CHEM 255

States of Matter II and Chemical Kinetics

II
Intermolecular forces
Content:
1. Kinetic Molecular Theory 5. Viscosity
2. Intermolecular forces 6. Refractive index
3. Boiling point 7. Optical activity
4. Vapour pressure
5. Surface tension

Dr. Michael Baah Mensah

Department of Chemistry, Faculty of Physical and Computational Sciences, College
of Science, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
 Kinetic Molecular Theory (KMT)
• KMT explains the behavior of gases in terms of the constant random motion
of gas molecules

• The major difference between the states of matter is the distance between
molecules 2
 Kinetic Molecular Theory (KMT)
• Lack of strong forces between gas molecules allows them to expand to fill the
volume of their container

• Liquid also has a definite volume, because molecules in a liquid do not break away
easily from attractive forces

• Solid molecules are held rigidly in position with virtually no freedom of motion.
Solid molecules are arranged in regular configurations in three dimensions

• The density of the solid form of a substance is higher than that of the liquid form,
however, with very few exceptions

3
 Intermolecular forces
• Intermolecular forces are attractive forces between molecules
• They are responsible for the nonideal behavior of gases and more
pronounced in liquids and solids

Condensation:
As the temperature of a gas drops, the average kinetic
energy of its molecules decreases. Eventually, at a
sufficient temperature, the molecules no longer have
enough energy to break away from the attraction of
neighboring molecules. At this point, the molecules
aggregate to form small drops of liquid. This transition
from the gaseous to the liquid phase is known as
condensation

4
 Intermolecular forces
• Intermolecular forces stabilize individual molecule, and intramolecular forces hold atoms
together in a molecule

• Intermolecular forces are primarily responsible for the bulk properties of matter (eg. melting
point, boiling point, surface tension, vapour pressure, viscosity)

• Generally, intermolecular forces are much weaker than intramolecular forces

It usually requires much less energy to evaporate a liquid than to break the bonds in the molecules of the
liquid. For example, it takes about 41 kJ of energy to vaporize 1 mole of water at its boiling point; but about
930 kJ of energy are necessary to break the two O-H bonds in 1 mole of water molecules
5
Types of intermolecular forces

Ion-dipole forces Dipole-dipole Hydrogen

NB: Not classified as van
der Waals force forces bonding

van der Waals Dipole-induced

forces dipole forces
Named after
Dutch physicist Dispersion
Johannes van der
Waals forces
6
 Ion-dipole forces
• Ion-dipole forces exist between an ion (a cation or an anion) and a polar molecule

• The strength of ion-dipole forces depends on the (i) charge and size of the ion and on the (ii)
magnitude of the dipole moment and size of the molecule
The charges on cations are generally more
concentrated because cations are usually smaller
than anions. Therefore, a cation interacts more
strongly with dipoles than does with an anion
having a charge of the same magnitude

• Hydration is one example of ion-dipole interaction

Hydration
7
 Dipole-dipole forces
• Dipole-dipole forces are attractive forces between polar molecules, that is, between molecules
that possess permanent dipole moments (and unsymmetrical)
HCl is unsymmetrical due the
electronegativity difference
between H and Cl

• Dipoles are electrostatic, and they can be understood in terms of the Coulomb’s law

• The larger the dipole moment, the greater the attractive force

• In liquids, polar molecules are not held as rigidly as in a solid, but they tend to align in a way
that, on average, maximizes the attractive interaction
Molecules that have a permanent
dipole moment tend to align with
opposite polarities in the solid phase
for maximum attractive interaction 8
 Hydrogen bonding
• Hydrogen bond, which is a special type of dipole-dipole interaction between the
hydrogen atom in a polar bond, such as N–H, O–H, or F–H, and an
electronegative O, N, or F atom.

