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Most cave chemistry revolves around calcite; CaCO3, the primary mineral in limestone. It is a slightly soluble mineral whose solubility increases with the introduction of carbon dioxide, CO2. It is paradoxical in that its solubility decreases as the temperature increases, unlike the vast majority of dissolved solids. This decrease is due to interactions with the carbon dioxide, whose solubility is diminished by elevated temperatures; as the carbon dioxide is released, the calcium carbonate is precipitated.
Most other solution caves that are not composed of limestone are composed of gypsum (calcium sulfate), the solubility of which is positively correlated with temperature.