6914-07-4Relevant academic research and scientific papers
Rotational and vibrational state distributions of HNC(0 v21 0) from the hot H atom reaction: H + (CN)2 → HNC + CN
Macdonald, R. Glen
, p. 10202 - 10211 (2000)
The reaction dynamics of the five-atom system, H + (CN)2, was investigated by probing the minor product channel producing the transient HNC molecule. The complete initial energy disposition, translation, rotation, and vibration was determined for the HNC(0 v21 0), v21= 0°, 11, product. The reaction was studied under bulk conditions and was initiated by energetic H atoms with a mean translational energy of 92 kJ mol-1. The HNC molecule was monitored by time- and frequency-resolved absorption spectroscopy with sub-Doppler resolution. The initial rotational state distribution of each HNC(0 v21 0) vibrational level was measured and found to be well-described by a Boltzmann distribution. Only two vibrational levels were detected so that the initial HNC product vibrational level distribution was determined as well. The absolute reaction cross section for the title reaction was measured to be 2 × 10-18 cm2 for H atoms with a nominal translational energy of 113 kJ mol.-1
Channeling of products in the hot atom reaction H + (CN)2 → HCN/HNC + CN and in the reaction of CN with CH3SH
Decker, Brian K.,Macdonald, R. Glen
, p. 6817 - 6825 (2007/10/03)
Infrared transient absorption spectroscopy was used to determine the total product branching fractions for the gas-phase hot atom reaction H + (CN)2 → HCN/HNC + CN (a) and the reaction CN + CH3SH → HCN/HNC + CH3S/CH2SH (b) at 293 K. The reactive H atoms had an initial mean translational energy of 92 kJ mol-1, with a 38 kJ mol-1 fwhm Gaussian energy distribution. The branching fractions determined for the product channels forming HCN and HNC, respectively, are 0.88 and 0.12 (±0.05) for reaction (a) and 0.81 and 0.19 (±0.08) for reaction (b). The bimolecular rate constant for reaction (b) was measured to be (2.7 ± 0.3) × 10-10 cm3 molec-1 s-1 at 293 K. The observed product branching fractions for reaction (a) are consistent with the assumption that the average reactive cross sections for the two product channels are approximately equal above their respective energy thresholds. The results for reaction (a) are compared with the related H + XCN (X = Br, Cl) reactions. The large rate coefficient for reaction (b) suggests an interaction via a long-range intermolecular potential, which is facilitated by the small ionization energy of CH3SH and large electron affinity of CN. The results for reaction (b) are compared with the related reactions of Cl and OH with CH3SH.
The formation of methyl isocyanate during the reaction of nitroethane over Cu-MFI under hydrocarbon-selective catalytic reduction conditions
Cant,Haynes,Nelson,Liu
, p. 487 - 494 (2007/10/03)
The reaction of nitroethane with NO in the presence of O2 was investigated over Cu-MFI catalyst. Nitroethane reacted readily in NO/O2 over Cu-MFI with initial conversion to CO2 and N2. Deactivation due to deposited material was observed below 330°C with the eventual emergence of isocyanates, mainly CH3NCO by dehydration, but with some HNCO, by deposit decomposition. Nitromethane reacted in a similar way but deactivation was slower. While HNCO was then the only isocyanate formed, significant amounts of HCN and NH3 were also observed. With both systems, nitrogen rose either by hydrolysis of isocyanate to amine (or ammonia) on Broensted sites and subsequent SCR reactions involving transition metal ions or through reaction of NO2 with deposits. The rates of these processes were sufficiently fast for nitroethane to be feasible as an intermediate during the SCR of NO by ethane on Cu-MFI.
Experimental and theoretical determination of the magnetic dipole transition moment for the Br(4p5)(2P1/2←2P3/2) fine-structure transition and the quantum yield of Br(2P1/2) from the 193 nm photolysis of BrCN
He,Seth, Michael,Tokue,Macdonald, R. Glen
, p. 7821 - 7831 (2007/10/03)
The integrated-absorption coefficients of several hyperfine lines of the magnetic dipole allowed transition of the bromine atom, Br, center at 3685.2 cm-1 were measured, and a value for the square of the magnetic dipole transition moment of the Br atom was determined. A theoretical calculation for the magnetic dipole transition moment was also carried out using a relativistic ab initio atomic structure formulation. The theoretical value was in excellent agreement with the value predicted assuming pure LS coupling, and in reasonable agreement with experiment. The Br atom was generated in equal concentration with the cyano radical (CN) by the 193 nm photolysis of cyanogen bromine, BrCN. The CN radicals were titrated by the rapid reaction with C3H8 to generate HCN and a small amount of HNC. Both time-resolved and frequency-scanned infrared absorption spectroscopy were used to monitor the Br, HCN, and HNC species. The photolysis of BrCN at 193 nm produced both the ground state Br(2P3/2) and the spin-orbit excited Br(2P1/2) atoms, and the yield for the production of Br(2P1/2) atoms was measured to be 0.31±0.01. The rate constants for the quenching of Br(2P1/2) by BrCN and C3H8 at 293 K were also determined.
