Hostname: page-component-7479d7b7d-68ccn Total loading time: 0 Render date: 2024-07-10T22:57:24.192Z Has data issue: false hasContentIssue false
  • English
  • Français

Characterization of ammonioleucite (NH4)[AlSi2O6] and ND4-ammonioleucite (ND4)[AlSi2O6] using IR spectroscopy and Rietveld refinement of XRD spectra

Published online by Cambridge University Press:  05 July 2018

M. Andrut ,
D. E. Harlov  and
J. Najorka
M. Andrut
Affiliation:
Institute for Mineralogy and Crystallography, University of Vienna - Geozentrum, A-1090 Vienna, Austria
D. E. Harlov
Affiliation:
GeoForschungsZentrum Potsdam, Telegrafenberg, D-14473 Potsdam, Germany
J. Najorka
Affiliation:
Corus Research, Development & Technology, Ceramics Research Centre, PO Box 10000, 1970 Ijmuiden, The Netherlands
Get access Rights & Permissions [Opens in a new window]

Abstract

Ammonioleucite, (NH4)[AlSi2O6], and its deuterated analogue ND4-ammonioleucite (ND4)[AlSi2O6] have been synthesized in 20–150 mg amounts at 300°C and 500 MPa in 5 mm wide, 4 cm long Au capsules using Rene’ metal hydrothermal autoclaves. The resultant product consists of 20–30 mm-size single tetragonal crystals as well as 50 –100 mm wide clumps of ingrown crystals. Infrared (IR) spectra obtained from powdered samples are assigned on the basis of Td symmetry for both the ammonium and deutero-ammoniumion. They show triply degenerate vibrational bands (i.e. v3 and v4), some overtones, and combination modes from NH4+ and ND4+. While Td symmetry for NH4+ in ammonioleucite is not strictly correct due to distortion of the NH+4 molecule, the non-cubic field is not large enough at room temperature to cause a substantial splitting in the bands. However, this perturbation is documented in the IR spectra by a substantial increase in the FWHH as well as the occurrence of shoulders on the broadened bands. In contrast, at lower temperatures, the observed band splittings in the former triply degenerated states of v3 and v4 could be explained by an effective local field with D2 symmetry.

Rietveld refinement indicates that ammonioleucite, like leucite, has a tetragonal structure with space group symmetry I41/a. Here the NH4+ molecule replaces the K+ cation on the 8-fold co-ordinated W site, which has m symmetry. Substitution of NH4+ for K+ in the leucite structure results in an increase of the cell parameter a, whereas c is slightly reduced. The mean <W–O> bond length of ammonioleucite is increased in comparison to leucite from 3.00 to 3.12 Å whereas the mean <T–O> bond length of 1.65 Å remains unchanged. This results in an increase in the volume of the polyhedron hosting the NH4+ molecule as well as a decrease in distortion for structural channels parallel to the <111> direction, formed by the arrangement of the six-fold rings, on which the W cations are located. The same effect is also observed, in general, when Rb+ or Cs+ is substituted for K+ in leucite.

Keywords

ammonioleuciteIR spectroscopyRietveld refinementXRD
Type
Research Article
Information
Mineralogical Magazine , Volume 68 , Issue 1 , February 2004 , pp. 177 - 189
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2004

