The dependence of the molar ratios of CO:formate products formed by electrochemical reduction of CO2 at Sn electrodes was studied in aqueous buffer solutions as a function of pH, with values of those ratios ranging from 1 to 0.15 over the pH range 2.9 to 7.8. However, decreasing pH led to decreased charge yields of CO2 reduction, due to increasing rates of the competing hydrogen evolution reaction. A reaction scheme was proposed to explain the observed relationship and a mathematical model was developed to quantify the dependence of the product ratios on pH and to predict the observed partial current densities of product formation at different pHs and electrode potentials. The reaction scheme was based on multiple protonation states of the intermediate in CO2 reduction; the higher the protonation state, the higher was the tendency of the intermediate to form CO. A generalised reaction mechanism for other electrode materials was also proposed. (C) 2014 Elsevier Ltd. All rights reserved.