Pulse radiolysis of solutions of tertiary aromatic amines in benzene

Kemp, Terence J.; Roberts, J. P.; Salmon, G. Arthur; Thompson, G. F.

doi:10.1021/j100868a045

Cited by 11 publications

(2 citation statements)

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“…It is well established that amines quench excited states of arenes, the product being an excited complex or exiplex in nonpolar media and ions in polar media (eq 11). The system A* + amine -*• A' + amine+ (11) pyrene/dimethylaniline has been studied in micellar systems,131 the products being pyrene anion, P~, and dimethylaniline cation, D+. The products are formed rapidly within the laser pulse in all micelles while the lifetime of the ions is very long (> 1 ms) in cationic micelles and is short (<1 jis) in homogeneous solution, as no barrier exists to neutralization of the ions.…”

Section: G Charge-transfer Reactionsmentioning

confidence: 99%

Radiation-induced reactions in organized assemblies

Thomas¹

1980

Chem. Rev.

374

156

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Section: G Charge-transfer Reactionsmentioning

confidence: 99%

Radiation-induced reactions in organized assemblies

Thomas¹

1980

Chem. Rev.

374

156

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“…In certain cases, absorption spectra of amine triplet states have been shown to be similar to those of the corresponding radical cations. 23 The weak absorption present at the end of the pulse may well be due to the amine triplet state, as small concentrations of solute triplet states are known to be formed upon radiolysis of acetonitrile.8 a For absorptions growing-in after the pulse, the formation and decay reactions were treated as separable processes. With the TPA absorption at 6 7 0 ~1 , the formation and decay processes occurred on similar time-scales, so there may be some error ; b variation in this rate constant with concentration may result from concurrent grow-in of TPA*+ absorption in this region ; C complex kinetics ; dat 1.99 x rnol dm-3 TPA ; e initial first-order component, kl 6.7 x lo5 s-I, followed by slow decay ; fsecond-order only to 50 % reaction.…”

Section: A P P a R A T U S A N D Proceduresmentioning

confidence: 99%

Solute ion and radical formation in the pulse radiolysis of acetonitrile solutions

Baptista¹

1974

J. Chem. Soc., Faraday Trans. 1

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Following microsecond pulse radiolysis of solutions of a variety of solutes in acetonitrile, absorptions assigned to solute cation radicals, anion radicals, excited states and neutral radicals are observed. Pulse radiolysis of solutions of tri-p-tolylamine or triphenylamine yields the amine radical cations, whose absorptions are observed to grow-in by a second-order process after the electron pulse. We report rate constants for this process, which is suggested to be electron transfer to acetonitrile radical cation or cation dimer. Yields of G 4 . 2 are reported for the oxidizing species. Oxidation via a different route involving hydrogen atom transfer is suggested to occur following pulse radiolysis of solutions of phenol or phenothiazine. Pulse radiolysis of solutions of benzophenone or biphenyl yields the solute radical anions in agreement with previous studies on this system. The mechanism of acetonitrile radiolysis is discussed with a consideration of this and previous studies.Because of its high dielectric constant, and low proton-donating ability, acetonitrile provides a convenient solvent for a wide variety of chemical studies.l A number of studies on the products of radiolysis of acetonitrile have been carried out.2-6 The main products from radiolysis of the pure liquid with either electrons or y-rays are hydrogen, methane, succinonitrile, propionitrile and a short-chain polymer. Experiments with acetonitrile solutions of ferric ~h l o r i d e , ~-~ i ~d i n e , ~ 9 RESULTS T R I -p -T OL Y LAMI N E (Me,TPA)Pulse radiolysis of argon saturated solutions of Me3TPA (5 x 10-4-10-3 mol dm-3) in acetonitrile yielded an absorption, A, , , 670 nm, which grew-in after the electron pulse on a time scale of a few microseconds (fig. 1). There was a weak absorption (ca. 15 % maximum optical density) in the same region at the end of the pulse. The build-up followed good pseudo-first-order kinetics to greater than three half-lives. However, the rate varied with the Me,TPA concentration, indicating an overall second-order rate law for the grow-in.

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The photochemistry of 3-heteroatom substituted 1,4-dienes

Leone

Mariano

1981

Res Chem Intermed

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Pulse radiolysis of solutions of tertiary aromatic amines in benzene

Cited by 11 publications

References 0 publications

Radiation-induced reactions in organized assemblies

Radiation-induced reactions in organized assemblies

Solute ion and radical formation in the pulse radiolysis of acetonitrile solutions

The photochemistry of 3-heteroatom substituted 1,4-dienes

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