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

Barrer, R.M., Baynham, J.W. and McCallum, N. (1953) Hydrothermal chemistry of silicates. Part V. Compounds structur ally related to analcime. Journal of the Chemical Society, 1953, 4035–4041.CrossRefGoogle Scholar
Bastoul, A.M., Pironon, J., Mosbah, M., Dubois, M. and Cuney, M. (1993) In-situ analysis of nitrogen in minerals. European Journal of Mineralogy, 5, 233–243.CrossRefGoogle Scholar
Beran, A., Armstrong, J. and Rossman, G.R. (1992) Infrared and electron microprobe analysis of ammonium ions in halophane feldspar. European Journal of Mineralogy, 4, 847–850.CrossRefGoogle Scholar
Burgina, E.B., Yurchenko, E.N. and Paukshtis, E.A. (1986) Pecularities of the vibrational spectra of molecules adsorbed on the surface of heterogeneous catalysts: theoretical analysis. Journal of Molecular Structure, 147, 193–20.CrossRefGoogle Scholar
Dollase, W.A. (1986) Correction of intensities for preferred orientations of the March model. Journal of Applied Crystallography, 19, 267–272.CrossRefGoogle Scholar
Grifths, P.R. and de Haseth, J.A. (1986) Fourier Transform infrare d spectr oscopy. (Chemi cal Analysis, Vol. 83). Wiley, New York.Google Scholar
Harlov, D.E., Andrut, M. and Pöter, B. (2001 a) Characterisation of buddingtonite (NH4)[AlSi3O8] and ND4-buddingtonite (ND4)[AlSi3O8] using IR spectroscopy and Rietveld re. nement of XRD spectra. Physics and Chemistry of Minerals, 28, 188–198.CrossRefGoogle Scholar
Harlov, D.E., Andrut, M. and Pöter, B. (2001 b) Characterisation of tobelite (NH4)Al2[AlSi3O10] (OH)2 and ND4-tobelite (ND4) Al2[AlSi3O10] (OD)2 using IR spectroscopy and Rietveldre. nement of XRD spectra. Physics and Chemistry of Minerals, 28, 268–276.CrossRefGoogle Scholar
Herzberg, G. (1955) Infra-Red and Raman Spectra of Polyatomic Molecules. Van Nostrand, New YorkGoogle Scholar
Hori, H., Nagashima, K., Yamada, M., Miyawaki, R. and Marubishi, T. (1986) Ammonioleucite, a new mineral from Tatarazawa, Fujioka, Japan. American Mineralogist, 71, 1022–1027.Google Scholar
Landolt-Börnstein, H. (1951) Physikalisch-chemische Tabellen, Vol. 2. Edwards Brothers, Ann Arbor, Michigan, USA.Google Scholar
Larson, A.C. and von Dreele, R.B. (1987) Generalized Structure Analysis System. Los Alamos National Laboratory Report No LA-UR-86-748, Los Alamos, New Mexico, USA.Google Scholar
Likhacheva, A.Yu., Paukshtis, E.A., Seryotkin, Yu.V. and Shulgenko, S.G. (2002) IR spectroscopic characterization of NH4-analcime. Physics and Chemistry of Minerals, 29, 617–623.CrossRefGoogle Scholar
March, A. (1932) Mathematische Theorie der Regelung nach der Korngestalt. Zeitschrift für Kristallogra. ja, 81, 285–297.Google Scholar
Mertz, L. (1965) Transformation in Optics. Wiley, New York.Google Scholar
Nakamoto, K. (1986) Infrared and Raman Spectra of Inorganic and Co-ordination Compounds. Wiley, New York.Google Scholar
Nishida, N., Kimata, M., Kyono, A., Togawa, Y., Shimizu, M. and Hori, H. (1997) First finding of thallium-bearing ammonioleucite; a signal for the ultimate stage of the hydrothermal process and for a far-reaching effect from seawater alteration of MORB. Annual Report of the Instit ute of Geoscience, University of Tsukuba, 23, 35–41.Google Scholar
Oxton, I.A., Knop, O. and Falk, M. (1975) Infrared spectra of the ammonium ion in crystals. I. Ammonium hexachloroplatinate (IV) a nd hexachlorotellur ate (IV). Canadian Journal of Chemistry, 53, 2675–2682.CrossRefGoogle Scholar
Oxton, I.A., Knop, O. and Falk, M. (1976) Determination of the symmetry of ammonium ions in crystals from the infrared spectra of the isotopically dilute NH3 D+ species. Journal of Physical Chemistry, 80, 1212–1217.CrossRefGoogle Scholar
Palmer, D.C., Dove, M.T., Ibberson, R.M. and Powell, B.M. (1997) Structural behaviour, crystal chemistry, and phase transitions in substituted leucite: Highresolution neutron diffraction studies. American Mineralogist, 82, 16–29.CrossRefGoogle Scholar
Plumb, R.C. and Hornig, D.F. (1950) Infrared spectrum, X-ray diffraction pattern, and structure of ammonium fluoride. Journal of Chemical Physics, 23, 947–953.CrossRefGoogle Scholar
Wagner, E.L. and Hornig, D.F. (1950) The vibrational spectra of molecules and complex ions in crystals. III. Ammonium chloride and deutero-ammonium chloride. Journal of Chemical Physics, 18, 296–304.CrossRefGoogle Scholar
Yamada, M., Miyawaki, R., Nakai, I., Izumi, F. and Nagashima, K. (1998) A Rietveld analysis of the crystal structure of ammonioleucite. Mineralogical Journal (Japan), 20, 105–112.CrossRefGoogle Scholar