4.

1: Energetics II
Definitions
Enthalpy of atomisation is the enthalpy change when one mole of gaseous atoms is formed from the original element in its most stable state at 1atm pressure and 298K. E.g. Na(s) Na(g) Enthalpy of hydration is the enthalpy change when one mole of gaseous ions is dissolved in excess water to form an infinitely dilute solution. E.g. Ca2+(g) + aq Ca2+(aq) Lattice energy is the exothermic enthalpy change when one mole of ionic solid is formed from its constituent ions. E.g. M+(g) + X- (g) M+X-(s)

Born-Haber cycles
A Born-Haber cycle is a Hesss law cycle in which: - the direct change is from elements to a solid ionic compound - the indirect route involves atomising the elements, ionising the atoms and bringing the gaseous ions together to form the solid ionic compound. Application of Born-Haber cycles Born-Haber cycles can be used to determine the electron affinity of an atom or the lattice enthalpy of an ionic solid.

Factors affecting lattice energy

Ionic charge The greater the charge, the stronger the force between the positive and negative ions. Therefore, the lattice energy is more exothermic. Sum of the ionic radii The smaller the sum of the ionic radii, the stronger is the force between the positive and negative ions. Therefore the lattice energy is larger. Lattice energy values calculated using the Born-Haber cycle are always more exothermic than values calculated using the purely ionic model. The lattice energy also depends upon the extent to which the anion is polarised by the cation, which causes a slight degree of covalency. Larger anions are

more easily polarised. Smaller, highly charged cations are powerful polarising agents. If a significant degree of polarisation occurs, the experimental lattice energy obtained from a Born-Haber cycle will be greater than that calculated from the purely ionic model.

Solubility and trends

A solute is soluble in a given solvent if the energy required to separate the solute particles is compensated for by the energy released in the attractions between the solute particles and the solvent molecules. Enthalpy of solution of ionic substances Using Hesss law, we can show that. Enthalpy of solution = -lattice energy + sum of hydration enthalpies of ions From this equation, we can see that if the exothermic hydration enthalpies compensate for the endothermic breakdown of the lattice (-lattice energy), enthalpy of solution will be negative, i.e. exothermic, and the ionic solid will dissolve in the solvent. Solubility of group 2 hydroxides - Solubility increases down the group. - The charge on the ions does not change. - The radius of the cation increases as the group is descended. The hydroxide ion has a radius similar to the group 2 cations, so the sum of the ionic radii increases significantly down the group. This means that the lattice energy decreases sharply down the group. - The hydration enthalpy of the cation is independent of the anion and also decreases sharply as the group is descended. - The lattice energy decreases slightly more than the hydration enthalpies, and so enthalpy of solution becomes more exothermic. - Hence the solubility of the group 2 hydroxides increases down the group. Solubility of group 2 sulphates - Solubility decreases down the group. - The charge on the ions does not change. - The radius of the cation increases as the group is descended. The sulphate ion has a very large radius compared to the group 2 cations, so the sum of the ionic radii is hardly affected. This means that the lattice energy decreases slightly down the group.

The hydration enthalpy of the cation is independent of the anion and also decreases sharply as the group is descended. The hydration enthalpies of the ions decreases more than the lattice energy of the ionic compound, and so enthalpy of solution becomes more endothermic. Hence the solubility of the group 2 sulphates decreases down the group.