Kinetics of the addition of acids to olefins with and without boron fluoride catalysis

1967 ◽  
Vol 45 (1) ◽  
pp. 11-16 ◽  
Author(s):  
G. A. Latrèmouille ◽  
A. M. Eastham
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Apparent Activation Energy ◽  
Trifluoroacetic Acid ◽  
Similar Rate ◽  
Ethylene Dichloride ◽  
Kcal Mole ◽  
Rate Law ◽  
Boron Fluoride ◽  
Kinetics Of

Isobutene reacts readily with excess trifluoroacetic acid in ethylene dichloride solution at ordinary temperatures to give t-butyl trifluoroacetate. The rate of the reaction is given, within the range of the experiments, by the expression d[ester]/dt = k[acid]2[olefin], and the apparent activation energy is about 6 kcal/mole. The rate of addition is markedly dependent on the strength of the reacting acid and is drastically reduced in the presence of mildly basic materials, such as dioxane. The boron fluoride catalyzed addition of acetic acid to 2-butene can be considered to follow a similar rate law, i.e. d[ester]/dt = k[acid·BF3]2[olefin], but only if some assumptions are made about the position of the equilibrium [Formula: see text]since only the 1:1 complex is reactive.

Kinetics of the Solid State Reaction between MoO3 and SrCO3

1972 ◽  
Vol 27 (6) ◽  
pp. 1020-1022 ◽  
Author(s):  
G. Flor ◽  
V. Massarotti ◽  
R. Riccardi
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Apparent Activation Energy ◽  
Solid State Reaction ◽  
Diffusion Mechanism ◽  
Optical Observations ◽  
Kcal Mole ◽  
Temperature Range ◽  
Kinetics Of

AbstractThe solid state reaction MoO3 + SrCO3 → SrMoO4+ CO2 has been studied on mixtures of powdered reagents. Thermogravimetric measurements in the temperature range 412° -498 °C have been made on different mixtures and under different atmospheres. Moreover, optical observations and conductometric measurements have been carried out. The results show that the reaction is governed by a diffusion mechanism with an apparent activation energy of (60 ± 1) kcal/mole and that the main diffusing species is the Mo6+ ion.

Aqueous dissolution kinetics of pyrochlore, zirconolite and brannerite at 25, 50, and 75 °C

2000 ◽  
Vol 88 (9-11) ◽  
Author(s):  
S. K. Roberts ◽  
W.L. Bourcier ◽  
H.F. Shaw
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Dissolution Rate ◽  
Dissolution Kinetics ◽  
Kcal Mole ◽  
Dissolution Rates ◽  
Flow Through ◽  
Kinetics Of ◽  
Total Dissolution ◽  
Calculated Average

We measured the rates of dissolution of pyrochlore, zirconolite, and brannerite in pH-buffered solutions of pH 2, 4, 6, 8, 10, and 12 at temperatures of 25, 50, and 75 °C in flow-through reactors. The dissolution rates for all phases show a minimum near pH 8. Zirconolite dissolves the slowest of the three phases, with a slightly higher rate for pyrochlore and a much higher dissolution rate for brannerite. Brannerite dissolves as much has 30 times faster than zirconolite. The rates increase with temperature, but the magnitude of the increase varies with pH. The calculated average apparent activation energy for dissolution is 6±3 kcal/mole. Dissolution is non-stoichiometric at all pHs. Ti and Hf are released most slowly, and are often below detection limits (1 ppb for Ti, 0.2 ppb for Hf). Releases of Ca, U, Gd, and Ce appear to be stoichiometric below pH 8. At pH 8 and above only U is measurable in solution. Dissolution rates are slow under all conditions, and commonly in the range of 1-100 nm total dissolution/year (between 10

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

Insect blood-brain barrier: a radioisotope study of the kinetics of exchange of a liposoluble molecule (n-butanol)

