SECONDARY KINETIC SALT EFFECT IN THE CASE OF HYDROXYL-ION CATALYSIS

1925 ◽  
Vol 47 (10) ◽  
pp. 2523-2531 ◽  
Author(s):  
J. N. Brönsted ◽  
Cecil V. King
Keyword(s):  
1960 ◽  
Vol 38 (11) ◽  
pp. 2237-2255 ◽  
Author(s):  
Ross Stewart ◽  
R. Van der Linden

Kinetic and oxygen-18 tracer experiments have been used in an attempt to elucidate the mechanism(s) of permanganate oxidation of cyanide. From pH 12 to 14.6 the oxidation is represented by the equation,[Formula: see text]From pH 12 to 6 the reaction was found to be complex and unstoichiometric yielding cyanate, carbon dioxide, cyanide ion, and finally cyanogen at pH 9 to 6.The rate of reduction of permanganate, as followed iodometrically and spectrophotometrically, is found to be markedly dependent on the pH of the medium and reactant concentration. The rate is negligible in acid solution but rapid in basic media.At pH greater than 12 two parallel processes are indicated which have been designated as reaction A and reaction B. Reaction A appears at low reactant concentrations 0.0004 M cyanide and higher hydroxyl ion concentrations pH 13 and is represented by the kinetic expression[Formula: see text]where k2 is independent of hydroxyl ion concentration and is insensitive to the presence of manganate and barium ions. A positive salt effect is observed and labeling experiments using permanganate enriched in oxygen18 showed that the oxygen introduced into the product cyanate comes mainly from the oxidant (70%–80% oxygen-18 transferred).The existence of a second process reaction B was indicated by the changing kinetics at higher reactant concentrations and lower basicities, by the non-linear Arrhenius plots, and by the observation that only 15–25% oxygen-18 transfer from permanganate to substrate had occurred at pH 13. The rate of this latter process is approximately represented by the kinetic expression[Formula: see text]These reactions are discussed in terms of mechanism


1952 ◽  
Vol 44 (3) ◽  
pp. 444-444
Author(s):  
N Chalapathi Rao ◽  
Hugh Winn ◽  
J Shelton

1981 ◽  
Vol 46 (12) ◽  
pp. 3104-3109 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Miroslav Večeřa

Rate constants of non-catalyzed hydrolysis of 3-acetyl-1,3-diphenyltriazene (I) and 3-(N-methylcarbamoyl)-1,3-diphenyltriazene (II) have been measured in the presence of salts (ammonium chloride, potassium chloride, lithium chloride, sodium chloride and bromide, ammonium sulphate, potassium sulphate, lithium sulphate, sodium sulphate and zinc sulphate) within broad concentration ranges. Temperature dependence of the hydrolysis of the substrates studied has been measured in the presence of lithium sulphate within temperature range 20° to 55 °C. The results obtained have been interpreted by mechanisms of hydrolysis of the studied substances.


1986 ◽  
Vol 51 (12) ◽  
pp. 2781-2785 ◽  
Author(s):  
M. Martín Herrera ◽  
J. J. Maraver Puig ◽  
F. Sánchez Burgos

A study is made on the kinetic salt effect on the reaction of hydrolysis of several charged esters in alkaline media. The results are interpreted on the basis of the coulombic interaction, the salting in of hydroxide ion and a third component depending on size of the substrate.


1998 ◽  
Vol 39 (3) ◽  
pp. 623-632 ◽  
Author(s):  
Martin Wickham ◽  
Martin Garrood ◽  
John Leney ◽  
Peter D.G. Wilson ◽  
Annette Fillery-Travis

Science ◽  
1971 ◽  
Vol 172 (3988) ◽  
pp. 1128-1132 ◽  
Author(s):  
R. C. Bubeck ◽  
W. H. Diment ◽  
B. L. Deck ◽  
A. L. Baldwin ◽  
S. D. Lipton
Keyword(s):  
New York ◽  

1976 ◽  
Vol 41 (24) ◽  
pp. 3920-3922 ◽  
Author(s):  
M. Gillard ◽  
F. Metras ◽  
S. Tellier ◽  
J. J. Dannenberg
Keyword(s):  

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