Chemistry in Non-Aqueous Solvents
Arising no doubt from its pre-eminence as a natural liquid, water has always been considered by chemists as the original solvent in which very varied chemical reactions can take place, both for preparational and for analytical purposes. This explains the very long-standing interest shown in the study of aqueous solutions. In this con nection, it must be stressed that the theory of Arrhenius and Ostwald (1887-1894) on electrolytic dissociation, was originally devised solely for solutions in water and that the first true concept of acidity resulting from this is linked to the use of this solvent. The more recent development of numerous physico-chemical measurement methods has made possible an increase of knowledge in this area up to an extremely advanced degree of systematization. Thus today we have available both a very large amount of experimental data, together with very refined methods of deduction and of quantitative treatment of chemical reactions in solution which enable us to make the fullest use of this data. Nevertheless, . it appears quite evident at present that there are numerous chemical processes which cannot take place in water, and that its use as a solvent imposes 2 INTRODUCTION limitations. In order to overcome these limitations, it was natural that interest should be attracted to solvents other than water and that the new possibilities thus opened up should be explored.
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SOLVENTS AND SOLUTES
I2 Solvation of Substances within a Molecular Solvent
I3 Ionic Associations Ionpairs in Molecular Solvents of Low Dielectric Constant
I4 State of Substances Dissolved in an Ionized Solvent Molten Salt
I5 Presentation of Reactions in Solution
ACIDITY AND PROTOLYSIS PHENOMENA
II1 Acidity in a Molecular Solvent of High Dielectric Constant
II2 Acidity of Acceptors of the Anion given up by an Amphiprotic Solvent
OTHER ION EXCHANGE SYSTEMS WITH PARTICIPATION OF SOLVENT
III2 Examples of Solvoacidity in Aprotonic Solvents
IV1 Solvent Intervention in OxidationReduction Phenomena
IV2 Influence of Acidity on OxidationReduction Phenomena
CORRELATION BETWEEN PROPERTIES IN DIFFERENT SOLVENTS
V2 Correlation Between AcidBase Properties in Different Solvents
V3 Correlation Between Other Properties
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absolute acidity acceptor acetamide acetic acid acetonitrile acid-base couples acid-base properties acids and bases ammonia amphiprotic solvents amphoteric anions aqueous solution autoprotolysis basic media carbonates cation chemical potential chloride chloroacid chlorobases complex compounds concentration conjugate base consider constituents corresponding Coulomb defined diagram dielectric constant different solvents dissociation dissolved donor effect electrochemical electrolyte electromotive force electrostatic enthalpy enthalpy of transfer equilibrium potential eutectic example experimental ferrocene formation free enthalpy H+ ion halides hydrofluoric acid hydrogen bonds hydrogen electrode interactions ion-pairs ionic association ions leads limited liquid ammonia low dielectric constant medium metallic cations metallic ions mixtures molecular solvents molten alkali molten salts neutral non-aqueous solvents oxide oxoacidity pH scale pH(aq pH2O protogenic protophilic pure pyridine reducing agents self-ionization sodium solubility solvent molecules solvents of low solvoacidity solvolysis strong acid strong base sub-lattice substance sulphuric temperature tion transfer activity coefficient Tremillon variation
Page 279 - Liquid Displacement Test Cell for Dielectric Constant ana Dissipation Factor up to 100 Me," presented at Conference on Electrical Insulation (NRC), October, 1959, and reviewed in Insulation, INULA, November, 1959, p. 26. (10) Maryott, AA, and Smith, ER, 'Table of Dielectric Constants of Pure Liquids," NBS Circular No. 514, 1951. (11) Hartshorn, L., Parry, JVL, and Essen, L., 'The Measurement of the Dielectric Constant of Standard Liquids," Proceedings, PPSBA, Physical Soc. (London), Vol 68B, July,...
Page 280 - Chariot, G. and Tremillon, B., 1963, Les reactions chimiques dans les solvants et les selsfondus, Gauthier-Villars, p.