The change in rheological and mechanical properties for some ionotropic cross-linked metal-alginate hydrogel complexes in particularly copper-alginate membranes in the presence of some organic solvents (benzene, toluene, xylene, carbon tetrachloride, ace-tone, chloroform, dichloroethane, isobutyl alcohol and ethyl alcohol) or buffer solutions (acetates, borates and universal buffers) have been investigated. The experimental results showed a remarkable tendency of the studied hydrogels for shrinking in polar solvents, whereas no influence was observed for the hydrogels in non-polar solvents. On the other hand, the gels were found to swell or shrink in the buffer solutions depending on the pH of the buffer used. The swelling extent for hydrogel spheres was found to decrease in the order Cu > Ba ≈ Ca > Zn > Pb-alginates in universal buffers of pH = 5.33. The factors affected this behavior have been examined and discussed
The kinetics of oxidation of N, N-dimethyl-N'-(pyridin-2-yl) formamidine (Py-F) by cerium(IV) was studied spectrophotometrically in aqueous perchloric acid solutions at a constant ionic strength of 1.0 mol dm-3 and at 20°C. The reaction showed first order dependence with respect to [Ce(IV)] and less than unit order with respect to [Py-F]. The reaction exhibited negative fractional-first order kinetics with respect to [H + ]. The rate of reaction was not significantly affected by variation of either ionic strength or dielectric constant of the reaction medium. Addition of cerium(III) product did not affect the reaction rate. A suitable mechanistic scheme for the oxidation reaction has been proposed. The final oxidation products were identified as 2-aminopyridine, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.
The kinetics of oxidations of atropine (ATR) by permanganate ion in both perchloric and sulfuric acid solutions was studied using spectrophotometric technique at a constant ionic strength of 1.2 moldm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [ATR] and [H + ] were found to be less than unity. The effect of acid concentration suggests that the reactions were acid-catalyzed. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of atropine were identified by spectral and chemical analyses as tropine and phenylmalonic acid. Under comparable experimental conditions, the oxidation rate of atropine in sulfuric acid was approximately three times higher than that in perchloric acid. The reactions constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.
The kinetics of thermal decomposition of Ca(II)-, Sr(II)-and Ba(II)-cross-linked metal-alginate biopolymeric complexes as biocatalysts have been studied using thermogravimetric (TG) and differential thermogravimetric (DTG) techniques in static air. The TG curves showed three stages of weight loss, whereas the DTG indicated the presence of a series of thermal peaks associated with the TG curves. The thermal dehydration of the coordinated water molecules was found to occur in the first stage, followed by decomposition of the formed dehydrated complexes through the other following stages. The second stage was corresponding to the formation of oxalates as intermediate fragments, whereas the third stage indicated the formation of metal oxides as final product of such decomposition. The kinetic parameters were computed by different models and tentative decomposition mechanism is discussed.
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