TITLE

Proposed reaction mechanisms for selenium UV photolysis vapor generation by computational methods

AUTHOR(S)
Takatani, Tait; Fitzgerald, Neil; Galbraith, John Morrison
PUB. DATE
June 2007
SOURCE
Analytical & Bioanalytical Chemistry;Jun2007, Vol. 388 Issue 4, p859
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The production of volatile analyte species by UV photolysis in the presence of low-molecular-weight organic acids as an alternative to chemical vapor generation has been of recent interest. The mechanism of this process is not well understood. Proposed mechanisms often involve photolytic cleavage of the organic acid as the initial step. Evidence suggests that this may not be the dominant route for UV photolysis vapor generation. In this work computational methods were applied to determine a possible alternative mechanism in the absence of free-radical production. The proposed mechanism specifically focused on selenium vapor generation. An energetically favored mechanism was found for UV photolysis of inorganic selenium in the presence of formic and acetic acids which is consistent with previously reported experimental results.
ACCESSION #
25277588

 

Related Articles

  • p-Hydroxyphenacyl photoremovable protecting groups - Robust photochemistry despite substituent diversity. Givens, Richard S.; Stensrud, Kenneth; Conrad, Peter G.; Yousef, Abraham L.; Perera, Chamani; Senadheera, Sanjeewa N.; Heger, Dominik; Wirz, Jakob // Canadian Journal of Chemistry;Mar2011, Vol. 89 Issue 3, p364 

    A broadly based investigation of the effects of a diverse array of substituents on the photochemical rearrangement of p-hydroxyphenacyl esters has demonstrated that common substituents such as F, MeO, CN, CO2R, CONH2, and CH3 have little effect on the rate and quantum efficiencies for the...

  • Morphologically different WO nanocrystals in photoelectrochemical water oxidation. Biswas, Soumya; Baeg, Jin-Ook; Moon, Sang-Jin; Kong, Ki-jeong; So, Won-Wook // Journal of Nanoparticle Research;Jan2012, Vol. 14 Issue 1, p1 

    Different morphologies of WO nanocrystals such as nanorods and nanoplates have been obtained under hydrothermal conditions using ammonium metatungstate as the precursor in presence of different organic acids such as citric, oxalic, and tartaric acid in the reaction medium. Detailed...

  • Photochromism of Dihydroindolizines Part XI: Synthesis of Novel Carbon-Rich Photochromic Dihydroindolizines-Based Potential Electronic Devices. Ahmed, Saleh Abdel-Mgeed // Research Letters in Organic Chemistry;2008, p1 

    Novel carbon-rich photochromic dihydroindolizine (DHI) derivatives substituted in the fluorene part (region A) in addition to the new spirocyclopropene 6 have been synthesized. The synthesis of dimethyl 2',7'-diethynylspiro[cycloprop[2]ene-1,9'-fluorene]- 2,3-dicarboxylate precursor 6 was...

  • Photoinitiated Reaction of Carboxylic Acids with Oxiranes. Shevchenko, V. V.; Pashinnik, V. E.; Batog, O. P.; Bondarenko, P. A. // Russian Journal of Organic Chemistry;Feb2004, Vol. 40 Issue 2, p278 

    Discusses the photoinitiated reaction of carboxylic acids with oxiranes. Use of polycarboxylic acids as hardener of epoxy resins; Photopolymerization of a mixture of epoxy resins with methacrylic acid; Initiation of an ionic polymerization of the acrylate derivative.

  • Field and laboratory studies of reactions between atmospheric water soluble organic acids and inorganic particles. Wang, Bingbing; Kelly, Stephen T.; Sellon, Rachel; Shilling, John; Tivanski, Alexei V.; Moffet, Ryan C.; Gilles, Mary K.; Laskin, Alexander // AIP Conference Proceedings;May2013, Vol. 1527 Issue 1, p465 

    Atmospheric inorganic particles undergo complex heterogeneous reactions that change their physicochemical properties. Depletion of chloride in sea salt particles was reported in previous field studies and was attributed to the acid displacement of chlorides with inorganic acids, such as nitric...

  • A quantum chemical study of photochemical processes in the reaction Se + O → SeO with allowance for the spin orbit interaction. Kobzev, G.; Urvaev, D.; Davydov, K.; Zaika, Yu. // Journal of Structural Chemistry;Feb2012, Vol. 53 Issue 1, p12 

    DFT, SA-MCSCF, and MRMP/MCQDPT2 methods in the 6-311++G(2 d) basis set are employed to consider the features of the formation reaction of key intermediates (SeOO, Se(O)) and photochemical dissociation of selenium dioxide with the formation of singlet oxygen. The cross-sections of potential...

  • Laser-induced chemical processes. Letokhov, V. S. // Physics Today;Nov80, Vol. 33 Issue 11, p34 

    Focuses on chemical reactions that are induced by lasers. Types of molecular photoexcitation; Types of selectivity; Information on nonselective laser photochemistry.

  • Equivalence of the Kobrak--Rice photoselective adiabatic passage and the Brumer--Shapiro strong.... Kobrak, Mark N.; Rice, Stuart A. // Journal of Chemical Physics;7/1/1998, Vol. 109 Issue 1, p1 

    Examines the nature of the photoselective adiabatic passage approach proposed for product formation control in chemical reactions. Insight into chemical reaction control in strong fields; Prediction of sodium dimer physical realistic simulation results; Use of intense laser fields to control...

  • Ultralow temperature kinetics of neutral–neutral reactions. The technique and results for the reactions CN+O2 down to 13 K and CN+NH3 down to 25 K. Sims, I. R.; Queffelec, J.-L.; Defrance, A.; Rebrion-Rowe, C.; Travers, D.; Bocherel, P.; Rowe, B. R.; Smith, I. W. M. // Journal of Chemical Physics;3/15/1994, Vol. 100 Issue 6, p4229 

    An entirely new experimental method is described which enables the rate constants of neutral–neutral gas-phase reactions to be measured at ultralow temperatures. The measurements are made by applying the pulsed laser photolysis (PLP), laser-induced fluorescence (LIF) technique of studying...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics