38

CHAPTER 2
THE PROPERTIES OF GASES AND SOLUTIONS

Aim & Goal: Gases, liquids, and especially solids surround us and give form
to our world. Chemistry at its most fundamental level is about atoms and the
forces that act between them to form larger structural units. This chapter
discusses approximation techniques for interacting classical particle systems
such as dense gases, liquids. In our study of gases, we showed that the
macroscopic properties of a gas (the pressure, volume, and temperature) are
related through an equation of state, and that for the limiting case of an ideal
gas, this equation of state can be derived from the relatively small set of
assumptions of the kinetic molecular theory. Solutions are homogeneous
mixtures typically composed of a major component that is a liquid and a minor
component that is dissolved in the liquid. But whereas the volume of a gas
depends entirely on the pressure, the volume of a liquid is largely independent
of the pressure. A key idea in thinking molecularly about a solution is to
imagine the intermolecular forces between the components. This unit will help
you see how these macroscopic properties of matter depend on the microscopic
particles of which it is composed. We have taken the opportunity to refresh
both the content of this chapter, keeping it flexible to use, accessible to
students.

2. 1 The Properties of Gases

All matter exists in three states: gas, liquid and solid. A molecular level
representation of gaseous, liquid and solid states is shown in Figure 2.1. A gas
consists of molecules separated wide apart in empty space. The molecules are
free to move about throughout the container. A liquid has molecules touching
each other. However, the intermolecular space, permit the movement of
molecules throughout the liquid. A solid has molecules, atoms or ions arranged
in a certain order in fixed positions in the crystal lattice. The particles in a solid
are not free to move about but vibrate in their fixed positions. Of the three
states of matter, the gaseous state is the one most studied and best understood.
We shall consider it first.
 39

Gas--The Liquid--The Solid--The

individual individual individual
molecules have molecules are molecules are
little attraction attracted to one strongly attracted
for one another another but can to one another and
and are free to slide over each cannot move
move about. other. around.

Figure2.1Molecular representation of the gaseous, liquid and solid states

2.1.1 General Characteristics of Gases
1. Expansibility
Gases have limitless expansibility. They expand to fill the entire vessel
they are placed in.
2. Compressibility
Gases are easily compressed by application of pressure to a movable
piston fitted in the container.
3. Diffusibility
Gases can diffuse rapidly through each other to form a homogeneous
mixture.
4. Pressure
Gases exert pressure on the walls of the container in all directions.
5. Effect of Heat
When a gas, confined in a vessel is heated, its pressure increases. Upon
heating in a vessel fitted with a piston, volume of the gas increases. The above
properties of gases can be easily explained by the Kinetic Molecular Theory
which will be considered later in this chapter.

2.1.2 Parameters of a Gas

A gas sample can be described in terms of four parameters (measurable
properties): the volume, V of the gas, its pressure, P, its temperature, T,
the number of moles, n, of gas in the container.
2.1.3 The Gas Laws
 40

The Ideal Gas Equation

We have studied three simple gas laws :

Boyle's Law V (T, n constant)

Charles' Law V T (n, P constant)

Avogadro's Law V n (P, T constant)
These three laws can be combined into a single more general gas law :

…. (2.1)

This is called the Universal Gas Law. It is also called Ideal Gas Law as
it applies to all gases which exhibit ideal behavior, i.e., obey the gas laws
perfectly. The ideal gas law may be stated as: the volume of a given amount of
gas is directly proportional to the number of moles of gas, directly proportional
to the temperature, and inversely proportional to the pressure. Introducing the
proportionality constant, R, in the expression (2.1) we can write

V=R (or) P V = nRT …. (2.2)

The equation (2.2) is called the Ideal-gas equation or simply the

general Gas Equation. The constant, R, is called the Gas constant. The ideal
gas equation holds fairly accurately for all gases at low pressures. The ideal-gas
equation is called an Equation of State for a gas because it contains all the
variables (T, P, V and n) which describe completely the condition or state of
any gas sample. The Numerical Value of R, from the ideal-gas equation, we
can write;

R=

We know that one mole of any gas at STP occupies a volume of

22.4 dm3. Substituting the values in the expression (2.1), we have

R= = 0.0821 atm dm3 mol-1 K-1

It may be noted that the unit for R is complex; it is a composite of all the units
used in calculating the constant. If the pressure is written as force per unit area
and volume as area times length, from (2.2)
(force/area) x area x length
R= nx T

R= , R = nx
 41

Hence R can be expressed in units of work or energy per degree per

mole. The actual value of R depends on the units of P and V used in calculating
it. The more important values of R are listed in Table 2.1.

Table 2.1. Value of ‘R’ in Different Units

0.0821 dm3 atm K-1 mol-1 8.314 x 107 erg K-1 mo1-1
82.1 cm3 atm K-1 mol-1 8.314 Joule K-1 mo1-
62.3 dm3mm Hg K-1 mol-1 1.987 cal K-1 mol-1

(a) Dalton’s Law of Partial Pressures

John Dalton visualized that in a mixture of gases, each component gas
exerted a pressure as if it were alone in the container. The individual pressure
of each gas in the mixture is defined as its Partial Pressure. Based on
experimental evidence, in 1807, Dalton enunciated what is commonly known
as the Dalton's Law of Partial Pressures. It states that: the total pressure of a
mixture of gases is equal to the sum of the partial pressures of all the gases
present. Mathematically the law can be expressed as
Ptotal = P1 + P2 + P3+---- ( V and T are constant)
where P1 , P2 , P3 are partial pressures of the three gases 1,2,3; and so on.
Dalton’s law of partial pressures follows by application of the ideal-gas
equation
PV = nRT
separately to each gas of the mixture. Thus we can write the partial pressures
P1 , P2 and P3 of the three gases

P1 = n1 , P2 = n2 , P3 = n3

where the n1, n2 andn3, are moles of gases 1, 2 and 3.The total pressure, Pt of the
mixture is

Pt = ( n1+ n2 + n3) (or)

Pt = ( ntoal)

In other words the total pressure of the gas mixture is determined by the total
number of moles present whether of just one gas or a mixture of gases.

Example 1. What pressure is exerted by a mixture of 2.00g of H2 and 8.00g of

N2 at 273 K in a 10 dm3 vessel? (H =1.008, N=14)
 42

Applying the ideal –gas equation Pt = ( ntoal)

we find the moles of each gas

moles of H2 = = 0.992 mol , moles of N2 = = 0.286 mol

nt = nH2 + nN2
= (0.992 + 0.286 ) mol = 1.278 mol

Pt = ( ntoal)

= 1.278 mol

= 2.864 atm

Alternative method:
we find the partial pressure of H2 and N2

PH2 = 0.992 mol = 2.223 atm

PN2 = 0.286 mol = 0.641 atm

Ptotal = PH2 + PN2 = ( 2.223 + 0.641) atm = 2.864 atm

(b) Graham’s Law of Diffusion

When two gases are placed in contact, they mix spontaneously. This is
due to the movement of molecules of one gas into the other gas (Figure 2.2).
This process of mixing of gases by random motion of the molecules is called
Diffusion. Thomas Graham observed that molecules with smaller masses
diffused faster than heavy molecules.

Figure 2.2 A light molecule diffuses quicker than a heavy molecule

In 1829 Graham formulated what is now known as Graham's Law of

Diffusion. It states that: under the same conditions of temperature and pressure,
 43

the rates of diffusion of different gases are inversely proportional to the square
roots of their molecular masses. Mathematically the law can be expressed as

where r1 and r2 are the rates of diffusion of gases 1 and 2, while M1 and M2 are
their molecular masses. When a gas escapes through a pin-hole into a region of
low pressure of vacuum, the process is called Effusion. The rate of effusion of
a gas also depends, on the molecular mass of the gas.
(i) Diffusion is mixing of gas molecules by random motion under conditions
where molecular collisions occur.
(ii) Effusion is escape of a gas through a pinhole without molecular collisions.
Dalton’s law when applied to effusion of a gas is called the Dalton’s Law
of Effusion. It may be expressed mathematically as

= ( P,T constant)

The determination of rate of effusion is much easier compared to the rate of

diffusion.
Example 2. 50 cm3 of gas A effuse through a pin-hole in 146 s. The same
volume of CO2 under identical conditions was effused in 115 s.
Calculate the molecular mass of A.

= , MA = 71 amu

2.1.4 Kinetic Molecular Theory of Gases

Maxwell and Boltzmann (1859) developed a mathematical theory to
explain the behavior of gases and the gas laws. It is based on the fundamental
concept that a gas is made of a large number of molecules in perpetual motion.
Hence the theory is called the kinetic molecular theory or simply the kinetic
theory of gases (The word kinetic implies motion). The kinetic theory makes
the following assumptions.
(a) Assumptions of the Kinetic Molecular Theory
 44

(i) A gas consists of extremely small discrete particles called molecules

dispersed throughout the container (Figures 2.3 to 2.6). The actual
volume of the molecules is negligible compared to the total volume of
the gas. The molecules of a given gas are identical and have the same
mass (m).

Figure 2.3 A gas is made of Figure 2.4 Actual volume

molecules dispersed of the gas
in space in the
container

Figure 2.5 Gas molecules are Figure 2.6 Molecules move in

in constant motion straight line and change
in all possible direction on collision
directions with another molecule
or wall of container
(ii) Gas molecules are in constant random motion with high velocities:
they move in straight lines with uniform velocity and change direction
on collision with other molecules or the walls of the container. Pool
table analogy is shown in Figure 2.7.

Figure 2.7 Gas molecules can be compared to billiard balls in random

motion, bouncing off each other and off the sides of the
pool table
(iii) The distance between the molecules is very large and it is assumed that
van der Waals attractive forces between them do not exist. Thus the gas
molecules can move freely, independent of each other.
(iv) All collisions are perfectly elastic. Hence, there is no loss of the kinetic
energy of a molecule during a collision.
 45

(v) The pressure of a gas is caused by the hits recorded by molecules on the
walls of the container.

