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83. Study of the system graphite-MnCl2-AlCl3
134
Abstracts
ma1 balance. Equilibrium conditions are described by a model based on the Polanyi-Dubinin theory (TVFM) and the kinetics are correlated by Fick law. 82. X-ray strnetural study of graphite-Fe& compounds F. Rousseaux, R. Vangelisti, M. Lelaurain and A. Herold (Laboratoire de Chimie du Solide Mb&al, LA 158, Service de Chimie Minerdle Apiliqub-CO l4054037 Nancy Cedex, France) and A. Plancon, D. Tchoubar and C. Tchoubar (Laboratoire de Cristallographie, FacultC des Sciences d’orleans, 45045 Orleans La Source France). Stage 1 and 2 samples, carefully characterized by chemical analysis and Mossbauer spectrometry, have been studied by X-ray diffraction. The experimental scattered intensity has been continuously collected along several cristallographic rows as 101,111,etc. . . in order to be compared with theoretical ones. The fit between experimental and computed curves led us to characterize the structure of the mean scattering domain by the number of stacked layers, the layer’s size, the stacking faults (random or not) probabilities.
83. Study of the system graphite-MnClrAlC13 T. Dziemianowicz and W. Forsman (Department of Chemical Engineering, University of Pennsylvania, Philadelphia, PA 19104), and R. Vangelisti and A. Herold (Laboratoire de Chimie du Solide Mineral, Universite de Nancy I, 54037 Nancy Cedex, France). Intercalation compounds of graphite with MnC12 have beeu synthesized by the direct action of the dichloride vapor, alone or in the presence of AU. Crystallographic, magnetic and electrical studies have enabled characterization of the rich stages.
84. Eleetrnuk diffraction of graphite intercalation compounds with metallfc dkhlorfdes R. Vangelisti and A. Herold (Laboratoire de Chimie du Solide Mineral, Associe au C.N.R.S. No. 158, Service de Chimie Minerale Apiliquee, C.O. 140-54037 Nancy Cedex, France). An electronic diffraction study has allowed comparing the results obtained on graphite intercalated with MnC&, CoC&, NiC& and CuC12. The two dimensional organization of the intercalant layer (planar cell parameters and angular orientations) with respect to that of graphite has been determined.
85. Ternary and quaternarycompounds derived from the 6rst stage graphftideof rubidium P. Lagrange, D. Guerard and A. Herold (Laboratoire de Chimie du Solide Mineral, L.A. t58, Service de Chimie Minerale Appliquee-CO 14&54037 Nancy Cedex, France) and D. G. Onn (Department of Physics, University of Delaware, Newark DE 19711). The hydrogenation of-the first stage compound RbCS leads to the second stage compound RbHupCs, comparable to KHz&s. The free graphitic intervals can be filled by new amounts of an alkali metal (K, Rb or Cs), which leads to new b&insertion compounds (1).
86. Kinetia of AsFs intercalation in highly-oriented pv
olytic graphite: dependenceof the 19FNMR chemiad shift on stage Gerald Ray Miller and Lewis Banks (Naval Research Laboratory, Code 6120, Washington, DC20375 and Department of Chemistry, University of Maryland, College Park, MD 20742) and M. J. Moran and H. A. Resing (Naval Research Laboratory, Code 6120, Washington, DC 20375). 19F NMR spectroscopy was used to follow the reaction of AsF, and HOPG. Conversion of stage 2 to stage 1 occurred at a constant rate [P(AsFs) = 3 atm.] as evidenced by the linear growth of the stage 1 line at a rate twice that of the decrease of the stage 2 line. 87. Thermodynamicsand kinetics of graphite intercalation by arsenic pentafluoride J. Milliken, J. E. Fischer and A. R. McGhie (University of Pennsylvania, Laboratory for Research on the Structure of Matter, Philadelphia, PA 19104). Intercalation of natural graphite powder with ASS has been studied in situ by differential scanning calorimetry. Isothermal intercalation as a function of pressure has yielded information on staging, kinetics of intercalation and the heat of reaction. In addition, apparatus design allows sampling at any time for determination of stage by X-ray diffraction. 88. Graphite intercalation compounds with derivates of the -OTeF, groap E. Stumpp and R. Kebschull (Anorganisch-chemisches Znstitut der Technischen Universitiit Clausthal, 3392 Clausthal-Zellerfeld, Federal Republic of Germany). It is known that the fluoride ion and the -0TeK group are closely related in their chemical properties. We, therefore, investigated the reaction of compounds of the type E(OTeF& with graphite. The preparation of E(OTeK), graphite intercalation compounds with E = H, Hg (x = 2), Cr02 (x = 2), Xe (x = 2), B (x = 3), Sb (x = 3) are reported and also the results of X-ray investigations. The interlayer spacings are very similar to those found in the analogous fluroide graphite intercalation compounds. 89. Intercalationof dilute inorganic acids in graphite H. Fuzellier, A. Metrot, B. Bouayad and A. Herold (Laboratoire de Chimie du Solide Mineral, associe’ au CNRS No. 158, Universite de Nancy I-CO 140-54037 Nancy Cedex, France). Graphite-acid lamellar compounds are synthetised by means of chemical or electrochemical oxidation with various acids (nitric, sulfuric, perchloric . . .). The composition of these compounds varies according to the acid dilution. Significant changes of the interplanar distance and of the electrical conductivity are observed for a given stage and are interpreted as “overcharging” and “overoxidation” processes for the 1st; for 2nd and higher stages with dilute acids, these processes may also occur. 90. Chemical and physical properties of new graphfteHNO, compounds H. Fuzellier, F. Rousseaux, J. F. MarCchi, E. McRae
Abstracts
ma1 balance. Equilibrium conditions are described by a model based on the Polanyi-Dubinin theory (TVFM) and the kinetics are correlated by Fick law. 82. X-ray strnetural study of graphite-Fe& compounds F. Rousseaux, R. Vangelisti, M. Lelaurain and A. Herold (Laboratoire de Chimie du Solide Mb&al, LA 158, Service de Chimie Minerdle Apiliqub-CO l4054037 Nancy Cedex, France) and A. Plancon, D. Tchoubar and C. Tchoubar (Laboratoire de Cristallographie, FacultC des Sciences d’orleans, 45045 Orleans La Source France). Stage 1 and 2 samples, carefully characterized by chemical analysis and Mossbauer spectrometry, have been studied by X-ray diffraction. The experimental scattered intensity has been continuously collected along several cristallographic rows as 101,111,etc. . . in order to be compared with theoretical ones. The fit between experimental and computed curves led us to characterize the structure of the mean scattering domain by the number of stacked layers, the layer’s size, the stacking faults (random or not) probabilities.
