Reactor modelling for electrochemical processes

This paper presents a relatively straightforward approach to the modelling of electrochemical reactors operated in batch or continuous modes. The models are based on ideal flow assumptions of either well-mixed or plug flow and incorporate reaction rate models based on electrochemical kinetics and mass transport at one electrode. General characteristics of the reactor models are described, particularly with regard to the need for good mass transport in metal recovery applications. An example is given on the use of the model in the recovery of a heavy metal (Cd²⁺) from an acidified solution containing Cd(II) and Fe(III) ions. The reaction rate model is based on experimental data.     

Oxidation of Silicon Carbide in Environments Containing Potassium Salt Vapor

At high temperatures in clean oxidizing environments, SiC forms a very protective SiO₂ film, but, in environments containing low levels of gaseous alkali salt contaminants or where condensed salts may deposit on the surface, the resistance of the film is significantly reduced. Oxidation kinetics of SiC were measured by continuous thermogravimetric analysis in a controlled environment containing CO₂, H₂O, and O₂ plus low levels of potassium-containing salts. Potassium was found to be incorporated into the SiO₂ scale and to significantly change its transport properties and its morphology. The rate of scale formation was found to increase directly in proportion to K in the scale. A change in mechanism was observed when water vapor was added to the reacting gas stream.     

Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

Antioxidant activity of anacardic acids

Anacardic acids, 6-pentadec(en)ylsalicylic acids isolated from the cashew Anacardium occidentale L. (Anacardiaceae) nut and apple, were found to possess preventive antioxidant activity while salicylic acid did not show this activity. These anacardic acids prevent generation of superoxide radicals by inhibiting xanthine oxidase (EC 1.1.3.22, Grade IV) without radical-scavenging activity. Notably, the inhibition kinetics of anacardic acids do not follow hyperbolic dependence of enzyme inhibition on inhibitor contents (Michaelis–Menten equation) but follow the Hill equation instead. Anacardic acid (C_15:1) inhibited the soybean lipoxygenase-1 (EC 1.13.11.12, Type 1) catalyzed oxidation of linoleic acid with an IC₅₀ of 6.8 μM. The inhibition is a slow and reversible reaction without residual enzyme activity. The inhibition kinetics indicate that anacardic acid (C_15:1) is a competitive inhibitor and the inhibition constant, K_I, was 2.8 μM. Anacardic acids act as antioxidants in a variety ways, including inhibition of various prooxidant enzymes involved in the production of the reactive oxygen species and chelate divalent metal ions such as Fe²⁺ or Cu²⁺, but do not quench reactive oxygen species. The C₁₅-alkenyl side chain is largely associated with the activity.     

Kinetic study of the reaction between molybdenum trioxide and gaseous carbon tetrachloride

The kinetics of the chlorination reaction of molybdenum trioxide with gaseous carbon tetrachloride has been studied at temperatures between 713 and 753 K. The effects of temperature, reaction time, residence time and gaseous reactant concentration on conversion were studied throughout the reaction. In all cases, there was an increase in conversion when the above operating variables were increased. The kinetic model proposed is consistent with and correlates the experimental data. In the range studied for the different variables, the step that controls the rate of reaction is the surface chemical reaction. Values of the rate constant and the activation energy were estimated.     

Dissolution kinetics of ulexite in acetic acid solutions

Ulexite is an important boron mineral used for the production of boron compounds. The aims of this study are to examine the dissolution kinetics of ulexite in acetic acid solutions, and to present an alternative process to produce boric acid. In order to investigate the dissolution kinetics of ulexite in acetic acid solutions, the concentration of solution, reaction temperature, solid-to-liquid ratio, and particle size were selected as experimental parameters. It was determined that the dissolution rate of ulexite increased with increasing solution concentration and temperature and decreasing particle size and solid-to-liquid ratio. The activation energy of the process was found to be 55.8 kJ/mol.     

Effect of mineral matter on coal self-heating rate

Adiabatic self-heating tests have been conducted on subbituminous coal cores from the same seam profile, which cover a mineral matter content range of 11.2-71.1%. In all cases the heat release rate does not conform to an Arrhenius kinetic model, but can best be described by a third order polynomial. Assessment of the theoretical heat sink effect of the mineral matter in each of the tests reveals that the coal is less reactive than predicted using a simple energy conservation equation. There is an additional effect of the mineral matter in these cases that cannot be explained by heat sink alone. The disseminated mineral matter in the coal is therefore inhibiting the oxidation reaction due to physicochemical effects.     

Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyaniline-multiwalled carbon nanotube composites: Characterization by WAXS and TGA

Polyaniline/carboxylated multi-walled carbon nanotube (PAni/c-MWNT) nanocomposites have been synthesized by micellar aided emulsion polymerization with various c-MWNTs compositions, viz., 0.5, 1, 5, and 10 wt %. The microcrystalline parameters such as the nanocrystal size (〈N〉), lattice strain (g), interplanar distance (d_hkl), width of the crystallite size distribution, surface weighted crystal size (D_s), and volume of the ordered regions were calculated from the X-ray data by using two mathematical models, namely the Exponential distribution and Reinhold distribution methods. The effects of heat ageing on the microcrystalline parameters of the PAni/c-MWNT nanocomposites were also studied and the results are correlated. The thermal stability and electrical resistivity of the PAni/c-MWNT nanocomposites were examined with thermogravimetric analysis (TGA) and a conventional two-probe method. The TGA data indicate that the thermal stability of the nanocomposites improved after the incorporation of c-MWNTs. The influence of temperature on the resistivity of the nanocomposites was also measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008