• Note that the O, N, and F atoms all possess at least one lone pair that can interact
with the hydrogen atom in hydrogen bonding
9
 Hydrogen bonding
• The average strength of a hydrogen bond is
quite large for a dipole-dipole interaction (up
to 40 kJ/mol). Thus, hydrogen bonds have a
powerful effect on the structures and
properties of many compounds

• For example, Hydrogen bonding is responsible

for the expansion of water when it freezes
The water molecules in the solid state have
tetrahedral arrangement for the two lone pairs
• The strength of a hydrogen bond is determined and two single bonds radiating out from the
by the coulombic interaction between the oxygen. The lone pairs on the “O” atom can be
lone-pair electrons of the electronegative attracted to nearby water molecules through
atom and the hydrogen nucleus hydrogen bonds and a cage like structure results

10
 Induced dipole
• If an ion or a polar molecule is placed near a nonpolar molecule (or an atom),
the electron distribution of the nonpolar molecule (or atom) is distorted due to
the attractive force exerted by the ion or polar molecule, resulting in the
formation of a kind of dipole

• The formed dipole in the nonpolar molecule (or atom) is said to be an induced
dipole because the separation of positive and negative charges in the nonpolar
molecule (or atom) is due to the proximity of an ion or a polar molecule 11
 Dipole-induced dipole forces
• The attractive interaction between an ion and the induced dipole is
called ion-induced dipole interaction

• The attractive interaction between a polar molecule and the induced

dipole is called dipole-induced dipole interaction

• The likelihood of an induced dipole depends on:

• Charge on the ion
• Strength of the dipole
• Polarizability of the atom or molecule
12
 Dispersion forces
• London dispersion force is a temporary attractive
force that results when the electrons in two adjacent
atoms or molecules occupy positions that make the
atoms form temporary dipoles (a short-lived charge
imbalance).
• This force is an induced dipole-induced dipole force
or attraction.
• Because of the constant motion of the electrons, an
atom or molecule can develop a temporary
(instantaneous) dipole when its electrons are
distributed unsymmetrically about the nucleus
• Dispersion forces depends on the proximity of
molecules (or how close) the molecules

13
 Dispersion forces
• Dispersion forces causes nonpolar substances to condense to liquids
and freeze into solids when the temperature is lowered sufficiently.
• Lower temperature suggests that the molecules have less kinetic energies and
they are closer to themselves due to the attractive forces

• Dispersion forces are present between any two molecules (even

polar molecules) when they are almost touching
• Dispersion forces are present between all molecules, whether they
are polar or nonpolar

14
Dispersion forces and molecular
size
• A quantum mechanical interpretation of temporary (instantaneous)
dipoles was provided by Fritz London in 1930.

• Dispersion forces are also called London dispersion forces

• London showed that the magnitude of this attractive interaction is

directly proportional to the polarizability of the atom or molecule

• The ease with which the electron distribution around an atom or

molecule can be distorted is called polarizability
15
Dispersion forces and molecular
size
• Larger and heavier atoms and molecules exhibit stronger dispersion
forces than smaller and lighter ones
• In a larger atom or molecule, the valence electrons are, on average, farther
from the nuclei than in a smaller atom or molecule. They are less tightly held
and can more easily form temporary dipoles

• London dispersion forces tend to be:

o stronger between molecules that are easily polarized (larger and heavier
atoms and molecules)
o weaker between molecules that are not easily polarized (smaller and lighter
atoms and molecules)
16
Energies of intermolecular
forces

17
Example: Please try

18
 Assignment 1
1. Explain why ice (solid water) floats on liquid water
2. Draw a table showing the differences between gas, liquid, and solid
3. Explain why the boiling point of HF is lower than that of water
4. Explain why neopentane (C5H12) is a gas whereas n-pentane (C5H12)
is a liquid, both at room temperature.

