States of matter

Binding forces between molecules:

In order for molecules to exist in aggregates in gases, liquids, and solids,
intermolecular forces must exist.

Cohesion and adhesion are manifestations of intermolecular forces.

Importance of intermolecular forces:

Knowledge of these forces is important for an understanding of;

1. Properties of gases, liquids and solids,

2. Interfacial phenomena,
3. Flocculation of suspension,
4. Stabilization of emulsions,
5. Compaction of powders in capsules, and
6. The compression of granules to form tablets.

Repulsive and attractive forces:

When molecules interact, both repulsive and attractive forces operate.

 As two molecules are brought close

together, opposite charges in the two
molecules are closer than the like
charges and cause the molecules to
attract one another.
 When the molecules are brought so
close that the outer charge clouds
touch, the molecules repel each other
like rigid elastic bodies.

N.B.

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  Attractive forces are necessary in order that molecules cohere.
 Repulsive forces are necessary in order that molecules do not interpenetrate
and annihilate one another.

Types of attractive intermolecular forces:

1) Van der Waals forces
A. Dipolar molecules frequently tend to align themselves with their neighbors,
so that the negative pole of one molecule points toward the positive pole of
the next. Thus, large groups of the molecules may be associated through
weak attractions known as dipole-dipole forces, Keesom forces or the
orientation effect.
B. Permanent dipoles are capable of inducing an electric dipole in non-polar
molecule in order to produce dipole-induced dipole interactions, Debye
forces or induction effect.
C. Non-polar molecules can induce polarity in one another by induced dipole-
induced dipole interactions, London forces or dispersion effect. This force is
responsible for attraction between non-polar molecules as hydrogen gas,
carbon tetrachloride and benzene.

2) Ion-dipole and ion-induced dipole forces

These forces occur between ions and polar or non-polar molecules.

A. Ion-dipole forces are responsible for the solubility of ionic crystalline

substances in water. The cation is attracted to the negative oxygen and the
anion is attracted to the hydrogen atom of the dipolar water molecules.
B. Ion-induced dipole forces are involved in the formation of the iodide

complex, I2 + KI− ⇌ KI3−

This reaction accounts for the solubility of iodine in a solution of potassium iodide.

3) Hydrogen bonds

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These bonds result from the interaction between a molecule containing a
hydrogen atom and strongly electronegative atom such as fluorine, oxygen or
nitrogen.

Because of the small size of hydrogen atom and its large electrostatic field, it can
move in close to the electronegative atom and form electrostatic type of attraction
known as hydrogen bond or Hydrogen Bridge.

Hydrogen bond exists in ice and in liquid water and is accounting for;

Its high boiling point,

High dielectric constant and
Low vapor pressure.

Hydrogen bond also exists between some alcohol molecules, carboxylic acids,
aldehydes, ketones, amines and polypeptides.

Hydrogen bonds of formic acid and acetic acid are sufficiently strong to yield
dimmers (two molecules attached together), which can exist even in the vapor
state.

Hydrogen fluoride in the vapor state exists as a hydrogen-bonded polymer.

Bond energies:

They serve as a measure of the strength of bond.

Types of bond Bond energies (Kcal/mole)

Hydrogen bond 2-8
Covalent bond 50-100
Ionic bond > 100

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 States of Matter

Gases, liquids and crystalline solids are the three states of matter. The molecules,
atoms, and ions in the solid state are held in close by intermolecular, interatomic,
or ionic forces.

 The particles of the solid can oscillate only about fixed positions.
 As the temperature of a solid substance is raised, the particles acquire
sufficient energy to disrupt the ordered arrangement of the lattice and pass
into the liquid form.
 Finally, when sufficient energy is supplied, the molecules pass into the
gaseous state.

Solids with high vapor pressure, such as iodine and camphor, can pass directly
from the solid to the gaseous state without melting (sublimation). The reverse
process, which is the recondensation to the solid state, is referred as deposition.

Certain asymmetric molecules frequently exhibit a forth phase, known as

mesophase (liquid crystalline state), which lies between the liquid and crystalline
states.

