y = m 𝑑𝑡 2 , Z = m𝑑𝑡 2 … (i)

Multiplying these by x, y and z respectively,

𝑑2𝑥 𝑑2 𝑦 𝑑2 𝑧
Xx = m 𝑑𝑡 2 , Yy = m 𝑑𝑡 2 , Zz = m𝑑𝑡 2 … (ii)

𝑑 𝑑𝑥 𝑑2 𝑥 𝑑𝑥
Now (𝑥 )=𝑥 +( )
𝑑𝑡 𝑑𝑡 𝑑𝑡 2 𝑑𝑡
14 PHYSICAL CHEMISTRY [I.5

𝑑2 𝑥 𝑑 𝑑𝑥 𝑑𝑥 1 𝑑 𝑑𝑥 2
Or x 𝑑𝑡 2 = (𝑥 )−( )= ( ) − (𝑑𝑥
𝑑𝑡
) … (iii)
𝑑𝑡 𝑑𝑡 𝑑𝑡 2 𝑑𝑡 𝑑𝑡
14 PHYSICAL CHEMISTRY [I.5

Performance of work against the internal pressure. Now, if U denotes the inherent energy of the given
mass of liquid, this is called internal energy in thermodynamic

𝜕𝑈
Terms, then ( 𝜕𝑉 ) dV denotes the energy-change associated with the volume-change constant
temperature. This is equal to the work performed in expanding the liquid by volume dV against
internal Pt. That is,

𝜕𝑈 𝜕𝑈
PtDv = ( 𝜕𝑉 ) 𝑑𝑉, or Pt = ( 𝜕𝑉 )

It can be reasonably assumed that the internal latent heat of vaporization is the work done in
vaporization of a gm-mole of volume V against the internal pressure Pt. Then,

𝜕𝑈 𝐿𝑡
Lt = ( 𝜕𝑉 ) 𝑉 = PtV1 or Pt = 𝑉

From which the internal pressure Pt may be evaluated.

𝑑𝑈 𝜕𝑃
Again, anticipating a thermodynamic relation ( 𝜕𝑉 ) = T (𝜕𝑇 ) − 𝑃,
𝜕𝑃
Where p is the external pressure and ( ) is the pressure-coefficient, and assuming that van der Waals
𝜕𝑇
equation is also valid for liquids, we can write,

𝜕𝑈 𝜕𝑃 𝑎 𝑎
Pt = ( 𝜕𝑉 )= T (𝜕𝑇 ) − 𝑝 = (𝑝 + 𝑉2
)−𝑃 = 2
𝑉

SURFACE TENSION
II.6. Surface Tension. Surface tension is the most significant of the characteristic properties
of liquids. Consider a liquid in contact with its vapour. A molecule in the bulk of the liquid is
subjected to forces of attraction from all directions by the surrounding molecules and is
practically in a uniform field of force. But for a molecule at the surface, the net attraction
towards the bulk of the liquid is much greater than that towards the vapour where the
attracting molecules are more widely dispersed (Fig.11.5). This means that the molecules at
the surface are pulled inwards. The result is liquid surfaces in absence of other forces tend to
contract to minimum areas. The surface layer seems to behave as a stretched membrane and
this pseudo-membrane tends to contract. It explains why a small amount of liquid, left freely,
such as mercury, rain droplet, etc., always takes spherical shape; because the sphere, for a
given volume, has the least surface area.
That there is much a pull on the molecules of the surface layer can be easily
demonstrated. If a circular copper-wire ring having a silk-thread tied loosely to the two
opposite points be dipped into a soap solution to that on withdrawal a thin film streaches
across the entire ring, the thread will freely swim in the film
14 PHYSICAL CHEMISTRY [I.5

Fig. 11.5 Fig. 11.6

Being attracted in all directions (Fig. II.6a). But if the film is punctured in one
14 PHYSICAL CHEMISTRY [I.5

(g) Graham’s Law of Effusion. The passing out of a gas through a fine orifice made in the wall of the
container is called effusion. The rate of effusion, i.e., the volume of the gas passing out, depends on
the density of the gas, the pressure and the temperature. The quantitative relation governing such
effusion was first found by Graham (1829). This law is enunciated as,

“At constant temperature and pressure, the rates of effusion of different gases vary inversely
as the square root of their densities.”