19
Intermolecular forces and bulk
properties of matter

20
 Boiling Point
• The boiling points of substances often reflect the strength
of the intermolecular forces operating among the
molecules
• At the boiling point, enough energy must be supplied to
overcome the attractive forces among molecules before
they can enter the vapor phase
• If it takes more energy to separate molecules of substance
A than of substance B, because A molecules are held
together by stronger intermolecular forces, then the
boiling point of A is higher than that of B
• The same principle applies also to the melting points of
the substances. In general, the melting points of
substances increase with the strength of the
intermolecular forces 21
 Effect of hydrogen bonding on
boiling point
• We expect the boiling point to
increase as we move down a
group,
• However, we see that three
compounds (NH3, H2O, and HF)
behave differently
• Hydrogen bonding is responsible
for the anomaly: high boiling
point of NH3, H2O, and HF
Boiling points of the hydrogen compounds of Groups 4A,
5A, 6A, and 7A elements.
22
 Vapour pressure
• 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 energetic
molecules escape from the liquid surface as
vapour.
• The process by which molecules of a liquid go into
|||||||||||||||||||
the gaseous state (vapours) is called Vaporization
or Evaporation. The reverse process whereby gas
Heating molecules become liquid molecules is called
Condensation.
23
 Vapour pressure
• If the liquid is placed in a closed vessel, the
molecules with high kinetic energies escape into
space above the liquid
• As the number of molecules in the gas phase
increases, some of them strike the liquid surface and
are recaptured (condensation).
• A stage comes when the number of molecules
escaping from the liquid is equal to the number of
molecules returning to the liquid. In other words,
the rate of evaporation exactly equals the rate of
condensation.
||||||||||||||||||| • Thus, a dynamic equilibrium is established between
the liquid and the vapour at the given temperature.
Heating 24
 Vapour pressure
• 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.
The vapour pressure of a liquid is defined as the pressure exerted by
the vapour in equilibrium with the liquid at a fixed temperature
• The vapour pressures of various liquids differ considerably, depending
upon the identity of the liquid with its particular intermolecular forces
For example, ethanol having weaker hydrogen bonding than water, evaporates faster
than water. Hence, we expect that ethanol (350 torr at 60 oC) will have higher vapour
pressure than water (150 torr at 60 oC) at the given temperature

25
 Effect of temperature on vapour
pressure
• If the temperature of the liquid is increased, the vapour pressure will
increase
This is so because at higher temperature more
molecules in the liquid will have larger kinetic energy
and will break away from the liquid surface. Therefore,
the concentration of vapour molecules will increase
before the equilibrium is re-established. Also, at higher
temperature, the average kinetic energy of the vapour
molecules will increase. Both vapour concentration
and kinetic energy are proportional to temperature.
Therefore, any increase of temperature will result in
the increase of vapour pressure.

26
 Determination of vapour
pressure
• The vapour pressure of a given liquid can be measured by either
Static method or Dynamic method
• Static method
A sufficient amount of the liquid whose vapour pressure is to
be determined is placed in the bulb connected to a mercury
manometer and a vacuum pump. All the air from the bulb is
removed by working the vacuum pump and the stopcock
closed. A part of the liquid evaporates. The system is then
maintained at a fixed temperature for enough time so that
the equilibrium is established. The difference in the levels of
mercury in the manometer is equal to the vapour pressure
of the liquid. By adjusting the thermostat at a different
temperature, the vapour pressure of the liquid at another
temperature can be determined. This method is used for
liquids having vapour pressures up to 1 atm
Determination of vapour pressure by 27
static method
 Determination of vapour
pressure
An inert gas is passed through the given liquid
• Dynamic Method at a constant temperature (T). The gas
saturated with the vapour of the liquid leaves
the flask at the exit tube. If V be the volume
of the gas passed and m the loss in weight of
the liquid, the vapour pressure is given by

where M = molecular weight of the liquid and

R = gas constant. This method is particularly
suited for liquids of very low vapour pressure
Determination of vapour pressure by
dynamic method 28
 Effect of vapour pressure on
•
boiling point
When a liquid is heated, tiny bubbles are formed in
it. These rise to the liquid surface and burst. The
temperature at which it happens is the boiling point
of the liquid.
• Consider an individual bubble: the liquid vaporizes
into it and the vapour pressure in the bubble keeps it
in form. However, the pressure of the atmosphere
exerted on the liquid top tends to collapse the
bubble. As the bubble goes to the surface, the
vapour pressure in the bubble equals the
atmospheric pressure. Thus the bubble collapses.
• The boiling point of the liquid may, therefore, be
defined as the temperature at which the vapour
pressure of the liquid is equal to the atmospheric
pressure. |||||||||||