(vi) The average kinetic energy of the gas molecules is directly

proportional to absolute temperature (Kelvin temperature). This implies
that the average kinetic energy of molecules is the same at a given
temperature.
(b) How does an ideal gas differ from real gases?
A gas that confirms to the assumptions of the kinetic theory of
gases is called an ideal gas. It obeys the basic laws strictly under all conditions
of temperature and pressure. The real gases as hydrogen, oxygen, nitrogen etc.,
are opposed to the assumptions (i), (ii) and (iii) stated above. Thus: The actual
volume of molecules in an ideal gas is negligible, while in a real gas it is
appreciable. There are no attractive forces between molecules in an ideal gas
while these exist in a real gas. Molecular collisions in an ideal gas are perfectly
elastic while it is not so in a real gas. For the reasons listed above, real gases
obey the gas laws under moderate conditions of temperature and pressure. At
very low temperature and very high pressure, the clauses (i), (ii) and (iii) of
kinetic theory is not hold. Therefore, under these conditions the real gases show
considerable deviations from the ideal gas behavior.
(c) Derivation of Kinetic Gas Equation
Starting from the postulates of the kinetic molecular theory of gases we
can develop an important equation. This equation expresses PV of a gas in
terms of the number of molecules, molecular mass and molecular velocity. This
equation which we shall name as the Kinetic Gas Equation may be derived by
the following clauses. Let us consider a certain mass of gas enclosed in a cubic
box (Figures 2. 8 and 2.9) at a fixed temperature.

Figure 2.8 Resolution of velocity 'v' Figure2.9 Cubic box showing

into Components vx, vy molecular collisions
and vz along X axis.
Suppose that :
the length of each side of the box = l cm
the total number of gas molecules = n
the mass of one molecule =m
the velocity of a molecule =v
The kinetic gas equation may be derived by the following steps:
(i) Resolution of Velocity 'v' of a single molecule along X, Y and Z axes.
 46

According to the kinetic theory, a molecule of a gas can move with

velocity v in any direction. Velocity is a vector quantity and can be
resolved into the components vx, vy, vx along the X, Y and Z axes. These
components are related to the velocity v by the following expression.
= +
Now we can consider the motion of a single molecule moving with the
component velocities independently in each direction.
(ii) The number of collisions per second on face A due to one molecule
Consider a molecule moving on OX direction between opposite faces A and
B. It will strike the face A with velocity 'vx' and rebound with velocity '-vx'.
To hit the same face again, the molecule must travel ‘l’ cm to return to face
A. Therefore,

the time between two collisions of face A = s

the number of collisions per second on surface A =

(iii) The total change of momentum on all faces of the box due to one
molecule only each impact of the molecule on the surface A causes a
change of momentum (mass x velocity )
the momentum before the impact = mvx
the momentum after the impact = m (-vx)
the change of momentum = mvx - (- mvx) = 2 mvx
But the number of collisions per second on surface A due to one molecule
= vx/2l
Therefore, the total change of momentum per second on face A caused by
one molecule
= 2mvx x (vx/2l ) = mvx2 / l
The change of momentum on both the opposite faces A and B along X-axis
would be double i.e., 2mvx2 /l. Similarly, the change of momentum along Y-
axis and Z-axis will be 2mvy2 /l and 2mvz2/l, respectively. Hence, the overall
change of momentum per second on all faces of the box will be

= +

= ( v2 = + + )

(iv) Total change of momentum due to impacts of all the molecules on all faces
of the box. Suppose there are N molecules in the box each of which is
moving with a different velocity v1 , v2 ,v3 ,etc. The total change of
momentum due to impacts of all the molecules on all faces of the box
 47

Multiplying by 'N' and dividing by 'n' , we have

= =

where u2 is the mean square velocity.

(v) Calculation of pressure from change of momentum; Derivation of
kinetic gas equation,
Since force may be defined as the change in momentum per second,

Force =

But Pressure =

P =

Since l3 is the volume of the cube , V , we have

P = (or) PV = mNu2

This is the fundamental equation of the kinetic molecular theory of

gases. It is called the Kinetic Gas equation. This equation although derived for
a cubical vessel, is equally valid for a vessel of any shape. The available
volume in the vessel could well be considered as made up of a large number of
infinitesimally small cubes for each of which the equation holds.
Significance of the term u. As stated in clause (4) u2 is the mean of the square
of the individual velocities of all the ‘N’ molecules of the gas. But u = .
Therefore u is called the Root Mean Square (or RMS) Velocity.

2.1.5 Kinetic Gas Equation in Terms of Kinetic Energy

If ' N' be the number of molecules in a given mass of gas, where ‘e’ is
the average kinetic energy of a single molecule.(e = mu2)

PV = mNu2 = N x mu2 = N x e

where ‘e’ is the average kinetic energy of a single molecule.

PV = Ne = E (nc  E )
 48

PV= E …. (2.3)
where ‘E’ is the total kinetic energy of all the ‘N’ molecules. The expression
(2.3) may be called kinetic gas equation in term of kinetic energy.
We know that the General ideal gas equation is
PV = nRT (n = number of mole) …. (2.4)
From (2.3) and (2.4)

E = nRT ….(2.5)

For one mole of gas, E= ….(2.6)

Since the number of gas molecules in one mole of gas in N0 (Avogadro

number)

the average kinetic energy of a gas molecule, e= =

e =

Example 3. Calculate the average kinetic energy of a hydrogen molecule at 0C.

e=

Here R = 8.314 x 107 erg K-1 mol-1; T =273 K ; N0 = 6.02 x 1023

e= x = 5.66 x 10-14 erg

Thus the average kinetic energy of H2 at 0 C is 5.66 x 10-14 erg.

Example 4. Calculate the kinetic energy of two moles of N2 at 27 C.

(R= 8.314 J K-1 mol-1 )

We know E = nRT

Here, T = 27 + 273 = 300 K; n=2; R = 8.314 J K-1 mol-1

E = x 2 x 8.314 x 300 = 7482.6 J

Therefore the kinetic energy of two moles of N2 is 7482.6 J.

 49

2.1.6 Deduction of Gas Laws from the Kinetic Gas Equation

(a) Boyle’s Law
According to the kinetic theory, there is a direct proportionality between
absolute temperature and average kinetic energy of the molecules i.e.,

mNu2 T (or) mNu2 = kT (or)

x mNu2 = kT (or) mNu2 = kT

Substitution the above value in the kinetic gas equation PV = mNu2 ,

we have PV = kT

The product PV , therefore , will have a constant value at a constant

temperature.
(b) Charles’ Law

PV = kT (or) V= x T

At constant pressure,

V=kT where

(or) V T
That is, at constant pressure, volume of a gas is proportional to Kelvin
temperature.
(c) Avogadro’s Law
If equal volume of two gases be considered at the same pressure,

PV = m1 N 1 ….Kinetic equation as applied to one gas

PV = m2 N 2 ….Kinetic equation as applied to 2nd gas

m1 N 1 = m2 N 2 …. (2.7)

When the temperature (T) of both the gases is the same, their mean
kinetic energy per molecule will also be the same.

i.e., m1 = m2 …. (2.8)
 50

dividing (2.7) by (2.8) , we have N1 = N2 (or) under the same conditions of

temperature and pressure, equal volumes of the two gases contain the same
number of molecules.

(d) Graham’s Law of Diffusion

If m1 and m2 are the masses and u1 and u2 the velocities of the
molecules of gases 1 and 2, then at the same pressure and volume

m1u12 = m2 u22

By Avogadro’s Law N1=N2 m1 u12 = m2 u22 (or)

2

The rate of diffusion (r) is proportional to the velocity of molecules (u),

therefore,

= =

2.1.7 Distribution of Molecular Velocities

While deriving Kinetic Gas Equation, it was assumed that all molecules
in a gas have the same velocity. But it is not so. When any two molecules
collide, one molecule transfers kinetic energy (½ mv2) to the other molecule.
The velocity of the molecule which gains energy, that increases and that of the
other decreases. Millions of such molecular collisions are taking place per
second. Therefore, the velocities of molecules are changing constantly. Since
the number of molecules is very large, a fraction of molecules will have the
same particular velocity. In this way there is a broad distribution of velocities
over different of velocities from the laws of probability. The distribution of
molecular velocities equation was followed.

3/2
=4 e C2 dc

where dNc = number of molecules having velocities between C and (C + dc)

N =total number of molecules; M =molecular mass; T = temperature on
absolute scale (K).
The relation stated above is called Maxwell’s law of distribution of
velocities. The ratio dnc /n gives the fraction of the total number of molecules
having velocities between C and (C+ dc). Maxwell plotted such fractions
 51

against velocity possessed by the molecules. The curves so obtained illustrate

the salient features of Maxwell distribution of velocities, Figure 2.10.

Figure 2.10 Distribution of molecular velocities in nitrogen gas N2 at

300 K and 600K
This figure showed distribution of velocities in nitrogen gas, N 2, at 300
K and 600 K. It will be noticed that:
(i) A very small fraction of molecules has either very low (close to zero) or
very high velocities.
(ii) Most intermediate fractions of molecules have velocities close to an
average velocity represented by the peak of the curve. This velocity is
called the most probable velocity. It may be defined as the velocity
possessed by the largest fraction of molecules corresponding to the
highest point on the Maxvellian curve.
(iii) At higher temperature, the whole curve shifts to the right (dotted curve
at 600K). This shows that at higher temperature more molecules have
higher velocities and fewer molecules have lower velocities.

2.1.8 Different Kinds of Velocities

In our study of kinetic theory we come across three different kinds of
molecular velocities:
(a) the Average velocity ( )
(b) the Root Mean Square velocity (u)
(c) the Most Probable velocity (vmn)
(a) Average Velocity
Let there be ‘n’ molecules of a gas having individual velocities v1, v2, v3
….vn. The ordinary average velocity is the arithmetic mean of the various
velocities of the molecules.

From Maxwell equation it has been established that the average velocity
is given by the expression
 52

Substituting the values R,T,  and M in this expression, the average

value can be calculated.

(b) Root Mean Square Velocity

If v1+ v2 + v3 +…..+vn are the velocities of n molecules in a gas, u2, the
mean of the squares of all the velocities is

u2 =

Taking the root

= is thus the Root Mean Square Velocity or

RMS velocity. It is denoted by u. The value of the RMS of velocity u, at a

given temperature can be calculated from the kinetic gas equation.