If a gas passes out through a porous wall, say of unglazed earthenware or compressed
graphite, etc., the process is called diffusion. The same law, as stated above, would be applicable in
the case of diffusion.
If r1 and r2 be the rates of effusion (or diffusion) of two gases having densities d1 and d2 (T-
and P constant), then,

𝑘 𝑘
r1 = and r2 =
√𝑑1 √𝑑2

r1 √d1
Or = … (1.15)
r2 √d2

𝑟√𝑑 = constant

i.e.,
This is established from the results recorded below.

EXPERIMENTAL RESULTS ON THE GRAHAM’S LAW OF DIFFUSION

Gas Density Velocity of diffusion r √𝑑

(Air = 1)

Hydrogen 0.0695 3.83 1.01

Oxygen 1.1056 0.9487 1.00
Nitrogen 0.9712 1.0144 1.00
Carbon dioxide 1.530 0.8122 1.04
Methane 0.559 1.344 1.00

Let t1 and t2 be the time required for the passage of the same volume v of the ywo gases through the
same hole.

𝑣 𝑣
= r1 and = r2
𝑡1 𝑡1

𝑟1 𝑡2 𝑑
= = √𝑑2 … (1.16)
𝑟2 𝑡1 1
 14 PHYSICAL CHEMISTRY [I.5

Since temperature and pressure are fixed, the molar volume vm

of both the gases must be the same. We have, thus,

𝑡2 𝑑 𝑣 𝑀
= √𝑑2 𝑣𝑚 = √𝑀2 … (1.17)
𝑡1 1 𝑚 1

where M1 and M2 are the respective mol. wts.

This relation enables us to determine the mol. Wt. of a gas by
comparing the time of its effusion through a given orifice with that of
a known gas. This is usually done in an effusiometer, one form of
which is shown in Fig.1.6.
A known gas, (say oxygen) is taken over mercury in the bulb A up to a fixed
mark y. The bulb is closed at the top by a three-way stop-cock. The exit is connected
to the funnel B. Sealed into the funnel B is a thin metal sheet with a small perforation
through which the gas can effuse out under the pressure of mercury in C. The time t 1
taken by the mercury to travel from y to x is noted. The experiment is repeated with
the gas of unknown mole. wt. M2 and the time t2 is also noted

Fig. 1.6. Effusiometer

14 PHYSICAL CHEMISTRY [I.5

From experimental observation. For an explanation of such behaviour of gases, some theoretical
foundation is essential. The abstract speculation in this direction must naturally begin with the ideas
as to the nature ultimate structure of the material world. As early as in 500 B.C. Leucippus and
Democritus in Greece and Kanádá in India proposed the atomic theory stating that matter was
discontinuous consisting of minute particles now called molecules and that these particles were
always in motion. Not much progress was made until Gassendi, and later on Hooke, in the
seventeenth century explained explain the physical phenomena of the gases on the assumption of the
existence of rapidly moving independent minute particles. The credit of a systematic attempt to
explain the properties of gases on a mechanical basis for the first time goes to Bernoulli (1738). It was
also soon realised that heat was a manifestation of molecular motion. In a solid the minute particles
(or molecules) are held very closely together and are entirely devoid of any translatory motion. If now
thermal energy to imparted into the solid, it takes the form of vibrational and rotational motion along
with some translatory movements. These are manifested as heat is added and the temperature rises.
With further increases in the absorption of thermal energy, the energy of vibration rises to such an
extent that the particles break away from the compact state and the solid is transformed into liquid
Further absorption of heat cause the particles to break away from the restraining forces holding them
together and the particles move away freely from the liquid to the gaseous state. The gases then are
essentially composed of freely-moving molecules. These basic ideas were at the root of the theory to
explain the behaviour of gases called kinetic theory of gases. The present state of the theory developed
as a result of the thoughts and contributions of not one but a host of great minds spread over centuries.
In nineteenth century especially, through the efforts of Joule, Kronig, Clausius, Boltzmann and
Maxwell, the theory succeeded to attain a rigid mathematical form
As in all theories, the kinetic theory of gases also begins with certain basis assumptions. The
tenets of the theory may be summarised as follows:
(1) Gases are composed of minute discrete particles, now called molecules.
In any one gas all the molecules are the same size and mass, but these differ from gas to gas.
(2) (a) The molecules within a container are in ceaseless chaotic motion with high velocities,
incessantly colliding with each other and with the walls of the container.
(b) In spite of the enormous number of collisions, the molecular density in any volume of
the gas is not distributed, i.e., the molecules at one place do not collect in larger number
that at another. At each collision, however, the velocities are altered in direction and in
magnitude.
(c) Between two collisions, a molecule moves in a straight line with uniform velocity.
The period during which the collision lasts is negligible compared with the time to
traverse the distance between two successive collisions, called the free path.
(3) The bombardment of the molecules on the walls of the container gives rise to the pressure
of the gas. The average force per unit area which the molecules exert in their impacts with
the walls per unit time is the pressure. The larger the number if impacts, the greater will
be the pressure.
(4) The molecules are supposed to be perfectly elastic. In the collisions between one another
or with the walls, no energy is lost.
(5) The dimension of the molecules are negligible compared to the free paths they transverse,
and at ordinary or low pressure, they are taken as point masses.

