UNIT

1
GASEOUS
STATE
KINETIC MOLECULAR THEORY OF GASES
The various gas laws describe the general behaviour of gases. These laws
hold for all
gases irrespective of the nature of the gas and are based on experimental
theory takes into account the molecular concept of matter as well as the observations. This
motion (kinetic
concept)of the particles.
The various postulates of the kinetic theory of gases are :
1. All gases consist of a very large number of minute particles, called
molecules.
2. The gas molecules are extremely small in size and are
separated by large distances.
The actual volume of the gas molecules is thus negligible as
compared to the total
volume occupied by the gas.
3. The pressure exerted by the gas is due to the bombardment of themolecules on the walls
of the vessel.
4. The gas molecules collide with one another and also with the walls of the
vessel.
These collisions are perfectly elastic and there is no loss of energy during these
collisions.
5. The distance between the gas molecules is very large. Thus, there is no
effective
force of attraction or repulsion between them.
6. The gas molecules move freely in all directions in straight lines. Their speed and
direction change when these collide with one another or with the walls of the vessel.
1. The average kineticenergy of the gas molecules is directly proportional to the absolute
temperature of the gas.
8. There is no effect of gravity on gas molecules.
 NEWCOLLEGE CHEMISTRY
Justification for the postulates. The justification for the above postulates is
given below :
1. Postulates 1and 2. When high pressure is applied on gases,
they get
The reason is that the empty space between the molecules decreases. compressed.
The volume
Occupied by molecules is about 0.014% of the total volume of the gas.
2. Postulate 3. When a molecule strikes the wall of the vessel, it exerts a
little force per
unit area, (i.e. pressure)on it. The total pressure which is the result of the hits due to
all the molecules per unit area gives the pressure of the
gas.
3. Postulate 4. Suppose the molecular collisions are not perfectly elastic.
Asaresult, the
molecules will lose energy at each collision. Their kinetic energy willgo on
and ultimately becomes zero. The molecules will come to rest and should decreasing
bottom of the vessel. Since molecules come to rest, they will not collide with settle at the
of the vessel. Thus, the gas should show no pressure. But this the walls
we say that molecular collisions are perfectly elastic. never happens. Hence,
4. Postulate 5. Gases can be compressed on the
be due to the force of attraction between the gasapplication of high pressure. It might
then gases fill the whole space available to them.molecules. When pressure is released,
Hence, there is no effective force of
attraction or repulsion between molecules.
5. Postulate 6. The haphazard motion of gas
molecules can be
light falling on the cinema screen. The solid dust particles areobserved in a beam of
hit by gas molecules
present in air. The dust particles come in haphazard motion, called
motion. Brownian
6. Postulate 7. When a gas is heated, following
(i)The temperature of the gas increases.
observations are noted :
(ü) The speed and hence the average K.E of the
molecules increases. Thus, the
average kinetic energy is directly proportional to absolute temperature.
7. Postulate 8. Heavier gases do not form the
lower layer in a mixture of gases: They
form a homogeneous mixture due to diffusion. Thus, there is no
gas molecules. effect of gravity on

DERIVATIONOF KINETIC GAS EQUATION PV = 1/3 mNc2

The kinetic gas equation can be derived
from the postulates of kinetic molecular
theory. The equation is valid for ideal gas only.
Consider a cube having each side equal to C
lcm. Let one mole of the gas consisting of B mC,
N -molecules* be present in it and m be the A
mass of each molecule. According to Cy -MC,
Maxwell's distribution of velocities, we know
that the molecules are moving with different
velocities in all the directions.
Consider a single molecule hraving
velocity equal to c cm/sec at a particular
instant. This velocity can be resolved into Fig. 1.1 Resolution of molecular velocity.
*Avogadro number of molecules.
 GASEOUS STATE

three co-ordinate axes, x, y, z parallel to the three sides of the cube.

