Order/disorder in natrolite group zeolites: A 29Si and 27Al MAS NMR study

Abstract Disordering of Si and Al in natrolite, scolecite, mesolite, and gonnardite was investigated with 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The results indicate that with the exception of one sample of natrolite (from San Benito County, California), the natrolite, mesolite, and scolecite samples studied all exhibit small degrees (<10% Al occupancy of Si sites) of Si-Al disorder. The spectra for these samples are consistent with Al avoidance. Gonnardite is confirmed to have extensive Si-Al disorder, with only slight preferential Si occupation of the T1 site. Fits of 29Si MAS NMR spectra and mathematical relations based on Al avoidance were used to calculate Si and Al occupancies across the tetrahedral sites in these minerals. Configurational entropies arising from Si-Al disorder in natrolite, mesolite, and scolecite can add an addition 1-2% [up to 11 J/(mol·K)] to the total entropies of these phases at 298.15 K, whereas it may add as much as 7% to that of gonnardite [up to 27.7 J/(mol·K)]. These results also concur with previous observations of a gap in Si-Al disordering between orthorhombic and tetragonal natrolite samples and suggest that the state of disorder in natrolite is a function of temperature. The 29Si MAS NMR spectrum of gonnardite is consistent with a disordered natrolite framework structure, and not an intergrowth of thomsonite and natrolite structural domains.

[1]  G. Artioli,et al.  X-ray structure refinement of mesolite , 1986 .

[2]  M. Ross,et al.  Crystalline solution series and order-disorder within the natrolite mineral group , 1992 .

[3]  H. E. Petch,et al.  Nuclear Quadrupole Coupling Tensors for Na23 and Al27 in Natrolite, a Fibrous Zeolite , 1962 .

[4]  A. Alberti,et al.  The determination of the Al-content in the tetrahedra of framework silicates , 1988 .

[5]  H. Flotow,et al.  Thermodynamic studies of zeolites: natrolite, mesolite and scoleciter , 2007 .

[6]  D. Michel,et al.  High-resolution solid-state NMR of silicates and zeolites , 1987 .

[7]  G. Y. Chao,et al.  Tetranatrolite from Mont St-Hilaire, Quebec , 1980 .

[8]  W. M. Meier,et al.  Atlas of Zeolite Structure Types , 1988 .

[9]  J. Klinowski,et al.  A simple correlation between isotropic 29Si-NMR chemical shifts and T–O–T angles in zeolite frameworks , 1984, Nature.

[10]  J. Klinowski,et al.  A re-examination of Si, Al ordering in zeolites NaX and NaY , 1982 .

[11]  M. Ross,et al.  The crystal structure of tetranatrolite from Mont Saint-Hilaire, Québec, and its chemical and structural relationship to paranatrolite and gonnardite , 2000 .

[12]  D. Massiot,et al.  Two-dimensional magic-angle spinning isotropic reconstruction sequences for quadrupolar nuclei. , 1996, Solid state nuclear magnetic resonance.

[13]  A. Alberti.  Crystal Chemistry of Si-Al Distribution in Natural Zeolites , 1991 .

[14]  D. Bird,et al.  Partial dehydration of laumontite: thermodynamic constraints and petrogenetic implications , 2001, Mineralogical Magazine.

[15]  A. Alberti,et al.  The crystal chemistry of natrolite, mesolite and scolecite , 1982 .

[16]  T. Armbruster,et al.  International Mineralogical Association, Commission on New Minerals and Mineral Names: Definition of a mineral , 1980, Mineralogical Magazine.

[17]  L. Du,et al.  New opportunities for high-resolution solid-state NMR spectroscopy of oxide materials at 21.1- and 18.8-T fields. , 2002, Solid state nuclear magnetic resonance.

[18]  G. Artioli,et al.  Gonnardite: Re-examination of holotype material and discreditation of tetranatrolite , 1999 .

[19]  É. Lippmaa,et al.  Ordering of silicon and aluminium ions in the framework of NaX zeolites. A solid-state high-resolution 29Si n.m.r. study , 1981 .

[20]  A. Alberti,et al.  Order-disorder in natrolite-group minerals , 1995 .

[21]  É. Lippmaa,et al.  Investigation of the structure of zeolites by solid-state high-resolution silicon-29 NMR spectroscopy , 1981 .

[22]  G. Artioli,et al.  Characterization of the Natural Zeolite Gonnardite. Structure Analysis of Natural and Cation Exchanged Species by the Rietveld Method , 1991 .

[23]  G. Artioli,et al.  Neutron diffraction study of natrolite, Na2Al2Si3O10.2H2O, at 20 K , 1984 .

[24]  W. M. Meier.  The crystal structure of natrolite , 1960 .

[25]  A. Alberti,et al.  How the structure of natrolite is modified through the heating-induced dehydration , 1983 .

[26]  D. Peacor.  High-temperature, single-crystal x-ray study of natrolite , 1973 .

[27]  G. Y. Chao.  Paranatrolite, a new zeolite from Mont St-Hilaire, Quebec , 1980 .

[28]  N. Yamnova,et al.  Crystal structure of tetranatrolite , 1986 .

[29]  G. Will,et al.  A neutron diffraction refinement of the crystal structure of natural natrolite, Na2Al2Si3O10· 2H2O , 1983 .

[30]  D. Bird,et al.  Zeolite Parageneses in the North Atlantic Igneous Province: Implications for Geotectonics and Groundwater Quality of Basaltic Crust , 2000 .

[31]  H. Helgeson,et al.  Summary and critique of the thermodynamic properties of rock forming minerals , 1978 .

[32]  J. Klinowski,et al.  Ordering of aluminium and silicon in synthetic faujasites , 1981, Nature.

[33]  É. Lippmaa,et al.  High‐Resolution 27Al NMR of Aluminosilicates. , 1986 .

[34]  L. P. Reeuwijk.  THE THERMAL DEHYDRATION OF NATURAL ZEOLITES , 1974 .

[35]  L. P. Ogorodova,et al.  Thermochemical investigation of natural fibrous zeolites , 1997 .

[36]  E. C. Beutner.  Slaty cleavage and related strain in Martinsburg Slate, Delaware Water Gap, New Jersey , 1978 .

[37]  G. Markl.  A new type of silicate liquid immiscibility in peralkaline nepheline syenites (lujavrites) of the Ilimaussaq complex, South Greenland , 2001 .

[38]  B. P. Baradanov.  High Temperature Crystal Chemistry , 1974 .

[39]  D. A. Slack,et al.  Investigation of the contributions to the silicon-29 MAS NMR line widths of zeolites and detection of crystallographically inequivalent sites by the study of highly siliceous zeolites , 1984 .

[40]  H. Kristmannsdóttir.  Zeolite zones in geothermal areas in Iceland , 1976 .

[41]  D. Bird,et al.  Timing and structural relations of regional zeolite zones in basalts of the East Greenland continental margin , 1997 .

[42]  S. Ashbrook,et al.  27Al Multiple-Quantum Magic Angle Spinning NMR Study of the Thermal Transformation between the Microporous Aluminum Methylphosphonates AlMePO-β and AlMePO-α , 1999 .

[43]  É. Lippmaa,et al.  High-resolution aluminum-27 NMR of aluminosilicates , 1986 .