• A liquid boils when the pressure of the vapour within the bubble equals the atmospheric
Heating
pressure exerted on the bubble at the liquid surface. 29
 Effect of vapour pressure on
boiling point
• Because the atmospheric pressure varies with altitude and
other conditions, the boiling points are reported at 760 torr (1
atm).
• Therefore, the normal boiling point of a liquid is the
temperature at which the vapour pressure of the liquid is 760
torr or 1 atm.
• The boiling point of a liquid can be lowered by reducing the
external pressure by using a vacuum pump. Then the vapour
pressure of the liquid is equal to the external pressure at a
lower temperature.
• The boiling point of a liquid can be increased by raising the Explain the principle of a
external pressure. Thus the vapour pressure of the liquid is domestic pressure cooker
equal to the external pressure at a higher temperature.
30
 Surface tension
• Surface tension arises from the intermolecular
forces of attraction in liquids
• A molecule in the interior of a liquid is
attracted equally in all directions by the
molecules around it
• A molecule in the surface of a liquid is
attracted only sideways and toward the
interior
• The forces on the sides being counterbalanced
the surface molecule is pulled only inward the
Surface tension is caused by liquid
the net
inward pull on the surface • Thus, there is a tendency on the part of the
molecules surface molecules to go into the bulk of the
liquid
31
 Surface tension
• The liquid surface is, therefore,
under tension and tends to
contract to the smallest possible
area in order to have the
minimum number of molecules at
the surface.
• It is for this reason that in air, The inward forces on the
surface molecules
drops of a liquid assume spherical minimize the surface
shapes because for a given area and form a drop

volume a sphere has the The surface tension (γ) of a liquid is defined as
minimum surface area the force (in dynes) acting at right angles to
the surface along 1 cm length of the surface
32
Units of surface tension
• In CGS system, the unit of surface tension is dyne per centimeter
(dyne cm–1)

• In SI system, the unit of surface tension is Newton per meter (Nm–1)

• Note that:
1 dyne cm–1 = 1 m Nm–1

33
Effect of temperature on surface
tension
• A change in temperature causes a change in surface tension of a liquid
• When temperature increases, there is an increase in kinetic energy of liquid
molecules (KE ∝ T), thereby decreasing intermolecular forces.
• It results in a decrease in the inward pull acting on the surface of the liquid.
In other words, surface tension decreases with an increase in temperature.
• Relationship between surface tension and temperature (by W. Ramsay and J.
Shields, 1893)

• where k is a constant (temperature coefficient), tc is the critical temperature

and t is any other temperature, represents molar surface energy of the
liquid.
34
Effect of temperature on surface
tension

35
 Determination of surface
tension
• Capillary-rise Method
• A capillary tube of radius r is vertically
inserted into a liquid. The liquid rises to
a height h and forms a concave
meniscus.
• The surface tension (γ) acting along the
inner circumference of the tube exactly
supports the weight of the liquid in the
column.
• By definition, surface tension is force
per 1 cm acting at a tangent to the
meniscus surface. If the angle between
(a) Rise of liquid in a capillary tube; (b ) Surface the tangent and the tube wall is θ, the

is 𝛾Cos𝜃
tension () acts along tangent to meniscus and its vertical component of surface tension
vertical component is Cos ; (c) Upward force 2rCos
36
counterbalances the downward force due to weight
Determination of surface
tension
• The total surface tension along the circular contact line of meniscus is 2πr times 𝛾Cos 𝜃:

• where r is the radius of the capillary. For most liquids, θ is essentially zero, and cos θ = 1. Then the

• The downward force on the liquid column is due to its weight which is mass × gravity (g).
Thus,

• Where is the density of the liquid, 𝒉𝝆𝒈 is pressure exerted by a liquid in a tube
• But Upward force = Downward force, thus

• In order to know the value of γ, the value of h is found with the help of a travelling
microscope (in mm) and density with a pycnometer
37
38
-3

39
 Determination of surface
tension A drop of liquid is allowed to form at the lower end
• Drop Formation Method of a capillary tube. The drop is supported by the
upward force of surface tension acting at the outer
circumference of the tube. The weight of the drop
(mg) pulls it downward. When the two forces are
balanced, the drop breaks. Thus, at the point of
breaking,

