Inorganic Hydrazine Derivatives E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 383

Veröffentlichungsjahr: 2014

Beschreibung

Traditionally, interest in the chemistry of hydrazine and its derivatives has been focused on the development of propellants and explosives, but in recent years a wide variety of new applications have emerged in fields such as polymers, pharmaceuticals, water treatment, agriculture and medicine. Inorganic Hydrazine Derivatives: Synthesis, Properties and Applications presents a comprehensive review of the research carried out in this field during the last four decades.

Methods for synthesizing inorganic hydrazine derivatives and complexes are systematically presented, together with details of their characterization, spectra, thermal analysis, crystal structure, and applications. Strong emphasis is given to controlling the reactivity of hydrazine derivatives from detonation to deflagration to decomposition. The monograph also highlights current developments and applications of inorganic hydrazine derivatives, including the synthesis of nanostructured materials.

Topics covered include:

• An introduction to hydrazine and its inorganic derivatives
• Hydrazine salts
• Metal hydrazines
• Metal hydrazine carboxylates
• Hydrazinium metal complexes
• Applications of inorganic hydrazine derivatives

This applications-based handbook is a valuable resource for academics and industry professionals researching and developing hydrazine compounds, high energy materials, nanomaterials, and pharmaceuticals.

Leseprobe

Contents

Cover

Title Page

Copyright

Dedication

List of Contributors

Foreword

Preface

Acknowledgements

Chapter 1: Hydrazine and Its Inorganic Derivatives

1.1 Introduction

1.2 Inorganic Hydrazine Derivatives

1.3 Characterization of Inorganic Hydrazine Derivatives

1.4 Applications of Inorganic Hydrazine Derivatives

References

Chapter 2: Hydrazine Salts

2.1 Introduction

2.2 Salts of the Monovalent Cation (N2H5+) – N2H5A

2.3 Salts of the Divalent Cation [(N2H5)22+ and N2H62+]

2.4 Salts of Monovalent (N2H5+) and Divalent [(N2H5)22+, N2H62+] Cations

2.5 Hydrazine Salts of Organic Acids

2.6 Summary

References

Chapter 3: Metal Hydrazines

3.1 Introduction

3.2 Metal Hydrazines – MX(N2H4)n, M = metal, X = SO4, SO3, N3, NCS, NO3, ClO4, RCOO, and so on, (n = 1–3)

3.3 Reactivity of Metal Salt Hydrazines (from Detonation to Deflagration to Decomposition)

3.4 Summary

References

Chapter 4: Metal Hydrazine Carboxylates

4.1 Introduction

4.2 Metal Hydrazine Carboxylates – M(N2H3COO)2

4.3 Metal Hydrazine Carboxylate Hydrates – M(N2H3COO)n·xH2O; n = 2, 3

4.4 Metal Hydrazine Carboxylate Hydrazines – M(N2H3COO)2·(N2H4)2

4.5 Hydrazinium Metal Hydrazine Carboxylate Hydrates –N2H5M(N2H3COO)3·H2O

4.6 Solid Solutions of Hydrazinium Metal Hydrazine Carboxylate Hydrates – N2H5 M(Co/Fe/Mn)(N2H3COO)3·H2O

4.7 Summary

References

Chapter 5: Hydrazinium Metal Complexes

5.1 Introduction

5.2 Hydrazinium Metal Sulfates

5.3 Hydrazinium Metal Oxalates

5.4 Hydrazinium Metal Halides

5.5 Hydrazinium Metal Thiocyanates – (N2H5)2M(NCS)4·2H2O, M = Co and Ni

5.6 Recent Studies on Hydrazinium Metal Complexes

5.7 Summary

References

Chapter 6: Applications of Inorganic Hydrazine Derivatives

6.1 Introduction

6.2 Applications of Hydrazine Salts

6.3 Energetic Materials

6.4 Combustible Metal Hydrazine Complexes

6.5 Miscellaneous Applications

References

Index

This edition first published 2014

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Library of Congress Cataloging-in-Publication Data

Inorganic hydrazine derivatives: synthesis, properties, and applications / edited by K.C. Patil and Tanu Mimani Rattan.

pages cm

Includes index.

Includes bibliographical references.

ISBN 978-1-118-71513-0 (hardback)

1. Hydrazines. 2. Hydrazines–Industrial applications. I. Patil, K. C., editor of compilation. II. Rattan, Tanu Mimani, editor of compilation.

QD181.N1I572014

661–dc23

2013037822

A catalogue record for this book is available from the British Library.

