The action of water on y-Ca,SiO,, either alone or in the presence of calcium hydroxide, quartz, or amorphous silica, has been studied mainly a t 150-600" and 5-350 bars. A new compound, of probable composition Ca8Si5Ols, is formed over a wide range of conditions; its appears to have a regularly interstratified structure composed of alternate layers of y-Ca,SiO, and kilchoanite (Ca,Si,O,).The supposed compound, " y-dicalcium silicate hydrate " or " dicalcium silicate hydrate (C)," which has been widely reported as forming under saturated steam pressures around ZOO", is a mixture consisting principally of a disordered form of Ca8Si5018 and calciochondrodite, Ca5(Si04),(OH),.Reaction sequences and equilibria are discussed ; a t least up to 450", the initial and early products are crystalline compounds (kilchoanite, calcio-chondrodite, Ca8Si5OI8) with structures related to that of y-Ca,SiO,.THE system CaO-SO,-H,O has been extensively studied under hydrothermal conditions because of its relevance to the manufacture of autoclaved building materials and to geological problems. Few studies have, however, been made much above 200" on the reaction of water with y-Ca,SiO,, either alone or in the presence of added lime or silica, and the present work was therefore undertaken. I t had two specific aims. First, a supposed compound of composition 2CaO,Si0,,0~3--1~OH2O, generally called y-dicalcium silicate hydrate or dicalcium silicate hydrate (C): has been reported by many workers to form under saturated steam pressures around 200". The status of this product as a distinct compound has been questioned,* and it was hoped to obtain more definite evidence as to its nature. Secondly, there is uncertainty about the stability under hydrothermal conditions at 200-600" of kilchoanite (a polymorph of Ca,Si,O, relative to assemblages such as foshagite [Ca,Si309(0H),] plus dellaite (Ca,Si,O,,H,), and it was hoped to obtain further evidence bearing on this problem.