Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

1969 ◽  
Vol 47 (24) ◽  
pp. 4808-4809 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Initial Step ◽  
Butyl Alcohol ◽  
Major Product ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Peroxide Decomposition ◽  
Butyl Peroxide

The thermal decomposition of di-tert-butyl peroxide in the presence of propane has been studied at total pressures up to 100 atm. At the highest propane concentrations, the major product of the decomposition is tert-butyl alcohol, and extrapolation to infinite propane pressure indicates that the initial step in the peroxide decomposition is exclusively the formation of two tert-butoxy radicals. The activation energy for the abstraction of hydrogen from propane by t-BuO radicals is discussed.

ChemInform Abstract: GAS PHASE THERMAL DECOMPOSITION OF TERT.-BUTYL ALCOHOL

1974 ◽  
Vol 5 (38) ◽  
pp. no-no
Author(s):  
DAVID LEWIS ◽  
MARK KEIL ◽  
MICHAEL SARR
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Butyl Alcohol ◽  
Tert Butyl ◽  
Tert Butyl Alcohol

THE DECOMPOSITION OF SILYL PEROXIDES

1964 ◽  
Vol 42 (5) ◽  
pp. 985-989 ◽  
Author(s):  
Richard R. Hiatt
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Half Life ◽  
Order Rate Constant ◽  
Butyl Alcohol ◽  
Base Catalysis ◽  
First Order ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Acid And Base

The thermal decomposition of tert-butyl trimethylsilyl peroxide has been investigated and found to be sensitive to acid and base catalysis and to the nature of the solvent. In heptane and iso-octane the first-order rate constant could be expressed as 1.09 × 1015e−41200/RT and in 1-octene as 3.90 × 1015e−41200/RT (sec−1). The half life at 203 °C was about 1 hour. The reaction was faster in aromatic solvents; in chlorobenzene it was complicated by formation of HCl from the solvent.Products of the reaction were acetone, tert-butyl alcohol and hexamethyldisiloxane.

The reactivity of allyl and propargyl alcohols with solvated electrons: temperature and solvent effects

1979 ◽  
Vol 57 (8) ◽  
pp. 839-845 ◽  
Author(s):  
Alexei M. Afanassiev ◽  
Kiyoshi Okazaki ◽  
Gordon R. Freeman
Keyword(s):  
Activation Energy ◽  
Ethylene Glycol ◽  
Rate Constants ◽  
Allyl Alcohol ◽  
Trap Depth ◽  
Activation Energies ◽  
Butyl Alcohol ◽  
Solvated Electrons ◽  
Tert Butyl ◽  
Tert Butyl Alcohol

The rate constants k1 for the reaction of solvated electrons with allyl alcohol in a number of hydroxylic solvents differ by up to two orders of magnitude and decrease in the order tert-butyl alcohol > 2-propanol > 1-propanol ≈ ethanol > methanol ≈ ethylene glycol > water. In methanol and ethylene glycol the rate constants (7 × 107 M−1 s−1 at 298 K) and activation energies (16 kJ/mol) are equal, in spite of a 32-fold difference in solvent viscosity (0.54 and 17.3 cP, respectively) and 3-fold difference in its activation energy (11 and 32 kJ/mol, respectively). The reaction in tert-butyl alcohol is nearly diffusion controlled and has a high activation energy that is characteristic of transport in that liquid (E1 = 31 kJ/mol, Eη = 39 kJ/mol). The activation energies in the other alcohols are all 16 kJ/mol, and it is 14 kJ/mol in water. They do not correlate with transport properties. The solvent effect is connected primarily with the entropy of activation. The rate constants correlate with the solvated electron trap depth. When the electron affinity of the scavenger is small, a favorable configuration of solvent molecules about the electron/scavenger encounter pair is required for the electron jump to take place. The behavior of the rate parameters for propargyl alcohol is similar to that for allyl alcohol, but k1, A1, and E1 are larger for the former. The ratio k(propargyl)/k(allyl) at 298 K equals 10.5 in water and decreases through the series, reaching 1.3 in tert-butyl alcohol. Rate parameters for several other scavengers are also reported.

