PHOTOLYSIS OF DIETHYL KETONE AT LOW PRESSURES: THE PRESSURE DEPENDENCY OF THE COMBINATION OF ETHYL RADICALS

1955 ◽  
Vol 33 (12) ◽  
pp. 1840-1852 ◽  
Author(s):  
R. K. Brinton ◽  
E. W. R. Steacie
Keyword(s):  
High Light Intensity ◽  
Methyl Radicals ◽  
Reaction Intermediates ◽  
Experimental Conditions ◽  
Diethyl Ketone ◽  
Pressure Dependency ◽  
Pressure Independent ◽  
Low Pressures ◽  
Ethyl Radicals ◽  
Kinetics Of

The photolysis of diethyl ketone has been investigated in the pressure range 0.01–30 mm. at 100°, 150°, 200°, and 250° with a variation in absorbed intensity of 1000-fold. Over this wide variation in experimental conditions the kinetics of the reaction show excellent agreement with the mechanism of Kutschke, Wijnen, and Steacie. Under conditions where the production of ethylene by decomposition of the pentanonyl radical was negligible (high light intensity and low ketone pressure), the ratio of the rate of ethylene formed to the rate of butane produced was determined to be 0.12 independent of the temperature. These data indicate that both the disproportionation and combination of ethyl radicals are homogeneous and pressure independent to as low as 0.01 mm. pressure. In addition it is probable that the two reactions are the result of different reaction intermediates as was postulated by Wijnen and Steacie. The abstraction reactionC2H5+C2H5COC2H5 → C2H6+C2H4COC2H5showed definite heterogeneous character at low pressures similar to the analogous reaction of methyl radicals with acetone studied by Ausloos and Steacie.

The mercury (63P1) photosensitized hydrogenation of ethylene. Kinetics of the reaction C2H5 + H2 = C2H6 + H

1968 ◽  
Vol 46 (20) ◽  
pp. 3275-3281 ◽  
Author(s):  
L. E. Reid ◽  
D. J. Le Roy
Keyword(s):  
Gas Phase ◽  
Molecular Hydrogen ◽  
Mercury Vapor ◽  
Experimental Conditions ◽  
Working Pressure ◽  
Extinction Coefficients ◽  
Secondary Reactions ◽  
Ethyl Radicals ◽  
Kinetics Of ◽  
Hydrogenation Of Ethylene

A quantitative study has been made of the reaction of ethyl radicals with molecular hydrogen in the gas phase in the temperature range 240 to 320 °C. The mercury (63Pi) photosensitized decomposition of hydrogen in the presence of ethylene was used to generate ethyl radicals. Extinction coefficients for the absorption of 2537 Å by mercury vapor were measured and Beer's law was shown to be obeyed under the experimental conditions used. The corrections required to allow for the nonuniformity of radical concentrations in the cell were small. After delineating the experimental conditions necessary to minimize secondary reactions, the rate constant (cm3 mole−1 s−1) for the reaction C2H5 + H2 = C2H6 + H was found to be given by log10k = 12.57 − 13.7/θ. Experiments in the presence of added carbon dioxide showed the absence of hot radical effects at the working pressure of 92 Torr of hydrogen.

Kinetics of tartrazine photodegradation by UV/H2O2 in aqueous solution

2014 ◽  
Vol 68 (1) ◽  
Author(s):  
Petruta Oancea ◽  
Viorica Meltzer
Keyword(s):  
H2o2 Concentration ◽  
Reaction Intermediates ◽  
Original Design ◽  
Experimental Conditions ◽  
First Order ◽  
Toc Removal ◽  
First Order Kinetics ◽  
Photodegradation Rate ◽  
Pseudo First Order ◽  
Kinetics Of

AbstractIn the present work, kinetics of tartrazine decay by UV irradiation and H2O2 photolysis, and the removal of total organic carbon (TOC) under specific experimental conditions was explored. Irradiation experiments were carried out using a photoreactor of original design with a low-pressure Hg vapour lamp. The photodegradation rate of tartrazine was optimised with respect to the H2O2 concentration and temperature for the constant dye concentration of 1.035 × 10−5 M. Tartrazine degradation and the removal of TOC followed the pseudo-first-order kinetics. The much higher k obs value for tartrazine degradation (7.91 × 10−4 s−1) as compared with the TOC removal (2.3 × 10−4 s−1) confirmed the presence of reaction intermediates in the solution.

