Thermochemistry of trans-Di-tert-butyl Hyponitrite
The heat of combustion of trans-di-tert-butyl hyponitrite, ΔHcomb = 1304.5 ± 1.8 kcal/mol, and its heat of vaporization, ΔHV = 17.7 ± 0.3 kcal/mol, determined by an effusion technique, were used to calculate ΔHf° = −41.3 ± 2.9 kcal/mol. This represents the first experimental determination of a heat of formation of a hyponitrite. From additivity relationships we estimate ΔHf°(trans-HON=NOH) = 3.1 ± 3.1 kcal/mol, in good agreement with two reported values obtained by MO methods. The activation energies for homolysis of a number of trans-hyponitrites were estimated from additivity relationships, but did not agree well with experimental values. This result is associated with a compensating, linear relation between Ea and log A in the hyponitrite series. © 1984, American Chemical Society. All rights reserved.
Journal of the American Chemical Society
Thermochemistry of trans-Di-tert-butyl Hyponitrite.
Journal of the American Chemical Society,
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