At relatively low pressure, because of the comparatively large distances between the
molecules, the forces at attraction between the molecules are also negligible.

(6) The temperature of a gas is a measure of the average kinetic energy of the molecules of
the gas in the system. If the temperature is raised, the molecules would move more vigorously
resulting in a larger number of impacts on the wall at a constant volume. That is why we find an
increase of pressure with rise in temperature at constant volume.
14 PHYSICAL CHEMISTRY [I.5

On the other hand, if the volume is decreased at a constant temperature, the molecules would strike
the walls more frequently and the pressure-increase would occur.
I.6. Evidence in support of kinetic Theory. Direct evidence in support of the basic assumption of the
theory, viz., existence of molecules and their motion cannot be given but, though indirect, convincing
proofs in this regard are obtained from the following:
(i) All gases diffuse readily into one another until these are homogenously mixed. If we let
loose a little chlorine gas near the floor of the room, the gas will diffuse on all sides and also to the
ceiling against gravity. This is possible only if there are small particles
which move in all directions.

(ii) The expansibility of a gas to an infinite extent is another

evidence. A gas spreads immediately throughout any empty space in
which it is placed. Obliviously the gas must be composed of minute
particles with motion. We have also seen how the increase in kinetic
energy may lead to vaporisation.

(iii) The rectilinear motion of the gas molecules was first

demonstrated experimentally by Dunoyer (1911) and subsequently by
others. In this experiment a vertical cylindrical tube was taken. The tube
was divided into three chambers by two partitions X and Y (Fig. I.14).
Each partitions had a small circular hole at the centre. In a small oven a
little sodium was taken at the bottom of the lowest compartment, and the
vessel was evacuated. On heating, sodium evaporated and the molecules
escaped rapidly in all directions, most of them being deposited on the
walls of the lowest chamber. Some of these will pass through the hole Y.
The experiment may varied by removing partitions Y and suspending a
disc there, when a shadow is formed on the deposit on the roof. This not
only shows that the molecules move in staright lines but also that there is
no repulsive force between the molecules. Had there been repulsive
forces, the molecules would deviate in the upper chambers and would not
follow rectilinear paths. Fig. 1.14. Dunoyer's Experiment

(iv) In 1827, the botanist Brown observed that pollen grains suspended in a liquid danced
about wildly even when the temperature was maintained constant. The same phenomenon, called
Brownian motion, is also observed when a colloidal suspension is examined under an ultra-
microscope. The motion of the suspended particles is irregular, spontaneous and perpetual, and takes
place in all kinds of media. This can be explained only if we assume that suspended particles are
really pushed from different directions by the molecules of the media. In consequence unbalanced
forces act on the particles and cause it to move about chaotically. We shall later on discuss, in more
details, the character of the Brownian motion. Besides these, the derivation of the gas laws from the
kinetic theory supports the latter.

