Kinetics of the Mercury-Photosensitized Decomposition of Propane. Part II. Reactions of the Propyl Radicals

1971 ◽  
Vol 49 (4) ◽  
pp. 549-554 ◽  
Author(s):  
M. M. Papic ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Kinetic Parameters ◽  
Dissociation Energy ◽  
Heat Of Formation ◽  
Entropy Changes ◽  
A Value ◽  
Yield Information ◽  
Temperature And Pressure ◽  
Kinetics Of

The results of the previous paper are analyzed to yield information about the reactions of the n-propyl and i-propyl radicals. The various combination and disproportionation reactions are considered. The rate of decomposition of the n-propyl radical was determined as a function of temperature and pressure, and limiting high-pressure and low-pressure kinetic parameters were obtained. The high-pressure activation energy is 32.6 kcal mol−1, and this leads to a value of 24.3 kcal mol−1 for the dissociation energy of the C—C bond in the n-propyl radical, to 22.2 kcal mol−1 for its heat of formation, and to 99.1 kcal mol−1 for the primary C—H dissociation energy in propane. Entropy changes are also calculated from the results.For the decomposition of the i-propyl E∞ = 38.7 kcal mol−1, and this leads to 37.7 kcal mol−1 for the C—H bond dissocation energy in this radical and to 19.3 kcal mol−1 for its heat of formation. The secondary C—H dissociation energy in propane is calculated to be 96.2 kcal mol−1. Corresponding entropy changes are calculated.

scholarly journals The dissociation energy of the C-N bond in benzylamine

1949 ◽  
Vol 198 (1053) ◽  
pp. 285-292 ◽  
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Dissociation Energy ◽  
Heat Of Formation ◽  
Molar Ratio ◽  
Kcal Mole ◽  
First Order ◽  
First Order Kinetics ◽  
Permanent Gases ◽  
Kinetics Of

The kinetics of the thermal decomposition of benzylamine were studied by a flow method using toluene as a carrier gas. The decomposition produced NH 3 and dibenzyl in a molar ratio of 1:1, and small quantities of permanent gases consisting mainly of H 2 . Over a temperature range of 150° (650 to 800° C) the process was found to be a homogeneous gas reaction, following first-order kinetics, the rate constant being expressed by k = 6 x 10 12 exp (59,000/ RT ) sec. -1 . It was concluded, therefore, that the mechanism of the decomposition could be represented by the following equations: C 6 H 5 . CH 2 . NH 2 → C 6 H 5 . CH 2 • + NH 2 •, C 6 H 5 . CH 3 + NH 2 •→ C 6 H 5 . CH 2 • + NH 3 , 2C 6 H 5 . CH 2 •→ dibenzyl, and the experimentally determined activation energy of 59 ± 4 kcal./mole is equal to the dissociation energy of the C-N bond in benzylamine. Using the available thermochemical data we calculated on this basis the heat of formation of the NH 2 radical as 35.5 kcal./mole, in a fair agreement with the result obtained by the study of the pyrolysis of hydrazine. A review of the reactions of the NH 2 radicals is given.

KINETICS OF THE DECOMPOSITIONS OF ETHANE AND PROPANE SENSITIZED BY AZOMETHANE: THE DECOMPOSITION OF THE NORMAL PROPYL RADICAL

1966 ◽  
Vol 44 (24) ◽  
pp. 2927-2940 ◽  
Author(s):  
M. C. Lin ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
Satisfactory Agreement ◽  
Rate Constant ◽  
Dissociation Energy ◽  
Low Temperatures ◽  
Heats Of Formation ◽  
Kcal Mole ◽  
Energy Diagram ◽  
A Value ◽  
Kinetics Of

The azomethane-sensitized pyrolysis of ethane was studied at low temperatures from 280 to 350 °C. Measurements were made of initial rates of formation of methane, nitrogen, and butane. From the rate of nitrogen production the rate constant for the azomethane decomposition into 2CH3 + N2 was[Formula: see text]A similar study of the propane decomposition, at temperatures from 260 to 300 °C, led to the value[Formula: see text]in satisfactory agreement. The rate of decomposition of the n-propyl radical into CH3 and C2H4 was obtained by comparing the rates of formation of C2H4 and n-C6H14; the rate constant was[Formula: see text]The activation energy of 31.4 kcal/mole, together with that of 8.9 kcal/mole for the reverse reaction obtained by Brinton, leads to a value of 20.3 kcal/mole for the dissociation energy of n-CH3—CH CH2 at 0 °K, and to a value of 22.8 at 25 °C. The corresponding values for the heats of formation 2of the n-propyl radical are 28.4 kcal/mole at 0 °K, and 23.1 kcal/mole at 25 °C. The dissociation energy of n-CH3CH2CH2—H is deduced to be 99.4 kcal/mole at 0 °K and 99.9 kcal/mole at 25 °C. An energy diagram is constructed for the various reactions of n-C3H7 and i-C3H7.

