- The volume-based thermodynamics (VBT) and attempted preparation of an isomeric salt, nitryl chlorate: [NO2][ClO3]
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Nitrosyl perchlorate, [NO][ClO4], is a known and stable salt. In this contribution we describe the attempt to synthesize the isomeric compound nitryl chlorate, [NO2][ClO3]. The results are discussed on the basis of volume-based thermodynamics (VBT).
- Bhasin, Kuldip K.,Crawford, Margaret-Jane,Jenkins, H. Donald Brooke,Klapoetke, Thomas M.,Liebman, Joel F.
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- Reactivity of BrNO2 and ClNO2 with solid alkali salt substrates
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The reactions of BrNO2 and ClNO2 with bromide have been studied in a Knudsen-cell reactor in order to better understand the elementary reactions of these potentially important tropospheric species in the presence of solid sea-salt aerosol. BrNO2 efficiently reacts with bromide to produce molecular bromine (γ > 0.3). To better understand the fate of BrNO2 in the Knudsen-cell reactor, we have developed a BrNO2 source based on the reaction of molecular bromine with solid KNO2. We have determined that the lifetime of BrNO2 under our experimental conditions is on the order of 10 s and is limited by heterogeneous decomposition reactions. The interaction of BrNO2 with KBr, KCl, and KNO2 was studied using the external BrNO2 source. ClNO2 can be converted to BrNO2 in the presence of solid bromide, characterized by an uptake probability of γ = 1.3 × 10-4, in good agreement with results obtained for several substrate presentations such as salt powder, grain, and single crystals. We compared these results with previous work and briefly discuss atmospheric implications.
- Caloz, Franc?ois,Seisel, Sabine,Fenter, Frederick F.,Rossi, Michel J.
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p. 7470 - 7479
(2007/10/03)
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- FTIR Study of the Kinetics and Mechanism for the Cl-Atom-Initiated Reactions of SiHCl3
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On the basis FTIR product analysis of the UV-visible (λ >= 300 nm) photolysis of Cl2-SiHCl3 mixtures in 700 torr of N2-O2, Cl atoms were shown to predominantly undergo an H-atom abstraction reaction rather than an attachement/displacement reaction with SiHCl3.The corresponding rate constant k was determined at 298 K to be 2.9 X 10E-11 cm3molecule-1s-1 by the competitive kinetic method with reference to the Cl + C6H6 reaction.IR absorption bands attributable to two new gaseous products, SiCl3OCl and SiCl3OH, were detected in the subsequent oxidation of the primary radical SiCl3.Kinetic and spectroscopic evidence was also obtained for the NO2-addition reaction of the oxy and peroxy radicals SiCl3O and SiCl3OO.A plausible mechanism for the formation of these products is presented.
- Niki, H.,Maker, P. D.,Savage, C. M.,Breitenbach, L. P.,Hurley, M. D.
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p. 3725 - 3729
(2007/10/02)
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