Iodide mediated electrolysis of acidic coke/coal suspension

Hydrogen is among the emerging energy vectors that are being developed to replace nonrenewable hydrocarbon energy sources. The preferred method to produce hydrogen without generating greenhouse gases is the electrolysis of water using renewable energy. The reduction of energy during the water electrolysis process is a desirable goal regardless of the source of electric power. Similar to ferrous/ferric mediation, iodide can be used as a mediator in the electrolysis of an acidic suspension of coke or coal. The iodide ion is oxidized at a far lower anodic potential than the alternative oxygen evolution reaction. This reduces the cell electrolysis voltage and, consequently, reduces electricity use. The iodide consumed at the anode is continuously regenerated by chemical reaction with the coke/coal in suspension.     

Preparation,structural elucidation,molecular weight determination,and molecular recognition of first‐ and second‐tier dendrimer molecules

1,3,5‐Triglyceratetriazine [first tier (G₁)] and tri(1,3,5‐triglycerate) triazine [second tier (G₂)] dendrimers were prepared with 1,3,5‐trichlorotriazine and sodium glycerate in a 1 : 3 mass ratio in an ethanolic medium.G₁ and G₂ were amorphous, white, solid substances. Their structures were elucidated with IR, ¹H‐NMR, and ¹³C‐NMR, and their thermal stability was studied with thermogravimetric analysis. The activation energy was calculated with the Freeman–Carroll model. Densities, viscosities, and surface tensions for 0.01–0.08 mol/kg aqueous solutions increased at 0.01 mol/kg for sodium glycerate, 1,3,5‐trichlorotriazine, 1,3,5‐triazine triglycerate chloride, G₁, and G₂. These values were measured at 298.15 K. The apparent molal volume, reduced viscosity, and inherent viscosity were calculated from the densities and viscosities, respectively. The data were regressed for the limiting densities, limiting apparent molal volumes, intrinsic viscosities, limiting inherent viscosities, and limiting surface tensions for solute–solvent interactions. The positive limiting apparent molal volume values were noted in the order of G₂ > 1,3,5‐triazine triglycerate chloride > G₁ > 1,3,5‐trichlorotriazine > sodium glycerate, with weaker hydrophilic intermolecular interactions of G₂. The higher intrinsic viscosity and limiting inherent viscosity values for G₂ implied stronger G₂–H₂O hydrophilic interactions, and the higher limiting apparent molal volume of G₂ indicated slightly higher dynamic conformational changes in comparison with G₁, with stronger structural activities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal melt-crystallization kinetics of isotactic polypropylene synthesized with a metallocene catalyst and compounded with different quantities of an α nucleator

The nonisothermal crystallization kinetics of a metallocene-made isotactic polypropylene (m-iPP) and its compounds with 0.1 wt % and 0.3 wt % of a sorbitol derivative [1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS); an α nucleator] were investigated by differential scanning calorimetry at different cooling rates from the melt. The nucleation efficiency was proved by a significant increase in the crystallization temperatures (accompanied by a slight augmentation of the degree of crystallinity and a decrease in the crystal sizes). This increase in the crystallization temperatures led to higher amounts of fractional content in the γ polymorph, even though DMDBS was supposed to be a nucleator for the α form. The Avrami and Ozawa methods effectively described only the early stage of crystallization, whereas a combined Avrami–Ozawa method was valid for the whole crystallization process. The values of the exponent for this method decreased for nucleated samples in the later stage of crystallization, especially in the case of m-iPP with 0.3 wt % DMDBS added (m-iPP03). The activation energy of the process and the surface free energy were also estimated. The production of considerable proportions of the γ polymorph in m-iPP03 corresponded to higher values of the activation energy and lower values of the surface free energy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Computer simulation of the effective double layer occurring on a catalyst surface under electro-chemical promotion conditions

In this work, the structural and energetic properties of two typical catalytic surfaces, Na/Pt(111) and O/Pt(111), are studied by means of quantum mechanical calculations and Monte Carlo Grand Canonical simulations. The simulations were performed with electrostatic potentials at different truncation schemes. In order to elucidate the modification of catalyst surfaces produced by the backspillover of ionic species onto Pt(111), the electrostatic field at the interface due to the electric double layer was also analyzed.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

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.