Über Reaktionen zwischen Phosphortrichlorid und Cyclohexen unter dem Einfluß von Y-Strahlung und von Wärme

1964 ◽  
Vol 19 (11) ◽  
pp. 999-1005 ◽  
Author(s):  
K. Wunder ◽  
H. Drawe ◽  
A. Henglein
Keyword(s):  
Activation Energy ◽  
Dose Rate ◽  
Phosphorus Trichloride ◽  
Square Root ◽  
Kcal Mole ◽  
Chain Reaction ◽  
Rate Determining Step ◽  
Γ Rays ◽  
G Value

1-chlorocyclohexyl-phosphorus dichloride is formed in a Kharasch type chain reaction when γ-rays act on mixtures of phosphorus trichloride and cyclohexene. The G-value is proportional to the reciprocal square root of the dose rate and reaches a maximum at 100°C. The activation energy of the rate determining step PCl2C6H10 · +PCl3→PCl2C6H10Cl+PCl2 · was found to amount to 6, 7 kcal/mole. At higher temperatures, the yield strongly decreases since another chain reaction predominates which produces cyclohexyl-phosphorus dichloride. The two chains have a common propagation step. 1-chlorocyclohexyl-phosphorus dichloride and cyclohexyl-phosphorus dichloride are also thermally formed at temperatures above about 150°C.

POLYMÉRISATION PAR LES RAYONS-X DU CHLORURE DE VINYLE À L'ÉTAT DE VAPEUR

1963 ◽  
Vol 41 (6) ◽  
pp. 1578-1587 ◽  
Author(s):  
Jan A. Herman ◽  
Pierre M. Hupin
Keyword(s):  
Activation Energy ◽  
Gas Phase ◽  
Average Molecular Weight ◽  
Negative Temperature ◽  
Solid Polymer ◽  
X Rays ◽  
Kcal Mole ◽  
Rate Of Polymerization ◽  
G Value ◽  
Termination Process

The polymerization of vinyl chloride in the gas phase by X rays gives a solid polymer of 1140 average molecular weight. The G value of monomer disappearance varies from 100 to 400 and depends on pressure and temperature. From the measure of the rate of polymerization it was possible to deduce the activation energy of the chain propagation steps: 2.5 kcal/mole, and that of the hindered termination process: 7.4 kcal/mole. The negative temperature co-efficient of the polymerization is explained by the importance of this hindered termination process.

Single Crystals of Ice Grown from KCl Solution and Their Dielectric Properties

1973 ◽  
Vol 51 (10) ◽  
pp. 1045-1052 ◽  
Author(s):  
Norikazu Maeno
Keyword(s):  
Activation Energy ◽  
Dielectric Properties ◽  
Crystal Lattice ◽  
Single Crystals ◽  
Low Frequency ◽  
Distribution Coefficients ◽  
Square Root ◽  
Dielectric Polarization ◽  
Kcal Mole ◽  
Upper Limit

Single crystals of ice were grown from KCl solution and their dielectric properties were investigated as functions of concentration, frequency, and temperature. It was found that a limited amount of chlorine was incorporated into the crystal lattice of ice but no trace of potassium. The upper limit of the substitutional incorporation of chlorine was approximately 1 × 10−4M(g moles/1). The distribution coefficients of the solutes were obtained as functions of the KCl concentration of the mother solution.The static dielectric constant of the single crystals of ice decreased due to the chlorine incorporation and the activation energy of its dielectric relaxation was reduced to 5.8 kcal/mole. The low-frequency conductivity increased with the square root dependence upon the chlorine concentration, and its activation energy was 6.1 kcal/mole. The mechanism of the dielectric polarization and conduction was discussed in relation to the defects introduced by chlorine built in the crystal lattice.

