7790-89-8Relevant academic research and scientific papers
Rotational spectrum and molecular properties of the dinitrogen-chlorine monofluoride complex
Cooke, Stephen A.,Cotti, Gina,Hinds, Kelvin,Holloway, John H.,Legon,Lister, David G.
, p. 2671 - 2676 (1996)
The ground-state rotational spectra of the three isotopomers 14N2...35ClF, 15N2...35ClF and 15N2...37ClF of a complex formed by dinitrogen and chlorine monofluoride have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The spectroscopic constants B0, DJ, χaa(A) (A) = 14Ni, 14No or Cl) and Mbb(Cl) are reported. The complex is shown to have a linear (or nearly linear) arrangement NoNi...ClF of the nuclei in the equilibrium conformation with r(Ni...Cl) = 2.920(2) A. The intermolecular stretching force constant, kσ = 5.00(5) N m-1, is implied by the centrifugal distortion constant DJ. Intepretation of the nuclear quadrupole coupling constants χaa(A) leads to the oscillation angles θav = cos-1〈cos2 θ〉1/2 = 17.8(5)° and φav = cos-1〈cos2 θ〉1/2 = 10(3)° for the N2 and ClF subunits, respectively. Additionally, the diffence χaa(Ni) - χaa(No) leads, on the basis of a simple model, to the conclusion that the polarisation of N2 attending complex formation is equivalent to the transfer of a fraction δ ≈ 0.02 of an electronic charge from No to Ni. A comparison of the properties of four related complexes N2...YF and OC...YF, where Y = Cl or H, is presented.
The complex OC...ClF identified as a pre-chemical intermediate by rotational spectroscopy of carbon monoxide-chlorine monofluoride mixtures
Hinds, K.,Holloway, J. H.,Legon, A. C.
, p. 407 - 414 (1995)
The ground-state rotational spectra of four isotopomers of the complex OC...ClF have been observed by using a fast-mixing nozzle in a pulsed-nozzle, Fourier-transform microwave spectrometer. The spectrum of the reaction product carbonyl chloride fluoride was detected but its intensity indicated that the extent of the reaction was small. The observed spectroscopic constants B(0), D(J), χ(aa)(Cl) and M(bb)(Cl) were interpretedto show that the pre-chemical complex has the nuclei collinear in the o rder OC...ClF, with r(C...Cl)=2.770(3)? and the intermolecular stretching force constant k(σ)=7.03(3) N m**-1. There is only a minor electric charge redistribution within ClF on complex formation.
From hypochlorites to perfluorinated dialkyl peroxides
Nissen, Jan H.,Wickemeyer, Lucas,Stüker, Tony,Steinhauer, Simon,Beckers, Helmut,Riedel, Sebastian
supporting information, (2019/12/26)
The synthesis and characterization of the new perfluorinated hypochlorite, undecafluoro-tert-pentyl hypochlorite, (C2F5)(F3C)2COCl, is reported. Its gas-phase infrared, UV/Vis and NMR spectra have been recorded and its spectroscopic properties are discussed and compared with quantum-chemical predictions and those of other known perfluorinated hypochlorites such as RFOCl [RF = F3C, (F3C)3C, (C2F5)(F3C)2C]. A synthetic route to otherwise difficult to access perfluorinated dialkyl peroxides, RFOORF, is also provided by low-temperature photolysis of the corresponding hypochlorite.
