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Abstract  

The groundwater at a former gasoline production site in Germany is heavily contaminated with aromatic hydrocarbons (mostly benzene) and is currently being treated in bioreactors under anaerobic conditions. To determine the reaction kinetics it is essential to know the mean residence time of the groundwater in these reactors. Most of the commonly used tracers (dyes and salts) did not give reliable results because of their interaction with the mineral matrix in the reactors. In this study radon (222Rn) dissolved in the groundwater is used as the tracer. The flow rate of groundwater through the reactors is 1 l/h. Over a period of 8 hours the radon-spiked groundwater was injected into the natural groundwater which has a very low radon concentration. The radon concentration of the discharged water is measured online at the reactor outlet. An increasing radon concentration at the reactor exit indicates the shortest residence time of the water. The time-dependent progress of the radon concentration provides detailed information about the flow behavior and residence times of water in the reactor.

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Abstract

This article studies the thermokinetics and safety parameters of cumene hydroperoxide (CHP) manufactured in the first oxidation tower. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was employed to determine reaction kinetics, the exothermic onset temperature (T0), reaction order (n), ignition runaway temperature (TC, I), etc. The n value and activation energy (Ea) of 15 mass% CHP were calculated to be 0.5 and 120.2 kJ mol−1, respectively. The heat generation rate (Qg) of 15 mass% CHP compared with hS (cooling rate) = 6.7 J min−1 K−1 of heat balance, the TS,E and the critical extinction temperature (TC, E) under 110 °C of ambient temperature (Ta) were calculated 111 and 207 °C, respectively. The Qg of 15 mass% CHP compared with hS = 0.3 J min−1 K−1 of heat balance was applied to determine the TC, I that was evaluated to be 116 °C. This article describes the best operating conditions when handling CHP, starting from the first oxidation tower.

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Abstract

Hydrogen phosphate (HPO4 2−) or poly(acrylic acid) (PAA) stabilized cobalt(0) nanoclusters were in situ generated from the reduction of cobalt(II) chloride during the catalytic hydrolysis of sodium borohydride (NaBH4) in the presence of stabilizers, HPO4 2− or PAA. Cobalt(0) nanoclusters stabilized by HPO4 2− or PAA were characterized by using UV–Visible spectroscopy, TEM, XPS and FT-IR techniques. They were employed as catalysts in the hydrolysis of NaBH4 to examine the effect of stabilizer type on their catalytic activity and stability. Detailed reaction kinetics of the hydrolysis of NaBH4 in the presence of both catalysts was studied depending on catalyst concentration, substrate concentration and temperature. PAA stabilized cobalt(0) nanoclusters provided higher total turnover number (TTON = 6,600) than that of HPO4 2− stabilized cobalt(0) nanoclusters (1,285 turnovers). However, the HPO4 2− stabilized cobalt(0) nanoclusters provided a lower activation energy (E a = 53 ± 2 kJ mol−1) than the PAA stabilized cobalt(0) nanoclusters (E a = 58 ± 2 kJ mol−1) for the hydrolysis of NaBH4. The use of two types of stabilizers in the preparation of the same metal(0) nanoclusters following the same methodology enables us to compare the electrostatic and steric stabilization in terms of the catalytic activity and stability of metal(0) nanoclusters.

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Recent remarkable progress in understanding and engineering enzymes and whole cells as highly selective and environment-friendly catalysts enabling novel routes for the production of pharmaceuticals, fine and platform chemicals, and biofuels has spurred the quest for fast biocatalyst screening and development of efficient processes with long-term biocatalyst use. Besides this, current efforts towards more sustainable production systems and bio-based products have triggered an intense research on chemo-enzymatic cascades and establishment of continuous end-to-end processing. Microreaction technology, which has in the last two decades changed the paradigm in the laboratory and production scale organic synthesis, is recently gaining attention also in the field of applied biocatalysis. Based on the trends highlighted within this article, microfluidic systems linked with appropriate monitoring and feedback control can greatly contribute to successful implementation of biocatalysis in industrial production. Microflow-based droplets facilitate ultrahigh-throughput biocatalyst engineering, screening at various operational conditions, and very fast collection of data on reaction kinetics using minute amounts of time and reagents. Harnessing the benefits of microflow devices results in faster and cheaper selection of substrate(s) and media, and development of suitable immobilization methods for continuous biocatalyst use. Furthermore, the use of highly efficient reactor designs integrated with downstream processing enabling also faster and more reliable scale-up can bridge the gap between the academic research and industrial use of biocatalysts.

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in the journal last year ( Reaction Kinetics, Mechanisms and Catalysis , 2010 , 101, 129–140; DOI 10.1007/s11144-010-0210-2 ). After the publication of the paper, the following facts became obvious to the editors. 1. The

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Awareness of the environmental aspects of the quality of crop production has increased in recent decades, leading to renewed interest in organics such as crop residues, green manures and organic manures. The effect of organics on urea transformation was investigated by conducting a laboratory incubation experiment in alluvial clay loam soil (Typic Ustifluvents) at 33±1°C with two moisture levels (1:1 soil:water ratio and field capacity). The rate of urea hydrolysis decreased as the time of incubation increased and the disappearance of urea N was associated with a corresponding increase in the (NH 4 + + NO 3 )-N content in soils treated with crop residues (rice straw and wheat straw), organic manures (poultry manure and farmyard manure) and green manures (cowpea and sesbania). In untreated soil, the time taken for the complete hydrolysis of the applied urea (200 μg urea N g −1 soil) was more than 96 h at both the moisture levels, whereas in amended soils it was completed in 48 h. The rate of urea hydrolysis was more rapid at field capacity than at the 1:1 soil:water ratio. Urea hydrolysis was higher in sesbaniatreated soils, followed by cowpea, poultry manure, farmyard manure, rice straw and wheat straw at both the moisture levels. At field capacity, 85.5% urea was hydrolysed in sesbania-treated soil as compared to 32% in untreated soil after 24 hours of incubation, while at the 1:1 soil:water ratio the corresponding values were 81.5 and 27.5%. Urea hydrolysis followed first order reaction kinetics at both the moisture levels.

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, 4593 – 4605 ; (g) Schäfer, R. Bubble Interactions, Bubble Size Distributions and Reaction Kinetics for the Autocatalytic Oxidation of Cyclohexane in a Bubble Column Reactor . PhD Thesis, University of Stuttgart , 2005 ; (h

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The measurement of meaningful activation energies

Using thermoanalytical methods. A tentative proposal

Journal of Thermal Analysis and Calorimetry
Authors: M. Reading, D. Dollimore, J. Rouquerol, and F. Rouquerol

The uncertainty surrounding the significance of the measured kinetic parameters of solid state decomposition reactions is discussed briefly. Some suggestions are made about what precautions should be taken in order to favour the measurement of undistorted results. Some criteria are proposed for deciding whether a measuredE value can be considered to have its usual meaning. The results of a series of experiments aimed at measuring the activation energy of the decomposition of calcium carbonate using a variety of methods, sample sizes and experimental conditions are presented. These results are compared with results found in the literature and it is concluded that it is possible to measure a reproducible value forE and it is tentatively proposed that this value is meaningful in terms of the energy barrier model of chemical reaction kinetics.

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Transdanubia. - Ann. Rep. of the Geological Institute of Hungary, 1996/II, pp. 191-198. Kissinger, H.E. 1957: Reaction kinetics in differential thermal analysis. - Anal. Chem., 29, pp. 1702

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precipitatated fraction These data can be used to calculate the reaction kinetics for isothermal treatments by varying the soaking temperature, by the relationship ( 8 ). The obtained results are shown in Fig. 7

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