This study was aimed at examining the use of the organophosphine oxides Cyanex (R) 921 and Cyanex (R) 923 for the extraction of formic, acetic and propionic acids from aqueous solutions. The stripping of monocarboxylic acids with water from the loaded extractants was also examined. The studies were aimed at determining the equilibrium conditions for extraction and stripping. Overall, the effect of the kind of extractant was not significant although Cyanex (R) 921 extracted carboxylic acids slightly better than Cyanex (R) 923 with 1:1 complexes being formed by both extractants with the acids during extraction. The efficiency of extraction depended on temperature, acid concentration and solvent, with toluene a better diluent for the extractants than octane or Exxsol (R) D 220/230. Extraction efficiency increased as the concentration of acid in the feed decreased and, also, as the temperature increased, the amount of acid extracted decreased. The extraction and stripping isotherms were determined. The apparent enthalpy and entropy of the extraction reaction were determined. Distribution data for the transfer of carboxylic acids from aqueous (NaCl) solutions to organic solvents in the presence of trialkylphosphine oxide were determined at 293 K with the distribution ratios increasing as the concentration of NaCl increased. (c) 2005 Society of Chemical Industry.