Liquid State
In solid the constituent particles (atoms, ions or molecule) are closely
packed. Hence they possess rigidity and have a definite volume and
shape.
In gases, the particles are completely free to move. They have neither definite
shape nor volume. They fill up the vessel of any volume and also take
up the shape of that vessel.
In a liquid the particle are not fixed as in solid, and the same time, they have
some freedom of motion though they are not as free to move as in
gas. Thus liquid show behavior in between that of gas and that of
solid
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Like solid, liquid have a definite volume
where as unlike solids but like gases they do not have a definite shape.
They take up the shape of the vessel in which they are put.
The term isotropic is used to explain the properties of the matter
in basic crystallography.
A true liquid is isotropic, meaning that its properties (optical-
and other properties such as thermal and electrical conductivity) are
uniform in all directions— the result of its molecules being in constant
random motion.
This is expressed by saying that liquid state is isotropic and
intermediate between gaseous state and solid state.
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Intermolecular force
Depend on intermolecular distance
Solid-particles are much closed
Liquid- particles have small distance
Gas- intermolecular distance so large
The intermolecular distances suggest that the cohesive force (the
intermolecular attractive force acting between two adjacent portions of a
substance, particularly of a solid or liquid ) It is this force that holds a piece of
matter together.
Cohesive force and Adhesive force
The force of cohesion is defined as the force of attraction between
molecules of the same substance. Each water molecule forms hydrogen bonds
with neighbouring.
The force of adhesion is defined as the force of attraction between
different substances, such as glass and water. 3
Cohesive force in
Solid- very strong
Gas-very weak
Liquid- are in between i.e. they are fairly strong to keep them in the
condensed state but not strong enough to hold them in fixed positions.
In fact, all the characteristic properties of liquids such as a vapour
pressure, surface tension, viscosity etc arise
due to the nature of the cohesive force existing in the liquids.
These forces (cohesive force) are three types-
(1) Dipole- dipole attraction-
Occur among the polar molecules
Polar molecules have permanent dipoles
The positive pole of one molecule is thus attracted by negative pole of
other molecule. For example HCl 4
(2) Dipole- induced Dipole attraction-
The positive end of a polar molecule may attract the electron
cloud of non-polar molecule lying close to it. Thus non-polar molecule
become polar, for example iron peace is brought close to a magnate.
The attraction between polar molecule (permanent dipole) and
non-polar molecule (induced dipole).
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(3) Induced dipole- induced dipole attraction (London force or dispersive
forces)-
It is easy to conceive ion-ion attractions, ion-dipole attractions
and dipole-dipole attraction.
What intermolecular forces attract non-polar molecules to each
other in liquid and solid state?
These forces are thought to arise from motion of electrons. At any
instant time, the electron cloud of molecule may be distorted so that
momentary dipole is produced in which one part of molecule is slightly
more negative than the rest.
The momentary dipoles induce dipole in the neighbouring
molecules. They are attracted to each other exactly in the same way as
permanent dipoles.
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The force of attraction between the induced momentary dipoles
are called London forces (weakest intermolecular force)
Van der Waal’s forces is general term which imply that all types
of intermolecular forces
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Structure of liquid
How constituent particles are arranged within the liquid ?
1. Volume changes on fusion and vaporization- when a pure solid melts,
(some disorder has been introduced) the increases in volume is only
about 1%
which much smaller than increases in volume which takes place when
the liquid changes into vapour (large disorder has been introduced) at
the boiling point (volume changes about 100-1000 times).
2. Enthalpy of fusion and vaporization- Amount of heat required to melt
one mole of a pure solid at melting point (∆Hf) is found to be much
smaller than the amount of heat required to convert one mole of liquid
into vapour at boiling point (∆Hvap).
for example Ice, ∆Hf = 6.1 kJmol-1 and water (∆Hvap) = 40.7 kJmol-1
greater the amount of heat absorbed, greater is the disorder introduced.
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3. X-Ray diffraction study- X-Ray diffraction studies of crystalline solid
show that particles are arranged perfectly and extends upto the edge of
the crystal (long range order)
Solid (long range order)
Gas (No order)
Liquid (short range order)
Models of liquids state
In case of solid the cohesive force are very strong which keep
vibrational energy.
In case of liquid the cohesive force are sufficiently strong so that
they can exist in the condensed state but not strong enough to hold the
particles in the fixed position so that they have some translational energy.
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The two common theories about liquids
1) Vacancy or hole theory -proposed by Erring and Ree theory Liquid can
be considered to consist of “molecule” and “hole” randomly distributed
between them.
Random congregation/group of molecules and holes
Due to presence of holes, the neighbouring molecules can easily jump
into them and thus show “gas-like” behavior,
Those molecules which do not have a hole in the neighbourhood
cannot jump and hence show “solid-like” behavior.
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If Vl and Vs are the respective molar volumes of the liquid and the solid then
Number of Holes Vl Vs
Number of molecules Vs
Suppose mole fraction of molecules; xs and mole fraction of holes; xg
So probability that a holes confer gas−like properties.
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2) Free volume theory- according to this theory, it is believed that a
molecule in a liquid is surrounded by 10-12 neighboring molecules,
only a small distance away from the molecule. Thus surrounding
molecule thus form a cage or cell around the central molecule.
Thus the central molecule has to move only a small distance to
collide with any of the neighboring molecules.
Thus the centre of the caged molecule can move within the space
shown by the shaded area. The volume thus available to a molecule can
moves are called as free volume.
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