Institute of Metals Division - Measurements of the Activity of Silver in Silver Sulfide Being Reduced by Hydrogen During and After Nucleation of Silver (TN)

UPON heating a metal oxide or sulfide in H2, first only oxygen or sulfur is removed from the surface. Thus the metal/nonmetal ratio in the oxide or sulfide increases and the thermodynamic activity of the metal increases accordingly. For the formation of metallic nuclei, a certain super saturation is necessary, i.e., the activity of the metal must become greater than unity. Once nuclei of the metal have been formed, the supersaturation is supposed to decrease. Even under steady-state conditions of a reduction process, however, the activity of the metal inside an oxide or sulfide phase must be greater than unity in order to have a driving force for the individual steps of the reduction process. As an example, consider the reduction of Ag2S with a high mobility of cations and electrons. As shown schematically in Fig. 1, the reduction process involves the following steps:' 1) sulfur removal along the entire Ag2S surface in form of H2S, 2) migration of Ag' ions and electrons from the Ag2S surface to nuclei of metallic silver, 3) transfer of Ag+ ions and electrons from the Ag2S phase to the metal. For a finite rate of step 3, the activity of silver in Ag2S next to the Ag2S-Ag interface must be greater than unity. Moreover, for a finite rate of step 2, the activity of silver at the gas-Ag2S interface must be still somewhat greater. Theoretical considerations lead to the tentative conclusion that at least under steady-state conditions the supersaturation will be rather low.' To test this conclusion, the average activity aAg of silver in a Ag2S tablet about 2 mm thick with a diameter of 5 mm was followed as a function of time by measuring the electromotive force E of the cell Pt I Ag | Agl I Ag2S I Pt where AgI is used as a solid electrolyte in which only Ag+ ions are mobile. The activity aAg is calculated as aAg=exp(-EF/RT) Since the diffusion coefficient for transport of silver in Ag2S is very high (- 3 . l0-2 sq cm per sec),3 the average activity aAg is representative for both the bulk and the surface of the Ag2S tablet. Experiments were conducted at about 400°C. The cell was surrounded by an aluminum block in order to secure a uniform temperature and to eliminate thermoelectric effects. With the help of a potentiometer, first a potential of 0.16 v was applied to the above cell in argon in order to obtain a well defined initial state with a Ag/S ratio close to 2.000.~ Then the cell was disconnected from the potentiometer and a gentle stream of H2 was passed along the Ag2S surface. In view of the removal of sulfur in form of H2S, the electromotive force E decreased within 20 to 30 min to zero corresponding to a Ag/S ratio of 2.003 and became negative, indicating a value of aAg> 1. A representative plot electromotive force E vs time is shown in Fig. 2. The minimum of the electromotive force characteristic of the onset of