A new approach to the mechanism of chlorine evolution: Separate examination of the kinetic steps using ac impedance on a rotating thin ring electrode

In the absence of a bulk diffusion effect, it is shown for the first time that the impedance spectra for the chlorine evolution reaction on a rotating thin ring electrode comprise three consecutive semicircles in the capacitive half of the complex plane. The first (highest frequency) semicircle is due to the charge-transfer resistance for chloride discharge and the simultaneous chlorine adsorption coupled to the double-layer capacitance. The second semicircle (around 5 Hz) is due to the adsorption and desorption of a chlorine intermediate. The third (lowest frequency, around 0.5 Hz) semicircle is due to the relaxation of surface oxygen species. The impedance data allow the steps of the overall reaction to be examined individually. On a Pt surface the rate of chloride discharge and simultaneous chlorine adsorption (the admittance of the first semicircle) is first order with respect to chloride concentration and has a potential-dependence close to 58 mV/decade. The rate of the adsorption and desorption process (the admittance of the second semicircle) is second order with respect to chloride concentration, and has a potential dependence close to 30 mV/decade. The time constant for the adsorption/desorption processes is ca 20 ms, independent of electrode potential in the range studied. These features are consistent with a mechanism in which a faster discharge reaction (Cl⁻ Cl_ad + e) is followed by a slower surface combination reaction (2Cl_ad → Cl₂), but inconsistent with mechanisms in which ion + atom desorption is predominant, the initial chloride discharge is slow, or a unipositively charged chlorine species is involved.     

反水锤的危害及防止

反水锤是发生在反击式水轮机尾水道中的一种特殊水锤现象，其压力峰值可达正常压力的几倍，甚至十多倍，以致造成肢解转轮、折断导叶、破坏顶盖、抬起转子的严重事故。因此，研究反水锤发生的原因，从而提出防止反水锤事故的措施尤为重要。     

乙醇电氧化的研究进展

简要地叙述了国内外乙醇电催化氧化的研究进展，着重介绍不同电极材料对乙醇电氧化的影响及目前所提山的机理，并对其可能的研究方向提出了建议。     

Production of biodiesel from waste fryer grease using mixed methanol/ethanol system

Transesterification of waste fryer grease (WFG) containing 5–6 wt.% free fatty acid (FFA) was carried out with methanol, ethanol, and mixtures of methanol/ethanol maintaining the oil to alcohol molar ratio of 1:6, and initially with KOH as a catalyst. Mixtures of methanol and ethanol were used for transesterification in order to use the better solvent property of ethanol and rapid equilibrium using methanol. Formation of soap by reaction of FFA present in WFG with KOH instigated difficulty in the separation of glycerol from biodiesel ester. To untangle this problem, two-stage (acid and alkali catalyzed) method was used for biodiesel synthesis. More than 90% ester was obtained when two-stage method was used compared to ∼ 50% ester in single stage alkaline catalyst. In the case of mixed alcohol, a relatively smaller amount of ethyl esters was formed along with methyl esters. Acid value, viscosity, and cetane number of all the esters prepared from WFG were within the range of the ASTM standard. Esters obtained from WFG showed good performance as a lubricity additive.     

U(Ⅳ)-U(Ⅵ)同位素交换反应动力学研究 Ⅰ.Fe~(2+)对U(Ⅳ)-U(Ⅵ)同位素交换反应的催化作用

一、前言由于U(IV)-U(VI)同位素交换体系具有相当大的同位素效应和很好的稳定性,并且容易实现两相回流,这对于分离U同位素的工业应用都是十分有利的。但是,U(IV)-U(VI)同位素交换反应速度非常慢,常温下H~+浓度为1.0—4.0 mol/l时,速度常数为1.0×10~(-4)l~2/mol·s。因此要用U(IV)-U(VI)交换体系浓缩铀同位素,必须研究U(IV)-U(VI)交换反应动力学,找到加快交换反应的方法。     

