17.1 - Phase equilibria
17.1.1 - State and explain the equilibrium established between a liquid and its own vapour. Liquid- vapour equilibrium is a dynamic equilibrium established when the rate of condensation equals the rate of vaporisation. The vapour pressure is independent of the volume of the container, liquid or vapour.
Liquid - vapour equilibrium
A liquid in an enclosed chamber will form an equilibrium with it's own vapour.
Fast moving particle in the liquid will escape from the surface and become part of the vapour, but slow moving particles in the vapour will be 'captured' by the liquid and become part of it. At a certain vapour pressure, the number of particles escaping (or evaporating) from the liquid will exactly equal the number being captured by it, and so a dynamic equilibrium is formed between the two.
Mixtures of liquids
When two liquids are in a mixture, particles from both liquids escape, forming a partial pressure for each above the mixture. The partial pressure of each liquid will be directly related to its volatility and to the mole fraction of it compared to the total number of mols in the liquid.
Separation of liquid mixtures
When it is necessary to separate the components of a mixture in which there is more than one volatile component, fractional distillation must be used. (simple distillation is when there is only one volatile fraction, and it is boiled off and the condensed).
Fractional distillation is achieved by continuous boiling of the two liquids while they are simultaneously being condensed (like in reflux) The more volatile liquid will escape from the top of the fractionating column side arm and be condensed in the cooling tube, while the less volatile component will be condensed in the fractionating tube of the column and returned to the boiling flask. In this way, it is possible to (in theory) completely separate the two components of the mixture.
17.1.2 - State and explain the qualitative relationship between vapour pressure and temperature. Students should be able to show the relationship graphically and explain it in terms of kinetic theory. When Kc >> 1, the reaction goes almost to completion. When Kc << 1, the reaction hardly proceeds.
Effect of temperature on vapour pressure
As the temperature increases, the average speed of particles is higher. As a result, more particles will have sufficient speed to escape the liquid, and fewer will be slow enough to be recaptured by the liquid. This means that as temperature increases, the equilibrium vapour pressure will also increase. This can be shown graphically with pressure against temperature, where, as temperature increases, so does the vapour pressure.
17.1.3 - State and explain the relationship between enthalpy of vaporisation, boiling point and intermolecular forces. Students should be able to predict the relative strength of the intermolecular forces of different liquids when given the physical properties or vice versa. Cross reference with 4.3
Enthalpy of vaporisation and boiling point
The boiling point (temperature) is reached when the vapour pressure is equal to atmospheric pressure. Liquids with a high boiling point have high intermolecular forces. The Enthalpy of vaporisation is a measure of the energy change when 1 mol of liquid is converted to gas at standard pressure. As a result a lower enthalpy of vaporisation implies that less energy is required to break the intermolecular bonds, and so a lower enthalpy of vaporisation will result in a higher vapour pressure.
|enthalpy of vapourisation||intermolecular forces||boiling point||vapour pressure|