An Apparatus for the Low Temperature Fractionation of Small Gas Samples

The photolysis of dirnethyl mercury in solution in n-hexane has been studied over the temperature range +25" C. to -80" C. The results indicate t h a t methane is produced by a n abstraction reaction involving the solvent, and ethane is produced by dimerization of methyl radicals. The mechanism of the reaction is discussed, and it is concluded t h a t the abstraction reaction involves radicals possessing considerable energy carried over from the photodissociation.

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

The Photolysis of Dimethyl Mercury in Hexane Solution at Low Temperatures

Derbyshire¹,

Steacie²

1954

“…The reaction products were analyzed by distilling the hydrocarbon fraction from the hydrogen cyanide a t -8S°C., after which the hydrocarbon fraction, containing small quantities of hydrogen cyanide, was separated into Cq, C3, Cq, and HCN fractions by distillation in a colunln of the type described by LeRoy (10). T h e still was modified so that it was possible to distill directly from the still-pot t o a condenser cooled by liquid nitrogen.…”

Section: Experimen'talmentioning

confidence: 99%

The Reaction of Active Nitrogen With Propylene

Trick¹,

Winkler²

1952

The reaction of nitrogen atoms with prop).lene has been found to prod~rce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4 fraction.With excess propylene, the nitrogen atoms were completely consu~ned and for the reaction a t 242'C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions a t lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic fiydrogel~. The ethvlene would then react with atomic nitrogen in a similar manner.

“…[ 4 ] , and [5]. If it is assumed that the acetonyl radicals produced in reaction [3] [5] of the order of magnitude of that of [2], i.e., unit!-.…”

Section: Introductionmentioning

confidence: 99%

Methyl Ethyl Ketone in the Photolysis of Acetone Vapor

Mandelcorn¹,

Steacie²

1954

By niass speclrorr~etric analyses, niethyl ethyl ketone was determined as a product of the photolysis of acetone between 100 and 284°C. According to the post~~lated mechanisni, ~iiethyl ethyl ketor~e together with methane and e t h a~~e accounted for approsirnately 05y0 of the methyl radicals procluced. INTRODUCTIONI t is no\v accepted that the mechanism for the photolj-sis oi acetone vapor between 100°C. and 250°C. is (6,7)Reaction [I] was shown to proceed with a quantum yielcl oi ~i n i t y in this temperature range (4). 'The kinetics of reactions [2] ancl [3] have been investigated (3,G,'i) in some detail. Methyl ethyl ketone was identifecl as a product but was not st~tdied quantitatively (1). Icetene was also found a t temperatures above 200°C., presumably resulting from the decomposition of acetonyl radicals (2) Considering reaction [I] T h e purpose of this work was t o study the material balances in the acetone photolysis when methyl ethyl ketone is included. I t serves a s the basis of an investigation of the kinetics of addition of methyl radicals to unsaiuratecl hydrocarbons, the loss of methyl radicals I)? acldition being related t o a clecrease in the material balance.