THE OXIDATION OF DI-tertiary-BUTYL PEROXIDE

1961 ◽  
Vol 39 (2) ◽  
pp. 278-284 ◽  
Author(s):  
A. R. Blake ◽  
K. O. Kutschke
Keyword(s):  
Carbon Monoxide ◽  
Major Product ◽  
Static System ◽  
Peroxy Radicals ◽  
Tertiary Butyl ◽  
Stationary Concentration ◽  
Methyl Hydroperoxide ◽  
Butyl Peroxide ◽  
High Yields ◽  
Butoxy Radical

The oxidation of di-t-butyl peroxide has been investigated in a static system at low conversion at 124 °C with sufficient oxygen present to suppress completely the formation of methane and ethane. The decomposition of the t-butoxy radical is unaffected by the presence of oxygen. A major product of the oxidation is formaldehyde whose yield rapidly approaches a stationary value. It is postulated that the major source of formaldehyde is the decomposition of methyl peroxy radicals, which may also abstract hydrogen from formaldehyde to form methyl hydroperoxide, and that this competition leads to the stationary concentration of formaldehyde actually observed. Methyl hydroperoxide was demonstrated to be unstable in the system and the predominant decomposition product was methanol, a compound also found in high yields in the oxidation. Experiments with added formaldehyde-C13 showed that formaldehyde can be converted to carbon monoxide in the system and indicated that formaldehyde was a likely precursor to the carbon monoxide found in the oxidation.

The oxidation of iso butene catalyzed by hydrogen bromide

1962 ◽  
Vol 268 (1334) ◽  
pp. 405-423 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Small Proportion ◽  
Main Chain ◽  
Hydrogen Bromide ◽  
Inert Gas ◽  
Static System ◽  
Peroxy Radicals ◽  
Methyl Group

The oxidation of iso butene catalyzed by hydrogen bromide in a static system between 100 and 200 °C has been investigated. In a boric oxide coated vessel below about 170 °C the pressure decreased continually during the reaction, the rate accelerating rapidly to a maximum and then falling gradually and the main products being BrCH 2 .C(CH 3 ) 2 .OOH and a diperoxide. The reaction ceased after only a small proportion of the olefin was oxidized owing to the HBr being used up. At 145 °C ρ max. ∝ [C 4 H 8 ] 0.35 [O 2 ] 0.5 [HBr] 1.76 . Added inert gas or packing the vessel had little effect on the rate, but the reaction was accelerated by added bromine, t .-butyl hydroperoxide and di- t .-butylperoxide and retarded by added alcohols. At 195 °C the pressure decreased to a minimum and then rose, most of the iso butene being now oxidized and other products, CH 2 =C(CH 3 )CH 2 OOH, methacrolein, acetone, carbon monoxide, carbon dioxide and water being formed in appreciable yields. It is suggested that autocatalysis is due to the reaction of a small proportion of the hydroperoxides produced with HBr to give radicals, and that the main chain carriers are bromine atoms and peroxy radicals, the former either adding to the double bond of the olefin or at the higher temperatures abstracting hydrogen from a methyl group and the latter abstracting hydrogen from HBr to give the hydroperoxides, adding to the double bond of iso butene to give eventually diperoxides or at the higher temperatures decomposing.

REACTIONS OF ALKOXY RADICALS: V. PHOTOLYSIS OF DI-t-BUTYL PEROXIDE

1958 ◽  
Vol 36 (9) ◽  
pp. 1227-1232 ◽  
Author(s):  
Garnett McMillan ◽  
M. H. J. Wijnen
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Energy Difference ◽  
Butyl Alcohol ◽  
Reaction Products ◽  
Butyl Ether ◽  
Alkoxy Radicals ◽  
Temperature Range ◽  
Butyl Peroxide ◽  
Butoxy Radical

The photolysis of di-t-butyl peroxide has been investigated over the temperature range 25 ° to 79 °C. As reaction products were observed: acetone, t-butyl alcohol, methyl t-butyl ether, i-butylene oxide, ethane, methane, and carbon monoxide. The following reactions, involving the t-butoxy radical, have been studied:[Formula: see text]An activation energy difference of E2 − E6 = 3 kcal has been obtained.

