Determination of D[(C2H5)3Sn—C2H5] by the toluene carrier method and studies of the reaction of C2H5 with toluene

1976 ◽  
Vol 54 (11) ◽  
pp. 1814-1819 ◽  
Author(s):  
Mary Daly ◽  
S. James W. Price
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Total Pressure ◽  
Flow System ◽  
Pyrolysis Products ◽  
Temperature Range ◽  
Carrier Flow ◽  
Full Analysis

The thermal decomposition of tetraethyltin in a toluene carrier flow System has been studied over the temperature range 725 to 833 K and decompositions of 3.4 to 98.0%. Total pressure in all runs were in the range 0.63 to 0.90 kPa and contact times of 0.59 to 4.2 s were used.The progress of the reaction was followed by carrying out full analysis of all pyrolysis products involving the C2H5 radical, assuming that all four C2H5 groups are released. In selected runs analysis for unreacted alkyl was also performed. The agreement between the two methods indicates that reaction 1 is followed rapidly by reactions 2, 3, and 4,[Formula: see text]or alternate reactions that result in the release of all four C2H5 groups each time reaction 1 occurs. The decomposition is essentially homogeneous and[Formula: see text]or −59 340/4.58T if the activation energy is expressed in cal rather than J. Combination of present values of k5 with data from previous studies

Determination of Conditions for the Suppression of CH3 + Sb(CH3)2→Sb(CH3)3 and Evaluation of D[(CH3)2Sb—CH3]

1972 ◽  
Vol 50 (7) ◽  
pp. 966-971 ◽  
Author(s):  
S. J. W. Price ◽  
J. P. Richard
Keyword(s):  
Activation Energy ◽  
Least Squares ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Methyl Radicals ◽  
Product Analysis ◽  
Temperature Range ◽  
Carrier Flow

The pyrolysis of trimethylantimony has been studied in a toluene carrier flow system over the temperature range 690–803 °K (total pressures 3.6–173.4 mm, contact times 1.0–13.5 s, decomposition 3.9–89.5%). The progress of the reaction was followed by measuring the amount of methane, ethane, and ethylbenzene formed. In 23 runs the undecomposed alkyl was also determined. The quantity found was in agreement with that expected from the product analysis if three methyl radicals are released for each molecule undergoing reaction. No heterogeneous reaction was detected.Deuterium labeling led to the conclusion that regeneration of the parent alkyl occurred during the course of the decomposition. This regeneration reaction was effectively eliminated by working at toluene pressures above 150 mm. Least squares analysis of the results obtained under conditions where regeneration should not be important givenLog10k/s−1 = 15.33 − (55 900 ± 1 000)/2.3RTThe activation energy should be a good approximation to D[(CH3)2Sb—CH3].Significant decomposition of SbCH3 probably does not occur. It seems most likely that free Sb is formed via 2Sb(CH3) → Sb(CH3)2 + Sb.

THE PYROLYSIS OF TRIMETHYLTHALLIUM

1965 ◽  
Vol 43 (7) ◽  
pp. 1961-1967 ◽  
Author(s):  
M. G. Jacko ◽  
S. J. W. Price
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Total Pressure ◽  
Flow System ◽  
Total Darkness ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Homogeneous Process ◽  
Carrier Flow ◽  
Reaction Proceeds

The pyrolysis of trimethylthallium has been studied in a toluene carrier flow system from 458 to 591 °K using total pressures from 5.6 to 33.0 mm. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed and, in 21 runs, by direct thallium analysis. All preparative and kinetic work was carried out in total darkness where possible. A shielded 10 W lamp was used when some illumination was necessary.The decomposition is approximately 80% heterogeneous in an unconditioned vessel and 14–27% heterogeneous in a vessel pretreated with hot 50% HF for 10 min. The reaction proceeds by the simple consecutive release of three methyl radicals. The rate constant depends only slightly on the total pressure in the system so that the activation energy of the homogeneous process, 27.4 kcal/mole, may be equated to D[(CH3)2Tl—CH3].