Gas phase photochlorination of perfluorocyclohexene

1969 ◽  
Vol 47 (6) ◽  
pp. 1067-1069 ◽  
Author(s):  
J. J. Cosa ◽  
C. A. Vallana ◽  
E. H. Staricco
Keyword(s):  
Activation Energy ◽  
Quantum Yield ◽  
Gas Phase ◽  
Photochemical Reaction ◽  
Total Pressure ◽  
Square Root ◽  
Kcal Mole ◽  
Kinetics Of

The kinetics of the gas phase photochemical reaction between perfluorocyclohexene and chlorine was studied between 10 and 50 °C. The system was irradiated with light of 4360 Å. The rate of the photochlorination was independent of the perfluorocyclohexene pressure and of the total pressure. It was found to be proportional to the first power of the pressure of Cl2 and to the square root of the intensity of absorbed light. At 30 °C, the quantum yield was found to be 200 when the initial Cl2 pressure was 100 Torr, and intensity of light absorbed 9.89 × 10−9 einstein l−1s−1.An activation energy of 5.1 kcal/mole could be assigned to the reaction C6F10Cl + Cl2.

IRRADIATION OF ONE MOLAR AQUEOUS CHLORAL HYDRATE SOLUTION WITH Co60-GAMMA-RAYS AND BETATRON X RAYS

1953 ◽  
Vol 31 (12) ◽  
pp. 1164-1172 ◽  
Author(s):  
G. R. Freeman ◽  
A. B. Van Cleave ◽  
J. W. T. Spinks
Keyword(s):  
Gamma Rays ◽  
Chloral Hydrate ◽  
Specific Yield ◽  
Square Root ◽  
X Rays ◽  
Chain Reaction ◽  
Peak Energy ◽  
Γ Rays ◽  
A Chain ◽  
Co60 Gamma

The production of acid by irradiation of 1 M chloral hydrate solutions is proportional to the dose at a given dose rate. The specific yield is the same for Co60 γ-rays as for 23 Mev. peak energy X rays and is a linear function of the inverse of the square root of the close rate. The reaction is apparently a chain reaction.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. I. The substitution of thiocyanate into the cis-Chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion in anhydrous dimethylsulphoxide and NN-dimethylformamide

1965 ◽  
Vol 18 (4) ◽  
pp. 453 ◽  
Author(s):  
LF Chin ◽  
WA Millen ◽  
DW Watts
Keyword(s):  
Activation Energy ◽  
Ion Pair ◽  
Second Order ◽  
Aprotic Solvents ◽  
Kcal Mole ◽  
Dissociative Mechanism ◽  
Thiocyanate Ion ◽  
First Order ◽  
Rate Determining Step ◽  
Dipolar Aprotic Solvents

The substitution of thiocyanate ion into the cis-chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion, cis-(Coen2(DMSO)Cl)2+, has been studied in the solvents dimethylsulphoxide (DMSO) and NN-dimethylformamide (DMF). In DMSO the reaction shows second-order characteristics which are accounted for by an ion-pair dissociative mechanism (SNIIP). The activation energy is 30.1 kcal mole-1. In DMF the entry is first-order, the rate determining step being solvolysis to the intermediate cis-(Coen2(DMF)Cl)2+ which has been isolated as the nitrate. In high thiocyanate concentrations the rate shows some thiocyanate dependence due to the competition of ion-paired thiocyanate with the DMF solvent for coordination following the DMSO dissociation. The activation energy for this substitution is 17.5 kcal mole-1.

Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

2019 ◽  
Author(s):  
Raghu Nath Dhital ◽  
keigo nomura ◽  
Yoshinori Sato ◽  
Setsiri Haesuwannakij ◽  
Masahiro Ehara ◽  
...  
Keyword(s):  
Activation Energy ◽  
Low Temperature ◽  
Dft Calculations ◽  
Bond Activation ◽  
Mild Conditions ◽  
Selective Transformation ◽  
Rate Determining Step ◽  
Highly Active ◽  
Harsh Conditions ◽  
Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the <i>beta</i>-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

Gas Cell Infrared and Attenuated Total Reflection Infrared Spectroscopic Studies for Organic–Inorganic Interactions in Adsorption of Fulvic Acid on the Goethite Surface Generating Carbon Dioxide

