Studies of Ionic Interactions in Solutions

Armitage, Gilbert Martin (1971) Studies of Ionic Interactions in Solutions. PhD thesis, University of Glasgow.

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The object of the present work was to examine the interactions which occur in aqueous solutions which contain alkaline earth cations and anions of dicarboxylic acids. The calcium-oxalate system was to be examined in detail with special reference to the protonated complexes formed by the species hydrogen oxalate. In order to examine the calcium hydrogen oxalate system, reliable values of the dissociation constants of oxalic acid were required so that the concentrations of anionic species in the solutions could be calculated. The thesis is divided into three parts. The first part describes the determination of the dissociation constants of oxalic acid in an ionic medium maintained at 0.1 molar by sodium perchlorate. A potentiometric titration method has been used and the results of the titrations are compared with earlier work on the dissociation constants of oxalic acid. Good agreement has been obtained. The second and principal part of the thesis involves the determination of the stability constants of a number of complexes formed between alkaline earth cations and anionic dicarboxylic acid ligands. The cation exchange method has been used and the theory of the method is described. The experimental difficulties which were encountered are introduced and the methods which were used to overcome these difficulties are described. The systems which were examined were the following: calcium oxalate, calcium malonate, calcium succinate, calcium tartrate, strontium oxalate, strontium tartrate, calcium hydrogen oxalate and strontium hydrogen oxalate. Where comparison with other published work was possible, good agreement was found. A critical comparison was made of the stabilities of corresponding acetate and hydrogen oxalate complexes and use was made of such other data in the literature as were relevant. The denticity of the hydrogen oxalate ligand was examined and it was deduced that bidenticity was possible. Dissociation of the hydrogen oxalate complexes to the unprotonated complex and a hydrogen ion was considered in the light of a recent paper by some Russian workers and it was found that the empirical relationship which they had suggested was obeyed. The relative stabilities of all the complexes with the exception of the protonated complexes were considered in terms mainly of entropy contributions to the total free energy change in the reactions. The effect of the cross linking of the cation exchanger on the stability constants obtained by the ion exchange method was examined in the third part of the thesis. A large number of experiments were performed on resins with cross linking of 8%, 10% and 12% DVB. The results of the experiments were not conclusive because excellent agreement was observed between the results obtained for the 8% and 10% cross linked resins, but the 12% resin appeared to be out of line, but to an inconclusive extent. As far as can be seen this is in agreement with some earlier unpublished work on the same topic.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry, Physical chemistry
Date of Award: 1971
Depositing User: Enlighten Team
Unique ID: glathesis:1971-78563
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 30 Jan 2020 15:10
Last Modified: 30 Jan 2020 15:10

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