three components along velocity of the molecule as,
The components are related to the
c2 = c? + c + c
along the x-axis with velocity equal to c,.
Now consider the movement of the molecule
Momentum of the molecule before striking the face
A = m Cx
its path with the same velocity but in the
After striking the face A, the molecule retraces
opposite direction.
Momentum of the molecule after colliding the face
A =- mCx
mnolecule of face A =m C, -(- m c) F Zm C,
.". Change in momentum per collision per
has totravel a distance equal to2/
Now in order to strike the face A again, the molecule
that
cm. As C, is the velocity of the molecule along x-axis, we say
Distance travelled per sec
Number of collisions in one second on face A = Distance between two collisions 21
transferred to face A =2mn Cg
We know that during one collision, the momentum
.. Momentum transferred on face A.during Cz
21
collisions
Cx me
Momentum transferred on face A per second per molecule) = 2m c, X 21
B per second per molecule
In the same way, the momentum transferred to opposite face
me?
2me?
alongx-axis =
.. Total momentum transferred to the two opposite faces, A and B,
Similarly, the total momentum transferred per second to the opposite faces alongy-axis
and along z-axis are respectively
2me; and
2mc?
the cube
.". The total momentumn per second per molecule to all the faces of
2mc2
2me 2me, 2me
2m
(c+ Cy + c) =
But there are N molecules moving with different velocities c1, C2, C3 ...Each molecule
will contribute to the transfer of momentum to all the faces of the cube.
Total momentum transferred to all the six faces of the cube by N molecules in one
second
2m 2mN cd +c~ +c+. 2m Ne2
[c? + c + e t ..] = N
-

where C= Root mean square velocity of the gas by definition.

c=tý+;+
,2

N
 6 NEW COLLEGE CHEMISTRY

The total momentum transferred per second is the rate of change of momentum which is
equivalent to force.
2m Nc2
Force, F=

But pressure is force per unit area or P= or F = Pressure X Area,

A
Pressure x Area 2m Ne2
Since area of cube = 6]2

.:. Px 6/ = 2m Ne2 or P = 1mNe2 ;P= 1 mNc2

V
(3 = V, volume occupied by one mole of gas)
Or Py = Me2
...i)
This relation is known as kinetic gas equation. As mN (mass of one
number molecular mass = M molecule x Avogadro

Also, P= De2
3 ...(iü)
This is the second form of gas equation
1 1M
Since, PV = Me2 or P=
1
or P =De
where D =density of the gas
Thisis another form of the gas equation.
MAXWELL BOLTZMANN DISTRIBUTION LAW OF
Need for the law. One fact that follows from the MOLECULARVELOCITIES
in a particular system cannot kinetic theory is that all the molecules
have the same energy.
Molecules in a gas or a liquid are continuously
their random motion. In each colliding with one another due to
collision,
(Momentum Mass xVelocity) with the result there will be an interchange of
that the velocity of both moleculesmomentum
velocity means achange in energy (kinetic energy 1 involved in
the collision will alter.A change in
collisions cause an interchange of energy Gme?), so that
remains constant but the energy of an between molecules. The total energy of the system
individual
Maxwell and Boltzmann, utilizing probability molecule will be continnously
changing.
distribution
is given by
of molecular velocity considerations, have shown that
depends on temperature and molecular weight of the actual
a gas, and
dN M 3/2
=47 e-Me /2RT m
n
2rRT cde = 4n 2kT 2 de
where dN is the number of 2rkT ...(1)
of n molecules of the gas. M, moleculess having
m and T are the velocities betweenc and c + de, out of atotal
gas respectively. Obviously dN/N is
the molecular weight and temperature (in K) of the
fraction of total
betweenc andc + dc. The equation (1) is known as number of molecules having velocities
the Maxwell
Boltzmann distribution
 7
GASEOUS STATE

divided by dc,
law for molecular velocities. If equation (1) is MPV AVERAGE

p=dncdc VELOCITY
we get
3/2 AMS
1 dN = 47 M p-Mc-12RT,2 ...(2) VELOCITY
N dc 277RT

