Reaction of photochemically generated hot hydrogen atoms with 1-butene

Gawlowski, J.; Gierczak, Tomasz; Niedzielski, Jan

doi:10.1016/0047-2670(80)80025-6

Cited by 11 publications

(3 citation statements)

References 30 publications

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“…The calculated rate constants k(E *) are higher than those previously calculated for sec-butyl radicals [13,151, which is attributable to the lower value of Eo (125.8 kJ mol-'1 used in the present work.…”

Section: Modeling Of Product Yieldscontrasting

confidence: 74%

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Production and decomposition of highly excited 2‐butyl radicals by the addition of hot hydrogen atoms to but‐2‐ene. Cross section for the addition reaction

Al-niami

Holbrook

Oldershaw

1988

Int J of Chemical Kinetics

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Highly excited 2-butyl radicals have been generated by addition of hot hydrogen atoms to but-2-ene. Atoms of initial energy 130 k J mol-' and 161 kJ mol-' were produced by photolysis of HzS. Rates of decomposition of the highly excited 2-butyl radicals were monitored by analysis of stabilization and decomposition products, and the extent of energy-loss of the hydrogen atoms in nonreactive collisions assessed by measuring the effect of added xenon on product yields. A model involving the cross-section for the addition reaction, energy transfer in nonreactive collisions between hydrogen atoms and but-2-ene, RRKM rate constants for decomposition of excited 2-butyl radicals, and collisional energy transfer from the radicals, has been used to calculate product yields for comparison with experimental values. It is concluded that the cross-section for addition of hydrogen atoms of energy about 130 kJ mol to but-2-ene is 0.055 ? 0.028 nm'. This value is compatible with the A factor for the thermal addition reaction.

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Section: Modeling Of Product Yieldscontrasting

confidence: 74%

“…An alternative procedure makes use of the intercepts of the linear plots involving only the points at higher pressure described by eq. (13). The intercept of such a plot is which approaches k 2 / k l as r = [H2Sl/[2-C4H81 becomes small.…”

Section: Kinetic Theory Calculation Of Cross-sectionmentioning

confidence: 95%

Production and decomposition of highly excited 2‐butyl radicals by the addition of hot hydrogen atoms to but‐2‐ene. Cross section for the addition reaction

Al-niami

Holbrook

Oldershaw

1988

Int J of Chemical Kinetics

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“…The curves calculated using the strong collision model and the step-ladder model at ( A E ) = 10 kcal mol-' agree very well with each other and with experiment. Small differences can be corrected easily by changes in the assumed yields for reactions (4) and (5) within the limits of 10%. The step-ladder model at (AE) = 5 kcal mol-' failed to reproduce the experimental yields for ethylene in the 1,Cpentadiene runs.…”

Section: Gierczak Gawcowski and Niedzielskimentioning

confidence: 99%

Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals

Gierczak

owski

Niedzielski

1986

Int. J. Chem. Kinet.

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Unimolecular reactions of mutual isomerization of cyclopentyl and 1‐penten‐5‐yl radicals have been investigated by chemical activation. The radicals were generated by adding energized hydrogen atoms (EH about 23 kcal mol−1) to the double bond of either cyclopentane or 1,4‐pentadiene. Based on the extensive steady‐state RRKM calculations employing the experimental data from this work as well as from the literature, the threshold energies for the cyclopentyl ring opening and closure are 32 ± 0.3 and 16.2 ± 0.3 kcal mol−1, respectively. The entropy of activation for the ring opening is close to zero.

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Addition of hot hydrogen atoms to 1‐butene in the gas phase and dissociation of excited butyl radicals

Gawlowski

Niedzielski

1981

Int J of Chemical Kinetics

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The reaction of hot hydrogen atoms originating from 253.7-and 228.8-nm photolyses of hydrogen sulfide with 1-butene was investigated. Of the hydrogen atoms undergoing addition a substantial part undergoes it in a first collision (37 and 48% a t 253.7 and 228.8 nm, respectively) yielding highly excited butyl radicals. The ratio of nonterminal to terminal addition is 0.5 and practically does not depend on the energy of the hydrogen atoms over the range of 15-33 kcal/mol. Comparing the results of 229-and 254-nm photolyses of hydrogen sulfide with those of 313-and 334-nm photolyses of hydrogen iodide with the use of the decomposition rate constants of n-butyl radicals calculated by the RRKM methods, the conclusion is reached that the hydrogen atom from H2S photodissociation has 90-95% of the available energy.

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Reaction of photochemically generated hot hydrogen atoms with 1-butene

Cited by 11 publications

References 30 publications

Production and decomposition of highly excited 2‐butyl radicals by the addition of hot hydrogen atoms to but‐2‐ene. Cross section for the addition reaction

Production and decomposition of highly excited 2‐butyl radicals by the addition of hot hydrogen atoms to but‐2‐ene. Cross section for the addition reaction

Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals

Addition of hot hydrogen atoms to 1‐butene in the gas phase and dissociation of excited butyl radicals

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