ISBN: 9781118715130

Dedicated To

“Eckart W. Schmidt – The Hydrazine man”

List of Contributors

Singanahally T. Aruna Surface Engineering Division, CSIR-National Aerospace Laboratories, Bangalore, India

Dasaratharam Gajapathy K.M.G. College of Arts & Science, Gudiyathum, India

Subbiah Govindrajan Department of Chemistry, Bharathiar University, Coimbatore, India

K. C. Patil Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India

Tanu Mimani Rattan Department of Physics, Sri Sathya Sai Institute of Higher Learning, Prasanthi Nilayam, India

Foreword

Of the two dozen or so known binary compounds of nitrogen and hydrogen, only three are economically significant. Arranged in descending order of importance these are ammonia, hydrazine, and hydrazoic acid. The discovery of phenylhydrazine (1875) and other substituted hydrazines by Fischer preceded that of hydrazine itself by several years. Curtius first prepared hydrazine from ethyl diazoacetate following a circuitous route (1887). Serious research on the structure and reactivity of hydrazine could begin only after its ready availability was assured by Raschig's discovery of its simple and effective synthesis via oxidative coupling of ammonia (1907). A relatively weak N–N bond, two nucleophilic nitrogen sites, multiple replaceable hydrogen atoms, variable reducing power, endothermicity, and high heat of combustion are among the factors that have added unique features to the chemistry of hydrazine. These in turn have prompted extensive uses of hydrazine and its derivatives in the chemical industry, encompassing polymers, agriculture, pharmaceuticals, explosives, water-treatment, and more. Hydrazine and its derivatives also feature in space missions, where the versatility and reliability of hydrazine-powered propellant systems have performed a signal role.

An account of the state of hydrazine chemistry preceding the middle of the last century was chronicled by Audrieth and Ogg in their book The Chemistry of Hydrazine (1951). Nearly three decades later, Schmidt's compendium Hydrazine and its Derivatives, Preparation, Properties, Applications appeared in 1984. The explosion in hydrazine literature (4400 references) was apparent and in the second edition (2001) of this authoritative book the number of references nearly doubled! Hydrazine and its derivatives very much remains a living arena for continued scrutiny and practical use.

Patil and his students have been intimately associated with several facets of hydrazine chemistry for many years at the Indian Institute of Science, Bangalore. They have enriched the basic chemistry by developing newer methods of preparing hydrazinium salts and by exploring the synthesis and structure of hydrazinium complexes of metal salts. They were also deeply involved with applied aspects such as in the development of energetic oxidizers for solid propellants and of detonators, some of which have commercial success stories to tell. The group also succeeded in preparing technologically important transition metal oxide nanomaterials utilizing combustible carboxylic metal hydrazine salts as starting materials.

The rich contributions of the group to both basic and applied inorganic chemistry of hydrazine have been documented in the literature over the years. Patil and Rattan have now carried out a commendable service by organizing the material into a logical and connected account laid out against the broader background of hydrazine chemistry. The outcome is the present monograph, which has six chapters and is appropriately titled Inorganic Hydrazine Derivatives: Synthesis, Properties and Applications. The chapters are divided into sections and subsections for both basic and applied activities and include recent work on these topics by other groups. I expect this book to become a must for all those with direct interest in hydrazine chemistry and technology. It should also arouse considerable general interest in the inorganic chemistry and material science communities. I feel very pleased to write this Foreword for a work that highlights the noteworthy contributions to the pure and applied chemistry of hydrazine derivatives from India in the last few decades. On visits to Bangalore I had the opportunity to watch Patil et al. making progress in silent dedication. It is now time for me to congratulate them as I browse through their text.

Animesh Chakravorty

Emeritus Professor and Ramanna Fellow

Indian Association for the Cultivation of Science

Kolkata, India

August 2013

Preface

The chemistry of hydrazine and its derivatives continues to be of interest to chemists, material scientists, and engineers due to their applications in propellants, explosives, polymers, pharmaceuticals, medical, and agricultural fields. Although there are several reviews on this subject there are very few books devoted to the chemistry of hydrazine. The latest voluminous work on hydrazine authored by Eckart W. Schmidt – the hydrazine man – was published over a decade ago in 2001. It contains a wealth of information, citing nearly 8400 references, signifying the importance of hydrazine and its derivatives. The research work of the authors has been cited in this book.

