Irregular solution thermodynamics of wood pulp in the superbase ionic liquid [-TBDH][AcO].

Knowledge of solution thermodynamics is fundamental for solution control and solvent selection processes. Herein, experimentally determined thermodynamic quantities for solutions of wood pulp (hardwood dissolving pulp, cellulose) in [-TBDH][AcO] are presented. activities ( ) and associated ( ) activity coefficients ( ), are determined to quantify inherent solution .

Bifluoride ([HF2](-)) formation at the fluoridated aluminium hydroxide/water interface.

This study uncovers bifluoride-type (difluorohydrogenate(i); [HF2](-)) species formed at mineral/water interfaces. Bifluoride forms at [triple bond, length as m-dash]Al-F surface sites resulting from the partial fluoridation of gibbsite (γ-Al(OH3)) and bayerite (α-Al(OH3)) particles exposed to aqueous solutions of 50 mM NaF. Fluoride removal from these solutions is proton-promoted and results in a strongly self-buffered suspensions at circumneutral pH, proceeds at a F : H consumption ratio of 2 : 1, and with recorded losses of up to 17 mM fluoride (58 F nm(-2)).

Aqueous Brønsted-Lowry Chemistry of Ionic Liquid Ions.

Ionic liquids have become commonplace materials found in research laboratories the world over, and are increasingly utilised in studies featuring water as co-solvent. It is reported herein that proton activities, aH (+) , originating from auto-protolysis of H2O molecules, are significantly altered in mixtures with common ionic liquids comprised of Cl(-), [HSO4 ](-), [CH3SO4 ](-), [CH3COO](-), [BF4](-), relative to pure water. paH (+) values, recorded in partially aqueous media as -log(aH (+)), are observed over a wide range (∼0-13) as a result of hydrolysis (or acid dissociation) of liquid salt ions to their associated parent molecules (or conjugate bases).

A quantitative ionicity scale for liquid chloride salts.

Knowledge of ionicity is requisite for successful identification of those salt qualities required to design and couple the most appropriate fluid for performance of an intended chemical function. We report on utilisation of (35)Cl(-) quadrupolar coupling constants (C(Q)) to quantitatively assess the ionicities of given chloride salts, by exploiting the electronic response of the quadrupolar chlorine atom as a function of its immediate chemical environment. We find that protic salts in particular, like their aprotic analogues, are highly ionised, while at the same time being highly associated, in stark contrast to literature reports claiming in general that they are of sub-ionic origin.

Brønsted acidity and the medium: fundamentals with a focus on ionic liquids.

Fundamental aspects of Brønsted acidity in ionic liquid systems, in relation to those of simple protic molecules in the gas phase, pure protic molecules in the condensed phase and solutions of protic molecules in molecular systems, are presented. The variety of acidities possible, beyond those observed in aqueous systems, is emphasised and discussed in terms of differences of solvent levelling, ionisation, dissociation, homo-/hetero-conjugate ion speciation and the stabilisation of proton-transfer products from solvent to solvent. It is argued that data regarding aqueous systems do not necessarily explain acid/base behaviour in other liquids satisfactorily.

The complex story of a simple Brønsted acid: unusual speciation of HBr in an ionic liquid medium.

Crystalline solids, co-existing in equilibrium with the 3-methyl-1H-imidazolium bromohydrogenates(I) ionic liquid, have been characterised by X-ray diffraction analysis. The Brønsted acidic, homo-conjugate [H(2)Br(3)](-) anions presented are discussed in terms of their structure and reactivity, in efforts to advance the understanding of Brønsted acidity in ionic liquid media.