Gas phase photoreaction of SO2 with n-pentane in the presence of NO

Makarov, Vladimir I.; Skubnevskaya, G. I.; Bazhin, N. M.

doi:10.1007/bf02068927

Cited by 8 publications

(7 citation statements)

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“…Hydrogen Abstraction Versus SO 2 Insertion. We tested the two reactive pathways that had been previously suggested in the literature, 30,32,34 with our computational approach. Both the hydrogen abstraction mechanism and a possible 3 SO 2 insertion mechanism, where insertion is followed by HOSO elimination, were investigated.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Dainton and Ivin first observed the reaction of 3 SO 2 with alkanes to form sulfinic acid . Subsequently, a number of follow-up studies attempted to characterize the reaction of 3 SO 2 with both alkanes and alkenes. ,− In general, it was found that 3 SO 2 adds across the double bond in alkenes. The intermediate molecule then either intramolecularly abstracts a hydrogen, forming sulfinic acid, or it decomposes back to the two reactant species, resulting in the quenching of 3 SO 2 and potential isomerization of the alkene. ,− The reaction of 3 SO 2 with alkanes was found to likely follow a different mechanism, proceeding through a hydrogen abstraction step from the hydrocarbon (RH) to form HOSO• and R• radicals, followed by subsequent reaction to form the sulfinic acid. , …”

Section: Introductionmentioning

confidence: 99%

“…33,38−41 The reaction of 3 SO 2 with alkanes was found to likely follow a different mechanism, proceeding through a hydrogen abstraction step from the hydrocarbon (RH) to form HOSO• and R• radicals, followed by subsequent reaction to form the sulfinic acid. 32,34 While these initial studies were able to describe the likely mechanism for the reaction of 3 SO 2 with alkanes, they were not able to provide absolute rate constants for the reaction. Badcock et al 34 and Sidebottom et al 11 were able to directly measure the quenching of 3 SO 2 by several alkanes (methane, ethane, propane, butane, and isobutane) by monitoring the decay of phosphorescence intensity from 3 SO 2 , which was directly excited to the triplet state using a 382.88 nm laser pulse.…”

Section: ■ Introductionmentioning

confidence: 99%

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Reactivity of Electronically Excited SO₂ with Alkanes

Kroll¹,

Frandsen

Rapf³

et al. 2018

J. Phys. Chem. A

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We studied the reaction of electronically excited sulfur dioxide in the triplet state (SO) with a variety of alkane species, including propane, n-butane, isobutane, n-pentane, n-hexane, cyclohexane, n-octane, and n-nonane. Reaction rate constants for the photoinitiated reaction of SO with all of these species were determined and found to be in the range from 3.7 × 10 to 5.1 × 10 cmmolecules. We found that reaction proceeds via a hydrogen abstraction to form HOSO• and organic radical (R•) species and that reactivity is correlated with the energy required to break a C-H bond and the length of the alkane chain. Abstraction rates were found to be fastest for reaction with hydrogen on a tertiary carbon. Similarly, abstraction from secondary carbons is found to be faster than from primary carbons. The reactivity of SO with alkanes increases with chain length as additional secondary carbons are added.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reactivity of Electronically Excited SO₂ with Alkanes

Kroll¹,

Frandsen

Rapf³

et al. 2018

J. Phys. Chem. A

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“…FromEq. (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14) we can see that unless Wn(P) is a constant (i.e., independent of p), the evolution of p,,(t) always exhibits a non-exponential decay. In the short-time region In the time range where P<'¥s1 and p<y•., we find .…”

Section: Theorymentioning

confidence: 99%

“…1997 205 W,'"(p) =2Jv,.P(p p + ri m 2 + y",,) + 0),,,,(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17) andrespectively. Notice that the inverse transform of Eq (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14). is given by W,.. (o)::: 2lv.,i:y; y,", 2…”

