Constant-rate titrations in studies of chemical kinetics. General technique for the elucidation of reaction mechanisms and the evaluation of rate constants. Titration of nitromethane with sodium hydroxide

1974 ◽  
Vol 46 (3) ◽  
pp. 386-390 ◽  
Author(s):  
Bruce H. Campbell ◽  
Louis. Meites ◽  
Peter W. Carr
Keyword(s):  
Sodium Hydroxide ◽  
Chemical Kinetics ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
General Technique ◽  
Constant Rate

scholarly journals Reaction Mechanisms and Rate Constants of Auto‐Catalytic Urethane Formation and Cleavage Reactions

ChemistryOpen ◽  
2021 ◽  
Author(s):  
Christoph Gertig ◽  
Eric Erdkamp ◽  
Andreas Ernst ◽  
Carl Hemprich ◽  
Leif C. Kröger ◽  
...  
Keyword(s):  
Rate Constants ◽  
Reaction Mechanisms ◽  
Urethane Formation ◽  
Cleavage Reactions

scholarly journals Kinetics and Mechanism of the Change of the 4-Nitrobenzylthio-System into 4,4′-Diformylazoxybenzene in Alkaline Dioxane-Water Media

1985 ◽  
Vol 40 (11) ◽  
pp. 1128-1132
Author(s):  
Y. Riad ◽  
Adel N. Asaad ◽  
G.-A. S. Gohar ◽  
A. A. Abdallah
Keyword(s):  
Acetic Acid ◽  
Sodium Hydroxide ◽  
Rate Constants ◽  
Main Product ◽  
Reaction Medium ◽  
Aqueous Dioxane ◽  
Proton Abstraction ◽  
First Order ◽  
Water Media ◽  
Different Temperatures

Sodium hydroxide reacts with α -(4-nitrobenzylthio)-acetic acid in aqueous-dioxane media to give 4,4'-diformylazoxybenzene as the main product besides 4,4'-dicarboxyazoxybenzene and a nitrone acid. This reaction was kinetically studied in presence of excess of alkali in different dioxane-water media at different temperatures. It started by a fast reversible a-proton abstraction step followed by two consecutive irreversible first-order steps forming two intermediates (α -hydroxy, 4-nitrosobenzylthio)-acetic acid and 4-nitrosobenzaldehyde. The latter underwent a Cannizzaro's reaction, the products of which changed in the reaction medium into 4,4'-diformylazoxybenzene and 4,4'-dicarboxyazoxybenzene. The rate constants and the thermodynamic parameters of the two consecutive steps were calculated and discussed. A mechanism was put forward for the formation of the nitrone acid.Other six 4-nitrobenzyl, aryl sulphides were qualitatively studied and they gave mainly 4,4'-diformylazoxybenzene beside 4,4'-dicarboxyazoxybenzene or its corresponding azo acid.

Syngas Chemical Kinetics And Reaction Mechanisms

2009 ◽  
pp. 29-70 ◽  
Author(s):  
Frederick Dryer ◽  
Marcos Chaos ◽  
Michael Burke ◽  
Yiguang Ju
Keyword(s):  
Chemical Kinetics ◽  
Reaction Mechanisms

The Importance of Variables and Parameters in Radiolytic Chemical Kinetics Modeling

1988 ◽  
Vol 127 ◽  
Author(s):  
M. G. Piepho ◽  
P. J. Turner ◽  
P. W. Reimus
Keyword(s):  
Chemical Kinetics ◽  
Rate Constants ◽  
Transient Species ◽  
Geologic Repository ◽  
Species Concentration ◽  
Waste Package ◽  
Long Term Performance ◽  
Term Performance ◽  
Over Time

ABSTRACTRadiolysis may significantly affect the long-term performance of nuclear waste packages in a geologic repository. Radiolysis of available moisture and air in an unsaturated or saturated environment will create transient species that can significantly change the pH and/or Eh of the available moisture. These changes can influence rates of containment corrosion, waste form dissolution, and radionuclide solubilities and transport.Many of the pertinent radiochemical reactions are not completely understood, and most of the associated rate constants are poorly characterized. To help identify the important radiochemical reactions, rate constants, species, and environmental conditions, an importance theory code, SWATS (Sensitivity With Adjoint Theory-Sparse version)-LOOPCHEM, has been developed for the radiolytic chemical kinetics model in the radiolysis code LOOPCHEM. The LOOPCHEM code calculates the concentrations of various species in a radiolytic field over time. The SWATS-LOOPCHEM code efficiently calculates: 1) the importance (relative to a defined response of interest) of each species concentration over time, 2) the sensitivity of each parameter of interest, and 3) the importance of each equation in the radiolysis model. The calculated results will be used to guide future experimental and modeling work for determining the importance of radiolysis on waste package performance. A demonstration (the importance of selected concentrations and the sensitivities of selected parameters) of the SWATS-LOOPCHEM code is provided for illustrative purposes, and no attempt is made at this time to interpret the results for waste package performance assessment purposes.

