10022-50-1Relevant articles and documents
Donaldson, J. D.,Senior, B. J.
, (1967)
Atmospheric Chemistry of FNO and FNO2: Reactions of FNO with O3, O(3P), HO2, and HCl and the Reaction of FNO2 with O3
Wallington, Timothy J.,Schneider, William F.,Szente, Joseph J.,Maricq, M. Matti,Nielsen, Ole John,Sehested, Jens
, p. 984 - 989 (1995)
Upper limits for the rate constants of the following gas phase reactions have been determined at 296 K: k(FNO+O3) -18, k(FNO+O(3P)) -13, k(FNO+HO2) -12, k(FNO+HCl) -18, and k(FNO2+O3) 8
Kinetics and mechanisms of the thermal gas-phase reactions of CF3OF and CF3OOCF3 with NO2
Czarnowski
, p. 83 - 94 (1999)
The kinetics of the reactions of CF3OF and CF3OOCF3 with NO2 have been investigated using a conventional static system. The reaction between CF3OF and NO2 has been studied in a quartz reactor in the temperature range of 313.2-334.2 K, varying the initial pressure of CF3OF between 19.4 and 165.2 Torr and that of NO2 + N2O4 between 18.2 and 179.2 Torr. Some experiments were made in presence of 506.5-600.8 Torr of N2. The total pressure had no influence on the reaction rate. COF2 and FNO2 were identified as reaction products. The expression obtained for the rate constant for the abstraction of fluorine atom from CF3OF by NO2 was: k1 = (1.1±0.2) × 109 exp(-16.4±1 kcal mol-1/ RT) dm3 mol-1 s-1. The reaction of CF3OOCF3 with NO2 has been studied in an aluminum reactor in the temperature range of 474.0-512.5 K, varying the initial pressure of CF3OOCF3 between 24.1 and 202.5 Torr and that of NO2 between 24.7 and 202.7 Torr. Several experiments were made in presence of 399.8-490.5 Torr of N2. The reaction rate was proportional to [CF3OOCF3]1/2. The reaction approached the first order with respect to NO2 at low pressure of NO2. Increasing the pressure of NO2, the ratio of the reaction rates increased more rapidly than the ratio of the corresponding concentrations of NO2. Three products were formed: COF2, FNO and O2. The expression obtained for the rate constant for the abstraction of the fluorine atom from the radical CF3O by NO2 was: k8 = (1.72±0.4) × 109 exp(-10.8±1 kcal mol-1/RT) dm3 mol-1 s-1. The mechanisms for both reactions were postulated. by Oldenbourg Wissenschaftsverlag, Muenchen.
Kinetics of the gas phase reaction OH + NO( + M) → HONO( + M) and the determination of the UV absorption cross sections of HONO
Pagsberg, Palle,Bjergbakke, Erling,Ratajczak, Emil,Sillesen, Alfred
, p. 383 - 390 (1997)
The reaction OH + NO( + M) → HONO( + M) with M = SF6 as a third body has been employed as a clean source for recording the near-ultraviolet absorption spectrum of HONO without interference from other absorbing species. The reaction was initiated by the pulse radiolysis of SF6/H2O/NO mixtures with total pressures in the range 10-1000 mbar at 298 K. The pressure dependence of the rate coefficient was studied by time-resolved UV and IR spectroscopy. By analysis of the fall-off curve we have derived a value for the limiting low pressure rate constant k0/[SF6] = (1.5 ± 0.1) × 10-30 cm6 molecule-2 s-1 at 298 K, using the values of k∞ = (3.3 ± 0.3) × 10-11 cm3 molecule-1 s-1 and Fcent = 0.81 reported by Troe and co-workers. The UV spectrum of HONO was recorded in the range 320-400 nm and an absolute absorption cross section of σ = (5.02 ± 0.76) × 10-19 cm2 molecule-1 has been determined for the strongest band of HONO located at 354.2 nm. Differential absorption cross sections to be used for field measurements of HONO were also investigated.
XeOF3-, an example of an AX3YE2 valence shell electron pair repulsion arrangement; Syntheses and structural characterizations of [M][XeOF3] (M = Cs, N(CH3) 4)
Brock, David S.,Mercier, Helene P. A.,Schrobilgen, Gary J.
, p. 10935 - 10943 (2010/09/16)
The XeOF3- anion has been synthesized as its Cs + and N(CH3)4+ salts and structurally characterized in the solid state by low-temperature Raman spectroscopy and quantum-chemical calculations. Vibrational frequency assignments for [Cs][XeOF3] and [N(CH3) 4][XeOF3] were aided by 18O enrichment. The calculated anion geometry is based on a square planar AX3YE 2 valence-shell electron-pair repulsion arrangement with the longest Xe-F bond trans to the oxygen atom. The F-Xe-F angle is bent away from the oxygen atom to accommodate the greater spatial requirement of the oxygen double bond domain. The experimental vibrational frequencies and trends in their isotopic shifts are reproduced by the calculated gas-phase frequencies at several levels of theory. The XeOF3- anion of the Cs + salt is fluorine-bridged in the solid state, whereas the anion of the N(CH3)4+ salt has been shown to best approximate the gas-phase anion. Although [Cs][XeOF3] and [N(CH 3)4][XeOF3] are shock-sensitive explosives, the decomposition pathways for the anions have been inferred from their decomposition products at 20°C. The latter consist of XeF2, [Cs][XeO2F3], and [N(CH3)4][F]. Enthalpies and Gibbs free energies of reaction obtained from Born-Fajans-Haber thermochemical cycles support the proposed decomposition pathways and show that both disproportionation to XeF2, [Cs][XeO2F3], and CsF and reduction to XeF2, CsF, and O2 are favorable for [Cs][XeOF3], while only reduction to XeF2 accompanied by [N(CH3)4][F] and O2 formation are favorable for [N(CH3)4][XeOF3]. In all cases, the decomposition pathways are dominated by the lattice enthalpies of the products.
