Micellar rate effects on reactions of hydroxide ion with phosphinate and thiophosphinate esters

1991 ◽  
Vol 4 (10) ◽  
pp. 618-628 ◽  
Author(s):  
Andrei Blaskó ◽  
Clifford A. Bunton ◽  
Young S. Hong ◽  
Marutirao M. Mhala ◽  
John R. Moffatt ◽  
...  
Keyword(s):  
1989 ◽  
Vol 67 (2) ◽  
pp. 305-309 ◽  
Author(s):  
Francisco Ortega ◽  
Elvira Rodenas

The rate of reaction of tris(1,10-phenanthroline)iron(II) ion (1a), tris(3,4,7,8-tetramethyl-1,10-phenanthroline)iron(II) ion (1b), and tris(4,7-diphenhyl-1, 10-phenanthroline)iron(II) ion (1c) with hydroxide ion, in cationic micelles, is strongly affected by the concentration of micellar counterion in solution. The reaction of la in CTACl is modestly speeded up by the addition of added KCl, while the reactions of 1b and 1c are strongly inhibited by the addition of large amounts of KCl and KBr to micellar solutions of CTACl and CTABr, respectively. These rate effects fit the pseudophase-ion exchange model, assuming the binding of the substrates to the micelles depends upon the counterion concentration. Keywords: counterion micellar effects, low-spin diimine iron(II) complexes.


Author(s):  
Steven I. Dworkin ◽  
Nick E. Goeders ◽  
James E. Smith
Keyword(s):  

1997 ◽  
Vol 12 (4) ◽  
pp. 225-229
Author(s):  
Cart-in A-S. Gustavsson ◽  
Chritofer T. Lindgren ◽  
Mikael E. Lindström

Abstract The amount of lignin reacting according to the slow residual phase, i.e. the residual phase lignin, is in many perspectives an interesting issue. The purpose of the present investigation was to develop a mathematical model to show how the amount of residual phase lignin in the kraft cooking of spruce chips (Picm ahies) depends on the conditions in the earlier phases of the cook. The variables studied were hydroxide ion concentration, hydrogen sulfide ion concentration and ionic strength. The liquor-to-wood ratio during pulping was very high to maintain approximately constant chemical concentrations throughout each experiment (so called "constant composition" cooks). An increase in hydroxide ion concentration andtor hydrogen sulfide ion concentration leads to a decrease in the amount of residual phase lignin, while an increase in ionic strength, i.e. sodium ion concentration, leads to an increase. A signiticant result is that the hydrogen sulfide ion concentration has a pronounced influence on the amount of residual phase lignin during a cook at a low hydroxide ion concentration. The amount of residual phase lignin expressed as % lignin on wood, L,, can be described by the following equation developed for "constant composition" cooks (when cooking with a constant sodium ion concentration of 2 mol/L): LT=0,55-0.32*[HO-](-1,3)*ln[HS-] This equation is valid for a concentration of HO- in the range from 0.17 to 1.4, and a hydrogen sulfide ion concentration from 0.07 to 0.6 mol/L.


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.


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