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Herrmann, Hartmut; Ervens, B.; Jacobi, Hans-Werner; Wolke, Ralf; Nowacki, P.; Zellner, R.

doi:10.1023/a:1006318622743

Cited by 246 publications

(125 citation statements)

References 142 publications

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“…This supposition is confirmed by both the experimental physicochemical characteristics of nitrogen dioxide (its small Henry's constant and low diffusion coefficient in water [14]) and the quantum chemical simulations of NO 2 (H 2 O) 50 systems we carried out. Intermolecular NO 2 .…”

Section: Neutral No 2 (H 2 O) N Complexessupporting

confidence: 69%

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Novakovskaya

Bezrukov

Stepanov

2004

Int J of Quantum Chemistry

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Neutral and negatively charged nitrogen dioxide molecule either individual or involved in a complex cluster with up to 50 water molecules is nonempirically simulated in the second order of the Møller-Plesset perturbation theory with the unrestricted Hartree-Fock function with the use of atomic basis functions of the 6-31ϩϩG** set and effective fragment potentials for a part of water molecules. The structures corresponding to the local minima of the potential energy surfaces of neutral and anionic clusters are considered, and their dissociation energies are estimated. The geometric parameters of the cavities formed around nitrogen dioxide and its anion in the H-bond network of water clusters are compared. The vertical electron detachment energies of the anions and the electron affinities of the parent neutral complex clusters depending on the number of water molecules involved are used for estimating the corresponding energetic characteristics of infinitely diluted aqueous nitrogen dioxide systems.

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Section: Neutral No 2 (H 2 O) N Complexessupporting

confidence: 69%

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Novakovskaya

Bezrukov

Stepanov

2004

Int J of Quantum Chemistry

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“…We estimate P 3 to be less than 1.7% (pH 2.25) or 4.8% (pH 1.78) for pK a < 0.48 [14]. Using data for CH 3 C(O)O − and CH 3 C(O)OH, we estimate that the rate constant for the reaction of SO 4 − with C n F 2n+1 C(O)OH is much smaller than the rate constant of SO 4 − with C n F 2n+1 C(O)O − (the rate constant for reaction of SO 4 − with CH 3 C(O)OH (2.5 × 10 5 mol −1 dm −3 s −1 ) at 298 K is two orders of magnitude smaller than the rate constant for reaction of SO 4 − with CH 3 C(O)O − (2.8 × 10 7 mol −1 dm [6]. Thus, in runs 1-14, we estimate the influence of C n F 2n+1 C(O)OH on the decay of C n F 2n+1 C(O)O − to be less than 2% during most of the reaction period.…”

Section: Influence Of Undissociated Forms C 2 F 5 C(o)oh Cf 3 C(o)omentioning

confidence: 94%

Rate constants for aqueous‐phase reactions of SO₄⁻ with C₂F₅C(O)O⁻ and C₃F₇C(O)O⁻ at 298 K

Kutsuna

Hori

2007

Int J of Chemical Kinetics

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Perfluorocarboxylic acids and their anions (PFCAs), such as perfluorooctanate (C7F15C(O)O−), have been generally recognized to be global pollutants and are believed to persist in the environment. Kinetic data for reactions of sulfate anion radicals (SO4−) with PFCAs are needed to evaluate the residence times of PFCAs in the environment, but no kinetic data have been reported, except for the rate constant for the reaction of SO4− with trifluoroacetate (CF3C(O)O−) (k1). In this study, using the fact that PFCAs react with SO4− to form shorter chain PFCAs, we determined rates relative to k1 of the reactions of photolytically generated SO4− with two short‐chain PFCAs, pentafluoropropionate (C2F5C(O)O−; k2) and heptafluorobutyrate (C3F7C(O)O−; k3), along with conversion ratios for conversion of C2F5C(O)O− into CF3C(O)O− (α) and conversion of C3F7C(O)O− into C2F5C(O)O− (β) and CF3C(O)O− (γ) at 298 K. Values of k1, k2, or k3 might change over the course of reaction with increasing ionic strength. Nevertheless, if the values of k1/k2, k2/k3, α, β, and γ remain almost constant during the reaction, a simple equation involving relative rates, such as k1/k2, can be used to relate the concentrations of C3F7C(O)O−, C2F5C(O)O−, and CF3C(O)O−. We compared the relative rates, such as k1/k2, and the conversion ratios determined from various experimental runs with different initial conditions to check whether relative rates and conversion ratios remained almost constant during each experimental run. The values of k1/k2, k2/k3, α, β, and γ seemed to remain almost constant, which facilitated determination of k2/k1 = 0.89 ± 0.07, k3/k1 = 0.84 ± 0.08, α = 0.88 ± 0.05, β = 0.75 ± 0.05, and γ = 0.17 ± 0.02. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 276–288, 2007

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“…[87,88] Reactions of SO 4 À with other atmospheric reactants could therefore interfere the S(IV) oxidation chain. Therefore, it is necessary to investigate and characterize the reactivity of this atmospheric oxidant in aqueous solution.…”

Section: Overviewmentioning

confidence: 99%

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

et al. 2010

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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.

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Untitled

Cited by 246 publications

References 142 publications

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Rate constants for aqueous‐phase reactions of SO₄⁻ with C₂F₅C(O)O⁻ and C₃F₇C(O)O⁻ at 298 K

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

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Untitled

Cited by 246 publications

References 142 publications

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Nitrite ion formation: Nonempirical simulation in terms of cluster model

Rate constants for aqueous‐phase reactions of SO4− with C2F5C(O)O− and C3F7C(O)O− at 298 K

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

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Rate constants for aqueous‐phase reactions of SO₄⁻ with C₂F₅C(O)O⁻ and C₃F₇C(O)O⁻ at 298 K