83. Study of the system graphite-MnClrAlC13 T. Dziemianowicz and W. Forsman (Department of Chemical Engineering, University of Pennsylvania, Philadelphia, PA 19104), and R. Vangelisti and A. Herold (Laboratoire de Chimie du Solide Mineral, Universite de Nancy I, 54037 Nancy Cedex, France). Intercalation compounds of graphite with MnC12 have beeu synthesized by the direct action of the dichloride vapor, alone or in the presence of AU. Crystallographic, magnetic and electrical studies have enabled characterization of the rich stages.
84. Eleetrnuk diffraction of graphite intercalation compounds with metallfc dkhlorfdes R. Vangelisti and A. Herold (Laboratoire de Chimie du Solide Mineral, Associe au C.N.R.S. No. 158, Service de Chimie Minerale Apiliquee, C.O. 140-54037 Nancy Cedex, France). An electronic diffraction study has allowed comparing the results obtained on graphite intercalated with MnC&, CoC&, NiC& and CuC12. The two dimensional organization of the intercalant layer (planar cell parameters and angular orientations) with respect to that of graphite has been determined.
85. Ternary and quaternarycompounds derived from the 6rst stage graphftideof rubidium P. Lagrange, D. Guerard and A. Herold (Laboratoire de Chimie du Solide Mineral, L.A. t58, Service de Chimie Minerale Appliquee-CO 14&54037 Nancy Cedex, France) and D. G. Onn (Department of Physics, University of Delaware, Newark DE 19711). The hydrogenation of-the first stage compound RbCS leads to the second stage compound RbHupCs, comparable to KHz&s. The free graphitic intervals can be filled by new amounts of an alkali metal (K, Rb or Cs), which leads to new b&insertion compounds (1).
86. Kinetia of AsFs intercalation in highly-oriented pv
olytic graphite: dependenceof the 19FNMR chemiad shift on stage Gerald Ray Miller and Lewis Banks (Naval Research Laboratory, Code 6120, Washington, DC20375 and Department of Chemistry, University of Maryland, College Park, MD 20742) and M. J. Moran and H. A. Resing (Naval Research Laboratory, Code 6120, Washington, DC 20375). 19F NMR spectroscopy was used to follow the reaction of AsF, and HOPG. Conversion of stage 2 to stage 1 occurred at a constant rate [P(AsFs) = 3 atm.] as evidenced by the linear growth of the stage 1 line at a rate twice that of the decrease of the stage 2 line. 87. Thermodynamicsand kinetics of graphite intercalation by arsenic pentafluoride J. Milliken, J. E. Fischer and A. R. McGhie (University of Pennsylvania, Laboratory for Research on the Structure of Matter, Philadelphia, PA 19104). Intercalation of natural graphite powder with ASS has been studied in situ by differential scanning calorimetry. Isothermal intercalation as a function of pressure has yielded information on staging, kinetics of intercalation and the heat of reaction. In addition, apparatus design allows sampling at any time for determination of stage by X-ray diffraction. 88. Graphite intercalation compounds with derivates of the -OTeF, groap E. Stumpp and R. Kebschull (Anorganisch-chemisches Znstitut der Technischen Universitiit Clausthal, 3392 Clausthal-Zellerfeld, Federal Republic of Germany). It is known that the fluoride ion and the -0TeK group are closely related in their chemical properties. We, therefore, investigated the reaction of compounds of the type E(OTeF& with graphite. The preparation of E(OTeK), graphite intercalation compounds with E = H, Hg (x = 2), Cr02 (x = 2), Xe (x = 2), B (x = 3), Sb (x = 3) are reported and also the results of X-ray investigations. The interlayer spacings are very similar to those found in the analogous fluroide graphite intercalation compounds. 89. Intercalationof dilute inorganic acids in graphite H. Fuzellier, A. Metrot, B. Bouayad and A. Herold (Laboratoire de Chimie du Solide Mineral, associe’ au CNRS No. 158, Universite de Nancy I-CO 140-54037 Nancy Cedex, France). Graphite-acid lamellar compounds are synthetised by means of chemical or electrochemical oxidation with various acids (nitric, sulfuric, perchloric . . .). The composition of these compounds varies according to the acid dilution. Significant changes of the interplanar distance and of the electrical conductivity are observed for a given stage and are interpreted as “overcharging” and “overoxidation” processes for the 1st; for 2nd and higher stages with dilute acids, these processes may also occur. 90. Chemical and physical properties of new graphfteHNO, compounds H. Fuzellier, F. Rousseaux, J. F. MarCchi, E. McRae