Quenching of I (<sup>2</sup>P<sub>1/2</sub>) by halogen cyanides

Badini, Raúl G.; Pasteris, L.; Argüello, Gustavo A.; Staricco, E. H.

doi:10.1002/kin.550210804

Cited by 4 publications

(5 citation statements)

References 26 publications

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“…0.89) as well as a good agreement with previous determinations [16]. A nonlinear least-squares fitting procedure was used to analyze the digitized experimental traces in order to obtain the pseudo-first-order decay rate constants at each quencher pressure.…”

Section: Kinetic Analysismentioning

confidence: 85%

“…The experimental setup of time-resolved atomic absorption is not much different from the one used previously [16]. Slight modifications introduced are briefly described.…”

Section: Methodsmentioning

confidence: 99%

“…With this approach, hydrocarbons [11,12], alkyliodides [13,14], perfluoralkyliodides [15], nitriles [16], interhalogens [1], and hydrogen halides [5], among others, have been studied and have provided information on the deactivation process, although not mechanistically detailed.…”

Section: Introductionmentioning

confidence: 99%

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Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Chiappero

Badini

Argüello

1997

Int. J. Chem. Kinet.

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I* emission. These have been extended to many systems to understand the mechanism involved in energy transfer processes. This problem has been tackled using several approaches: (a) Direct measurement of state-to-state E-v rate constants; (b) Temperature dependence of the bulk or overall quenching rate constants; (c) Isotope effects on the observed quenching rate constants; and (d) study of the quenching efficiencies of a "family" of compounds.Although the first approach is the most satisfactory and direct, only in few cases is it experimentally achievable. Few systems (HF, H 2 , and H 2 O) [5][6][7][8] have been studied directly (case a) because of the complexity added by the acceptor intramolecular energy redistribution which grows with the number of vibrational degrees of freedom. Based on the kinetic analysis of the system, state-to-state energy transfer studies are limited up to triatomic acceptor molecules. INTRODUCTIONThe study of the electronically excited iodine atom, I ( 2 P 1/2 ) (hereafter called I*) constitutes a case example of a system which can undergo electronic to vibrational-rotational energy transfer. The I* is only about 0.92 eV above the ground state and this energy excess hardly contributes to the already low reactivity of the iodine atom in gas phase. Actually, there are few systems in which reactive quenching of I* is present (i.e., interhalogens, ozone) [1 -4].Extensive studies have been carried out measuring quenching efficiencies of several compounds on the ABSTRACTThe deactivation of I( 2 P 1/2 ) by R-OH compounds (R ϭ H, C n H 2nϩ1 ) was studied using time-resolved atomic absorption at 206.2 nm. The second-order quenching rate constants determined for H 2 O, CH 3 OH, C 2 H 5 OH, n-C 3 H 7 OH, i-C 3 H 7 OH, n-C 4 H 9 OH, i-C 4 H 9 OH, s-C 4 H 9 OH, t-C 4 H 9 OH, are respectively, 2.4 Ϯ 0.3 ϫ 10 Ϫ12 , 5.5 Ϯ 0.8 ϫ 10 Ϫ12 , 8 Ϯ 1 ϫ 10 Ϫ12 , 10 Ϯ 1 ϫ 10 Ϫ12 , 10 Ϯ 1 ϫ 10 Ϫ12 , 11.1 Ϯ 0.9 ϫ 10 Ϫ12 , 9.8 Ϯ 0.9 ϫ 10 Ϫ12 , 7.1 Ϯ 0.7 ϫ 10 Ϫ12 , and 4.1 Ϯ 0.4ϫ 10 Ϫ12 cm 3 molec Ϫ1 s Ϫ1 at room temperature. It is believed that a quasi-resonant electronic to vibrational energy transfer mechanism accounts for most of the features of the quenching process. The influence of the alkyl group and its role in the total quenching rate is also discussed.

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Section: Kinetic Analysismentioning

confidence: 85%

“…The experimental setup of time-resolved atomic absorption is not much different from the one used previously [16]. Slight modifications introduced are briefly described.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Chiappero

Badini

Argüello

1997

Int. J. Chem. Kinet.

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“…The experimental set-up has been discussed elsewhere [9], so that only a brief description will be given. Excited iodine atoms were obtained from flash photolysis of CF 3 I, with…”

Section: Methodsmentioning

confidence: 99%

Deactivation of I(2P1/2) by CH3Cl, CH2Cl2, CHCl3, CCl3F, and CCl4

Chiappero

Argüello

1998

Int. J. Chem. Kinet.

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“…This combination greatly reduced the scattered light of the flash with respect to an arrangement previously used. 2 The discharge energies employed to photolyse the substrate were 50J, thus assuring a very low degree of photolysis of CF31. From the absorption curves, the I* concentration was estimated' as ca.…”

Section: Traamentioning

confidence: 99%

Quenching kinetics of I(²P_½) by cyanides. Isotope effect in the quenching by CH₃(D)CN

Badini¹,

Pasteris²,

Argüello³

et al. 1989

J. Chem. Soc., Faraday Trans. 2

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Quenching of I (²P_1/2) by halogen cyanides

Cited by 4 publications

References 26 publications

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Deactivation of I(2P1/2) by CH3Cl, CH2Cl2, CHCl3, CCl3F, and CCl4

Quenching kinetics of I(²P_½) by cyanides. Isotope effect in the quenching by CH₃(D)CN

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Quenching of I (2P1/2) by halogen cyanides

Cited by 4 publications

References 26 publications

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Quenching of I(2P�) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

Deactivation of I(2P1/2) by CH3Cl, CH2Cl2, CHCl3, CCl3F, and CCl4

Quenching kinetics of I(2P½) by cyanides. Isotope effect in the quenching by CH3(D)CN

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Quenching of I (²P_1/2) by halogen cyanides

Quenching kinetics of I(²P_½) by cyanides. Isotope effect in the quenching by CH₃(D)CN