The Kinetic Theory for the Liquid State

Continual heating: solid liquid (melting point)

vapour/gas(boiling point) The energy content of the particles increases in the order: solid < liquid < gas. In the liquid state, molecules move in rapid & random manner & have vibrational, rotational, translational motions Molecules of liquid are held together so close & very little space between them. Liquids are more difficult compress than gases.

 Molecules in liquid are held together by 1 or more

attractive forces. The molecules of gas can move past one another, so a liquid can flow, can be poured and assumes the shape of its container. 1 mol of substance: volumesolid < volume liquid < volumegas.

Properties of Matter
Property
Shape

Solid Fixed

Liquid Not fixed

Gas Not fixed

Volume
Compressibility

Fixed
Cannot

Fixed
Cannot

Not fixed
Can

Density
Attractive forces between particles Ekinetic between particles

High
High Low

Intermediate Low
Intermediate Low

Intermediate Very high

State or phase change

There are 3 states of matter: solid, liquid and

vapour are considered phases

temeparature
Boiling point Liquid & vapour at equilibrium D C liquid vapour

Solid & liquid A at equilibrium B Melting point

solid

Time

The Melting Process (Fusing)

When a solid is heated, its particles gain Ekinetic &

vibrate more quickly. At melting point, the particles gain enough Ekinetic to overcome the attractive forces between the particles & break away from one another. The particles move away from their original positions becomes a liquid ~ melting process The heat energy absorbed during change of phase from solid to liquid is called latent heat of fusion. Molar latent heat of fusion (enthalpy of fusion) ~ amount of heat required to change 1 mole of a pure solid into a liquid.

The Freezing Process

A liquid becomes a solid if heat energy is

removed from it. When the temperature is lowered, the Ekinetic of the particles decreases. The motion of the particles in the liquid slows down. A point (temperature) is reached when the intermolecular forces are strong enough to hold the particles together in a fixed, orderly positions.

The Vaporisation Process

If a liquid is in an open container & exposed, the particles at

the surface may have enough energy to overcome the intermolecular forces and escape as vapour ~ vaporisation. The rate of vaporisation increases with a rise in temperature a decrease in external pressure an increase in the surface area of the liquid.

Vapour Pressure
As figure 3.2(a), before starting evaporation, the

mercury level of manometer is equal. Soon, the molecules are moving from liquid as concentration of molecules in vapour phase increases & vapour pressure established. As the molecules escape from the liquid surface to form vapour, some of these molecules will also enter the liquid by condensation.

Figure 3.2

 Initially, the rate of vaporisation > the rate of condensation

Hence, the vapour pressure will increase with time.

When the rate of vaporisation = the rate of condensation &

a dynamic equilibrium is established. The concentration of the vapour is max. & the max. vapour pressure is exerted. This max. vapour pressure is called the saturated vapour pressure (SVP) of the liquid at the said temperature. The Saturated vapour pressure increases with temperature.

 The shaded area

under the curve shows the fraction of particles that have enough kinetic energy (Evaporisation) to vaporise.

 If the temperature of liquid is increased, more

particles will possess energy higher than Evaporisation & the rate of evaporation will increase.

Boiling Point & Vapour Pressure

The vapour pressure of a liquid

increases with temperature (does not depend on the amount of the liquid present). If a liquid is heated in an open container, a point is reached when the vapour pressure of the liquid = the atmospheric pressure is called as boiling point). This process is called boiling.

 Example: water boils at 100oC at 101.3

kPa (1 atm). If the external pressure is reduced, the boiling point is decreased. The boiling point of a liquid at 1 atm (101.3 kPa) is called the normal boiling point.

Volatility & Vapour Pressure

When 2 liquids are compared

(same temperature), the liquid which evaporates more readily is described as being more volatile. Eg. Volatility of water < ethanol < ether. At the same temperature, a substance which is more volatile will have a higher vapour pressure but a lower boiling point.

 Molar latent heat of vaporisation (enthalpy of

vaporisation)~ the quantity of heat energy required to change 1 mole of a pure liquid into a gas at its boiling point. The higher the value of Hvaporisation, the higher the boiling point of the liquid.

Physical Properties Vapour pressure Boiling point

Hvaporisation

Volatile liquid
High Low Low

Non-volatile liquid Low

High High

Types of Solids
Crystalline Amorphous
(non-crystalline)

Particles are closely packed Have an ordered 3-D arrangement

The particles are randomly arranged Have no ordered structure

Lattice Structures & Unit Cells

Crystal lattice (space lattice)

~ the regular arrangement of atoms, molecules or ions in a crystalline solid. Lattice refers to a pattern of points in an ordered & repeated arrangement. A crystal lattice consists of a basic unit called the unit cell. Unit cell ~ a small repeating unit that makes up a crystal. The unit cell contains a group of particles in a crystal that is repeated in 3-D throughout the crystal lattice.

 Each unit cell is represented by the lengths of cell

edges or sides (a, b, c) & the angles between the edges (, , ). Angle ~ angle between sides b and c. Angle ~ angle between sides a and c. Angle ~ angle between sides a and b.