= 47
2kT a'!!
1 dN
where the quantity N dc is called the probability (p) offinding Fig. 1.2 Maxwell distribution
of velocities.
molecules with the velocity c.
at a particular temperature,
On plotting the probability|p N dc versus the velocityc
curve, it is clear that :
we get the curve shown in fig. 1.2.From the
(i) Probability of a molecule being motionless is almost zero.
increases with c, passes through a
(ü) For velocities greater than zero, probability
maximum and then falls away towards zero.
improbable ie., fraction of molecules
(üi) Both very low and very high velocities are highly
having very low and very high velocities is very small. f1 ,T1
(w) Probability of molecules having velocities T2
which are neither very low nor very high is very fo--
large i.e., fraction of molecules having velocities T3
which are neither very low nor very high is large.
The velocity (a) which is possessed by maximum
fraction of gas molecules is called most probable
velocity (MPV).It corresponds to the peak of curve.
It is important to note that molecular ’ VELOCITY OF MOLECULES
distribution of velocities at a given temperature does
Fig. 1.3 Distribution of velocities at
not change with time (under some defined three different temperatures.
conditions). This is because, during collisions, the
molecules having particular velocity get interchanged but their average number remains
same. This will become clear if we compare the number of molecules having a particular hall,
velocity to the number of persons (out of total population of a town) visiting a cinema (similar
then the number of persons visiting a cinema hall on a particular day of each week
conditions) is the same though the persons visiting the cinema hall may be diferent.
Temperature dependence or Effect of Temperature on Maxwell's Distribution
of Velocities. On plotting probability (p) versus velocity at different temperatures T,, T
that
and T, (Tg > T, > T), curves shown in Fig. 1.3 are obtained. It is clear from the curves
on increasing temperature.
() The peak of the curve shifts towards right.
() The peak of the curve shifts downwards and is flattened.
(üi) The most probable velocity increases (ag > ay > a).
(iu) The fraction of molecules possessing the most probable velocity decreases
6>fa> fs).
(0) Higher velocities become more probable.
 NEW COLLEGE CHEMISTRY
8

DIFFERENT TYPES OF VELOCITIES

colliding
The molecules in a gas due to their constant rapid motion are continuously
with one another. Their velocities are, therefore, constantly changing. For a quantitative
description of the behaviour of gases, we make use of three different types of molecular
Velocities, UIZ., average velocity c , most probable velocity aand the root mean square velocity c.
I. Average velocity . It is the arithmetic mean of the different velocities of all the
otecures present in a given mass of a gas. Ifc,, C9, C3 ..c, are individual velocities and N is the
total number of molecules, then
Cn
C= =
...(6)
N N
i =1
When N, N2, Ng ... molecules possess velocities C1, C2, C3 . respectively.

The average velocity. "1°1 t n°2 + ngC3 + . . n

N, + N + N3

C= EN;c; 1
EN,
=

N Ne; ...(7)
where N,= N is the fixed total number of molecules.
Average velocity is also given by the expression.
8kT |8kT
Or
V M TM
where k = Boltzman constant ; m = mass of single
molecule of the gas
R= gas constant and M =
molecular mass of the gas.
2. Most probable velocity (a). The velocity
of the gas is termed the most possessed by maximum number of molecules
probable velocity. The
maximum (peak) of the distribution curve (Fig. 5.2).most probable velocity corresponds to the
An expression for most
for distribution of velocities probable
with
velocity can be obtained by differentiating the equation
for amaximum. The expression for respect to c and setting the result
equal to zero as required
most probable velocity is :
1
a= 2RT2 2kT)2
M M ...(10)
3. Root mean
square velocity (Crmsp). It is the
of the different velocities of the gas molecules. If n1, n2, square root of the mean of the squares
C2, C3 ..., then ng ...
root mean square
velocity Crmsu iS given by molecules possess velocities C1,

Crmsv ncítngcó t ngc +

nË t n1 tng
GASEOUS STATE
9

When C1, C2, C3 ... are the individual velocities and n is the total number of
then molecules,

Crmsv n
..(11)
The mean square speed is given by
2 2
c2
cí tcý tc+ 1 1
n

Root mean square velocity can be calculated by using the

relation below:
Thus 3RT |3kT |3PV
Crmsu = = ve' = 3P
M m VM Vp
Relationship between Different Types of
considerations, the following relations are obtained : Velocities. From kinetic theory
(i) Most probable velocity = 2 X or a = 2
V3 Crmsu
V3
8
(ü) Average velocity =XX Root
=

37 Root mean square velocity

V or C= 0.9213 X Crmsu
The three types of velocities are related as :
2RT 8RT |3RT
a:c: C
rmsu ::1:1.128: 1.224
V M VM M
Thus, average velocity of gas molecules at a given temperature is greater than that of its
most probable velocity but is smaller than its
corresponding root mean square velocity.
 NEW COLLEGE CHEMISTRy
28