The present monograph, Inorganic Hydrazine Derivatives: Synthesis, Properties and Applications, is a compendium of the research work carried out during the last four decades by the authors at the Indian Institute of Science, Bangalore. An attempt has been made to present the work on inorganic hydrazine derivatives over six chapters. Details of the synthesis, spectra, thermal analysis, crystal structure, and applications of inorganic derivatives of hydrazine such as hydrazine salts, metal hydrazines, metal hydrazine carboxylates, and hydrazinium metal complexes are expounded in a systematic manner. Recent contributions by other groups working in similar areas have also been examined. The monograph also highlights current developments and applications of inorganic hydrazine derivatives, including the synthesis of nanostructured materials.

Chapter 1 – Hydrazine and its Inorganic Derivatives briefly describes the chemistry of hydrazine, its physical and chemical properties. A clear distinction is made between hydrazine and hydrazine hydrate in terms of structure and properties. Since there is hardly any difference in the chemical properties of the two, a case is made for the use of hydrazine hydrate instead of the hazardous and toxic anhydrous hydrazine. A brief literature survey on the synthesis and crystal structure of various hydrazine salts and metal hydrazine complexes is presented. Various thermoanalytical and spectroscopic techniques used in the characterization of hydrazine compounds and metal complexes are discussed.

Chapter 2 – Hydrazine Salts discusses the synthesis and characterization of the inorganic salts of hydrazine. A novel and simple method of preparing hydrazinium salts by the heterogeneous reaction of solid ammonium salts with hydrazine hydrate is presented. The preparation and characterization of numerous N2H5A salts, where A = halide, , , , SCN−, acetate, and so on, are profiled. The formation of N2H5HF2 and N2H5HSO4 by this method is reported for the first time. These salts are characterized by infrared spectroscopy and differential thermal analysis (DTA), and their properties compared with those of N2H6F2 and N2H6SO4, respectively. Interestingly, few hydrazine salts form hydrates: for example, N2H5ClO4·0.5H2O and N2H6X·2H2O, . Infrared spectroscopy, thermal analysis, and conductivity measurements show that the water in these compounds is partially present as oxonium ion (H3O+) and is involved in hydrogen bonding with N2H4.

Chapter 3 – Metal Hydrazines presents the synthesis and properties of metal hydrazine complexes. These compounds are of interest from the point of view of bonding, structure, and reactivity. The hydrazine molecule with its two free electron pairs can coordinate to a metal ion either as a monodentate or bridged bidentate ligand. Several metal hydrazine complexes containing different anions, such as oxalate, perchlorate, nitrate and azide, sulfate, sulfite, hydrazine carboxylate, and so on, are prepared and investigated. In all these complexes hydrazine is usually present as a bridged bidentate and, occasionally, as a monodentate ligand. The thermal reactivity of these metal hydrazines varies from explosion → deflagration → decomposition, depending upon the anion. Transition metal perchlorate, nitrate, and azide hydrazines are primary high energy materials (HEMs). Non-transition metal hydrazines of Li, Mg, and Al perchlorate, nitrate and azide, and so on, and transition metal hydrazine complexes of oxalate, sulfite, and hydrazine carboxylate, deflagrate. The rest simply decompose, with the loss of hydrazine.

Chapter 4 – Metal Hydrazine Carboxylates gives an account of the preparation of various metal hydrazine carboxylate complexes such as M(N2H3COO)2·x H2O, M = Ca, Mg, Mn, Cu, and Cr; Ln(N2H3COO)3·3H2O, Ln = rare earth ion; M(N2H3COO)2(N2H4)2 and N2H5M(N2H3COO)3·H2O, M = Mn, Fe, Co, Ni, and Zn. These complexes are investigated by infrared spectroscopy and thermal analysis. The characteristic N–N stretching frequency is used to distinguish between monodentate N2H4 (νN–N 930 cm−1), ionic (νN–N 965 cm−1), and N2H3COO− (νN–N 990–1005 cm−1) species. Transition metal hydrazine carboxylates decompose in air at low temperatures (75–200 °C) to yield nanosize oxide materials. The decomposition is autocatalytic; once initiated it is accompanied by swelling due to the evolution of large amounts of gases like NH3, H2O, H2, and CO2.

Chapter 5 – Hydrazinium Metal Complexes highlights the coordinating ability of the hydrazinium cation, . The synthesis and structure of several hydrazinium metal sulfate and oxalate complexes are presented. Single-crystal structures are showcased of N2H5M(SO4)2 where, M = Mn, Fe, and Cd; N2H5Nd(SO4)2·H2O, (N2H5)2Cu(C2O4)5·2H2O, (N2H5)6(UO2)2(C2O4)5·2H2O, (N2H5)2(UO2)2(C2O4)2·H2O, and so on. Interestingly, ion coordinates to the metal ion in sulfate complexes but is outside the coordination sphere of the metal ion in oxalate complexes.

