Intensity/Distance Profile Raman Microprobe Spectroscopy to Study Adsorption and Orientation of Species In Metal/Solution Boundary Region.

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Abstract

Dependence of adsorption and orientation of species in metal / solution boundary region upon the applied potential as well as the solution pH was investigated for quinoline / mercury system by using the intensity / distance profile Raman microprobe spectroscopy. Generally, the Raman peak intensity - distance profile is that the real concentration - distance profile is convoluted by a window function determined by the focal depth of the objective lens. The treatment of the deconvolution to reproduce real concentration / distance profile was developed. The distance profile of adsorption and orientation in the boundary region was estimated with the precision of several ., m. Quinoline molecules existing in alkaline solutions were adsorbed on the mercury surface in three orientations: a perpendicular orientation from -1.1 to -0.5 V, a flat orientation -0.3 to -0.1V, and a mixture of them from -0.5 to -0.3V. In acidic solutions, quinolinium ions were adsorbed on the mercury surface in different three orientations: a perpendicular orientation with NH+ site directed toward mercury surface from -0.6 to -0.4 V, the opposite perpendicular orientation with NH+ site toward bulk solution from +0.2 to +0.4V through random orientations from -0.4 to +0.2V. The thickness of the adsorption layer of quinoline and that of quinolinium ion were estimated.

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