Intermolecular Forces and Phase

Equilibrium
Dr Kanyanta
Adapted from Dr. E. Funjika and Kalulu Mulenga
1
A phase is a homogeneous part of the system in contact with
other parts of the system but separated from them by a well-
defined boundary.
2 Phases

Solid phase - ice

Liquid phase - water

2
 Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
“Measure” of intermolecular force
boiling point
Generally, intermolecular
melting point
forces are much weaker
than intramolecular forces. Hvap
Hfus
Hsub 3
 Intermolecular Forces

Dipole-Dipole Forces

Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

4
 Intermolecular Forces
Ion-Dipole Forces

Attractive forces between an ion and a polar molecule

Ion-Dipole Interaction

5
Interaction Between Water and Cations

in solution
6
 Intermolecular Forces
Dispersion Forces
Attractive forces that arise as a result of temporary
dipoles induced in atoms or molecules

ion-induced dipole interaction

dipole-induced dipole interaction 7

Induced Dipoles Interacting With Each Other

8
 Intermolecular Forces
Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction
between the hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.
A H…B or A H…A
A & B are N, O, or F

9
Example 11.2
Which of the following can form hydrogen bonds with water?

CH3OCH3

CH4

F2

HCOOH

Na+
Example 11.2
Example 11.1
What type(s) of intermolecular forces exist between the
following pairs?

(a)HBr and H2S

(b)Cl2 and CBr4

(c)I2 and

(d)NH3 and C6H6

 Total attraction
pre
• Hydrogen bond m ium

– Dipole-dipole
– Dispersion
n t TV
d i f f e re s
* L ik e l p a c k a g e
• Dipole-dipole a n n e
ch
– Dispersion

• Dispersion ba
sic

13
van der Waals forces

• Dipole-dipole
• Dipole-induced dipole
• Dispersion

14
 Intermolecular Forces
Dispersion Forces Continued

Polarizability is the ease with which the electron distribution

in the atom or molecule can be distorted.

Polarizability increases with:

• greater number of electrons
• more diffuse electron cloud

Dispersion forces usually

increase with molar mass.

15
 Differences in Melting and
Boiling point
• Melting and boiling
points increase as the
number of electrons
in a molecule
increases
• More electrons =
larger molar mass

16
Why is the hydrogen bond considered a “special”
dipole-dipole interaction?

Decreasing molar mass

Decreasing boiling point

17
 Properties of Liquids

Surface tension is the amount of energy required to stretch

or increase the surface of a liquid by a unit area.

Strong
intermolecular
forces

High
surface
tension

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 Properties of Liquids

Cohesion is the intermolecular attraction between like molecules

Adhesion is an attraction between unlike molecules

Adhesion

Cohesion

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 Properties of Liquids

Viscosity is a measure of a fluid’s resistance to flow.

Strong
intermolecular
forces

High
viscosity

20
3-D Structure of Water
Water is a Unique Substance

Maximum Density
40C
Density of Water

Ice is less dense than water

21
A crystalline solid possesses rigid and long-range order. In a
crystalline solid, atoms, molecules or ions occupy specific
(predictable) positions.
An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.

A glass is an
optically
transparent fusion
product of
inorganic
materials that has
cooled to a rigid
state without
crystallizing
Crystalline Non-crystalline
quartz (SiO2) quartz glass 22
An Arrangement for Obtaining the X-ray Diffraction Pattern
of a Crystal.

23
 Reflection of X-rays from Two Layers of Atoms

Extra distance = BC + CD = 2d sin = n (Bragg Equation)

24
 Types of Crystals
Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity

CsCl ZnS CaF2

25
 Types of Crystals
Covalent Crystals
• Lattice points occupied by atoms
• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity
carbon
atoms

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diamond graphite
 Types of Crystals
Molecular Crystals
• Lattice points occupied by molecules

• Held together by intermolecular forces

• Soft, low melting point

• Poor conductor of heat and electricity

water benzene

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 Types of Crystals
Metallic Crystals
• Lattice points occupied by metal atoms
• Held together by metallic bonds
• Soft to hard, low to high melting point
• Good conductors of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-

mobile “sea”
of e-

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Types of Crystals

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Phase Changes

Least
Order

Greatest 30
Order
 Effect of Temperature on Kinetic Energy

T2 > T1

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The equilibrium vapor pressure is the vapor pressure
measured when a dynamic equilibrium exists between
condensation and evaporation

H2O (l) H2O (g)

Dynamic Equilibrium
Rate of Rate of
condensation
= evaporation

32
 Measurement of Vapor Pressure

Before At
Evaporation Equilibrium
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Molar heat of vaporization (Hvap) is the energy required to
vaporize 1 mole of a liquid at its boiling point.
Clausius-Clapeyron Equation
Hvap P = (equilibrium) vapor pressure
ln P = - +C
RT T = temperature (K)
R = gas constant (8.314 J/K•mol)

Vapor Pressure Versus Temperature

34
Alternate Forms of the Clausius-Clapeyron Equation

At two temperatures

or

35
Example 11.7
Diethyl ether is a volatile, highly flammable organic liquid that is
used mainly as a solvent.

The vapor pressure of diethyl ether is 401 mmHg at 18°C.

Calculate its vapor pressure at 32°C.
The boiling point is the temperature at which the
(equilibrium) vapor pressure of a liquid is equal to the
external pressure.

The normal boiling point is the temperature at which a liquid

boils when the external pressure is 1 atm.

37
 The critical temperature (Tc) is the temperature above which
the gas cannot be made to liquefy, no matter how great the
applied pressure.

The critical pressure

(Pc) is the minimum
pressure that must be
applied to bring about
liquefaction at the
critical temperature.

38
 The Critical Phenomenon of SF6

T < Tc T > Tc T ~ Tc T < Tc

39
 Solid-Liquid Equilibrium

H2O (s) H2O (l)

The melting point of a solid

or the freezing point of a
liquid is the temperature at
which the solid and liquid
phases coexist in
equilibrium.

40
Molar heat of fusion (Hfus) is the energy required to melt
1 mole of a solid substance at its freezing point.

41
Heating Curve

42
 Solid-Gas Equilibrium

H2O (s) H2O (g)

Molar heat of sublimation

(Hsub) is the energy required
to sublime 1 mole of a solid.

Hsub = Hfus + Hvap

( Hess’s Law)

43
Example 11.8
Calculate the amount of energy (in kilojoules) needed to heat
346 g of liquid water from 0°C to 182°C.

Assume that the specific heat of water is 4.184 J/g · °C

over the entire liquid range and that the specific heat of steam
is 1.99 J/g · °C.
A phase diagram summarizes the conditions at which a
substance exists as a solid, liquid, or gas.

Phase Diagram of Water

45
Phase Diagram of Carbon At 1 atm
Dioxide CO2 (s) CO2 (g)

46
Effect of Increase in Pressure on the Melting Point
of Ice and the Boiling Point of Water

47