The hydrogen chloride catalysed decomposition of t-butyl isopropyl ether

1972 ◽  
Vol 25 (4) ◽  
pp. 785 ◽  
Author(s):  
NJ Daly ◽  
LP Steele
Keyword(s):  
Hydrogen Chloride ◽  
Isopropyl Alcohol ◽  
Arrhenius Equation ◽  
Volume Ratio ◽  
Butyl Alcohol ◽  
Reaction Vessel ◽  
Isopropyl Ether ◽  
First Order

Hydrogen chloride catalyses the decomposition of t-butyl isopropyl ether at 319-420�. The major products are isobutene and isopropyl alcohol; traces of propene and t-butyl alcohol are formed. The reaction is first order in each reagent and the Arrhenius equation is followed. K2 = 1012.97�0.14exp(-32110 � 400/RT) The rate is not affected by the addition of cyclohexene or by an increase in the surface-to-volume ratio of the reaction vessel. The formation of traces of propene is discussed.

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.

The thermal decompositions of carbamates. I. Ethyl N-Methyl-N-phenylcarbamate

1971 ◽  
Vol 24 (12) ◽  
pp. 2541 ◽  
Author(s):  
NJ Daly ◽  
F Ziolkowski
Keyword(s):  
Carbon Dioxide ◽  
Gas Phase ◽  
Rate Constants ◽  
Volume Ratio ◽  
Reaction Vessel ◽  
First Order ◽  
Order Rate

Ethyl N-methyl-N-phenylcarbamate decomposes in the gas phase over the range 329-380� to give N-methylaniline, carbon dioxide, and ethylene. The reaction is quantitative, and is first order in the carbamate. First-order rate constants are described by the equation ������������������� k1 = 1012.44 exp(-45,380/RT) (s-1) and are unaffected by the addition of cyclohexene or by increase in the surface to volume ratio of the reaction vessel. The reaction is considered to be unimolecular and likely to proceed by means of a mechanism of the type represented by the pyrolyses of acetates, xanthates, and carbonates.

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 trimethylacetyl bromide

1970 ◽  
Vol 23 (3) ◽  
pp. 525 ◽  
Author(s):  
BS Lennon ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Hydrogen Bromide ◽  
Transition States ◽  
Volume Ratio ◽  
Reaction Vessel ◽  
Chain Mechanism ◽  
Radical Chain ◽  
First Order ◽  
Polar Transition

Trimethylacetyl bromide decomposes at 298-364� into isobutene, carbon monoxide, and hydrogen bromide in a first-order manner with rate given by k1 = 138 x 1014exp(-48920/RT) sec-1 The rate is unaffected by addition of the products or of inhibitors, or by increase of the surface/volume ratio of the reaction vessel. The likely radical chain mechanism is considered and rejected. The reaction is believed to be a molecular one, and possible cyclic and polar transition states are discussed.

The thermal decompositions of carbamates. II. Methyl N-methylcarbamate

1972 ◽  
Vol 25 (7) ◽  
pp. 1453 ◽  
Author(s):  
NJ Daly ◽  
F Ziolkowski
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Gas Phase ◽  
Rate Constants ◽  
Volume Ratio ◽  
Reaction Vessel ◽  
Phase Reaction ◽  
Methyl Isocyanate ◽  
Gas Phase Reaction ◽  
First Order

Methyl N-methyloarbamate decomposes in the range 370-422� to give methyl isocyanate and methanol. The reaction is first order in carbamate, and the variation of the rate constants with temperature is given by the equation. k = 1012.39 exp(-4806O/RT) (s-l; activation energy in cal mol-l) Rate constants are unaffected by the addition of isobutene or by increase in the surface to volume ratio of the reaction vessel. The addition of alcohols or amines does not reverse the process. The decomposition is considered to be a homogeneous, unimolecular gas-phase reaction, probably proceeding through a four-centred transition state.

Solubility and Thermodynamic Transfer Functions of Cesium Dianilinetetraisothiocyanatochromate(III)

1998 ◽  
Vol 63 (3) ◽  
pp. 293-298
Author(s):  
Vladislav Holba
Keyword(s):  
Experimental Data ◽  
Isopropyl Alcohol ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Aqueous Methanol ◽  
Gibbs Energies ◽  
Gibbs Energy Of Transfer ◽  
Energy Of Transfer ◽  
The Given ◽  
Reference Electrolyte

The solubilities of cesium dianilinetetraisothiocyanatochromate(III) in water as well as in aqueous methanol, isopropyl alcohol, tert-butyl alcohol and acetonitrile were measured as a function of temperature and solvent composition. The Gibbs energies, enthalpies and entropies of transfer of the salt from water to the given solvents have been evaluated from experimental data. The contribution of [Cr(C6H5NH2)2(NCS)4]- ion to the Gibbs energy of transfer of the investigated salt has been calculated using the tetraphenylarsonium tetraphenylborate (TATB) reference electrolyte assumption.