PV = mNu2 ….. Kinetic Equation

u2 =

For one mole of gas

PV = RT

Therefore, u2 = …. M is molar mass

u= ….(2.9)

By substituting the values of R, T and M, the value of u (RMS velocity)

can be determined. RMS velocity is superior to the average velocity considered
earlier. With the help of u, the total kinetic energy of a gas sample can be
calculated.
(c) Most Probable Velocity
As already stated the most probable velocity is possessed by the largest
number of molecules in a gas. According to the calculations made by Maxwell,
the most probably velocity, vmp, is given by the expression.

vmp =
 53

Relation between Average Velocity, RMS Velocity and Most Probable

Velocity

= x = = 0.9213

= x 0.9213

That is, Average velocity = 0.9213 x RMS velocity

= x = = 0.8165 (or)

vmp= u x 0.8165 …. (2.10)

That is, Most Probable Velocity = 0.8165 x RMS velocity
RMS can be easily calculated by the application of Kinetic Gas
equation. Knowing the value of RMS, the average velocity and the most
probable velocity can be found from expression (2.9) and (2.10).
Calculation of Molecular Velocities
Case 1. Calculation of molecular velocity when temperature alone is given

PV = mNu2 (Kinetic gas equation)

where N = N0 (Avogadro’s number)

Thus we have,
M = m x N0 = molecular mass of the gas

 u= = (PV = RT for 1 mole)

But R = 8.314 x 107 ergs K-1 mol-1

= 0.8314 x 108 ergs K-1 mol-1

u =

u = 1.58 x 104 x cm s-1

where 'T' is Kelvin temperature and 'M' the molar mass.

Example 5. Calculate the root mean square velocity of CO2 molecule at

1000 C.(C = 12, O = 16)
 54

T = 273 + 1000 = 1273 K; M = 44 amu

u=

u = 1.58 x 104 x

we have u = 1.58 x 104 x

u = 84985 cm s-1 or 849.85 m s-1

Case 2. Calculation of molecular velocity when temperature and pressure both
are given. In such cases we make use of the following relation based
on Kinetic Gas equation.

u=

We know that 1 mole of a gas at STP occupies a volume of 22400 cm 3

(known as molar volume). But before applying this relation the molar volume
is reduced to the given conditions of temperature and pressure.
Example 6. Calculate the RMS velocity of chlorine molecules at 12 C and
78 cm pressure. (  =13.6, g = 981 cm s-2)
At STP: At given conditions:
V1 = 22400 cm3 V2= ?
T1 = 273 K T2 = 12 + 273 = 285 K
P1 = 76 cm P2 = 78 cm

Applying =

we have V2 = = = 22785 cm3

we know that u=

P = h g = 78 x 13.6 x 981 dynes cm-2

V= 22785 cm3; M = 71
 55

u=

u = 31652 cm s-1 (or) 316.52 m s-1

Case 3. Calculation of molecular velocity at STP

Example7. Calculate the average velocity of nitrogen molecule at STP.
In this example we have,
P = 1 atm = 76 x 13.6 x 981 dynes cm-2
V = 22,400 cm3 , M = 28
Substituting these values in the equation

u=

We have = = 49,330 cm s-1

Average velocity = 0.9213 x 49330 cm s-1 = 45,447 cm s-1

Case 4. Calculation of Molecular Velocity when pressure and density are
given

u= or u =

where P is expressed in dynes cm-2 and D in g cm-3.

Example 8. Oxygen at 1 atmosphere pressure and 0 C has a density of 1.4290

grams per cubic decimeter. Find the RMS velocity of oxygen
molecules.
We have P = 1 atm = 76 x 13.6 x 981 dynes cm-2

D = 1.4290 g dm-3 = g cm-3

= 0.001429 g cm-3

Applying u=

we get u= = 46138 cm s-1

 56

Case 5. Calculation of most probable velocity

Example 9. Calculate the most probable velocity of nitrogen molecules, N2,
at 15 C. ( R = 8.314 x 107 erg K-1 mol-1)
T = 273 + 15 = 288 K

u = 1.58  104 , vmp = u  0.8165

vmp = 0.8165  1.58  104 = 1.290  104

(OR)

vmp = =

= 1.29 x 104= 1.29 x 104 = 4.137 x 104 cm s-1

2.1.9 Deviation from Ideal Behavior

An ideal gas is one which obeys the gas laws or the gas equation PV=RT
at all pressures and temperatures. However no gas is ideal. Almost all gases
show significant deviations from the ideal behavior. Thus the gases H 2, N2, CO2
which fail to obey the ideal-gas equation are termed non ideal or real gases.
(a) Compressibility Factor
The extent to which a real gas departs from the ideal behavior may be
depicted in terms of a new function called the Compressibility factor, denoted
by ‘Z’. It is defined as

Z=

The deviations from ideality may be shown by a plot of the

compressibility factor, Z, against P. For an ideal gas, Z = 1 and it is
independent of temperature and pressure. The deviations from ideal behavior of
a real gas will be determined by the value of Z being greater or less than 1. The
difference between unity and the value of the compressibility factor of a
gas is a measure of the degree of non ideality of the gas. For a real gas, the
deviations from ideal behavior depend on (i) pressure and temperature. This
will be illustrated by examining the compressibility curves of some gases
discussed below with the variation of pressure and temperature.
(b) Effect of Pressure Variation on Deviations
Figure 2.11 shows the compressibility factor, Z, plotted against pressure
for H2, N2 and CO2 at a constant temperature. At very low pressure, for all these
 57

gases Z is approximately equal to one. This indicates that at low pressures (up
to 10 atm), real gases exhibit nearly ideal behavior. As the pressure is
increased, H2 shows a continuous increase in Z (from Z = 1). Thus the H2 curve
lies above the ideal gas curve at all pressures. For N 2 and CO2, Z first decreases
(Z< 1). It passes through a minimum and then increases continuously with
pressure (Z > 1). For a gas like CO 2 the dip in the curve is greatest as is most
easily liquefied.

200 400 600 800 1000

Pressure (atm)
Figure 2.11 Z versus P plots for H2, N2 and CO2 at 300 K

(c) Effect of Temperature on Deviations

Figure 2.12 shows plots of Z or PV/ RT against P for N2 at different
temperatures. It is clear from the shape of the curves that the deviations from
the ideal gas behavior become less and with increase of temperature. At
lower temperature, the dip in the curve is large and the slope of the curve is
negative. That is, Z < 1. As the temperature is raised, the dip in the curve
remains horizontal for an appreciable range of pressures. At this temperature,
the minimum in the curve vanishes and the curve remains horizontal for an
appreciable range of pressures. At this temperature, PV/ RT is almost unity and
the Boyle’s law is obeyed. Hence this temperature for the gas is called Boyle’s
temperature. The Boyle temperature of each gas is characteristic e.g., for N2 it
is 332 K.

Z 2

0
0 300 600 900 1200
P
Figure 2.12 Z versus P plots for N2 at different temperatures.
Conclusion
From the above discussions we conclude that:
 58

(i) At low pressures and fairly high temperatures, real gases show nearly ideal
behavior and the ideal-gas equation is obeyed.
(ii) At low temperatures and sufficiently high pressures, a real gas deviates
significantly from ideality and the ideal-gas equation is no longer valid.
(iii) The closer the gas is to the liquefaction point, the larger will be the
deviation from the ideal behavior.

2.1.10 Explanation of Deviations–van der Waals Equation

van der Waals (1873) attributed the deviations of real gases from ideal
behavior to two erroneous postulates of the kinetic theory. These are:
(1) the molecules in a gas are point masses and possesses no volume.
(2) there are no intermolecular attractions in a gas.
Therefore, the ideal gas equation PV = nRT derived from kinetic theory
could not hold for real gases. van der Waals pointed out that both the pressure
(P) and volume (V) factors in the ideal gas equation needed correction in order
to make it applicable to real gases.
(a) Volume Correction
The volume of a gas is the free space in the container in which
molecules move about. Volume V of an ideal gas is the same as the volume
of the container. The dot molecules of ideal gas have zero – volume and the
entire space in the container is available for their movement. However, van der
Waals assumed that molecules of a real gas are rigid spherical particles which
possess a definite volume.

Figure 2.13 Volume of a Real gas

The volume of a real gas is, therefore, ideal volume minus the volume
occupied by molecules (Figure 2.13). If ‘b’ is the effective volume of
molecules per mole of the gas, the volume in the ideal gas equation is corrected
as: (V – b)
For ‘n’ moles of the gas, the corrected volume is: (V – nb)
where ‘b’ is termed the excluded volume which is constant and characteristic
for each gas.
 59

Figure 2.14 Excluded volume for a pair of gas molecules

Excluded volume is four times the actual volume of molecules. The
excluded volume is not equal to the actual volume of the gas molecules. In fact,
it is four times the actual volume of molecules and can be calculated as
follows. Let us consider two molecules of radius r colliding with each other
(Figure 2.14). Obviously, they cannot approach each other closer than a
distance (2r) apart. Therefore, the space indicated by the dotted sphere having
radius (2r) will not be available to all other molecules of the gas. In other
words the dotted spherical space is excluded volume per pair of molecules.
Thus,

excluded volume for two molecules = (2r)3 = 8

excluded volume per molecule (Vc) = x 8 = 4 Vm

where Vm is the actual volume of a single molecule. Therefore, in general,

excluded volume of the gas molecules is four times the actual volume of
molecules.
(b) Pressure Correction
A molecule in the interior of a gas is attracted by other molecules on all
sides. These attractive forces cancel out. But a molecule about to strike the wall
of the vessel is attracted by molecules on one side only. Hence it experiences
an inward pull (Figure 2.15).
Inward pull Molecular attraction balanced

Figure 2.15 (a) A molecule about to strike the wall has a net inward pull;
(b) A molecule in the interior of gas has balanced attractions.
Therefore, it strikes the wall with reduced velocity and the actual
pressure of the gas, P, will be less than the ideal pressure. If the actual pressure
P, is less than Pideal by a quantity ‘p’, we have
P = Pideal - p or Pideal = P + p
 60

‘p’ is determined by the force of attraction between molecules (A) striking the
wall of container and the molecules (B) pulling them inward. The net force of
attraction is, therefore, proportional to the concentration of (A) type molecules
and also of (B) type of molecules. That is,

P CA x CB (or) p x (or) p= …… (2.13)

where n is total number of gas molecules in volume V and a is proportionality

constant characteristic of the gas. Thus the pressure P in the ideal gas equation
is corrected as:

for ‘n’ moles of gas.

van der Waals Equation

Substituting the values of corrected pressure and volume in the ideal gas
equation, PV = nRT, we have

(V – nb) = nRT
This is known as van der Waals equation for ‘n’ moles of a gas.
Constant ‘a’ and ‘b’ in van der Waals equation are called van der Waals
constants. These constants are characteristic of each gas.
Determination of ‘a’ and ‘b’

From the expression (1), the value of a is given by the relation : a =

If the pressure is expressed in atmospheres and volume in dm3,

a= =

Figure 2.16 The striking molecule A is pulled

inward by molecules B which
reduces the velocity of A and
causes the decrease of pressure

Thus ‘a’ is expressed in atm dm6 mol-2 units.

