Chemistry of hydrazine derivatives

Abstract

The chemistry of hydrazine and its derivatives is of interest because of their use as rocket fuel, solid propellant oxidizers, explosives, antioxidants, insecticides, food preservatives, pharmaceuticals and materials for resins, coatings, adhesives, etc. Since most of the work is classified, attempt has been made to synthesize and characterize a variety of hydrazine derivatives. The chemistry of hydrazine and its derivatives relevant to our work has been critically reviewed in Chapter?1. Chapter 2 describes a simple and novel method of preparation of hydrazinium derivatives. A number of simple hydrazinium salts have been prepared, characterized by chemical analysis and infrared spectra. Thermal properties have also been studied by differential thermal analyses. A new fluoride derivative of hydrazine has been reported for the first time. Chapter?3 describes the preparation of N?H?HF? by chemical and thermal methods. The thermal properties of N?H?HF? are compared with those of N?H?F?. Chapter?4 deals with the reaction of ammonium metal double sulphates with hydrazine hydrate. The reaction proceeds through (i) (N?H?)?M(SO?)?·3N?H?, (ii) (N?H?)?[M(OH)?(N?H?)?], (iii) M(N?H?COO)?(N?H?)?, (iv) N?H?[M(H?2H?COO)?] to give corresponding hydrates, (v) N?H?M(N?H?COO)?·H?O. Possible reaction mechanisms for the observed intermediates and products have been given. Mössbauer studies of the iron complexes (N?H?)?Fe(SO?)?·3N?H? – I, (N?H?)?[Fe(OH)?(N?H?)?] – II, Fe(N?H?COO)?(N?H?)? – III, N?H?[Fe(N?H?COO)?] – IV, N?H?Fe(N?H?COO)?·H?O – V have been investigated and included as Appendix in Chapter?4. In Chapter 5 the thermal decomposition of the various compounds described in Chapter?4 has been studied using TGA, DTA, mass spectra, infrared spectra and X?ray. The results are discussed in greater detail in this chapter. A number of new energetic oxidizers for possible use in solid propellants have been synthesized. Chapter?6 deals with the preparation, characterization and thermal properties of (i) N?H?Al(ClO?)?·2N?H?, (ii) Li?Al(ClO?)?, (iii) Al(ClO?)?·3N?H?. Aluminium perchlorate hydrazinate has been investigated as a solid propellant oxidizer in place of ammonium perchlorate which is used universally as a solid propellant oxidizer.