Where
m = mass of the drop
g = acceleration due to gravity
r = outer radius

Stalagmome A drop forming from a tube of The apparatus employed in the drop formation
ter radius r method is called Stalagmometer or Drop pipette
40
Determination of surface
tension
• The stalagmometer is cleaned, dried and filled with the experimental liquid, up to
mark A. Then the surface tension is determined by one of the two methods given
below:
a) Drop-weight Method: About 20 drops of the given liquid are received from the
stalagmometer or drop-pipette in a weighing bottle and weighed. Thus, weight of
one drop is found. The drop-pipette is again cleaned and dried. It is filled with a
second reference liquid (say water) and weight of one drop is determined as before.
…………………..(1)
………………….(2)
Dividing eqn. (1) by (2), we obtain

• Knowing the surface tension of the reference liquid from Tables, that of the liquid
under study can be found.
41
Determination of surface
tension
b) Drop-number Method: The drop-pipette is filled up to the mark A with the
experimental liquid. The number of drops is counted as the meniscus travels from
A to B. Similarly, the pipette is filled with the reference liquid as the meniscus
passes from A to B. Let n1 and n2 be the number of drops produced by the same
volume V of the two liquids.
Thus

Thus, we can write that

• The value of is determined with a pycnometer or density bottle. Knowing and

from reference tables, can be calculated. 42
43
Determination of surface
tension
• Ring-detachment Method

du Nouy ring du Nouy

with Tensiometer 44
a suspending
• In this method the force required to
• One end of the torsion wire is fixed while the
detach a platinum ring (du Nouy
ring) from the liquid surface is other is attached to a knob carrying a pointer.
measured. • The pointer moves on a fixed scale. The scale
• This force (F) is exactly equal to the is previously calibrated by taking different
downward pull due to surface weights on the beam and noting the scale
tension γ acting along the reading when it is lifted from the horizontal
circumference of the ring. position.
• Twice the length of the • The liquid whose surface tension is to be
circumference (2 × 2πr) is taken since determined is placed in a watch glass so that
the liquid is in contact with both the the Pt ring just touches its surface. The knob
inside and the outside of ring. Thus, of the torsion wire is then slowly turned till
the ring is just detached from the surface.
• Where r is the radius of the ring • The reading shown by the pointer on the scale
gives the force F. The surface tension is then
• The apparatus employed is called the
calculated from the equation.
du Nouy Tensiometer
45
Determination of surface
tension
• Maximum Bubble Pressure Method • In this method air-pressure is
applied slowly through a capillary
tube dipping in the experimental
liquid.
• A bubble is formed at the end of the
capillary.
• Slowly the bubble grows and
becomes hemispherical. Then it
breaks away when the pressure
recorded by the manometer is
noted. This is the maximum
A simple apparatus for maximum bubble pressure pressure required to make a bubble
method at the end of the capillary.
46
 Determination of surface
tension
• At the moment of breaking, the forces due to
maximum pressure P equals that of the opposing
hydrostatic pressure Ph and the surface tension γ
at the circumference of the capillary. Thus,

Applied pressure on • where r = radius of capillary; = density of the

• Knowing the value of P, h, 𝜌 and r, γ can be found

bubble is liquid; h = depth of liquid.
opposed by hydrostatic
pressure and surface
tension
47
Viscosity

Flow of a liquid on a glass

surface
• A liquid may be considered to be consisting of molecular layers arranged one over
the other.
• When a shearing force is applied to a liquid, it flows. However, the forces of
friction between the layers offer resistance to this flow.
• Viscosity of a liquid is a measure of its frictional resistance
48
 Viscosity
• Considering a liquid flowing on a glass surface
(shown on previous slide). The molecular layer in
contact with the stationary surface has zero
velocity. The successive layers above it move with Two parallel layers moving in
increasingly higher velocities in the direction of the a liquid
flow.
• Consider two adjacent moving layers of a liquid.
Let these be separated by a distance dx and have a
velocity difference dv.
• The force of friction (F) resisting the relative
motion of the two layers is directly proportional
to the area A and the velocity difference dv, while is the proportionality
it is inversely proportional to the distance constant or Coefficient of
between the layers. Viscosity or simply
viscosity of a liquid49
Viscosity
• η has a specific value for a given liquid at the same temperature.
• Viscosity of a liquid 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.
• The reciprocal of viscosity is called Fluidity and is denoted by φ

50
Units of Viscosity
• The dimensions of the coefficient of viscosity (η) may be derived from
the equation:

• Thus, in CGS system the unit of η is expressed as g cm–1 s–1. It is called

poise (P).
• In practice smaller units centipoise (10–2 poise) and millipoise (10–3
poise) are used.
• The SI unit is kg m–1 s–1
• 1 P = 1 g cm–1 s–1 = 0.1 kg m–1 s–1
51
52
Measurement of Viscosity - The
Ostwald Method
• Viscosity of a liquid can be determined with the help of Pioseulle’s
equation. The expression governs the flow of a liquid through a
capillary.

