Temperature Dependence of Disproportionation–Combination Ratios for Alkyl Radicals in Liquid Methane

1971 ◽  
Vol 49 (17) ◽  
pp. 2861-2867 ◽  
Author(s):  
Hugh A. Gillis
Keyword(s):  
Activation Energy ◽  
Temperature Dependence ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Transition States ◽  
Alkyl Radicals ◽  
Liquid Methane ◽  
Ethyl Radicals

The ratios of rate constants for disproportionation to combination have been measured for ethyl radicals and for i-propyl radicals in liquid methane between −181 and −94 °C. The radicals were generated by γ-radiolysis of dilute methane solutions of ethylene-d4 or propylene-d6. The activation energy for combination was found to exceed that for disproportionation by 290 ± 30 cal mol−1 for ethyl radicals and by 255 ± 25 cal mol−1 for i-propyl radicals. In both cases the disproportionation—combination ratio in the liquid, extrapolated to room temperature, is greater than that in the gas phase by a factor of about 2.5. These results are interpreted as indicating that disproportionation and combination reactions proceed by way of different transition states.

Kinetics and Temperature Dependence of the Hydration of NO+ in the Gas Phase

1973 ◽  
Vol 51 (3) ◽  
pp. 456-461 ◽  
Author(s):  
Margaret A. French ◽  
L. P. Hills ◽  
P. Kebarle
Keyword(s):  
Temperature Dependence ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Transfer Reaction ◽  
Negative Temperature ◽  
Ion Source ◽  
Third Order ◽  
The Third ◽  
Kinetics Of

The kinetics of the atmospherically important hydration sequence: NO+(H2O)n−1 + H2O = NO+(H2O)n and the transfer reaction NO+(H2O)n + H2O = HNO2 + H+(H2O)n were examined in nitrogen containing small quantities of NO and H2O with a pulsed high pressure ion source mass spectrometer. The room temperature mechanism and rate constants were found to be in agreement with earlier work in other laboratories. The temperature dependence of the reaction was examined for the range 27–157 °C. The transfer reaction does not occur at higher temperatures so that the NO+ hydration equilibria for n = 1 and 2 could be measured leading to ΔH1,0 = 18.5 and ΔH2,1 = 16.1 kcal/mol. The third order forward clustering rate constants were found to have negative temperature coefficients.

Cope Rearrangement in Bicyclo[5.1.0]octa-2,5-diene and its Mono- and Di-Hetero Analogues: A DFT Study

2017 ◽  
Vol 70 (6) ◽  
pp. 683
Author(s):  
Priya Yadav ◽  
Shilpa Yadav ◽  
Asha Gurjar ◽  
Raj K. Bansal
Keyword(s):  
Activation Energy ◽  
Gas Phase ◽  
Density Functional ◽  
Room Temperature ◽  
Transition States ◽  
Cope Rearrangement ◽  
Functional Theory ◽  
Concerted Mechanism ◽  
Free Activation Energy ◽  
Cope Rearrangements

The Cope rearrangements of bicyclo[5.1.0]octa-2,5-diene and its 4-hetero-(aza/oxa/phospha) and 4,8-dihetero analogues were investigated using density functional theory at the B3LYP/6–31+G* level in gas phase. The rearrangements of bicyclo[5.1.0]octa-2,5-diene and its symmetrical 4,8-dihetero analogues followed a concerted mechanism involving synchronous transition states. In other cases, although a concerted mechanism was observed, asynchronous transition states were involved. In the case of bicyclo[5.1.0]octa-2,5-diene, a degenerate Cope rearrangement was expected to occur at room temperature (25°C) due to a low free activation energy (ΔG‡ = 14.46 kcal mol–1). However, under similar conditions, the rearrangement of 4,8-dioxabicyclo[5.1.0]octa-2,5-diene was much slower (ΔG‡ = 23.85 kcal mol–1) and the 4,8-diaza- and diphospha analogues did not undergo Cope rearrangement. The Cope rearrangements of 4-phospha-, 8-aza-, 8-aza-4-oxa-, 8-aza-4-phospha-, and 8-oxa-4-phospha-bicyclo[5.1.0]octa-2,5-dienes were exergonic and were expected to occur spontaneously to form the corresponding products. In contrast, rearrangement of 8-oxabicyclo[5.1.0]octa-2,5-diene, though exergonic, was accompanied by a decrease in entropy, due to which Cope rearrangement would occur much more slowly and a mixture of both valence isomers would be formed. The Cope rearrangements of 4-aza-, 4-oxa-, 4-aza-8-oxa-, 8-phospha-, 4-aza-8-phospha-, 4-oxa-8-phospha-, and 4,8-diphospha-bicyclo[5.1.0]octa-2,5-dienes were endergonic; consequently either no Cope rearrangement would take place or it would occur sluggishly.

