Effect of the aqueous–organic solvent structure on the cobalticenium–cobaltocene redox potential: The redox couple as a basis for determination of the single ion transfer energies

The redox potentials of the cobalticenium–cobaltocene couple have been determined voltammetrically in several aqueous–organic mixed solvents. The cosolvents studied were dimethylformamide, acetone, 1,4-dioxane (all three disrupting the 3D network of the water’s hydrogen bonds), propylenecarbonate (at low content structure-making, at higher – structure-breaking), and glycerol that incorporates into the 3D network. Cobalticenium spectra demonstrate the absence of ion pairs and solute–cosolvent complexes. The liquid junction potentials water-mixed solvent in the range of the cosolvent concentrations studied are small. At equal volume fractions of structure-breaking cosolvents the shifts of redox potential relative to water are similar. The potential shifts are more than by order of magnitude higher than those corresponding to the change of the mixed solvent’s dielectric constant. This is explained as due to disruption of the water hydrogen bonded structure, and disappearance therefore of the water anomalous dielectric response. The cobalticenium redox potential in the hypothetic “structureless” water was estimated as being ∼70 mV more positive than in real water. This is the potential that should be compared directly with the data for practically unstructured aprotic solvents.     

Microwave Dielectric Behaviour of 1,2‐Propanediol‐Water Mixture Studied Using Time Domain Reflectometry Technique

The dielectric behaviour of 1,2‐propanediol was investigated to understand the effect of the hydroxyl group on the dielectric parameters. The measurement of permittivity ?î and ?îî of 1,2‐propanediol was carried out in the frequency range 10 MHz to 20 GHz at 25 °C temperature. Static permittivity and dielectric relaxation time are extracted from a 1,2‐propanediol‐water mixture using the bilinear calibration method and non‐linear least squares fit method. Calculated Kirkwood correlation factor contains information regarding solute‐solvent interaction. The hydrogen bonded model suggested by Luzar is applied to determine the molecular parameters. The excess dielectric parameters and Bruggeman factor show the systematic change in the dielectric parameter of the system with change in concentration.     

Numerical and approximate studies on the theoretical dielectric relaxation of colloidal suspensions in the time domain

In this work we show numerical calculations on the dielectric behavior of colloidal suspensions in the time domain. The theory elaborated by DeLacey and White ((1981) J Chem Soc Faraday Trans 2 77:2007–2039) for dilute suspensions in the frequency domain, will be the basis for the present study. The different contributions, and their relative importance, to the transient current density generated in the suspensions after the application of a step electric field, are calculated from the dielectric response function associated to the DeLacey and White's model. In particular, we analyze the conduction and absorption current densities in the transient states upon changing the concentration of the supporting electrolyte in the suspension. With the aim of characterizing the response of the suspension for short times, an approximation to the distribution function of relaxation times that best fits the dielectric model, is calculated. Finally, an exhaustive analysis of the behavior of the dielectric response function is carried out, together with a comparison with other models in the time domain.     

An Ozone Generator of Miniaturization and Modularization with the Narrow Discharge Gap

The method of ionization discharge has a key action on the process of the ionization and decomposition of O₂ molecule as well as the re-decomposition of O₃ molecule. In this paper, an ozone generation of miniaturization which was fabricated by stacking discharge modules with rectangle is introduced, only volume of 23.0×53.0×42.0 cm³ for ozone production capacity of 1 kg/hr. In addition, the ozone concentration and its production efficiency are significantly improved in comparison with a conventional ozone generator, which have the highest ozone concentration of 308 g/Nm³ and the production efficiency of 118 g/kWh at ozone concentration of 200 g/Nm³.     

Electrical conductivity and permittivity of water-AOT-n-heptane microemulsions

Measurements of the electrical conductivity and of the complex permittivity of water-sodium bis(2-ethylhexyl) sulfosuccinate (AOT)-n-heptane microemulsions are reported. The experimental results are rationalized in terms of a hopping mechanism of AOT anions within clusters of reversed micelles. The dependence of the hopping rate and of the cluster dimensions upon the ratio [water]/[AOT] and temperature is discussed.     