Prediction of fire classification for wood based products. A multivariate statistical approach based on the cone calorimeter

Wood has long traditions as a building material, and is often used in construction elements, and as interior and exterior surfaces in the Nordic countries. In most applications, there are reaction to fire requirements to products used as surfaces, e.g. in escape routes and larger public spaces. Most wood products will therefore have to be treated with fire retardant (FR) agents to fulfil the strict requirements to properties connected to heat release and flame spread. Unfortunately, FR agents usually also increase the smoke production, as they cause a more incomplete combustion of the wood. The wood product manufacturers seek to find the optimal amount of FR additives where both heat release and smoke production in the classifying test are within the requirements given in the building regulations. This paper describes models for prediction of the European reaction to fire classes of wood products. The models are based on multivariate statistical analysis, and use test results from the cone calorimeter test as input. The presented models are, with very good precision, able to predict which Euroclass and additional smoke class a wood based product would obtain if it were to be tested in the single burning item test. Copyright © 2006 John Wiley & Sons, Ltd.     

Phase separation studies in RIM polyurethanes catalyst and hard segment crystallinity effects

Polyurethanes were prepared from pure 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butane diol (BDO) or 1,2-ethane diol (EDO) and α,ω-hydroxyl poly(propylene oxide) (PPO) by reaction injection moulding (RIM). Hard segment (MDI + BDO or EDO) level was 45–50 wt%. The PPO had about 20% ethylene oxide copolymerized in at the chain ends to provide 80% primary OH end groups. M_n was varied from 2000 to 4000. Dibutyl tin dilaurate catalyst and mould temperature were varied. Dynamic mechanical, wide-angle X-ray, differential scanning calorimeter, molecular weight and tensile elongation measurements were made on the RIM polyurethanes. At low reaction rates (low catalyst or temperature) highly crystalline, well phase separated but low molecular weight polymers were produced. At high catalyst or temperature levels more poorly phase separated but high molecular weight, tough polymers resulted. Higher M_n PPO gave better phase separation and EDO gave higher melting temperatures. Preventing hard segment crystallinity by substituting asymmetric MDI or glycols resulted in phase compatibility.     

MGD工艺技术的特点

应炼油厂要求，FCC既要多产柴油，又需多产液化气，石油化工科学研究院开发了MGD工艺。该工工艺遵循催化裂化的反应机理，把分段进料和汽油回炼紧密组合为一个体系，较好地达到了用掺渣油原料多产柴油和液化气的目的，其汽油烯烃和硫含量降低。从而使炼油厂调合汽油达到产品规格。工艺实施容易，改造投入少、见效快，受到炼油厂欢迎，并迅速推广应用。浅释了MGD工艺的反应机理，并提出了应用中应该注意的问题。     

Effects of calcination temperature on phase and microstructure evolution of BaTi4O9 powders

Calcining of the mixture of BaCO₃ and TiO₂ with a ratio 1:4 at different temperatures was carried out to synthesize BaTi₄O₉ powders. Phase evolution of the samples was studied using the differential thermal analysis (DTA) and X-ray diffractometry (XRD). Both techniques confirmed that the formation of BaTi₄O₉ started around 1000 °C. The XRD peaks showed that BaTi₄O₉ was most pronounced at 1250 °C. X-ray line broadening methods were employed to study the variation of particle size and microstrain of the BaTi₄O₉ powders. The Voigt function in a single line and the pseudo-Voigt function in the variance methods were used in our case. We found that both functions resulted in the same trends, i.e., the particle size increased with the temperature with the biggest size of 180 and 160 nm, whilst the microstrain yielded the opposite trend with the lowest values of 6.2 × 10^–3 and 1.1 × 10^–3. The scanning electron microscopy (SEM) study revealed the size of the large particles formed, due to agglomeration, to be about 0.5–1.9 μm. Furthermore, it was shown that irregular shapes of BaTi₄O₉ powders necked to each other appeared at 1000 °C and grew into ellipse and rod shapes at 1250 °C. Electronic Publication