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.

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 The Pyrolysis of Tetramethyltin

1972 ◽  
Vol 50 (1) ◽  
pp. 50-54 ◽  
Author(s):  
R. P. Johnson ◽  
S. J. W. Price
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Methyl Radicals ◽  
Product Analysis ◽  
First Order ◽  
Carrier Flow ◽  
Pressure Limit

The pyrolysis of tetramethyltin has been studied in a toluene carrier flow system from 803–941 °K using total pressures of 10.6 to 52.4 mm. Contact times varied from 0.49 to 13.8 s and the amount of decomposition from 1.35–98.7%. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed. No appreciable heterogeneous reaction was detected and the first order rates constants appear to have been determined at the high pressure limit. The quantity of undecomposed alkyl was also measured and was found to be in agreement with the product analysis if four methyl radicals are released for each molecule undergoing reaction.Least squares analysis gives[Formula: see text]with an estimated uncertainty in E of ± 1 kcal mol−1. The activation energy should be a good approximation to D[(CH3)3Sn—CH3].

The pyrolysis of trimethylarsine

1970 ◽  
Vol 48 (20) ◽  
pp. 3209-3212 ◽  
Author(s):  
S. J. W. Price ◽  
J. P. Richard
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Rate Constants ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Methyl Radicals ◽  
Product Analysis ◽  
First Order ◽  
Carrier Flow ◽  
Pressure Limit

The pyrolysis of trimethylarsine has been studied in a toluene carrier flow system from 764 to 858 °K using total pressures from 6.35 to 35.5 mm. Contact times varied from 0.9 to 3.7 s and the amount of decomposition, from 1.2 to 73 %. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed. No heterogeneous reaction was detected and the first order rate constants appear to have been determined at approximately the high pressure limit. In seven runs the undecomposed alkyl was also measured. The quantity found was in agreement with the product analysis if three methyl radicals are released for each molecule undergoing reaction.Least squares analysis of the results gives[Formula: see text]The activation energy should be a good approximation to D[(CH3)2As—CH3]. The product analysis and the values of k4/k51/2 are consistent with the simple consecutive release of three methyl radicals but thermodynamic and kinetic considerations may preclude this possibility.

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

The Pyrolysis of Trimethylthallium and Evaluation of D[(CH3)2Tl—CH3]

1973 ◽  
Vol 51 (9) ◽  
pp. 1397-1401 ◽  
Author(s):  
S. J. Price ◽  
J. P. Richard ◽  
R. C. Rumfeldt ◽  
M. G. Jacko
Keyword(s):  
Contact Time ◽  
Total Pressure ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Product Analysis ◽  
Carrier Flow

The pyrolysis of trimethylthallium has been studied in a mercury free toluene carrier flow system (452–536 °K, total pressure 6.7–39.3 mm, contact time 0.9–5.1 s, 5.4–90.2% decomposition). In a vessel cleaned with boiling concentrated HNO3 and coated by decomposing 0.1 g Tl(CH3)3 no heterogeneous reaction could be detected. The extent of reaction measured by product analysis (CH4, C2H6, C6H5C2H5) assuming three CH3 per Tl(CH3)3 undergoing reaction 1

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].

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.

scholarly journals An air carrier flow system for the spectrophotometric determination of water in biodiesel exploiting bleaching of the cobalt chloride complex

Talanta ◽  
2015 ◽  
Vol 131 ◽  
pp. 21-25 ◽  
Author(s):  
Andréia C. Pereira ◽  
Boaventura F. Reis ◽  
Fábio R.P. Rocha
Keyword(s):  
Spectrophotometric Determination ◽  
Cobalt Chloride ◽  
Flow System ◽  
Chloride Complex ◽  
Carrier Flow ◽  
Air Carrier

THE REACTION OF METHYL RADICALS WITH FORMALDEHYDE

1959 ◽  
Vol 37 (4) ◽  
pp. 672-678 ◽  
Author(s):  
S. Toby ◽  
K. O. Kutschke
Keyword(s):  
Activation Energy ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Formyl Radical ◽  
Temperature Range ◽  
Abstraction Reaction

Azomethane was photolyzed in the presence of up to 30 mole per cent formaldehyde and formaldehyde-d2 at temperatures from 80 °C to 180 °C. The value of the activation energy for the abstraction reaction with methyl radicals was found to be 6.2 kcal mole−1 for CH2O and 7.9 kcal mole−1 for CD2O. The results indicated that the formyl radical was stable over the temperature range studied.

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