External reflection FTIR spectroscopy of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) on an...

External reflection Fourier transform infrared spectroscopy (ER-FTIRS) has been used to study the adsorption of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) at the air-water interface under nonequilibrium conditions. An overflowing cylinder (OFC) was used to generate a continually expanding liquid surface with a surface age of 0.1-1 s. ER-FTIR spectra were acquired by a single bounce of p- or s-polarized radiation from the flowing surface of the OFC. The C-H stretching region of CTAB spectra was analyzed both by subtraction of a reference spectrum of pure water and by a chemometric technique known as target factor analysis (TFA). The TFA method is shown to give lower scatter in the weight of the component assignable to the adsorbed CTAB monolayer and to permit analysis of spectra at lower bulk surfactant concentrations. The surface sensitivity of ER-FTIRS is demonstrated both experimentally and by theoretical modeling. Modeling shows that surfactant adsorbed at the surface and dissolved in the bulk solution can be distinguished by reflection spectroscopy but also highlights potential errors that can arise from the neglect of the bulk surfactant contribution to the ER-FTIR spectra. Polarized spectra are consistent with an isotropic distribution of transition dipole moments of the hydrocarbon chains in CTAB. Component weights of the CTAB monolayer determined by TFA are compared with an independent determination of values of the dynamic surface excess, Gammadyn, by neutron reflection and ellipsometry. The relationship between the component weights and Gammadyn shows a small but significant deviation from linearity. Possible explanations for this deviation are discussed. The feasibility of using TFA to deconvolute ER-FTIR spectra of mixtures of hydrocarbon surfactants is demonstrated.