Computations by Means of Macroscopic Chemical Kinetics

2006 ◽  
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad
Keyword(s):  
Chemical Kinetics ◽  
Reaction Mechanisms ◽  
Parallel Machines ◽  
Electronic Device ◽  
Chemical Mechanism ◽  
Chemical Systems ◽  
Universal Turing Machine ◽  
Sequential Machines ◽  
Logic Functions

The topic of this chapter may seem like a digression from methods and approaches to reaction mechanisms, but it is not; it is an introduction to it. We worked on both topics for some time and there is a basic connection. Think of an electronic device and ask: how are the logic functions of this device determined? Electronic inputs (voltages and currents) are applied and outputs are measured. A truth table is constructed and from this table the logic functions of the device, and at times some of its components, may be inferred. The device is not subjected to the approach toward a chemical mechanism described in the previous chapter, of taking the device apart and testing its simplest components. (That may have to be done sometimes but is to be avoided if possible.) Can such an approach be applicable to chemical systems? We show this to be the case by discussing the implementation of logic and computational devices, both sequential machines such as a universal Turing machine (hand computers, laptops) and parallel machines, by means of macroscopic kinetics; by giving a brief comparison with neural networks; by showing the presence of such devices in chemical and biochemical reaction systems; and by presenting some confirming experiments. The next step is clear: if macroscopic chemical kinetics can carry out these electronic functions, then there are likely to be new approaches possible for the determination of complex reaction mechanisms, analogs of such determinations for electronic components. The discussion in the remainder of this chapter is devoted to illustrations of these topics; it can be skipped, except the last paragraph, without loss of continuity with chapter 5 and beyond. A neuron is either on or off depending on the signals it has received. A chemical neuron is a similar device.

scholarly journals Theoretical investigation of the reaction mechanisms and kinetics of CFCl2CH2O2 and ClO in the atmosphere

RSC Advances ◽  
2020 ◽  
Vol 10 (44) ◽  
pp. 26433-26442
Author(s):  
Yunju Zhang ◽  
Bing He
Keyword(s):  
Theoretical Investigation ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Basis Sets ◽  
Thermal Rate Constants ◽  
Product Distributions ◽  
Kinetics Of

The reaction between CFCl2CH2O2 radicals and ClO was studied using the B3LYP and CCSD(T) methods associated with the 6-311++G(d,p) and cc-pVTZ basis sets, and subsequently RRKM-TST theory was used to predict the thermal rate constants and product distributions.

Carbohydrates in alkaline systems. II. Kinetics of the transformation and degradation reactions of cellobiose, cellobiulose, and 4-O-β-D-glucopyranosyl-D-mannose in 1 M sodium hydroxide at 22 °C

1969 ◽  
Vol 47 (21) ◽  
pp. 3957-3964 ◽  
Author(s):  
Donald J. MacLaurin ◽  
John W. Green
Keyword(s):  
Sulfuric Acid ◽  
Sodium Hydroxide ◽  
Column Chromatography ◽  
Rate Constants ◽  
Reaction Rate ◽  
Reaction System ◽  
Reaction Rate Constants ◽  
Degradation Reactions ◽  
Fructose 2 ◽  
Kinetics Of

Rates of isomerization, epimerization, and degradation reactions were measured for cellobiose (7), cellobiulose (8), and 4-O-β-D-glucopyranosyl-D-mannose (9) at 0.001 M in 1 M NaOH under N2 in the dark at 22 °C. Reaction system resolution was by column chromatography on anion resins in the borate form. Assay for D-glucose (1), D-fructose (2), D-mannose (3), and 7,8, and 9 was by continuous automated colorimetry of column effluent with orcinol–sulfuric acid as reagent. Reaction rate constants (h−1) found: k78 0.078, k79 0.0005, k7,10 0.002, k87 0.022, k89 0.003 k81 0.065, k8,12 0.023, k97 0.002, k98 0.013, k9,11 0.006 where 10,11, and 12 are other products than 1,2,3,7,8, and 9. Details for preparation of 8 and 9 are given.

Stability of the Nerve Gas Antidote BIS (4-Hydroxyiminomethyl-1-Pyridinomethyl) Ether Dichloride (Toxogonin®)

1968 ◽  
Vol 2 (9) ◽  
pp. 234-243 ◽  
Author(s):  
Inga Christenson
Keyword(s):  
Aqueous Solution ◽  
Hydrochloric Acid ◽  
Sodium Hydroxide ◽  
Rate Constants ◽  
Kinetics Of Hydrolysis ◽  
Dilute Aqueous Solution ◽  
Nerve Gas ◽  
Ph Range ◽  
Kinetics Of ◽  
Hydrolysis Of

The products and kinetics of hydrolysis of the nerve gas antidote bis(4-hydroxyiminomethyl - 1 - pyridinemethyl) ether dichloride (Toxogonin ®) have been investigated. A survey of these studies is given: The hydrolytic reactions were studied in the pH range 1 M hydrochloric acid to 1 M sodium hydroxide at 25, 45, 75 and 85° C. Rate constants were determined in dilute aqueous solution, generally with an initial Toxogonin concentration of 0.01 mg per ml. In addition, a report is given concerning two-year storage of 25 percent (w/v) Toxogonin solutions at pH 2.5, 3.0 and 3.5. The solutions were stored in glass or polypropylene ampuls at 5, 15, 25 and 45°C. At 5 and 15C° decomposition was negligible, at 25 and 45 °C average decomposition was 1.5 percent and 3.3 percent, respectively.

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