Carbon-13 kinetic isotope effects in the decarbonylation of formic acid of natural isotopic composition in phosphoric acid media

1994 ◽  
Vol 183 (2) ◽  
pp. 301-311 ◽  
Author(s):  
M. Zieliński ◽  
A. Zielińska ◽  
H. Papiernik-Zielińska
Keyword(s):  
Phosphoric Acid ◽  
Formic Acid ◽  
Isotopic Composition ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Natural Isotopic Composition ◽  
Acid Media ◽  
Kinetic Isotope

α-DEUTERIUM KINETIC ISOTOPE EFFECTS IN SOLVOLYSES OF endo-NORBORNYL p-BROMOBENZENESULFONATE

1965 ◽  
Vol 43 (8) ◽  
pp. 2254-2258 ◽  
Author(s):  
C. C. Lee ◽  
Edward W. C. Wong
Keyword(s):  
Acetic Acid ◽  
Formic Acid ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Aqueous Dioxane ◽  
Kinetic Isotope ◽  
Different Temperatures

endo-Norbornyl-2-d p-bromobenzenesulfonate was synthesized and the isotope effects, as measured by kH/kD, were determined over a range of temperatures for solvolyses in 30% water – 70% dioxane, acetic acid, and formic acid. Values of kH/kD are of the order of 1.20. The data appear to indicate slightly higher isotope effects as the solvents are changed from aqueous dioxane to acetic acid to formic acid, as well as somewhat higher isotope effects at lower temperatures. Possible mechanistic implications of these results are presented. Relative titrimetric acetolysis rates, kexo/kendo, at different temperatures, and enthalpies and entropies of activation for these acetolyses are evaluated and discussed.

Kinetic Isotope Effects in Complex Reaction Networks: Formic Acid Electro-Oxidation

ChemPhysChem ◽  
2007 ◽  
Vol 8 (3) ◽  
pp. 380-385 ◽  
Author(s):  
Yan-Xia Chen ◽  
Martin Heinen ◽  
Zenonas Jusys ◽  
Rolf Jürgen Behm
Keyword(s):  
Formic Acid ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Reaction Networks ◽  
Complex Reaction ◽  
Kinetic Isotope ◽  
Electro Oxidation

Carbon-13 Kinetic Isotope Effects in the Decarbonylation Of Liquid Formic Acid in Water Solution

1999 ◽  
Vol 35 (3) ◽  
pp. 157-165 ◽  
Author(s):  
M. Zieliński ◽  
N. Ogrinc ◽  
I. Kobal ◽  
A. Zielińska ◽  
H. Papiernik-zielińska
Keyword(s):  
Formic Acid ◽  
Water Solution ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

The Bimolecular Decay of the α - Hydroxymethylperoxyl Radicals in Aqueous Solution

1978 ◽  
Vol 33 (7) ◽  
pp. 786-788 ◽  
Author(s):  
Eberhard Bothe ◽  
Dietrich Schulte-Frohlinde
Keyword(s):  
Aqueous Solution ◽  
Formic Acid ◽  
Room Temperature ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

The bimolecular decay of the hydroxymethylperoxyl radical in aqueous solution (k = 2.1 x 109 M-1s-1) leads mainly (80%) to one molecule of hydrogen peroxid and to two molecules of formic acid. 2 HOCH2OO· → H2O2 + 2 HCOOH Deuterium kinetic isotope effects show that the decay occurs at room temperature via a short lived (τ < 10-4 s) tetroxid.

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