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.
