Band cyanide adsorption

The adsorption of CN on a polycrystalline copper electrode has been studied experimentally by Lee et al. [116], Since copper oxidizes more readily than gold and silver, the results depend strongly on the cyanide concentration. At low cyanide concentration in solution (2x 10 M), a potential dependent band between 2084 and 2120cm was assigned to the linearly adsorbed CN ion (Fig. 33, p. 172). 

The adsorption of cyanide on Pd electrodes was studied by using a combination of polarization and potential modulation (FT-IRRAS and SNIFTIRS) [124]. The reason for this combination is to enhance the surface signal, since two FT-IRRAS spectra taken at two different potentials were ratioed to obtain the SNIFTIRS spectrum. Despite this effort, a solution band at 2135 cm" (also observed with s-polar-ized light) persists in the spectrum (Fig. 36). The spectrum in this Figure taken with p-polarized radiation presents, however, a strong band at 1980 cm", which was attributed to a bridged-bonded cyanide ion, and a weak band at 2065 cm" assigned to linearly adsorbed C-down CN". 

Fleischmann et al [22] compared benzotriazole and 2-mercaptobenzoxazole as inhibitors of copper corrosion in KCl solutions containing low concentrations of cyanide. Benzotriazole proved to be an ineffective inhibitor in cyanide media, while 2-mercaptobenzoxazole remained effective. SERS showed that cyanide, revealed by a broad band centred at 2090 cm displaced benzotriazole from the Cu surface, whereas 2-mercaptobenzoxazole displaced adsorbed cyanide. A synergetic inhibition of Cu corrosion by benzotriazole and benzylamine, both in chloride and chloride/cyanide media, was also shown [22]. As SERS showed that benzylamine had not been adsorbed, its beneficial effect was ascribed to an improved film formation. Subsequent 4or measurements showed that benzotriazole, MBO, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole were all effective inhibitors of copper corrosion in neutral chloride solutions, but the inhibition efficiency of benzotriazole was decreased at pH 1-2 [23]. SERS spectra showed that, at pH 7, benzotriazole and its anionic form were coadsorbed and Cl was excluded from the interface. However, at pH < 2 undissociated benzotriazole and CH were coadsorbed, such that Cu underwent corrosion. In contrast, the anion from 2-mercaptobenzothiazole was the only adsorbed species at pH between 7 and 2 only at pH 1 was the neutral 2-mercaptobenzothiazole molecule detected. Competitive adsorption experiments showed that the inhibitive action of benzotriazole and 2-mercaptobenzothiazole in neutral/acid media could be explained in terms of adsorption strength. 

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