A thermodynamic formalism is presented for the determination of the stepwise protonation constants of polyammonium ions adsorbed on solid surfaces. The extrastabilities of the ammonium ions w.r.t. their stability in bulk solution are related to the ion exchange constants of the respective ammonium ions versus hydrogen.
Examples are given for ethyleneidiamine and histamine on montmorillonite. The monoammonium form of both amines are stabilized to the same extent. The excess stability constant relating to the second protonation of histamine exceeds the one for ethylenediamine by an order of magnitude. The contribution of the individual ionic groups to the overall exchange affinity is discussed.
Bulk Solution Standard Free Energy Change Excess Stability Thermodynamic State Function Free Energy Loss
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