 Crystal lattices can be classified into 7 crystal

system according to the symmetry of the unit cell. Crystal systems are sometimes called primitive unit cells. The 7 crystal system are Cubic Tetragonal Orthorhombic Monoclinic Triclinic Rhombohedral Hexagonal

Cubic

Examples: sodium chloride

barium fluoride potassium iodide iron copper

Tetragonal

Examples: calcium chromate (VI)

barium peroxide tin

Orthorhombic

Examples: sulphur (rhombic)

lead(II) chloride silver nitrate barium carbonate

Monoclinic

Examples: sulphur

magnesium chloride calcium iodate(V)

Triclinic

Examples: copper(II) sulphate

bismuth nitrate calcium carbide

Rhombohedral

Examples: bismuth

antimony arsenic

Hexagonal

Examples: scandium

aluminium chloride iron(II) bromide phosporous(V) oxide

 A unit cell is described as primitive if all

the lattice points are placed at the corners of the cell only. In some unit cells, the lattice points are also located at the faces or centres of the cells ~ multi-primitive unit cell. There are 7 multi-primitive lattices. Cubic lattice has 2 multi-primitive lattices; Orthorhombic has 3 multi-primitive lattices; Tetragonal has 1 multi-primitive lattices; Monoclinic has 1 multi-primitive lattices.

The Cubic System

The simplest unit cell is the cubic unit cell. There are 3 types of cubic unit cells:

Simple cubic cell (primitive) ~ the lattice points are located only at the corner of the unit cell. Body-centered cubic cell (multi-primitive) ~ additional lattice point in the centre of the unit cell. Face-centered cubic cell (multi-primitive) ~ additional atom located at each of its faces.

Simple cubic
Skeletal view

Body-centered cubic

Face-centered cubic

Spacefilling view

 There are 4 types of lattice

points: at the corner of the unit cell on the face of the unit cell on the edge of the unit cell in the centre of the unit cell Atoms at the corners or on the faces of the unit cell are shared with other neighbouring unit cells. Thus, only a section of the atom belongs to a given unit cell.

How to calculate the number of chemical units in a unit cell?

Atom at the corner is shared between 8 unit cells.

Thus, only 1/8 of each corner atom belongs to the unit cell. Atom at the edge is shared between 4 unit cells. So, only of the atom belongs to the unit cell. Atom on the face is shared between 2 unit cells. So, of the atom belongs to the unit cell. Atom in the centre exists as 1 atom in the unit cell.

Example: the packing of Na+ & Cl in s solid NaCl

A unit cell of NaCl

8
1

Type of lattice point

Contribution towards One Unit Cell

Body centred cubic

At the corner Cell edge

1 8

1 4

1 4
1 2 1

On the face In the centre

1 2
Face centred cubic 1 8

Allotropy
Elements that can exist in more than 1 structural

form (under same temperature & pressure) are said to exhibit allotropy. The different structural forms of the same element are called allotropes. Some important allotropes: Carbon ~ diamond, graphite & fullerenes Sulphur ~ rhombic & monoclinic sulphur Phosphorus ~ red & white phosphorus Tin ~ tin (grey tin), tin (white tin) & tin Oxygen ~ oxygen (O2) & ozone (O3)

The Allotropes of Sulphur

Both rhombic & monoclinic sulphur crystals consist of S8

molecules. The sulphur atoms are arranged in the form of a puckered ring.

Characteristics

Rhombic Sulphur (-sulphur)

Monoclinic Sulphur (-sulphur)

Structure Colour Lemon yellow Deep yellow

Type of lattice Crystalline shape Melting point Density

Orthorhombic Octahedral shape

113oC 2.07 g cm3

Monoclinic Long & narrow needle shape 119oC 1.94 g cm3

 Monoclinic sulphur is the stable allotrope at

temperature above 95.5 oC. Rhombic sulphur is the stable allotrope at temperature below 95.5 oC. 95.5 oC ~ this temperature is called the transition temperature.
> 95.5oC

Rhombic sulphur
<95.5oC

Monoclinic sulphur

The Allotropes of Carbon

Diamond Fullerene

Graphite

Diamond

Graphite

Face-centered cubic structure

A layered lattice structure in the hexagonal crystalline system

Each C atom is joined to 4 other Each C atom is covalently carbon atoms by covalent bonds in bonded to 3 other carbon atoms in a tetrahedral arrangement the same plane, forming layers of hexagonal C atom rings.

 Each carbon atom is sp3 hybridised; bond angle is 109.5o

All

Each carbon atom is sp2 hybridised; bond angle 120o The unhybridised p electrons form a delocalised electrons cloud enable graphite to conduct electricity & giving it shiny appearance. The weak van der Waals forces between the layers enable them to slide over each other. It is used as a lubricant. Strong covalent bonds within each layer resulted in high melting point (3925 K). Density = 2.3 g cm-3 Uses: Lubricants & as inert electrodes in electrochemical & electrolysis cells

the 4 valence electrons of the C atoms involved in the formation of covalent bonds making diamond a non-conductor of electricity. The 3-D network of covalent bonds binds all the atoms into a giant molecular structure. This reflected in the great hardness & high melting point (3823 K).