I.7. Velocity of Gas Molecules. It would be useful to mention here some elementary considerations
which are made in the computation of velocities of the gas molecules.
(i) Suppose a molecule has a velocity c1 and sup x, y and z are its components along three
axes perpendicular to one another. Then,

C12 = x2+y2+z2

(ii) In a given mass of gas, a larger number of molecules would have the
Same velocity c1 in magnitude but in different directions. Evidently, the magnitudes of the
components along any given axis, say x-axis would be different Let the component-velocities of the
different molecules along x axis be denoted by X1, X2, X3……….etc. Since all directions are equally
possible, the components in the two opposite directions along x-axis must balance one another, i.e.,
mean value of the components, x = 0. Similarly, along the other two axes, y = 0 and z = 0.
But the mean of the squares of these components will not be zero, for squares are all positive.
That is, x2 ≠ 0. This is also true along other two axes.
Now there is no preference for any particular direction, all directions being equally probable,
the mean values of the squares along all the three axes must be equal. Then,

𝑥2 = 𝑦 2 = 𝑧2 … (1.23)

The bar overhead indicates the mean values.

So, c12 = 𝑥 2 + 𝑦 2 + 𝑧 2 = 3𝑥 2
1
𝑥 2 = C12 ... (1.24)
3

This relation would be generally true for all magnitudes of the velocity, c 1.
(iii) All the molecules have not got the same velocity. Even if we start with the same velocity for
all the molecules, very soon due to ceaseless collisions, different molecules would acquire different
kinetic energies and hence different velocities.
Suppose a given quantity of gas contain N molecules. Out of these total N molecules, n1
molecules with a velocity c1, n1 molecules with a velocity c2 have each kinetic energy €1, n2
molecules with velocity c2 have each kinetic energy €2, and so on. Then

N = n1 + n2 + n3 +….
N€ = n1 €1 + n2€2+n3€3+…..

Where € is the kinetic energy possessed by a molecule on an average. We have, therefore, when m is
the mass of a molecule,
1 1 1 1
N× 2 m𝑐 2 = n1× 2mc2+ n2× 2mc2 +n3× 2mc2 +……

Where c is the velocity of each molecule on the supposition that each molecule has the same average
kinetic energy.
𝑛1 𝑐1 + 𝑛2 𝑐2 + 𝑛3𝑐3 +⋯
Simplifying 𝑐2 = 𝑁
… (1.25)

Hence, 𝑐 2 is the mean of the squares of the velocity and briefly termed root-mean-square velocity

𝑛1𝑐1 + 𝑛2 𝑐2 + 𝑛3𝑐3 +⋯
So, c= √ … (1.26)
𝑁

Or c is the root of the mean-square velocity and briefly termed root-mean-square velocity.
The arithmetic mean of the velocities, denoted by ca is given by

𝑛1 𝑐1 + 𝑛2 𝑐2 + 𝑛3𝑐3 +⋯
ca = 𝑁
This is often mentioned as average velocity and its velocity and is evidently different from the root-
mean-square-square velocity, c. It should also be noted that the mean square velocity 𝑐 2 is not the
same as the square of the mean speed, (ca2).

For example suppose there are five molecules having speeds 3,4,5,6 and 7 metres per second.
Then,

32 +42 +52+62+72+
𝑐2 = 5
= 27 metres/sec.

3+4+5+7+7
ca2 = ( 5
) = 25 metres/sec.
and

It will be seen later that c = 1.085 ca

Shall remain constant. Through there is slight variation at high pressures, all gases tend to obey this
relation at very low pressures. Thus, if we measure at constant temperature 0℃ the volumes of 1gm-
mol of different gases at different pressures and plot the PV-values against P, we get the lines as.1.5.
Extrapolation of these lines to P = 0 shows that all of them converge on the PV- axis at a point PV =
22.414 litre-atmospheres. So, at 1 atmosphere and 0℃ (0r 273.16 K) the volume of a gm-mole of any
gas is 22.414 litres.
(iv) Value of the gas constant ‘R’. The general equation of state of n gm-moles of any gas is
given by

𝑤 𝑤
Pv = nRT, i.e., Pv = 𝑀 RT (𝑠𝑖𝑛𝑐𝑒 𝑛 = 𝑚
)

For 1 gm-mole, Pv = RT
V denotes the volume of a gm.-mole.
Since we know the volume of a gm.-mole of gas at standard temperature and pressure, it is possible to
evaluate the gas constant, R.

