Chapter 11

Intermolecular Forces, Liquids, and Solids

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CONTENTS 11.1 Introduction: A Molecular Comparison 11.2 Types of Intermolecular Forces : 11.2.1 Ion-dipole forces 11.2.2 Dipole-dipole forces 11.2.3 Hydrogen bonding 11.2.4 London dispersion forces 11.2.5 Comparison between forces
11.3 Properties of Liquids 11.3.1 Viscosity and surface tension
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11.4 Phase Change 11.4.1 Energy changes accompanying phase change 11.4.2 Cooling curve 11.4.3 Critical temperature and pressure 11.5 Vapour pressure 11.6 Phase diagram 11.6.1 Phase diagram of CO2 11.6.2 Phase diagram of water
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11.7 Structure of solids 11.7.1 Crystalline and amorphous solids 11.7.2 Unit cell - PC, FCC & BCC structure
11.8 Bonding in Solids 11.8.1 Molecular solids 11.8.2 Covalent-network solids 11.8.3 Ionic and metallic solids

Learning Outcomes
Able to differentiate the 4 main intermolecular forces (IMF)
Able to relate IMF of a compound to the boiling

point, surface tension, viscosity and vapor pressure Able to use phase diagram in problem solving Able to use knowledge on unit cell of an element to calculate molar mass, density, radius etc.
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11.1 Introduction: A Molecular Comparison Solid - Liquid - Gas

Solid - Liquid - Gas

State Volume Gas Liquid Assumes vol. & Assumes shape shape of of the portion of container container but not volume Compressible Virtually incompressible Occurs slowly Readily Solid Retain its own shape & volume

Compressibili ty Diffusion Flow

Virtually incompressible Extremely low Does not flow

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Occurs rapidly Readily

11.2 Intermolecular Forces

The attraction between molecules is an

intermolecular force. Intermolecular forces are much weaker than ionic or covalent bonds. When a substance melts or boils, intermolecular forces are broken. When a substance condenses, intermolecular forces are formed. Boiling points/melting points indicate the strength of intermolecular forces.
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11.2 Types of Intermolecular Forces

Ion-dipole force

+ -

+
+ -

Dipole-dipole force +

Hydrogen bonding A - H London-Dispersion force

:B -

11.2.1 Ion-Dipole Forces

Exists between ions and the partial charge on

the end of polar molecules/dipole Important for solutions of ionic compounds in polar liquids E.g.: NaCl in water Magnitude of attraction increases: charge of the ion increases magnitude of dipole moment increase Ionic bonding > Ion-dipole > Dipole-dipole
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Ion-Dipole Forces
+

+
+

+
+

+ + +

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11.2.2 Dipole-dipole Forces

Exists between neutral polar molecules The partially positive end of one molecule attracts the partially negative end of another. O Weaker than ion-dipole forces E.g.: CO---CO
C O O C

O
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Dipole-dipole Forces
Attractions are greater + + than repulsion, so the + + - + molecules + feel a net + attraction to each other
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Dipole-dipole Forces
For molecules of approximately equal mass and size, strength of attraction increases with increasing polarity
Mass (amu) 44 46 44 Dipole moment () 0.1 1.3 3.9 Boiling point (K) 231 248 294

CH3CH2CH3 CH3OCH3 CH3CHO

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Dipole-dipole Forces
For molecules of comparable polarity, those with smaller molecular volumes generally experience higher dipole-dipole attractive forces.

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11.2.3 Hydrogen Bonding

Special type of intermolecular attraction.

Hydrogen bonding is a special case of dipoledipole interactions.

