The e[sup [minus]] + 1,3,-butadine [rightleftharpoons] 1,3-butadiene[sup [minus]] equilibrium in n-hexane

Journal Article · Thu Jul 21 00:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100080a008· OSTI ID:6908798

Holroyd, R A; Schwarz, H A; Stradowska, E ^[1]; Ninomiya, Shiro; Itoh, Kengo; Nishikawa, Masaru ^[2]

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1. Brookhaven National Lab., Upton, NY (United States)
2. Univ. of Tokyo (Japan)

The rate constants for attachment of excess electrons to 1,3-butadiene (k[sub a]) and detachment from the butadiene anion (k[sub d]) in n-hexane are reported. The equilibrium constant, K[sub eq] = k[sub a]/k[sub d], increases rapidly with pressure and decreases as the temperature increases. At -7[degree]C attachment is observed at 1 bar. At high pressures the attachment rate is diffusion controlled. The activation energy for detachment is about 21 kcal/mol; detachment is facilitated by the large entropy of activation. The reaction volumes for attachment range from -181 cm[sup 3]/mol at 400 bar to-122 cm[sup 3]/mol at 1500 bar and are largely attributed to the electrostriction volume of the butadiene anion ([Delta][bar V][sub el]). Values of [Delta][bar V][sub el] calculated by a model, which includes a glassy shell of solvent molecules around the ion, are in agreement with experimental reaction volumes. The analysis indicates the partial molar volume of the electron in hexane is small and probably negative. It is shown that the entropies of reaction are closely related to the partial molar volumes of reaction. 22 refs., 5 figs., 5 tabs.

• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6908798
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 98:29; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
BUTADIENE
CHEMICAL REACTION KINETICS
ELECTRONS
EQUILIBRIUM
PRESSURE DEPENDENCE
TEMPERATURE DEPENDENCE
ACTIVATION ENERGY
COMPILED DATA
DIFFUSION
ENTROPY
FREE ENERGY
HEXANE
MATHEMATICAL MODELS
ALKANES
DATA
DIENES
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HYDROCARBONS
INFORMATION
KINETICS
LEPTONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
POLYENES
REACTION KINETICS
THERMODYNAMIC PROPERTIES
400201* - Chemical & Physicochemical Properties
661300 - Other Aspects of Physical Science- (1992-)
990200 - Mathematics & Computers