Since ‘nb’ is excluded volume for n moles of gas,

b= =
 61

If volume is expressed in dm3, b is expressed in dm3 mol-1 units.

SI units of a and b. If pressure and volume are taken in SI units, we have

a= = = Nm4 mol-2

and b = Volume mol-1 = m3 mol-1

The values of ‘a’ and ‘b’ can be determined by knowing the P, V and T
of a gaseous system under two different conditions. Table 2.2 gives values of
‘a’ and‘ b’ for some common gases.
Table 2.2 van der Waals constants for some common gases
a b
Gas
atm dm6 mo1-1 N m4 mo1-2 L mol-1 103 m3 mol-1

Hydrogen 0.245 0.0247 0.0266 0.0266

Oxygen 1.360 0.1378 0.0318 0.0318
Nitrogen 1.390 0.1408 0.0391 0.0391
Chlorine 6.493 0.6577 0.0562 0.0562
Carbon dioxide 3.590 0.3637 0.0428 0.0428
Ammonia 4.170 0.4210 0.0371 0.0371
Sulphur dioxide 6.710 0.6780 0.0564 0.0564

Example 10. Calculate the pressure exerted by 1.00 mol of methane (CH4) in
a 250 cm3 container at 300 K using van der Waals equation.What
pressure will be predicted by ideal gas equation?
a = 2.253 dm6 atm mol-2, b = 0.0428 dm3 mol-1; R = 0.0821 dm3 atm mol-1 K

(V – nb) = nRT …van der Waals equation

Dividing by (V- nb) and solving for P

P= -

Substituting n = 1, R = 0.0821 L atm mol-1K-1 , V = 0.250 dm3, T = 300 K and

the values of a and b, we have

P= - = 82.8 atm

The ideal gas equation predicts that

 62

nRT
P= V =

= 98.5 atm

2.2 The Properties of Solutions

Solids, liquids, and gasses are all around us and given form to our world.
Chemistry at its most fundamental level is about atoms and the forces that act
between them to form larger structural units. This unit will help you see how
these macroscopic properties of matter depend on the microscopic particles of
which it is composed.

Water is the only common substance

that can exist naturally as a gas, liquid,
or solid at the relatively small range of
temperatures and pressures found on
the Earth’s surface. Sometimes, all
three states are even present in the
same time and place, such as this
wintertime eruption of a geyser in
Yellowstone National Park.
The characteristics of atoms in solids, liquids and gases are expressed in Table
2.3 and their characteristics properties are described in Figure 2.17.

Table 2.3 Characteristics Properties of Gases, Liquids and Solids

State Volume/Shape Density Compressibility Motion of
of molecules
matter
Gases Assumes the volume Low Very Very free
and shape of its compressible motion
container
Liquid Definite volume but High Only slightly Slide past one
assumes the shape of compressible another freely
its container
Solid Definite volume and High Virtually Vibrate about
shape incompressible fixed positions

Solid: order arrangement, molecules

in contact
Liquid: Some disorder, molecules in
contact
Gas: complete disorder, molecules
not in contact
 63

Solid Liquid Gas

Figure 2.17 The nature of atoms in solid, liquid and gas

The contrast at the microscopic level between solids, liquids and gases is
most clearly seen in the simplified schematic views above. The molecular units
of crystalline solids tend to be highly ordered, with each unit occupying a fixed
position with respect to the others. In liquids, the molecules are able to slip
around each other, introducing an element of disorder and creating some void
spaces that decrease the density. Gases present a picture of almost total
disorder, with practically no restrictions on where anyone molecule can be.
The intermolecular attractions that hold molecules together in liquids and solids
also play a central role in the formation of solutions. When one substance (the
solute) dissolves in another (the solvent), particles of the solute disperse
throughout the solvent. The solute particles occupy positions that are normally
taken by solvent molecules. Intermolecular forces give rise to a number of
structural features and properties of liquids.
2.2.1 Intermolecular Forces (IMFs)
Molecules within a liquid are pulled in all directions by intermolecular
forces: there is no tendency for them to be pulled in any one way. However,
molecules at the surface are pulled downward and sideways by other
molecules, but not upward away from the surface. These intermolecular
attractions thus tend to pull the molecules into the liquid and cause the surface
to tighten like an elastic film. Because there is little or no attraction between
polar water molecules and, the non-polar wax molecules on a freshly waxed
car, a drop of water assumes the shape of a small round bead, because a sphere
minimizes the surface area of a liquid. A measure of the elastic force in the
surface of a liquid is surface tension. Liquids that have strong intermolecular
forces also have high surface tensions. In the liquid state the molecules are in
contact with each other. The forces of attraction between the molecules are
strong enough to hold them together. The intermolecular forces in liquids are
collectively called van der Waals forces. These are weak attractive forces in
large number of substances like HCl,Cl2 , Br2 , etc. The strength of van der
Waals forces range from 0.1 to 10 kJ mol –1. Hydrogen bonding occurs in
substances having hydrogen covalently bonded to a highly electronegative
atom Figure 2.18.
 64

Figure 2.18 Van der Waals forces and hydrogen bonding

The strength of hydrogen bond is the order of 10 to 40 kJ mol –1. It is about one-
tenth as strong as covalent bond. The intermolecular forces in liquids are three
kinds. The vapour pressure of a liquid is the partial pressure of the vapour over
the liquid at equilibrium. The vapour pressure of different liquids depends upon
their nature and the intermolecular forces. For example, ethyl alcohol has
weaker hydrogen bonding than water and evaporates faster than water. With
rise in temperature the vapour pressure increases. The important factors on
which the vapour pressure of a liquid depends are: nature of the liquid, effect of
temperature, dipole-dipole interactions, London forces and hydrogen bonding.

(a) Nature of the Liquid

If the intermolecular forces of attraction in liquid are weak, the
molecules are easily leave the liquid and come into the vapour phase and hence
the vapour pressure is higher. For example, the vapour pressures of ether,
acetone, benzene, etc., are higher than that of water at the same temperature.
This is illustrated in Figure 2.19. Acetic acid gives lower vapour pressure than
water as the former has greater the molecular forces caused by hydrogen
bonding.

760 mmHg
Vapour pressure

Temperature
Figure 2.19 Vapour Pressure-Temperature curves for some liquids

(b) Effect of Temperature

 65

As the temperature of a liquid is increased, the number of molecules

with higher kinetic energy increases. Hence the vapour pressure of the liquid
increases. This is again evident from each curve in above Figure.

(c) Dipole-dipole Interactions

Such interactions occur in polar molecules. Take the example of HCl. It
is a polar-molecule with one end having a partial positive charge and the other
end having a partial negative charge. Such molecules are called dipoles. The
positive end of one molecule attracts the negative end of another molecule.
Such attractive forces are called dipole-dipole attraction. The strength of such
forces is generally 1% of that of a covalent bond. It may be observed that
attractive forces between the opposite poles are stronger than the repulsive
forces between like poles. Thus, there is a net force of attraction. It is illustrated
in the Figure 2.20.
H+ Cl-

weak forces
of attraction

Figure 2.20 The attraction between polar HCl molecules

(d) London Forces

Fritz London in 1930 explained the force of attraction between non-
polar molecules. A non-polar molecule is formed between the atoms of similar
electronegativity by sharing of electrons. The shared electron pairs lie exactly
in the middle.

H H O O

Hydrogen molecule Oxygen molecule

Even these molecules exhibit weak attractive forces. London explained

this by saying that according to principle of probability, at a particular instant,
the electrons may shift to one side of the molecule making that negative and the
 66

other side positive, thus creating a dipole. Such a dipole is called instantaneous
dipole. The negative pole of such a molecule repels the electrons of
neighbouring non-polar molecule making that end positive and the other end
negative.
Thus, an induced dipole is created. The instantaneous dipole and
induced dipole will now attract each other. Because of the mobile nature of
electrons, instantaneous dipole may disappear the next moment and another
dipole is formed. Attraction between instantaneous and induced dipole is
responsible for attractive forces between non-polar molecules. This is
illustrated in Figure 2.21.
 

A A

Instantaneous Non-polar
dipole molecule

A A

Instantaneous Induced
dipole dipole
London f orce

Figure 2.21 Representation of London Force

Momentary attractions between the instantaneous dipole and induced

dipole in liquid molecules are called London Forces. The strength of London
forces depends upon the number of electrons in the other orbit and the size of
the molecule. Thus argon with a greater number of electrons and larger
molecular size has a higher boiling point than helium.
(e) Hydrogen Bonding
Hydrogen bond occurs in molecules containing hydrogen and an
electronegative atom like O, N and F, covalently bonded. Take for example, the
case of H2O molecule. In this molecule, oxygen being electronegative attracts
the shared pair of electrons towards itself making H slightly positive and O
slightly negative.
Now negative O is attracted by positive H of the second molecule and a
weak bond is created between the two, which is called hydrogen bond.

 
H O H O H O

H H H

Hydrogen bond
Hydrogen bond is the strongest of all intermolecular forces including the
dipole-dipole interaction and London forces. It may be mentioned that all three
 67

intermolecular forces mentioned above are collectively called van der Waals
forces.
Figure 2.22 shows that each water molecule can take part in four
hydrogen bonds with neighboring molecules - it has two partially positive Hs
and two partially negative sites on the O. These sites of potential H-bonding are
arranged in a nearly tetragonal geometry. Because of this arrangement, each
water molecule can interact through H-bonds with four other water molecules.

