Pulse Radiolysis of Aqueous Thiocyanate Solution

Milosavljevic, Bratoljub H.; LaVerne, Jay A.

doi:10.1021/jp046088a

Cited by 49 publications

(49 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that a recent study 9 has questioned this reference value while a second one has validated it and even extended its application to various ionic strengths 10. In this context, it has been decided to derive all rate coefficients by using the reference rate coefficient reported by Chin and Wine 6 as the latter has been widely used as mentioned before 4,5,7,8.…”

Section: Methodsmentioning

confidence: 99%

Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Gligorovski

Rousse

George

et al. 2009

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The kinetics of the oxidation of functionalized organic compounds of atmospheric relevance by the hydroxyl radical (OH) was measured in the aqueous phase. Competition kinetics, using the thiocyanate anion (SCN − ) as competitor, was applied using both a laser flash photolysis long path absorption (LP-LPA) setup and a Teflon AF waveguide photolysis (WP) system. Both experiments were intercompared and validated by measuring the rate coefficients for the reaction between OH and acetone where values of k 1 = (1.8 ± 0.4) × 10 8 M −1 s −1 were obtained with the WP system, which agrees very well with the rate constant of k 1 = (2.1 ± 0.6) ×

show abstract

Section: Methodsmentioning

confidence: 99%

Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Gligorovski

Rousse

George

et al. 2009

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

“…Compared to the reaction of OH towards organic compound, only a few reactions with inorganic compound have been newly studied including rate constants for the OH reactions with chloride, bromide, iodide, [57] carbonate, bicarbonate, thiosulphate, sulfite, H 2 O 2 and thiocyanate, [58] for all others Kwon et al [49] Kwon et al [49] state that the rate constant of OH with chloride is 2.8 10 9 m À1 s À1 at pH 8.75. It has long been known that a direct oxidation of chloride by OH will only possible in acidic solution as this reaction is not a concerted one-step electron transfer, but a sequence of three coupled equilibria, one of which requires the reaction of a proton to lead to the release of a chlorine atom.…”

Section: Inorganic Compoundsmentioning

confidence: 99%

“…The peak absorbance of (SCN) 2 À is reached after approximately 5 ms according to the study of Milosavljevic and LaVerne. [58] Sink reactions for the (SCN) 2 À radical anion in aqueous solution are recombination reactions or the reaction with the SCN radical (Table 10). [58,62,66,69] An effect which could influence the measured peak absorbance of (SCN) 2 À in laser photolysis experiments when H 2 O 2 is applied as radical precursor are absorptions of the added reactants at the H 2 O 2 photolysis wavelength.…”

Section: Kineticsmentioning

confidence: 99%

Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

et al. 2010

View full text Add to dashboard Cite

The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for rate constant prediction include empirical correlations as well as structure activity relationships (SAR) either with or without the usage of quantum chemical descriptors. Recently published estimation methods for OH, NO(3) and SO(4)(-) radical reactions in aqueous solution are finally summarized, compared and discussed.

show abstract

“…The reaction of SCN À with HO Á (Eq. (3)) has previously been described (Milosavljevic and LaVerne, 2005):…”

Section: Thiocyanate Competition Methodsmentioning

confidence: 99%

Radiolysis of the polyethylene/water system: Studies on the role of hydroxyl radical

Billamboz

Grivet

Foley

et al. 2010

Radiation Physics and Chemistry

View full text Add to dashboard Cite

Pulse Radiolysis of Aqueous Thiocyanate Solution

Cited by 49 publications

References 21 publications

Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

Radiolysis of the polyethylene/water system: Studies on the role of hydroxyl radical

Contact Info

Product

Resources

About