Flow calorimetry can provide useful information about surface chemical reactions in soils that cannot be obtained readily by other methods. When flow calorimetry is conducted over a range of surface coverages, different sorption heats can be calculated to yield information about how binding energies vary with coverage, i.e., surface heterogeneity. The purpose of this study was to determine heats of exchange for K/Ca and K/Pb systems using flow calorimetry and to evaluate the degree of surface heterogeneity with respect to cation exchange. Surface horizon samples from a Typic Acrorthox and Typic Tropohumult from Puerto Rico were used. Lead was adsorbed specifically in both soils, but no adsorption heat was detected for this reaction in either soil. However, heats associated with reversible cation exchange between K and Pb were observed. Heats for K/Ca exchange were greater than those generated for K/Pb exchange in both soils. Heats of exchange were greater in the Ultisol than in the Oxisol. The differential heats of exchange were independent of exchange composition for both K/Pb and K/Ca exchange in the Oxisol, indicating that all cation exchange sites were similar energetically. In the Ultisol, the differential heats of exchange increased as exchangeable K decreased, indicating that the exchange sites were not similar energetically. These differences were attributed to the presence of smectite in the Ultisol, which was able, in part, to collapse when saturated with K.
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