KINETICS OF THE EXCHANGE OF CHLORINE ATOMS BETWEEN HYDROGEN CHLORIDE AND BENZYL CHLORIDE. SOLVENT EFFECTS
Technical Report
·
OSTI ID:4702899
The rate of exchange of chlorine atoms between hydrogen chloride and p- nitrobenzyl chloride (PNBC) in 82% dioxane-- 18% water by weight solution is represented by the rate law: Re = 2.59 x 10/sup 6/ STAPNBC!e/sup -20,900/RT/ + 1.60 x 10/sup 9 alpha STAHC1! STAPNBC!e/sup -19,900 /RT/ where alpha is the degree of dissociation of the hydrogen chloride and R, is the rate of exchange in mole liter/sup -1/ sec/sup -1/. The reaction mechanlsm is believed to be an example of concurrent S/sub N/1 and S/sub N/2 processes in which the chloride ion rather than the hydrogen chloride ion-pair is the effective nucleophilic reagent. Ordinary fluorescent light has no detectable effect on the rate of exchange, and the overall rate of exchange is decreased by added lithium perchlorate. Analytical expressions were developed which allow for the hydrolysis of the organic halide during the exchange. No exchange was detected between hydrogen chloride and p-nitrobenzyl chloride in anhydrous benzene after 363 hours at 60.00 deg . Similarly, no exchange was observed with benzyl chloride in benzene and acetone. The exchange with benzyl chloride proceeds at a faster rate in ethanol than in dioxane. In dioxane, p-nitrobenzyl chloride exchanges at a faster rate than benzyl chloride. (auth)
- Research Organization:
- New Mexico. Univ., Albuquerque; Los Alamos Scientific Lab., N. Mex.
- DOE Contract Number:
- W-7405-ENG-36
- NSA Number:
- NSA-17-040772
- OSTI ID:
- 4702899
- Report Number(s):
- LADC-5361
- Country of Publication:
- United States
- Language:
- English
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·
OSTI ID:7256990
Related Subjects
ACETONE
ANIONS
ARYL RADICALS
ATOMS
BENZENE
BENZYL RADICALS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE
DIOXANE
ETHANOL
FLUORESCENCE
HETEROCYCLICS
HYDROCHLORIC ACID
HYDROLYSIS
LIGHT
LITHIUM COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORIC ACID
REACTION KINETICS
SOLUTIONS
SOLVENTS
TOLUENE
WATER
ANIONS
ARYL RADICALS
ATOMS
BENZENE
BENZYL RADICALS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE
DIOXANE
ETHANOL
FLUORESCENCE
HETEROCYCLICS
HYDROCHLORIC ACID
HYDROLYSIS
LIGHT
LITHIUM COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORIC ACID
REACTION KINETICS
SOLUTIONS
SOLVENTS
TOLUENE
WATER