1976 ◽  
Vol 64 (1) ◽  
pp. 119-130
Author(s):  
M. V. Thomas
Keyword(s):  
Activation Energy ◽  
Temperature Sensitivity ◽  
Nerve Cord ◽  
Previous Investigation ◽  
Time Course ◽  
Kcal Mole ◽  
Similar Time ◽  
Kinetics Of ◽  
Butanol Concentration ◽  
Good Agreement

About 90% of the butanol uptake by the cockroach abdominal nerve cord washed out with half-times of a few seconds, in good agreement with an electrophysiological estimate, and the temperature sensitivity suggested an activation energy of 3 Kcal mole-1. The remaining activity washed out far more slowly, with a similar time course to that observed in a previous investigation which had not detected the fast fraction. Its size was similar to the non-volatile uptake, and was considerably affected by the butanol concentration and incubation period. It apparently consisted of butanol metabolites, which could be detected by chromatography.

Aromatic oxidation by cobaltic acetate in acetic acid

1969 ◽  
Vol 47 (3) ◽  
pp. 387-392 ◽  
Author(s):  
Koichiro Sakota ◽  
Yoshio Kamiya ◽  
Nobuto Ohta
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Acetic Acid ◽  
Bond Energy ◽  
Hydrogen Abstraction ◽  
Steric Factor ◽  
Benzyl Acetate ◽  
Kcal Mole ◽  
First Order ◽  
Reversible Electron Transfer

A detailed kinetic study of oxidation of toluene and its derivatives by cobaltic acetate in 95 vol% acetic acid is reported. The reaction was found to be profoundly affected by a steric factor and rather insensitive to the C—H bond energy. The order of reactivities of various alkylbenzenes is quite reversal to that of hydrogen abstraction reactions. The reaction was of first-order with respect to toluene, of second-order with respect to cobaltic ion and of inverse first-order with respect to cobaltous ion. The oxidation by cobaltic ion seems to proceed via an initial reversible electron transfer from toluene to cobaltic ion, yielding [Formula: see text] which is oxidized into benzyl acetate by another cobaltic ion. The apparent activation energy for toluene was found to be 25.3 kcal mole−1, and the same activation energy was found for ethylbenzene, cumene, diphenylmethane, and triphenylmethane.

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.

scholarly journals Kinetics of carbothermic reduction of synthetic chromite

2014 ◽  
Vol 50 (1) ◽  
pp. 15-21 ◽  
Author(s):  
Y. Wang ◽  
L. Wang ◽  
J. Yu ◽  
K.C. Chou
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Reduction Process ◽  
X Ray Diffraction ◽  
X Ray ◽  
Chromite Ore ◽  
Current Reduction ◽  
Increasing Temperature ◽  
Isothermal Mode ◽  
Kinetics Of

In order to optimize the current reduction process of chromite, a good knowledge of reduction mechanism involved is required. The basic component in chromite ore is FeCr2O4, thus, kinetic investigation of synthetic FeCr2O4 with different amount of carbon were carried out in the temperature range of 1473K to 1673K under both isothermal and non-isothermal mode. The iron can be easily reduced compared with chromium. And higher reduction degree of chromite can be achieved by increasing temperature and carbon content. With the supporting of X-ray Diffraction and Scanning Electron Microscope methods, the formation of metallic products followed the sequence: Fe-C alloy, (Fe,Cr)7C3and Fe-Cr-C alloy. Kinetics analysis showed that the first stage was controlled by nucleation with an apparent activation energy of 120kJ/mol, while the chromium reduction was controlled by crystallochemical transformation with an apparent activation energy of 288kJ/mol.