P = 1 atmosphere, T= 273 K, V= 22,414 litres

𝑃×𝑉 1(𝑎𝑡𝑚)×22,141(𝑙𝑖𝑡𝑟𝑒𝑠)
∴ R= 𝑇
= 273
= 0.082 litres-atmospheres

Per degree pre mole. In c.g.s. units,

𝑃×𝑉 76×13,595×981(𝐷𝑌𝑁𝐸𝑆−𝑐𝑚 −2 )×22414 (𝑐𝑚 3)

R= 𝑇 = 273
= 8.314×107 ergs per degree per mole.

Since 1 calorie = 4.184 × 107 ergs

8.314 ×107
∴ R = 4.184 ×107 = 1.987 calories per degree per mole.

For ordinary calculations, the value of R may be taken as equivalent to (approximately) 2 calories per
degree per mole. Evidently, R has the dimensions of energy.
Problem: calculate the pressure exerted on the walls of a 3-litre flask when 7 gms of Nitrogen are introduced into
the same at 27℃.

𝑤 𝑅𝑇
We have P = 𝑀 ∙ 𝑣
( mol.wt.of N2 = 28)

7 .082 ×(273+27)
= 28 × 3
= 2.05 atmospheres.
(R used in litre-atmosphere and the volume in litres)
Problem: What is the molecular weight of a gas, 1.28 gms of which occupy 10 litres at a pressure of 750 mm and
at 27℃ ?
𝑤
Pv = ∙ 𝑅𝑇
𝑀

𝑤 12,8×0.082×(273+27)
Or M= ∙ 𝑅𝑇 = 750 = 31.84
𝑃𝑣 ×10
760

(e) Dalton’s Law of Partial Pressures. If a vessel contains a mixture of two or more gases, then the
individual pressures of the different gases will depend upon the relative proportions of the constituent.
The individual pressures are usually expressed as the partial pressures of the same temperature.
Dalton studied the relation between the partial pressures of the constituent and the total pressure of the
mixture and stated his law of partial pressures, as
“The total pressure of a mixture of gases is equal to the sum of the partial pressures of the
constituent gases (at the same temperature).’’
 I.16. Experimental Verification of Maxwell’s Law. The validity of the Maxwell distribution Law
has been directly tested by a number of investigators. Though the experimental techniques are
different, the principle followed was essentially the same in these experiments. We may describe here
briefly the out line of one such investigation carried out by Zartman in (1931) and, later on, by Ko
(1934).

A little bismuth was taken in a steel crucible (C), (Fig.I.24) and

bismuth was heated by radiation from a hot tungsten filament. The
enclosure within the crucible was filled up with bismuth vapour and
the temperature was determined by thermocouples. Through a fine
channel in the crucible, a narrow molecular beam of bismuth
streamed out and passed up through collimating slits, S1 and S2. The
slits could be closed by magnetic shutter M if necessary. Just above
the slit S2 was kept a rapidly revolving drum having a small aperture
S3 on the side which was co-axially adjusted to S1 and S2.
Obviously then, during the revolution, once in each turn, when the
drum-slit came opposite to the slit S2, a small portion of the beam
entered the drum. Within the drum, just diametrically opposite to
slit was fixed a glass-plate X with a thin coating of Bi. The
molecules which entered the slit S3 ran straight to the opposite wall
and deposited on the plate X. Since the molecules have different
speeds, all of them would not arrive at the same spot. By the time,
the molecules would start from S and reach X, the drum moves
through a certain angle. The slower moving molecules would strike
at points further and further away. In this way a velocity spectrum
was obtained on the glass plate. The whole assembly was kept at
high vacuum of nearly 10−5 mm and the drum had a revolution of
30000 per minute. The density of the deposit at different points was
measured by micro photometry. These densities were proportion to
the numbers. The knowledge of the diameter of the drum and the
frequency of its revolution enabled the calculation of the velocities
of the molecules. The velocity-distribution was found to satisfy the
Maxwell relation quite well.

