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Precipitation has to be an exothermic process. We know this because the overall entropy change having to be positive (second law of thermodynamics) - and because the entropy change of the system is negative (two liquids forming one solid and one liquid) the entropy change of the surroundings must be positive (and also large enough to make up for the decrease in entropy of the system) for the overall entropy to be positive and the reaction to be spontaneous. Positive entropy of the surroundings equates to a negative value for delta H (and therefore an exothermic process).

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