Conformation Of Chemisorbed Oleate At A Calcite Surface

The surface chemistry of the calcite/oleate flotation system was examined by in-situ FT-NIR/IRS. Spectra of combination and overtone bands of aliphatic stretching vibrations revealed gauche/trans conformational changes that occurred solely as a function of temperature. The conformational changes were attributed to the simple "melting" behavior associated with phase transitions. It was concluded that chemisorbed oleate at calcite surfaces is gel-like at temperatures below 22oC, resembles a coagel between 22oC and 31oC, and becomes micelle-like at temperatures above 31oC. By comparison, chemisorbed oleate at fluorite surfaces also undergoes these phase transitions but is additionally dependent on adsorption density. The conformational changes were observed at high chemisorption densities (> 2.0x10-10 mol/cm2) and attributed to molecular forces, primarily van der Waal's interactive forces, among neighboring chemisorbed oleate molecules. Similar analysis of in-situ FT-NIR/IRS spectra of surface-precipitated calcium dioleate at calcite surfaces did not exhibit this behavior thereby confirming that surface-precipitated calcium dioleate remains in an all-trans conformation. The results help explain why surface polymerization is not observed at calcite surfaces but is observed at fluorite surfaces.