Fig. I.24. Experimental verification of Maxwell

distribution Law

C. REAL GASES: EQUATIONS OF STATE

I.17. Ideal Gases and Real Gases. Careful experiments have revealed that the gas laws such as
Boyle’s Law, Charles’ Law etc.., are only approximately obeyed by the various gases. Even at
ordinary pressures, the deviations from the laws are appreciable. It is only at very low pressures and
relatively high temperatures, the gases tend to behave in accordance with the gas-laws. Moreover the
deviations vary from gas to gas. The equation PV = RT (for one mole) is applicable for approximate
calculations only and is quite insufficient for accurate measurement. In order to study the deviations
of various gases under different conditions, it was found useful to introduce the concept of ideal
gases. A gas, really a hypothetical one, which follows the gas-law rigorously under all circumstance,
has been named an ideal gas or a perfect gas, distinct from the real gases with which we carry put our
experiments.
The ideal gas will then observe the relation PV = RT and this may, therefore, be called the
equation of state for a perfect gas.
 It may be remembered that the gas laws have been derived from the postulates of the kinetic
theory. Now that these laws are found to be only approximate, it is obvious that some of the postulates
of the theory are inadequate and need modifications. The deviations from the ideal laws are primarily
due to two factors which are not taken account of in the kinetic theory, namely (i) the volume actually
Occupied by the molecules themselves and (ii) the forces of attraction existing between the molecules.
According to the kinetic theory, the volume occupied by the molecules themselves is regarded
as negligible compared to the total volume of the gas, i.e., the gas-molecules are regarded as point-
masses in an ideal gas. But in the real gas the volume of the molecules themselves is quite appreciable
at ordinary pressures.
To obtain a clear picture, let us have a quantitative idea.

At N.T.P one gm.-mole occupies 22400 c.c. (approx...) and contains 6 × 1023 molecules. The
volume available for each molecule on an average is thus 22400/6 × 1023 = 3.7 × 1021 c.c.
The collision diameter (sec.I.19) of a molecule σ = 2× 10−8 cm. approx.., so, that the space
4 4
Occupied by each molecule itself is 3 𝜋𝜎 3 = 3 𝜋(2 × 10−8 )3 ≈ 3.3 × 10−23 c.c. That is, at N.T.P,

the space occupied by the molecule itself is about one-thousandth of the volume of it habits.

If the pressure be increased to say 10 atmospheres, the volume inhabited by a molecule would be
approximately 3.7 × 1021 while the space occupied by itself will be unaltered. So the molecule, for its own
existence, would take up one per cent of the volume, which is by no means negligible.

Again, in the kinetic theory it has been presumed that no inter-molecular force exists and as
such collisions are perfectly elastic, the energy is all kinetic. But, in fact, there does not existence a
force of attraction between the molecules. On cooling, the gases are converted into liquids when the
molecules exhibit appreciable cohesion. This indicates that a similar attraction exists between the
molecules in the gas-phase also. More clear evidence comes from the experiments of Joule and
Thomson. When a stream is a fall of temperature called Joule-Thomson effect. The only explanation
is that the outgoing molecules have to overcome the attraction of molecules from behind and thus
have to perform work. The energy thus spent causes the lowering in temperature, In an ideal gas, there
is no attractive force between the molecules and hence no cooling would be expected.
Due to inter-molecular attraction, the number of impacts on the wall is restrained, i.e., the
number of collisions with the wall would have been greater if there were no attractive force on the
colliding molecules from behind. In consequence the pressure exerted on the wall is less. Thus the
pressure of one atmosphere actually exerted by oxygen, at 0℃, would be about (1+0.0025)
atmospheres had it behaved as an ideal one.
It is only at very low pressures when the gas-volume is quite large the space occupied by the
molecules themselves becomes negligible comparatively; and because the molecules are then far
apart, the force of mutual attraction becomes too feeble. So, at very low pressure, the real gases would
satisfy the postulates of the kinetic theory. That is why real gases are observed to obey PV = RT
relation at very low pressures. The expression PV = RT is therefore a limiting law only.
Before proceeding to obtain a P-V relation which would present the behaviour of real gases in
all conditions, we may examine some of the experimental facts to find out the nature of the failure of
the ideal gas equation.

