Reaction of hydrogen cyanide and deuterium behind reflected shock waves

Brupbacher, J. M.; Kern, R. D.

doi:10.1021/j100647a001

Cited by 7 publications

(4 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…H2, D2 + CN --HCN, DCN + H, D 0.73 (15) H, D + C2N2 -*-HCN, DCN + CN 0.715 (16) H2, D2 + C2N2d -2HCN, DCN 0.72 (17)…”

Section: Discussionmentioning

confidence: 99%

“…A more definite statement may be made with regard to the role of cyanogen in the HCN + D2 exchange. 15 The proposal involved the following steps.…”

Section: Discussionmentioning

confidence: 99%

“…Calibration experiments on the ir system consisted of doubly distilled hydrogen cyanide which had been prepared for an earlier study. 15 The diluent gas for the TOF experiments was a mixture of Matheson Research Grade 99% Ne-1% Ar. For the ir experiments Liquid Carbonic argon (99.99%) was used as the diluent.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Reaction of cyanogen and hydrogen behind reflected shock waves

Brupbacher¹,

Kern²

1973

J. Phys. Chem.

Self Cite

View full text Add to dashboard Cite

The metathetical reaction, C2N2 + H2 <=r 2HCN, has been studied by shocking equimolar amounts of the reactants in the presence of an inert gas diluent over the temperature range 1850-2650°K. A complementary shock tube facility was utilized to obtain the data from the reflected shock zone by recording the infrared emission of HCN and the time-resolved mass spectra at m/e 27 (HCN) and 52 (C2N2). The total density variation was 1.8-4.4 X 10~8 mol/cm3. Observation times were typically 500 psec during which period an equilibrium condition was established for the higher temperature experiments. The growth of the mole fraction of HCN, /hcn, was found to be a nonlinear function of time and to depend upon the inert gas concentration, [M]. The data from the two independent techniques of infrared emission and mass spectrometry were fitted to the bimolecular rate expression that includes the back reaction, In |[(X -4)/Hcn -(X + 2X1/2)]/[(X-4)/HCn -(X -where the forward rate constant is given by fci = 102®-3S±0-21 exp(-61,610 ± 2010/RT) cm3 mol-1 sec-2 [M]-°-75. These results rule out the direct bimolecular reaction. This complex reaction is discussed in terms of an atomic mechanism and a mechanism involving vibrationally excited species. Experiments on an equimolar mixture of cyanogen and deuterium revealed a lowering of the preexponential factor in reasonable agreement with that predicted from the square root of the inverse ratio of reduced masses.

show abstract

“…H2, D2 + CN --HCN, DCN + H, D 0.73 (15) H, D + C2N2 -*-HCN, DCN + CN 0.715 (16) H2, D2 + C2N2d -2HCN, DCN 0.72 (17)…”

Section: Discussionmentioning

confidence: 99%

“…A more definite statement may be made with regard to the role of cyanogen in the HCN + D2 exchange. 15 The proposal involved the following steps.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Reaction of cyanogen and hydrogen behind reflected shock waves

Brupbacher¹,

Kern²

1973

J. Phys. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Reports on spectroscopic detection of HCN behind shock waves are scarce. In early work of Brupbacher and Kern, , who recorded the first kinetic profiles of HCN (and DCN) behind shock waves by detecting the CH stretch band emission centered at 3.0 ± 0.1 μm (mostly referred to as the ν 1 band), equimolar mixtures of 1–2% HCN/D 2 or C 2 N 2 /H 2 in argon were shock-heated to investigate the isotope exchange mechanism and the formation of HCN, respectively. Later, Chang and Hanson investigated the pressure broadening of the P(10) line in the ν 1 band using tunable diode laser spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Mid-infrared Frequency Modulation Detection of HCN and Its Reaction with O Atoms behind Shock Waves

Stuhr

Friedrichs

2022

J. Phys. Chem. A

View full text Add to dashboard Cite

Hydrogen cyanide (HCN) is the primary cyanide species in combustion processes and plays a key role in the formation of NO x in the combustion of fossil fuels, nitrogencontaining biofuels, and blended hydrocarbon−ammonia mixtures. Robust, sensitive, and time-resolved in situ laser diagnostic methods are needed to gain insight into the combustion chemistry of HCN. Mid-infrared frequency modulation spectroscopy (MIR-FMS) has recently been established as such a quantitative technique for HCN detection behind shock waves. With a minimum detectable fractional absorption of 2 × 10 −4 at a time resolution of 5 μs, an improved spectrometer design enabled the detection of HCN behind shock waves down to the ppm mole fraction level. An Allan noise analysis revealed that a further improvement toward shot-noise limited detection should be possible when fast mid-infrared photodetectors with a higher saturation limit will become available. HCN kinetic profiles in the presence of O( 3 P) atoms from thermal N 2 O decomposition have been measured in the temperature range 1448 K < T < 1954 K. The determined total rate constants for the key HCN oxidation reaction HCN + O, k/(cm 3 mol −1 s −1 ) = 1.88 × 10 14 exp(−64.5 kJ mol −1 /RT)(+28%, −37%), turn out to be largely consistent with previous measurements. These data complete the set of available rate constant studies, by now covering the temperature range 450 K < T < 2500 K and relying on the detection of almost all feasible reactant and product species.

show abstract

ChemInform Abstract: RK. VON HCN UND DEUTERIUM NACH REFLEKTIERTEN STOSSWELLEN

Brupbacher¹,

Kern²

1972

Chemischer Informationsdienst

View full text Add to dashboard Cite

Reaction of hydrogen cyanide and deuterium behind reflected shock waves

Cited by 7 publications

References 1 publication

Reaction of cyanogen and hydrogen behind reflected shock waves

Reaction of cyanogen and hydrogen behind reflected shock waves

Mid-infrared Frequency Modulation Detection of HCN and Its Reaction with O Atoms behind Shock Waves

ChemInform Abstract: RK. VON HCN UND DEUTERIUM NACH REFLEKTIERTEN STOSSWELLEN

Contact Info

Product

Resources

About