• where V is the volume of the liquid flowing through the capillary in

time t, P the pressure-head, r the radius of the tube and l is the
length.
• The experimental measurement of P, r, l and V offers considerable
difficulty. Therefore, it is not possible to find the absolute coefficient
of viscosity (η) straight away from Poiseulle’s equation.
53
Measurement of Viscosity - The
Ostwald Method
• Ordinarily, the viscosity of a liquid is determined with respect to that of
water. This is called Relative Viscosity.
• Let t1 and t2 be the times of flow of a fixed volume (V) of the two liquids
through the same capillary. The expression for relative viscosity (η1/η2) can
be derived from the Poiseulle’s equation.
• …….(1) ……….(2)

• Since the pressure-head is proportional to density () of the liquid, thus;

• Substituting the value of the viscosity coefficient of water (η2), we can find
the absolute viscosity of the given liquid (η1). 54
Ostwald Viscometer
• The apparatus commonly used for the determination of relative viscosity
of a liquid is known as Ostwald viscosimeter or viscometer.
• Viscometer: The left-hand limb is essentially a pipette with two
calibration marks A and B. A length of capillary tube joins the pipette to
a bulb C in the right-hand limb. A definite volume of liquid (say 25 ml) is
poured into the bulb C with a pipette. The liquid is sucked up near to the
top of the left-limb with the help of a rubber tubing attached to it. The
liquid is then released to flow back into the bulb C. The time (t 1) from A
to B is noted with a stopwatch. Then the apparatus is cleaned and the
experiment repeated with water, taking about the same volume. The
time of flow of water (t2) from A to B is recorded. The density of the
liquid () and water () are determined with the help of a pycnometer or
density bottle. Using the equation below, the absolute viscosity of the
liquid can be found at the temperature of the experiment.

Ostwald
Viscometer 55
56
 Effect of temperature on
viscosity of a liquid
• In general, the viscosity decreases with increase in
temperature. The variation of viscosity (η) with
temperature can be expressed by the following relationship

• Where A and E are constant (preexponential factor) and

Arrhenius activation energy, respectively
• Taking logarithms on both sides

• A plot of log η versus 1/T should be a straight line

• It has also been found that there is 2% decrease in viscosity Plot of log η
versus I/T
for every increase in one degree of temperature of any
liquid
57
Refractive Index

𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑔h𝑡 𝑖𝑛 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒

𝑛=
𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑔h𝑡 𝑖𝑛𝑎𝑖𝑟

Refraction of light through a denser liquid medium

The refractive index (n) of a substance is defined as the ratio of the

velocity of light in vacuum or air, to that in the substance
58
Refractive Index
• When a ray of light passes from air into a liquid, its direction is changed.
This change of direction is called refraction.
• The refractive index of a liquid with respect to air is given by Snelle’s
Law:

• where i is the angle of incidence and r the angle of refraction

• The refractive index of a liquid can be easily determined to a high
degree of accuracy.
• It is a characteristic property of a liquid. It varies with temperature and
wavelength of light used.
59
Refractive Index
• The wavelength of D-line of the sodium spectrum (589 nm) is
generally used for the purpose.
• If the refractive index of a liquid is measured at 20 oC and using D-line
of sodium, it is represented by the following symbol.

589

• Because refractive index is a ratio, it has no units.

60
Specific Refraction
• Lorenz and Lorenz (1880) from purely theoretical considerations,
derived the following relation for the refractive power of substance

• where Rs is the Specific Refraction, the density and n the refractive

index.
• The value of Rs was constant at all temperatures

61
Molar Refraction
• Molar refraction is defined as the product of specific refraction and
molecular mass.
• Thus, molar refraction of a liquid (RM) is obtained by multiplying equation Rs
equation by molecular mass (M).