The Langmuir-Hinshelwood Reaction between Oxygen and CO at Ir(111) Surfaces

1979 ◽  
Vol 34 (1) ◽  
pp. 81-88 ◽  
Author(s):  
J. Küppers ◽  
A. Plagge
Keyword(s):  
Activation Energy ◽  
Computer Program ◽  
Apparent Activation Energy ◽  
Gas Phase ◽  
Close Agreement ◽  
Reaction Path ◽  
Kcal Mole ◽  
Reaction Step ◽  
Per Se ◽  
Reaction Processes

Abstract The reaction of oxygen and CO to form CO2 has been investigated using an Ir (111) surface as an acting catalyst. Both instationary and stationary reaction processes have been established via separate gas exposing techniques. The instationary reaction process, achieved from coadsorbed CO and O which per se is an LH reaction is found to be controlled by an apparent activation energy of 10.7 kcal/mole. The stationary reaction with both CO and O2 continuously present in the gas phase has been simulated using a proper computer program, involving both LH and ER reaction steps. By comparison with experimental results, close agreement is found when ruling out any ER reaction step from the reaction path.

Characteristics and thermal decomposition kinetics of wood-SiO2 composites derived by the sol-gel process

Holzforschung ◽  
2017 ◽  
Vol 71 (3) ◽  
pp. 233-240 ◽  
Author(s):  
Ke-Chang Hung ◽  
Jyh-Horng Wu
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Apparent Activation Energy ◽  
Sol Gel ◽  
Weight Percent Gain ◽  
Weight Percent ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Sol Gel Process ◽  
Kinetics Of

Abstract Wood-SiO2 composites (WSiO2Cs) were prepared by means of the sol-gel process with methyltrimethoxysilane (MTMOS) as a reagent, and the physical properties, structure and thermal decomposition kinetics of the composites has been evaluated. The dimensional stability of the WSiO2Cs was better than that of unmodified wood, especially in terms of the weight percent gain (WPG), which achieved values up to 30%. The 29Si-NMR spectra show two different siloxane peaks (T2 and T3), which supports the theory about the formation of MTMOS network structures. Thermal decomposition experiments were also carried out in a TG analyzer under a nitrogen atmosphere. The apparent activation energy was determined according to the iso-conversional methods of Friedman, Flynn-Wall-Ozawa, modified Coats-Redfern, and Starink. The apparent activation energy between 10 and 70% conversion is 147–172, 170–291, 189–251, and 192–248 kJ mol−1 for wood and WSiO2Cs with WPGs of 10, 20, and 30%, respectively. However, the reaction order between 10 and 70% conversion calculated by the Avrami theory was 0.50–0.56, 0.35–0.45, 0.33–0.44, and 0.28–0.48. These results indicate that the dimensional and thermal stability of the wood could be effectively enhanced by MTMOS treatment.

Chemical Vapor Deposition of SiO2 from Ozone-Organosilane Mixtures near Atmospheric Pressure

1992 ◽  
Vol 282 ◽  
Author(s):  
K. V. Guinn ◽  
J. A. Mucha
Keyword(s):  
Activation Energy ◽  
Chemical Vapor Deposition ◽  
Vapor Deposition ◽  
Atmospheric Pressure ◽  
Chemical Vapor ◽  
Zero Order ◽  
Kcal Mole ◽  
Consumption Ratio ◽  
Zero Order Kinetics ◽  
Kinetics Of

ABSTRACTThe kinetics of deposition of SiO2 by the reaction of tetramethylsilane (TMS) with ozone (O3) has been studied over the temperature range 180 – 380° C and compared with available data for the same process using tetraethoxysilane (TEOS). Both processes exhibit the same activation energy (17 kcal/mole) below 300 ° C which falls-off at higher temperatures due to transport limitations. Transition from first- to zero-order kinetics occurs with increasing concentrations of TMS and O3, which gives an overall O3/TMS consumption ratio of 10 at 258° C and5 at 325° C. TEOS is estimated to be 5 times more reactive than TMS above 300° C and over 10 times more reactive in the kinetically-limited regime below 300° C. Results suggest that O3-induced SiO2 deposition proceeds via surface reactions and is limited by heterogeneous decomposition of ozone.

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