Abstract
The complex formation between different crown ethers and the cryptand [222] with alkali metal and ammonium ions in chloroform has been investigated by means of calorimetric titrations. The stability constants, reaction enthalpies and entropies for complex formation in chloroform have been determined. The complexation of alkali metal ions is favored by enthalpic contributions and influenced by both the ligand and the nature of the cation. The reaction enthalpies for complex formation of different ammonium salts with cryptand [222] are higher compared to the corresponding values for the reaction with different 18-crown-6 derivatives in chloroform due to the complete encapsulation of ammonium ion by the cryptand [222]. The benzo group attached to the crown ethers and the nature of the anion borne by the ammonium ion influence complex formation of ammonium with crown ethers. In the case of ammonium salts, competitive measurements have been carried out to underline the influence of the anion upon the complex formation. From the reaction enthalpies for complexation of ammonium ions, the contributions for the formation of hydrogen bonds are calculated using experimental data.
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Taken in part from the Ph.D. thesis of R.-C. Mutihac, University Duisburg-Essen, 2007.
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Buschmann, HJ., Mutihac, RC. & Schollmeyer, E. Complex Formation of Crown Ethers and Cryptands with Alkali Metal and Ammonium Ions in Chloroform. J Solution Chem 38, 209–217 (2009). https://doi.org/10.1007/s10953-008-9358-z
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DOI: https://doi.org/10.1007/s10953-008-9358-z