Kinetics of the Fully Inhibited Thermal Decomposition of Bistrifluoromethyl Peroxide, CF3OOCF3

1975 ◽  
Vol 53 (10) ◽  
pp. 1442-1448 ◽  
Author(s):  
Bernard Descamps ◽  
Wendell Forst
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Rate Constant ◽  
Chromatographic Analysis ◽  
Static Method ◽  
Experimental Conditions ◽  
Experimental Expression ◽  
Kinetics Of ◽  
Rate Of Accumulation

The pyrolyosis of CF3OOCF3 (BTMP) was studied in the gas phase from 5 to 100 Torr BTMP pressure and between 197 and 244 °C in a clean nickel reactor by the static method. CF3O radicals, due to the initial split[Formula: see text] were scavenged by SO3F radicals produced in situ by the thermal decomposition of their dimer S2O6F2. Under these conditions, CF3OOSO2F is the only product of BTMP pyrolysis, as shown by gas chromatographic analysis. Thus the BTMP pyrolysis becomes fully inhibited and the rate of accumulation of CF3OOSO2F is a measure of k1. The rate constant k1 turns out to be pressure-insensitive under the experimental conditions, from which it is inferred that k1 is actually k1∞, the limiting high-pressure unimolecular rate constant for reaction 1. Its temperature dependence yields the result[Formula: see text]This result is compared with other values of the O—O bond dissociation energy in BTMP. The experimental expression for k1 ∞ is used to construct the pressure falloff of k1 following the procedure of Forst. The calculation confirms that falloff begins only below 10 Torr.

Simultaneous photochemical generation of ozone in the gas phase and photolysis of aqueous reaction systems using one VUV light source

1997 ◽  
Vol 35 (4) ◽  
pp. 41-48 ◽  
Author(s):  
T.M. Hashem ◽  
M. Zirlewagen ◽  
A. M. Braun
Keyword(s):  
Gas Phase ◽  
Light Source ◽  
Organic Pollutants ◽  
Vacuum Ultraviolet ◽  
Oxidative Degradation ◽  
Reaction System ◽  
Photochemical Reactions ◽  
Experimental Conditions ◽  
Photochemical Generation ◽  
Kinetics Of

A more efficient use of vacuum ultraviolet (VUV) radiation produced by an immersed Xe-excimer light source (172 nm) was investigated for the oxidative degradation of organic pollutants in aqueous systems. All emitted VUV radiation from one light source was used in two simultaneous but separate photochemical reactions: (1) photochemical generation of ozone by irradiating oxygen in the gas phase and (2) photolysis of the aqueous reaction system. The gas stream containing the generated ozone is sparged into the reaction system, thus enhancing the oxidative degradation of organic pollutants. The photochemically generated ozone in the gas phase was quantitatively analyzed, and the kinetics of the degradation of 4-chlorophenol (4-CP) and of the dissolved organic carbon (DOC) were determined under different experimental conditions. The results show that the rates of degradation of the substrate and of the DOC decrease in the order of the applied processes, VUV/O3 > O3 > VUV.

Electron transfer between ferrocene and hexacyanoferrate(III) across the water/1,2-dichloroethane interface

1988 ◽  
Vol 53 (5) ◽  
pp. 903-911 ◽  
Author(s):  
Josef Hanzlík ◽  
Jan Hovorka ◽  
Zdeněk Samec ◽  
Štefan Toma
Keyword(s):  
Electron Transfer ◽  
Aqueous Phase ◽  
Rate Constant ◽  
Potential Range ◽  
Ion Transfer ◽  
Potential Sweep ◽  
Experimental Conditions ◽  
Chemical Decomposition ◽  
Kinetics Of

Kinetics of electron transfer between ferrocene or its derivative (1,1'-diethyl- or 1,1'-distearoylferrocene) in dichloroethane and hexacyanoferrate(III) in water was studied by means of convolution potential sweep voltammetry. Within the accessible range of experimental conditions no effect of either the potential or concentrations of reactants on the rate constant of electron transfer from the organic to the aqueous phase (ko→w = 1 . 10-7 m4 mol-1 s-1) was observed. Electron transfer was shown to occur far from the potential range, in which the ferricenium ion transfer can take place. However, the reaction was complicated by the chemical decomposition of ferricenium in dichloroethane (k = 0·346 s-1).

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

1961 ◽  
Vol 14 (4) ◽  
pp. 534 ◽  
Author(s):  
MFR Mulcahy ◽  
DJ Williams
Keyword(s):  
Excellent Agreement ◽  
Rate Constant ◽  
Flow Reactor ◽  
Reaction Times ◽  
Static Method ◽  
Flow Conditions ◽  
Gaseous Reaction ◽  
Flow Method ◽  
Butyl Peroxide ◽  
Kinetics Of

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 mercury (63P1) photosensitized hydrogenation of ethylene. Kinetics of the reaction C2H5 + H2 = C2H6 + H

1968 ◽  
Vol 46 (20) ◽  
pp. 3275-3281 ◽  
Author(s):  
L. E. Reid ◽  
D. J. Le Roy
Keyword(s):  
Gas Phase ◽  
Molecular Hydrogen ◽  
Mercury Vapor ◽  
Experimental Conditions ◽  
Working Pressure ◽  
Extinction Coefficients ◽  
Secondary Reactions ◽  
Ethyl Radicals ◽  
Kinetics Of ◽  
Hydrogenation Of Ethylene

A quantitative study has been made of the reaction of ethyl radicals with molecular hydrogen in the gas phase in the temperature range 240 to 320 °C. The mercury (63Pi) photosensitized decomposition of hydrogen in the presence of ethylene was used to generate ethyl radicals. Extinction coefficients for the absorption of 2537 Å by mercury vapor were measured and Beer's law was shown to be obeyed under the experimental conditions used. The corrections required to allow for the nonuniformity of radical concentrations in the cell were small. After delineating the experimental conditions necessary to minimize secondary reactions, the rate constant (cm3 mole−1 s−1) for the reaction C2H5 + H2 = C2H6 + H was found to be given by log10k = 12.57 − 13.7/θ. Experiments in the presence of added carbon dioxide showed the absence of hot radical effects at the working pressure of 92 Torr of hydrogen.

The thermal decomposition of cyclobutane-1,2-dione

1985 ◽  
Vol 63 (11) ◽  
pp. 2945-2948 ◽  
Author(s):  
J.-R. Cao ◽  
R. A. Back
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Vapor Pressure ◽  
Gas Phase ◽  
Rate Constant ◽  
Surface Reaction ◽  
Order Rate Constant ◽  
Reaction Vessel ◽  
Arrhenius Parameters ◽  
First Order

The thermal decomposition of cyclobutane-1,2-dione has been studied in the gas phase at temperatures from 120 to 250 °C and pressures from 0.2 to 1.5 Torr. Products were C2H4 + 2CO, apparently formed in a simple unimolecular process. The first-order rate constant was strongly pressure dependent, and values of k∞ were obtained by extrapolation of plots of 1/k vs. 1/p to1/p = 0. Experiments in a packed reaction vessel showed that the reaction was enhanced by surface at the lower temperatures. Arrhenius parameters for k∞, corrected for surface reaction, were log A (s−1) = 15.07(±0.3) and E = 39.3(±2) kcal/mol. This activation energy seems too low for a biradical mechanism, and it is suggested that the decomposition is probably a concerted process. The vapor pressure of solid cyclobutane-1,2-dione was measured at temperatures from 22 to 62 °C and a heat of sublimation of 13.1 kcal/mol was estimated.

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