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Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
1 | P a g e
 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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
2 | P a g e
(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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
3 | P a g e
 SUMMARY OF TYPES OF INTERMOLECULAR FORCES:
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
4 | P a g e
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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
5 | P a g e
 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:
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
6 | P a g e
 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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
7 | P a g e
 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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
8 | P a g e
 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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
9 | P a g e
 DETERMINATION OF SURFACE TENSION:
(1) Capillary-rise Method
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
10 | P a g e
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
11 | P a g e
(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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
12 | P a g e
 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).
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
13 | P a g e
 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:
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
14 | P a g e
 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).
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
15 | P a g e
 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).
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
16 | P a g e
(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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
17 | P a g e
(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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
18 | P a g e
 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:
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
19 | P a g e
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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
20 | P a g e
 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.
Physical Chemistry I (Liquid state) Dr Fatah Eltaboni
21 | P a g e
SPECIFIC ROTATION
 The specific rotation which is characteristic of an optically active
substance, is expressed as:
MEASUREMENT OF OPTICAL ACTIVITY

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Liquid state

  • 1. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 1 | P a g e  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.
  • 2. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 2 | P a g e (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.
  • 3. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 3 | P a g e  SUMMARY OF TYPES OF INTERMOLECULAR FORCES:
  • 4. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 4 | P a g e 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.
  • 5. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 5 | P a g e  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:
  • 6. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 6 | P a g e  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.
  • 7. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 7 | P a g e  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.
  • 8. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 8 | P a g e  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.
  • 9. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 9 | P a g e  DETERMINATION OF SURFACE TENSION: (1) Capillary-rise Method
  • 10. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 10 | P a g e
  • 11. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 11 | P a g e (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.
  • 12. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 12 | P a g e  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).
  • 13. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 13 | P a g e  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:
  • 14. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 14 | P a g e  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).
  • 15. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 15 | P a g e  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).
  • 16. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 16 | P a g e (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.
  • 17. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 17 | P a g e (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.
  • 18. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 18 | P a g e  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:
  • 19. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 19 | P a g e 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.
  • 20. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 20 | P a g e  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.
  • 21. Physical Chemistry I (Liquid state) Dr Fatah Eltaboni 21 | P a g e SPECIFIC ROTATION  The specific rotation which is characteristic of an optically active substance, is expressed as: MEASUREMENT OF OPTICAL ACTIVITY