A new family of ionic liquids based on the 1-alkyl-2-methyl pyrrolinium cation

Five new salts based on 1-alkyl-2-methyl pyrrolinium ion are reported, two involving the iodide ion and three involving the bis(trifluoromethanesulfonyl) amide ion. The iodide salts have melting points around 100 °C, while the amide salts have melting points around room temperature. Two of the amide salts can be easily quenched into the glassy state and exhibit glass transition temperatures around −70 °C. The 2-methyl pyrrolinium cation bears structural similarities to the aromatic imidazolium cations on one hand and the cyclic ammonium cation family based on the pyrrolidinium cation on the other. The properties of the salts reported here are compared within these two related families of salts.     

计算机控制的SEESR实验系统的研制

SEESR(Simultaneous Electrochemical ESR)是研究电极过程中的自由基中间体行为的理想和方便的手段。在以前研制的ESR仪数据系统的基础上,我们应用IBM-PC/XT微机与JES-FE1XG型(JEOL产)ESR谱仪及HDV-7型恒电位仪研制了一套由计算机控制的SEESR实验装置。该系统可以完成包括循环伏安法、电流阶跃、电位阶跃及电位反转等多种电化学方法的SEESR实验。系统还具有包括数据平滑、曲线拟合等功能的多种数据处理软件,使用方便。我们应用模型化合物对该系统进行了实际测量,所得结果与文献报道一致。     

Validity of dynamic electrochemical impedance spectra of some amine corrosion inhibitors in petroleum/water corrosive mixtures by Kramers-Kronig transformation

In our previous works, the corrosion inhibition properties of propylamine (PA), iso-propylamine (i-PA), butylamine (BA), tert-butylamine (t-BA), hexylamine (HA), ethylenediamine (EDA), diethanolamine (DEA), 3-amino-1-propanol (3-AP), 2-dimethylethanolamine (2-DEA), cyclohexylamine (CHA), N-methylcyclohexylamine (N-MCA) and dicyclohexylamine (DCHA) have been investigated by means of electrochemical impedance spectroscopy (EIS) with a carbon steel rotating disc electrode in some petroleum/water corrosive mixtures containing acetic acid and NaCl at 25 °C. In this work, the Kramers-Kronig transformations (KKTs) were applied to evaluate the validity of the impedance data of these amine compounds in hydrodynamic condition. The results obtained showed that experimental impedance data did not satisfy in K-K relations completely viz. indicated some errors. These errors were related to stray capacitances, external transmission line effects, pits formation and change in interface during data acquisition at high and low frequencies regions. In addition, the selection of a suitable equivalent circuit strongly emphasized to better interpret of EIS data which in turn cause better resulted KKTs spectra. With considering obtained transformations, more effective inhibitor was selected with regard to its charge transfer resistance, the corrosion capacitance and well satisfying in K-K relations.     

Ultrasonic measurement of the inter-electrode gap in electrochemical machining

During the process of electrochemical machining the dependency of the inter-electrode gap with time and process parameters can be used to determine process characteristics and to define the shape of the workpiece surface relative to the tool surface. Defining process variables to map out the required gap-time function requires the use of time-consuming iterative trials. In-line monitoring of the gap would enable process control and tool to workpiece transfer characteristics to be achieved (for ideal conditions) without the requirement to generate such parameter maps. This work explores the use of ultrasound applied as a passive, non-intrusive, in-line gap measurement system for ECM. The accuracy of this technique was confirmed through correspondence between the generated gap-time and current time data and theoretical models applicable to ideal conditions. Gap measurements are also used to demonstrate and quantify the degree of departure from ideal behaviour for an In718/chloride system as the electrolyte flow rate is reduced from 16 to 4 l min⁻¹. The monitoring of the gap size has also been shown to be effective when determining shape convergence under ideal conditions, for the example case of a 2D sinusoidal profile.     

Diffusion Bonded EDM Electrode with Micro Holes for Jetting Dielectric Liquid

This paper describes improvement of machining characteristics of electrical discharge machining of deep slots using a tool electrode which has micro holes for jetting dielectric liquid over the working surface. The tool electrode was made by the diffusion bonding of two copper plates, over an interface on which micro grooves for jetting the dielectric fluid were formed using electrolyte jet machining. In conventional machining, it is difficult to drill micro holes at the end of a slim electrode and circulate the dielectric fluid from the other end. Hence a solid tool electrode is used and periodically lifted up during machining to flush debris particles out of the discharge gap. Use of the newly developed tool electrode was found to shorten the processing time and improve machining accuracy significantly compared with the conventional solid tool electrode. Since the holes are micro, the outlet shapes are not replicated onto the bottom surface of the slot machined.     

Investigations of ultrathin polypyrrole films: Formation and effects of doping/dedoping processes on its optical properties by electrochemical surface plasmon resonance (ESPR)

In the present work an investigation of the effects of the electropolymerization mode on the optical properties associated to the doping/dedoping processes of nanometric films of polypyrrole (PPy) is reported, monitoring in situ and in real time using simultaneously surface plasmon resonance and electrochemical techniques (ESPR). The electropolymerization of pyrrole was performed by potentiostatic, potentiodynamic and galvanostatic methods and the use of the ESPR technique showed that the electropolymerization mode is essential to the stability of polymer and the reversibility of its optical properties during the doping and dedoping processes. Thus, the optical properties of oxidized and reduced film were obtained by nonlinear least square fitting using Fresnel equations for a four-layer system. Then, the values of the real and imaginary parts of the complex dielectric constant for PPy fims were correlated with the polymer doping level. Finally, quartz crystal microbalance measurements were also applied to obtain correlation between doping/dedoping processes and the changes in the real and imaginary parts of the dielectric constant of the polypyrrole film, showing that the doping and dedoping processes in the polypyrrole film can act directly on its optical properties while the ESPR technique can give the same information indirectly.     

Anodic oxidation of mecoprop herbicide at lead dioxide

The electrochemical oxidation of an aqueous solution containing mecoprop (2-(2-methyl-4-chlorophenoxy)propionic acid) has been studied at PbO₂ anodes by cyclic voltammetry and bulk electrolysis. The influence of current density, hydrodynamic conditions, temperature and pH on the degradation rate and current efficiency is reported. The results obtained show that the use of PbO₂ leads to total mineralization of mecoprop due to the production of oxidant hydroxyl radical electrogenerated from water discharge. The current efficiency for the electro-oxidation of mecoprop is enhanced by low current density, high recycle flow-rates and high temperature. In contrast, the pH effect was not significant. It has also been observed that mecoprop decay kinetics follows a pseudo-first-order reaction and the rate constant increases with rising current density.     

Oxidation of some aliphatic polyols on anodically deposited MnO2

Galvanostatic steady state current potential measurements were carried out for oxidation of a series of aliphatic alcohols having varying number of hydroxyl groups. The anodically deposited layer of MnO₂ on platinum was used as the electrode material. The deposit was characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrode potential measurements. The catalytic role of MnO₂ in the electro-oxidation of alcohols was indicated by the chronopotentiograms and the cyclic voltammograms. An analysis of the electrochemical data indicated a catalytic EC mechanism in which Mn (V) is generated electrochemically and consumed chemically in succession. Based on this and the hydrogen bonding interaction between alcoholic hydroxyl groups and MnO₂ layer, a mechanism was proposed which accounts for the variation in the observed electrochemical reaction orders. Tafel behaviour was found to be followed only approximately. Current efficiency of the electrochemical oxidation of polyols was studied. Replacement of platinum by carbon as current collector was found to leave the electrocatalytic activity of the MnO₂ deposit practically unaltered.