H-bonding requires:
H bonded to a small electronegative element (most important for compounds of F, O, and N) An unshared electron pair on a nearby small electronegative ion or atoms (usually F, O, or N on another molecule)
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11.2.3 Hydrogen Bonding

E.g.:
H

O H

O H

N H

O H

Ion-dipole > Hydrogen bonding > Dipole-dipole

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Hydrogen Bonding

Hydrogen bond

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Hydrogen Bonding
Hydrogen bonding is important in :
Stabilising the structure of protein

Folding of protein molecules

Survival of aquatic in frozen lake

Ice is less dense than water Ice floats so forms an insulating layer on top of lakes or river. Therefore, aquatic life can survive in winter.
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11.2.4 London Dispersion Forces

What intermolecular forces exist between nonpolar molecules in liquid and solid state ? Dipole-dipole attractions cannot exist between non-polar atoms or molecules Non-polar molecules do not have permanent dipoles but all nonpolar substances can be liquefied Therefore, there must exist some kind of attractive interactions between the particles
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London Dispersion Forces

Two schematic presentations of the

instantaneous dipoles on two adjacent helium atoms, showing the electrostatic attraction between them

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London Dispersion Forces

In a collection of helium atoms, the average distribution of electrons about each nucleus is spherically symmetrical The atoms are nonpolar and posses no permanent dipole moment

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London Dispersion Forces

In any atom or molecule, electrons constantly

moving The nucleus of one molecule (or atom) attracts the electrons of the adjacent molecule (or atom). For an instant, the electron clouds become distorted. In that instant a dipole id formed (called an instantaneous dipole)
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London Dispersion Forces

One instantaneous dipole can induce another

instantaneous dipole in ad adjacent molecule (or atom). These two temporary dipoles attract each other. The attraction is called London-dispersion force (LDF) , or simply a dispersion force.
LDF is the weakest of all intermolecular forces. LDF exist between all molecules (polar or nonpolar)
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London Dispersion Forces (LDF)

What affects the strength of a dispersion force?

Molecules must be very close together for these attractive forces to occur. POLARIZABILITY is the ease with which an electron distribution can be deformed. The larger the molecule, the more polarize it is. LDF increase as molecular weight increases. LDF depend on the shape of the molecule.
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London Dispersion Forces

Factors affecting London dispersion force : 1. Molecular weight
increase in mol. wt. (increase in atomic radii) results in increase number of electrons the larger the molecule, the farther its electron from the nuclei, the greater its polarizability greater polarizability, the greater the strength of London dispersion force
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London Dispersion Forces

E.g. : Noble gases . As go down the periodic table, mol. wt. increase (atomic radii increase) , resulting greater boiling point
Mol. Wt (amu) 4.0 20.2 39.9 83.8 131.3 Boiling point (K) 4.6 27.3 87.5 120.9 166.1

Substance He Ne Ar Kr Xe

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London Dispersion Forces

Factors affecting London dispersion force 2. Shape of molecule
greater the surface area available for contact, greater the dispersion force e.g.: straight chain molecule >branched chain molecule
Neopentane (bp=282.7K)

N-pentane (bp=309.4K)
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11.2.5 Comparison between Forces

LDF are found in all substances. Their strength depends on molecular shapes
Dipole-dipole forces add to the effect of LDF. They are found only in polar molecules. Ion-dipole interactions are stronger than Hbonding.
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and molecular weights.

11.2.5 Comparison between Forces

H-bonding is a special case of dipoledipole interactions.

It is the strongest of intermolecular forces H-bonding is most important for H

compounds of N, O, and F.

involving neutral species.

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11.2.5 Comparison between Forces

If ions are involved, ion-dipole (if a dipole

is present) and ionic bonding are possible.
bonding.

Ion-dipole interactions are stronger than H-

Ordinary ionic or covalent bonds are

much stronger than these interactions!
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11.3 Properties of Liquids

11.3.1 VISCOSITY

Viscosity - resistance of liquid to flow. Liquid flows by sliding molecules over each other. The stronger the intermolecular forces, the higher the viscosity. Viscosity usually decreases with an increase in temperature.
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Properties of Liquids
11.3.2 SURFACE TENSION

bulk molecules (those in liquid) are equally attracted to their neighbours surface molecules are only attracted inwards to the bulk molecules therefore surface molecules are packed more closely than bulk molecules Surface tension - amount of energy required to increase the surface area of a liquid by a unit amount.
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Explaining Surface Tension

11_16

Surface

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Properties of Liquids
SURFACE TENSION (CONT..)
Strong intermolecular forces cause higher surface tension.