BEHAVIOUR OF REAL GASES

gas which obeys tha
Deviations of Gas laws from Ideal Behaviour. Ideal gas. A
general gas equation and other gas laws under all conditions of temperature and pressure ie
gas :
known as ideal gas or perfect gas. The molecules of an ideal
()Occupy negligible or no volume.
(ü) Have no inter-molecular attractive forces.
However, none of the known gases obeys the gas laws or the gas equation (PV = nRT)
under all conditions of temperature and pressure. Hence, the concept of ideal gas is only
theoretical or hypothetical. At best, the gases behave in nearly ideal manner at low pressures
and high temperatures.
Real gas. Agas which does not obey general gas equation and all other gas laws strictly
but tends towards ideality at low pressure and high temperature is known as a real gas.
Difference Between ldeal and Real Gas
Ideal gas Real gas
1. It obeys gas laws (PV = RT) under all 1. It obeys gas laws only at high
conditions of temperature and pressure. temperature and low pressure.
|2. It does not exist in actual practice. Gases 2. All gases are real gases.
like N2, Hz, etc., which can't be liquefied
easily are nearly ideal. 3. Volume occupied by molecules is not
|3. Volume occupied by gas molecules is negligible
negligible as compared to the total
volume of gas. 4. Attractive forces between gas molecules
4. Attractive forces between gasmolecules are appreciable due to which pressure
exerted is less than that calculated from
are negligible. gas laws.
Compressibilty Factor Showing Deviations from Ideal Behaviour. All known
gases are real gases. Amagat, Andrew and other scientists studied the behaviour of various
gases under different conditions of temperature and pressure. They found that all gases
show deviations from ideal behaviour and
deviations are considerable at high N2
2.0 H2
pressures and low temperatures.
Further, it has been found that the Z=pV/nRT He
1.5 Z>1 CO2
most easily liquefiable and highly soluble
gases show larger deviations. Thus gases 1.0
IDEAL
like carbon dioxide, sulphur dioxide, and GAS
ammonia show much larger deviations 0.5
(Z=1)
than hydrogen, nitrogen, oxygen etc.
A convenient way of showing the Z<1
deviation of gas from ideal behaviour is 0
to plot compressibility factor 200 400 600 800 1000
Z(Z=PV/nRT)against the pressure. For AT 273 K(0°C) PRESSURE (atm)
an ideal gas, PV=nRT and so Z= PV/nRT Fig. 1.10 Plot of Z against P for some gases at
is equal to one at any pressure (Fig. 1.10). 273 K (0°C).
 29
GASEOUS STATE
we find that the curves
However, this is not the case for actual gases, From the Fig. 5.10,
the following characteristics:
obtained on plotting Zagainst pressure for different gases have
approaches zero. "Thus, at low
(i) All the curves approach the ideal value as the pressure
pressures, all gases behave as ideal gases.
underperfect deviation.
(iü) At moderate pressures, Z <lie., there is negative or behaviour.
It means that the gas is more compressible than expected from ideal
deviation. It
(ii)At high pressure, Z >l ie. there is positive or overperfect
means that the gas is less compressible than expected from ideal behaviour.
are less
(iw) For H, and He, Z is always greater thanone. This means that these gases
compressible than expected from ideal behaviour at all pressures.
(u) Extent of deviation at any temperature or pressure depends upon the nature of gas.
Gases like CO, which can be liquefied easily, show larger deviations.
It may be noted that deviations decrease with increase in temperature. At best, the realL
gases show ideal behaviour only at low pressure and high temperature. The temperature
Boyle's
above which a gas behaves like an ideal gas and obeys the gas law is called
temperature.
Behaviour of Real Gases. A real gas is that which actually exists whether it obeys gas
of real
laws strictly or not. Rayleigh, Andrew, van der Waal and others studied the behaviour
gases like H2, Ng, O2, SO2, COz, etc. under varying conditions of temperature and pressure.
They found that these gases do not obey the gas laws or the gas equation strictly.
Under ordinary conditions of temperature
