The polarographic behavior of the complex formed by V(V) and 2,3–dihydroxybenzaldehyde (2,3–DHBA) in the solution containing acetate buffer (pH 5,2) has been investigated. By means of a.c. polarography, chronovoltammetry and other techniques, it has been shown that the electrode process is complicated by the adsorption of 2,3-DHBA and its vanadium complex. The kinetic and adsorption parameters of the electrode process have been determined: adsorption equilibrium constant B= 1,32⋅105 mol-1⋅dm3, the attraction constant γ = 1,2, the maximum surface concentration Гmax = 9,10⋅10-11 mol⋅ cm-2; the share of the electrode surface occupied by one particle of the adsorbed complex S = 1,81 nm2 and the free adsorption energy ΔG = - 39,1 kJ· mol-1.
The polarographic catalytic current in acid solutions of Mo(VI), 2,3-dihydroxybenzaldehyde (2,3-DHBA) and chlorate ions has been investigated. The scheme of reactions taking place in the solutions and on the electrode has been elaborated. The increase of the catalytic current is explained by the formation of the active intermediate complex [Mo(V)×2,3-DHBA (ClO3-)]. The rate constant of formation for the active intermediate complex K = 2.5 × 106 mol-1 × dm3 × s-1, the activation energy of reaction Ea=14.0 kcal×mol-1 and the activation entropy ∆Sa¹= -28.3 e.u. have also been determined.
The effect of thionine, azure I and methylene blue on the electroreduction of tellurium(IV) has been studied in the solutions of oxalic, tartaric and trihydroxyglutaric acids. It has been shown that the electrode process is complicated by adsorption of all components of the electrochemical reaction. This causes an increase of the tellurium analytical signal. The determinations is not hampered by great excesses of various elements. Optimal conditions were found according to which determinations were carried out of tellurium in binary mixtures Pb-Te, Cd-Te, Fe-Te, Bi-Te and of tellurium admixtures in bismuth of high purity, doped by tellurium.
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