Synthesis of Hydrazine by the Fixation Process

  • T.J. Jermyn

Student thesis: Doctoral ThesisDoctor of Philosophy


A critical review of the literature concerning organic derivatives of hydrazine, the ammonia-chlorine reaction and the electrolytic formation of hydrazine has been carried out. Apparatus was constructed to study the electrolysis of liquid ammonia, the formation of chloramine and the fixation of chloramine with a ketone to form an isohydrazone. In the latter case the reaction was carried out in a 3" diameter stirred tank and also in a 1" diameter, 2' high column reactor where the liquid phase was continuously recirculated.
Two methods of analysis of azines and isohydrazones in a ketone solution have been developed. One is a colorimetric technique using
p-dimethylaminobenzaldehyde and the other involves the hydrolysis of the
organic derivative to hydrazine sulphate.
Hydrazine was detected in low concentration in some of the electrolytic
experiments carried out but it was concluded that this method did not show sufficient promise to warrant further investigation. The gas phase formation of chloramine and acetone isohydrazone has also been studied but in this system difficulties were encountered with the chlorine jet blocking with ammonium chloride.
The formation of isohydrazones in a stirred tank reactor has been
investigated in some detail and the effect of several parameters was
determined. The yield was found to be extremely sensitive to chlorine
concentration and in order to obtain yields of more than 90 per cent, the
molar concentration of chlorine in the gas phase had to be of the order of 5 per cent. An optimum temperature in the region of 0°C was also detected. These results disagree with those quoted in previous studies but extensive experimental work has confirmed the information presented in this thesis. It has also been shown that at high yields the chloramine formation reaction took place in the gas phase.
Date of AwardNov 1969
Original languageEnglish
SupervisorG.V. Jeffreys (Supervisor)


  • chemical engineering
  • hydrazine
  • synthesis
  • fixation

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