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Non-Aqueous Solvents in Inorganic Chemistry: The Commonwealth and International Library: Chemistry Division
Non-Aqueous Solvents in Inorganic Chemistry: The Commonwealth and International Library: Chemistry Division
Non-Aqueous Solvents in Inorganic Chemistry: The Commonwealth and International Library: Chemistry Division
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Non-Aqueous Solvents in Inorganic Chemistry: The Commonwealth and International Library: Chemistry Division

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Non-Aqueous Solvents in Inorganic Chemistry gives a concise treatment of the important inorganic non-aqueous solvents, emphasizing why they do in fact exhibit solvent power, how they are prepared and handled experimentally, how they can be used as media for the synthesis or analysis of inorganic and organometallic compounds, and how far the various acid-base concepts can be useful in accounting for many (but not all) of the reactions observed. This book is intended primarily for the undergraduate reader—both for the intending Chemistry Honours or R.I.C. graduate and the non-specialist student of chemistry. The subject matter is presented in a simple and readable form, without the inclusion of elaborate tables of properties and with the minimum of detail necessary for comprehension. Therefore, those working for the A- and S-level chemistry examinations for the G.C.E. could read much of the book with profit; and the research student who aspires to work in the field of non-aqueous solvents will, it is hoped, find this book a useful introduction to a fascinating branch of inorganic chemistry.
LanguageEnglish
Release dateOct 22, 2013
ISBN9781483159416
Non-Aqueous Solvents in Inorganic Chemistry: The Commonwealth and International Library: Chemistry Division

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    Non-Aqueous Solvents in Inorganic Chemistry - A. K. Holliday

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    PREFACE

    By the end of the nineteenth century, two non-aqueous inorganic solvents — liquid ammonia and liquid sulphur dioxide — had already been investigated. Today, a large number and great variety of such solvents are known, but the early work has had a great influence on the way in which our knowledge of these newer solvents has developed. The investigations on ammonia and sulphur dioxide were notable in being concerned experimentally with the manipulation of low-boiling, reactive liquids and theoretically with the extension of the simple acid–base concepts of the original Ionic Theory to non-aqueous systems. These trends can be seen very clearly in Franklin’s classical monograph on liquid ammonia chemistry — The Nitrogen System of Compounds (1935). The influence of this early viewpoint can be realized when one recognizes how many of the newer non-aqueous solvents are low-boiling reactive liquids and how often acid–base concepts have been invoked to explain the observations made. Much of this later work has been very fruitful, but until recently attention has not been directed to the use of substances with a higher-temperature liquid range, or to the use of non-aqueous solvents for (e.g.) oxidation or synthetic reactions. Only in the last decade has work on solvents such as pure sulphuric acid and fused salts begun to show valuable results, and this has been due in great measure to the development of newer methods — and especially spectroscopic methods — of studying solute–solvent systems.

    In writing this book, our aim has been to give a concise treatment of the important inorganic non-aqueous solvents, emphasizing why they do in fact exhibit solvent power, how they are prepared and handled experimentally, how they can be used as media for the synthesis or analysis of inorganic and organo-metallic compounds, and how far the various acid–base concepts can be useful in accounting for many (but not all) of the reactions observed. It has not been easy to achieve this aim in the final chapter, on high temperature solvents, because the latter (mainly fused salts) have as yet been little used for synthesis or analysis in the laboratory, although their use on a large scale has been known for many years. However, a considerable amount of physico-chemical information is now available for fused salt systems, and we have endeavoured to show the relevance of this to the investigation of reactions in these systems. This field of study is likely to be of great importance in inorganic chemistry in the future.

    This book is intended primarily for the undergraduate reader — both for the intending Chemistry Honours or R.I.C. graduate and the non-specialist student of chemistry. We have therefore tried to present the subject-matter in a simple and readable form, without the inclusion of elaborate tables of properties and with the minimum of detail necessary for comprehension. Therefore, those working for the A- and S-level chemistry examinations for the G.C.E. could read much of the book with profit; and the research student who aspires to work in the field of non-aqueous solvents will, it is hoped, find this book a useful introduction to a fascinating branch of inorganic chemistry.

    A.K.H. and A.G.M.

