Surface Phase Transitions Of Adsorbed Collector Molecules As Revealed By In Situ FT-IR/IRS Spectroscopy

Introduction Researchers have long speculated regarding the adsorption state of collectors on mineral surfaces. Only recently have analytical techniques become available that allow direct in situ analysis of adsorbed layers. With reactive internal reflection elements (IREs), Fourier transform infrared spectroscopy coupled with internal reflection spectroscopy (FT-IR/IRS) allows for unobtrusive investigation of the adsorbed layer (Harrick, 1979). This technique has been used both for the in situ identification of adsorbed species and for the direct calculation of collector adsorption density in real time from infrared spectral data (Miller and Kellar. 1988). The reactive mineral IRE serves both to internally reflect the infrared light and to act as a substrate at which collector adsorption can be monitored. Shown in Fig. I is a schematic of light being internally reflected in an IRE. As the light is totally reflected at the interface, an evanescent wave propagates a short distance (typically a few microns) away from the IRE, and sampling of the interfacial region occurs. Because of multiple internal reflections, great sensitivity can be obtained. Flotation systems for which this method has been demonstrated include CaF2/oleate, Al2O3/dodecylsulfate, CaCO3/oleate, ZnS/xanthate and KCI/octylamine (Miller and Kellar, 1988; Kellar et al., 1989, 1990; Miller et al., 1990). Of particular interest to flotation chemists is the conformational behavior of the alkyl chain of adsorbed collector molecules. In the simplest sense, conformation can bethought of as the relative flexibility of the hydrocarbon chain caused by rotations about carbon-carbon single bonds. The flexibility is described by the amount of gauche/trans conformations in the alkyl chain. Figure 2 shows examples of gauche and trans conformations (rotational isomers or rotamers) in a hydrocarbon chain. These two conformations are observed when the terminal methylene groups in any four-carbon subchain are on the same side (gauche) or opposites sides (trans) of the plane of the middle carbon-carbon bond. A gauche conformer (rotamer) is thus a state of maximum potential energy, whereas a trans conformer is a state with minimum potential energy. The difference between these states has been found to be approximately 0.5 to 0.8 kcal/mole (Mead et al., 1986). The relative number of butane molecules present as gauche conformers with respect to trans conformers can be calculated from the Boltzmann equation (Mead et al., 1986). At 25° C approximately 66% of the butane molecules are trans rotamers. [ ] However at 100° C, only 33% of butane molecules are trans rotamers. Exposing the hydrocarbon chain to a polar, rather than an a polar, medium should also cause an increase in the number of gauche butylene groups in a hydrocarbon chain, although this effect has been difficult to observe experimentally (Mead et al., 1986). Forming a crystalline hydrocarbon is equivalent to decreasing the temperature, which greatly increases the amount of trans butylene groups present in the chain. From the preceding discussion, a picture of the solution species of concern can be developed. The collector monomer should exhibit the greatest number of gauche rotamers and most likely will look crumpled or balled-up to reduce the surface area in contact with water. The micellar form is expected to be aggregated, with the hydrocarbon chain existing in a less polar environment. These characteristic conformational features have been examined by FT-IR spectroscopy for various liquid phases of alkanoic acids (Umemura et al., 1981; Cameron et al., 1982a; Yang et al., 1986; Wong, 1987; Wong and Mantsch, 1983; Cross et al., 1992), phospholipid membranes (Fringe Ii, 1980; Casal and Mantsch, 1985: Wong et al.. 1988;