Figure 2.22 The structure of water and hydrogen bonds

2.2.2 The Solutions

A solution is a homogeneous mixture of two or more substances on
molecular level. The constituent of the mixture present in a smaller amount is
called the solute and the one present in a larger amount is called solvent. A
solution is a homogenous mixture of two or more substances that exist in a
single phase. For example of in a solution of salt water, salt is the solute and
water is the solvent. In solutions where water is the solvent, the solution is
referred to as an aqueous solution. Chemists characterize solutions by their
capacity to dissolve a solute. A saturated solution contains the maximum
amount of solute that will dissolve in a given solvent at a specific temperature.
An unsaturated solution contains less solute than it has the capacity to
dissolve. A third type supersaturated solution contains more solute than is
present in a saturated solution. Supersaturated solutions are not very stable. In
time, some of the solute will come out of a supersaturated solution as crystal.
A solution does not have to involve liquids. For instance, air is a
solution that consists of nitrogen, oxygen, carbon dioxide, and other trace
gases, and solder is a solution of lead and tin. The general rule of thumb for
solutions is the idea that like dissolves like. Polar, ionic substances are soluble
in polar solvents, while nonpolar solutes are soluble in nonpolar solvents. For
example, alcohol and water, which are both polar, can form a solution and
iodine and carbon tetrachloride, which are both nonpolar, make a solution.
However, iodine will not readily dissolve in polar water.
 68

In a solution, the particles are really small anywhere from 0 to 100 nm.
They never settle on standing, they cannot be separated by filtering, and light
will pass through a solution unchanged. One type of mixture that is not a
solution is known as the colloid. In a colloid, particles are between 100 and
1000 nm in size still too small for our eyes to distinguish, but particles this
small will not settle. As is the case in solutions, the particles cannot be filtered,
but they do scatter light. Some examples of colloids include gelatin, fog,
smoke, and shaving cream. Another type of mixture that is not considered a
solution is known as a suspension. Suspensions have much larger particles:
usually over 1000 nm. Particles in a suspension will settle on standing, can
often be separated by a filter, and may scatter light, but they are usually not
transparent. Some examples of suspensions are muddy water, paint, and some
medicines, like Pepto-Bismol.
(a) The Molecular View of Solution Process
The intermolecular attractions that hold molecules together in liquids
and solids also play a central role in the formation of solutions. When one
substance (the solute) dissolves in another (the solvent), particles of the solute
disperse throughout the solvent. The solute particles occupy positions that are
normally taken by solvent molecules. The ease with which a solute particle
replaces a solvent molecule depends on the relative strengths of three types of
interactions:
 solvent-solvent interaction
 solute-solvent interaction
 solvent-solute interaction
For simplicity, we can imagine the solution process taking place in three
distinct steps Figure 2.23. In order for a solute to be dissolved in a solvent, the
attractive forces between the solute and solvent particles must be great enough
to overcome the attractive forces within the pure solvent and pure solute. The
solute and the solvent molecules in a solution are expanded compared to their
position within the pure substances.
The process of expansion, for both the solute and solvent, involves a
change in the energy of the system: this process can be either exothermic or
endothermic. After dissolving, the solute is said to be fully solvated (usually by
dipole-dipole or ion-dipole forces), and when the solvent is water, the solute is
said to be hydrated. The separation of the solute particles from one another
prior to dissolving is an endothermic process for both solvent and solute (steps
1 and 2), but when the solute and solvent combine with each other, this is an
exothermic process (step 3). If the energy
 69

Figure 2.23 The molecular view of solution process

released in step 3 is greater than the energy absorbed in steps 1 and 2, the
solution forms and is stable.
(b) Enthalpy of Solutions
Let’s look at how the intermolecular forces (IMFs) are changed during
the formation of the solution. There are two key parts to the changes in the
forces. The largest changes are for the solute. Before mixing, the solute
molecules only interact with other solute molecules. In the solution, the solute
molecules only interact with solvent molecules. Thus the changes result from
the loss of the solute-solute interaction and the gain of the solute- solvent
interactions. (It should be noted that along with this, there is a small loss of
solvent-solvent interactions). We can write this out as
ΔHsolution =ΔHlattice energy + ΔHsalvation

The first term is the change in enthalpy on forming the solution. The
other two terms are the change broken down into the two changes discussed in
the details above. In the solution process, the loss of solute-solute interaction
and the gain in solute-solvent interactions occurred. The first term is noted here
as the Lattice Energy. This is what we typically associate with the energy of
forming an ionic solid from separated ions. This is the energy required to pull
the solute apart. The second term is the enthalpy of solvation. This is the
energy released when the solute interacts with the solvent.  As we are often
talking about solutions made with water as the solvent, this term is often
referred to as the enthalpy of hydration, ΔHhydration.

(c) Types of Solutions

The common solutions are those where the solute is a solid and the
solvent is a liquid. In fact, substance in any three states of matter (solid, liquid,
gas) can act as solute or solvent. Thus there are seven types of solutions.
All solutes that dissolve in water fit into one of two categories:
electrolytes and non-electrolytes. An electrolyte is a substance that, when
dissolved in water, results in a solution that can conduct electricity. Strong
 70

acids, strong bases, and soluble salts are in this category. Non-electrolytes are
substances that are predominantly covalently bonded, generally will not
produce ions in solution, and therefore are considered nonconductors. A non-
electrolyte does not conduct electricity when dissolved in water. Weak
electrolytes consist of solutes that dissociate only a little in solution. Weak
acids, weak bases, and slightly soluble salts are in this category.

Table 2.4 Types and Examples of Solutions

No. State of solute State of Solvent Example
1 Gas Gas Air
2 Gas Liquid (Carbonated Oxygen in water, CO2 in water
drinks)
3 Gas Solid Adsorption of H2 by palladium
4 Liquid Liquid Alcohol in water
5 Liquid Solid Mercury in silver
6 Solid Liquid Sugar, Salt
7 Solid Solid (Steel) Metal alloys, Carbon in iron

2.2.3 Solution and its Concentration

The substance which is present in smaller amount is called a solute and
the one which is present in a large amount is called solvent. A solution
containing a relatively low concentration of solute is called Diluted solution.
A solution of high concentration is called Concentrated solution. The
concentration of a solution is the amount of solute present in a given amount of
solution i.e.

Concentration =

Ways of Expressing Concentration

(i) Percent by Weight
It is the weight of solute as a per cent of the total weight of the solution
i.e.

% by weight of solute =

(ii) Mole Fraction

 71

It is the ratio of number of moles of solute and the total number of moles
of solute and solvent.

Xsolute =

Xsolute = and Xsolute =

where n is the number of moles of solute and N the number of moles of

solvent.
(iii) Molarity
It is the number of moles of solute per dm3 of solution.

i.e., Molarity, M =

(iv) Molality
It is the number of solute per kilogram of solvent

i.e. Molality, m =

(v) Normality
It is defined as the number of gram equivalents of solute per cubic
decimeter of solution.

Normality, N =

(vi) Formality
It is the number of formula weight in grams dissolved per cubic
decimeter of solution. When formula weight is equal to the molecular weight,
the formality and molarity are the same.

Example 11: Determine the molality of a solution containing 86.53 g of

sodium carbonate (molar mass is 105.99 g mol -1) in 1dm3 of solution at
20 ºC. The density of the solution at this temperature is 1.0816 g cm-3.
To calculate the amount of Na2CO3 in 100 g of water
Density of solution = 1.0816 g cm-3
 Mass of 1 dm3 solution = 1.0816 g cm-3 × 1000 cm3
= 1081.6 g
Molar mass of Na2CO3 = 105.99 g mol-1
Amount of Na2CO3
 72

mol of solute = molar mass

86.53g
=
105.99 g mol-1
= 0.816398 mol
Amount of water = (1081.6 - 86.53) = 995.07 g

To calculate the molality, formula used

mole of solute
Molality, m =
mass of solvent in kg

= 0.816398 mol
995.07 x 10-3 kg

= 0.820443 mol kg-1 (or) m

Molality of sodium carbonate solution = 0.820443 m
2.2.4 Solutions of Solids in Solids
Solution of a solid in another solid can be prepared by melting them
together and subsequent cooling of the mixture. For example, gold in silver
when mixed together, melted and cooled, yield solid solutions which are
perfectly homogeneous. Sometimes solid solutions may be obtained by simply
pressing together the two metals and thus establishing better contact when one
metal would diffuse into the other. Solutions of gold and lead have been
obtained by this method. The study of solutions of solids in solids is of great
practical importance in metallurgy. The formation of solid solutions is not
limited to metals only. Organic substances like naphthalene and β-naphthol
when melted together form the so-called mixed crystals on cooling which are a
solid solutions of one of them in the other.

2.2.5 Solutions of Solids in Liquids

Solutions of this type are most commonly met with. The process of a
solid substance in a solvent is explained by the electrical forces operating
between the molecules or ions of the solute and the molecules of the solvent. It
is a common observation that polar solutes dissolve easily in polar solvents
while they remain insoluble in non-polar solvents. For example, sodium
chloride is fairly soluble in water which is highly polar solvent, while it is
insoluble in a non-polar solvent like chloroform. On the other hand, a non-polar
solute does not dissolve in a polar solvent e.g, benzene which is non-polar is
insoluble in water. The electrical attraction between the oppositely charged
ends of the solute and the solvent molecules results to form a solution.
Water being highly polar is one of the best solvents for ionized solutes.
An ionic substance, when placed in water furnishes cations and anions. The
 73

ions are surrounded by solvent molecules with their oppositely charged ends
directed towards the ion Figure 2.24.

Figure 2.24 The nature of dissolution of NaCl in water molecules

The ion enveloped by a layer of the solvent molecules in this manner, is
called a Solvated ion or Hydrated ion in case water is the solvent. Thus
sodium chloride dissolves in water to give Na + and Cl- ions. The Na+ ion is
hydrated to have around a layer of water molecules so that their negative ends
are directed towards it. The Cl - ion, on the other hand, attracts positive ends of
water molecules which envelop it.
Solubility
The solubility is defined as the maximum amount of the solute that
will dissolve a given quantity of solvent at a specific temperature.
Temperature affects the solubility of most substances. In this section the
temperature dependence of solubility of some ionic compounds in water. For
example, the solution process of CaCl2 is exothermic, and that of NH 4NO3 is
endothermic. But the solubility of both compounds increases with increasing
temperature.
When a solid is placed in a solvent, molecules or ions break away from
the surface and pass away the solvent. The particles of the solid thus detached
and free to diffuse throughout the solvent to give a uniform solution. The solute
and solvent molecules are constantly moving about in the solution phase
because of kinetic energy possessed by them. Some of the particles are
deflected back toward the solid on account of collisions and other molecules.
These then strike the solid surface and may get entangled in its crystal lattice
and thus get deposited on it. This process by which the solute particles from
solution are re-deposited or re-crystallized is often taken of as re-crystallization
or precipitation. In a solution in contact with solid solute, therefore, two
opposing processes are operating simultaneously;
(a) Dissolution: the particles of the solute leaving the solid and passing into
solution.
(b) Re-crystallization: the particles of the solute returning from the solution
and depositing (or re-precipitating) on the solid.
 74

