Simple electrostatic model for enthalpies of formation of singly substituted alkanes

Simple electrostatic model for enthalpies of formation of singly substituted alkanes

In earlier work, Benson and Luria (J. Am. Chem. Soc. 1975 97, 704-709) showed that the greater stability of branched alkanes, compared to normal alkanes, could be explained on the basis of the electrostatic interactions between the atoms involved. This approach is extended herein to molecules contai...

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Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 115; no. 2; pp. 625 - 631
Main Authors: Laurencelle, Nicole, Pacey, Philip D
Format: Journal Article
Language:English
Published: United States American Chemical Society 01-01-1993
Subjects:
400201 - Chemical & Physicochemical Properties
ALCOHOLS
ALKANES
AMINES
ENTHALPY
FORMATION HEAT
HYDROCARBONS
HYDROXY COMPOUNDS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERACTIONS
MATHEMATICAL MODELS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHYSICAL PROPERTIES
REACTION HEAT
STABILITY
THERMODYNAMIC PROPERTIES
THIOLS
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Summary:In earlier work, Benson and Luria (J. Am. Chem. Soc. 1975 97, 704-709) showed that the greater stability of branched alkanes, compared to normal alkanes, could be explained on the basis of the electrostatic interactions between the atoms involved. This approach is extended herein to molecules containing single heteroatoms, N, O, S, Cl, Br, and I. Charges are assigned to atoms according to differences between their electronegativities and the electronegativities of atoms to which they are covalently bonded. Carbon atoms partially share the charges so established. Electrostatic energies are calculated for all pairs of atoms in the molecules. Covalent bonds are assigned energies in a simple scheme of bond additivity. Enthalpies of formation of 23 alkyl derivatives, estimated in this way, agree with experimental values within 1.4 kJ mol[sup [minus]1] on average, a difference which is close to the average quoted experimental uncertainty. 33 refs., 4 figs., 2 tabs.
Bibliography:ark:/67375/TPS-MBPWQ5S9-7
istex:761D985F94E7D8659C9177286D97F77364D4E9A6
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00055a035