Determination of D[(CH3)3Pb—CH3] by the Toluene Carrier Method

1972 ◽  
Vol 50 (16) ◽  
pp. 2639-2641 ◽  
Author(s):  
K. M. Gilroy ◽  
S. J. Price ◽  
N. J. Webster
Keyword(s):  
Least Squares ◽  
Flow System ◽  
Methyl Radicals ◽  
Product Analysis ◽  
Method Of Least Squares ◽  
Temperature Range ◽  
Carrier Flow

The pyrolysis of tetramethyl lead has been studied in a toluene carrier flow system over the temperature range 671–753 °K (contact times 0.72–1.67 s, 3–77% decomposition). The reaction was followed by measuring the amount of methane, ethane, and ethylbenzene formed. Comparison of the extent of reaction based on product analysis and on alkyl recovery indicates that approximately four methyl radicals are released for each molecule undergoing reaction 1.[Formula: see text]The method of least squares gives k1 = 5.0 × 1014 exp (−49 400/RT) sB1 with an estimated uncertainty of ± 1 000 cal mol−1 in E1. Under the conditions used E1 should be a reasonable measure of D[(CH3)3Pb—CH3].

scholarly journals Determination of the Activation Energy of Polar Firn by D.C. Resistivity Measurements

1967 ◽  
Vol 6 (48) ◽  
pp. 911-915 ◽  
Author(s):  
M. P. Hochstein ◽  
G. F. Risk
Keyword(s):  
Activation Energy ◽  
Resistivity Measurements ◽  
Temperature Range

The activation energy ϵe1 of polar firn samples determined by D.C. resistivity measurements is a function of temperature and density. In the temperature range −2° C. to −10° C. ϵe1 decreases with decreasing temperature reaching a nearly constant value for temperatures colder than −10°C.; in the temperature range −10°C. to −21°C. ϵe1 was found to decrease with increasing density and to lie between 0.7 eV. and 0.4 eV.

scholarly journals Determination of the Activation Energy of Polar Firn by D.C. Resistivity Measurements

1967 ◽  
Vol 6 (48) ◽  
pp. 911-915 ◽  
Author(s):  
M. P. Hochstein ◽  
G. F. Risk
Keyword(s):  
Activation Energy ◽  
Resistivity Measurements ◽  
Temperature Range

The activation energyϵe1of polar firn samples determined by D.C. resistivity measurements is a function of temperature and density. In the temperature range −2° C. to −10° C.ϵe1decreases with decreasing temperature reaching a nearly constant value for temperatures colder than −10°C.; in the temperature range −10°C. to −21°C.ϵe1was found to decrease with increasing density and to lie between 0.7 eV. and 0.4 eV.

THE KINETICS OF THE THERMAL DECOMPOSITION OF VINYL ISOPROPYL ETHER

1953 ◽  
Vol 31 (4) ◽  
pp. 418-421 ◽  
Author(s):  
Arthur T. Blades
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Free Radical ◽  
Ethyl Ether ◽  
Close Agreement ◽  
Flow System ◽  
Isopropyl Ether ◽  
Radical Decomposition ◽  
A Minor ◽  
Kinetics Of

The thermal decomposition of vinyl isopropyl ether in the presence of toluene has been studied in a flow system in the temperature range 447–521 °C. In this range, the data indicate a purely intramolecular decomposition into propylene and acetaldehyde, the activation energy for the reaction being in close agreement with that found for the decomposition of vinyl ethyl ether. At 570 °C. a minor free radical decomposition of the ether becomes apparent. Some qualitative studies of the decomposition of vinyl isobutyl ether are also reported.

The thermal decomposition of RDX at temperatures below the melting point. II. Activation energy

1970 ◽  
Vol 23 (4) ◽  
pp. 749 ◽  
Author(s):  
JJ Batten ◽  
DC Murdie
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Melting Point ◽  
Kinetic Parameter ◽  
Arrhenius Equation ◽  
Kcal Mole ◽  
Decomposition Products ◽  
Sample Geometry ◽  
Temperature Range ◽  
Definition Of

The activation energy has been determined in the temperature range 170-198�. If the sample was spread the activation energy was independent of the definition of the kinetic parameter substituted in the Arrhenius equation and was 63 kcal mole-1. In the case of the unspread samples the activation energies of the induction, acceleration, and maximum rates were 49, 43, and 62 kcal mole-1 respectively. The effect that sample geometry has on the activation energy is attributed to gaseous decomposition products influencing the reaction.

