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The Heats of Combustion of Gaseous Cyclotetradecane and trans-Stilbene - a Tale of Long-standing Confusion

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Ernest L. Eliel

W.R.Kenan Jr. Laboratories, Department of Chemistry CB#3290, University of North Carolina, Chapel Hill, NC 27599-3290, USA

Jan J. Engelsman

Free University of Amsterdam, Amsterdam, The Netherlands

J. Chem. Educ., 1996, 73 (9), p 903

DOI: 10.1021/ed073p903

Publication Date (Web): September 1, 1996

Abstract

This paper embodies the belated publication of a thesis submitted by JJE to the Free University of Amsterdam in 1955; heretofore the data (heat of sublimation of cyclotetradecane, 21.34+/-0.10 kcal/mol or 89.33+/-0.42 kJ/mol; heat of sublimation of trans-stilbene, 20.68+/-0.08 kcal/mol or 86.57+/-0.33 kJ/mol) were available only in a printed version of the thesis. In conjunction with a subsequent determination of the heat of combustion of solid cyclotetradecane, this led to the conclusion that the compound was strain-free.

That these data were not published at the time had unfortunate consequences: The strain energy of cyclotetradecane was susequently computed to be 12.6 kcal/mol (52.7 kJ/mol) on the basis of an erroneous value of the heat of sublimation determined independently in 1964. This was corrected only in 1992 through a third determination which gave a value for the strain energy close to that found in 1955, i.e. near zero.

The heat of formation of trans-stilbene is of interest in connection with the energetics of the photochemically interesting cis-stilbene - trans-stilbene interconversion. Different methods gave conflicting values: a high one near 5 kcal/mol (21 kJ/mol) from heats of hydrogenation and of equilibration as a function of temperature and a low one near 3 kcal/mol (12.6 kJ/mol) as a result of heats of combustion combined with heats of vaporization given in the literature. However, using the heat of sublimation of trans-stilbene given above, the combustion method converges with the other two in pointing to the higher of the two values for the correct enthalpy of isomerization.

Keywords (Audience):

Graduate Education / Research

Keywords (Domain):

Organic Chemistry

Keywords (Subject):

Alkanes / Cycloalkanes

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This article has been cited by 4 ACS Journal articles (4 most recent appear below).

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On the Origin of Nonvertical Triplet Excitation Transfer: The Relative Role of Double-Bond and Phenyl-Vinyl Torsions in the Stilbenes
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The Journal of Physical Chemistry A2001 105 (26), 6273-6276
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  The results of theoretical calculations at the B3LYP-DFT level using the 6-31+G(d,p) basis set on the ground and triplet states of the stilbenes (c-1, t-1) and of 2,3-diphenylnorbornene (2) are described. They are not consistent with the premise that ...
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Mapping the Potential Energy Surfaces of the 1,6-Diphenyl-1,3,5-hexatriene Ground and Triplet States
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