Hostname: page-component-848d4c4894-sjtt6 Total loading time: 0 Render date: 2024-07-08T00:26:08.707Z Has data issue: false hasContentIssue false
  • English
  • Français

Powder diffraction analysis of an interstratified marcasite/pyrite structure

Published online by Cambridge University Press:  10 January 2013

Neil E. Johnson ,
Sidney S. Pollack ,
Elizabeth A. Frommell  and
Patricia A. Eldredge
Neil E. Johnson
Affiliation:
U.S. Department of Energy, Pittsburgh Energy Technology Center (PETC), P.O. Box 10940, Pittsburgh, Pennsylvania 15236-0940
Sidney S. Pollack
Affiliation:
U.S. Department of Energy, Pittsburgh Energy Technology Center (PETC), P.O. Box 10940, Pittsburgh, Pennsylvania 15236-0940
Elizabeth A. Frommell
Affiliation:
U.S. Department of Energy, Pittsburgh Energy Technology Center (PETC), P.O. Box 10940, Pittsburgh, Pennsylvania 15236-0940
Patricia A. Eldredge
Affiliation:
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901
Get access Rights & Permissions [Opens in a new window]

Abstract

A synthetic catalyst precursor formed by sulfiding ferrihydrite (Fe3+O(OH)) in the presence of a hydrogen donor produces X-ray diffraction patterns resembling a mixture of both naturally occurring FeS2 polymorphs marcasite and pyrite. The diffraction peaks display a differential broadening, however, wherein only those peaks coincident to both marcasite and pyrite are strong and sharp, a feature that cannot be accounted for by a simple physical mixture. The broadening is analogous to that found in hexagonal cobalt, where occasional stacking faults produce interstratification of the hexagonal and cubic close-packed forms, resulting in strongly coherent diffraction only along the stacking direction. The crystal structures of marcasite and pyrite are virtually identical if viewed perpendicular to the (101) and (001) planes, respectively. Calculation of diffraction patterns based upon models of interstratifying marcasite and pyrite layers along these planes demonstrates that a sequence with marcasite-to-pyrite and pyrite-to-marcasite stacking fault probabilities of 0.22 provides a good fit to the experimental pattern. This interstratified material is a precursor to a species that shows catalytic activity for cleaving C-C bonds between aromatic rings and benzylic carbon atoms at low (<350 °C) temperatures.

Keywords

marcasitepyriteinterstratificationstacking faults
Type
Research Article
Information
Powder Diffraction , Volume 10 , Issue 3 , September 1995 , pp. 198 - 203
Copyright
Copyright © Cambridge University Press 1995

