title: Anhydrous formic acid and acetic anhydride as solvent or additive in nonaqueous titrations.
abstract: The use and importance of formic acid and acetic anhydride (Ac2O) is increasing in nonaqueous acid-base titrations, but their interaction with the solutes is poorly understood. This paper attempts to clarify the effect of the solvents; NMR and spectrophotometric investigations were done to reveal the interactions between some bases and the mentioned solvents. Anhydrous formic acid is a typical protogenic solvent but both the relative permittivity and acidity are higher than those of acetic acid (mostly used in assays of bases). These differences originate from the different chemical structures: liquid acetic acid contains basically cyclic dimers while formic acid forms linear associates. Ac2O is obviously not an acidic but an aprotic (very slightly protophilic) solvent, which supposedly dissociates slightly into acetyl (CH3CO+) and acetate (AcO-) ions. In fact, some bases react with Ac2O forming an associate: the Ac+ group is bound to the delta- charged atom of the reactant while AcO- is associated with the delta+ group at appropriate distance.
authors.affiliation: Department of Inorganic and Analytical Chemistry, Eötvös University, Budapest, Hungary. buvari@para.chem.elte.hu
authors.forename: A
authors.initials: A
authors.lastname: Buvári-Barcza
authors.forename: I
authors.initials: I
authors.lastname: Tóth
authors.forename: L
authors.initials: L
authors.lastname: Barcza
mesh_terms: D000089:Acetic Anhydrides / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D012997:Solvents / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000089:Acetic Anhydrides; D005561:Formates; D007202:Indicators and Reagents; D012997:Solvents; C030544:formic acid; C031800:acetic anhydride