I.18.Deviation of the Real Gases from the Ideal Gas-laws. Experiments from different directions
have shown that the ideal gas-laws are inadequate for representing the behaviour of the real gases.
Some of the results are mentioned here.
(a) In accordance with the Boyle’s Law, PV = constant, at a given temperature, the pressure
of a gas plotted against its volume would give a rectangular hyperbola. At fairly high temperatures,
the P-V isothermals are found to be hyperbolic, though not exactly coinciding with the rectangular
ones theoretically predicted. But at temperatures below the critical ones, the P-V curves are far from
hyperbolic and really exhibit two discontinuities. . The historically famous experiments of Andrews
on the study of relations for carbon dioxide are represented in Fig. I,8, which indicates the wide
deviations from the Boyle’s Law. Similar deviations are observed with other gases too. The failure of
the relation, PV = RT
Where c is the root-mean-square velocity. Now the root-mean-square velocity c is proportional Ca, the
average velocity of the molecules (Sec.1.7)

3𝑝
Hence, Ca = k`√ 𝑝

When there is a fine orifice on the wall of the vessel containing the gas, the number of
molecules which will effuse out is proportional to the average speed of the molecules Ca at any given
temperature. That is, the rate of effusion re is proportional to Ca.

3𝑝
Hence, re = k`.k`` √ 𝑝

So, at a given pressure and temperature, the rate of effusion of a gas is inversely proportional to the
square-root of its density. This is Graham’s Law.

I.11 The Boltzmann constant. The universally accepted value of the Avogadro number N0 is 6.03×
1023 . We shall take up the method of its determination in a subsequent chapter. The value of the gas
constant R is 8.32× 107 ergs per degree per mole.

Hence, the magnitude of the Boltzmann constant,

𝑅 8.32×107
k = 𝑁 = 6.03×1023 = 1.38× 10−16 ergs per degree.
0

I,12 Calculation of kinetic energy and velocity of a molecule. A few examples are worked out
below to illustrate the calculation of kinetic energy and velocity of molecules.

Example. The density of air at N.T.P. is 0, 00129 gms/c.c. Calculate the root-mean-square velocity of
oxygen at N.T.P.?

1 3𝑝 3×76×981×13.6
P = 3 𝑝𝑐 2 , hence, c = √ 𝑝 = √ 0.00129
= 4.86× 104 cms/sec.

Example : The normal density of hydrogen is 0.000089 gms/c.c., What is the root-mean-square
velocity of oxygen at N.T.P.?

Now, density of oxygen = 16× 0.000089

3×76×981×13.6
∴𝑐= √ 16×0.000089
= 4.6 × 104 cms/sec.

Example : Calculate the kinetic energy of a molecule of hydrogen at 0℃

𝐸 8.32×107×273
€ = 𝑁 = 32 𝑅𝑇
𝑁
3
= ∙
2 6.03×1023
0 0

=5.678× 10−14 ergs.

Example : Calculate the kinetic energy of one gm of oxygen at 47℃

1
One gm oxygen = 82 gm-mole.
 3𝑅𝑇
K.E. of a gm-mole, E = 2

𝐸 3𝑅𝑇 3
K.E. of 1gm = = = × 8.32 × 107 × 320 = 1,24 × 109 ergs.
32 64 64

Example : At what temperature will the r.m.s. velocity of oxygen be one and half times of its value at
N.T.P.?
1 3
We know 2
𝑚𝑐 2 = 2
kT or c ∞ √𝑇

3
Suppose the temperatures required is T` when the velocity will be 𝑐.
2

3
𝑐 𝑇 𝑇 9
Or 2 = √ = √ , 𝑤ℎ𝑒𝑛𝑐𝑒 T`= × 273 = 614.25° 𝐴𝑏𝑠
𝑐 𝑇 273 4