Fused “Onium” Salts as Acids

Abstract

A study by Franklin, Kraus and their co-workers of many different reactions' in liquid ammonia as solvent has served to establish definitely the existence of a series of ammond-compounds which are derived from ammonia, as the parent substance, in much the same way that the usual acids, bases and salts are related to water. Other investigators have shown that this behavior is by no means limited only to water and ammonia as solvents. Many other substances, such as hydrazine, hydrogen sulphide, hydroxylamine, acetic acid, phosgene and sulphur dioxide may serve as parent solvents for solvo-systems2 of acids, bases and salts. General recognition of these facts has resulted in a decided change in opinion as to the definitions of certain classes of compounds, particularly when it was shown that many so-called salts, when dissolved in solvents other than water, exhibited properties typical of acids. Further than this, the acid or basic character of many substances, as defined by their behavior in water, was found to change completely upon solution in other solvents. Thus, urea reacts with the ammono-base, sodium amide, in liquid ammonia to yield a well-defined salt, but in 100 per cent acetic acid it may be titrated with perchloric acid. Such apparent anomalies made it necessary to characterize an acid or a base specifically in relation to a particular solvent. Considerable confusion resulted, especially with respect to nomenclature, since the number of solvent systems could apparently be increased without limit.

Thermal decomposition of ammonium nitrate

“…Unlike Cl, metals may affect AN decomposition more as reaction partners than as catalysts . Audrieth and Schmidt viewed that Cu acts as a reaction partner (ie, it is consumed and is not just a catalyst) and suggested that some other metals may react similarly:…”

Characterization of Aluminum Powders: IV. Effect of Nanometals on the Combustion of Aluminized Ammonium Nitrate‐Based Solid Propellants

“…The slow reactions of nanometals in mixtures with AN under DSC are largely determined by the reactivity of their oxide films and metals themselves with the AN melt. n-Cu and n-Ni and their oxides, as well as n-Mo, are reacted with AN melt in the temperature range from 250 to 300°C with the release of heat and formation of nitrates and metal oxides soluble in AN melt (except MoO 3 [33]). For n-Zn, the small exothermal peak in the temperature range 320-340°C was followed by a small endothermal peak.…”

Acid-base relationships at higher temperatures

“…The characterization of 'onium' salts as acids, per se, in the dry and fused state is one of the most useful extensions of the modern Br0nsted theory of acidity. Indeed, the very simplicity of this concept has caused it to escape investigation until now" (8).…”