scholarly journals Acidic hydrolysis of astilbin and its application for the preparation of taxifolin from Rhizoma Smilacis Glabrae

2020 ◽  
pp. 174751982094835
Author(s):  
Xiao-Lin Qiu ◽  
Qing-Feng Zhang
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Hydrolysis Reaction ◽  
Simple Method ◽  
Acidic Hydrolysis ◽  
A Value ◽  
Hcl Concentration ◽  
Hydrolysis Of

The acidic hydrolysis of astilbin to produce its aglycone, taxifolin, was investigated in this study. The effects of aq. HCl concentration and temperature on the reaction were studied, and the kinetic parameters were calculated. The results showed that with higher aq. HCl concentration and temperature, the hydrolysis of astilbin became faster. The activation energy of the hydrolysis reaction under 1 mol L−1 aq. HCl was calculated with a value of 148.6 kJ mol−1. The reaction was successfully applied to produce taxifolin from a sample of Rhizoma Smilacis Glabrae. A simple method for the purification of taxifolin from Rhizoma Smilacis Glabrae was developed with purity of 97.5%.

Kinetics and Activation Parameters for the Alkaline Aqueous Rearrangement of Trichorfon [O,O-Dimethyl-(2,2,2-Trichloro-1-Hydroxyethyl) Phosphonate] to Dichlorvos [O,O-Dimethyl-O-(2,2-Dichloroethenyl)Phosphate]

2001 ◽  
Vol 36 (3) ◽  
pp. 589-604 ◽  
Author(s):  
Julian M. Dust ◽  
Christopher S. Warren
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Activation Parameters ◽  
Base Catalysis ◽  
Rearrangement Product ◽  
Exponential Factor ◽  
First Order ◽  
Pseudo First Order ◽  
Order Plot ◽  
Kinetics Of

Abstract The kinetics of the alkaline rearrangement of O,O-dimethyl-(2,2,2-trichloro-1- hydroxyethyl)phosphonate, (trichlorfon, 1), the active insecticidal component in such formulations as Dylox, was followed at 25±0.5°C by high pressure liquid chromatography (UV-vis detector, 210 nm). The rearrangement product, O,Odimethyl- O-(2,2-dichloroethenyl)phosphate (dichlorovos, 2), which is a more potent biocide than trichlorfon, undergoes further reaction, and the kinetics, consequently, cannot be treated by a standard pseudo-first-order plot. A two-point van't Hoff (initial rates) method was used to obtain pseudo-first-order rate constants (kѱ) at 25, 35 and 45°C: 2.6 × 10-6, 7.4 × 10-6 and 2.5 × 10-5 s-1, respectively. Arrhenius treatment of this data gave an activation energy (Ea) of 88 kJ·mol-1 with a pre-exponential factor (A) of 5.5 × 109 s-1. Kinetic trials at pH 8.0 using phosphate and tris buffer systems show no buffer catalysis in this reaction and indicate that the rearrangement is subject to specific base catalysis. Estimates are reported for pseudo-first-order half-lives for trichlorfon at pH 8.0 for environmental conditions in aqueous systems in the Corner Brook region of western Newfoundland, part of the site of a recent trichlorfon aerial spray program.

Study on Curing Kinetics of MEP-15/593/660 System

2014 ◽  
Vol 988 ◽  
pp. 31-35
Author(s):  
Jia Le Song ◽  
Chan Chan Li ◽  
Zhi Mi Zhou ◽  
Chao Qiang Ye ◽  
Wei Guang Li
Keyword(s):  
Activation Energy ◽  
Differential Scanning Calorimetry ◽  
Kinetic Parameters ◽  
Curing Kinetics ◽  
Conversion Ratio ◽  
Scanning Calorimetry ◽  
Degree Of Cure ◽  
Curing Kinetic ◽  
The Relationship ◽  
Kinetics Of

Curing kinetics of MEP-15/593 system and MEP-15/593/660 system is studied by means of differential scanning calorimetry (DSC). Curing kinetic parameters are evaluated and the relationship between diluent 660 and the curing properties is investigated. The results show that the diluent 660 can not only reduce viscosity and activation energy, but also improve the degree of cure and conversion ratio.

