Discussion – Existence of an Induction Period in the Oxidation of Galena and Lead Sulfide in Water – Gutierrez, Claudio

I feel sure that the apparent anomolies between his findings and ours arise as a result of the different experimental methods used. The modem oxygen electrode method he used is sensitive to nano moles of oxygen uptake whereas the method we used was only sensitive to micro moles at best. Furthermore, our experimental method did not permit measurements to be made in the first ten to fifteen minutes of reaction, the very time he is observing. Direct comparison of his data to ours is made difficult because of not knowing the specific area of the samples he used. However, we found that precipitation of PbS using sodium sulphide gave rise to samples of area approximately 30 m2 g - 1. Noticing the rapid decline in oxidation rate over ten minutes, as reported in Table 1, one can conclude that we could not measure the rate after ten minutes using our method. Taking the above area I estimate that at these rates only a small fraction of surface would be oxidised in a period of hours. I can only conclude that at some point a change in oxidation mechanisms occurs giving rise to a much faster rate such as we observed. Finally, I would like to comment on the apparent inertness of the homogeneously precipitated lead sulphide sample 11. This method of preparation we found to give specific areas of 20 to 30 times less than other methods and this would account for the very low oxidation rate.