HNC/HCN Ratio in Acetonitrile, Formamide, and BrCN Discharge

0359561 - ÚFCH JH 2012 RIV US eng J - Journal Article
Ferus, Martin - Kubelík, Petr - Kawahata, K. - Dryahina, Kseniya - Španěl, Patrik - Civiš, Svatopluk
HNC/HCN Ratio in Acetonitrile, Formamide, and BrCN Discharge.
Journal of Physical Chemistry A. Roč. 115, č. 10 (2011), s. 1885-1899. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA AV ČR IAA400400705; GA AV ČR IAAX00100903; GA ČR GAP208/10/2302; GA ČR GA202/09/0800
Institutional research plan: CEZ:AV0Z40400503
Keywords : transform infrared spectroscopy * transition sipole moment * HNC/HCN abundance ratio
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.946, year: 2011

Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH3CN), and formamide (HCONH2). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v(1) were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms.
Permanent Link: http://hdl.handle.net/11104/0006442