Murmanite and lomonosovite as Ag-selective ionites: kinetics and products of ion exchange in aqueous AgNO3 solutions

Products and kinetics of ion exchange of heterophyllosilicate minerals lomonosovite and murmanite with aqueous AgNO₃ solutions under low-temperature conditions have been studied using scanning electron microscopy, electron microprobe analysis, single-crystal X-ray diffraction, infrared spectroscopy, ²³Na nuclear magnetic resonance spectroscopy and dynamic calorimetry. Both minerals show strong affinity for silver in cation exchange. Simplified formulae of Ag-exchanged forms of murmanite and lomonosovite are (Ag_3.0Ca_0.5Na_0.5) (Ti,Nb,Mn,Fe)_3.7?4 (Si₂O₇)₂O₄·4(H₂O,OH) and (Ag_8.2Na_1.2Ca_0.3) (Ti,Nb,Mn,Fe)_3.9?4 (Si₂O₇)₂ (PO₄)_1.9O₄·xH₂O, respectively. The reaction of ion exchange for murmanite follows the first-order kinetic model up to ca. 70–80 % conversion. The rate of the process is described by the equation k(h^?1) = 10^7.64±0.60 exp?(12.2 ± 0.9)·10³/RT]. The average heat release value in the temperature range 39.4–72 °C is 230 J g^?1. The cation exchange is limited by processes in solid state, most probably binding of silver.