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.
The reaction between copper(I) sulphide and excess copper(II) sulphate in the temperature range 600–750 K was investigated by methods of thermal analysis as well as by measuring the phase composition as a function of the fractional conversions. The reaction proceeds in four stages. The transient products are Cu2S, a Cu2SO2 phase and CU2SO4, and the final product is CU2O with the non-defect structure. The initial composition of the substrate mixture strongly influence the reaction kinetics.
Authors:Shivani Suri, K. K. Bamzai, and Vishal Singh
Non-isothermal kinetic parameter of pure and cadmium-doped barium phosphate single crystal grown by room temperature solution technique have been investigated. Single crystal X-ray diffraction establishes grown crystal to be orthorhombic in nature. Scanning electron microscopy supplemented with energy dispersive X-ray analysis was used to study the surface features and to find the exact stoichiometric composition of the grown crystal. Fourier transform infrared spectroscopy studies confirm the presence of various functional groups. The effect of cadmium doping on pure barium phosphate single crystal was studied using thermogravimetry analysis. Thermogravimetry studies shows that the pure crystal was stable up to a temperature of 330 °C whereas doped crystal was stable up to a temperature of 240 °C, i.e., pure crystals were more stable than doped ones. Various solid-state reaction kinetics, i.e., activation energy (Ea), frequency factor (Z), and entropy (ΔS∗) was calculated out to find the mechanism of thermal decomposition at different stages for pure and cadmium doped barium phosphate.
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.
Authors:Jian-Zhong Guo, Zhao-Yin Hou, and Xiao-Ming Zheng
in the journal last year ( ReactionKinetics, 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.
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
)-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
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.
Authors:Christine Fräulin, Günter Rinke, and Roland Dittmeyer
, 4593 – 4605 ;
(g) Schäfer, R. Bubble Interactions, Bubble Size Distributions and ReactionKinetics for the Autocatalytic Oxidation of Cyclohexane in a Bubble Column Reactor . PhD Thesis, University of Stuttgart , 2005 ;
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.
These data can be used to calculate the reactionkinetics for isothermal treatments by varying the soaking temperature, by the relationship ( 8 ). The obtained results are shown in Fig. 7