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Date of Award
Doctor of Philosophy (Ph.D.)
An extensive literature has been established on the use of high frequency conductometric methods in chemical analysis and research. The fact that the instruments respond to chemical changes without having electrodes immersed in the reacting solutions has attracted the attention of many investigators. Until the last few years, practically all of the investigations were concerned with aqueous solutions, with the exception of measurements of dielectric constants.
There seemed no logical reason for not extending the use of the high frequency instruments to the study of Bronsted acid-base reactions, organic syntheses, rates of reaction, and the other commonly studied aspects of non-aqueous chemistry. A few early works were published with regard to esterifications and the titration of weak acids in organic solvents; but no extensive reports were forthcoming on the general utility of high frequency titrimetry in non-aqueous systems until the paper of Grove and Jeffrey (1960). Since 1960, an increasing interest has been shown in nonaqueous use of high frequency titrimeters, as well be shown in the next chapter.
It seemed only a matter of time until someone would perform the research necessary to allow the use of solvents which could be kept in the liquid state (at atmospheric pressure) only at low temperatures. The classical example of such a solvent is liquid ammonia which boils at -33.4°C., but a great deal of work has been done in other low temperature solvents such as sulfur dioxide, hydrogen cyanide and hydrogen fluoride. A major obstacle to the use of such low temperature liquids with high frequency titrimeters was the lack of a suitable cell; one which could maintain the low temperature necessary to preserve the liquid state for the protracted periods of time required to perform titrations.
Thus it was th purpose of the present investigation to develop a cell which would permit the use of high frequency titrimeters for studying low temperature, nonaqueous solvents--specifically ammonia. On the assumption that a suitable cell could be constructed, a further aspiration of the research was to investigate the response of high frequency titrimeters to a sufficient number of liquid ammonia reactions to show that an attractive area of chemical research had been exposed by the development of the cell.
Hileman, Jack Charles. (1963). High Frequency Titrations In Liquid Ammonia. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/2872