Kinetic mechanism of ClONO2 uptake on polycrystalline film of NaCl
Zelenov,Aparina,Kashtanov,Shestakov,Gershenzon
, p. 6771 - 6780 (2008/10/09)
Kinetic studies and the mechanism determination of ClONO2 uptake on polycrystalline NaCl were carried out using a coated-insert flow tube reactor combined with high-resolution, low-energy electron-impact mass spectrometer under the following conditions: p =1-2 Torr, linear flow velocity v = 3.5-75 m s-1, T = 293 and 387 K, [ClONO2] = (0.5-25) × 1012 molecules cm-3. The salt was deposited as a film from nonsaturated aqueous solution on the sliding rod. The temporal dependences of the uptake coefficient and the partial uptake coefficients leading to a formation of the prime Cl2 and HOCl products were measured for different ClONO2 concentrations. These dependences are established to be described by γ = γ0 exp(-t/τ) + γs, γ0.s-1 = a0.S + b0.s[ClONO2]. In the framework of the proposed kinetic model, the data are explained and the main elementary kinetic parameters of the uptake are evaluated. The model is based on a combination of Langmuir adsorption, formation of surface complexes on initial active sites, Z ch, followed by their unimolecular decomposition. Decomposition is proposed to proceed concurrently in two channels, one of which is a released surface site that conserves the properties of the initial site. In the other channel, the initial Zch transforms into Zph followed by steady-state uptake and reproduction of final Zph. The model gives an analytical expression for experimental parameters γ0, γs, and τ in terms of elementary rate constants and the reactant volume concentration. The final objective of the proposed model is the extrapolation of γ0, γs, and r parameters to real tropospheric conditions.
Temperature Dependence of the Rate Constant for the Reaction F( 2P) + Cl2 → FCl + Cl at T = 180-360 K
Nesbitt, Fred L.,Cody, Regina J.,Dalton, Douglas A.,Riffault, Veronique,Bedjanian, Yuri,Le Bras, Georges
, p. 1726 - 1730 (2007/10/03)
The absolute rate constant for the reaction F(2P) with Cl 2 has been measured using the discharge flow kinetics technique coupled to mass spectrometric detection at T = 180-360 K and 1 Torr He nominal pressure. Experiments were performed at NASA Goddard Space Flight Center (GSFC) in Greenbelt, MD, and Laboratoire de Combustion et Systemes Reactifs-CNRS in Orleans, France. Results of k = (5.7 ± 0.8) × 10-11 and (6.2 ± 0.8) × 10-11 cm3 molecule-1 s-1 independent of temperature were obtained by each laboratory, respectively. When the results from both laboratories were combined into one data set, an average temperature independent value of k1 = (6.0 ± 1.1) × 10-11 cm3 molecule-1 s-1 was obtained. A very slight positive temperature dependence with k1(T) = (6.5 ± 1.5) × 10-11 exp{-(20 ± 60)/T} cm3 molecule-1 s-1 may also be derived from the combined data in the range T = 180-360 K.
Synthese binaerer und ternaerer fluoride
Mueller, B. G.
, (2008/10/08)
Die Druckfluorierung mit elementarem Fluor (p(F2) ~ 1-3E+3 bar) oder wasserfreier HF (im folgenden aHF= anhydrous HF) [p(HF) ~ 1-200 bar]) bzw. Mischungen von beiden ist eine Moeglichkeit bzw. Methode, thermisch empfindliche oder fluechtige binaere wie auch ternaere Fluoride in unterschiedlichen Oxidationsstufen insbesondere auch in einkristalliner Form darzustellen.
Reaction of CF3OCl with Lewis Acids and with Br2 and I2
Minkwitz, Rolf,Konikowski, Detlef
, p. 1277 - 1280 (2007/10/03)
The reactions of CF3OCl with SbX5 (X = F, Cl) and AsF5 at 195 K yield the adducts CF3OCl*SbX5 and CF3OCl*AsF5 respectively.At 213 K CF3OCl*SbCl5 forms SbCl4F, Cl2 and OCF2, while compounds CF3OCl*MF5 (M = As, Sb) slowly decompose giving ClF, OCF2 and mixed M(V) halides.The formation of IF5, OCF2 and Cl2 in the oxidative fluorination of I2 with CF3OCl at 293 K is described.Br2 reacts with CF3OCl to give BrF3 under similar conditions. - Keywords: Trifluoromethyl Hypochlorite Antimony Pentachloride and Pentafluoride Adduct; Trifluoromethyl Hypochlorite Arsene Pentafluoride Adduct; Vibrational Spectra; NMR Spectra
Isolation of H2S...ClF in a pre-reactive mixture of H2S and ClF expandedin a coaxial jet and characterization by rotational spectroscopy
Bloemink, H. I.,Hinds, K.,Holloway, J. H.,Legon, A. C.
