Reactive extraction is a commonly applied process to recover carboxylic acids from aqueous solutions. Such processes are nowadays designed using process simulation software. However, the essential prerequisite for such a simulation is the availability of a reliable thermodynamic model for the encountered phase equilibrium. Industrial experience revealed that even very small amounts of a strong electrolyte (e.g., sodium chloride) can considerably reduce the amount of carboxylic acid extracted from the aqueous into the organic phase. This contribution presents new experimental results for the influence of sodium nitrate, sodium chloride, sodium sulfate, sodium citrate and hydrochloric acid on the partitioning of citric acid to the coexisting aqueous/organic liquid phases of the system water + methyl isobutyl ketone (organic solvent) + tri-n-octylamine (chemical extractant) at 25 degreesC. A detailed discussion of the experimental results reveals that the dramatic decrease of the partition coefficient of carboxylic acid is caused by the chemical loading of the extractant by the inorganic acid, i.e. both acids (the weak carboxylic acid as well as the strong inorganic acid) compete for the sodium ions (in the aqueous phase) and for the amine (in the organic phase). In phase equilibrium the amine is predominantly loaded with the inorganic acid while the sodium salt of the carboxylic acid remains in the aqueous phase. That behavior is described by a thermodynamic framework that is able to predict the complex liquid-liquid equilibrium from information determined exclusively from investigations on subsystems. (C) 2004 Elsevier B.V. All rights reserved.