Kinetics and Mechanism of Pyrite Exsolution from Pyrrhotite

Pyrite exsolution from pyrrhotite at 325 °C occurs by heterogeneousnucleation of pyrite and subsequent growth by volume diffusionof iron away from the nuclei. Sulfur atoms are required to moveonly short distances and although their diffusivity is muchlower than iron, their movement is not the rate determiningfactor. The exsolution rate is primarily dependent on the nucleationrate, which increases with the degree of supersaturation. Inaddition, the impurities in National Bureau of Standards 55diron or 500 ppm of As, Sb, or Bi retard the exsolution rateby two or more orders of magnitude at 325 °C. This reductionis primarily the result of a lower nucleation rate and is believedto be due to a decreased vacancy mobility caused by a high bindingenergy of vacancies with the slow diffusing impurities. Thusthe strain associated with the nucleation cannot be as easilyrelieved. The impurities may also reduce the growth rate bycausing a decrease in mobility of the pyrite interface. The most important general aspect of this study is the effectof a few hundred parts per million of an impurity on the exsolutionrate of this reaction. This suggests that the rate of othermineral reactions may also be dependent on impurities; however,the importance of this factor in any particular mineral reactionrequires experimental verification.