The stability of hydrogen atoms in irradiated aqueous solutions

Ultee, C. J.; Kepford, C. R.

doi:10.1016/0009-2614(69)80247-2

Cited by 2 publications

(1 citation statement)

References 11 publications

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“…Ultraviolet illumination of ferrous ions iil 6 !MII,SO, at 77 K results in the formation of trapped hydrogen atoms, H, hv (254 nm) + Fe (11) + H + -t H, + Fe (111) When the sample is warmed to -100 K, the 506 G e.s.r. d o~~b l e t characteristic of H, decreases in intensity (9). When the sample contains an organic solute, the decrease in the H, signal is generally accompanied by a concornitant increase in a g -2 free radical signal.…”

Section: Methodsmentioning

confidence: 97%

Electron Spin Resonance Studies of Aliphatic Ammonium Ion Radicals in Aqueous Sulfuric Acid Glasses

Falle¹,

Sargent²

1974

Can. J. Chem.

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The reaction of hydrogen atoms with n-butylammonium ions in 6 M sulfuric acid glasses yields a characteristic eight-line e.s.r. spectrum, which is attributable to CH3ĊHCH2CH2NH3+. Evidence is drawn from computer simulated spectra and from the spectra of other alkylammonium radicals to account for this spectrum. Qualitative agreement between the simulated and experimental spectra is achieved by assuming that the CH3ĊHCH2— moiety can adopt a range of conformations and can also undergo torsional motion about the sp2 carbon – methylene carbon bond. The site of hydrogen abstraction from alkylammonium ions is evidently influenced by both NH3+ and CH3 groups; abstraction tends to occur away from the former and adjacent to the latter.

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Section: Methodsmentioning

confidence: 97%

Electron Spin Resonance Studies of Aliphatic Ammonium Ion Radicals in Aqueous Sulfuric Acid Glasses

Falle¹,

Sargent²

1974

Can. J. Chem.

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ESR Study of the Behavior of H Atoms Trapped in Frozen Perchloric Acid Solutions

Ultee¹

1970

The Journal of Chemical Physics

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Aqueous solutions of perchloric acid were irradiated at 77°K with Co-60 γ rays and then examined by ESR spectroscopy. The H atoms formed in these systems are stable at 77°K and decay only on warming the samples. The kinetics of the H-atom decay were examined in detail for 0.13 mole fraction HClO4 solutions over the temperature range 100–130°K. There are two types of trapped H atoms, both of which decay with first-order kinetics. The least stable type has a decay rate constant given by k = 1.84 × 103exp(− 3.24 × 103 / RT) sec−1 and the second-type decays with a rate constant given by k = 9.43 × 1010exp(− 8.02 × 103 / RT) sec−1. The first-order decays are interpreted as resulting from a mechanism which has an activated release of H atoms from their traps as the rate-determining step. The resulting mobile or free H atoms then react rapidly with other radicals to complete the reaction. Based on this mechanism, the trapping energies for the two types of sites are 3.24 and 8.02 kcal/g atom, respectively.

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The stability of hydrogen atoms in irradiated aqueous solutions

Cited by 2 publications

References 11 publications

Electron Spin Resonance Studies of Aliphatic Ammonium Ion Radicals in Aqueous Sulfuric Acid Glasses

Electron Spin Resonance Studies of Aliphatic Ammonium Ion Radicals in Aqueous Sulfuric Acid Glasses

ESR Study of the Behavior of H Atoms Trapped in Frozen Perchloric Acid Solutions

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