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confidence: 99%

Effect of A Magnetic Field on Photophysical Processes of Molecules

Lin

Hayashi

Kono

et al. 1997

J Chinese Chemical Soc

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A main purpose of this paper is to present a density matrix treatment of the magnetic quenching of molecular luminescence. Unlike the previous theories, which only consider the magnetic effect on the nonradiative rate constant, the present theory describes the time-evolution of the system under the action of a magnetic field. Our theory can treat both the steady state and transient molecular luminescence affected by a magnetic field. 203 INTRODUCfIONMagnetic quenching of molecule fluorescence in the gas phase was lust observed for CS 2 by Matsuzaki and Nagakura.' Since this work, similar magnetic effects have been observed for a number of molecules such as S02, 2 formaldehyde.I" glyoxal'" pyrazine,"!' pyrimidine,12.13 and striazine. 14) To interpret the magnetic effect on radlationless transitions of molecules, some theoretical investigations have been reported.":" The magnetic field effect on fluorescence in isolated molecules has recently been reviewed by Ohla.'s Magnetic quenching of fluorescence implies that the nonradiative decay in the singlet excited state is accelerated by a magnetic field. This magnetic field acceleration of nonradiativc decay arises from a field-induced change in level mixing between the initially prepared level and the dark manifold of the neighboring levels by the Zeeman interaction. Two mechanisms have been proposed. According to the direct mechanism, which originates from non-diagonal matrix elements of the Zeeman term between singlet states, the internal conversion is accelerated by the field-induceddirect coupling between the two different electronic states. According to the indirect mechansim, which arises from non-diagonal matrix elements of the Zeeman term among the spin sublevels in a triplet state, the intersystem crossing rate from the prepared singlet level to the triplet manifold is increased by such a coupling.In this paper, we apply the density matrix method to study the dynamics of the system in the presence of a magnetic field. We shall carefully examine the nature of the short-time decay and the long-time decay. Our theoretical treatment takes into account both direct and indirect mechanisms of magnetic quenching; it can also treat both the steady state and transient molecular luminescence affected by a magnetic field. We shall also study the effect of a magnetic field on single-rovibronic-level rate constants of radiationless transitions. THEORYThe time-resolved properties of a molecular system are best described in a zeroth-order representation essentially determined by experimental excitation and detection conditions." One thus introduces a model where a clear distinction is made between the optically bright states which can be initially prepared by impulsive excitation and tl\e reo maining dark states. These states are not cigenstates of the true molecular Hamiltonian Ii and are mixed by the intramolecular interaction tr and the Zeeman interaction fr z (if an external magnetic field exists). The resulting excitation energy exchanges between the bright and dark man...

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Studies of the photochemical reactions of sulfur dioxide with pentane in the presence of nitrogen oxide

Makarov

Skubnevskaya

Bazhin

1981

Int J of Chemical Kinetics

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The spectrum of the intermediate product ascribed to nitrosopentane has been detected in the photolysis of the SO*-pentane (RH)-NO mixture. This result has been interpreted in terms of the radical mechanism by assuming the H-atom abstraction from RH by the excited SO2 molecules to be the primary act. The contribution of the singlet and triplet SO2 states to the product formation rate and the ratio of the singlet-to-triplet rate constants have been evaluated. At NO pressures above 5 tom, the product formation rate significantly deviates from the Stern-Volmer dependence.

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Gas phase photoreaction of SO2 with n-pentane in the presence of NO

Cited by 8 publications

References 2 publications

Reactivity of Electronically Excited SO₂ with Alkanes

Reactivity of Electronically Excited SO₂ with Alkanes

Effect of A Magnetic Field on Photophysical Processes of Molecules

Studies of the photochemical reactions of sulfur dioxide with pentane in the presence of nitrogen oxide

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Gas phase photoreaction of SO2 with n-pentane in the presence of NO

Cited by 8 publications

References 2 publications

Reactivity of Electronically Excited SO2 with Alkanes

Reactivity of Electronically Excited SO2 with Alkanes

Effect of A Magnetic Field on Photophysical Processes of Molecules

Studies of the photochemical reactions of sulfur dioxide with pentane in the presence of nitrogen oxide

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Product

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Reactivity of Electronically Excited SO₂ with Alkanes

Reactivity of Electronically Excited SO₂ with Alkanes