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Title: Polarisation studies of amine salts and related compounds
Author: Bauge, Kjell
Awarding Body: University of London
Current Institution: Royal Holloway, University of London
Date of Award: 1962
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In benzene solution the dielectric polarization and dipole moments have been measured for a number of tertiary and quaternary alkylammonium salts, and for some of the former the infrared absorption spectra have also been studied. The state in solution of the tertiary salts can be formulated by the equilibrium: [equation] Since the equilibrium between Steps 1 and 2 is concentration dependent, and that between steps 2 and 3 is not, and also because the equilibrium is shifted to the right on increasing acid strength, the polarization changes with both these variables. At low concentrations and for weak acids the polarization increases non-linearly with increasing concentration and acid strength. As this increases, a progressively larger part of the plot becomes linear and takes on anincreasingly negative slope for the stronger acids. The latter effect is due to polyions. From the polarization variation with concentration,the overall equilibrium constant between unassociated acid and amine and associated species has been evaluated; and by some assumptions as to the values of the dipole moments of hydrogen bonded species and ion pairs, and were estimated. Some of the quaternary salts showed a marked decrease of polarisation with concentration owing to association of the ion pairs; and a modified procedure, used by Pohl, Hobbs and Gross in studies of carboxylic acid dimerization, has been employed in the evaluation of the dipole moments. By an extension of Debye's theory the charge distances in ion pairs have been calculated and the results are in good agreement with the corresponding Bjerrum distances. The infrared measurements showed presence of free acid and amine, hydrogen bonded species and ionic species in a measure predicted by the above equilibrium.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Molecular Chemistry