Complex Ions of Chromium. VI. Kinetics of Formation of Diol Bonds in Chromium(III) Solutions1-3

1956 ◽  
Vol 78 (13) ◽  
pp. 3006-3009 ◽  
Author(s):  
David M. Grant ◽  
Randall E. Hamm
1994 ◽  
Vol 72 (7) ◽  
pp. 1637-1644 ◽  
Author(s):  
Joaquin F. Perez-Benito ◽  
Driss Lamrhari ◽  
Conchita Arias

The kinetics of formation of the thioester involved as an intermediate in the reaction between chromium(VI) and DL-penicillamine in aqueous media (pH = 1–8) containing different buffers (acetate, citrate, and phosphate) has been studied by monitoring the disappearance of chromium(VI) at 370 nm and application of the initial-rates method. The initial rate is directly proportional to the initial concentrations of both oxidant and reductant, and the rate vs. pH plots show bell-shaped profiles. The reaction is catalyzed by the buffer present in the medium, the catalytic power of each buffer increasing in the order acetate < citrate < phosphate. This is explained in terms of a mechanism involving the formation of a complex between the acidic form of the buffer and HCrO4− previous to the formation of the thioester. Potassium chloride and sodium sulfate do not seem to have important specific effects on the reaction rate, their effect being that of an acceleration of the reaction as the ionic strength increases. On the contrary, the sulfates of magnesium, manganese(II), and zinc (the latter only in the presence of acetate buffer) have specific effects, indicating the probable formation of several complexes. The spectrophotometric detection of the thioester at 430 nm has allowed to confirm some of the conclusions extracted from the measurement of initial rates, and suggests that this intermediate might approach a steady-state behavior in the three buffers at pH > 6.25, and also that a bimolecular reaction with DL-penicillamine might be involved in its destruction.


1979 ◽  
Vol 44 (3) ◽  
pp. 912-917 ◽  
Author(s):  
Vladimír Macháček ◽  
Said A. El-bahai ◽  
Vojeslav Štěrba

Kinetics of formation of 2-imino-4-thiazolidone from S-ethoxycarbonylmethylisothiouronium chloride has been studied in aqueous buffers and dilute hydrochloric acid. The reaction is subject to general base catalysis, the β value being 0.65. Its rate limiting step consists in acid-catalyzed splitting off of ethoxide ion from dipolar tetrahedral intermediate. At pH < 2 formation of this intermediate becomes rate-limiting; rate constant of its formation is 2 . 104 s-1.


1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.


2021 ◽  
Vol 329 ◽  
pp. 115537
Author(s):  
Nazia Iqbal ◽  
S.M. Shakeel Iqubal ◽  
Aejaz Abdullatif Khan ◽  
Tasneem Mohammed ◽  
Ali Mohamed Alshabi ◽  
...  

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Veniamin Zheleznov ◽  
Aleksey Golikov ◽  
Tatiana Sokolnitskaya ◽  
Sergey Ivannikov

Abstract The sorption kinetics of uranyl ions micro-quantities from fluoride solutions by nanostructured materials with anatase mesoporous structures has been studied. Using the model of competitive sorption of ions and positively charged complexes of uranyl ion on deprotonated hydroxyl groups of an anatase, kinetic curves of changes in the ratio of ionic forms of uranium in solution were calculated. Modeling was carried out under the assumption of a two-stage mechanism of uranium complex ions sorption. The modeling considered the influence of the uranyl ion carbonate complexes formation. The shift in equilibrium among ionic forms of uranyl correlates with the stability of the complexes in solution.


Polyhedron ◽  
1995 ◽  
Vol 14 (10) ◽  
pp. 1299-1306 ◽  
Author(s):  
Ki-Young Choi ◽  
Dong Won Kim ◽  
Choon Pyo Hong

2021 ◽  
pp. 130612
Author(s):  
Eliara Acipreste Hudson ◽  
Hauster Maximiler Campos de Paula ◽  
Yara Luiza Coelho ◽  
Nícolas Glanzmann ◽  
Adilson David da Silva ◽  
...  

1994 ◽  
Vol 33 (18) ◽  
pp. 4070-4076 ◽  
Author(s):  
Eva Toth ◽  
Erno Brucher ◽  
Istvan Lazar ◽  
Imre Toth

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