This paper reports a molecular dynamics study of the pK(w) of water, pK(a) of HCl and pK(b) of NaOH in supercritical water at a pressure of 1000 atm. The extent of acid/base dissociation is known to be an important factor in the corrosion of supercritical water reaction vessels. This work describes classical molecular dynamics simulations using the SPC/e water model to gain insight into the controlling factors. The results indicate that the dissociation of water has a maximum at 448 K, whereas both the dissociation of HCl and NaOH become less favourable with increasing temperature due to a decrease in entropy. The simulation results are compared to values calculated from the generalised Born theory, and there is a qualitative agreement in the trend. (C) 2013 Elsevier B.V. All rights reserved.