Density = 3.5 g cm-3 Uses: Diamond-tipped tools are used for cutting & engraving; diamond has a high refractive index making it a prized jewel.

Fullerenes
Fullerene (full name:

Buckminsterfullerene) with a molecular formula of C60, is the third allotrope of carbon, discovered in 1985. The C60 molecule has 32 faces; 12 pentagonal faces & 20 hexagonal faces. Each C atom undergoes sp2 hybridisation. Fullerenes are used to make superconductors, semiconductors, lubricants, micro-ballbearings in nanomachines & catalyst.

The Phase Diagram of a Pure Substance

Most matters can exist in 3 physical phases ~ solid,

liquid & gas, depend on temperature & pressure. E g. At high T & low P, substance usually exist as gas. Sometimes, an equilibrium exists between 2 phases ~ liquid-vapour, solid-vapour & solid-liquid. All this information can be summarised on a graph known as a phase diagram or vapour pressure diagram. The phase diagram enables us to predict the physical state of a substance under different temperature & pressure.

The Phase Diagram of Water

The graph is divided into 3 areas. Each area represents

a single phase (or physical state). Each line indicates the conditions of temperature & pressure when 2 phases exist in dynamic equilibrium.

The Curve TB
Is called the vapour pressure curve. It shows the boiling point of water at different

pressure. The normal b.p. of water is 100 oC at 1.0 atm & liquid & vapour exist together in dynamic equilibrium.

The Curve AT
Shows the saturated vapour pressure of ice (solid

water) at different temperature. Sublimation of the water molecule from the surface of ice. Known as sublimation curve. Ice water vapour

The Line CT
Is called the melting temperature curve. Shows the melting point of ice (or the freezing point

of water) at different pressures. The line is unusual because it slopes to the left. This shows that as pressure increases, the melting point of ice decreases

The Curve OD
This is a metastable condition, because water usually

does not exist as a liquid below its freezing point. This phenomenon is called supercooling. Supercooling ~ the cooling of a liquid to below its freezing point without change from liquid to solid state.

The Point O
Known as the triple point. It marks the conditions of temperature & pressure

(0.006 atm & 0.01 oC) when ice, liquid & water vapour are in dynamic equilibrium.

The Point B
Critical point for water which occurs at 218 atm (critical

pressure) & 374 oC (critical temperature). Once the critical point is reached, there are no longer 2 separate phases, because the densities of the gas & liquid are equal. The liquid & the vapour become indistinguishable.

The properties of water

Water has high specific heat.

Density of water solid (ice) is less than its

liquid form. Because, volume of ice is greater than water liquid.

The Unusual Behaviour of Water

During the process of freezing, the volume of most

substances will decrease when the liquid changed into solid. The behaviour of water is unusual. Ice crystals have an open structure due to hydrogen bonding. When water freezes to form ice, its volume increases slightly. Conversely, when ice melts to form water, its volume decreases slightly. Liquid phase is denser than solid phase.

Effect of Pressure on Melting Point

If volume of solid > liquid (same mass), the melting

point decreases with increases in pressure. Explaination: An increase in pressure will push the molecules closer. Density liquid water > solid ice. Thus, increasing the pressure favours the formation of liquid water. [For substance with the same mass, the smaller the volume, the higher the density. An increase in pressure favours the higher density physical state.] Since the latent heat of fusion is absorbed during melting, the temperature of the system will fall & the melting temperature curve slopes to the left.

 The effect of pressure on melting point can be

predicted by using Le Chateliers principle. When the pressure on a system in equilibrium is increased, the equilibrium will shift in the direction to lower the pressure (to smaller volume). Consider the equilibrium between water & ice:
Volume increases

Water
Volume decreases

Ice

When the ice melts, the volume of the system will

decrease & the pressure of system will be lowered. The new equilibrium is established at a higher pressure & a lower temperature.

The Phase Diagram of Carbon Dioxide

Basically, it same as the phase

diagram of water. But, there are 2 differences: The triple point O is above the atmospheric pressure (5.1 atm, -57 oC). Below triple point, solid CO2 will sublime to vapour. The line OC slopes to the right (typical behaviour of most substances). It implies that an increase in pressure will increase the melting point of CO2.

 The effect of pressure on melting point curve depend on the

relative densities between solid & liquid. The density of solid CO2 > liquid CO2 because CO2 molecules are held together closely made the volume smaller.
Volume increases

Solid carbon dioxide

Volume decreases

Liquid carbon dioxide

An increase in pressure will push the molecules closer

together. So, an increase in pressure favours the formation of solid CO2. When the liquid becomes solid, the latent heat of fusion will be liberated. The temperature of the equilibrium system will increase. So, when the external pressure is increased, the melting point will also increase.

Uses of Dry Ice in Industry

Uses Refrigerant Explanation Very cold & does not leave messy liquid when sublimes Cloud seeding Spread into cloud to accelerate rain fall Films / stage Produce special effects of performance cloud / mist / fog. Carbonated drink Carbonate salt produced is used to make drinks. Fire extinguisher CO2 is compressed & used as agent.