scholarly journals Critical Evaluation of Rate Constants and Equilibrium Constants of Hydrogen Peroxide Photolysis in Acidic Aqueous Solutions Containing Chloride Ions

2004 ◽  
Vol 33 (3) ◽  
pp. 747-763 ◽  
Author(s):  
Xiao-Ying Yu
Keyword(s):  
Hydrogen Peroxide ◽  
Aqueous Solutions ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Critical Evaluation ◽  
Chloride Ions

Kinetic and thermodynamic control of pseudobase formation from C-3 substituted 1-methylquinolinium cations

1984 ◽  
Vol 62 (7) ◽  
pp. 1301-1307 ◽  
Author(s):  
John W. Bunting ◽  
Norman P. Fitzgerald
Keyword(s):  
Aqueous Solutions ◽  
Rate Constants ◽  
Kinetic Data ◽  
Mixing Time ◽  
Equilibrium Constants ◽  
Substituent Effects ◽  
Stopped Flow ◽  
Thermodynamic Control ◽  
Preferred Species ◽  
Substituted 1

The kinetic and thermodynamic control of pseudobase formation from 3-W-1-methylquinolinium cations has been studied for a variety of substituents (W). Spectral data indicate that, in both aqueous and methanolic solution, the C-2 pseudobases predominate at equilibrium for W = H and Br, while the C-4 pseudobases are the thermodynamically preferred species for W = CONH2, CO2CH3, CN, and NO2. Stopped-flow studies indicate that in all cases the C-2 pseudobases are the kineticallycontrolled products upon basification of the aqueous solutions of these cations. Equilibrium constants (pKR+) have been measured for pseudobase formation at both C-2 and C-4 for each W in all cases where they are experimentally accessible. Substituent effects upon [Formula: see text] correlate with σm for W, while [Formula: see text] depends upon σp−. These substituent effects allow the prediction of [Formula: see text] and [Formula: see text] for the 1-methylquinolinium cation. Rates of C-2 to C-4 pseudobase equilibration have been measured in all cases where the latter species is thermodynamically more stable. These kinetic data allow the evaluation of rate constants for C-4 pseudobase equilibration with each cation. In all cases except W = CN, C-2 pseudobase formation is complete within the mixing time of the stopped-flow instrument.

Cefoxitin interferes with the "Clini-Skreen" column method for urinary 17-hydroxycorticosteroids.

1987 ◽  
Vol 33 (7) ◽  
pp. 1219-1222
Author(s):  
M H Kroll ◽  
A J Jackson ◽  
R J Elin
Keyword(s):  
Aqueous Solutions ◽  
Absorption Spectra ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Molar Absorptivity ◽  
The Other ◽  
Absorbance Maximum ◽  
Column Method ◽  
Apparent Concentration

Abstract Cefoxitin interferes with determination of urinary 17-hydroxycorticosteroids. The apparent concentration of hormone is increased from three- to 10-fold in samples from patients receiving cefoxitin when the Amberlite XAD-2 "Clini-Skreen" column is used. To determine the mechanism of interference, we reacted aqueous solutions of cefoxitin, cortisol, cortisone, and 11-deoxycortisol with phenylhydrazine; recorded the adsorption spectra; and determined the molar absorptivities and the equilibrium and rate constants. Also, we recorded the absorption spectra of phenylhydrazine with eight other cepha antibiotics and benzylpenicillin. Cortisol, cortisone, 11-deoxycortisol, and cefoxitin react with phenylhydrazine and absorb light with superimposable spectra and absorption maxima of 410 nm. The other antibiotics react with phenylhydrazine but absorbance maxima of the products vary, none being at 410 nm. Cortisol, cortisone, and 11-deoxycortisol react with phenylhydrazine 35-fold faster, have equilibrium constants ninefold greater, and have molar absorptivities 1.6 times that of cefoxitin. Thus, cefoxitin interferes with determination of urinary 17-hydroxycorticosteroids by forming a chromophore with the same absorbance maximum and with a molar absorptivity similar to cortisol, but much more slowly.

scholarly journals Kinetik und Mechanismus der Substitutionsreaktionen von Komplexverbindungen, XLVIII / Kinetics and Mechanism of the Substitution Reactions of Complexes, XLVIII

1975 ◽  
Vol 30 (5-6) ◽  
pp. 393-398 ◽  
Author(s):  
J. Zsakó ◽  
Cs. Várhelyi ◽  
Z. Finta ◽  
J. Kiss-Jakab
Keyword(s):  
Activation Energy ◽  
Aqueous Solutions ◽  
Kinetic Parameters ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Ionic Species ◽  
Protolytic Equilibrium ◽  
Substitution Reactions ◽  
Basic Solutions ◽  
Ph Range

In aqueous solutions the nonelectrolyte [Co(DH)2(NO2)(H2O)] participates in protolytic eqilibria and thus it exists in 7 different forms. Rate constants of the aquation, which leads to the substitution of the nitro group, have been measured in the pH-range between 3.72 and 8 at various temperatures. From these data rate constants, activation energies and entropy values of the aquation of 2 ionic species have been derived, as well as equilibrium constants for the protolytic equilibrium between these species. The kinetic parameters obtained have been compared to those of the aquation of the ionic species which exist in acid and basic solutions and the correlation between structure and activation energy of the aquation has been discussed.

