The mechanism of adsorption of long-chain alkylamines at pH 6-7 onto quartz was studied using FTIR and XPS spectroscopy. The spectroscopic data were correlated with potential and Hallimond flotation results. For the first time it was shown that (1) amine cation in the first monolayer is H-bonded with surface silanol group and this H-bond becomes stronger after the break in the adsorption characteristics (isotherm, potential, floatability); (2) at the break the origin of the adsorbed amine species changes qualitatively, and along with alkylammonium ion attached to deprotonated silanol group, molecular amine appears at the surface and, as a result, monolayer thick patches of well-oriented and densely packed adsorbed amine species form rendering the surface highly hydrophobic; and (3) at higher amine concentration, bulk precipitation of molecular amine takes place. The counterion was found to influence both these steps. A model of successive two-dimensional and three-dimensional precipitation was suggested to explain amine adsorption on a silicate surface.
Using FTIR (DRIFTS and IRRAS) and XPS spectroscopy, ζ potential measurements, and Hallimond flotation tests, we confirmed that long-chain primary amines are adsorbed on silicates at pH 6-7 through the 2D-3D precipitation mechanism. The orientation and packing of dodecyl-and hexadecylammonium acetate and chloride adsorbed on albite in the different regions of the adsorption isotherm were determined. It was shown that these characteristics depend strongly on the substrate. Coadsorption of the counterion was not revealed, but the counterion was found to affect indirectly the adsorption at concentrations above the concentration of the bulk amine precipitation.
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