Reaction mechanism of the direct carboxylation of methanol to dimethylcarbonate: experimental and theoretical studies

The formation of dimethylcarbonate (DMC) from MeOH and CO₂ under [Nb(OMe)₅]₂ catalysis follows a different route (“acid-plus-base activation” of methanol) with respect to other known catalytic systems such as Sn(IV) and dicyclohexylcarbodiimide (DCC) that promote a “double-base activation”. The reaction intermediates and related transition states obtained from density functional (DFT) calculations are presented. Experimental data also feature a different reaction mechanism.     

Effects of sulfide and lead nitrate addition to a gold cyanidation circuit using potentiodynamic measurements

Corrosion potentiodynamic polarization experiments on a gold electrode in a cyanide solution with 0–30ppm lead addition and 0–20ppm sulfide were carried out. Solutions containing 300ppm NaCN, adjusted to a pH 11.1 by NaOH and bubbled with air were used at atmospheric pressure and room temperature. If the concentration of lead ions was equal or larger than the sulfide ions a change of potential towards the more negative potential (a potential drop) was observed and this was accompanied by a significant increase in the corrosion rate (up to 10mmy^-1 in certain circumstances). If lead nitrate was added to a solution with a gold electrode that had been previously passivated by sulfides, the corrosion rate typically rose from about 0.3 to 0.95mmy^-1. The addition of lead nitrate to sulfides in cyanide solution can create a synergetic effect which results in an increase in dissolution rates of gold in cyanide solutions and this is accompanied by a drop in the corrosion potential of gold and a dramatic decline in thiocyanate and free sulfide concentrations.     

Studies on syntheses and permeabilities of special polymer membranes: 38. Formation mechanism of finger-like cavities in membranes from cellulose nitrate and single solvent

The relationship between the permeation characteristics of an aqueous polymer solution and the asymmetric structure of cellulose nitrate membranes was investigated under various conditions. The conditions and mechanism of the formation of finger-like cavities in cellulose nitrate membranes are discussed in some detail.     

Rate and mechanism of divalent metal transport through supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier

The rate and mechanism of copper, cobalt, nickel and zinc transport through a supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier were studied, respectively. The permeation rate equations have been derived taking into account aqueous film diffusion, interfacial chemical reaction and membrane diffusion as simultaneous controlling steps. The possible rate-controlling steps were estimated by comparing the relative values of the three successive resistances. The measured permeation rates of zinc agreed well with the proposed mechanism in this study.     

A wall-jet electrode reactor and its application to the study of electrode reaction mechanisms Part III: Study of the mechanism of the a.c. electrolytic graining of aluminium in hydrochloric acid

The mechanism of the a.c. electrolytic graining of aluminium in hydrochloric acid is determined from the analysis of the potentiostatic transient behaviour of the system aluminium–electrolyte under anodic and cathodic polarization and comparison of experimentally determined transients with calculated values derived from a candidate mechanistic scheme. It has been established, that the oxidation of aluminium in the development of a distinct surface morphology occurs according to the Al3+ ions being dissolved from the surface and removed to the bulk of the solution, hence forming pits. Al(Cl)3 is a solid intermediate. The morphology developed, is determined by the excess of Cl– ions created at the electrode surface, with respect to the bulk concentration. The accumulation of Cl– ions is governed by the ratio between the rate constant for the formation of Al(Cl)3, set by the flux of charges forced across the electrode–solution interface per unit surface area taking part in the active dissolution of aluminium and the mass transport rate of the Cl– ions. The reduction of H+ ions in the cathodic half period of the applied alternating current is mass transport controlled. The concomitant rise in interfacial pH causes Al3+ ions formed in the preceding anodic half period, which are not yet removed from the electrode–solution interface, to precipitate as aluminium.