A non-ideal system containing several solutes, e.g. methanol, acetone, and 2-butanol in n-hexane was studied. Traditionally defined excess molar volumes (based on pure component molar volumes) of the multi-component solutions were measured in the limit of infinite dilution in n-hexane using a vibrating-tube densitometer at 298.15 K and 1.0125 x 10(5)Pa. An experimental design in the concentration range 0.00 15 < x(solute-i) < 0.023 was explored, optimizing the metric distance among the solutes to avoid clustering. The partial molar volumes of methanol, acetone, and 2-butanol at infinite dilution determined from the multi-component data were very consistent with the values obtained from separate binary experiments. Next a total molar volume response surface model was developed. Only experimental total volume and component moles are needed for analysis. The partial molar volumes of all the solutes were accurately predicted from the multi-component data alone. A new expression for excess molar volume is proposed to express component interactions. This approach is undoubtedly of considerable usefulness for determination of the partial molar properties of non-isolated but observable species in multi-component reactive solutions. (c) 2005 Elsevier Ltd. All rights reserved.