and pressure, the real gases show much more H2(100°c)
He(100°C)
deviations from the ideal gas behaviour. Ifa plot
N2(100°c)
is drawn for P x Vvalues against corresponding
pressure,a straight line should result. But in the
Fig. 1.11, we see that for H, and He, the value of H2(17c)
Px Vincreases with the increase in pressure. He(17°c)
In case of CO, and N, we see that with the -N2(17t)
increase in pressure, the value of P x V first
decreases, reaches minimum and then starts co2(100°C)
increasing. It has been found that at low
temperatures and very high pressures, the
behaviour of the real gases deviates more from
PRESSURE (atm)
ideality
Causes of Deviation. The deviation from Fig. 1.11 Deviationfromideal gas behaviour.
ideal gas behaviour gives us an idea to scrutinize
the kinetic theory which forms the basis of the gas laws. The following assumptions of the
kinetic theory seem to be faulty and they are probably the causes of deviation.
1. According to the kinetic theory, the molecules of the gas are supposed to be point
masses having negligible volumes as compared to the volume of the gas. If this be so, the gas
must haveazero volume at absolute zero. But this is wrong, the gas has some volume at that
temperature, however,smallit may be. This shows that when the distance between one molecule
and another practically vanishes, the volume stillleft will be mainly due to the volume of the
molecules themselves. The volume of an individual molecule is termed molecular volume.
 NEW COLLEGE CHEMISTRY
30
assumption is wrong, and the molecules of gases possess their own volume
However,
Henceatthe
high temperatures and low pressures, the distance between moleculeesincreases
gas increase. In comparison to a large volume of the gas th
So does the volume of the
molecular volume may be neglected.
The kinetic theory also assumes that the molecules of a gas have no mutual attraction
2. temperatures and high pressures
But this is not correct because gases liquify at very low one another. They can
Under these conditions, the molecules of a gas come very close to another.
coalesce to form a liquid, only if they have mutual attraction for one they possess
Hence, it is wrong to assume that molecules have no mutual attraction rather
inter-molecular attractive forces which are commonly called van der Waal's forces.
DEVIATION OF REAL GASES FROM IDEAL GAS BEHAVIOUR
1. Deviation from Boyle's
law. The curve obtained between PV
and P for a gas at constant 40 CO
temperature is called Isotherm (see
Fig. 1.12). The isotherm for an ideal PV
(LITRE
ATM)35 cH4
gas should be a straight line. Amagat -H2
and Regnault gave Isotherms for H2, 30 -Ne
He, N, O and CO at 0°C
temperature which are not straight 25
lines parallel to the pressure axis.
())At low pressures. All Isotherms - IDEAL GAS - -
20 CO
meet the ideal gas isotherm at zero CH4
pressure. Thus, at low pressures, all
gases behave like ideal gases. 15
200 400 600 800
(ii) At moderate pressure. An P (ATMOSPHERES)
under perfect or negative deviation is
observed at moderate pressure. Fig. 1.12 Plot of PV against P for different gases at 0C.
Negative deviation is not shown by hydrogen 2.6
and helium gases. These, however, show
negative deviations at very low temperatures. L100
The deviation is maximum for gases which are PRESSURE
xVOLUME
2.2
easily liquefied (e.g., CO,). -25°
(iüi) Atvery high pressure. An overperfect 20
or positive deviation is observed at very high 1.8
pressure. Gases donot obey the gas laws at all. 50
(iv) At different temperatures. If the
temperature of a gas is changed, the shape of 1.4
the isotherm does not change (Fig. 1.13). As
temperature falls, the deviations become more ,5
20
pronounced. The extent of negative deviation 1.0
depends on how near the gas is to the -250
temperature at which it liquefies. This is the -70°
reason why: (i) CO2 shows greater negative 200 400 600 800 1000
deviation than N2, and (ii) H2 which liquefies PRESSURE IN ATMOSPHERES
at very low temperature shows positive
deviation. Fig. 1.13 Effect of temperature deviations on
Nitrogen from ideal behaviour.
 31
GASEOUS STATE

