Radiolysis of Hydrocarbon Mixtures

Manion, J. P.; Burton, Milton

doi:10.1021/j150497a005

Cited by 222 publications

(75 citation statements)

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“…If the mechanism of the "unimolecular" yield is where C61112* represents an excited intermediate state, then the reduction of the yield can only be due to quenching of the C6H12* by the biphenyl. This is an example of the energy-transfer process postulated by Manion and Burton (2).…”

Section: Discussionmentioning

confidence: 67%

RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂

Dyne¹,

Jenkinson²

1960

Can. J. Chem.

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The yield of Dz formed by a unimolec~~lar process in the y-ray irradiation of cyclohexane-dl? has been deduced from the isotopic composition of hydrogen evolved from C G H~~-C~D~~ mixtures. A value of 0.25 molecule/100 ev is found for this molecular" yield. This y~e l d is only slightly reduced by iodine but is considerably reduced in the presence of biphenyl.is the principal gaseous product formed in the fast-electron irradiation of cyclohexane, its initial yield being 5.5-5.8 molecules/100 ev. This yield is quite sharply reduced by snlall additions of solutes. Solutions containing -5 X moles/liter iodine, for instance, haveG(1-I?) , -4.0 (1); solutions of cyclohexane with benzene (1, 2), biphenyl, and terphenyls (3,4) show a similar behavior. From a study of curves of G(I-12) vs. iodine concentration, Burton et al. ( I ) conclude t h a t hydrogen is produced by two mechanisms each with a yield of 2 to 3 molecules/100 ev, one of which is lllore rapidly suppressed by iodine than the other. Studies of G(1-12) in biphenyl solutions lead to a similar conclusioll (3,4).The two mechanisms could be (a) a binlolecular mechanism involving hydrogen-atom abstraction from the parent lllolecule and (b) a unilnolecular mechanism in which ~nolec-ular hydrogen is split off in one step from an excited parent molecule. These two types of ~nechanisrns are sometimes referred to as "radical and molecular" or "intermolecular and intramolecular".The existence of two such processes has been demonstrated by Dewhurst (5) in the radiolytic decomposition of 72-hexane. high probability of "molecular" processes in organic lnolecules is shown by Dorflllan's work on the gas-phase radiolysis of ethane (6) where it was shown that 66% of the molecular hydrogen is formed by a molecular detachment process not involving free hydrogen atoms.By exan~ining the variation of the D ? yield in C G D I~-C G H~? mixtures we have determined the value of the 'uni~nolecular' yield of D2 from CGDls Its value is low, G(D2) (unimolecular) being 0.25 n~olecule/lOO ev.

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Section: Discussionmentioning

confidence: 67%

RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂

Dyne¹,

Jenkinson²

1960

Can. J. Chem.

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“…The amount of iodinated paint solvents decreases with the aging time and aging conditions (Tietze et al, 2013C). While the formation of volatile organic iodides from the aromatic paint resin requires high temperatures or high radiation doses (Manion and Burton, 1952) it is more likely that the more mobile paint solvents interact with iodine to form volatile organic iodides (Tietze, 2012;Tietze et al, 2013C).…”

Section: Organic Iodide Production From Irradiated Mixtures Of Paint mentioning

confidence: 99%

Iodine–paint interactions during nuclear reactor severe accidents

Bosland

Dickinson

Glowa

et al. 2014

Annals of Nuclear Energy

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“…I t is reasonable to expect that either of the reactions G and 7 might occur, depending on the relative heights of the energy levels involved (2,9). T h e energies of tile lowest excited states and the ionization potentials of c~~clohexanone and benzene are shown in Table IV.…”

Section: (I) Belszc~ze Solz~tionsmentioning

confidence: 99%

Radiolysis of Cyclohexanone: Ii. Effect of Solutes on Products Involving C—h Bond Rupture

Singh¹,

Freeman²

1964

Can. J. Chem.

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Some of the products \\.hose fornl,ation, during the racliolysis of c)~clohesanone, in\.ol\-es the rupture of C-1-1 boncls arc hydrogen, cyclohexanol, 2,2'-dil~etoclicyclohes.1, and probabl>-other "dimers" of cyclohesanone.Benzene appears to inhibit the formation of hydrogen mainly by an activation transfer process. The influence of 2,3-dimethyl-1,3-b~1tadiene (DMB) on the hydrogen yield is liiore comples ant1 probably involves more than one inhibition reaction.Less than one mole percent of Dh4B or of oxygen inhibits the formation of cyclohesaiiol nncl of clirners to below their limits of detection on the analytical system (G < 0.2). This is probably due to the scavenging of free radicals (G(scavengeab1e radicals) = 4). Benzene is i u~~c h less efficient than DMB or oxygen in inhibiti~~g the formation of cyclohesanol and of climcrs of cyclohesanone.

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Radiolysis of Hydrocarbon Mixtures

Cited by 222 publications

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RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂

RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂

Iodine–paint interactions during nuclear reactor severe accidents

Radiolysis of Cyclohexanone: Ii. Effect of Solutes on Products Involving C—h Bond Rupture

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Radiolysis of Hydrocarbon Mixtures

Cited by 222 publications

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RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C6D12 AND C6H12

RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C6D12 AND C6H12

Iodine–paint interactions during nuclear reactor severe accidents

Radiolysis of Cyclohexanone: Ii. Effect of Solutes on Products Involving C—h Bond Rupture

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RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂

RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C₆D₁₂ AND C₆H₁₂