A Stirred-Flow Reactor for Investigating the Kinetics of Gaseous Reactions: Application to the Decomposition of Di-t-butyl Peroxide

Abstract

The uncertainty regarding temperature and flow conditions which attaches to the conventional flow method of determining the rate of a gaseous reaction can be substantially reduced by using a stirred-flow reactor. The reagents, products, and carrier-gas (if any) are mixed sufficiently vigorously for the composition of the gas in the reactor to be virtually uniform. A reactor designed to achieve the required degree of mixing at pressures of about 1 cmHg and reaction times of the order of 1 sec to 1 min is described. The rate constant of the decomposition of di-t-butyl peroxide was determined over the temperature range 430-550 �K. The values derived on the assumption of complete mixing in the reactor were independent of the degree of conversion and in excellent agreement with those obtained by previous authors using the static method.

The thermal decomposition of azobenzene

“…similar to that tlcscribcd by Mulcahy and Williarns (8) for stirrctl-flow systcms. was madc of quartz, with a volunic of 13 16 cni3.…”

Gas-phase thermolysis oft-butylsulfenamides:N, N-dimethylt-butylsulfenamide, 2,6-dimethylpiperidinylt-butylsulfenamide, andN-t-butylt-butylsulfenamide

“…The structures of the synthesized sulfenarnides was confirmed by NMR and mass spectrometry in the previously reported instruments [l]. ' [6,7,12].…”

Gas-phase thermolysis ofN-cyanomethyl-N-ethyl aniline,N-cyanomethyl-N-ethyl-p-anisidine, andN-cyanomethyl-N-ethyl-p-nitroaniline

“…All the starting materials and solvents were obtained from Aldrich. The thermolyses were carried out in a flow system fitted with a spherical, quartz, capacity stirred-265 mL flow reactor [5]. The reactants were introduced in the reactor as 0.1 -0.05 molar solutions in toluene by means of a precision peristaltic pump at (10 mL) rates of over periods of Ϫ1 0.5 -0.3 mL.min , The reactor was fitted with a Leybold 20 -30 min.…”

“…The first-order rate coefficients were calculated with the expression [5] where F is the k ϭ F/(1 Ϫ F) fraction reacted and the residence time given by fi. ϭ PV/RT⌺ Table I shows the gas reaction products distributions for CEAN, CEPA, and ECNA for samples of runs.…”