Water has a high surface tension (Hbonding) Hg(l) has even higher surface tension (there are very strong metallic bonds between Hg atoms)
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Properties of Liquids
SURFACE TENSION (CONT..)
Cohesive forces

Intermolecular forces that bind molecules to one another Adhesive forces Intermolecular forces that bind molecules to a surface
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Properties of Liquids
To illustrate this: Meniscus - the shape of the liquid surface

if adhesive forces > than cohesive forces the liquid is attracted to its container, meniscus is U-shaped (e.g. water in glass) if cohesive forces > than adhesive forces meniscus curved downwards (e.g. Hg in glass)
Capillary action the rise of liquids up very narrow

tubes. The liquid climbs until adhesive and cohesive forces are balanced by gravity.
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Liquid Levels in Capillaries: Capillary Rise

11_19a

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11.4 Phase Changes

A phase change occurs when the matter is

transformed from one physical state to another

During phase change temperature remains constant

Sublimation Vaporization Melting or Fusion Deposition Condensation Freezing

: : : : : :

Solid Liquid Solid Gas Gas Liquid

Gas Gas Liquid Solid Liquid Solid

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Phase Changes
11.4.1 Energy changes accompanying phase changes During phase change, the energy change of the system are as given below Sublimation DHSUB > 0 (Endothermic) Vaporisation DHVAP > 0 (Endothermic) Melting OR Fusion DHFUS > 0 (Endothermic) Deposition DHDEP < 0 (Exothermic) Condensation DHCON < 0 (Exothermic) Freezing DHFREEZ < 0 (Exothermic)
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11.4.1 Energy changes accompanying phase changes

The amount of energy required to cause a phase

change increases as the strength of the intermolecular forces increases

Generally heat of fusion is less than heat of

vaporisation Less energy is needed to allow particles to move past one another than to separate them totally
Steam can cause severe burns, when it comes in

contact with skin because condensation (exothermic)

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11.4.2 Cooling curve

Cooling curve for the conversion of gaseous water to ice.

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11.4.2 Cooling curve

+
Supercooling:
When a liquid is cooled below its freezing point and it still remains a liquid.

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11.4.3 Critical Temperature and Pressure

Gas can be liquefied by compressing them at a suitable T

As temperature increases, gas become more difficult to liquefy because of the increasing kinetic energy
For every substance, there exist a temperature above which the

gas cannot be liquefied, regardless of the pressure

CRITICAL TEMPERATURE (TC) - the highest temperature at

which a substance can exist as a liquid (using pressure)

CRITICAL PRESSURE (PC) - the pressure required to bring

about liquefaction at TC

The greater the intermolecular forces, the easier it is to liquefy a

substance, thus the higher the TC of the substance.

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11.5 Vapour Pressure

What is vapor pressure ?

We place a quantity of ethanol ( b.p. 78.3C @ 1 atm) in an evacuated container

some of the molecules on the surface of the liquid have enough energy to escape the attraction of the bulk liquid
these molecules moves into the gaseous phase as the number of molecules in the gas phase increases, some of the gas phase molecules struck the surface and returns to the liquid
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Measurement of the Vapour Pressure of Water

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Vapour Pressure
It will reach a condition where the rate at which molecules return to the liquid is equal to the rate they escape from the liquid. At this condition ; the number of molecules in the gas phase reaches a steady state pressure of the vapor remains constant dynamic equilibrium is attained between the rate of condensation and rate of evaporation pressure of the vapor remains constant (vapor pressure)
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Vapour Pressure
Vapour pressure of a liquid is defined as the pressure exerted by its vapor when the liquid and the vapor

state are in dynamic equilibrium (Dynamic equilibrium is a condition in which two opposing processes occur simultaneously at equal rates.)

