Radiation-induced cis-trans isomerization of solutions of 2-pentene in cyclohexane

Ingen, J. W. F. Van; Cramer, W. A.

doi:10.1021/j100700a030

Cited by 7 publications

(5 citation statements)

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“…4 Norbornadiene (Shell Chemie N.V.) was purified by distillation in a spinning band column. The following chemicals were used as obtained (with purities as stated by the suppliers).…”

Section: Methodsmentioning

confidence: 99%

“…In the course of our investigations of the gamma radiolysis of solutions of olefins in cyclohexane I - 4 we have studied solutions containing [2,2, 1Jbicycloheptadiene (norbornadiene, NBD). Like the mono-olefins studied, NBD reduces the yields of products originating from cyclohexane.…”

Section: Introductionmentioning

confidence: 99%

“…3 It is particularly applicable to triplet exciton bands. 4 Another aim of this investigation was to follow the changes in a density-of-states function with changes in pairwise interaction parameters, within the restricted Frenkel exciton theory. A large number of computa-tions have been collected (only a few shown here), providing some insight into the nature of these relationships.…”

Section: Introductionmentioning

confidence: 99%

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Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Ingen¹,

Tieghem²,

Cramer³

1970

The Journal of Chemical Physics

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Articles you may be interested inElectric field induced cubic to monoclinic phase transition in multiferroic 0.65Bi(Ni1/2Ti1/2)O3-0.35PbTiO3 solid solution Appl. Phys. Lett. 105, 162901 (2014); 10.1063/1.4899058Equations of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide Radiation-induced isomerization of norbornadiene (NBD) into quadricyclene (Q) was studied in cyclohexane solutions. From the effects of charge and radical scavengers it could be concluded that at low NBD concentrations isomerization is initiated by a reaction of NBD with electrons and probably proceeds via singlet excited NBD. Low yields of Q show that this is not an efficient process. At higher NBD concentrations the isomerization becomes more efficient, indicating that other reactions may begin to contribute. Selfquenching of NBD* also becomes important at higher concentrations. In the presence of SF s , electron transfer from NBD-to this second solute occurs. Enhanced isomerization yields are observed in the presence of benzene, toluene, and acetophenone. Scavenger studies indicate that triplet-excited states of these solutes contribute to this increase in G(isom). They are formed by charge transfer from cyclohexane positive ions to the aromatic additives followed by neutralization. Complex formation between triplet-excited aromatic molecules and NBD is suggested to be an essential step in the isomerization reaction. Relative reactivities towards cyclohexane positive ions, estimated for methanol, toluene, and benzene, are, respectively, 1.0,0.32, and 0.27. Calculated lifetimes of triplet-excited acetophenone, toluene, and benzene are between 10-6 and 10-7 sec. The excited states all react with NBD with rate constants between 5 X 10 8 and 5X10 9 M-l·sec-1 •

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“…4 Norbornadiene (Shell Chemie N.V.) was purified by distillation in a spinning band column. The following chemicals were used as obtained (with purities as stated by the suppliers).…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Ingen¹,

Tieghem²,

Cramer³

1970

The Journal of Chemical Physics

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“…On the other hand the yields of propane and butane decrease. Assuming that CH,SF,, C,H,SF,, and C2H,F result from recombination-disproportionation processes [2], [3], and [4] of SF,' with CH,' and C2H,' radicals [2] CH3' + SF,' 3 CH3SF5 P I ClH,' + SF,' + C,H5SF,…”

Section: C2h6 + Sf Sj'stenzmentioning

confidence: 99%

“…Recently, new effects caused by the presence of SF, were brought to light: ( a ) chain cis-trans isomerization of olefins (1)(2)(3)(4)(5)(6), ( b ) elimination of some highly unsaturated hydrocarbons produced in radiolysis (6)(7)(8), (c) energy transfer to SF, from excited species formed in liquid systems during radiolysis (9). The assumption was advanced that the former two effects should be attributed to SF,' radicals formed in ion neutralization processes [I] R H t + SF,-+ SF,' + products In this work we present arguments in favor of the formation of the SF,' species and its participation in radical reactions.…”

Section: Introductionmentioning

confidence: 99%

Radiolysis of Ethane + Sulfur Hexafluoride and Ethylene + Sulfur Hexafluoride Gaseous Systems. Formation of SF₅^• Radical and its Reactivity

Gawlowski¹,

Herman²

1974

Can. J. Chem.

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Can. J. Chem. 52,3631 (1974).Neutralization processes of ions in radiolysis of ethane or ethylene + sulfur hexafluoride systems lead to the formation of the SF,' radical. Con~pounds of the general formula RSF, are formed as a result of recombination reactions with hydrocarbon radicals. In the mixture ethane + 0.3% s u l f~~r hexafluoride the radiochemical yield of SF,' is GSr5, = 2.8 + 1. The presence of ammonia decreases GSr5 to ca. 0.2, suggesting that the neutralization process of NH,+(NH3),, with SF,-ions follows some unknown path. In the present work some reactions of the SF,' radical are studied. Preliminary results indicate that the presence of SF, influences very little, if at all, the yield of atonlic hydrogen.

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Literatur

Warwel

Hemmerich

Fragstein

et al. 1975

Strahlen- Und Photochemisch Initiierte Konfigurationsisomerisierung Höhermolekularer Monoolefine Mit Metallalkylen Der III. Und

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Radiation-induced cis-trans isomerization of solutions of 2-pentene in cyclohexane

Cited by 7 publications

References 1 publication

Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Radiolysis of Ethane + Sulfur Hexafluoride and Ethylene + Sulfur Hexafluoride Gaseous Systems. Formation of SF₅^• Radical and its Reactivity

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Radiation-induced cis-trans isomerization of solutions of 2-pentene in cyclohexane

Cited by 7 publications

References 1 publication

Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Radiation-Induced Isomerization of [2,2,1] Bicycloheptadiene (Norbornadiene) to [2,2,1,02,6,03,5] Quadricycloheptane (Quadricyclene) in Cyclohexane Solutions

Radiolysis of Ethane + Sulfur Hexafluoride and Ethylene + Sulfur Hexafluoride Gaseous Systems. Formation of SF5• Radical and its Reactivity

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Radiolysis of Ethane + Sulfur Hexafluoride and Ethylene + Sulfur Hexafluoride Gaseous Systems. Formation of SF₅^• Radical and its Reactivity