Abstract--Heats of compression of glass bead-water and clay-water mixtures were determined from the peak heights of the thermograms produced when these mixtures were subjected to pressure in a Calvet differential microcalorimeter. It is known that the heat of compression is directly proportional to the peak height. When the latter quantity was plotted against the pressure applied to any mixture, two intersecting straight lines were obtained. The change in slope at the point of intersection was interpreted as being the result of a pressure-induced higher-order phase transition in the water.The differential peak height, e, was defined as the rate of change of peak height with pressure/g of water present in the mixture. Hence, it is directly proportional to the rate of change of the heat of compression with pressure/g of water. Values of E were determined for both glass bead-water and clay-water mixtures containing different proportions of solids. It was found that E remained nearly constant with increasing proportions of glass beads, whereas, it varied in a non-uniform way with increasing proportions of clay, Also, its values in the clay-water mixtures were relatively high. Calculations showed that the difference in E values for the two mixtures could not be ascribed to the exchangeable cations associated with the clay particles. Consequently, it was ascribed to the effect of the particle surfaces on the structure of the vicinal water.The nature of water in clay-water systems has been discussed in several reviews (Low, 1961;Martin, 1962;Graham, 1964;Low and White, 1970). From these reviews it is evident that a controversy exists. The available evidence has been interpreted as being in favor of long-range order in the interlayer water, as being opposed to such order, or as being inconclusive. To help resolve the controversy, the authors conducted experiments on the heat of compression of water in aqueous systems of Na montmorillonite. Our hypothesis was that the structure of this water is different from that of bulk water. Therefore, it should respond differently to the application of pressure and yield a different heat of compression.Some of our results have already been published (Kay and Low, 1972). They show that the heat of compression of the water-montmorillonite system, its electrical resistance and the e.m.f, between reversible electrodes inserted in it, undergo an abrupt change at 20-30 psi. This abrupt change occurs only if the concentration of montmorillonite is above ~ 3.0% by vol and if a small amount of adsorbed hydrous aluminum oxide is present. It was interpreted as being the result of a pressure-induced, higher-order structural transition in the water.Additional tests of our hypothesis are reported in the present paper. In particular, it is our intention to show how the heat of compression of an aqueous Na-montmorillonite system changes with the concentration of Na-montmorillonite and with the * Journal paper no. 5531, Purdue University, Agricultural Experiment Station.t Present address: Department...