Charle's law. According to Charle's law, "At a constant pressure,

Deviation from increase or decrease by 1/273 of its
mass of a gas at 0°C should
the volume of the given temperature." Amagat, Andrew and others found
original volume for every 1°Crise or fall in
at low pressure and maximum deviation at high
that the gases show minimum deviation
pressure from ideal gas behaviour.
mole of all gases occupy
Deviation fromn Avogadro's law. According to this law one
22.4 litre volume at NTP".
volume occupied is not 22.4 litre. For
Experiments in different gases reveal that this respectively.
litres at NTP
example, O, and cO, 0ccupy 22.393 litres and 22.262 limitations of gas equation,
The above deviations from different laws are called
PV = nRT.

Note. 1. At low pressure and high temperature, a gas occupies large volume. The volume
enclosing the gas.
occupied by the gas molecules is about 0.014% of total volume
cause under perfect
The inter-molecular attractive forces become very small and
(or negative deviation) behaviour.
molecules come closer. The empty
2. At high pressure and low temperature, the gas Thus, volume decreases and the
space between gas molecules becomes lesser. attractive forces
size of the molecules becomes important. The inter-molecular
become very high due to size of molecules and cause over perfect (or positive
deviation) behaviour.

CORRECTION FOR DEVIATIONS-VAN DERWAAL'S EQUATION FOR REAL GASES

To account for the behaviour of real gases, the equation of state for ideal gases was
modified to make allowance for:
(i) Volume of the gas molecules themselves.
(iü)The intermolecular attractive forces.
The modified equation of state which explainsthe deviations of real gases from ideality is
known as van der Waal's equation of state and was given by J.D. van der Waal's in 1873.
He applied the corrections as follows :
(i) Volume Correction. According to van der Waal, the actual compressible volume of
gas is always less than the volume of the container because of the space occupied by the gas
molecules themselves. The difference between the measured volume and the compressible
volume is related to the size of the molecules. van der Waal simply replaced the volume term
Vin the gas equation by the expression (V b)where bis aconstant depending upon the
nature of the gas and is known as co-volume or excluded volume. The excluded volume is
the volumne within which the molecules can't move. It might be thought that the co-volume of
the gas would be the actual volume of the gas molecules themselves. However, this is not true
and the co-volume has been foundto be four times the actual volume of gas molecules. Corrected
volume for nmoles of the gas is (V - nb). After taking into consideration the co-volume of the
molecules of a gas, the ideal gas equation is modified to P (V - nb) = nRT
i) Correction for the attractive forces i.e., pressure correction. Consider a
gas molecule A lying in the interior of the container. It experiences no net attractive torce
 NEWCOLLEGE CHEMISTRY
32
molecules.
since it is uniformly surrounded by similar of the
On the other hand, a molecule B near the wall and will,
container is not uniformly surrounded
therefore, experience an attractive force towards the
centre of the container (Fig. 1.14).
Thus at the instant, the molecule is about to strike
with the wall, its velocity will be decreased and the
consequent change of momentum will be less than that NO NET
derived by the simple kinetic theory treatment. The NET INWARD FORCE
FORCE
measured pressure will be less than expected for an Fig. 1.14 Correction due to molecular
ideal gas under the same conditions. attraction.
The inward attractive force on the molecule about
to strike the wall of the container will be proportional to the number of molecules, in the buk
of the gas and, therefore, to the density of the gas (n/).Also the number of molecules striking
the container wall at any given instant will also be proportional to the density of the gas. Thus:
n
Force on the gas molecules near the wall « X
n? an?
or pressure defect, po where a is a constant.
y?
After taking into consideration the co-volume and pressure defect, the ideal gas equation
is medified to
an2
P+ (V - nb)= nRT ...)