The combination of methyl radicals: photolysis of acetone at low pressures

1954 ◽  
Vol 223 (1154) ◽  
pp. 283-295 ◽  
Keyword(s):  
Relative Rate ◽  
Methyl Radicals ◽  
Third Body ◽  
Low Pressures ◽  
Kinetics Of ◽  
Photo Decomposition ◽  
Activated Complex

The kinetics of the photo-decomposition of acetone at low pressures (20 to 0.2 mm) are consistent with the participation of a third body in the recombination of methyl radicals. Various added gases increase the relative rate of formation of ethane; approximate values, relative to acetone, are given for their efficiencies in deactivating excited ethane molecules by collision. The rate of spontaneous redissociation of the activated complex is less than 6 x 10 7 s -1 at 520° K, and increases with temperature.

The mechanism of the acetaldehyde pyrolysis

1967 ◽  
Vol 297 (1450) ◽  
pp. 365-375 ◽  
Keyword(s):  
Carbon Monoxide ◽  
Main Chain ◽  
Small Contribution ◽  
Methyl Radicals ◽  
Additional Source ◽  
Elementary Processes ◽  
Order Coefficient ◽  
Kinetics Of Formation ◽  
Low Pressures ◽  
Kinetics Of

Previous work on the acetaldehyde pyrolysis is shown to be vitiated by the presence, in the acetaldehyde, of impurities, mainly ethanol and crotonaldehyde. The reaction has been reinvestigated with the use of acetaldehyde, prepared from paraldehyde, which is free from these and other impurities. On the basis of a study of the kinetics of formation of the major products (methane and carbon monoxide) and of a number of minor products (hydrogen, acetone, propionaldehyde, ethane and ethylene) a reaction mechanism is proposed. This includes all of the reactions in the original Rice-Herzfeld scheme, together with a number of other elementary processes, in particular CH 3 + CH 3 CHO → CH 4 + CH 2 CHO. The decomposition of the radical CH 2 CHO into CH 2 CO and H provides an additional source of hydrogen, the rate of production of which is therefore not a measure of the rate of the initiation process. Acetone is believed to arise mainly by the reaction CH 3 + CH 3 CHO → CH 3 COCH 3 + H, and only to a negligible extent by the combination of CH 3 and CH 3 CO. The main chain-ending step is concluded to be CH 3 + CH 3 → C 2 H 6 , with a small contribution from CH 3 + CH 2 CHO → CH 3 CH 2 CHO. The work provides further evidence for the falling off, at low pressures, of the second order coefficient for the combination of methyl radicals. Rate constants for various elementary processes are deduced from the rates of formation of the various products, and are shown to be consistent with values obtained directly.

scholarly journals Kinetics of Non-Enzymatic Synthesis of Dipeptide Cbz-Phe-Leu with AOT Reversed Micelles

Processes ◽  
2021 ◽  
Vol 9 (6) ◽  
pp. 1003
Author(s):  
Michiaki Matsumoto ◽  
Tadashi Hano
Keyword(s):  
Enzymatic Synthesis ◽  
Maximum Yield ◽  
Side Reactions ◽  
Experimental Conditions ◽  
Operational Conditions ◽  
Ph Dependency ◽  
Optimum Water Content ◽  
Short Time ◽  
Kinetics Of ◽  
Aot Reversed Micelles

The non-enzymatic synthesis of N-benzyloxycarbonyl-L-phenylalanyl-L-leucine (Cbz-Phe-Leu) from lipophilic N-benzyloxycarbonyl-L-phenylalanine (Cbz-Phe) and hydrophilic L-leucine (Leu), by N, N’-dicyclohexylcarbodiimide (DCC) as a condensing agent, was carried out using a reversed micellar system composed of bis(2-ethylhexyl) sodium sulfosuccinate (AOT) as a surfactant and isooctane. We successfully synthesized Cbz-Phe-Leu in a short time and investigated the effects of its operational conditions, the DCC concentration, w0, and the pH on the kinetic parameters and the maximum yields. For dipeptide synthesis, we had to add an excess of DCC with the substrates because of the side reactions of Cbz-Phe. From the pH dependency of the reactivity, a partially cationic form of Leu was better for a synthesis reaction because of the enrichment of Leu at the interface by anionic AOT. The optimum water content on the dipeptide synthesis was w0 = 28 due to the competition of the peptide synthesis and the side reactions. The maximum yield of Cbz-Phe-Leu was 0.565 at 80 h under optimum experimental conditions.