The formation of HAlX2 (X = Cl, Br) in the thermolysis of intramolecularly coordinated alanes Me2N(CH2)3AlX2: A matrix isolation study
Mueller, Jens,Wittig, Bob
, p. 1807 - 1810 (2008/10/08)
High-vacuum thermolyses of the intramolecularly coordinated alanes Me2N(CH2)3AlX2 with X = Cl, Br (1, 2) were investigated with matrix isolation techniques. Among the products, which were identified with IR spectroscopy, ab initio calculations, and known literature data, are monomeric HAlCl2 and HAlBr2. The experimental vibrational frequencies of these hydrides matches well the calculated harmonic frequencies at the MP2(fc)/6-311G+(2d, p) and B3LYP/6-311G+(2d, p) level of theory. Beside the monomeric HAlX2, the argon matrices of the thermolysis experiments contained CH4, HCN, H2C=CH2, H2C=NMe, [H2CCHCH2]?, H2C=CHCH3, and AlXn (n = 1-3; X = Cl or Br).
Metal cyanonitrosyl complexes: Synthesis, magnetic, thermal and spectral studies of some novel mixed-ligand cyanonitrosyl {MnNO}6 complexes of manganese(I) with potentially mono- and bidentate aniline derivatives
Maurya,Singh,Dubey,Shukla
, p. 647 - 660 (2008/10/09)
Novel mixed-ligand cyanonitrosyl {MnNO}6 complexes of manganese(I), formed by the interaction of pentacyanonitrosyl-manganate(I) anion, [Mn(NO)(CN)5]3-, with potentially bidentate aniline derivatives, viz., o-phenylenediamine (o-PDA, I), m-phenylenediamine (m-PDA, II), and potentially monodentate aniline derivatives, o-anisidine (o-ANS, III), m-anisidine (m-ANS, IV), p-anisidine (p-ANS, V), o-phenetidine (o-PD, VI) and m-phenetidine (m-PU, VII), are described. The resulting mixed-ligand complexes, which have been characterized by analytical data, electrical conductances, magnetic measurements, electronic spectra, thermogravimetric analyses and infrared spectral studies, have the compositions [Mn(NO)(CN)2(o-PDA)(H2O)], [Mn(NO)(CH)2(m-PDA)-(H2O)2] or [Mn(NO)(CN)2(L)2(H2O)] (where L = III, IV, V, VI or VII). Suitable octahedral structures have been proposed for the complexes. Manganese(I) has a low-spin {MnNO}6 electron configuration in these complexes.
THE UV PHOTOLYSIS OF AZIDOMETHANE AND 3-AZIDOPROPYNE IN NITROGEN MATRICES
Braathen, G. O.,Klaboe, P.,Nielsen, C. J.,Priebe, H.
, p. 197 - 200 (2007/10/02)
IR spectra of azidomethane, 3-azidopropyne and 3-azido-1-d-propyne in nitrogen matrices have been recorded during UV photolysis.In contrast to the simple photolytic reaction of matrix isolated azidomethane (azidomethane -> methyleneimine -> HCN + HNC), 3-azidopropyne apparently displays more complex reaction paths.
Vibrational product states from reactions of CN- with the hydrogen halides and hydrogen atoms
Maricq, M. Matti,Smith, Mark A.,Simpson, C. J. S. M.,Ellison, G. Barney
, p. 6154 - 6170 (2007/10/02)
Infrared chemiluminescence is observed from the C-H stretch manifold v3 of HCN formed in the gas phase ion-molecule reactions: CN- + HX -> HCN(v3) + X-, with (X=Cl, Br, I), and for CN- + H -> HCN(vsu
Production of Hydrogen Cyanide by the Ammonia Reforming of Toluene
Weigert, Frank
, p. 97 - 98 (2007/10/02)
HCN can be produced from toluene and ammonia in the presence of hydrogen faujasite zeolites at high temperature.
