Thermal decomposition of alcohols. II. 2-Methylpropan-2-ol

1975 ◽  
Vol 28 (8) ◽  
pp. 1725 ◽  
Author(s):  
WD Johnson
Keyword(s):  
Thermal Decomposition ◽  
Free Radical ◽  
Arrhenius Equation ◽  
Initial Rate ◽  
Radical Mechanism ◽  
Reaction Products ◽  
Radical Process ◽  
First Order ◽  
Free Radical Mechanism

The thermal decomposition of 2-methylpropan-2-ol has been investigated from 503 to 612�C, over initial pressures ranging from 40 to 275 mm and in the presence of toluene from 520 to 602�C. The decomposition is homogeneous and first order with respect to the initial concentrations of alcohol giving the Arrhenius equation (R = 8.31 J mol-1 K-1) �������������������������� K=1012.7exp(-249,800/RT) s-1 for the initial rate. The decomposition of this alcohol is inhibited by the reaction products, mainly 2-methylpropene, and by the addition of toluene. There are contributions from the unimolecular elimination of water (k = 1013.6exp(-268,000/RT)s-1) and from a flee radical process (k = 1011.0 x exp(-227,000/RT) s-1). A free radical mechanism, which explains the minor products of the reaction and the varying results of other workers, is proposed.

The kinetics of the oxidation of ammonia by nitrous oxide

1964 ◽  
Vol 17 (2) ◽  
pp. 202 ◽  
Author(s):  
TN Bell ◽  
JW Hedger
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Free Radical ◽  
Rate Equation ◽  
Radical Mechanism ◽  
15N Isotope ◽  
Free Radical Mechanism ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Decomposition Of Nitrous Oxide

Ammonia is oxidized by nitrous oxide smoothly and homogeneously at temperatures between 658 and 730� and total pressures up to 250 mm. The products of reaction, nitrogen, water, and hydrazine are accounted for by a free-radical mechanism initiated by oxygen atoms which result from the thermal decomposition of nitrous oxide. Ammonia labelled with the 15N-isotope was used to distinguish between the nitrogen formed from the nitrous oxide and that from the ammonia. The kinetics follow an empirical rate equation, ������������� Rate = k'[N2O]1.56 + k"[N2O]0.61[NH3]. This is of a form which shows the importance of the ammonia molecule participating in the activation of nitrous oxide through bimolecular collision. Assigning a collisional efficiency of unity for like N2O-N2O collisions, the efficiency of ammonia in the process ������������ NH3 + N2O → NH3 + N2O* is determined as 0.85.

The thermal decomposition of t-butyl methyl ether

1968 ◽  
Vol 21 (11) ◽  
pp. 2711 ◽  
Author(s):  
NJ Daly ◽  
C Wentrup
Keyword(s):  
Thermal Decomposition ◽  
Methyl Ether ◽  
Arrhenius Equation ◽  
Reaction Products ◽  
First Order ◽  
Comparison Of The Results ◽  
Butyl Methyl Ether ◽  
Kinetic Form

The rates of the thermal decomposition of t-butyl methyl ether have been measured in the range 433-495�. The reaction products are isobutene and methanol, and the kinetic form is first order. The Arrhenius equation K1 = 1014.38exp(-61535/RT) sec-1 describes the variation of rate with temperature. The reaction behaviour is consistent with a unimolecular mechanism. Comparison of the results with those obtained for the production of isobutene from various t-butyl compounds indicates that the reaction has some degree of heterolytic character.

The thermal decomposition of t-butyl ethyl ether

1968 ◽  
Vol 21 (6) ◽  
pp. 1535 ◽  
Author(s):  
NJ Daly ◽  
C Wentrup
Keyword(s):  
Thermal Decomposition ◽  
Ethyl Ether ◽  
Arrhenius Equation ◽  
Reaction Products ◽  
First Order ◽  
Kinetic Form

The rates of decomposition of t-butyl ethyl ether have been measured in the range 433-484�. The reaction products are ethanol and isobutene, and the kinetic form is first order. The Arrhenius equation k1 = 1017.18exp(-59740/RT)sec-1 is followed. The reaction behaviour is consistent with a unimolecular mechanism for the decomposition.

Comparative QSAR evidence for a free-radical mechanism of phenol-induced toxicity

2000 ◽  
Vol 127 (1) ◽  
pp. 61-72 ◽  
Author(s):  
Corwin Hansch ◽  
Susan C. McKarns ◽  
Carr J. Smith ◽  
David J. Doolittle
Keyword(s):  
Free Radical ◽  
Radical Mechanism ◽  
Free Radical Mechanism

Dirhodium(II)-Catalyzed Diamination Reaction via a Free Radical Pathway

2021 ◽  
Author(s):  
Zhiying Fan ◽  
Zhifan Wang ◽  
Ruoyi Shi ◽  
Yuanhua Wang
Keyword(s):  
Free Radical ◽  
Bond Formation ◽  
Mechanistic Study ◽  
Radical Mechanism ◽  
Free Radical Mechanism

Unlike C-N bond formation with classical dirhodium(II)-nitrenoids as the key intermediate, dirhodium(II)-catalyzed 1,2-and 1,3-diamination reactions are realized by a free radical mechanism. A mechanistic study revealed that the reactions undergo...

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