Decomposition of peroxobenzoic acid in benzene catalyzed by transition metal 2,4-pentanedionates

1984 ◽  
Vol 49 (3) ◽  
pp. 673-679 ◽  
Author(s):  
Pavel Lederer ◽  
Eva Mácová ◽  
Josef Vepřek-Šiška
Keyword(s):  
Transition Metal ◽  
Reaction Rate ◽  
Reaction Products ◽  
Acid Decomposition ◽  
Analogous Experiment ◽  
Catalytic Effects

The decomposition of peroxobenzoic acid in benzene was studied, and catalytic effects of Fe(III), Mn(III), Co(II), Co(III), and Cr(III) on the reaction rate and the composition of the reaction mixture were investigated. An analogous experiment carried out in perdeuterobenzene and determination of the distribution of deuterium in the reaction products provided evidence for the participation of the solvent in peroxobenzoic acid decomposition.

New developments in the ab initio determination of transition metal alloys phase diagram

1993 ◽  
Vol 90 ◽  
pp. 249-254 ◽  
Author(s):  
C Wolverton ◽  
M Asta ◽  
S Ouannasser ◽  
H Dreyssé ◽  
D de Fontaine
Keyword(s):  
Phase Diagram ◽  
Transition Metal ◽  
Ab Initio ◽  
Metal Alloys ◽  
New Developments ◽  
Transition Metal Alloys

Alcohol Determination by HPLC with Postcolumn Derivatization Based on the Thiosulfate-catalyzed Reaction of Alcohols and Cerium(IV) and Fluorescence Detection of Cerium(III)

2020 ◽  
Vol 16 ◽  
Author(s):  
Ikko Mikami ◽  
Eri Shibayama ◽  
Kengo Takagi
Keyword(s):  
Detection Limit ◽  
Fluorescence Detection ◽  
Reaction Rate ◽  
Detection Method ◽  
Fluorescence Detector ◽  
Reaction Solution ◽  
Optimum Detection ◽  
Postcolumn Derivatization ◽  
Sensitive Method

Background: Determination of a reducing substance based on the reaction between Ce(IV) and a reducing substance and fluorescence detection of Ce(III) generated has been reported as a selective and sensitive method. However, this method could not be applied to the determination of alcohol due to the low reaction rate of alcohol and Ce(IV). Objective: We found that thiosulfate catalytically enhanced reaction of alcohols (such as, methanol, ethanol, and propanol) and Ce(IV). Utilizing this effect, we developed a new method for the determination of alcohols. Results: In the presence of thiosulfate, an increase in fluorescence intensity was detected by injecting alcohol at concentrations of several millimolar, whereas it was not observed even at the concentration of 10% v/v (2 M for ethanol) in the absence of thiosulfate. The optimum detection conditions were determined to be 4.0 mM Ce(IV) sulfate and 0.50 mM thiosulfate, and the detection limit (S/N = 3) of ethanol under these conditions was 1 mM. In the calibration curves, changes in the slope were observed when the alcohol concentrations were approximately 10–25 mM. Using a thiosulfate solution containing ethanol as the reaction solution, a calibration curve without any change in slope was obtained, although the concentration of ethanol at the detection limit increased. The alcohols in the liquor and fuel were successfully analyzed using the proposed detection method as a postcolumn reaction. Conclusion: This new alcohol detection method using a versatile fluorescence detector can be applied to the postcolumn reaction of HPLC omitting need of time-consuming pretreatment processes.

Kinetics and mechanism of redox reactions of U(III) ions with monochloroacetic and dichloroacetic acids

1979 ◽  
Vol 44 (2) ◽  
pp. 401-405 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Alcohol Concentration ◽  
Kinetics And Mechanism ◽  
Solvent Structure ◽  
Influence Of Ph ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reactions of U3+ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U3+ with CHCl2COO- ions and oxidation of U3+ with CHCl2.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

scholarly journals Mechanistic Study on the Reaction of pinB-BMes2 with Alkynes Based on Experimental Investigation and DFT Calculations: Gradual Change of Mechanism Depending on the Substituent

2021 ◽  
Author(s):  
Linlin Wu ◽  
Chiemi Kojima ◽  
Ka Ho Lee ◽  
Shogo Morisako ◽  
Zhenyang Lin ◽  
...  
Keyword(s):  
Experimental Investigation ◽  
Transition Metal ◽  
Dft Calculations ◽  
Kinetic Analysis ◽  
Reaction Rate ◽  
Mechanistic Study ◽  
Isomer Ratio ◽  
Gradual Change ◽  
Isomeric Mixture ◽  
Metal Free

Transition-metal free direct and base-catalyzed 1,2-diborations of arylacetylenes using pinB-BMes2 provided syn/anti-isomeric mixture of diborylalkenes. The kinetic analysis showed that the reaction rate and isomer ratio were affected by reaction...

Reuse of Fried Oil to Obtain Biodiesel: Zeolites Y as a Catalyst

2007 ◽  
Vol 5 (1) ◽  
Author(s):  
A. Brito ◽  
M. E. Borges ◽  
R. Arvelo ◽  
F. Garcia ◽  
M. C. Diaz ◽  
...  
Keyword(s):  
Fixed Bed ◽  
Weight Ratio ◽  
Degree Of Conversion ◽  
Transesterification Reaction ◽  
Molar Ratio ◽  
Catalytic Reactor ◽  
Reaction Products ◽  
Waste Oil ◽  
Catalytic Effects ◽  
Fried Oil

The transesterification reaction is the most utilized process to obtain biodiesel. Fried oil transesterification reactions with methanol have been studied using several zeolites Y and interchanged with CsCl and KOH. The reaction has been carried out both in a slurry reactor and a fixed bed catalytic reactor. The catalytic effects of zeolites have been tested within a temperature range of 60-476°C, 2.5-5% catalyst/waste oil weight ratio, and 6:1 - 100:1 methanol/oil molar ratio. Cosolvents (THF, n-hexane) in the reaction feedstock effect have also been studied as well as catalyst regeneration effects. Viscosity of both the oil and the transesterification reaction products was determined as an initial guide to investigate the degree of conversion to biodiesel as well as FAME content by GC. When interchanged zeolites are used conversions are improved, getting the best yields (98% FAME) for the Y756 zeolite interchanged with KOH. Viscosities of the reaction product obtained reached values next to diesel standard ones.

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