Physical Chemistry I (Liquid State) : DR Fatah Eltaboni

Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
 LIQUID STATE:
 Liquid is a fluid that conforms to the shape of its container but

retains a constant volume (independent of pressure)
 TYPES OF INTERMOLECULAR FORCES IN LIQUIDS:
(1) Dipole-dipole attractions (2) London forces (3) Hydrogen bonding.
(1) DIPOLE-DIPOLE ATTRACTIONS:
 Dipole-dipole attractions exist between molecules that are polar.

This requires the presence of polar bonds and an unsymmetrical
molecule.
(2) LONDON FORCES:
 London forces exist in non-polar molecules.
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(3) HYDROGEN BONDING (HB):
 HB is a unique type of intermolecular attraction. There are two

requirements:
i. Covalent bond between an H atom and either F, O, or N. These

are the three most electronegative elements.
ii. Interaction of the H atom in this kind of polar bond with a lone
pair of electrons on a nearby atom like F, O, or N.
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 SUMMARY OF TYPES OF INTERMOLECULAR FORCES:
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VAPOUR PRESSURE OF LIQUID:

 When a liquid is placed in an open vessel, it evaporates.
 The molecule which has kinetic energy (KE) can overcome the
intermolecular forces ONLY can evaporates.
 The process by which molecules of a liquid go into the gaseous

state (vapours) is called VAPORISATION.
 The reverse process by which gas molecules become liquid

molecules is called CONDENSATION.
 THE VAPOUR PRESSURE OF A LIQUID is defined as: the

pressure exerted by the vapour in equilibrium with the liquid at a
fixed temperature.
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 EFFECT OF TEMPERATURE ON VAPOUR PRESSURE:
 DETERMINATION OF VAPOUR PRESSURE OF LIQUID

(1) THE STATIC METHOD:
 This method is used for liquids having vapour pressures up to one

atmosphere.
(2) THE DYNAMIC METHOD:
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 Where (M) = molecular weight of the liquid and (R) = gas constant.
This method is used for liquids of very low vapour pressure.
 EFFECT OF VAPOUR PRESSURE ON BOILING POINTS:
 When a liquid is heated, tiny bubbles are formed in it. These rise
to the liquid surface and burst.
 The temperature at which liquid bubbles are burst is the boiling

point of the liquid.
Figure. Burst bubbles of boiled water
 The BOILING POINT of the liquid defined as the temperature at

which the vapour pressure of the liquid is equal to the
atmospheric pressure.
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 Because the atmospheric pressure varies with altitude and other

conditions, the boiling points are reported at 1 atm (760 torr).
Therefore the normal boiling point of a liquid is the temperature
at which the vapour pressure of the liquid is 1 atm. As evident
from Fig. 11.9, the boiling point of ethanol is 78ºC and of water,
100ºC.
 The boiling point of a liquid can be increased by raising the

external pressure. Thus the vapour pressure of the liquid is equal
to the external pressure at a higher temperature.
 A domestic pressure cooker works on this principle. The

pressure inside the cooker is maintained above one atmosphere
and the liquid contained in it would boil at a higher temperature
than 100ºC. Thus the food is cooked in a shorter time.
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 THE SURFACE TENSION OF LIQUID (ᵞ):
 The surface tension (ᵞ) is defined as: the force that causes the
molecules on the surface of a liquid to be pushed together and
form a layer.
 UNITS OF SURFACE TENSION:

 In CGS system is (dyne cm–1). In SI system, the unit is (Nm–1).
 EFFECT OF TEMPERATURE ON SURFACE TENSION:
 Surface tension decreases with increase in temperature.
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 DETERMINATION OF SURFACE TENSION:

(1) Capillary-rise Method
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(2) Drop Formation Method (3) Ring-detachment Method
(4) Maximum Bubble Pressure Method
 VISCOSITY:
 A liquid may be considered to be consisting of molecular layers

arranged one over the other.
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 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.
 Consider two adjacent moving layers of a liquid separated by a

distance (dx) and have a velocity difference (dv). The force of
friction (F) resisting the relative motion of the two layers:
 Where (η) (Greek letter eta) is the proportionality constant. It is

known as the Coefficient of Viscosity or simply viscosity of a
liquid.
 (η) has a specific value for a given liquid at the same

temperature.
 The reciprocal of viscosity is called Fluidity and is denoted by (φ).
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 The viscosity decreases with increase in temperature.
 UNITS OF VISCOSITY:
 The unit of the coefficient of viscosity ( η ) may be derived from

equation (2).
 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).
 One poise is equal to one-tenth of the SI unit i.e.1 poise = 1 g cm–1

s–1 = 0.1 kg m–1 s–1
 MEASUREMENT OF VISCOSITY - THE OSTWALD METHOD:
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 Viscosity of a liquid can be determined with the help of

Pioseulle’s equation.
 Where (V) is the volume of the liquid flowing through capillary in

time (t), (P) the pressure, (r) the radius of the tube and (l )its
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.
 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 Pioseulle’s equation.
Since P α d
 Substituting the value of the viscosity coefficient of water (η2) we

can find the absolute viscosity of the given liquid (η1).
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 Experiment:
(1). A definite volume of liquid (say 25 ml) is poured into the bulb
(C) with a pipette.
(2).The liquid is sucked up near to the top of the left-limb with the
help of a rubber tubing attached to it.
(3).The liquid is then released to flow back into the bulb (C).
(4). The time (t1) from (A) to (B) is noted with a stopwatch.
(5).Then the apparatus is cleaned and the experiment repeated

with water, taking about the same volume.
(6). The time of flow of water (t2) from (A) to (B) is recorded.
(7).The density of the liquid (d) and water (dw) are

determined with the help of a (pyknometer).
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(8)The relative viscosity coefficient is calculated from the

expression:
(9).Knowing the value of the viscosity coefficient of water (ηw) at

the temperature of the experiment, the absolute viscosity
coefficient (η) of the given liquid can be found.
 REFRACTIVE INDEX:
 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.
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(Unit-less)
 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 the liquid with respect to air is given by

