The ratios Na/Li, K/Li, Na/Cs and K/Cs have been calculated for exchange equilibria among the Li and Cs silicates spodumene, petalite, eucryptite, and pollucite, and the alkali feldspars albite and K-feldspar plus quartz, in pure water and in chloride solutions at temperatures from 100° to 700°C and pressures from 0.5 to 4 kbar, using available thermodynamic data for minerals and the modified HKF equation of state for aqueous species. For exchange equilibria between Li-bearing aluminosilicates and the alkali feldspars, the activities of the alkali metals in solution under most of the conditions investigated follow the order Li>Na>K, and Na/Li and K/Li decrease with decreasing temperature. For exchange equilibria between pollucite and the alkali feldspars the order is Na>K>Cs in solution; Na/Cs and K/Cs increase strongly with decreasing temperature. The absolute values of these alkali metal ratios are in good agreement with the few available experimental data. The effect of chloride ion pairing on the calculated ratios is slight and does not consistently improve agreement between theory and experiment. These results suggest that the alteration of eucryptite, petalite or spodumene to albite and/or K-feldspar should be a normal consequence of the closed system evolution of rare element pegmatites upon cooling, in agreement with the ubiquity of such phenomena world-wide. On the other hand, alteration of pollucite to albite or K-feldspar upon cooling is only likely to occur if external fluids, with very high Na/Cs and/or K/Cs ratios, gain access to the pegmatite. Owing to the heterogeneity of rare element pegmatites, the fluid need not be external to the entire pegmatite, but could be simply external to the particular zone containing pollucite. Fluids in equilibrium with typical subsolidus rare metal pegmatite assemblages will invariably have high Li contents, thus explaining the common occurrence of Li-metasomatic halos about pegmatites. These same fluids are predicted to have relatively low Cs contents, in apparent agreement with the lesser role of Cs relative to Li in metasomatic halos. However, preferential formation of complexes of the alkali metals with fluoride, borate or aluminosilicate components potentially could alter the calculated alkali metal behaviors.