Optical properties of CeBO3 and CeB3O6 compounds: first-principles calculations and experimental results

The cerium borates o-CeBO₃, m-CeBO₃ and CeB₃O₆ have been shown to be isostructural to their lanthanum derivatives. From diffuse reflectance, electron energy loss spectroscopy (EELS) and band structure calculations, it has been evidenced that a Ce³⁺ 4f-5d transition is responsible for weak absorption peaks around 3.5 eV while the O2p-Ce5d charge transfer gives rise to a strong absorption around 7 eV. Starting from self-consistent full potential LAPW calculations, the dielectric tensors of the three compounds were computed and compared to experimental data. It results in a satisfactory fit between the observed and the calculated extinction coefficient k and the index of refraction n.     

Dielectric Relaxation of Aqueous Trimethylamineoxide Solutions

Dielectric relaxation was examined for aqueous trimethylamineoxide (TMAO) solutions over a wide concentration (c) range. The dielectric relaxation of TMAO was described by a Debye-type function with a relaxation time of about 3 × 10^–11 s, with the strength proportional to c. The number of water molecules tightly hydrated to unprotonated TMAO was estimated to be two. Ab initio calculations predict the magnitudes of the dipoles for individual TMAO and TMAO tightly hydrated by two water molecules, to be 4.9 and 4.2 D, respectively. When the amount of HBr added was increased, dielectric spectra were described by two modes with relaxation times, about 3 × 10^–11 and the about 8 × 10^–10. The fast relaxation was assigned to the rotational mode of unprotonated TMAO tightly hydrated by two water molecules, and the slow mode to the rotational mode of dimers formed between a protonated and unprotonated TMAO due to hydrogen bonding.     

Temperature compensated, high permittivity dielectric resonators for millimeter wave systems

The properties of selected low loss, temperature compensated high permittivity microwave and millimetre wave dielectrics are summarised and experimental convenience suggests that planar hybrid microstrip is the preferred circuit technology for the initial studies of dielectric resonators at the millimetre wavelengths. Data are presented for temperature stabilised oscillators and some simple band pass filters are discussed.This paper is based on a talk given by G. B. Morgan, Dielectric resonators for millimetre wave circuits, Digest No. 1983/8, Inst. of Elect. Eng. Colloquium on Millimetre Waves, pp. 6.1–6.5, Jan. 1983.     

介电限域效应对SnO_2纳米微粒光学特性的影响

半导体纳米微粒作为一种新兴材料，在声、光、电、磁、热及催化等方面显示出全新的异于体相材料和分子或原子的特性，在理论和实验上已引起。们极大的兴趣I‘，’］．当纳米微粒的尺寸接近或小于激于玻尔半径时，表现出明显的量子尺寸效应，其表现光学能隙变大，一些半导体粒子如CdS，Cdse等纳米微粒的量予尺寸效应已经被人们利用有效质量近似模型做了定性解释。八但是，由于纳米微粒尺寸小，具有相对大的表面积，因而粒子周围的介质可以强烈地影响它们的光学性质【’，‘1．我们采用胶体化学方法，对SnO。阶电常数为13）半导体纳米微粒…     

介质阻挡放电脱除甲醛的化学动力学模拟

对大气压介质阻挡放电脱除甲醛进行了化学动力学模拟, 建立了时空平均化的模型, 并对相关的结果进行了实验验证. 分析了各主要物种的浓度随放电时间的变化, 在模拟空气气氛下, HCHO主要由O·和OH·自由基脱除, 其中, OH·自由基的作用更为突出. 强调了氮分子的第一电子激发态N2(A3∑+u)的作用, 它与O2、H2O 分子的碰撞增加了O·和OH·自由基的浓度,在氮气气氛中, N2(A3∑+u)态是使HCHO脱除的主要物种.讨论了HCHO初始浓度、气体流量对HCHO 脱除比能耗和产物中CO2/CO 摩尔比值的影响, HCHO 初始浓度较高时, 甲醛脱除的比能耗较低, 在输入能量密度<60 J·L-1, HCHO 初始浓度较低时, 产物中nCO2 /nCO值较高.