Characterization of smectite and illite by FTIR spectroscopy of interlayer NH+ 4 cations

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Abstract:

FTIR spectroscopy has been applied to NH+ 4-exchanged dioctahedral clay minerals to determine the molecular environment of NH+ 4 and to quantify N concentration. FTIR under vapour-pressure control, coupled with heating and freezing treatments has shown that NH+ 4 ion symmetry varies with the nature of clay minerals. NH+ 4 has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the T d symmetry group.The NH+ 4-bending vibration is centred at 1450 and 1425 cm-1.

The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH+ 4 tetrahedron which acquires a C 2v symmetry. As a consequence, the T d-C 2v transition can be used to characterize the smectite-illite transition. Quantification of NH+ 4 content per half unit cell is provided by n NH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH+ 4-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH+ 4 is chosen for the calculation because it is not affected by superimposed contributions.

Keywords: AMMONIUM; HYDRATION; ILLITE; IR SPECTROSCOPY; SMECTITE; TOBELITE

Document Type: Research Article

DOI: http://dx.doi.org/10.1180/0009855033820089

Publication date: June 1, 2003

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