Carboxyl Stretching Vibrations Of Spontaneously Adsorbed And Lb Transferred Calcium Carboxylates As Determined By FTIR Internal Reflection Spectroscopy

The nature of adsorbed calcium carboxylates (oleate and stearate) has been investigated by in-situ/ex-situ Fourier transform infrared internal reflection spectroscopy (FTIR/IRS). Previous spectroscopic studies in alkaline solution have shown that adsorbed carboxylate is characterized by a C-O stretching vibration at about 1550 em?1 for less than monolayer coverage. Similar results were found in this study. More specifically, in this study such a singlet at 1550 cm-1 was found for LB monolayers of calcium distearate transferred as a condensed layer at a high film pressure to the surfaces of fluorite and germanium. Normally the spectrum of bulk calcium distearate reveals a doublet at 1575 and 1540 cm-1, characteristic of a three dimensional 7-fold coordination for calcium carboxylate complexes. This doublet is generally found for carboxylate multilayers formed by spontaneous adsorption at the surface of calcium minerals. In this regard, the spectral evidence suggests that whenever the calcium dicarboxylate is constrained at a surface as a condensed layer, the 7-fold coordination can not be satisfied and the surface carboxylate is forced into a two dimensional symmetrical coordination with a singlet at 1550 cm-1. On the other hand, if the Langmuir-Blodgett (LB) monolayer calcium distearate film is transferred at a low film pressure the doublet is observed. This analysis is further confirmed by the spectral results for LB transferred calcium distearate monolayers at a hydrophobic silicon surface. Even though these are condensed monolayers formed at high film pressure, the carboxylate group, oriented away from the surface, is no longer constrained by the surface force field, and thus exhibits the characteristic doublet of the bulk calcium distearate salt.