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Different mechanisms both lead to the production of the naphthalene–OH adduct in the 355 nm and 266 nm laser flash photolysis of the mixed aqueous solution of naphthalene and nitrous acid

Paper ID Volume ID Publish Year Pages File Format Full-Text
28553 44080 2006 9 PDF Available
Title
Different mechanisms both lead to the production of the naphthalene–OH adduct in the 355 nm and 266 nm laser flash photolysis of the mixed aqueous solution of naphthalene and nitrous acid
Abstract

The 355 nm and 266 nm nanosecond laser flash photolysis of the mixed aqueous solution of naphthalene (Np) and nitrous acid (HNO2) were performed to investigate the photo-initiated microscopic reactions in this binary component system. Following the 355 nm laser flash, HNO2 was readily photolyzed to NO and OH, and the latter fragment added to the Np ring to form the Np–OH adduct at the rate constant of (1.1 ± 0.1) × 1010 M−1 s−1. Following the 266 nm laser flash, Np was populated first to its lowest excited singlet state (S1) and then to its lowest excited triplet state (T1) via intersystem crossing. Np(S1) and Np(T1) both formed the [Np···HNO2]* exciplex with HNO2, and the fast dissociation of this exciplex again produced the Np–OH adduct. The second-order quenching rate constants of Np(S1) and Np(T1) by HNO2 were measured to be (6.0 ± 0.2) × 109 M−1 s−1 and (4.8 ± 0.2) × 109 M−1 s−1, respectively. It was very interesting to conclude that although both the 355 nm and the 266 nm irradiation of the mixed aqueous solution of Np and HNO2 produced the Np–OH adduct, the mechanisms leading to this species varied essentially for the two cases. This work suggested an unexpected way of releasing OH by HNO2 other than its direct photolysis, namely via forming exciplex with the excited Np (and possibly other polycyclic aromatic hydrocarbons, PAHs) in the environment.

Keywords
Nitrous acid; Naphthalene; Naphthalene–OH adduct; Laser flash photolysis; Exciplex
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Different mechanisms both lead to the production of the naphthalene–OH adduct in the 355 nm and 266 nm laser flash photolysis of the mixed aqueous solution of naphthalene and nitrous acid
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 181, Issues 2–3, 31 July 2006, Pages 348–356
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us