Acid-base properties of phosphoric and acetic acid in aprotic organic solvents - A complete thermodynamic characterisation.
Anal Chim Acta
; 1046: 77-92, 2019 Jan 10.
Article
em En
| MEDLINE
| ID: mdl-30482305
ABSTRACT
Knowledge regarding the acid-base behaviour in non-aqueous media has remained relatively scarce in spite of its importance for many aspects of chemistry. The research presented in this work fills some of particularly important gaps in the corresponding thermodynamic data. We report on a detailed study of acid-base properties of dihydrogen phosphate and acetate in aprotic organic solvents (acetonitrile, dimethyl sulfoxide, and dimethylformamide). It was found that several processes, i.e. protonation, homoassociation, and dimerisation play important roles in defining the basicity of these widely important anions. In the case of dihydrogen phosphate, formation of higher homoassociates (two anions, one acid molecule and vice versa) was detected, whereas acetate formed only simple homoassociates of 11 stoichiometry. The dimerisation of dihydrogen phosphate and acetic acid were confirmed to be important processes as well. The thermodynamics of the above mentioned reactions was characterised in detail by means of various experimental methods:
ITC, spectrophotometry, NMR-spectroscopy, and conductometry. Reliable equilibrium constants and other thermodynamic reaction functions were determined. The obtained results were discussed in terms of hydrogen bonding potential of the anions and their conjugated acids, as well as solvent properties, i.e. their ability to solvate the species involved in the studied processes.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Anal Chim Acta
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Croácia