Modification of thermal alkylation with HCl
Conference
·
· Prepr., Div. Pet. Chem., Am. Chem. Soc.; (United States)
OSTI ID:6640181
Thermal alkylation of ethylene in the presence of HCl was studied. The bulk of the alkylation experiments was done using methane as an internal standard. Preliminary experiments showed that the ethylene/isobutane alkylation reaction did not produce observable product methane. Further if the reasonable assumption is made that the percent of the methane internal standard which might be lost via alkylation to propane would be less than the percent of isobutane alkylated to 2-methylpentane, the data showed that this source of error was trivial. The effects of HCl on the alkylation reactions are pronounced. The C/sub 6/ product distribution appears to asymptotically approach a limiting value at high (HC1)/(C/sub 2/H/sub 4/)/sub 0/ which is consistent with an equilibrium between t-butyl and isobutyl radicals. The relative yields also represent mutual equilibrium among the free radicals. In that case the yield of each product relative to 2,2-dimethylbutane should be K/sub RH/ + tBu reversible ..-->.. R. + iC/sub 4/H/sub 10/ (/sup K/R. + C/sub 2/H/sub 4//sup k/tBu + C/sub 2/H/sub 4/0). Although the available thermodynamic data do not have sufficient precision to permit accurate calculation of relative rate constants from data such calculations were carried out and the results were sufficiently self consistent to warrant reporting them in qualitative terms. Of the four primary free radicals studied, the neopentyl radical had the lowest rate of addition to ethylene. In general rate of radical addition to ethylene and radical thermodynamic stability were inversely correlated, the more stable radicals being less reactive. Under conditions where radicals tend toward mutual equilibrium, the thermodynamic factor is dominant, the stable radicals producing most of the product despite their lack of reactivity.
- Research Organization:
- Exxon Research and Engineering Co., Linden, NJ
- OSTI ID:
- 6640181
- Report Number(s):
- CONF-770814-P2; CONF-780305-P2
- Conference Information:
- Journal Name: Prepr., Div. Pet. Chem., Am. Chem. Soc.; (United States) Journal Volume: 23:1
- Country of Publication:
- United States
- Language:
- English
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