Dissolution due to Hydrogen Bonding

Many non-ionic substance such as sugar also dissolve in water. The
dissolution is due to hydrogen bonding that occurs between water and sugar
molecules. The hydrogen bonding takes place through the hydroxyl group of
the sugar molecules. The water molecules are thus able to pull away the
molecules of sugar from the crystal, which dissolve. In fact, every sugar
molecule is surrounded by a number of water molecules, and these aggregates
are free to migrate throughout the solution.
Fractional Crystallization
Fractional crystallization is the separation of a mixture of substance
into pure compounds on the basis of their differing solubility. For example, a
sample of 90 g of KNO 3 that is contaminated with 10 g of NaCl. To purify the
KNO3 sample, the mixture was dissolved in 100 mL of water at 60 C and then
gradually cooled the solution to 0 C. At this temperature the solubility of
KNO3 and NaCl are 12.1 g/100 g and 34.2 g/100 g H2O, respectively. Thus (90
– 12) g or 78 g of KNO 3 will crystallize out of the solution, but all of the NaCl
will remain dissolved. The KNO3 crystals can be separated from the solution by
filtration.
2.2.6 Solution of Gases in Gases
When a gas is mixed with another gas a completely homogeneous
solution results provided of course they do not react chemically. It is obvious
that such gaseous solutions will have completely miscibility.
According to the kinetic theory, a gas consists of tiny molecules moving
about in a vacant space and thus when one gas is dissolved in another gas they
form a homogeneous solution quite readily. In such a gaseous mixture, the
components can be present to an unlimited extent.
Dalton’s Law of Partial Pressures
Since in a gaseous mixture the constituent molecules exist separately, it
is obvious that the properties of the mixture will be the sum of properties of the
components. Thus Dalton (1842) was the first to show that the total pressure
exerted by a gaseous mixture is the sum of the individual or partial pressures of
the component gases. If P1, P2, P3,…. will be the partial pressures of the
constituents, the total pressure P of the mixture is given the expression:
P = P1 + P2 + P3 +….
Like other gas laws, Dalton’s law holds strictly only when the partial
pressures are not too high. This law can be experimentally tested by comparing
the total pressure of a gaseous mixture with the sum of the individual pressure
of each gas before mixing.
Example 12: At constant temperature, 250 mL of nitrogen under 720 mm
pressure and 300 mL oxygen under 650 mm pressure were put
into a one-litre flask. What will be final pressure of the mixture?
Since P1V1 = P2V2 at constant temperature (Boyle’s law)
 75

PN2 x 1000 = 720 x 250 = 180 mmHg

PO2 x 1000 = 380 x 650 = 247 mmHg
According to Dalton’s law of partial pressure
P = PN2 + PO2
= 180 + 247 = 427 mmHg

2.2.7 Solutions of Gases in Liquids

The solubility of a gas in a solvent depends upon the pressure and
temperature. The solubility of the gases in water usually decreases with
increasing temperature. When water is heated in a beaker, bubbles of air form
on the side of the glass before the water boils. The dissolved air molecules
begin to “boil out” of the solution long before the water if self boils. When
gases dissolve into liquids we have a slightly different situation.  Now we don’t
have to overcome any intermolecular forces in pulling the solute molecules
away from each other.  They are in the gas phase and already apart.  Thus
ΔHsolution= ΔHsolvation since the lattice-energy term is zero (because it is a gas with
no IMFs).   Since the solvation term is negative, we find that ΔHsolution < 0.  
Since this is exothermic, this is helping to reduce the free energy upon forming
the solution.  This is important since the entropy is sure to be decreased.  The
solute was a gas.  This is the highest entropy state.  So even though we are
making a mixture, the entropy will be going down.
Henry's Law
When a gas is enclosed over its saturated solution, the following
equilibrium exists.
gas gas in solution
If pressure is increased on the system, the equilibrium will move in the
direction which will reduce the pressure (Le Chatelier's Principle). The
pressure can be reduced by more gas dissolving in solvent. Thus solubility or
concentration of a gas in a given solvent is increased with increase of pressure.
A kinetic molecular explanation of the effect of pressure on gases solution
system is illustrated in Figure 2.25.

Figure 2.25 Solubility of gases in solutions A, B

This figure showed straight forward figure out; press the double of the
pressure, the concentration (mole fraction) becomes double. This seems a bit
random, but in fact Henry’s Law crops up in everyday life.  
 76

Henry’s Law states that for a gas in contact with a solvent at constant
temperature, concentration of the gas that dissolved in the solvent is directly
proportional to the pressure of gas. On the other hand, the mole fraction of gas
dissolved in the liquid (like the concentration) is directly proportional to
the pressure of the gas over the liquid. The solubility of a gas in solvent
depends on the pressure and the temperature. The effect of pressure on
solubility of a gas can be predicted quantitatively by Henry's law which states
that the solubility of a gas is directly proportional to the partial pressure of the
gas above the solution. Mathematically,
CP or C=kP
where 'C ' is the concentration of the gas in solution, k, the proportionality
constant known as Henry's law constant, and 'P', the pressure of the gas. The
value of 'k' depends on the nature of the gas and solvent and the units of 'P' and
'C' used.
Have you ever wondered how they get all the CO2 into carbonated beverages? 
The practical demonstration of Henry’s law is the
effervescence of a soft drink when a cap of the bottle
is removed. Before the beverage of the bottle is
sealed, it is pressurized with a mixture of air and CO 2
saturated with water vapour. Because of the high
partial pressure of CO2 in the pressurizing gas
mixture, the amount dissolved in soft drink is many
times the amount that would dissolve under normal
atmospheric condition. When the cap is removed, the
pressurized gas escape, eventually the pressure in the
bottle falls to atmospheric pressure, the amount of
CO2 dissolved decreases and bubbles appear. The
amount of CO2 remaining in the beverage is
determined only by the normal atmospheric partial
pressure of CO2, 0.0003 atm. The excess dissolved
CO2 comes out of solution, causing the effervescence.
Example 13: The solubility of pure oxygen in water at 20 C and 1.00
atmosphere pressure is 1.38 x 10-3 mol dm-3. Calculate the
concentration of oxygen at 20 C and partial pressure of 0.21
atmosphere.
According to the Henry’s law
C = kP
k = C/P

k =

Concentration of O2 at given pressure

C = kP
 77

Concentration of O2 = 1.38 x 10-3 mol dm-3/ atm x 0.21 atm

= 2.9 x 10-4 mol dm-3
Example 14: At 20 C the solubility of nitrogen gas in water is 0.0150 g dm -3
when the partial pressure of N2 is 580 torr. Find the solubility of N2
in H2O at 20 C when its partial pressure is 800 torr.
According to the Henry’s law
k = C1/P1 k = C2/P2
k is the same values for two cases,
C1/P1 = C2/P2
C1 = 0.0150 g dm-3 C2 = ?
P1 = 580 torr P2 = 800 torr

C2 = = 0.0207 g dm-3

Most of the gases obey Henry’s law, but there are some important exceptions.
For example, if the dissolved gas reacts with water, higher solubilities can
result. The solubility of ammonia is much higher than expected because of the
reaction
NH3 + H2O NH4+ + OH-
Carbon dioxide also reacts with water, as follows:
CO2 + H2O H2CO3
Another interesting example is the dissolution of molecular oxygen in blood.
Normally oxygen gas is only sparingly soluble in water. However, its solubility
in blood is dramatically greater because of the high content of hemoglobin (Hb)
molecules, which are eventually delivered to the tissues for use in metabolism:
Hb + 4O2 Hb(O2)4
It is this process that accounts for the high solubility of molecular oxygen in
blood.
Limitations of Henry's Law
It applies closely to gases with nearly ideal behavior.
1. At moderate temperature and pressure.
2. If the solubility of the gas in the solvent is low.
3. The gas does not react with the solvent to form new species. Thus
ammonia (or HCl) which react with water do not obey Henry's law.
NH3 + H2O NH4+ + OH-
4. The gas does not associate or dissociate on dissolving in the solvent.

Raoult’s Law (Vapour-Pressure Lowering)

If a solute is nonvolatile (i.e., it does not have a measurable vapor
pressure), the vapor pressure of its solution is always less than that of the pure
 78

solvent. This relationship between solution vapor pressure and solvent vapor
pressure depend on the concentration of solute in the solution. This relationship
is expressed by Raoult’s Law which states that the partial pressure of a solvent
over a solution is given by the vapor pressure of the pure solvent, , times the
mole fraction of the solvent in solution, X1.
P1= X1
In a solution containing only one solute, X1 = 1 – X2, where X2 is mole
fraction of the solute. P1= (1 – X2)

P1= – X2

P1 - = P = - X2

- P = X2
The decrease in vapor pressure, P, is directly proportional to the solute
concentration (measured in mole fraction). If both components of a solution are
volatile (i.e., have measurable vapour pressure), the vapour pressure of the
solution is the sum of the individual partial pressures.
PA =XA and PB = XB

where PA and PB are the partial pressures over the solution for components A
and B; XA and XB are their mole fraction, and are the vapor pressure of
the pure substances.
The vapor pressure of a solution is less than that of the pure solvent.
One driving force in physical and chemical process is an increase in disorder-
the greater the disorder, the more favourable the process. Vapourization
increases the disorder of a system because molecules in a vapor have less order
than those in liquid. Because a solution is more disorder than a pure solvent,
the difference in disorder between a solution and a vapor is less than that
between a pure solvent and a vapor. The solvent molecules have less of a
tendency to leave a solution than to leave the pure solvent to become vapor,
and the vapor pressure of a solution is less than that of the solvent.

2.2.8 Solutions of Liquids in Liquids

The solutions of liquids in liquids may be divided into three classes as
follows:
1. Liquids that are completely miscible (e.g., alcohol and water)
2. Liquids that are partially miscible (e.g., ether and water)
3. Liquids that are practically immiscible (e.g., benzene and water)
(a) Solubility of Completely Miscible Liquids
Liquids like alcohol and water mix in all proportions and in this respect
they could be compared to gas. The properties of such solutions, however, are
 79

not strictly additive, and therefore their study has not proved of much interest.
Generally the volume decreases on mixing but in some cases it increases.
Sometimes heat is evolved when they mixed while in others it is absorbed. The
separation of this type of solutions can be effected by fractional distillation.
(b) Solubility of Partially Miscible Liquids
A large number of liquids are known which dissolve in one another only
to a limited extent, e.g., ether and water. Ether dissolves about 1.2% water; and
water also dissolves about 6.5 % ether. Since their mutual solubilities are
limited, they are only partially miscible. When equal volumes of ether and
water are shaken together, two layers are formed, when one of the saturated
solution of ether in water and the other of a saturated solution of water in ether.
These two solutions are referred to as conjugate solutions. For example,
Phenol-water system, Triethylamine-Water system, and Nicotine-Water system
are partially miscible liquid systems.

