Employing force-field calculations to predict equilibrium constants and other thermodynamic properties for the dimerization of 1,3-cyclopentadiene

Journal Article · Wed Feb 22 23:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100341a081· OSTI ID:5113176

Lenz, T G; Vaughan, J D ^[1]

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1. Colorado State Univ., Fort Collins (USA)

Although there have been many experimental investigations of the Diels-Alder dimerization of 1,3-cyclopentadiene, there remains considerable uncertainty in such thermodynamic properties as {Delta}H{degree}, {Delta}S{degree}, {Delta}G{degree}, and K{sub p} for the reaction at various temperatures. Despite this uncertainty, the reaction is a good subject for computational models, because it is one of the few Diels-Alder reactions which has been studied extensively in the laboratory both in the gas and liquid phase over a wide range of temperatures. This paper describes application of a force-field model to calculate thermodynamic properties of the monomer and both endo and exo isomers of the dimer for temperatures ranging from 273 to 500 K. The Boyd MOLBD3 force-field program modified to include (1) -ene and -diene parameters introduced by Anet and Yavari and (2) five-member and methylene bridge parameters suggested by the present authors was used for the calculations. Calculated equilibrium constants for both the gas and liquid phase, and other thermodynamic properties, agreed satisfactorily with what appear to be somewhat inconsistent existing experimental data. This work thus indicates that force-field methods hold promise as a useful alternative to experimental methods for the study of equilibrium of chemically reactive systems involving nontrivial molecules.

• DOE Contract Number: FG02-86ER13582
• OSTI ID: 5113176
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:4; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CHEMICAL REACTIONS
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
DIMERIZATION
HYDROCARBONS
INFORMATION
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
POLYENES
POLYMERIZATION
POTENTIALS
THEORETICAL DATA
THERMODYNAMIC PROPERTIES