    CHAPTER I

    THE NATURE AND SCOPE OF INORGANIC NON-AQUEOUS SOLVENTS

    Publisher Summary

    This chapter focuses on the nature and scope of suitable nonaqueous solvents for inorganic chemistry. There are two considerations that influence the choice of suitable solvent systems: (1) the possibility of dissociating the solute into ions and (2) the possibility of setting up acid–base systems in which the solvent might participate. The application of the acid–base concept has been the dominant theme in the development of nonaqueous solvents in inorganic chemistry. The protonic solvents water and ammonia behave as bases by uniting with a proton. In terms of electron-pair bonding, this requires donation of an electron pair from base to proton. In the Lux–Flood acid–base concept, oxide ions are regarded as the transferable species corresponding to protons in the Lowry–Bronsted scheme. Experimentally, the studies in a nonaqueous solvent require the preparation and purification of the solvent, the means of manipulation, and the methods for the observation of phenomena in it. The means of manipulation depend upon physical properties such as the melting point to boiling point temperature range.

    Water is such a common and therefore readily obtainable substance that it was an obvious choice as a solvent by the very early chemists. The extraordinary versatility of water as a solvent was soon recognized and the solubilities of many substances were determined over the range 0–100°C. It was not surprising that other solvents were almost completely neglected until the development of organic chemistry produced, simultaneously, organic substances which were often insoluble in water and organic liquids which could be used as solvents instead of water.

    The process by which a simple organic molecule, e.g. a paraffin hydrocarbon, dissolves in (say) benzene is comparatively simple. The relatively weak intermolecular forces between the solute hydrocarbon molecules permit dissolution and are replaced by solvent-solute interactions which, again, are weak; the driving force leading to solution is here the change to a state of higher entropy which the solute molecules attain by solution and hence the solubility usually increases markedly with temperature.

    By contrast, the process of solution in water is always complicated, and even now it is not in general possible to make quantitative predictions about solubilities. The complications arise because in water there are already relatively strong, specific and directed intermolecular forces — hydrogen bonds — which give to the liquid water some semblance of an ordered crystalline structure. The mechanism by which, for example, an ionic solid

    such as sodium chloride dissolves, is not then simply a matter of the reduction of the strong inter-ionic attractions in the crystals by a continuous medium of high dielectric constant. The reorientation of the solvent consequent upon solvation of both cation and anion plays an important role in the energetics of solution. However, covalent solids can sometimes dissolve in water and here hydrogen bonding between solute and solvent is generally the factor favouring solubility; solutes containing —OH or —NH2 groups, such as alcohols, carbohydrates, amines and amino-compounds are typical examples of this type of behaviour.

    Although many non-ionic substances undergo hydrolysis in water by an essentially bimolecular process in which a water molecule attacks the solute molecule, apparent hydrolysis — appearing as a decrease in pH — is not uncommon in solutions of salts of multivalent ions. Here, however, the change in pH is due to an increased dissociation of water molecules co-ordinated around highly charged cations, i.e. the process is essentially unimolecular.

    The frequent occurrence of hydrolysis, real or apparent, does limit the usefulness of water as a solvent; the other limitation is of course the rather narrow liquid range which does not permit the study in solution of substances of low thermal stability or of species stable only at high temperatures. The use of organic solvents to overcome either of these limitations is itself subject to the severe limitation imposed by the very low solubility of many inorganic substances in such solvents; for this reason, organic liquids have not been widely investigated as solvents for inorganic systems, although solvents such as dimethylformamide, dimethyl sulphoxide and the glymes (e.g. diglyme, 1, 2-dimethoxyethane) are now used to an increasing extent.

    The approach to the problem of finding suitable non-aqueous solvents for inorganic chemistry has not in general been made systematically because of the difficulties, already mentioned, which attend any quantitative theoretical approach to the problem of solubility. In practice, two considerations have often influenced the choice of suitable solvent systems; the possibility of dissociating

    the solute into ions and the possibility of setting up acid–base systems in which the solvent might participate. Hence solvents possessing a dielectric constant which is greater than about 10 and an electrical conductance, possibly due to some degree of self-ionization, have often been chosen for study. Even a low degree of self-ionization does not, however, preclude the use of a solvent for ionic substances, thus, for example, dinitrogen tetroxide, N2O4, whilst having a low degree of self-ionization can still be used as an effective solvent for many

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