Determination of the Arrhenius parameters for disilane .dblarw. silane + silicon dihydride and .DELTA.H.degree.f (SiH2) by RRKM analysis for forward and reverse reaction rate data

1992 ◽  
Vol 96 (19) ◽  
pp. 7683-7695 ◽  
Author(s):  
Harry K. Moffat ◽  
Klavs F. Jensen ◽  
Robert W. Carr
Keyword(s):  
Reaction Rate ◽  
Reverse Reaction ◽  
Rate Data ◽  
Arrhenius Parameters

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.

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.

scholarly journals New Kinetic Spectrophotometric Method for Determination of Folic Acid in Pharmaceutical Formulations

2015 ◽  
Vol 50 ◽  
pp. 169-178
Author(s):  
Mouhammed Khateeb ◽  
Basheer Elias ◽  
Fatema Al Rahal
Keyword(s):  
Folic Acid ◽  
Spectrophotometric Method ◽  
Pharmaceutical Formulations ◽  
Fixed Time ◽  
Rate Data ◽  
Sulfuric Acid Medium ◽  
Significant Difference ◽  
Kinetic Spectrophotometric ◽  
Comparison Of The Results

A simple and sensitive kinetic spectrophotometric method has been developed for the determination of folic acid (FA) in bulk and pharmaceutical Formulations. The method is based on the oxidation of FA by Fe (III) in sulfuric acid medium. Fe (III) subsequently reduces to Fe (II) which is coupled with potassium ferricyanide to form Prussian blue. The reaction is followed spectrophotometrically by measuring the increase in absorbance at λmax 725 nm. The rate data and fixed time methods were adopted for constructing the calibration curves. The linearity range was found to be 1–20 μg mL-1 for each method. The correlation coefficient was 0.9978 and 0.9993, and LOD was found to be 0.91 and 0.09 μg mL-1 for rate data and fixed time methods, respectively. The proposed method has been successfully applied to the determination of FA in formulations with no interference from the excipients. Statical comparison of the results shows that there is no significant difference between the proposed and pharmacopoeial methods

scholarly journals Photocatalytic Activity: Experimental Features to Report in Heterogeneous Photocatalysis

Materials ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 1990 ◽  
Author(s):  
Md. Hoque ◽  
Marcelo Guzman
Keyword(s):  
Reaction Rate ◽  
Monochromatic Light ◽  
Heterogeneous Photocatalysis ◽  
Research Articles ◽  
Quantum Yields ◽  
Characterization Methods ◽  
Valuable Data ◽  
Photocatalytic Activities ◽  
Scientific Papers

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic light. In this regard, an astonishing number of recent research articles include claims of highly efficient (photo)catalysts or similar terms about materials with superior or enhanced efficiency for a given reaction without proper experimental support. Consequently, the comparison of the efficiencies of photocatalysts may result as being meaningless, especially when reports are only based on expressions determining (1) a reaction rate per weight of catalyst or its surface area, (2) quantum efficiencies or quantum yields, and (3) turnover frequencies or turnover numbers. Herein, we summarize the standards needed for reporting valuable data in photocatalysis and highlight some common discrepancies found in the literature. This work should inform researchers interested in reporting photocatalysis projects about the correct procedures for collecting experimental data and properly characterizing the materials by providing examples and key supporting literature.

Determination of global kinetic parameters by optimization procedure using burning velocity measurements

2018 ◽  
Vol 13 (6) ◽  
pp. 50
Author(s):  
Gleb V. Grenkin ◽  
Alexander Yu. Chebotarev ◽  
Valeri I. Babushok ◽  
Sergey S. Minaev
Keyword(s):  
Kinetic Parameters ◽  
Equivalence Ratio ◽  
Reaction Rate ◽  
Functional Dependence ◽  
Burning Velocity ◽  
Optimization Procedure ◽  
Optimal Parameters ◽  
Velocity Measurements ◽  
Equilibrium Calculations

The optimization procedure was developed to derive the global kinetic parameters using experimental dependence of burning velocity on the equivalence ratio. The simple model of laminar premixed flame propagation with assumed constant parameters was used to demonstrate the features of the suggested procedure. The suggested method allows finding optimal parameters for the defined functional dependence of the reaction rate on the temperature and reactant concentrations. The dependence of combustion adiabatic temperature on equivalence ratio is assumed to be known from the flame equilibrium calculations. The global kinetic parameters of combustion reaction were determined for methane, ethylene and propane mixtures with air on the basis of experimental data on burning velocity as function of the equivalence ratio. The calculated overall kinetic parameters are compared with parameters obtained by other methods within similar global model.

scholarly journals A Basic Program for Serum Cholinesterase Phenotyping Using a Microcomputer

1984 ◽  
Vol 21 (1) ◽  
pp. 43-44
Author(s):  
Jane F Loughlin ◽  
J F Tuckerman ◽  
A R Henderson
Keyword(s):  
Reaction Rate ◽  
Basic Program ◽  
Serum Cholinesterase ◽  
Full Account

We have modified a basic program for serum cholinesterase phenotyping using a microcomputer. This program accepts the reaction-rate result of total and inhibitor assays of activity, allows the patient to be identified and prints out a full account of the fitting process thus allowing adequate documentation. We believe that this modification enhances the usefulness of the program to laboratories engaged in the routine determination of serum cholinesterase phenotyping.

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