Liquid State

1. Introduction:
As you have studied in the previous class, liquids can be obtained from gases by cooling the latter
below their respective critical temperature followed by the treatment of high pressure. Effect of cooling
is to decrease the thermal energies of molecules and the effect of pressure is to decrease the volume of
the system so as to allow the molecules to come closer, thereby increasing the force of attraction amongst
them. Alternatively, liquids can be obtained by heating solids upto or beyond their melting points. Thus
we see the properties of liquids lie in between those of solids and gases. For example liquids are less
compressible than gases but a little more compressible than solids. They are less dense than solid but
more dense than gases. The two important properties of liquids, namely, the fixed volume but no fixed
shape arises mainly because of the following two facts
(I).The energies binding the molecules are larger than their average thermal energy.
(II).Their binding energies are not strong enough to stop the motion of the molecules altogether, as in
the case of solids, with the result that molecules can move from one place to another but cannot escape
from the liquid unless they are present at the surface.

1.1 INTERMOLECULAR FORCES

Since the molecules in a liquid are not far apart from each other, the intermolecular forces are fairly
strong. The characteristic properties of liquid arise from the nature and the magnitude of these
intermolecular forces.
Intermolecular forces in liquids are collectively called von der Waal’s forces. These forces are
essentially electrical in nature and result from the attraction of charges of opposite sign. The principle
kinds of intermolecular forces are:

(a)Dipole-dipole interaction
(b)London forces
(c )Hydrogen bonding.

Dipole-dipole interaction:
We have seen that HCl is an example of a polar molecule. Such molecule have a partial positive charge
at one end and a partial negative charge at the other.

Fig 1 Weak attraction between polar HCl molecules

They are called dipoles. The positive end of one dipole attracts the negative end of the other.
The thermal energy of molecules tends to disturb these attractions but still there exists a net
attraction between the polar molecules. These forces are referred to as dipole-dipole attractions.
Generally such attractions are about 1% as strong as covalent bond. It is to be noted that the
attractions between the opposite poles are greater than repulsive forces between like poles.
Thus these molecules have a net attraction to each other.

London forces
In 1930 Fritz London first offered a simple explanation of weak forces between nonpolar
molecules or atoms. In a molecule (or atom) electrons are constantly moving. Most of the time
electrons in the molecules could not be visualized as distributed symmetrically. However
according to the principle of probability, for an instant the electrons may concentrate on one
side of the molecule than the other. This causes the molecule (A) to become momentarily polar
and we call it instant dipole.

Fig 2. Explanation of London forces

The negative side of the instantaneous dipole repels the electrons of an adjacent
molecule (B). As a result the second molecule B also becomes a dipole by induced polarity.
This is called induced dipole Fig 2.
The instantaneous dipole A and the induced dipole B will now attract each other.
Because the electrons keep moving an instant dipole may vanish the next moment and new are
produced. This continual process produces a weak overall attraction between molecules of
liquid.
The momentary attraction between the molecules of liquid caused by
instantaneous-dipole and induced- dipole attractions are called London forces. These
London forces are present in polar molecules also in addition to other von der Waal’s forces.
The strength of the London forces depends as to how easily the electron cloud in a
particular molecule is deformed. This is determined by the number of electrons and also on the
size of the molecule. Thus Argon (-245.90C) with a greater number of electron and larger
molecular weight has a higher boiling point than helium (-268.90C).

Hydrogen bonding
In compounds of hydrogen with strongly electronegative elements, such as
fluorine, oxygen and nitrogen, the electron pair shared between the two atoms lies far
away from the hydrogen atom as a result of which the hydrogen atom becomes highly
electropositive with respect to other atom which become electronegative. This
phenomenon of charge separation in water is represented as shown in the fig 3. The
electronegativity difference in H and O is so large that the electron pair in the covalent
bond, H-O is shifted toward O. It leaves a partial positive charge on the H atom. This
leads to a strong electrostatic attraction between positively charged H atom and an
unshared electron pair on the O atom of another molecule. Thus you can understand
that two or more molecules may associate together to form large cluster of molecule.
This is shown below for the association of several molecules of hydrogen fluoride.

...H+δ –F-δ .....H+δ –F-δ ......H+δ –F-δ .....

Fig 3. Hydrogen bond

In this case, while the length of covalent bond between H and F atoms is
found to be 1.00A0, the length of the hydrogen bond between H and F atoms of
neighbouring molecules has been found to be 1.55A0. this cluster of HF molecules
may be describedas (HF)n
The attractive force which binds hydrogen atom of one molecule with
electronegative atom of another molecule, generally of the same substance is
known as the hydrogen bond.
The hydrogen bonding is the strongest of all intermolecular forces including the
dipole-dipole attractions and London forces.
In the above discussion you have seen that cluster of HF molecule is
describedas (HF)n and cluster of water molecule may be described as (H2O)n
Alcohols and carboxylic acids also form associated molecules for the same
reason, as shown below

Alcohohols Carboxylic Acids

1.2. CHARACTERISTIC PROPERTIES OF LIQUIDS

As you have studied earlier in this unit that the properties of liquids arise from
(i) The nature and
(ii) The magnitude of intermolecular forces of attraction existing
between theirmolecules. The important properties of liquids are
1. Vapour pressure
2. Surface tension
3. Viscosity
4. Refraction
Now you will study these properties in detail
Vapour pressure
When a liquid is an open vessel, it evaporates. You have studied in the gases unit,
that the gas molecules have a particular velocity. This is so in case of liquids also. Only a few
liquid molecules have lower or higher velocity, i.e. lower or higher kinetic energies. The
energy distribution of molecules in a liquid is shown in Fig 4.

Fig 4. Energy distribution of molecules of a liquid

It is clear from the Fig 4. that the number of molecules with high kinetic energies, as
shown by the shaded portion ABCD of the dotted curve is very small. This number, however,
increases with rise in temperature, as shown by the shaded portion FBCE ofthe bold line
curve.
When a liquid is placed in an open vessel it evaporates. The molecules in the liquid
are moving with different kinetic energies. The molecules that possess above average kinetic
energies can overcome the intermolecular forces that hold them in the liquid. These energies
molecules escape from the surface as vapour. This process by which molecules of a liquid
goes into gaseous state is called vaporisation or evaporation. The reverse process whereby
gas molecules become liquid is called condensation.
 When a liquid is place in a closed vessel, the molecules with high kinetic energies
escape into space above the liquid as shown in fig 4.5. as the number ofmolecule in the gas
phase increases, some of them strike the liquid surface and are recaptured (condensation).

Fig 4.1 Illustration of vapour pressure

A stage comes when the number of molecules escaping from the liquid is equal to the number
of molecules returning to the liquid. Thus a dynamic equilibrium is established between the
liquid and the vapour at a given temperature.
Liquid ⇄ vapour
Now the concentration of the vapour in the space above the liquid will remain
unchanged with lapse of time. Hence the vapour will exert a definite pressure at the
equilibrium. Hence vapour pressure of a liquid defined as:
The pressure exerted by the vapour in equilibrium with the liquid at a fixed temperature
is the vapour pressure of the liquid.
As the temperature rises, the number of molecules escaping from the liquid surface
increases as there in increase in the number of vapour molecules in the space above the liquid
when equilibrium is attained.
Hence vapour pressure of the liquid increases with increase of temperature.