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Berner, R. A. (1964). “Iron sulfides formed from aqueous solution at low temperatures and atmospheric pressure,” J. Geol. 72, 293–306.CrossRefGoogle Scholar
Bragg, W. L. (1914). “The analysis of crystals by the X-ray spectrometer,” Proc. R. Soc. London Ser. A 89, 468–489.Google Scholar
Brock, K. J., and Slater, L. D. (1978). “Epitaxial marcasite on pyrite from Rensselaer, Indiana,” Am. Mineral. 63, 210–212.Google Scholar
Brostigen, G., Kjekshus, A. and Rømming, C. (1973). “Compounds with the marcasite type crystal structure. VIII. Redetermination of the prototype,” Acta Chem. Scand. 27, 2791–2796.CrossRefGoogle Scholar
Buerger, M. J. (1931). “The crystal structure of marcasite,” Am. Mineral. 16, 361–395.Google Scholar
Cowley, J. M. (1976). “Diffraction by crystals with planar faults. I. General theory,” Acta Cryst. A 34, 83–87.CrossRefGoogle Scholar
Deer, W. A., Howie, R. A., and Zussman, J. (1962). Rock Forming Minerals, Volume 5, Non-silicates (Wiley, New York).Google Scholar
Dódony, I., Pósfai, M., and Buseck, P. R. (1994). “Structural relationship between pyrite and marcasite,” Proc. 16th IMA, 100.Google Scholar
Edwards, O. S., and Lipson, H. (1942). “Imperfections in the structure of cobalt. I. Experimental work and proposed structure,” Proc. R. Soc. London Ser. A 180, 268–277.Google Scholar
Eggleton, R. A., and Fitzpatrick, R. W. (1988). “New data and a revised structural model for ferrihydrite,” Clays Clay Mineral. 36, 111–124.CrossRefGoogle Scholar
Evans, B. J., Johnson, R. G., Senftle, F. E., Cecil, C. B., and Dulong, F. (1987). “The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances,” Geo. Cosmo. Acta 46, 761–775.CrossRefGoogle Scholar
Fagot, M., Levade, C., Couderec, J. J., and Bras, J. (1981). “Observation of lattice defects in orfhorhombic iron disulfide (marcasite),” Phys. Chem. Mineral. 7, 253–259.CrossRefGoogle Scholar
Farcasiu, M., Eldredge, P. A., and Petrosius, S. C. (1993). “Complex iron catalytic systems: relative catalytic activity of various components,” ACS, Div. Fuel Chem 38, 53–59 (preprint).Google Scholar
Fayard, M., Gratias, D., and Portier, R. (1980). “A model for stacking faults in pyrite,” Phil. Mag. A 41, 125–128.CrossRefGoogle Scholar
Finklea, S. I., Cathey, L., and Amma, E. L. (1976). “Investigations of the bonding mechanism in pyrite using the Mössbauer effect and X-ray crystallography,” Acta Cryst. A 32, 529–537.CrossRefGoogle Scholar
Fleet, M. E. (1982). “Synthetic smythite and monoclinic Fe3S4,” Phys. Chem. Mineral. 8, 241–246.CrossRefGoogle Scholar
Fleet, M. E. (1970). “Structural aspects of the marcasite–;pyrite transformation,” Can. Mineralogist 10, 225–231.Google Scholar
Grønvold, F., and Westrum, E. F. Jr., (1976). “Heat capacities of iron dis-ulfides. Thermodynamics of marcasite from 5 to 700 K, pyrite from 300 to 780 K, and the transformation of marcasite to pyrite,” J. Chem. Therm. 8, 1039–1048.CrossRefGoogle Scholar
Kakinoki, J. and Tomura, Y. (1965). “Diffraction by a one-dimensionally disordered crystal. I. The intensity equation,” Acta Cryst. 19, 137–147.CrossRefGoogle Scholar
Lennie, A. R., and Vaughan, D. J. (1992). “Kinetics of the marcasite-pyrite transformation: An infrared spectroscopic study,” Am. Mineral. 77, 1166–1171.Google Scholar
Lepp, H. (1957). “The synthesis and probable geologic significance of melnikovite,” Econ. Geol. 52, 528–535.CrossRefGoogle Scholar
Michalski, E. (1988). “The diffraction of X-rays by close-packed polytypic crystals containing single stacking faults. I. General theory,” Acta Cryst. A 44, 640–649.CrossRefGoogle Scholar
Moore, D., and Reynolds, R. C. J. (1989). X-Ray Diffraction and the Identification and Analysis of Clay Minerals (Oxford, U. P., New York).Google Scholar
Murowchick, J. B. (1992). “Marcasite inversion and the petrographic deter-mination of pyrite ancestry,” Econ. Geol. 87, 1141–1152.CrossRefGoogle Scholar
Murowchick, J. B., and Barnes, H. L. (1986). “Marcasite precipitation from hydrothermal solutions,” Geo. Cosmo. Acta 50, 2615–2629.CrossRefGoogle Scholar
Rakovan, J., Schoonen, M. A. A., and Reeder, R. J. (1993). “Marcasite epitaxy on pyrite, Deep Tunnel Project, Chicago, Illinois,” GSA Abstr., 25, A439.Google Scholar
Reynolds, R. C. Jr. (1980). “Interstratified clay minerals,” in Crystal Structures of Clay Minerals and Their X-Ray Identification, edited by Brindley, G. W. and Brown, G. (Mineralogical Society, London), Chap. 3.Google Scholar
Rickard, D. T. (1969). “The chemistry of iron sulfide formation at low temperatures,” Acta Univ. Stockholm, Contrib. Geol. 20, 67–95.Google Scholar
Schoonen, M. A. A. and Barnes, H. L. (1991a). “Reactions forming pyrite and marcasite from solution: I. Nucleation of FeS2 below 100 °C,” Geo. Cosmo. Acta 55, 1495–1504.CrossRefGoogle Scholar
Schoonen, M. A. A., and Barnes, H. L. (1991b). “Reactions forming pyrite and marcasite from solution: II. Via FeS precursors below 100 °C,” Geo. Cosmo. Acta 55, 1505–1514.CrossRefGoogle Scholar
Schoonen, M. A. A., Barnes, H. L. (1991c). “Reactions forming pyrite and marcasite from solution: III. Hydrothermal processes,” Geo. Cosmo. Acta 55, 3491–3504.CrossRefGoogle Scholar
Smith, D. K., Nichols, M. C., and Zolensky, M. E. (1983). A FORTRAN IV program for calculating X-ray powder diffraction patterns, version 10. Bulletin of the College of Earth and Mineral Sciences, Pennsylvania State University.Google Scholar
Smith, G. S., and Snyder, R. L. (1979). “FN: A criterion for rating powder diffraction patterns and evaluating the reliability of powder pattern indexing,” J. Appl. Cryst. 12, 60–65.CrossRefGoogle Scholar
Treacy, M. M. J., Newsam, J. M., and Deem, M. W. (1991). “A general recursion method for calculating diffracted intensities from crystals containing planar faults,” Proc. R. Soc. London Ser. A, 433, 499–520.Google Scholar
Wilson, A. J. C. (1942). “Imperfections in the structure of cobalt. II. Math-ematical treatment of proposed structure,” Proc. Royal Soc. London Ser. A 180, 277–285.Google Scholar
Young, R. A., and Wiles, D. B. (1982). “Profile shape functions in Rietveld refinements,” J. Appl. Cryst. 15, 430–438.CrossRefGoogle Scholar