Condensed Phase Matter

Solids and Liquids

Solids
Fixed shape, high density, low compressibility due to strong bonding between atoms
The atoms pack regularly to give a crystalline solid (left, long range order) or irregularly to give an
amorphous solid (right, disorder)

1. Molecular/atomic solids

Contains either molecules with covalently bonded atoms or free atoms

Held together by dispersion forces, dipole forces and/or H-bonding

E.g. Naphthalene (dispersion forces only), mp= 80C

2. Network solids

Have very high melting points unlike molecular solids:

E.g: two elements with similar atomic radii P (left) and Si (right)
- both sp3-hybridised (VBT, see slide 58-91)

e.g. Carbon: network solids

Diamond (left), sp3-hybridised, highly refractive insulator= 3D
network
Covalent bonding

Graphite (right), sp2-hybridisation, opaque 2D-conductor= 2D network

Covalent bonding only in sp2-plane, dispersion forces between planes

3. Metallic

No covalent bonding at all but a sea of mobile

valence electrons about a regular array of metal
cations
MP dependent on the number of valence electrons and the cationic radius of metal

e.g. Sodium, Tungsten [electrical and thermal conductors, ductile]

4. Ionic (REVISION)

Strongly attracted cations and anions held together electrostatically

Must be electrically neutral i.e. charges on ions dictate composition
Melting points exceptionally high despite lack of covalency (c.f network)

e.g. Melting point depend on:

- charge on anions and cations (higher=higher
mp)

Size of cations and anions:

- decreasing size leads to higher mp
(higher charge density) as does similar size

Solids- Properties

Covalent solids: hard and non malleable, require numerous covalent bonds to break before melting,
hence high mp
Ionic solids are brittle. Unlike metallic bonding, the charge carriers are not mobile and ANY distortion
results in electrostatic repulsion between ions

Liquids- a rare phase

The liquid phase is one of the rarest

e.g. there are only two liquid elements
 This seems counterintuitive because of the abundance of water on Earth

A narrow phase where the kinetic energy means the substance cannot remain independent (leads to
condensation), but is high enough to ensure free movement

Like solids, liquids are compact (have a specific volume) and like gases, are fluid and can flow from place
to place

THREE IMPORTANT PROPERTIES

Surface Tension

Surface tension is the resistance of a liquid to increase its surface area

- from attractive and cohesive intermolecular forces between molecules

In the liquid, each molecule experiences and participates in equal intermolecular

forces in all directions (see bottom image)

At the surface, a molecule is pulled back into the liquid by the same intermolecular
forces

Water is attracted to glass leading to a meniscus

Capillary Action- a result of adhesive forces

In a tube of small enough diameter, a liquid with an affinity for the tube will climb the walls due to
adhesive forces

This is counterbalanced by gravity (cf. Mercury barometer) i.e. the water can only rise so far:

Viscosity- how a liquid flow

 How viscous (or viscid) a liquid is derives from the strength of its IMFs and its molecular shape
- highly viscous liquids have stronger intermolecular bonding interactions than low viscosity liquids
- highly viscous liquids have higher surface areas

e.g.
Glycerol (H bonding)
Oil (dispersion)
Mercury (metallic bonding)

Liquid to Gas Co-existence

Our senses tell us that molecules escape from liquids,

even below their bp; e.g. petol, perfume, alchohol
Any substance has a kinetic energy distribution
Any exposed liquid will have some of its molecules in
the gas phase
A molecule may not have enough kinetic energy on
average to become a gas, but some molecules will be
able to escape into the gas phase

Vapour Pressure

The partial pressure of a liquid in a closed container gradually increases once the system has been
sealed
As partial pressure increases some gas molecules strike the liquid surface and are recaptured
Equilibrium is reached once the rates of gas to liquid and liquid to gas transitions are the same
The partial pressure of the gas above the liquid at equilibrium is the vapour pressure of liquid

Once the vapour pressure of a substance in an open container reaches the external pressure, the
substance is at its boiling point
 At 1 Atm (1.013 x 105Pa), this is the normal bp

Liquid materials can go into gas phase

Increase/decrease pressure= change bp

The vapour pressure of a liquid varies with temp

As temp INCREASES, vapour pressure also INCREASES

Vapour Pressure and the van der Waals constant a

The vapour pressure of a liquid (or solid) is proportional

to the a constant from the van der Waals equation

Thus a substance with strong IMFs will have a higher

critical temperature (the temp at which NO pressure
value can induce liquidation)

