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.

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.

Catalysis by hydrogen halides in the gas phase. XI. Tertiary butyl ethyl ether and hydrogen chloride

1966 ◽  
Vol 19 (3) ◽  
pp. 401 ◽  
Author(s):  
VR Stimson ◽  
EJ Watson
Keyword(s):  
Gas Phase ◽  
Hydrogen Chloride ◽  
Ethyl Ether ◽  
Arrhenius Equation ◽  
Hydrogen Halide ◽  
Hydrogen Halides ◽  
Tertiary Butyl ◽  
First Order ◽  
Mechanism Of The Reaction ◽  
Kinetic Form

Hydrogen chloride catalyses the decomposition of t-butyl ethyl ether at 320-428�. Isobutene is quantitatively the product and the kinetic form is first order in the ether and in hydrogen chloride. The Arrhenius equation:��������� k, = 1012'16exp( -30,60O/RT) (sec-l ml mole-=) is followed. The mechanism of the reaction seems similar to those of other hydrogen halide catalysed decompositions of ethers and alcohols.

The thermal decomposition of diethyl ether. III. The action of inhibitors and the mechanism of the reaction

1958 ◽  
Vol 245 (1240) ◽  
pp. 49-67 ◽  
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Diethyl Ether ◽  
Rate Constant ◽  
Initial Pressure ◽  
Direct Analysis ◽  
Reaction Products ◽  
First Order ◽  
Molecular Decomposition ◽  
Induced Reaction

Small quantities of nitric oxide reduce the rate of thermal decomposition of diethyl ether at 525 °C to about one-quarter. Much larger amounts accelerate the decomposition, but the concentration ranges in which the ‘ maximally inhibited ’ reaction and the ‘ nitric-oxide-induced’ reaction can be studied are so widely separated that these reactions can be treated as two distinct entities. The ‘uninhibited’ reaction constitutes a third. Reaction products and kinetics are recorded for all three, and nitric oxide consumption is measured for the first two. In all three the major products are the same, with secondary differences which are discussed. In the presence of nitric oxide small amounts of cyanides and other compounds are formed. In the nitric-oxide-induced reaction 1.4 molecules of ether are decomposed for each molecule of nitric oxide used up: in the maximally inhibited reaction the ratio, which is dependent on the ether pressure, is very much greater. The rate of the maximally inhibited reaction is independent of the concentration of nitric oxide, or of propylene, and the same for the two inhibitors (as is now proved by direct analysis). The first-order rate constant varies with the initial pressure of ether according to the equation k inhib. = ( A [ether])/(1 + B [ether]) + C [ether]. The rate constant of the uninhibited reaction varies with ether pressure according to an expression which, although probably of different algebraical form, is empirically similar to the above over a considerable range. The nitric-oxide-induced reaction is nearly of the first order with respect both to ether pressure and to nitric oxide pressure. The maximally inhibited reaction is shown to be most probably a molecular decomposition of the ether. The uninhibited reaction is predominantly a chain reaction, the mechanism of which is discussed. The nitric-oxide-induced reaction, it is suggested on the basis of the experimental evidence, is largely initiated by a generation of radicals in an attack of nitric oxide on ether. It is possibly also in part a molecular decomposition of ether caused by collision with nitric oxide.

Thermal decomposition of citraconic anhydride

1971 ◽  
Vol 24 (4) ◽  
pp. 771 ◽  
Author(s):  
NJ Daly ◽  
F Ziolkowski
Keyword(s):  
Carbon Dioxide ◽  
Thermal Decomposition ◽  
Gas Phase ◽  
Rate Constant ◽  
Arrhenius Equation ◽  
Volume Ratio ◽  
Reaction Vessel ◽  
First Order ◽  
First Order Kinetics ◽  
Citraconic Anhydride

Citraconic anhydride decomposes in the gas phase over the range 440- 490� to give carbon dioxide, carbon monoxide, and propyne which undergoes some polymerization to trimethylbenzenes. The decomposition obeys first-order kinetics, and the Arrhenius equation ������������������� k1 = 1015.64 exp(-64233�500/RT) (s-1) describes the variation of rate constant with temperature. The rate constant is unaffected by the addition of isobutene or by increase in the surface/volume ratio of the reaction vessel. The reaction appears to be unimolecular and if a diradical intermediate is involved it may not be fully formed in the transition state.

Catalysis by hydrogen halides in the gas phase. X. Tertiary butyl methyl ether and hydrogen chloride

1966 ◽  
Vol 19 (3) ◽  
pp. 393 ◽  
Author(s):  
VR Stimson ◽  
EJ Watson
Keyword(s):  
Gas Phase ◽  
Surface Area ◽  
Hydrogen Chloride ◽  
Methyl Ether ◽  
Rate Equation ◽  
Hydrogen Halides ◽  
Tertiary Butyl ◽  
First Order ◽  
Tertiary Butyl Methyl Ether ◽  
Butyl Methyl Ether

The decomposition of t-butyl methyl ether catalysed by hydrogen chloride takes place at 337-428�. It is first order in each reactant and the rate is not affected by increase in surface area or inhibitor. The rate equation is: K2 = 1012.46exp(-32100/RT) (sec-l ml mole-l) The reaction is believed to be molecular and its properties are in accord with those of other such catalysed decompositions.

Kinetics and mechanism of the thermal decomposition of the thiosulphatopentaamminecobalt(III) ion in dilute aqueous acid

1986 ◽  
Vol 64 (2) ◽  
pp. 311-313
Author(s):  
Anthony Martin Newton
Keyword(s):  
Thermal Decomposition ◽  
Acetic Acid ◽  
Sodium Acetate ◽  
Major Product ◽  
Order Kinetic ◽  
Sodium Acetate Buffer ◽  
Reaction Products ◽  
First Order ◽  
Aqueous Acid ◽  
Reactive Complex

In acetic acid – sodium acetate buffer of pH 5.6 (25 °C) the Co(NH3)5S2O3+ ion undergoes redox decomposition rather than aquation. First-order kinetic are observed and the reaction products Co2+, NH3, and S4O62− are due to internal reduction of Co(III) by coordinated S2O32−. In dilute perchloric acid of pH < 4 the rate is retarded, first-order plots are not linear, and S4O62− is not a major product of the reaction. It is proposed that, in dilute HClO4, protonation of Co(NH3)5S2O3+ depletes the concentration of the reactive complex and that decomposition of coordinated HS2O3− occurs. Conversion of O-bonded S2O32− to S-bonded S2O32− in the reactive complex is also considered.

Thermal decomposition of alcohols. I. 2-Methylbutan-2-ol (t-Pentyl alcohol)

1974 ◽  
Vol 27 (5) ◽  
pp. 1047 ◽  
Author(s):  
WD Johnson
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
Arrhenius Equation ◽  
Consecutive Reaction ◽  
First Order ◽  
Order Rate

The thermal decomposition of 2-methylbutan-2-ol has been investigated from 432 to 570�C, over initial pressures ranging from 26 to 288 mmHg, and in the presence of toluene from 519 to 570�C. The decomposition is first order and homogeneous, involving the unimolecular elimination of water from the alcohol. 2-Methylbut-1-ene and 2-methylbut-2-ene decompose through a consecutive reaction under these conditions. The Arrhenius equation giving the variation of the first-order rate constants with temperature was found to be (R = 8.31 J mol-1 K-1) k = 1011.8 exp(- 23OOOO/RT) s-l

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