Investigation of phenol degradation : True reaction kinetics on fixed film titanium dioxide photocatalyst

This study of photocatalytic oxidation of phenol over titanium dioxide films presents a method for the evaluation of true reaction kinetics. A flat plate reactor was designed for the specific purpose of investigating the influence of various reaction parameters, specifically photocatalytic film thickness, solution flow rate (1–8 l min−1), phenol concentration (20, 40 and 80 ppm), and irradiation intensity (70.6, 57.9, 37.1and 20.4 W m−2), in order to further understand their impact on the reaction kinetics. Special attention was given to the mass transfer phenomena and the influence of film thickness. The kinetics of phenol degradation were investigated with different irradiation levels and initial pollutant concentration. Photocatalytic degradation experiments were performed to evaluate the influence of mass transfer on the reaction and, in addition, the benzoic acid method was applied for the evaluation of mass transfer coefficient. For this study the reactor was modelled as a batch-recycle reactor. A system of equations that accounts for irradiation, mass transfer and reaction rate was developed to describe the photocatalytic process, to fit the experimental data and to obtain kinetic parameters. The rate of phenol photocatalytic oxidation was described by a Langmuir–Hinshelwood type law that included competitive adsorption and degradation of phenol and its by-products. The by-products were modelled through their additive effect on the solution total organic carbon.

Ozone-induced dissociation of conjugated lipids reveals significant reaction rate enhancements and characteristic odd-electron product ions

Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for \[M + X](+) ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

Effect of Bottom Bubbling Conditions on Surface Reaction Rate in Oxygen-Water System

In secondary steelmaking, the enhancement of the reaction rate in the low carbon period during the decarburization of steel is considered the most effective method to produce ultralow carbon steel. In a previous study, it was revealed that the surface reaction is dominant during the final stage of the actual refining process. In order to improve the surface reaction rate, it is necessary to enlarge the reaction region, which is usually achieved by increasing the plume eye area. In this study, water model experiments were carried out to estimate the influence of bottom stirring conditions on the gas-liquid reaction rate; for this purpose, the deoxidation rate during the bottom bubbling process was measured. Five types of nozzle configurations were used to study the effect of the plume eye area on the reaction rate at various gas flow rates. The results reveal that the surface reaction rate is influenced by the gas flow rate and the plume eye area. An empirical correlation was developed for the reaction rate and the plume eye area. This correlation was applied to estimate the gas-liquid reaction rate mat the bath surface.

Microscopic theory of chemical-reaction rate

In this paper we deduce the formulae for rate-constant of microreaction with high resolving power of energy from the time-dependent Schrdinger equation for the general case when there is a depression on the reaetional potential surface (when the depression is zero in depth, the case is reduced to that of Eyring). Based on the assumption that Bolzmann distribution is appropriate to the description of reactants, the formula for the constant of macrorate in a form similar to Eyring's is deduced and the expression for the coefficient of transmission is given. When there is no depression on the reactional potential surface and the coefficient of transmission does not seriously depend upon temperature, it is reduced to Eyring's. Thus Eyring's is a special case of the present work.

Method for determining reaction rate of mild steel containers during melting of magnesium-aluminium alloys and effect of aluminium content on directionally solidified microstructures

A magnesium alloy of eutectic composition (33 wt-'%Al) was directionally solidified in mild steel tubes at two growth rates, 32 and 580 mum s(-1,) in a temperature gradient between 10 and 20 K mm(-1). After directional solidification, the composition of each specimen varied dramatically, from 32'%Al in the region that had remained solid to 18%Al (32 mum s(-1) specimen) and 13%Al (580 mum s(-1) specimen) at the plane that had been quenched from the eutectic temperature. As the aluminium content decreased, the microstructure contained an increasing volume fraction of primary magnesium dendrites and the eutectic morphology gradually changed from lamellar to partially divorced. The reduction in aluminium content was caused by the growth of an Al-Fe phase ahead of the Mg-Al growth front. Most of the growth of the Al-Fe phase occurred during the remelting period before directional solidification. The thickness of the Al-Fe phase increased with increased temperature and time of contact with the molten Mg-Al alloy. (C) 2003 Maney Publishing.

Pd embedded in porous carbon (Pd@CMK-3) as an active catalyst for Suzuki reactions: accelerating mass transfer to enhance the reaction rate

Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon (Pd@CMK-3) has been prepared by a strategy involving immersion, ammoniahydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd(0) and Pd(II) species co-exist and were embedded in the matrix of the porous carbon (CMK-3). The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency (TOF) could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 °C. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.[Figure not available: see fulltext.] © 2014 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.