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Title: Association constants in water at high temperatures
Author: Simpson, Peter William George
ISNI:       0000 0001 3413 5673
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1979
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A non-linear, spectrophotometric, least-squares computer program has been used to calculate 'best fit' association constants and extinction coefficients for various complexes in aqueous solution without the need to use buffers or to make measurements of pH. Spectrophotometric studies at temperatures between 5° and 200°C in aqueous solution have been undertaken of the protonation of the diacidic bases 2,2',2"-terpyridine, 4,4'-bipyridine and 2-aminomethylpyridine. Two association constants each have been determined for 2,2',2"-terpyridine and 4,4'-bipyridine and one association constant, that of the ring nitrogen atom, for 2-aminomethylpyridine. Protonation constants have also been determined for the ring nitrogen atoms of 8-aminoquinoline, 8-hydroxyquinoline and pyridine. With the exception of 2-aminomethylpyridine, all the compounds exhibited straight line van't Hoff plots within the estimated experimental error (~+/-0.02log(K) units). Values for the standard enthalpy and entropy of reaction have been calculated which are of higher precision than have been available previously. In addition, the overall association constant for the complex ion bis (2,2',2"-terpyridine) iron (II) has been measured at temperatures between 25 and 200 C using techniques similar to those employed in the studies of base protonation. The association constant for the first chloro-complex of cadmium (II) has been studied between 25° and 250°C using a silver-silver chloride concentration cell with transference. Studies were made in perchloric acid media at ionic strengths of 0.8, 1.3 and 2.3mol. kg[-1] and the results interpreted in terms of changes in the mean activity coefficient of the bulk electrolyte with ionic strength and temperature. Finally, the association constant for the first chloro-complex of copper(II) was studied spectrophotometrically to 100+/-C in a perchloric acid medium of ionic strength 1.0mol.l[-1].
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available