(c) Vapour Pressure of mixture of Non-Miscible Liquids

The picture  shows two immiscible liquids. These are

liquids with very different IMFs, for example oil (long
hydrocarbon chain, non-polar) and water (polar, H-bonding). 
Again, “like dissolves like,” “like is miscible with like.” In a
mixture of non-miscible liquids, each component exerts its
own vapour pressure independent of others and the total
vapour pressure is equal to the sum of individual vapour
pressures of all the liquids.
This generalization is the basic principle of steam distillation. The
number of molecules of each component in the vapour will be proportional to
its vapour pressure i.e. to the vapour pressure of the pure liquid at that
temperature. Hence

where n1 and n2 are the number of moles of the two components, P1 and P2 are

their vapour pressures. =

where w1 and w2 are the masses of two liquids with their molecular masses M1
and M2, respectively. From this we can calculate the molecular mass of one
component if that of other is given.
Example 15: Nitrobenzene(C6H5NO2) is completely miscible with water. A
mixture of two liquids boils at 99 ºC and 753 torr pressure. The
vapour pressure of water is 733 torr at this temperature. Find out
the weight composition of liquid mixture.(C=12,H=1,N=14,O=16)
 80

P1 = Vap. pressure of mixture – Vap. pressure of water

= 753 torr – 733 torr = 20 torr
P2 = 733 torr
M1 of nitrobenzene (C6H5NO2) = 123 g cm-3
M2 of water = 18 g cm-3
Substitution of values

= = 0.1864

0.1864
= 1

w1 : w2 = 0.1864 : 1
0.1864
% composition of nitrobenzene = x 100 = 15.71
1  0.1864

% composition of water = 100 – 15.71 = 84.29

2.2.9 Surface Tension

It is defined as the energy required to increase the surface area of a
liquid by a unit amount. It is measured by dynes cm –1 (CGS unit) or in Newton
per meter, Nm–1 (SI units) or Jm–2.As a result of the inward pull on the
molecules at the surface, the surface of the liquid tends to contract to the
smallest possible area for a given volume of the liquid. It is for this reason that
the drops of a liquid are spherical because for a given volume, a volume, a
sphere has minimum surface area.
(a) Surface Energy
To increase the area of surface, some work has to be done against the
inward pull. Consider a soap solution film contained in rectangular wire frame
ABCD in which the side CD is movable in Figure 2.26.
A C E

B D F

Figure 2.26 Concept of surface energy

In order to extend the surface area of the film, the movable wire has to be
pulled from position CD to position EF. Thus some work has to be done
 81

against surface tension. The work in ergs required to be done to increase or

extend the surface area by 1 sq. cm is called surface energy. The units of
surface energy are, therefore, erg per sq. cm (or joule per sq. metre in S.I.
system).
In terms of dimensions,
Surface energy = work per sq. cm. = (Force × length) per sq. cm.

= dyne cm-1

These units are the same as those of surface tension. Thus the surface
energy is same thing as surface tension.

(b) Capillary Rise

When one end of a capillary tube is put into a liquid that wets glass, the
liquid rises into the capillary tube to a certain height. This rise is obviously due
to the inward pull of surface which pushes the liquid into the capillary tube in
following Figure 2.27.

Capillary
tube

Figure 2.27 Rise of a liquid in a Capillary tube

In case of liquids which do not wet glass e.g., mercury, the level inside
the capillary falls below the level outside. Further whereas the upper surface of
a liquid that wets glass is convex. Such a surface is called Meniscus (Greek:
moon). The angle which the curved surface (i.e., meniscus) makes with the
wall of the tube is called contact angle in the following Figure 2.28.

Figure 2.28 Contact angle for a liquid (a) that wets glass (b) that does not
wet glass
 82

(c) Determination of Surface Tension

(i) Capillary Rise Method
The formula used for the determination of surface tension by capillary
rise method is

Where h is the height to which liquid rises in a capillary tube of radius r, d is

density of the liquid and g the force of gravity.

(ii) Drop-Weight Method

The formula used in drop weight method is

where γ1 and γ2 are the surface tension of given liquid and water, m1and m2the
masses of one drop of each liquid and water respectively. Knowing the surface
tension of reference liquid γ2, the surface tension of the liquid under study can
be calculated.

(iii) Drop-Number Method

The formula used is

= ×

where γ1 and γ2 are the surface tension of given liquid and water respectively,
n1 and n2 are the number of drops in a given volume, d1 and d2 are their
densities.

Example 16: When 12.0 cm3 of water is allowed to flow through a

stalgamometer, 50.0 drops of water were obtained and when the
same volume of liquid is allowed to flow, the number of drops
formed was 35. If the density of the liquid is 1.2 g per cm 3 and the
surface tension of water is 72 dyne cm–1, calculate the surface
tension of the liquid.
Quantities given
n1 = 35 d1 = 1.0 g cm-3 r1 = 72 dyne cm-1
n2 = 50 d2 = 1.2 g cm-3
 83

= or  =
2

r2 =

= 123.428 dyne cm-1

2.2.10 Viscosity
Viscosity is the resistance to flow that is exhibited by all liquids. It may
be defined as the force of resistance per unit area which will maintain unit
velocity difference between two layers of a liquid at a unit distance from each
other Figure 2.29. It is denoted by η. Its units are mass length –1 time–1 i.e. kg
m s (SI units) or g cm s (CGS units) and 1 poise = 1 g cm s = 0.1 kg m–
–1 –1 –1 –1 –1 –1
1 –1
s . Consider a liquid flowing through a narrow tube in Figure. All parts of the
liquid do not move through the tube with the same velocity. Imagine the liquid
to be made up of a large number of thin cylindrical coaxial layers. The layer
which is in contact with inner walls of the tube is almost stationary.

v cm/sec
x cm

v + dv cm/sec

Figure 2.29 Flow of a liquid through a narrow tube

As we move from the walls towards the centre of the tube, the velocity
of the cylindrical goes on increasing. It is maximum at the centre. Conversely,
we may say that as we move from the centre towards the walls, the velocity of
the layers keeps on decreasing. In other words, every layer offers some
resistance of friction to the layer immediately below it. This force of friction
which one part of the liquid offers to another part of the liquid is called
viscosity. It has been found that the force of friction (f) between two cylindrical
layers each having area A sq. cm, separated by a distance x cm, and having a
velocity difference of v cm/sec., is given by

F  Av/x

f=

where  is a constant known as coefficient of viscosity.

If x = 1cm, A = 1sq. cm and v = 1 cm/s, then f = 

Hence coefficient of viscosity may be defined as the force of friction (in
dynes) required to maintain a velocity difference of a cm/s between two partial
layers, 1 cm apart and each having an area of 1 sq. cm.
 84

Example 17: In a measurement of viscosity by Ostwald's viscometer at 20.2

ºC, water takes 30 s to flow between the upper and lower marks while the flow
of another liquid of density 1.5 g cm–3 takes 35 s. Taking density of water at
20.2 ºC to be 0.9982 g cm–3, calculate the viscosity of the other liquid if the
viscosity of water at this temperature is 10 centi Poise.

= 10 centipoise d1 = 0.9982 g cm-3 r1 = 30 s

d2 = 1.5 g cm-3 r2 = 35 s
Substitution of values

= 0.1753 poise

(a) Fluidity

Reciprocal of viscosity is fluidity represented by  . Thus  = Unit

of fluidity is poise-1. The increasing of the temperature, the kinetic energy of

the molecules of the liquid will be increased. Hence the liquid starts flowing
faster. In other words, the viscosity of a liquid decreases with increase in
temperature. It has been found that the decrease is about 2% per degree rise of
temperature. Arrhenius gave the following relationship between viscosity and
temperature:
where A and B are the constants for the liquid and T is the absolute
temperature. The above equation may be written as

log (or) log

Thus the plot of vs is a straight line.

(b) Determination of Viscosity

(i) Ostwald's Method
 85

The formula used for the determination of viscosity by the Ostwald's

method is

where V is the volume of the liquid flowing through a capillary in time t, P is

the pressure-head, r, the radius of the tube and l its length. The relative
viscosity is given by the relation

Where t1 and t2 are times of flow of fixed volume (V) of two liquids with
densities d1 and d2 respectively. Knowing the value of η2 , η1 can be calculated.
(ii) Relationship between Viscosity and Chemical Constitution
(a) In a homologous series, the viscosity increases as we go up a series and
the increase per CH2 group is almost constant.
(b) In compounds involving chain isomerism, the n-isomers have generally
greater viscosity than the branched chain isomers.
(c) In compounds involving geometrical isomerism, trans-isomers have
higher value of viscosity than the corresponding cis-isomers.
According to Dunstan's rule, for non-associated or normal liquids, the
following equation holds

where d = density of the liquid, = coefficient of viscosity, M = Molecular

mass
For associated liquids, the value is much greater than 80.

2.2.11 Refractive Index

When a ray of light travels from one medium to another, it undergoes a
change in direction as shown in Figure 2.30. This phenomena is called
refraction. If a ray of light travels from air or vacuum to a more dense medium
(i.e., any liquid or solid), then the ratio of the sine of the angle of incidence, i,
to the sine of the angle of refraction, r, is constant depending upon the nature of
the medium. This constant is called the refractive index of the medium. It is
usually represented as 
normal
air
or
vacuum Incident ray

liquid
or
solid Refracted ray
 86

Figure 2.30 Refraction of light from air to a more dense medium

Thus

=

This is called Snell's law. The value of refractive index is also found to
depend upon the wavelength of the light used and the temperature. There are
usually specified as subscripts and superscripts respectively. Thus
indicates a refractive index taken at 20 ºC with light corresponding to yellow
D-line of the sodium spectrum obtained from sodium vapour lamp.
Alternatively, the refractive index of a medium is also defined as the
ratio of the velocity of light in vacuum to the velocity of light in the medium,
i.e.,

(i) Specific Refraction

It is given by the formula

Rs = ×

where RS is the specific refraction, d the density and n is the refractive

index.

(ii) Molar Refraction

It is the product of specific refraction and molecular mass

RM = ×

where M is the molecular mass of the substance.

The instrument used for the measurement of refractive index is called a
refractometer. The two common refractometers are Pulfrich refractometer and
Abbe's refractometer.