and this is known as the van der Waal's equation of state for real gases. For one mole of a
gas, it becomes:
P+ (V b) = RT ...ü)
y2
This equation is obeyed, with reasonable accuracy, upto quite high pressures.
Units for van der Waal's Constants
(i) Units of 'a'. According to van der Waal's equation for n moles of a gas,
pressure defect,
'a
n Pressure x (volume)
p=
n? (mole)2
Thus, units of 'a' are related to the dimensions of pressure and volume, e.g., if pressure
is expressed in pascals and volume in m³, then the unit of 'a' should be Pa m$ mol-4,
However, the more covenient units are atm dm mol-, when the pressure is expressed in
atmospheres and volume in dm³ (litres).
Significance of 'a'. The constant 'a' is related to the intermolecuiar attractive forces.
Greater the value of 'a', stronger are the intermolecular attractive forces. Gases having greater
value of a' can be liquefied more easily and vice-versa.
(ü) Units of "b'. b' is the incompressible volume per mole of gas. Hence, units of 'b
must be the units of volume i.e., m' molr! or dm3 mol-!
The constant 'b' is related to the size of the molecule. Larger the size of the molecule,
larger is the value of 'b'.
 33
GASEOUS STATE
due to their small
and helium. These gases high
Exceptional behaviour of hydrogen forces of attraction even at pressures. In
masses, have extremely small intermolecular
words, the factor 1S negligible at high pressures. Hence, the van der Waal's equation
other v2
reduces to
P (V- b) = RT Or PV = RT + Pb
PV =1+ Pb Pb
or Z=1+
Or RT RT RT
ofP.
Hence, Z is always greater than one and increases with increase
the table 1.4.
The values of van der Waal's constantsfor some gases are given in
Table 1.4 van der Waal's constants for some gases
a (atm. litre mole-2) b (litre mor)
Gas or (dm mo)
or (dm atm mo)
0.024 0.0266
Hydrogern 0.0237
Helium 0.034
0.21 0.0171
Neon 0.0248
2.25
Methane 0.0318
1.36
Oxygen 0.0427
Carbon dioxide 3.59
6.71 0.0564
Sulphur dioxide 0.0562
6.49
Chlorine

DISCUSSION OF VAN DER WAA'S EQUATION

departure of real gases from
After deriving van der Waal's equation, let us discuss the
ideal behaviour at different temperatures and pressures.
pressure is not very high, then
Case I. When pressure is not too high. When the
volume, V, will be sufficiently large and b can be ignored in comparison.
(V- b) = RT
Thus, the van der Waal's equation for one mole of gas
P+

= RT or PV = RT
can be written as P+ 2V= RT. Or PV+
V V

pressure increases, V decreases.

Thus, the product, PV, is less than RT bya factor V As
goes on decreasing. This
Therefore, we say that with increase in pressure, the value of PV
explains the dip in the isotherms of most of the gases.
high, the volume,
Case II. When the pressure istoo high. When the pressure is very
P is very high, the
V, will be very small. Now, b cannot be ignored in comparison to V. Since
quantity T.9 may become negligible in comparison to P.
= RT + Pb.
"Thus, van der Waal's equation becomes P (V- b) = RT or PV
 NEW COLLEGE CHEMISTR
34

than
pressure increases,
RT by a factor Pb. As the reaching a
the
value of
Thus, PV is now greater
shows why the value of PV,
after minimum, increases
Pb and hence PVincreases. This
with further increase of pressure.
temperature, the value of predominates at low
In short, we say that at ordinary
Pb is predominant. At some 1ntermediate range of pressuro
pressures. But at high pressure,
effects balance each other. In this range, the gases are said to behave ideally, Thi
the two in the isotherms of gases like carbon
explains the existence of a small horizontal portion
monoxide and methane.
temperature is very high at a given
Case III. When temperature is high. If the
pressure, the volume becomes sufficiently large. Due to this, the
value of becomes negligibly
small. At this stage b can also be neglected in comparison toPV= V. Under these conditions the
van der Waal's equation approaches the ideal gas equation, RT
Thus, we say that at high temperatures, the deviations become less.
Exceptional behaviour of hydrogen and helium. We know that hydrogen and
helium have comparatively small masses. Thus, the attractive forces between their molecules
are too small. The attraction term, (attraction factor), is negligible at ordinary temperature.
y2
Therefore, PV = RT + Pb
This explains why there is a continuous increase in the value of PV with increase in
pressure in these two gases at ordinary temprature (Fig. 4.12).
From the above discussion, it is clear that van der Waal's equation explains fairly
satisfactorily the behaviour of real gases.
Limitations of van der Waal's equation. It has been found that van der Waal's
equation is much more accurate than the ideal gas equation. The appreciable deviations which
are observed in this equation are only at very high pressure and at low temperatures. The
reason for the deviations is that the values of the van der Waal's constants, a andb, do not
remain constant over the entire ranges of temperature and pressure. Thus, we say that van
der Waal's equation is valid over the specific ranges of
temperature and pressure.
Example 25. Calculate the of gas