M. Sh.

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 A.The gaseous state
 Gas molecules travel in random paths frequently colliding with one another
and with the walls of the container in which they are confined.
 They exert a pressure, "a force per unit area”, expressed in dynes per cm².
 The volume of gas is usually expressed in liters or cubic centimeters.
 The temperature involved in gas equations is given in absolute or Kelvin
degrees (K°). “Zero degree on the centigrade scale is equal to 273.15 K°”

(Boyle’s law) this law relates

the volume and pressure of
a given mass of gas at
constant temperature.

PαV PV = K

(Gay-Lussac and Charles’s law) another law states that

“the volume and absolute temperature of a given mass
of gas are directly proportional at constant pressure”.

VαT V = KT

These equations can be combined to obtain the relationship

P1V1 / T1 = P2V2 / T2

The ratio P V / T is constant for all gases and can be expressed mathematically as;

P V / T = R or P V = R T

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In which R is the constant value for the P V / T ratio of an ideal gas. This equation
is correct only for 1 mole (i.e. 1 gram molecular weight) of gas; for n moles it
becomes:

P V=nRT

This equation is known as the General ideal gas law.

The molar gas constant (R) is highly important in physical chemical science.

Determination of the numeric value of gas constant R

If 1mole of an ideal gas is chosen; its volume under standard conditions of

temperature and pressure (STP), i.e. at 0 °C and 760 mmHg, has been found to be
22.414 liters.

Substituting this value in the equation, we obtain

P x V = n xRx T

1 atm x 22.414 liters = 1 mole x R x 273.16 °K

R = 0.08205 liter atm / mole deg.

Determination of the molecular weight by using ideal gas law

The approximate molecular weight of a gas can be determined by use of the ideal
gas law

The number of moles of gas n is replaced by its equivalent g/M, in which g is the
grams of gas and M is the molecular weight.

PV = (g/M) RT

M = g RT / PV

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The kinetic molecular theory of gases

1. The gases are composed of particles called molecules, the total volume of
these molecules is so small that it can be neglected compared to the space
in which the molecules are confined (this conditions occurs only at low
pressure and high temperature, molecules are far from each other)
2. The particles of the gas do not attract one another but moves with
complete independence (at low pressure).
3. The particles exhibit continuous random motion owing to their kinetic
energy. The average kinetic energy is directly proportional to the absolute
temperature of the gas or E = 3/2 RT.
4. The molecules exhibit perfect elasticity, (no loss of speed after they collide
with one another and with the wall of the confining vessel).
PV = 1/3 nmc²
P is the pressure and V the volume occupied by any number of n of
molecules of mass m having an average velocity c (usually written as µ).

B.The Liquid State

Liquefaction of gas

 When a gas is cooled, it loses some of its kinetic energy in the form of heat,
and velocity of the molecules decreases.
 If pressure is applied to the gas, the molecules are brought with the effect of
the Van der Waals interaction forces and pass into the liquid state.
 Because of these forces, liquids are considerably denser than gases and
occupy a definite volume.
 The transitions from a gas to a liquid and from a liquid to a solid depend not
only on the temperature, but also on the pressure to which the substance is
subjected.

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Important definitions

Critical temperature: it is the temp above which it is impossible to liquefy a gas

irrespective of the pressure applied.

Critical pressure: it is the pressure required to liquefy gas at its critical

temperatures.

The critical temperature of water is 374°C and its critical pressure is 218 atm. The
highest critical value of water comes from:

1) Strong dipolar forces, and

2) Hydrogen bonds.
The critical temperature serves as a rough measure of the attractive forces
between molecules.

Methods of achieving liquefaction

A. Liquefaction by adiabatic expansion method.

The gas is allowed to expand in a vacuum insulated flask (Dewar flask). As a result,
the temperature of gas falls. If these procedures are repeated, the total drop in
the temperature may be sufficient to cause liquefaction.

