Mechanistic study of electrochemical oxidation of 4-tert-butylcatechol: A facile electrochemical method for the synthesis of new trimer of 4-tert-butylcatechol

The electrochemical trimerization of 4-tert-butylcatechol via anodic oxidation of 4-tert-butylcatechol (1) is described. The mechanism of trimerization has been studied in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The electrochemical synthesis of trimer 3a has been successfully performed in an undivided cell in good yield and purity.     

Time resolved study of electrode reactions using Fourier transform impedance spectroscopy: mutually correlated adsorption kinetics of Cu and ClO4 on gold

This work demonstrates the time resolved capability of Fourier transform electrochemical impedance spectroscopy (FT-EIS) for in situ kinetic studies of electrode reactions. The model system studied here is a gold electrode, employed as a substrate for dc voltage controlled deposition and stripping of copper in the presence of ClO₄⁻ ions in an aqueous electrolyte. Full Nyquist plots are collected through 1-s intervals during the occurrence of dc voltage controlled surface reactions. Distinctly different signatures of deposition and stripping of Cu are observed in the time resolved EIS data. Mutually coupled EIS features of ClO₄⁻ and Cu²⁺ indicate how the two types of ions affect each other’s adsorption kinetics as functions of the applied dc voltage.     

Investigation of the Metal–Oxide Buried Interfacial Zone with Linear Sweep Voltammetry

Interest in copper as a technologically important material needs to be met with greater understanding of the fundamental chemical reactions of copper. In particular, there is still a lack of universal agreement on the oxidation process of bulk copper and thin copper films. In this study, the authors demonstrate the use of linear sweep voltammetry (LSV) to study buried structures in the oxide layers on copper. In particular, LSV can be used to detect reactions at buried interfaces. It is also emphasized that surface scientists should recognize Cu₃O₂ and the decomposition of copper oxides at the metal–oxide interface in new studies on copper oxidation and in interpreting already existing copper oxidation data. The two key parameters that drive oxide growth and decomposition are demonstrated to be oxygen activity and the free energies of formation of the oxides (per mole of oxide ion). The complex nature of the oxidation of copper, as well as other metals and alloys, can be described qualitatively using the Modified Cabrera–Mott (C–M) Model. Surface studies of oxidation of metals and alloys need to be supported and complemented by other techniques such as chemical or electrochemical methods.     

Cyclic voltammetric study of zinc and zinc oxide electrodes in 5.3 M KOH

The behaviour of zinc and zinc oxide in 5.3 M KOH in the presence of alkaline earth oxides, SnO, Ni(OH)₂ and Co(OH)₂ was examined by cyclic voltammetry. The influence of the alkaline earth oxides was compared with additives of established effects (Bi₂O₃, LiOH, Na₂CO₃ and CdO). The alkaline earth oxide each exhibits a distinct behaviour towards zincate. Whereas, a single process of interaction with zincate was shown by CaO; two modes of reaction were obtained with SrO and BaO. Solid solution formation was noticed with BeO and MgO. The other additives forming solid solution with ZnO were CdO, SnO. The ionic sizes of Ni(OH)₂ and Co(OH)₂ allow solid solution formation with Zn(OH)₂. Both Bi₂O₃ and Na₂CO₃ enter into complexation with zincate. LiOH forms two distinct zincates, of which one is an oxo zincate leaching the `hydroxyl' functionality. Cyclic voltammetry revealed the deposition of the oxide/hydroxide additives as metal prior to the onset of zinc deposition and the potential range for this additive metal deposition is almost the same for different additives (SnO, CdO, Ni(OH)₂). The beneficial action of these additives to zinc alkaline cells is associated with a substrate effect. The implication of this electrocatalytic deposition of metals on a zinc oxide electrode is also discussed.     

Copolymerization of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate by rare earth calixarene complexes

Rare earth (Nd, Y, La) p-tert-butylcalix[n]arene (n=4, 6, and 8) complexes alone have been developed to catalyze random and block copolymerizations of trimethylene carbonate (TMC) and 2,2-dimethyltrimethylene carbonate (DTC). The random or block structure and thermal behavior of the copolymers have been characterized by SEC, NMR, DSC, XRD and PLM. Random copolymer with M_w of 14,100 and M_w/M_n of 1.36 was prepared by neodymium p-tert-butylcalix[6]arene complex under the conditions: [TMC+DTC]₀/[Nd]=400, 80 °C, 8 h. The reactivity ratios of TMC and DTC are measured to be r_TMC=4.68 and r_DTC=0.163, respectively. Random copolymerization could be well designed by the feeding ratio to prepare copolymers with controlled T_m and T_g. Only 8% TMC units in the polymer chain destroyed the crystallization of PDTC showing no T_m of the copolymer in the DSC analysis.     