, p. 113 - 120 (2008/10/08)
The reaction between H2S and ClF was precluded and H2S...ClF isolated bya coaxial supersonic expansion of the gaseous components into the Fabry -Perot cavity of a pulsed-nozzle, Fourier-transform microwave spectrometer. The ground-state rotational spectra of seven isotopomers of H2S...ClF were analysed and gave in each case the spectroscopic constants 1/2(B(0)+C(0)), D(J), χ(aa) (Cl) and M(bb) (Cl). Interpretation of these constants revealed the complex to have a geometry of C(s) symmetry with the S...Cl-F nuclei collinear in the order shown, with the angle 180°-φ=84.2(4)° between the C(2) axis of H2S and the S...Cl-F axis, and with r(S...Cl)=2.857(3)?.
The reactions of positive and negative halogen ions with Cl2 and Br2
Spanel, P.,Tichy, M.,Smith, D.
, p. 8660 - 8666 (2007/10/02)
A selected ion flow tube study has been carried out at 300 K of the reactions of some atomic and molecular positive and negative halogen ions with Cl2 and Br2 from which the rate coefficients k and ion product distributions have been determined.For the energetic F+ ion reactions, dissociative charge transfer is the dominant process, while for the Cl+ ions, only nondissociative charge transfer occurs.For the less energetic Br+ and I+ reactions, dihalogen molecular ions are important products.All these positive ion reactions proceed quite efficiently, i.e., the k are appreciable fractions of kc, their respective collisional rate coefficients, except for the reactions of Cl2 with the lower energy ions of the spin-orbit triplet of I+, i.e., I+(3P1,0), for which k ca. 0.07kc, this being due to the endothermicities of the reactions.The molecular ion Cl2+ undergoes rapid nondissociative charge transfer with Br2, a process which is, of course, endothermic for the reaction of Br2+ with Cl2 and so no reaction is observed.The less-energetic atomic negative ion reactions proceed-via atom exchange-in which the atomic negative ion of the reactant molecular species and a dihalogen molecule are produced.For those reactions that are exothermic, the k are, within error, equal to (2/3)kc, implying that they proceed via complexes which separate statistically back to reactants (1/3) and forward to products (2/3).Both the Br- + Cl2 and Cl- + Br2 reactions are somewhat less efficient (i.e., k c), a result of the slight endothermicities of the reactions.Of the molecular negative ion reactions, electron transfer is the major process in the Cl2- reaction with Br2, whereas the reaction of Br2- with Cl2 proceeds relatively slowly producing the triatomic ion BrCl2-.
Eine gaskinetische Studie zur Reaktion von HOCl mit F-, Cl- und H-Atomen bei Raumtemperatur
Vogt, R.,Schindler, R.N.
, p. 819 - 829 (2007/10/02)
Chemical Kinetics / Elementary Reactions / Fluorescence / Mass Spectrometry / Radicals.The reactions of HOCl with F-, Cl- and H-atoms were investigated at room temperature in a discharge flow system equipped with an OH-resonance fluorescence cell and a mass spectrometric detector.All kinetic studies were carried out under pseudo first order conditions with HOCl being the minority component.Branching ratios for individual processes were obtained by following simultaneously the rates of HOCl consumption and product formation.The following rate constants (in units cm3 molecule-1 s-1) were determined: .Calibration for using reaction (1) for gas titration is discussed.The data are evaluated to yield ΔHf = -79.7 kJ mol-1 for the heat of HOCl formation.