SNELLE’S LAW:
where i is the angle of incidence and r the angle of refraction

 Refractive index is a characteristic property of a liquid. It
depends on: temperature and wavelength of light used.
 The wavelength of D-line of the sodium spectrum is used to

measure refractive index of a liquid.
 SPECIFIC REFRACTION (Rs):
 Where (Rs) is the Specific Refraction, (d) the density and (n) the
refractive index.
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 The value of (Rs) is constant at all temperatures.
 MOLAR REFRACTION (RM):
M: molar mass (g/mol), d: density (g/cm3), RM: cm3/mol
 The value of molar refraction is characteristic of a substance and

is temperature-independent.
 DETERMINATION OF REFRACTIVE INDEX:
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MOLAR REFRACTION AND CHEMICAL CONSTITUTION
Example: Ethyl alcohol (CH3CH2OH). Its refractive index at 295.9 K for

D-line is 1.3611 and its density is 0.7885 g cm–3. The molar mass of
ethyl alcohol is 46 (2 × 12 + 1 × 6 + 1 × 16).
The molar refraction can be calculated using the relation
 OPTICAL ACTIVITY:
 A beam of ordinary light consists of electromagnetic waves
oscillating in many planes. When passed through a polarize, only
waves oscillating in a single plane pass through. Its called
polarized light.
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 A compound that can rotate the plane of polarized light is called

OPTICALLY ACTIVE. This property of a compound is called
optical activity.
 A compound which rotates the polarized light to the left

(anticlockwise), is said to be levorotatory. A compound that
rotates the 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.
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SPECIFIC ROTATION
 The specific rotation which is characteristic of an optically active

substance, is expressed as:
MEASUREMENT OF OPTICAL ACTIVITY
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Physical Chemistry I (Liquid state) Dr Fatah Eltaboni

 Liquid is a fluid that conforms to the shape of its container but

 TYPES OF INTERMOLECULAR FORCES IN LIQUIDS:

(1) Dipole-dipole attractions (2) London forces (3) Hydrogen bonding.

(1) DIPOLE-DIPOLE ATTRACTIONS:

 Dipole-dipole attractions exist between molecules that are polar.

(2) LONDON FORCES:

 London forces exist in non-polar molecules.

(3) HYDROGEN BONDING (HB):

 HB is a unique type of intermolecular attraction. There are two

i. Covalent bond between an H atom and either F, O, or N. These

 SUMMARY OF TYPES OF INTERMOLECULAR FORCES:

VAPOUR PRESSURE OF LIQUID:

 The process by which molecules of a liquid go into the gaseous

 The reverse process by which gas molecules become liquid

 THE VAPOUR PRESSURE OF A LIQUID is defined as: the

 EFFECT OF TEMPERATURE ON VAPOUR PRESSURE:

 DETERMINATION OF VAPOUR PRESSURE OF LIQUID

 This method is used for liquids having vapour pressures up to one

 EFFECT OF VAPOUR PRESSURE ON BOILING POINTS:

 The temperature at which liquid bubbles are burst is the boiling

Figure. Burst bubbles of boiled water

 The BOILING POINT of the liquid defined as the temperature at

 Because the atmospheric pressure varies with altitude and other

 The boiling point of a liquid can be increased by raising the

 A domestic pressure cooker works on this principle. The

 THE SURFACE TENSION OF LIQUID (ᵞ):

 UNITS OF SURFACE TENSION:

 EFFECT OF TEMPERATURE ON SURFACE TENSION:

 Surface tension decreases with increase in temperature.

 DETERMINATION OF SURFACE TENSION:

(2) Drop Formation Method (3) Ring-detachment Method

(4) Maximum Bubble Pressure Method

 A liquid may be considered to be consisting of molecular layers

 When a shearing force is applied to a liquid, it flows. However,

 Viscosity of a liquid is a measure of its frictional resistance.

 Consider two adjacent moving layers of a liquid separated by a

 Where (η) (Greek letter eta) is the proportionality constant. It is

 (η) has a specific value for a given liquid at the same

 The reciprocal of viscosity is called Fluidity and is denoted by (φ).

 The viscosity decreases with increase in temperature.

 The unit of the coefficient of viscosity ( η ) may be derived from

 Thus in CGS system the unit of η is expressed as (g cm–1 s–1). It is

 In practice smaller units centipoise (10–2 poise) and millipoise (10–

 The SI unit is (kg m–1 s–1).

 One poise is equal to one-tenth of the SI unit i.e.1 poise = 1 g cm–1

 MEASUREMENT OF VISCOSITY - THE OSTWALD METHOD:

 Viscosity of a liquid can be determined with the help of

 Where (V) is the volume of the liquid flowing through capillary in

 The viscosity of a liquid is determined with respect to that of

 Substituting the value of the viscosity coefficient of water (η2) we

(5).Then the apparatus is cleaned and the experiment repeated

(7).The density of the liquid (d) and water (dw) are

(8)The relative viscosity coefficient is calculated from the

(9).Knowing the value of the viscosity coefficient of water (ηw) at

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

 The refractive index of the liquid with respect to air is given by

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