An experimental study of the reactivity of the hydroxide anion in the gas phase at room temperature, and its perturbation by hydration

1981 ◽  
Vol 59 (11) ◽  
pp. 1615-1621 ◽  
Author(s):  
Scott D. Tanner ◽  
Gervase I. Mackay ◽  
Diethard K. Bohme
Keyword(s):  
Experimental Study ◽  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Gas Phase Reactions ◽  
Flowing Afterglow ◽  
Hydroxide Anion

Flowing afterglow measurements are reported which provide rate constants and product identifications at 298 ± 2 K for the gas-phase reactions of OH− with CH3OH, C2H5OH, CH3OCH3, CH2O, CH3CHO, CH3COCH3, CH2CO, HCOOH, HCOOCH3, CH2=C=CH2, CH3—C≡CH, and C6H5CH3. The main channels observed were proton transfer and solvation of the OH−. Hydration with one molecule of H2O was observed either to reduce the rate slightly and lead to products which are the hydrated analogues of the "nude" reaction, or to stop the reaction completely, k ≤ 10−12 cm3 molecule−1 s−1. The reaction of OH−•H2O with CH3—C≡CH showed an uncertain intermediate behaviour.

COMBINATION AND DISPROPORTIONATION OF ETHYL RADICALS: INFLUENCE OF THE REACTION H+C2H5 = C2H6

1955 ◽  
Vol 33 (5) ◽  
pp. 821-829 ◽  
Author(s):  
Moyra J. Smith ◽  
Patricia M. Beatty ◽  
J. A. Pinder ◽  
D. J. Le Roy
Keyword(s):  
Light Intensity ◽  
Excellent Agreement ◽  
Mercury Concentration ◽  
Rate Constants ◽  
Room Temperature ◽  
Low Light ◽  
Ethylene Concentration ◽  
Light Intensities ◽  
Ethyl Radicals ◽  
Hydrogenation Of Ethylene

The mercury (3P1) photosensitized hydrogenation of ethylene has been studied at room temperature as a function of ethylene concentration, mercury concentration, and light intensity. In addition to combination and disproportionation, ethyl radicals have been shown to take part in the reaction[Formula: see text]The conditions favoring this reaction have been established and anomalous values previously found for the ratio of ethane to butane have been explained. The value obtained for the ratio of the rate constants for the disproportionation and combination of ethyl radicals, 0.15 ±.01, is in excellent agreement with the values obtained by other methods. Hexane formation is of some importance at low light intensities and high ethylene concentrations, and is adequately accounted for by the reactions[Formula: see text]

Untersuchungen mit Hilfe der Elektronenzyklotronresonanz-(ECR)-Technik XVI .Wechselwirkung von HNO3 und CINO3 mit niederenergetischen Elektronen in der Gasphase / Studies by the Electron Cyclotron Resonance-(ECR)-Technique. XVI. Interactions of Thermal- Energy Electrons with the Molecules HNO3 and CINO3

1984 ◽  
Vol 39 (6) ◽  
pp. 542-547 ◽  
Author(s):  
D. Wecker ◽  
R. N. Schindler
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Electron Capture ◽  
Thermal Energy ◽  
Rate Constants ◽  
Cyclotron Resonance ◽  
Room Temperature ◽  
Electron Cyclotron Resonance ◽  
Free Electrons ◽  
Strong Similarity

Using the ECR-technique the capture of thermal-energy free electrons was investigated by the molecules HNO3 and ClNO3. The following rate constants at room temperature were obtained: k(HNO3) =(1.4 ±0.7)· 10-8 cm3 sec-1 ;k (ClNO3) = (3.9 ± 1.2)· 10-9 cm3 sec-1 .An apparent activation energy of AE = (1.6 ± 0.5) kcal · mol-1 was found for the reaction with ClNO3. From the energy dependences of the both reactions together with thermodynamic considerations it is suggested that electron capture by ClNO3 occurs via dissociative attachment whereas with HNO3 a negative parent ion can be formed. Strong similarity is pointed out to exist between HONO2 and ClONO2 towards capture of electrons and the reaction with O2- respectively.

Studies in solvolysis. Part VIII. An entropy correlation related to the reaction of various nucleophiles with malachite green

1977 ◽  
Vol 55 (4) ◽  
pp. 686-692 ◽  
Author(s):  
Stephen Harvey Morris ◽  
John Marshall William Scott ◽  
Frederick Steele
Keyword(s):  
Temperature Dependence ◽  
Malachite Green ◽  
Methyl Iodide ◽  
Rate Constants ◽  
Transition States ◽  
Reaction Coordinate ◽  
Similar Correlation ◽  
Displacement Reactions

The entropies of activation related to the reactions of aqueous malachite green with the nucleophiles water, hydroxide, hydrazine, ammonia, hypochlorite, and sulphite have been calculated from the temperature dependence of the rate constants appropriate to these reactions. The entropies of the transition states for these reactions have been characterized and the transition states shown to be 'reactant like'. A similar correlation, based on data for a series of nucleophiles attacking methyl iodide, suggests that the transition states for the SN2 displacement reactions are also 'reactant like' with respect to the attacking nucleophile. A relationship between two distinct parameters each of which is related to the position of transition states along the reaction coordinate is considered.

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