Research on Pyrolysis Kinetics of Shenhua Coal and Direct Liquefaction Residue

2012 ◽  
Vol 550-553 ◽  
pp. 2758-2762 ◽  
Author(s):  
Xi Jie Chu ◽  
Yong Gang Wang ◽  
Li Hong Zhao
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Kinetic Parameters ◽  
Heating Rate ◽  
Coal Pyrolysis ◽  
Pyrolysis Kinetics ◽  
Differential Heating ◽  
Pyrolysis Behavior ◽  
Direct Liquefaction ◽  
Kinetics Of

The pyrolysis tests of Shenhua coal and Shenhua direct liquefaction residue have been carried out using thermogravimetric at the differential heating rate. The kinetic parameters k and E were calculated using DAEM method. Results show DAME model can describe the pyrolysis behavior of Shenhua coal within the range of 20% to 95%, the activation energy of coal pyrolysis ranges from 53.98 to 279.38 kJ/mol, and DAME model can describe the behavior of Shenhua direct liquefaction residue within the range of 10% to 80%, the activation energy of residue pyrolysis is about 170 kJ/mol. The results of which are basically consistent with the experimental data.

scholarly journals The kinetics of the extraction of caffeine from guarana seed under the action of ultrasonic field with simultaneous cooling

2019 ◽  
Vol 9 (1) ◽  
pp. 26-36 ◽  
Author(s):  
Biljana Koturevic ◽  
Borivoj Adnadjevic ◽  
Jelena Jovanovic
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Reaction System ◽  
Ultrasonic Field ◽  
Conventional Heating ◽  
Isothermal Kinetics ◽  
Correlation Relationship ◽  
Exponential Factor ◽  
Caffeine Extraction ◽  
Kinetics Of

AbstractThe kinetics of isothermal extraction of caffeine from guarana seed under the action of ultrasonic field with simultaneous cooling (UESC) was investigated. The isothermal kinetics curves were measured at temperatures range T = 17-58°C. Using the model-fitting method it was determined that the kinetics of caffeine extraction can be described by a theoretical Jander three-dimensional diffusional model. The values of the rate constant were calculated for different temperatures, as well as the kinetic parameters (activation energy (Ea) and pre-exponential factor (lnA)). Based on the results obtained, it is concluded that the rate constants of caffeine extraction under UESC are about 2 times higher in comparison to the values obtained for the extraction in the conditions of conventional heating (CH). The activation energy of the caffeine extraction under the UESC $\left( E_{\text{a}}\,^{\text{UESC}}=19.4\,\text{kJ}\cdot \text{mo}{{\text{l}}^{-1}} \right)$is lower than the values are for CH $\left( E_{\text{a}}\,^{\text{CH}}=21.8\,\text{kJ}\cdot \text{mo}{{\text{l}}^{-1}} \right).$Energy consumption for UESC is four times lower than for CH conditions. It is shown that there is a linear correlation relationship between kinetic parameters obtained for UESC and CH conditions. The changes in the values of kinetic parameters are explained by the model of selective transfer of energy from the reaction system to the reactant molecules.

Effect of Temperature on the Electrode Kinetics of Totally Irreversible and Quasi-Reversible Polarographic Reductions

1977 ◽  
Vol 32 (4) ◽  
pp. 416-419 ◽  
Author(s):  
Sudhindra Swarup Sharma ◽  
S. K. Jha ◽  
Mukhtar Singh
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Effect Of Temperature ◽  
Electrode Kinetics ◽  
Polarographic Behaviour ◽  
Kinetics Of ◽  
Reversible Reduction

The polarographic behaviour of Ni(II), Co(II), Zn(II) and Mn(II) has been studied in 0.1 M KNO3. The temperature span studied varies from 15 to 55 °C. The reduction of Ni(II) and Co(II) has been found to be totally irreversible and that of Zn(II) and Mn(II) quasi-reversible over the temperature span studied. The kinetic parameters, kf,h0 and ana for the totally irreversible reductions have been calculated by KOUTECKY’S treatment while for quasi-reversible reduction the kinetic parameters (a and ks,h) have been evaluated by GELLINGS’ method. The activation energy of the totally irreversible reductions has also been determined. The effect of temperature has been discussed in terms of the variations in the values of the kinetic parameters.

Thermal Cure and Ceramization Kinetics of Perhydropolysilazane

2013 ◽  
Vol 575-576 ◽  
pp. 81-86 ◽  
Author(s):  
Feng Ling Ma ◽  
Hui Min Qi ◽  
Ya Ping Zhu ◽  
Xiao Wen Ren ◽  
Fan Wang
Keyword(s):  
Activation Energy ◽  
Weight Loss ◽  
Thermogravimetric Analysis ◽  
Kinetic Parameters ◽  
Nitrogen Atmosphere ◽  
Thermal Cure ◽  
Exponential Factor ◽  
Kinetics Of

The kinetics of the thermal cure and ceramization of preceramic prehydropolysilazane (PHPS) was investigated by thermogravimetric analysis (TGA) under nitrogen atmosphere. The results indicated that the gases captured during the thermal cure and ceramization process of PHPS, which had three main weight loss events. The corresponding kinetic parameters including activation energy, pre-exponential factor and empirical order of the thermal cure and ceramization stages were evaluated by using Ozawa and Kissinger metnods, respectively.

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