Synthesis and Determination of the Kinetic Parameters for Non-Isothermal Decomposition of Complexes Ln(thd)3phen

2006 ◽  
Vol 530-531 ◽  
pp. 506-512 ◽  
Author(s):  
Wilton Silva Lopes ◽  
Crislene Rodrigues da Silva Morais ◽  
A.G. de Souza
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Lanthanide Complexes ◽  
Reaction Order ◽  
Decomposition Reaction ◽  
Cylindrical Symmetry ◽  
Boundary Reaction ◽  
Phase Boundary Reaction ◽  
Kinetics Of

In this work the kinetics of the thermal decomposition of two ß-diketone lanthanide complexes of the general formula Ln(thd)3phen (where Ln = Nd+3 or Tm+3, thd = 2,2,6,6- tetramethyl-3,5-heptanodione and phen = 1,10-phenantroline) has been studied. The powders were characterized by several techniques. Thermal decomposition of the complexes was studied by non-isothermal thermogravimetry techniques. The kinetic model that best describes the process of the thermal decomposition of the complexes it was determined through the method proposed by Coats-Redfern. The average values the activation energy obtained were 136 and 114 kJ.mol-1 for the complexes Nd(thd)3phen and Tm(thd)3phen, respectively. The kinetic models that best described the thermal decomposition reaction the both complexes were R2. The model R2 indicating that the mechanism is controlled by phase-boundary reaction (cylindrical symmetry) and is defined by the function g(α) = 2[1-(1-a)1/2], indicating a mean reaction order. The values of activation energy suggests the following decreasing order of stability: Nd(thd)3phen > Tm(thd)3phen.

Thermoreactivity of Sol-Gel Precursor for ZnO-Based Thin Films

2006 ◽  
Vol 514-516 ◽  
pp. 73-77 ◽  
Author(s):  
Viorica Muşat ◽  
Paula M. Vilarinho ◽  
Regina da Conceição Corredeira Monteiro ◽  
Elvira Fortunato ◽  
E. Segal
Keyword(s):  
Differential Equation ◽  
Thin Films ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Organic Compounds ◽  
Sol Gel ◽  
Hexagonal Lattice ◽  
Kinetic Investigation ◽  
Temperature Range ◽  
Carbonate Hydroxide

The thermoreactivity of a zinc acetate non-alkoxide solution used for the preparation of ZnO-based thin films was investigated in the temperature range 20-600°C by TG-DTA, XRD and SEM data. We found that the formation in air of ZnO crystallites from the sol-gel precursor occurs above 150°C simultaneously with the decomposition of an intermediary compound, most probably carbonate hydroxide (sclarite and/or hydrozincite). At 200 °C, the crystalline structure is well defined in terms of ZnO hexagonal lattice parameters, although residual organic compounds and water were not yet fully removed and an amorphous phase coexists. A kinetic investigation on the thermal decomposition of sol-gel precursor from DTA data using Kissinger differential equation is also presented. Apparent activation energy values of about. 100 kJ mol-1 corresponding to the nonisothermal decomposition of solid precursors in the temperature range 170-250oC have been found.

scholarly journals Pyrolytic characteristics and kinetics of Guanzhong wheat straw and its components for high-value products

BioResources ◽  
2021 ◽  
Vol 16 (1) ◽  
pp. 1958-1979
Author(s):  
Bingtao Hu ◽  
Zhaolin Gu ◽  
Junwei Su ◽  
Zhijian Li
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Wheat Straw ◽  
Pyrolysis Products ◽  
Transportation Fuels ◽  
Temperature Range ◽  
Model Free ◽  
System A ◽  
Gas Products ◽  
Kinetics Of

Wheat straw produced annually in the Shaanxi Guanzhong region is a potential biomass feedstock for the production of transportation fuels and specialized chemicals through combustion, pyrolysis, or gasification. In this work, the pyrolytic characteristics, evolved gas products, and kinetics of Guanzhong wheat straw and its components were first investigated with a thermogravimetry-Fourier infrared spectroscopy (TG-FTIR) system. A comparative kinetic study was conducted using different model-free methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Kissinger, and the Coats-Redfern methods. The main pyrolysis products identified by FTIR include H2O, CH4, CO2, and CO as well as aromatics, acids, ketones, and aldehydes. Kinetic results showed that the pyrolytic apparent activation energy of the straw is approximately 200 kJ/mol obtained via FWO and KAS methods at the conversion range of 0.4 to 0.75, which was 30 kJ/mol higher than the value 171.1 kJ/mol obtained by the Kissinger method. The apparent activation energy of cellulose in its main pyrolysis region is 135.5 kJ/mol and is about three times larger than that of hemicellulose (49.5 kJ/mol). The apparent activation energy of lignin at the temperature range of 45 to 116 °C was 34.5 kJ/mol, while that value at the temperature range of 120 to 252 °C was 6.64 kJ/mol.

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