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Vapour Pressure and Boiling Point

Liquids boil when the external pressure at the liquid surface equals the vapour pressure.
The normal boiling point is the boiling point at 760

mmHg (1 atm). The temperature of the boiling point increases as the external pressure increases. Two ways to get a liquid to boil:
Increase temperature or decrease pressure.
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11.6 Phase Diagram

Under appropriate condition, equilibrium can exist

between: liquid - gas solid - liquid solid - gas

We can summarise these conditions as phase diagram Phase diagram - a plot of pressure vs. temperature summarizing all equilibria between phases.
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Phase Diagram
(Explanation for Figure) A-B = vapor pressure curve, represent equilibrium between liquid and gas phase Vapor pressure curve ends at the critical point A = triple point (temp. & pressure at which all three phases are in equilibrium A-D = change in melting point with increasing pressure The solid is denser than liquid. An increase in pressure will result in more compact solid phase i.e. higher temperature are required to melt a solid in high pressure
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11.6.1 Phase Diagrams for Carbon Dioxide

Notice that the solidliquid equilibrium (melting point) line of CO2 follows the normal behaviour i.e. its melting point increases with increasing temperature. For solid CO2 to exist as liquid the pressure must exceed 5.11 atm CO2 does not melt, but sublimes at 1 atm
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11.6.2 Phase Diagram for Water

The melting point of water decreases with increasing pressure Liquid form is more compact than its solid form

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11.8 Bonding in Solids

The melting point and hardness depends on arrangement of particles attraction forces between them

We can classify solids according to types of forces (4 types)

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Bonding in Solids
Molecular (formed from atoms or molecules)

usually soft with low melting point and conductivity

Covalent network (formed from atoms)

very hard with very high melting point and poor conductor
Ionic (formed from ions)

hard, brittle, high melting point and poor conductivity

Metallic (formed from metal atoms)

soft or hard with high melting point, good conductivity and ductile)
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11.8.1 Molecular Solids

Intermolecular forces Dipole-dipole, London dispersion and H-bonds. Weak intermolecular forces give rise to low melting point. Efficient packing of molecules is important (since they are not regular spheres) E.g. : Benzene (m.p 5C & b.p 80C) Toluene (m.p -95C & b.p 111C)

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Molecular Solids
E.g. : Benzene VS Toluene
Benzene m.p 5C, b.p 80C Symmetrical planar molecule packed efficiently in solid form - high melting point IMF in liquid state lower than toluene Toluene m.p -95C, b.p 111C Lower symmetry, prevents from packing efficiently Intermolecular forces depend on close contact - not effective IMF in liquid state larger than benzene
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11.8.2 Covalent-Network Solids

Atoms are held together in large networks or chain by

covalent bonds Covalent bonds are stronger than intermolecular forces E.g. Diamond & Graphite Diamond Each carbon atom is bonded to 4 other carbon atom Graphite The carbon atoms are arranged in layers of interconnected hexagonal rings The layers are held by dispersion forces Readily slide past one another
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Structures of Diamond and Graphite

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11.8.3 Ionic Solids

Ions are held together by ionic bonds The strength of ionic solids depends on the charges of the

ions NaCl MgO

---> Na+ Cl---> has m.p. of 801C ----> Mg 2+ O 2- ----> has m.p. of 2852C

The structure adopted by ionic solids depends largely on

the charges and relative sizes of the ions E.g.: NaCl (Na+ has CN of 6 and surrounded by 6 Cl) whereas CsCl (Cs is surrounded by 8 Cl- atoms) increase in CN results in increase in structure
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11.8.4 Metallic Solids

Metallic solids have metal atoms in the HCP

and FCC or BCC arrangements

The bonding is due to valence electrons that

are delocalized throughout the entire solid the metal nuclei floats in a sea of electrons

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Metallic Solids
Hardness and melting point depends on strength of

bonding Bonding strength increases with increase in bonding electrons e.g. Na (one valence electron- m.pt= 97.5C) Cr (6 valence electrons - m.pt = 1890c)
Mobility of electron explains why electrons are good conductor of heat and electricity

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END of CHAPTER

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