An infrared laser study of the atomic oxygen (3P) + carbon disulfide reaction

2011

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The kinetics of the NCCO + NO(2) reaction was studied by transient infrared laser absorption spectroscopy. The total rate constant of the reaction was measured to be k = (2.1 ± 0.1) × 10(-11) cm(3) molecule(-1) s(-1) at 298 K. Detection of products and consideration of possible secondary chemistry shows that CO(2) + NO + CN is the primary product channel. The rate constants of the NCCO + CH(4) and NCCO + C(2)H(4) reactions were also measured, obtaining upper limits of k (NCCO + CH(4)) ≤ 7.0 × 10(-14) cm(3) molecule(-1) s(-1) and k (NCCO + C(2)H(4)) ≤ 5.0 × 10(-15) cm(3) molecule(-1) s(-1). Ab initio calculations on the singlet and triplet potential energy surfaces at B3LYP/6-311++G**//CCSD(T)/6-311++G** levels of theory show that the most favorable reaction pathway occurs on the singlet surface, leading to CO(2) + NO + CN products, in agreement with experiment.

Section: Methodsmentioning

confidence: 84%

Kinetics of the NCCO + NO₂ Reaction

2011

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“…19,20 One of the CN (V ) 1 r V ) 0) transitions was located and identified at 2071.41 cm -1 ; this corresponds to the R(8) line. 21 IR and UV light were made collinear and passed through a single-pass 143-cm absorption cell, and the transmitted infrared light was detected by a 1-mm diameter InSb detector (Cincinnati Electronics, ∼1 µs response time) and signal averaged on a digital oscilloscope.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of the CN + CS₂ and CN + SO₂ Reactions

2010

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Diode infrared laser absorption spectroscopy was used to measure the rate constant (k(1)) of the CN + CS(2) reaction for the first time. k(1) was determined to be substantially pressure dependent with a value k(1) = (7.1 ± 0.2 to 41.9 ± 2.9) × 10(-12) cm(3) molecule(-1) s(-1) over 2-40 Torr at 298 K. The potential energy surface (PES) of the reaction was calculated using an ab initio method at B3LYP/6-311++G(d, p)//CCSD(T)/6-311++G(d, p) level of theory. Both experimental and computational results suggest that collision stabilization of the adduct NCSCS may dominate the reaction. The rate constant of the CN + SO(2) reaction was measured to be very slow with an upper limit of k(2) ≤ 3.1 × 10(-14) cm(3) molecule(-1) s(-1), in disagreement with an earlier reported measurement. The PES of this reaction reveals an entrance barrier against formation of the low energy adduct NCOSO, in agreement with the experimental result.

“…11,12 IR and UV light passed through a single-pass 143-cm absorption cell, and the infrared light was detected by a 1-mm diameter InSb detector (Cincinnati Electronics, ∼1 µs response time) and the signal was averaged on a digital oscilloscope. To account for small-probe laser thermal deflection affects, signals were collected with the diode laser slightly detuned off the spectroscopic absorption lines, and such transients were subtracted from the on-resonant transients.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of the NCO + HCNO Reaction

2006

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The kinetics of the NCO + HCNO reaction were studied using infrared diode laser absorption spectroscopy. The total rate constant was measured to be k(1) = (1.58 +/- 0.20) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K. After detection of products and consideration of secondary chemistry (primarily O + HCNO and CN + HCNO), we conclude that NO + CO + HCN is the major product channel (phi = 0.92 +/- 0.04), with a minor contribution (phi = 0.04 +/- 0.02) from CO2 + HCNN.