2021 ◽  
pp. 000370282199121
Author(s):  
Yuki Nakaya ◽  
Satoru Nakashima ◽  
Takahiro Otsuka
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Fulvic Acid ◽  
Spectroscopic Studies ◽  
Reaction Model ◽  
Total Reflection ◽  
Attenuated Total Reflection ◽  
Gas Cell ◽  
Rate Determining Step ◽  
Ir Spectroscopic

The generation of carbon dioxide (CO2) from Nordic fulvic acid (FA) solution in the presence of goethite (α-FeOOH) was observed in FA–goethite interaction experiments at 25–80 ℃. CO2 generation processes observed by gas cell infrared (IR) spectroscopy indicated two steps: the zeroth order slower CO2 generation from FA solution commonly occurring in the heating experiments of the FA in the presence and absence of goethite (activation energy: 16–19 kJ mol–1), and the first order faster CO2 generation from FA solution with goethite (activation energy: 14 kJ mol–1). This CO2 generation from FA is possibly related to redox reactions between FA and goethite. In situ attenuated total reflection infrared (ATR-IR) spectroscopic measurements indicated rapid increases with time in IR bands due to COOH and COO– of FA on the goethite surface. These are considered to be due to adsorption of FA on the goethite surface possibly driven by electrostatic attraction between the positively charged goethite surface and negatively charged deprotonated carboxylates (COO–) in FA. Changes in concentration of the FA adsorbed on the goethite surface were well reproduced by the second order reaction model giving an activation energy around 13 kJ mol–1. This process was faster than the CO2 generation and was not its rate-determining step. The CO2 generation from FA solution with goethite is faster than the experimental thermal decoloration of stable structures of Nordic FA in our previous report possibly due to partial degradations of redox-sensitive labile structures in FA.

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.

The slow oxidation of methane

1956 ◽  
Vol 235 (1201) ◽  
pp. 158-173 ◽  
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Induction Period ◽  
Hydrofluoric Acid ◽  
Pressure Rise ◽  
Pressure Change ◽  
Kcal Mole ◽  
Gaseous Products ◽  
Oxidation Of Methane ◽  
Reproducible Manner

Mixtures of methane and oxygen behave in a reproducible manner at temperatures of 440 to 520°C and initial pressures of 100 to 350 mm when reacting in Pyrex vessels freshly cleaned with hydrofluoric acid. The apparent order of the reaction ranged from 2∙3 to 2∙6 and the overall activation energy from 29 to 41 kcal/mole. Analyses of the products formed have been made, together with measurements of pressure change. Formaldehyde is formed from the commencement of the reaction including the induction period, but its concentra­tion reaches a maximum near the stage where the pressure rise is a maximum, and then falls off. Hydrogen peroxide is also formed, less rapidly in the earliest stage, but its rate of formation overtakes that of formaldehyde and it reaches an even higher concentration. No other peroxides were detected, nor was methanol found. Hydrogen was present in the gaseous products. These observations are not in full accord with some of the conclusions derived from earlier investigations.

scholarly journals On the explosion of chain-thermal reactions

1982 ◽  
Vol 24 (2) ◽  
pp. 194-202 ◽  
Author(s):  
R. O. Ayeni
Keyword(s):  
Activation Energy ◽  
Asymptotic Analysis ◽  
Upper Bound ◽  
Homogeneous Model ◽  
Chain Reaction ◽  
Isothermal Reaction ◽  
Thermal Reactions ◽  
Spatially Homogeneous ◽  
Branched Chain ◽  
A Chain

AbstractA chain reaction of oxygen (reactant) and hydrogen (active intermediary) with mtrosyl chloride (sensitizer) as a catalyst may be modelled mathematically as a non-isothermal reaction. In this paper we present an asymptotic analysis of a spatially homogeneous model of a non-isothermal branched-chain reaction. Of particular interest is the so-called explosion time and we provide an upper bound for it as a function of the activation energy which can vary over all positive values. We also establish a bound on the temperature when the activation energy is finite.

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