Copolymerization of Isobutene and Isoprene at “High” Temperature with Syncatalyst Systems Based on Aluminum Organic Compounds

1976 ◽  
Vol 49 (4) ◽  
pp. 937-959 ◽  
Author(s):  
S. Cesca ◽  
M. Bruzzone ◽  
A. Priola ◽  
G. Ferraris ◽  
P. Giusti
Keyword(s):  
Energy Savings ◽  
Ion Pairs ◽  
Great Part ◽  
Methyl Chloride ◽  
Reactivity Ratio ◽  
Experimental Conditions ◽  
Noticeable Increase ◽  
Catalyst Systems ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract New catalyst systems based on alkylaluminum derivatives and halogen or interhalogen compounds were found highly efficient in the synthesis of high-molecular-weight IIR at temperatures above − 50°C. The reaction mechanism was studied in detail for the system Et2AlCl + Cl2. The reactions occurring between chlorine, isobutene, Et2AlCl, and the solvent (CH3Cl) were elucidated and studied under various experimental conditions (e.g. presence or absence of light, simultaneous presence of the copolymerization system components, temperature, type of halogen, use of model compound of isobutene). It was concluded that halogenium ions, i.e. Cl+, Br+, or I+, are the initiating species. Kinetic and conductometric investigations showed that scarcely dissociated ion pairs, e.g. Cl+[Et2AlCl2]−, were formed in the absence of monomer; but in the presence of isobutene, a noticeable increase of the electrical conductivity and rapid polymerization occurred. The maximum polymerization rate was first order with respect to the concentrations of monomer, Cl2, and Et2AlCl. In the homopolymerization of isobutene, transfer to monomer and termination reactions were negligible. The MW of IIR was found to be mainly dependent on the concentrations of the catalyst components, on isoprene concentration, and on temperature. The reactivity ratio of isobutene with isoprene was found to be r1=2.5±0.5 at −35°C, while the activation energies relative to MW were −5.8 ± 0.4, kcal/mol for polyisobutene, and −5.7 ± 0.7 and − 4.3 ± 0.5 kcal/mol for IIR containing, respectively, 1.3 and 1.9 mol% of isoprene. The evaluation of some physicochemical and technological properties of typical IIR produced with the system Et2AlCl + Cl2, indicated that isoprene is randomly distributed along the chains and that the MWD is monomodal, while the glass transition temperature, tensile properties, mechanical-dynamic spectra, and kinetics of vulcanization are very similar to those of commercial IIR. Very preliminary data, referring to several classes of new catalyst systems yielding IIR having good properties, were also obtained. The syncatalyst systems here described can work in a homogeneous phase consisting of an aliphatic hydrocarbon besides methyl chloride, still giving IIR with high MW. Therefore, a completely homogeneous process can be envisioned for the synthesis of IIR at −50°C thus avoiding a great part of the fouling problems of the slurry process. The economic advantage of using “high” temperatures of polymerization is briefly discussed in terms of energy savings.

Kinetics of the decomposition of ammonia on platinum at low pressures

1967 ◽  
Vol 63 ◽  
pp. 476 ◽  
Author(s):  
A. J. B. Robertson ◽  
E. M. A. Willhoft
Keyword(s):  
Low Pressures ◽  
Kinetics Of

Effect of Excess PbO on the Kinetics of the Growth of PMNT Polycrystals by Templated Grain Growth Method

2005 ◽  
Vol 475-479 ◽  
pp. 1137-1140
Author(s):  
Lili Zhao ◽  
Feng Gao ◽  
Wei Min Wang ◽  
Chang Sheng Tian
Keyword(s):  
Grain Growth ◽  
Templated Grain Growth ◽  
Experimental Conditions ◽  
Precipitation Mechanism ◽  
Oriented Structure ◽  
Diffusion Controlled ◽  
The Matrix ◽  
Growth Method ◽  
Final Composition ◽  
Kinetics Of

The oriented 0.67Pb (Mg1/3Nb2/3)O3-0.33PbTiO3 (PMNT) polycrystals were prepared by the conventional ceramic technique and the templated grain growth method adding excess PbO in the matrix. Kinetics of the development of oriented structure was investigated systemically. In the presence of PbO liquid phase, the oriented PMNT polycrystals mainly grow by the dissolution-precipitation mechanism. The diffusion is determined by the sintering temperature and the PbO-excess content in the matrix. The thickness of oriented PMNT polycrystals displays a t1/3 dependence, which is characteristic of diffusion-controlled growth. For the thicker oriented structure, 20% excess PbO in the PMNT matrix and 1150oC for 10h are the proper experimental conditions. Moreover, the addition of PbO in the matrix hardly affects the final composition of ceramic matrix.

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