Phase Changes: Dependent on Intermolecular and Bonding Forces

When heat added- providing more energy

when 0 degrees, more energy has to be put in to actually change state

Phase Diagrams

The most stable phase of a substance at a range of T and P values can be represented pictorially by a
phase diagram
Blue Lines= phase boundaries, typically non linear scales
No line is straight and densities are not featured
 Blue arrows represent phase change processes and their correct terms
On any black line the substance is in a state of dynamic equilibrium-
The point where solid, liquid and gas meet is the triple point and represents dynamic equilibrium
between all three stable states
The normal bp and normal mp occur at a fixed P of 1.013 x 105 (dotted line)
Solid-Gas phase boundary always meets at origin of T-P axes

Dependence of mp and bp on T and P

The temperature for conversion between the gas phase and condensed phase depends strongly on
pressure
- compressing a gas increases collisions and favours condensation

The melting point is almost independent of P making the phase boundary almost a vertical line (since 2
condensed phases)
- pressure has hardly any effect on how compact a liquid or gas is

Phase Diagrams and Vapour Pressure

the vapour pressure of a solid or liquid is the pressure, P, at the point where that temperature, T,
intersects the solid-gas or liquid-gas phase boundary

Phase diagram for water Standard conditions

How to sketch a phase diagram

If provided with some key physical data for a substance, you should now be able to sketch a phase
diagram and predict phase changes qualitatively at specified conditions
i. Sketch P and T axes (vertical and horizontal respectively)
ii. Place a triple point in the lower left quadrant
iii. Place a critical point (if given in the upper right quadrant)
iv. Use the normal BP and MP (P= 1.013 x 105) to provide two further points
v. Draw linking lines to the extremes of the diagram, except the line that meets at the critical point
(line meets the origin of T-P axis)

Examples

NH3 has a normal boiling point of 240K and melting point of 196K. It has a triple point at P=0.0612 x 10 5
Pa and T= 195K
 SO2 has a normal boiling point of 263K and melting point of 200K. Its triple point is at 197K/167Pa and
its critical point is at 430K/7.9 x 106Pa. Solid SO2 has a vapour pressure of 132Pa at 178K.

Supercritical Fluids

We can liquefy gases by increasing the pressure of a system or cooling

As pressure increases, the gas is compressed into an even smaller volume
If the temperature is not too high, condensation/sublimation occur
 At a high enough temperature, no phase change occurs

What does SUPERCRITICAL look like?

On heating a liquid, more and more liquid molecules join the gas phase, increasing its density
At the same time, the liquid phase becomes less dense due to expansion
At the point where the densities become equal, we can no longer distinguish liquid from gas
The temperature and pressure at which this occurs is the critical point

Supercritical CO2
 As we all know CO2 is a by-product of many man-made
processes
Clean CO2, suitable for industrial applications, is freely
available from the brewing industry: non-toxic, non-corrosive,
easy to purify
The critical point of CO2 is not too far from standard
conditions:
7.38 x 106 Pa (70atm) at ambient T
It is commonly used to:
De-fat potato chips
Extract essential oils from plants
Extract pesticides from meat for analysis

Caffeine Withdrawal

Supercritical (sc) fluids have some important

commercial applications
Most important among these is the use of sc CO2 as a
solvent for industrial processes:
- Low viscosity
- High diffusion, even through solids
- No disposal issues

Decaffeination of coffee beans

Properties of Solutions

Solubility: a substance that is soluble in a liquid = solute, liquid that does the dissolving= solvent
There is a limit to the amount of a solute that can dissolve in a solvent
E.g. 365g NaCl(s) can dissolve in 1L water at 20C
E.g. 0.00089g AgCl(s) can dissolve in 1L water at 10C
A solution with the maximum amount of solute is a saturated solution

Strict Definition
Strictly speaking, a solution is a homogenous mix of two or more pure
substances
gas-gas combinations can be solutions, as can solid-solid (alloys)

for this course only liquid based solutions

Structure of Solutions

The laws of thermosdynamics govern whether a solute will dissolve

in a solvent

2 major thermodynamic factors:

- bond energies biggest driving force
- entropy (disorder/chaos) little change

The bond energies of the solid and solvent must be compensated

by the new bonds formed in the solution

Bond Energy Inputs and Outputs

The process of solid-liquid dissolution (dissolving a solid in a

solvent) is scarcely favoured by entropy (condensed matter to condensed matter)
Bond energies are the determining factor.

Energy inputs (cost energy):

- solute-solute affinities need to be overcome so solid
can disperse
- solvent-solvent intermolecular forces must be
overcome to allow solute to sit between solvent
molecules
- weak interaction between solid, solvent

Bond energy output (gives energy)

- solute-solvent bonds release energy

- strong interaction between solid and solvent

So how does this process affect the solution temp?

