A YEAR ago the authors published a paper on the solubility of sulphur dioxide in molten copper.1 The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is:
Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above l00 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures.
Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu20 and (a; 2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy.
In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of SO2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements.
The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.