Substituent effect in addition of cyanide ion to p-substituted 1-benzyl-3-carbamoylpyridinium chlorides

1983 ◽  
Vol 48 (5) ◽  
pp. 1401-1407 ◽  
Author(s):  
Františka Pavlíková-Raclová ◽  
Josef Kuthan
Keyword(s):  
Aqueous Solutions ◽  
Rate Constants ◽  
Substituent Effect ◽  
Equilibrium Constants ◽  
Substituent Effects ◽  
Cyanide Ion ◽  
Quaternary Salts ◽  
Half Wave ◽  
Substituted 1 ◽  
Mechanism Of The Reaction

The rate constants k2 and equilibrium constants K = k2/k-2 of the title process (A) have been measured in aqueous solutions of eight quaternary salts of nicotinamide I (R = p-XC6H4CH2) at 298 K. The substituent effects of X = CH3O, CH3, H, F, Cl, COOCH3, CN, and NO2 exhibiting the Hammett dependence have been correlated with half-wave potentials of reduction of the depolarizers I, and the correlation results have been discussed with respect to mechanism of the reaction (A).

Oxidation of (1-hydroxybenzyl)ferrocene and its derivatives substituted in phenyl ring with bis(triphenylsilyl) chromate

1982 ◽  
Vol 47 (12) ◽  
pp. 3375-3380 ◽  
Author(s):  
Jaroslav Holeček ◽  
Karel Handlíř ◽  
Milan Nádvorník ◽  
Milan Vlček
Keyword(s):  
Linear Dependence ◽  
Rate Constants ◽  
Oxidation Rate ◽  
Phenyl Ring ◽  
Equilibrium Constants ◽  
Aprotic Solvents ◽  
Protonation Equilibrium ◽  
Oxidation Of Alcohols ◽  
Hammett Σ Constants ◽  
Sulphuric Acid Medium

Kinetics have been studied of oxidation of (1-hydroxybenzyl)ferrocenes substituted in phenyl ring with bis(triphenylsilyl) chromate in benzene solutions as well as protonation of these alcohols in sulphuric acid medium. Logarithms of the oxidation rate constants (kobs, 20-40 °C) and those of the protonation equilibrium constants (KR+, 25 °C) show linear dependence on the Hammett σ constants, the ρ constant values being -0.86 to -0.40 and -2.50, respectively. These negative values suggest that the both processes are influenced by the same effects and confirm the mechanism proposed earlier for oxidation of alcohols with ferrocenyl substituent by action of bis(triphenylsilyl) chromate in aprotic solvents.

Association of benflurone in aqueous solutions studied by measuring the activity of chloride ions

1986 ◽  
Vol 51 (11) ◽  
pp. 2437-2443
Author(s):  
František Kopecký ◽  
Mária Vojteková ◽  
Milan Pešák
Keyword(s):  
Aqueous Solutions ◽  
Chloride Ions ◽  
Ion Selective Electrode ◽  
Selective Electrode ◽  
Measured Range

The conventional activity of chloride ions was measured by an ion-selective electrode at 25 °C in aqueous solutions of benflurone, i.e. 5-(2-(N,N-dimethylamino)ethoxy)-7-oxo-7H-benzo(c)fluorene hydrochloride, without or with additions of KCl. These results suggest a gradual association of benflurone; the formation of a hetero-associate, (BH+)2Cl-, followed by higher associates was evaluated in the measured range up to 0.1 mol l-1.

The reactions of oligoalcohols with arsenic, arsenous, boric and germanic acids

1980 ◽  
Vol 45 (10) ◽  
pp. 2645-2655 ◽  
Author(s):  
Antonín Mikan ◽  
Miloš Bartušek
Keyword(s):  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Dilute Aqueous Solutions

The reactions of sorbitol, mannitol, adonitol, dulcitol, glucose and glycerol with H3AsO4, H3AsO3, H3BO3 and GeO2 acids in dilute aqueous solutions were studied by potentiometric neutralization titrations. The formation of the following chelates was demonstrated: As(V)L3-, As(III)L(OH)2-, HAs(III)L(OH)2, BL2-, GeL2(OH)- and GeL32- and the equilibrium constants for their formation were found. Conditions for formation of these chelates of organic oligohydroxy compounds are discussed.

Sign in / Sign up

Export Citation Format

Share Document