B. Liquefaction by joule-Thomson effect.

By allowing the expansion of pre-cooled, highly compressed gas into a region of

low pressure. The drop on temperature leads to liquefaction of gas.

Difference between vapor and gas

Vapor: is a substance that was liquid or solid at room temperature and passes into
the gaseous state when heated to a sufficiently high temperature, such as,
menthol and ethanol which are vapor at sufficiently high temperature.

Gas: is a substance that exists in the gaseous state even at room temperature,
such as oxygen and carbon dioxide.

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Vapor pressure of liquids
 When a liquid is placed in an evacuated container at a constant temperature
the molecules the highest energies break away from the surface of the liquid
and pass into the gaseous state and some of the molecules subsequently
return to the liquid state or condense.
 When the rate of condensation equals the rate of vaporization at a definite
temperature the vapor becomes saturated and a dynamic equilibrium is
established, the pressure of the saturated vapor above the liquid is then
known as the equilibrium vapor pressure.
 As the temperature of the liquid is elevated more molecules approach the
velocity necessary for escape and pass into the gaseous state. As a result, the
vapor pressure increases with rising temperature.

The figure shows that any point on

the curve represents a condition in
which the liquid and vapor exist
together in equilibrium.

If the temperature of any liquids is

increased while the pressure is held constant or if the pressure is decreased while
the temperature is held constant, all the liquid is passed into vapor state

 The vapor pressure serves as a measure of the attractive forces between

molecules.

The relation between the vapor pressure and absolute temperature of a liquid is
expressed by the Clausius-Clapeyron equation:

P 2 Δ H (T 2−T 1)
LOG =
P 1 2.303 RT 1T 2

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Where;

 P1 and P2 are the vapor pressures at absolute temperatures T1 and T2.

 ∆ H the molar heat of vaporization

Heat of vaporization: It is heat absorbed by 1 mole of liquid when it passes into

the vapor state.

Boiling point
It is the temperature at which the vapor pressure of the liquid equals the external
or atmospheric pressure

If a liquid is placed in an open container and heated until the vapor pressure
equals the atmospheric pressure, the vapor is seen to form bubbles that rise
rapidly through the liquid and escape into the gaseous state.

All the absorbed heat is used to change the liquid to vapor, and the temperature
does not rise until the liquid is completely vaporized.

Heat of vaporization

It is the heat that is absorbed when water vaporizes at the normal boiling point.

Water, at 100 °C, has heat of vaporization 539 cal/g (9720cal/mole).

Benzene, at 80.2 °C, has heat of vaporization 91.4 cal/g

Relation of boiling point to pressure

The pressure at sea level is about 760 mm Hg; at higher elevations, the
atmospheric pressure decreases and the boiling point is lowered. At a pressure of
700 mm Hg water boils at 97.7 °C; at 17.5 mm Hg, it boils at 20 °C. The Change in
boiling point can be calculated by Clausius-Clapeyron equation.

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Relation of boiling point to chemical structure and attractive forces between
molecules

The boiling point may be considered as the temperature at which thermal

agitation can overcome the attractive forces between the molecules of a liquid

Therefore, the boiling point, vapor pressure and heat of vaporization provide an
indication of the magnitude of the attractive forces.

 The B.P. of normal hydrocarbon, simple alcohol and carboxylic acid increase
with increasing the molecular weight because attractive Vander Waals forces
become greater with increasing number of atoms.
 Branching of the hydrocarbon chain produce less compact molecules with
reduced attraction and decrease in B.P occurs.
 Alcohols boil a higher temp than saturated hydrocarbon of the same M.wt.
because of association of school molecules through hydrogen bond.
 The B.P of carboxylic acids is abnormal because the acids form a dimer
through hydrogen bonding which may remain even in the vapor state.
 The B.P. of straight chain primary alcohol and carboxylic acids increase about
18°C for each additional methylene group.
 Non-polar substances which attract together by London force have low B.P
and low heat of vaporization.
 Polar molecules (such as, ethyl alcohol, water) attracted together through
hydrogen bond, have high boiling point and high heat of vaporization.

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