The thermal dissociation of tertiary butyl peroxide in presence of nitric oxide

1957 ◽  
Vol 239 (1217) ◽  
pp. 154-164 ◽  
Keyword(s):  
Nitric Oxide ◽  
Thermal Dissociation ◽  
Spectrometric Analysis ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Tertiary Butyl ◽  
Butyl Peroxide ◽  
Pressure Changes ◽  
Butoxy Radical ◽  
Ethane Formation

In the presence of nitric oxide the decomposition of gaseous tertiary butyl peroxide has been shown to follow essentially the course: (i) (CH 3 ) 3 COOC(CH 3 ) 3 → k 1 2(CH 3 ) 3 CO, (ii) (CH 3 ) 3 CO → k 2 (CH 3 ) 2 CO + CH 3 , (iii) 2CH 3 → k 3 C 2 H 6 , (iv) (CH 3 ) 3 CO + NO → k 4 (CH 3 ) 3 CONO, (v) CH 3 + NO → k 5 CH 3 NO → other products. Rates of reaction have been measured by observation of pressure changes and mass-spectrometric analysis for peroxide, acetone, ethane, nitric oxide and tertiary butyl nitrite at various stages. The ratio k 4 / k 2 at 160°C, determined from the rate of formation of acetone in presence of nitric oxide, is approximztely 0⋅7 (with concentrations expressed in mm Hg). If the ‘collision yield' or 'steric factor’ for the union of methyl radicals is near unity, that for the combination of methyl radicals and nitric oxide is about 7 x 10 -5 , from experiments on the rate of ethane formation. If the rate constants for the combination of nitric oxide with methyl and tertiary butoxy radicals respectively are assumed equal, k 2 is estimated to be about 10 3 s -1 at 160°C. A rough estimate for the corresponding activation energy ( E 2 ) gives 13⋅2 ± 2⋅4 kcal/mole for the decomposition of the tertiary butoxy radical, compared with a (redetermined) value of 38 kcal/mole for that of the peroxide itself.

Zirconocene mediated acetylboron chemistry

2018 ◽  
Vol 54 (45) ◽  
pp. 5724-5727 ◽  
Author(s):  
Zhongbao Jian ◽  
Constantin G. Daniliuc ◽  
Gerald Kehr ◽  
Gerhard Erker
Keyword(s):  
Carbon Monoxide ◽  
Major Product ◽  
Zirconium Hydride

Carbon monoxide reacts with zirconium hydride and methyl–B(6F5)2 to give a Zr-bound acetyl(hydrido)borate as the major product. This reacts further with CO to form a Zr-coordinated borata-β-lactone.

Design and use of an Efficient Plasma Jet Reactor for High Temperature Gas/Solid Reactions

1983 ◽  
Vol 30 ◽  
Author(s):  
F. W. Giacobbe ◽  
D. W. Schmerling
Keyword(s):  
Carbon Monoxide ◽  
High Temperature ◽  
Arc Discharge ◽  
Plasma Jet ◽  
Direct Result ◽  
Discharge Region ◽  
Plasma Flame ◽  
Powdered Carbon ◽  
High Yields ◽  
Experimental Trials

ABSTRACTA unique and efficient plasma jet reactor has been developed and used to study the high temperature production of carbon monoxide from a reaction between powdered carbon and a pure carbon dioxide plasma. The plasma jet reactor was designed to allow the injection of powdered carbon above the arc discharge region rather than into the plasma flame below the arc discharge region. High yields of carbon monoxide, produced at relatively high efficiencies, were a direct result of this technique. The plasma jet was also designed to enable rapid changing and testing of various anode insertsAverage yields of carbon monoxide in the product gases were as high as 80–87% in selected experimental trials. Carbon monoxide was produced at rates exceeding 15,000 1/hr (at STP) with a power expenditure of 52 Kw.

Di-tertiary-butyl Peroxide Decomposition and Combustion with Air: Reaction Mechanism, Ignition, Flame Structures, and Laminar Flame Velocities

2016 ◽  
Vol 31 (3) ◽  
pp. 2260-2273 ◽  
Author(s):  
N. Sebbar ◽  
P. Habisreuther ◽  
H. Bockhorn ◽  
I. Auzmendi-Murua ◽  
J. W. Bozzelli
Keyword(s):  
Reaction Mechanism ◽  
Laminar Flame ◽  
Tertiary Butyl ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
Flame Structures

Studies of radiation-induced reactions of ethylene in aqueous solution II. Reactions in the presence of oxygen as studied by pulse radiolysis and γ -irradiation techniques

1967 ◽  
Vol 300 (1463) ◽  
pp. 443-454 ◽  
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Rate Constants ◽  
Pulse Radiolysis ◽  
Major Product ◽  
Peroxy Radicals ◽  
Ferrous Ions ◽  
Constant Composition ◽  
Γ Irradiation ◽  
Radiation Induced

