ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The rate of proton/deuteron transfer reactions of 2,4,6-trinitrotoluene (TNT), 2,2′4,4′6,6′-hexanitrobibenzyl (HNBB) and 2,4,6-trinitrobenzyl chlorides (TNB) with tertiary amines was followed spectrophotometrically. The rate constants obtained under various conditions were interpreted in terms of isotope, solvent and steric effects. The Arrhenius plots curved upward at low temperatures for TNT and TNB, indicating clearly the intervention of tunnelling. The tunnelling parameteres were calculated semi-empirically on the basis of Bell's theory. The observed rate constants at low temperatures agreed well with the predicted values. In the present systems, some side and consecutive reactions involving the formation of 2,2′,4,4′6,6′-hexanitrostilbene took place, and in some cases interrupted the rate measurements in the proton/deuteron transfer steps.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610080602
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