Example 18: The refractive index of carbon tetrachloride is 1.4573 and its
density is 1.5952 g cm–3. Calculate its molar refraction. (C=12,
Cl=35.5)
 87

Quantities Given
n = 1.4573 d = 1.5952 g cm-3 M = 12 + 4 × 35.5 = 154 g mol-1

Rm = ×

= ×

= × = 26.30 cm3 mol-1

(iii) Optical Activity

A compound that can rotate the plane of polarized light is called
optically active compound. This property of a compound is called optical
activity.

(iv) Specific Rotation

It is expressed as

[ ] =

where [α] is the specific rotation in degrees, α ,the observed angle of rotation in
degrees l ,the length of the sample in decimeter, C , the concentration of the
sample solution in g cm–3.

Example 19: A solution of a certain optically active substance in water

containing 5.2 g in 30 ml is introduced in a 20 cm long polarimeter
tube. It rotated plane polarized light by 6.2º. Calculate the specific
rotation.
Quantities given

= 6.2º l = 20 cm = 2 dm c = g cm-3
º

[ ] = [ ] = = 17.88º

Exercises
 88

1. At what temperature would ethane molecules have the same r.m.s. velocity
as methane molecules at 27°C?
2. (a) Derive an expression for the pressure of an ideal gas by means of the
kinetic theory and show that the total kinetic energy of the molecules in one
mole of an ideal gas is equal to 3/2 RT.
(b) Calculate the root mean square velocity of oxygen molecules at 25°C.
3. (a) Derive the kinetic gas equation for an ideal gas.
(b) Calculate the root mean square velocity for oxygen molecules at 26.85
°C, given that gas constant is 8.314 x 107 ergs mol-1 K-1.
4. (a) Indicate what do you mean by the terms ‘mean’ and ‘r.m.s’ of gas
molecules.
(b) Calculate the root mean square (rms) speed of CO2 molecules at 27°C.
5. For ammonia gas van der Waals constants a and b are 4.0 dm6 atm mol-1 and
0.036 dm3 mol-1, respectively. Calculate critical volume.
(R =0.082 dm3 atm K-1mol-1 )
6. (a) What do you understand by the distribution of molecular velocities of a
gas? Illustrate your answer with the help of a diagram.
(b) Calculate the root mean square velocity of CO2 at 27°C.
7. Discuss the causes of deviation of real gases from ideal gas behaviour. How
are they accounted for in the van der Waals equation?
8. (a) Prove that for gases Cp - Cv = R. Define the terms involved. How does it
help in determining the aromaticity of the gases?
(b)Explain the law of corresponding state.
9. (a) What are the limitations of the equation PV = RT? What improvements
have been suggested by van der Waals?
(b) How van der Waals equation can be applied for the calculation of
Boyle's temperature? Also define Boyle's temperature.
(c) Show that van der Waals equation reduces to ideal gas equation at
Boyle's temperature.
10. Calculate average velocity of oxygen molecule at 25°C. (R = 8.314 JK-1
mol-1)
11. (a) What is kinetic gas equation? Derive Boyle's law and Charles' law from
it.
(b) Define mean free path and collision diameter.
(c) On the basis of kinetic theory of gases, show that for monoatomic gases
Cp - Cv=R.
12.What are the real gases? In which conditions real gases deviate from ideal
gas behaviour? Describe these deviations and derive van der Waals
equation.
13. What is compressibility factor? How van der Waals equation of state
accounts for the non-ideal behaviour of gases?
14. Write down the expression for the Maxwell's distribution of molecular
speed and discuss its characteristics.
15. (a)Write the wrong assumptions of kinetic theory of gases and derive the
van der Waals equation.
 89

(b)Explain deviation of gases from ideal gas behaviour with the help of a
graph.
16. Derive the relation between Cp and Cv for an ideal gas.
17. Starting from kinetic gas equation derive (i) Avogadro's law; and (ii)
Graham's law of diffusion.
18. What are ideal and non-ideal gases? What are the chief causes of deviation
of real gases from ideal behaviour? Derive van der Waals equation and
show how these are accounted for in this equation.
19. Show that the total pressure (P) exerted by an ideal gas containing 'N'

molecules and occupying volume `V is given by : P = .

20. What is critical phenomenon? Derive expression for the critical constants of
a gas using van der Waals equation of state. How do you find our the van
der Waals constants from the critical values of pressure, temperature and
volume?
21. (a)Discuss the effect of temperature on molecular velocity.
(b) Derive a relationship between Cp and Cv for an ideal gas.
22. At what temperature would ethane molecule have the same r.m.s. velocity
as methane molecules at 27 °C?
23. Find the relationship between kinetic energy and temperature.
24. A 10.0 L flask contains 64 g of oxygen at 27 °C. Calculate its pressure
using
(i) van der Waals equation and (ii) ideal gas equation
Given that a = 4.17 atm dm3 mo1-2 and b = 0.037 dm3 mo1-1
25. Starting from van der Waals equation, derive the values of critical volume
and critical pressure in terms of van der Waals constants 'a' and 'b'. van der
Waals constants for carbon dioxide are a = 3.6 atm dm6 mo1-2 and b=4.28
x 10-2 dm3 mol-1. Calculate critical volume and critical pressure of the gas.
26. Calculate RMS velocity of methane molecule at 370 K (R = 8.314 JK-1
mo1-1, M = 16 x l03 kg)
27. Oxygen has a density of 1.429 g per dm3at NTP. Calculate the r.m.s. and
average velocity of its molecules.
28. (a) What is meant by root mean square velocity of gaseous molecules? How
is it different from average velocity?
(b) Calculate the average kinetic energy per molecule of CO2 gas at 27 °C.
(R = 1.987 cal deg -1 mo1-1)
29. Oxygen has a density of 1.429 g dm 3 at NTP. Calculate the r.m.s. and
average velocity of its molecules.
30. (a) What were the reasons which led van der Waals to modify the ideal gas
equation? Write down the modified equation.
(b) One mole of diethyl ether occupies 15 dm 3at 227°C. Calculate the
pressure if van der Waals constants for diethyl ether are a = 17.38 atm
dm6 mo1-2 and b = 0.134 dm3 mo1-1.
31. Two gases P and Q having molecular masses 44 and 64 respectively are
enclosed in a vessel. Their masses are 0.5 g and 0.3 g respectively and the
 90

total pressure of the mixture is 740 mm. Calculate the partial pressures of
the two gases.
32. Calculate the total pressure in a 10 dm3cylinder which contains 0.4 g of
helium, 1.6 g of oxygen and 1.4 of nitrogen at 27 °C. Also calculate the
partial pressure of helium gas in the cylinder. Assume ideal behavior for
gases.
33. Calculate the average kinetic energy in Joules of the molecules in 8.0 g of
methane 27 °C . Answer.1870.65 J
34. Calculate the root mean square velocity of Ozone kept in a closed vessel at
20 °C and 82 cm mercury pressure.
35. Calculate the total pressure in a mixture of 4 g of oxygen and 3 g of
hydrogen confined in a total volume of one dm3 at 0°C.
36. Discuss various intermolecular forces in liquids.
37. What are the important factors that affect the vapour pressure?
38. What is meant by heat of vaporization ( Hv) of a liquid?
39. Give the relationship between (i) Boiling point and critical temperature
(ii) Boiling point and heat of vaporization (Trouton's rule).
40. Why is the drop of a liquid spherical?
41. What is meant by surface energy?
42. Why does a liquid rise in a capillary tube? What is meant by meniscus and
contact angle?
43. Explain the terms (i) Viscosity (ii) Coefficient of viscosity.
44. What is fluidity? What are the units of fluidity?
45. How does the viscosity of a liquid change with temperature?
46. Discuss relationship between viscosity and chemical constitution.
47. Explain the term refractive index.
48. (i) What is a refractometer (ii) What are different types of refractometer.
49. At 20 ºC, toluene rises 1.95 cm in a capillary tube of radius 0.3412 mm.
Calculate the surface tension of toluene. The density of toluene at 20 ºC is
0.866 g cm–3.
50. 49 g of H2SO4 are dissolved in 250 cm3 of solution. Calculate the molarity
of the solution.
51. In an Ostwald viscometer, the flow times for two liquids A and B are in the
ratio 4:5. If the density of liquid B is twice as high as that of A, calculate
the ratio of their viscosities.
52. How long a machine oil take to pass through a viscometer if water under the
same conditions takes one minute ? Density of water = 1.0 x 10 3 kg m–3;
η=0.00101 Nm–2 s; Density of oil = 0.97 x 103 kg m-3; η= 0.060 Nm–2 s.
53. The number of drops of water counted in a stalgamometer at 298 K is 300
whereas the number of drops for ethyl alcohol is 320. Calculate the surface
tension of ethyl alcohol given that the density of water = 0.998 g cm –3,
density of ethyl alcohol is 0.9614 g cm–3 surface tension of water = 72.75
dyne cm–1.
54. In a measurement of viscosity with Ostwald's viscometer, water takes 580 s
to flow through a given volume, while an organic liquid takes 395 s.
Calculate the viscosity of organic liquid. Density of organic liquid and
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water are 0.7807 g cm–3 and 0.9984 g cm–3 respectively. Viscosity of water
is 1.01centipoise.
55. A sample of spirit contains 92% ethanol by weight, the rest being water.
What is the mole fraction of its constituents?
56. A capillary tube of internal diameter 0.2 mm is dipped into water when
water rises 15 cm. Calculate the surface tension of water.
57. 45 g of glucose, C6H12O6, are dissolved in 500 g of water. Calculate the
molality of the solution.
58. Calculate the ionic strength of a solution containing 0.2 M NaCl and 0.1 M
Na2SO4.
59. 8.0575 x 10–2 kg of Glauber's salt is dissolved in water to obtain 1 dm 3 of a
solution of density 1077.2 kg m–3. Calculate the molarity, molality and mole
fraction of Na2SO4 in the solution.

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Prescribed Text
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Bahl, A., Bahl, B.S. and Tuli, G.D. (2009), Essentials of Physical Chemistry (A
Textbook for BSc Classes as per UGC Model Syllabus), Chand, S. &
Company Ltd., Ram Nagar, New Delhi, India.
Whitten, K.W., Davis, R.E., Peck, M.L. and Stanley, G.G.,(2010),
“Chemistry”, 9th Ed., Broook/Cole, Cengage Learning, Canada.

References Text
Chang, R. and Goldsby, K. A. (2012), "Chemistry", Eleventh Edition,
MacGraw-Hill Companies, Inc., USA.

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