• The value of molar refraction is characteristic of a substance and is

temperature-independent.
• Since it depends on the wavelength of light, the values of molar refraction are
generally reported for D-line of sodium.
• Since the value of refractive index (n) is dimensionless, from the above
equation it is evident that RM has the units of the molar volume i.e., cm3 mol–1.
62
63
 Determination of Refractive
Index
• The refractive index of a liquid can be determined with the help of an
instrument called Abbe Refractometer
• A thin film of the liquid is placed between the two
prisms. Light from a sodium lamp is made to fall on
lower side of the lower prism with the help of a
mirror. The hypotenuse surface of the lower prism is
ground and, therefore, light enters the liquid at all
angles of incidence.
• However, no ray can enter the upper prism with
greater angle of refraction than the grazing incidence
(i.e., at an angle) slightly less than 90 oC. Thus the view
in the telescope appears to be divided into two bands,
one bright and one dark.
• The prism assembly is rotated with the help of a side
knob till the cross wire of the telescope coincides with
the edge of the bright band. A pointer attached to the
The Abbe
prism assembly indicates the refractive index on the
refractometer
scale calibrated to read refractive indices directly64
Molar Refraction and Chemical
Constitution
• The molar refraction (RM) is an additive property i.e. molar refraction of a molecule
is the sum of the molar refraction of its constituent atoms. It is helpful in
determining the constitution of a compound.
• The molar refraction values are calculated for various possible structures and the
formula which is in accordance with the calculated molar refraction is the correct
formula (or structure) of that compound.
• The molar refraction values for some atoms and bonds are given in the Table below

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 Optical activity
• A beam of ordinary light consists of
electromagnetic waves oscillating in many planes.
• When passed through a polarizer (e.g., a Polaroid
lens), only waves oscillating in a single plane pass
through.
• The emerging beam of light having oscillations in
a single plane is said to be plane polarized.
• When plane-polarized light is passed through
certain organic compounds, the plane of polarized
light is rotated. Plane-polarized light
• A compound that can rotate the plane of
polarized light is called optically active. This
property of a compound is called optical activity
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Optical activity
• A compound which rotates the plane-polarized light to the left (anticlockwise), is said to
be levorotatory.
• A compound that rotates the plane-polarized light to the right (clockwise), is said to be
dextrorotatory.
• By convention, rotation to the left is given a minus sign (–) and rotation to the right is
given a plus sign (+). For example, (–)-lactic acid is levorotatory and (+)-lactic acid is
dextrorotatory

Optical Activity illustrated 68

 Specific rotation
• The rotation of plane-polarized light is an intrinsic property of optically active molecules.
• When a polarized beam of light is passed through the solution of an optically active
compound, its plane is rotated through an angle α (angle of rotation).
• This rotation depends on the number of optically active molecules encountered. Therefore, α
is proportional to both the concentration and the length of the sample solution.
• The specific rotation which is characteristic of an optically active substance, is expressed as

• Where is specific rotation, is observed angle of rotation in degrees, is length of the sample
solution in decimeter (dm; 10 cm) and c is the concentration of the sample solution in g/ml
• Thus, from the equation above, the specific rotation can be defined as the observed angle of
rotation at a concentration of 1 g/ml and path length of 1 dm. Conventionally, a specific
rotation is reported as , where t stands for temperature and D for D-line of sodium used for
determination.

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Measurement of Optical Activity

polarimeter
Schematic diagram of a polarimeter

• Optical activity is measured with the help of an instrument known as polarimeter.

• This is basically a system of polarizers with a sample tube placed in between.
70
Measurement of Optical Activity
• First, an optically inactive medium (air or solvent) fills the sample
tubes and polarized sodium light emerging from the polarizer passes
through it. The analyzer is then turned to establish a dark field. This
gives a zero reading on the circular scale around the analyzer.
• Then the solution of the given optically active compound is placed in
the sample tube. The plane of polarized light passing through it is
rotated. The analyzer is turned to re-establish the dark field. The
angle of rotation (α) is then noted in degrees on the circular scale.
• The specific rotation is calculated using the expression stated in
previous slide.

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