Effects of high concentrations of aqueous tetramethylammonium chloride and other salts on the dissociation of phenylphosphonic acid and on the enolization of acetone

Journal Article · Thu Mar 31 23:00:00 EST 1988 · J. Solution Chem.; (United States)

DOI:https://doi.org/10.1007/BF00650411· OSTI ID:6364963

Gulinski, J; Maciejewska, U; Stewart, R

The dissociation constants of benzoic acid and phenylphosphonic acid have been determined in aqueous solutions containing tetramethylammonium chloride at concentrations up to 15 and 13 molal, respectively. The second dissociation constant of phenylphosphonic acid has also been determined in concentrated solutions of alkali halides. Whereas the organic electrolyte increases the observed pK values of the acids, the inorganic electrolytes decrease them. The rate of enolization of acetone, catalyzed by phenylphosphonate dianion is increased by the presence of tetramethylammonium chloride, but is decreased by the presence of inorganic salts, in accordance with the changes in the apparent acidity constants of phenylphosphonate monoanion that the two different kinds of electrolyte bring about. The slope of the Broensted plot for the inorganic salts is 0.76; that for the organic electrolyte is 0.46. Non-quaternary ammonium salts also increase the rate of the phenylphosphonate dianion catalyzed enolization of acetone, but this appears to be due to a considerable extent to the formation of reactive iminium ion intermediates.

• Research Organization: Univ. of British Columbia, Vancouver (Canada)
• OSTI ID: 6364963
• Journal Information: J. Solution Chem.; (United States), Journal Name: J. Solution Chem.; (United States) Vol. 17:4; ISSN JSLCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETONE
ALCOHOLS
ALKALI METAL COMPOUNDS
AMINES
AMMONIUM CHLORIDES
AMMONIUM COMPOUNDS
AMMONIUM HALIDES
BASES
BENZOIC ACID
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
DISSOCIATION
ELECTROLYTES
ENOLS
ESTERS
HALIDES
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
KETONES
KINETICS
LITHIUM CHLORIDES
LITHIUM COMPOUNDS
LITHIUM HALIDES
MONOCARBOXYLIC ACIDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PH VALUE
PHOSPHONATES
PHOSPHONIC ACID ESTERS
POTASSIUM CHLORIDES
POTASSIUM COMPOUNDS
QUATERNARY COMPOUNDS
REACTION KINETICS
SODIUM CHLORIDES
SODIUM COMPOUNDS
TESTING
TITRATION
YIELDS