The interactions between solid and solvent when broken up more energetically favourable than those
between then 2 individual systems

QUESTION:
When GaCl3 dissolves in room temperature diethyl ether, some of the ether evaporates (bp: 34C)
True or False; GaCl3 forms weaker bonds with diethyl ether than those in pure GaCl3 and diethyl ether

Answer: False. If energy is given out, then its because it is making/forming more stable bonds in the
system that is forming increase in heat

Aqueous Solutions
 Hydrogen bonding in water is strong
There is substantial energy cost when hydrating a solute, and the substance will only dissolve if that
energy is repaid
Solutes that dissolve in water:
Ionic- they dissociate to give ions that form strong ion-dipole bonds
Non ionic, but ionise in water to form strong ion-dipole bonds
Hydrogen bond forming- have either H bond donors or acceptors (ideally both)
Polar- form strong dipole-dipole bonding interactions with water
These patterns are consistent with the like dissolves like principle of solute solubility

Like dissolves like- liquid-liquid miscibility

Ethanol freely dissolves in water, but benzene does not

What happens to a solutions temp when strong H- bonds form?

- Temp goes up as a result of favourable interactions

Ethanol dissolved in water- the H bond causes a

Low Polarity Solvents and Ionic Solutes large amount of energy to be released when these
liquids are mixed/dissolved
Liquids like benzene, long chain alkanes (e.g. petroleum) and
carbon tetrachloride CCl4, dissolve non/low polarity solutes
In these solvents, the forces of intermolecular attraction are predominantly dispersion forces
The solutions formed are similarly dispersion force rich- enough to overcome any resistance towards
dissolving

Properties of Solutions- Mark II

The properties of gases can be effectively modelled under moderate conditions using the ideal gas law
This is because at these conditions, the influence of IMFS and molecule/atom size are minimal
We cannot make this assumption for solutions b/c
Density is higher
IMFs highly influential

The influence of T and P on solutions (or condensed matter) cannot be predicted as easily

Solution composition (+ properties of parent species) are the best guide to the properties of a
solution

Ideal Solutions (gases)

An ideal solution is defined as one where all the intermolecular forces (solute-solute, solvent-solvent
and solute-solvent) are equivalent no change in temp, no energy given out, no change in Energy

For many solvent mixtures, the vapour pressure of the mixture can be predicted accurately by assuming
the solution is ideal

A non ideal solution results when this is not the case

Raoults Law
 Addition of a non-volatile solute to a volatile solvent increases the boiling point of the solvent
REMEMBER: the bp of a substance is the temp where the vapour pressure = atmospheric pressure
As long as the solution is sufficiently dilute, Raoults law describes the relationship between solvent
vapour pressure (Psolution) mole fraction of the solvent (Xsolvent) and the vapour pressure of the pure
solvent (Psolvent)

Raoults Law: Psolution = (Xsolvent)(Psolvent)

This linear relationship can also be used to discern the mole fraction of the
solute

Xsolvent = 1- Xsolute

Psolution = (1- Xsolute t)(Psolvent) Psolution = Psolvent - (Xsolute)(Psolvent)

Leading to a P term: P = (Xsolute)(Psolvent)

Visual representation

Example Calculation

What is the vapour pressure of a solution of 10g candle wax in 40g of carbon
tetrachloride at 23C. Mw candle wax 310.59gmol-1, Mw CCl4 153.81gmol-1, and the
vapour pressure of CCl4 is 1.32 x 104 Pa at 23C.

Solutions Containing Two Volatile Components

 When two or more components are volatile, the
vapour contains molecules of each species

The vapour pressure is composed of partial

pressures from each species

By Raoults law, the partial pressure of a component

is proportional to its mole fraction in the liquid-
liquid solution

Example
What is the vapour pressure of a solution of 50:50 acetone:water at 20C? At 20C the
vapour pressures of acetone and water are 2.13 x 104 Pa and 2.3 x 103 Pa
respectively. Assume the solution obeys Raoults law

We need to calculate the partial pressures of each and add them

Derivations from Raoults Law

Positive deviation: when the A:B intermolecular forces are weaker than the A:A and B:B forces, a mixture
of A and B will give a higher vapour pressure (Ptotal) than predicted by Raoults Law.

Negative deviation: when the A:B intermolecular forces are stronger than the A:A and B:B forces, a mixture
of A and B will give a lower vapour pressure (Ptotal) than predicted by Raoults Law.
Distillation

The composition of the vapour above a mixture of solvents is usually different from solution (richer in
more volatile species)
collection of the condensed vapour enriches the volatile component
It is not practical to conduct repeated distillations to achieve complete separations
A fractionation column is used= high surface area column that affects many mini evaporation-
condensation cycles

Oil: fractional distillation on an industrial scale