The objective of this research was to carry out a comparative study of the volumetric properties of 2-pyridinemethanol, 3-pyridinemethanol, 2-(hydroxymethyl)piperidine, and 3(hydroxymethyl)piperidine in aqueous media. The density and excess volumes of mixing as a function of temperature (T = 293.15-318.15 K) over the entire concentration range are examined for aqueous solutions of 2,3-pyridinemethanols, and the density and partial molar volumes of aqueous solutions are investigated for the corresponding 2,3-(hydroxymethyl)piperidines. The minimum values of the excess molar volumes, v(E). are observed, -0.59 cm(3) mol(-)1 for 2-pyridinemethanol-water solutions and -0.47 for 3-pyridinemethanol-water solutions. These are about 0.61% and 0.49% respectively, of the molar volume. The thermal expansion coefficients alpha(T) at 298.15 K calculated from the density data,exhibited significant positive deviations, (about 30%) from ideality for 2-pyridinemethanol-water mixtures, and 3-pyridinemethanol-water mixtures. The partial molar volume of 2,3-(hydroxymethyl)piperidines in water at selected temperatures was evaluated by extrapolating the apparent molar volume versus molality plots to m = 0. In addition, the partial molar expansivity, E-0, the isobaric coefficient of thermal expansion, alpha(T), the interaction coefficient, S-v, and the Hepler's constant have also been computed. The data are interpreted in terms of the effect of the primary alcohol functional group on the inter/intramolecular and additional hydrophilic interactions between the molecules. (C) 2012 Elsevier B.V. All rights reserved.