Di-tert-butyl peroxide decomposition behind shock waves

1976 ◽  
Vol 54 (4) ◽  
pp. 581-585 ◽  
Author(s):  
David K. Lewis
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Single Pulse ◽  
First Order ◽  
Tert Butyl ◽  
First Order Kinetics ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
Temperature Work ◽  
Lower Temperature

The homogeneous, gas phase thermal decomposition of di-tert-butyl peroxide has been studied in a single pulse shock tube. Samples containing 0.05% to 0.5% reactant in argon were heated to 528–677 K at total pressures of about 1 atm. Acetone and ethane were the only significant products. The reaction obeyed first order kinetics. The Arrhenius parameters, log A (s−1) = 15.33 ± 0.50, Eact (kJ/mol) = 152.3 ± 5.8, are in agreement with the bulk of the earlier reported results of lower temperature work, and with a recently reported result obtained via the very low pressure pyrolysis technique. Indications from some of the earlier work that the A factor may decline at high temperatures are not supported by the present study.

scholarly journals Production and Surfactant Properties of Tert-Butyl α-d-Glucopyranosides Catalyzed by Cyclodextrin Glucanotransferase

Catalysts ◽  
2019 ◽  
Vol 9 (7) ◽  
pp. 575 ◽  
Author(s):  
Humberto Garcia-Arellano ◽  
Jose L. Gonzalez-Alfonso ◽  
Claudia Ubilla ◽  
Francesc Comelles ◽  
Miguel Alcalde ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nuclear Magnetic Resonance ◽  
Critical Micellar Concentration ◽  
Butyl Alcohol ◽  
Major Product ◽  
Tertiary Alcohol ◽  
Cyclodextrin Glucanotransferase ◽  
Tert Butyl ◽  
Organic Cosolvents ◽  
Tert Butyl Alcohol

While testing the ability of cyclodextrin glucanotransferases (CGTases) to glucosylate a series of flavonoids in the presence of organic cosolvents, we found out that this enzyme was able to glycosylate a tertiary alcohol (tert-butyl alcohol). In particular, CGTases from Thermoanaerobacter sp. and Thermoanaerobacterium thermosulfurigenes EM1 gave rise to the appearance of at least two glycosylation products, which were characterized by mass spectrometry (MS) and nuclear magnetic resonance (NMR) as tert-butyl-α-D-glucoside (major product) and tert-butyl-α-D-maltoside (minor product). Using partially hydrolyzed starch as glucose donor, the yield of transglucosylation was approximately 44% (13 g/L of tert-butyl-α-D-glucoside and 4 g/L of tert-butyl-α-D-maltoside). The synthesized tert-butyl-α-D-glucoside exhibited the typical surfactant behavior (critical micellar concentration, 4.0–4.5 mM) and its properties compared well with those of the related octyl-α-D-glucoside. To the best of our knowledge, this is the first description of an enzymatic α-glucosylation of a tertiary alcohol.

Gas phase thermal decomposition of tert-butyl alcohol

1974 ◽  
Vol 96 (14) ◽  
pp. 4398-4404 ◽  
Author(s):  
David Lewis ◽  
Mark Keil ◽  
Michael Sarr
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Butyl Alcohol ◽  
Tert Butyl ◽  
Tert Butyl Alcohol

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

scholarly journals Impacts of Sn(II) doping on the Keggin heteropolyacid-catalyzed etherification of glycerol with tert-butyl alcohol

2021 ◽  
pp. 116913
Author(s):  
Márcio José da Silva ◽  
Diego Morais Chaves ◽  
Sukarno Olavo ferreira ◽  
Rene Chagas da Silva ◽  
Jose Balena Gabriel Filho ◽  
...  
Keyword(s):  
Butyl Alcohol ◽  
Tert Butyl ◽  
Tert Butyl Alcohol
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