The radiolysis of dilute aqueous solutions containing ethylene and oxygen has been investigated. Pulse radiolysis was used to measure the rate constants for the addition of hydroxyl radicals to ethylene, the binary decomposition of the resulting hydroxyethyl radicals and their addition to ethylene and reaction with oxygen to yield peroxy radicals. The rate constants have also been determined for the mutual interaction of the peroxy radicals and their reaction with ferrous ions. The principal products of γ -irradiation were aldehydes and organic hydroperoxides. Hydrogen peroxide was found in yields close to the molecular yield from water. The polymer produced in the absence of oxygen was not formed, and glycollaldehyde, reported as a major product by previous workers, could not be detected. At constant composition of the gas mixtures, product yields were unaffected by total pressure in the range up to 40 atm, but were strongly dependent on the proportion of oxygen. Aldehyde yields were markedly greater at pH 1.2 than in neutral solution. The influence of ferrous ions an d of added hydrogen peroxide has been determined. The pulse radiolysis and γ -irradiation experiments complement one another and show that the radiation-induced oxidation of ethylene in aqueous solution involves the same primary reactions as occur in the absence of oxygen, followed by the formation and further reactions of peroxy radicals.

The gas-phase photochemistry and thermal decomposition of glyoxylic acid

1985 ◽  
Vol 63 (2) ◽  
pp. 542-548 ◽  
Author(s):  
R. A. Back ◽  
S. Yamamoto
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Absorption Spectrum ◽  
Gas Phase ◽  
Singlet State ◽  
Glyoxylic Acid ◽  
Static System ◽  
First Order ◽  
Increasing Temperature ◽  
Homogeneous Formation

The photolysis of glyoxylic acid vapour has been studied at five wavelengths, 382, 366, 346, 275, and 239 nm, and pressures from about 1 to 6 Torr, at a temperature of 355 K. Major products were CO2 and CH2O, initially formed in almost equal amounts, while minor products were CO and H2. Except at 382 nm, the system was complicated by the rapid secondary photolysis of CH2O. Three primary processes are suggested, each involving internal H-atom transfer followed by dissociation.The absorption spectrum is reported and shows the three distinct absorption systems. A finely-structured spectrum from about 320 to 400 nm is attributed to a transition to the first excited π* ← n+ singlet state; a more diffuse absorption ranging from about 290 nm to a maximum at 239 nm is assigned to the π* ← n− state, while a much stronger absorption beginning below 230 nm is attributed to the π* ← π transition. Product ratios vary with wavelength and depend on which excited state is involved.The thermal decomposition was studied briefly in a static system at temperatures from 470 to 710 K and pressures from 0.4 to 8 Torr. Major products were again CO2 and CH2O, but the latter was always less than stoichiometric. First-order rate constants for the apparently homogeneous formation of CO2 are described by Arrhenius parameters log A (s−1) = 7.80 and E = 30.8 kcal/mol. Carbon monoxide and H2 were minor products, and the CO/CO2 ratio increased with increasing temperature and showed some surface enhancement at lower temperatures. The SF6-sensitized thermal decomposition of glyoxylic acid, induced by a pulsed CO2 laser, was briefly studied, with temperatures estimated to be in the 1100–1600 K range, and the CO/CO2 ratio increased with increasing temperature, continuing the trend observed in the static system.

THE KINETICS OF CUPRENE GROWTH

1950 ◽  
Vol 28b (7) ◽  
pp. 358-372
Author(s):  
Cyrias Ouellet ◽  
Adrien E. Léger
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Carbon Monoxide ◽  
Apparent Activation Energy ◽  
Copper Catalyst ◽  
Maximum Velocity ◽  
Static System ◽  
Reaction Velocity ◽  
First Order ◽  
Kinetics Of

The kinetics of the polymerization of acetylene to cuprene on a copper catalyst between 200° and 300 °C. have been studied manometrically in a static system. The maximum velocity of the autocatalytic reaction shows a first-order dependence upon acetylene pressure. The reaction is retarded in the presence of small amounts of oxygen but accelerated by preoxidation of the catalyst. The apparent activation energy, of about 10 kcal. per mole for cuprene growth between 210° and 280 °C., changes to about 40 kcal. per mole above 280 °C. at which temperature a second reaction seems to set in. Hydrogen, carbon monoxide, or nitric oxide has no effect on the reaction velocity. Series of five successive seedings have been obtained with cuprene originally grown on cuprite, and show an effect of aging of the cuprene.

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