Chemical reaction rates of quasi free electrons in nonpolar liquids

Journal Article · Mon Apr 01 04:00:00 EDT 1974 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100601a008· OSTI ID:4336146

Allen, Augustine; Holroyd, Richard A.

A method is described for determining reaction rates of molecules dissolved in nonpolar liquids with electrons produced by ionization of the solvent. It is based on modification by the added substance of the current- growth curve which is seen when the liquid, in an electric field, is suddenly exposed to X-rays, and uhich is used for mobility determination by the Hudson method. The rate constants for recombination of electrons with positive ions, determined by the Langevin method in n-pentane, n-hexane, and tetramethylsilane, are diffusion controlled and hence proportional to the electron mobilities; this rate constant in tetramethylsilane is 5 x 10/sup 16/ M/sup -1/ sec/sup -1/. The electron reactions wit h CCl/sub 4/, CH/sub 3/I, and O/sub 2/ are not diffusion controlled; the rates are generally higher in solvents which show higher electron mobilities, but the increase is less than proportional. Different behavior is shown with C/sub 2/H/sub 5/Br; the electron reaction rate is lower in the highelectron-mobility solvents neopentane and tetramethylsilane than in hexane or 2,2,4-trimethylpentane, and its temperature coefficient, which is positive in hexane, becomes unexpectedly negative in the former solvents, and amounts to -- 1.7% per degree in neopentane. New electron mobility determinations are reported for methylcyclohexane, n-hexane, n-pentane, cyclohexane, neopentane, and tetramethylsilane.

• Research Organization: Brookhaven National Lab., Upton, NY
• Sponsoring Organization: USDOE
• NSA Number: NSA-29-029112
• OSTI ID: 4336146
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 8 Vol. 78; ISSN 0022-3654
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

*CATIONS-- CHEMICAL REACTION KINETICS
*ELECTRONS-- CHEMICAL REACTION KINETICS
2-2-DIMETHYLPROPANE BROMINATED ALIPHATIC HYDROCARBONS
ALKANES
ALKENES
BROMINATED ALIPHATIC HYDROCARBONS
CARBON TETRACHLORIDE
ELECTRON MOBILITY
HEXANE
IODINATED ALIPHATIC HYDROCARBONS
IONIZATION
N40300* --Chemistry--Radiation Chemistry
ORGANIC BROMINE COMPOUNDS
ORGANIC IODINE COMPOUNDS
OXYGEN
PENTANE
SILANES
TETRACHLOROMETHANE
X RADIATION