Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Repetition Blindness Occurs in Nonwords.

Theorists have predicted that repetition blindness (RB) should be absent for nonwords because they do not activate preexisting mental types. The authors hypothesized that RB would be observed for nonwords because RB can occur at a sublexical level. Four experiments showed that RB is observed for word-nonword pairs (noon noof), orthographically similar nonwords (glome glame), and identical repetitions (plass plass). More RB was found for words than for nonwords. Prior researchers may have failed to find RB for nonwords because display conditions that allow 2 words to be reliably encoded are insufficient for nonwords, or because observers coped with low ability to encode nonwords by using guessing strategies that do not require creating a mental type or tokenizing it. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Creep Crack Growth in Polypropylene Film with Various Crack Lengths at Diverse Stresses and Temperatures

Creep crack growth rates were measured using centrally cracked tension specimens of thin polypropylene film with different crack lengths at various stresses and temperatures. The creep crack growth rates were correlated with the stress intensity factor. There was the region of the minimum constant crack growth rate which occupied more than 70% of the total creep failure life. This constant creep crack growth rate characteristics were analyzed on the basis of the stress-dependent Arrhenius type thermally activated process.     

Streaming potential measurements on stainless steels surfaces: evidence of a gel-like layer at the steel/electrolyte interface

Electric charges at the surface of a passive stainless steel are generally considered as concentrated either in the passive film itself, or at the metal/passive film interface, or in the electrical double layer at the film solution interface. Rest potential time dependence after immersion of a passive surface in aqueous electrolytes suggests however that slow processes occur in the onset of the surface charge. Specific experiments, such as streaming potential measurements and electrochemical impedance spectroscopy in a thin electrolyte cell, were carried out for understanding better this phenomenon. An AISI 304 type austenitic stainless steel with polished or bright annealed surface finishes was immersed in NaCl aqueous solutions with various pH and chloride concentrations. The streaming potential time evolution shows two steps: a first rapid one (∼2 min) is attributed to the onset of the surface charge. The second step is much slower (approximately several hours) and possibly due to an interphase layer between the passive film and the solution. Following this idea, the whole kinetics is controlled by cation migration across the interphase when the pH is larger than the isoelectric pH (pH_iep), while chloride ions are incorporated in the interphase when pH < pH_iep. Impedance measurements allow determining both the kinetics of charge transport and the thin cell conductivity. When glass is used as reference material for the cell walls instead of stainless steel, the Nyquist plots show a high-frequency response. For stainless steel cell walls, a low-frequency response is observed, attributed to a slow charge reorganisation inside the interphase layer. The charge distribution at metal/electrolyte interface is discussed in terms of a gel-like layer which possibly takes place at the passive film/electrolyte interface.     

A disposable single-use electrochemical sensor for the detection of uric acid in human whole blood

We report here a non-enzymatic detecting electrode strip for fast monitoring of uric acid in human whole blood. A single-use amperometric uric acid sensor strip, incorporating a three-electrode configuration, has been fabricated on a polypropylene substrate using low cost screen-printing (thick-film) technology. Both the working and counter electrodes were prepared by screen-printing commercial carbon ink. The integration on the same support of pseudo-reference electrode was obtained by screen-printing a commercial silver ink and subsequent electrochemical pretreatment. Simply by placing a 20 μl human whole blood drop on the strip is enough for uric acid analysis by square-wave voltammetry. Real human whole blood samples were analyzed by this method and compared to the phosphotungstic acid clinical test procedure with satisfactory results.     

Electrochemical chlorination of azulene derivatives: Insight into the mechanism of anodic oxidative chlorination

The cyclic voltammetry behavior of a series of five 1-substituted azulenes has been investigated as well as the electrochemical chlorination of these compounds. In the case of azulene compounds containing electron withdrawing groups which have higher oxidation potentials than that of the chloride ion, the electrochemical chlorination led usually to 3-chloro derivatives. The electrochemical chlorination fails for azulenes with lower oxidation potentials. Additionally some polyhalogenated compounds were obtained by controlled potential electrolyses. The paper also discusses the reaction mechanism of the electrochemical halogenation of 1-substituted azulenes.     

Electrochemical noise analysis for estimation of corrosion rate of carbon steel in bicarbonate solution

We have investigated the electrochemical noise behavior of carbon steel in fully deaerated aqueous bicarbonate solutions, and discussed the optimum conditions of the noise analysis for estimating corrosion rate of the steel. Noise of the potential difference and of the short-circuit current between two identical steel coupons were successfully measured. The time-series noise patterns were transformed into frequency domain by fast Fourier transformation, and then their power spectrum densities (PSDs) at a frequency were determined to be compared with the corrosion rate. The PSDs of the potential and of the current varied with changing environmental factors of bicarbonate concentration, pH, and immersion time. The factors also controlled the corrosion rate of the steel. The PSDs were associated with the corrosion rate, and then it was found that the PSDs of the potential and of the current showed linear correlation with the corrosion rate in log-log scale. There was also linear relationship between the corrosion rate and a spectral noise resistance obtained from the PSDs of the potential and the current. The linearities of the three correlations were better at a lower analyzed frequency. Furthermore, the PSDs of the current and the noise resistance indicated more linear correlation with the corrosion rate than that of the potential. As the simplicity of the measurement system is additionally considered, it is concluded that the PSD of the current noise at an analyzed frequency of 3 mHz is the optimum conditions for estimating the corrosion rate from 10⁻² to 10⁰ A m⁻² in this study.     

高炉喷吹废塑料燃烧动力学研究

为了提供高炉喷吹废塑料新技术工业化应用的理论依据，通过对其动力学参数的求解，研究了高炉喷吹废塑料的燃烧动力学，得出了该燃烧反应是一级反应，且在温度为200℃、塑料配比为20％～25％时活化能最低、燃烧阻力小的结论。     

Automatic processing of psychological distance: Evidence from a Stroop task.

A picture-word version of the Stroop task was used to test the automatic activation of psychological distance by words carrying various senses of psychological distance: temporal (tomorrow, in a year), social (friend, enemy), and hypotheticality (sure, maybe). The pictures implied depth, with the words appearing relatively close to or distant from the observer. The participants classified the spatial distance of words faster when the word's implicit psychological distance matched its spatial distance (e.g., a geographically close word was classified faster when it was "friend" than when it was "enemy"). The findings are consistent with the idea that psychological distance is accessed automatically, even when it is not directly related to people's current goals, and suggest that psychological distance is an important dimension of meaning, common to spatial distance, temporal distance, social distance, and hypotheticality. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Propane conversion over zeolite catalysts: Comments on the role of Ga

The activation of propane using zeolite H-Y and Ga³⁺ exchanged zeolite Y indicates that in the presence of Ga³⁺ the mechanism of propane activation is changed from a cracking pathway to a dehydrogenation pathway. The presence of both Ga³⁺ and H⁺ are required to achieve this effect.