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MODULE G: THE LIQUID

STATE
CHM 1101
Oct. 23, 2014

Liquids: An Introduction
In a liquid, the atoms or molecules are usually separated

by somewhat greater distances than in a solid.

Movement of atoms or molecules gives a liquid its most
distinctive property: the ability to flow.
Covers the bottom and assumes the shape of its
container.

Mixtures
Mixtures can be classified as either heterogeneous or

homogeneous
Heterogeneous mixture - mixing of components is visually
non-uniform and has distinct regions of different
composition e.g. sugar & salt, oil & water.
Homogeneous mixture mixing is uniform, (at least to the
naked eye) and has a constant composition throughout e.g.
seawater (sodium chloride with water) and brass (copper
with zinc).
Homogeneous mixtures can be classified according to the
size of their constituent particles as either solutions or
colloids

Solutions
A solution is a homogenous mixture of substances in

which no settling occurs.

Contain particles with diameters in the range 0.12 nm.

Colloids, such as milk and fog, contain larger particles,

with diameters in the range 2500 nm.

Solutions
For solutions in which a gas or solid is dissolved in a

liquid, the dissolved substance is called the solute and

the liquid is called the solvent.
The ability of a solid to go into solution depends on the
strength of attraction among particles.

Dissolution
Solids in liquids: the smaller the magnitude of the solute-

solute interactions, the more readily dissolution occurs.

Solubility is the mass of a substance that can dissolve in
100 g of water at a given temperature.

Dissolution
Liquids in liquids: When a liquid dissolves in another, it is

said to be miscible.
Polar liquids dissolve in polar solvents, e.g. ethanol, C 2H5OH, will

dissolve in water, H2O.

Non-polar liquids are soluble in other nonpolar solvents, e.g.

toulene and hexane are miscible.

Gases in liquids: some nonpolar gases (CO2 and O2) will

dissolve in polar solvents such as water. Gases such as

HF, HCl and CO2 will dissolve in water due to hydrogen
bonding, ionization and other reactions.

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Water

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Solutions and Solubility

Solubility of solids in liquids as temperature increases?
Solubility of liquid and gases as temperature increases?
The effect of pressure changes on solubility of solids and

liquids in liquids?
Solubility of gases in solvents increases as

partial pressures of gases increase.

E.g. Carbonated water.

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Henrys Law
The pressure of a gas above the surface of a solution is

proportional to the concentration of the gas in the solution.

- the pressure of the gas above the solution

Henrys constant (specific for a given gas and solvent at a T)
- the concentration of the dissolved gas in molarity or mole fraction

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Using Henrys Law

At 0C and an O2 pressure of 1.00 atm, the aqueous

solubility of O2(g) is 48.9 mL O2 per litre. What is the

molarity of O2 in a saturated water solution when the O2 is
under its normal partial pressure in air, 0.2095 atm?

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Vapour pressure
The pressure exerted by a vapour in dynamic equilibrium

with its liquid is called the vapour pressure.

Liquids with high vapour pressures at room temperature are

said to be volatile, and those with very low vapour pressures

are non-volatile.
Liquid boils when its vapour pressure equals atmospheric
pressure.
Volatility is determined by intermolecular forces.

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Vapour Pressure

(a) A mercury barometer.

(b) The pressure exerted by the
vapour in equilibrium with a liquid
injected to the top of the mercury
column depresses the mercury
level. (c) Compared with (b), the
vapour pressure is independent
of the volume of liquid injected.
(d) Compared with (c), the vapour
pressure is independent of the
volume of vapour present. (e)
Vapour pressure increases with
an increase in temperature

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Vapour pressure
The weaker the intermolecular forces, the more volatile

the liquid (the higher its vapour pressure).

Liquid

Vapour Pressure
(mm Hg)

Diethyl ether

534

Volatile

Acetone

231

Volatile

Water

23.8

Moderately
volatile

0.0018

Non-volatile

Mercury

Volatility

What can we say about the intermolecular forces?

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Vapour Pressure
Liquids with strong inter-molecular
forces would have low vapour
pressures.
Vapour Pressure increases with T
up to a maximum of B.P. of liquid.

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Raoults Law
In the 1880s, the French chemist F. M. Raoult found that a

dissolved solute (impurity) lowers the vapour pressure of the

solvent.
Raoults Law states: the partial pressure exerted by a solvents
vapour above an ideal solution, PA, is the product of the mole
fraction of solvent in the solution, XA and the vapour pressure of
the pure solvent at the given temperature, PA
PA = XA P
A

The vapour pressure of a volatile liquid is directly proportional the

mole fraction of that liquid in an ideal mixture.

Applies only to ideal solutions and to all volatile components of the solutions

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Ideal Mixture of Volatile Liquids

Ideal mixtures obey Raoults Law.
Intermolecular forces before and after mixing are

approximately the same.

The tendency of the molecules to escape is unchanged in

an ideal mixture.

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Ideal Mixture of Volatile Liquids

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Predicting Vapour Pressures of Ideal Mixtures of

Volatile Liquids
Example 1
The vapour pressures of pure benzene and pure toluene
at 25C are 95.1 and 28.4 mmHg, respectively. A solution
is prepared in which the mole fractions of benzene and
toluene are both 0.500. What are the partial pressures of
the benzene and toluene above this solution? What is the
total vapour pressure?
Pbenz = 47.6 mmHg
Ptol
Ptotal

= 14.2 mmHg
= 61.8 mmHg

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Predicting Vapour Pressures of Ideal Mixtures of

Volatile Liquids
Example 2
What are the partial and total vapour pressures of a

solution obtained by mixing 35.8 g benzene, and 56.7 g

toluene at 25C? At 25C, the vapour pressure of the
C6H6 = 95.1 mmHg and the vapour pressure of C6H5CH3 =
28.4 mmHg.
Remember:

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Vapour Composition
Vapour in equilibrium with two volatile liquids will contain

more molecules of the more volatile liquid.

Example 3: What is the composition of the vapour in
equilibrium with the benzene/toluene solution of Example
1?
Need to find the mole fraction of each component in the vapour phase.

There is more benzene in the vapour phase than in the

liquid phase.

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Vapour Composition