Cyclic total reflux batch distillation with two reflux drums

The present work proposes a novel cyclic total reflux (CTR) operation of batch distillation with two reflux drums working alternatively. A mathematical model is set up for the process. The computational comparison of the novel policy with the regular constant reflux and non-cyclic total reflux (NCTR) operations is also presented. The experimental runs of the new mode show that it can be operated and controlled more easily. The novel operation is significantly time saving compared to the mode of regular constant reflux theoretically and experimentally. The two reflux drum mode of CTR is also suitable for the separation of the mixture containing a large amount of light component.     

Electrochemistry of chlorogenic acid: experimental and theoretical studies

Cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as well as quantum chemical methods, are used for electrochemical study of chlorogenic acid, as an important biological molecule. The standard formal potential, diffusion coefficient, and heterogeneous electron transfer rate constant of chlorogenic acid in aqueous solution are investigated. Acidic dissociation constant of chlorogenic acid is also obtained. Quantum mechanical calculations on oxidation of chlorogenic acid in aqueous solution, using density functional theory are presented. The change of Gibbs free energy and entropy of oxidation of chlorogenic acid are calculated using thermochemistry calculations. The calculations in aqueous solution are carried out with the use of polarizable continuum solvation method. Theoretical standard electrode potential of chlorogenic acid is achieved to be 0.580 V versus standard calomel electrode (SCE) which is in agreement with the experimental value of 0.617 V obtained experimentally in this work. The difference is consistent with the values we previously reported for other quinone derivatives.     

电化学方法研究KOH溶液中高铁酸根的性质

在铂微盘电极上利用电位阶跃和循环伏安技术,求出了高铁酸根离子在不同温度、不同浓度的KOH溶液中的扩散系数.探讨了高铁酸根离子在KOH溶液中扩散传质过程的特点对超铁电池放电性能所造成的影响.另外,循环伏安试验发现高铁酸根离子在KOH溶液中的电化学还原是一个多步过程.     

Electrodeposition of Zn–Mn alloys in acidic and alkaline baths. Influence of additives on the morphological and structural properties

Electrodeposition of Zn–Mn alloys on steel was achieved using alkaline pyrophosphate-based baths or acidic chloride-based baths. Cyclic voltammetry was used to determine the potential ranges where the various redox processes were taking place. It appeared that the reduction of Mn(II) was generally hidden by the other reduction reactions, especially by the hydrogen evolution reaction. Zn–Mn alloys containing up to 25 at.% Mn in the alkaline bath and 12 at.% in the acidic bath could be obtained at the cost of very low current efficiencies. The characterisation of the deposits obtained either by galvanostatic polarisation or potentiostatic polarisation was performed by Scanning Electron Microscopy and X-Ray Diffraction. Various Zn–Mn phases were obtained, depending on the current densities, the composition of the deposit and that of the electrolytic bath. Two commercial additives usually used for zinc electrodeposition, one in alkaline baths, the other in acidic baths, were tested. Their effects upon the composition, the morphology and the microstructure of the deposit were investigated.     

Passivity and Corrosion of Cu–<Emphasis Type="BoldItalic">x</Emphasis>Zn (<Emphasis Type="BoldItalic">x</Emphasis> = 10–40 wt%) Alloys in Borate Buffer Containing Chloride Ions

The electrochemical behaviour of Cu–xZn alloys and of Cu and Zn metals was studied by cyclic voltammetry and chronopotentiometry in borate buffer, pH = 9.2, with and without the addition of chloride ions in the range from 0.01 m to 1 m. In general, the shape of voltammograms of four Cu–xZn alloys with 10 – 40 wt.% of zinc resembles that of copper more than that of zinc. With increasing zinc content several characteristics of zinc are observed. In borate buffer containing chloride anions, Cu–xZn alloys are susceptible to pitting corrosion. The breakdown potential, E_b, at which the current density in the passive region starts to increase abruptly, becomes more negative with increasing zinc content in the alloy. The general relationship E_b = a + b log c_NaCl held in all cases, with constants a and b, however, being dependent on the zinc content of the alloy and on the chloride concentration. The corrosion resistance of Cu–xZn alloys was less than that of copper metal but significantly greater than that of zinc.