Several hydrazinium metal chloride complexes (N2H5)2MCl4·2H2O, where M = Fe, Cu, Co, Ni, Pt, and Pd, N2H5CuCl3, (N2H5)2ZnCl4, (N2H5)3MnCl5, and (N2H5)4FeCl6 have been synthesized and investigated for their crystal structure. Single-crystal structures presented are of (N2H5)2MCl4·2H2O, M = Fe and Pt, (N2H5)3MnCl5, and so on. In all these complexes ions are coordinated to the metal ion. Hydrazinium metal thiocyanates (N2H5)M(NCS)4·2H2O, where M = Co and Ni, have been prepared and the single-crystal structure of the cobalt compound is shown.

Chapter 6 – Applications of Inorganic Hydrazine Derivatives summarizes the uses of inorganic hydrazine derivatives. Some interesting properties and reactions of hydrazine salts have emerged from these investigations. These include flame retardancy of hydrazinium phosphates, solid-state rearrangement of hydrazinium thiocyanate to thiosemicarbazide (N2H5SCN → N2H5CSNH2), and the use of N2H5SCN as an analytical reagent for the quantitative estimation of copper. Hydrazinium hydrazinecarboxylate formed by the reaction of commercial ammonium carbonate with hydrazine hydrate reacts with acetonitrile at room temperature to give a triazole compound. Triazoles find applications in a wide variety of agrochemicals and medicine. The perchlorate, nitrate, and azide salts of hydrazine, N2H5NO3, N2H5N3, N2H5ClO4·0.5H2O, N2H6(ClO4)2·2H2O, and so on, are potentially energetic oxidizers and are being considered for use in solid propellant compositions. However, they are highly hygroscopic and incompatible with conventional polymeric fuels and in solid propellants. These problems have been overcome successfully by complexing both hydrazine perchlorates with ammonia as well as by doping with Mg2+ ions. Transition metal hydrazines containing anions like nitrate, azide, and perchlorates have been investigated as detonators. Surprisingly, the thermolysis of Mg(N3)2(N2H4)2 gives a blue colored residue that shows strong IR absorption at 2100 cm−1, which is characteristic of molecular nitrogen.

The deflagrating nature of metal hydrazines is used in the preparation of ferrites and cobaltites. Commonly used recording material like γ-Fe2O3 and Co-doped γ-Fe2O3, is prepared by the thermal decomposition of iron hydrazine carboxylates in a single step. Similarly, nano-size ferrites (MFe2O4, NixZn1–xFe2O4, and MnxZn1–xFe2O4) and cobaltites (MCo2O4) are obtained at very low temperatures (300 °C) by the thermal decomposition/combustion in air of solid solution precursors of the type N2H5MFe(N2H3COO)3·H2O and N2H5MCo(N2H3COO)3·H2O, where M = Mg, Mn, Fe, Co, Ni, and Zn.

Finally, the work carried out and presented in this monograph has been quite exciting, creative, and rewarding to the authors. It is hoped that it will inspire future researchers and entrepreneurs working in academic institutes and defense and space research laboratories.

Acknowledgments

We gratefully acknowledge the collaboration of the following colleagues: Professors C.C. Patel, V.R. Pai Vernekar, S.R. Jain, H. Manohar, and K. Kishore and Drs. Nethaji, Damodar Pujari, and I.I. Mathews (Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore), and Professor Zhu Shanguan (Nanjing University of Science and Technology, China).

We also acknowledge the valuable research contributions of former PhD students: Drs Jayant Budukuley, R. Soundara Rajan, M. Ramanath, J.J. Vittal, C. Nesmani, D. Gajapathy, S. Govindrajan, P. Ravindranathan, N.R.S. Kumar, M.M.A. Sekhar, S. Ekambaram, N. Arul Das, S.T. Aruna, S. Shanmugaraju, Arun Kumar Bar, and Mr. G.V. Mahesh.

We are grateful to Professor A.G. Samuelson, Chairman, Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore for the support and co-operation extended. We thank Professor K. Venkataramaniah and Dr Siva Sankar Sai of Sri Sathya Sai Institute of Higher Learning, Prasanthi Nilayam for their encouragement.

Our sincere thanks are to Sanjay Rattan for editing the manuscript. Finally, we are grateful to Professor Animesh Chakravorty for readily agreeing to write the Foreword to our book.

K. C. Patil

Tanu Mimani Rattan