Kinetics and mechanism of the reaction between oxidized cytochrome c and ascorbic acid

1991 ◽  
Vol 56 (2) ◽  
pp. 478-490 ◽  
Author(s):  
Joaquin F. Perez-Benito ◽  
Conchita Arias
Keyword(s):  
Ascorbic Acid ◽  
Cytochrome C ◽  
Redox Reactions ◽  
Arrhenius Equation ◽  
Horse Heart Cytochrome ◽  
First Order ◽  
Acidic Form ◽  
Ph Range ◽  
Horse Heart Cytochrome C ◽  
Mechanism Of The Reaction

The reaction between horse-heart cytochrome c and ascorbic acid has been investigated in the pH range 5.5 – 7.1 and at 10.0 – 25.0 °C. The rate shows a first-order dependence on the concentration of cytochrome c, it increases in a non-linear way as the concentration of ascorbic acid increases, it increases markedly with increasing pH and, provided that the ionic strength of the medium is high enough, it fulfills the Arrhenius equation. The apparent activation energy increases as the pH of the solution increases. The results have been explained by means of a mechanism that includes the existence of an equilibrium between two forms (acidic and basic) of oxidized cytochrome c: cyt-H+ -Fe3+ + OH- cyt -Fe3+ + H2O, whose equilibrium constant is (6.7 ± 1.4). 108 at 25.0 °C, the acidic form being more reducible than the basic one. It is suggested that there is a linkage of hydrogenascorbate ion to both forms of cytochrome c previous to the redox reactions. Two possibilities for the oxidant-reductant linkage (binding and adsorption) are discussed in detail.

scholarly journals Influence of the Porosity of Polymer Foams on the Performances of Capacitive Flexible Pressure Sensors

Sensors ◽  
2019 ◽  
Vol 19 (9) ◽  
pp. 1968 ◽  
Author(s):  
Sylvie Bilent ◽  
Thi Hong Nhung Dinh ◽  
Emile Martincic ◽  
Pierre-Yves Joubert
Keyword(s):  
Experimental Data ◽  
Linear Model ◽  
Dielectric Material ◽  
Pressure Sensors ◽  
Volume Ratio ◽  
Measurement Range ◽  
Polymer Foams ◽  
First Order ◽  
Non Linear ◽  
Flexible Pressure Sensors

This paper reports on the study of microporous polydimethylsiloxane (PDMS) foams as a highly deformable dielectric material used in the composition of flexible capacitive pressure sensors dedicated to wearable use. A fabrication process allowing the porosity of the foams to be adjusted was proposed and the fabricated foams were characterized. Then, elementary capacitive pressure sensors (15 × 15 mm2 square shaped electrodes) were elaborated with fabricated foams (5 mm or 10 mm thick) and were electromechanically characterized. Since the sensor responses under load are strongly non-linear, a behavioral non-linear model (first order exponential) was proposed, adjusted to the experimental data, and used to objectively estimate the sensor performances in terms of sensitivity and measurement range. The main conclusions of this study are that the porosity of the PDMS foams can be adjusted through the sugar:PDMS volume ratio and the size of sugar crystals used to fabricate the foams. Additionally, the porosity of the foams significantly modified the sensor performances. Indeed, compared to bulk PDMS sensors of the same size, the sensitivity of porous PDMS sensors could be multiplied by a factor up to 100 (the sensitivity is 0.14 %.kPa−1 for a bulk PDMS sensor and up to 13.7 %.kPa−1 for a porous PDMS sensor of the same dimensions), while the measurement range was reduced from a factor of 2 to 3 (from 594 kPa for a bulk PDMS sensor down to between 255 and 177 kPa for a PDMS foam sensor of the same dimensions, according to the porosity). This study opens the way to the design and fabrication of wearable flexible pressure sensors with adjustable performances through the control of the porosity of the fabricated PDMS foams.

Catalysis by hydrogen halides in the gas phase. XIX. 2,3-Dimethylbutan-2-ol and hydrogen bromide

1968 ◽  
Vol 21 (10) ◽  
pp. 2385 ◽  
Author(s):  
RL Johnson ◽  
VR Stimson
Keyword(s):  
Gas Phase ◽  
Arrhenius Equation ◽  
Hydrogen Bromide ◽  
Phase Decomposition ◽  
Hydrogen Halides ◽  
First Order

The gas-phase decomposition of 2,3-dimethylbutan-2-ol into 2,3-dimethylbut-1-ene, 2,3-dimethylbut-2-ene, and water, catalysed by hydrogen bromide at 303-400�, is described. The rate is first-order in each reactant and the Arrhenius equation k2 = 1011.88 exp(-26490/RT) sec-l ml mole-1 is followed. The olefins appear to be in their equilibrium proportions. The effects of substitutions in the alcohol at Cα and Cβ on the rate are discussed.

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