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Its all to do with enthlapy and entropy.

Anything which is soluble usually has a negative standard enthlapy of solution - the energy involved when 1 mole of solute dissolves in a solvent to give an infinately dilute solution. However, NaCl has a slightly positive enthalpy of solution, yet it dissolves.

The reason for this is entropy - the change in the amount of disorder. When NaCl dissolves in solution, there is more chaos, more molecules within the solution. Any process that has a large positive entropy change will be favourable - spontaneous and can occur (reaction will 'go').

However, with CaO, the Ca2+ formed in solution has a high affinity (attraction to) for water molecules, hence a lot of water molecules are arranged orderly - less chaos and hence a negative entropy. This should in effect make the compound insoluble, however, the slight solubility is due to it still having a negative enthalpy change of solution - hence despite entropy it is still slightly soluble.

(You may be asking how is dissolving CaO possible if entropy is negative? The entropy of the system maybe negative, but the entropy of the surroundings is positive (dissolving gives out heat - exothermic), hence the overall entropy (sum of both entropies) is positive and the reaction will 'go'.

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