Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

1995 ◽  
Vol 22 (5) ◽  
pp. 615-618 ◽  
Author(s):  
Z. Zhao ◽  
R. E. Stickel ◽  
P. H. Wine
1968 ◽  
Vol 46 (14) ◽  
pp. 2353-2360 ◽  
Author(s):  
A. N. Strachan ◽  
D. E. Thornton

Ketene has been photolyzed at 3660 and 3130 Å both alone and in the presence of the inert gases C4F8 and SF6. The quantum yield of carbon monoxide has been determined at both wavelengths as a function of pressure and temperature. At 3660 Å the quantum yield decreases with increasing pressure but increases with increasing temperature. At 3130 Å the quantum yield with ketene alone remains 2.0 at both 37 and 100 °C at pressures up to 250 mm. At higher pressures of ketene or with added inert gas the quantum yield decreases with increasing pressure. The results are interpreted in terms of a mechanism in which intersystem crossing from the excited singlet state to the triplet state occurs at both wavelengths, and collisional deactivation of the excited singlet state by ketene is single stage at 3660 Å but multistage at 3130 Å.


1969 ◽  
Vol 47 (18) ◽  
pp. 3345-3353 ◽  
Author(s):  
R. A. Cox ◽  
K. F. Preston

An investigation has been made into the effect of inert gas additions on product quantum yields for the photolysis at 2800 and 2490 Å of mixtures of ketene and oxygen and for the photolysis at 2800 Å of mixtures of ketene and carbon monoxide. Concentration ratios of O2 (or CO) to CH2CO were chosen so that the reaction of CH2(3Σg−) with CH2CO could be ignored and C2H4 formation could be attributed entirely to the reaction[Formula: see text]Quenching of the C2H4 quantum yield by inert gases was interpreted in terms of collisional deactivation of CH2(1A1) to the ground state[Formula: see text]and rate constant ratios k2/k1 have been determined for a number of gases: He (0.018), Ar (0.014), Kr (0.033), Xe (0.074), N2 (0.052), N2O (0.10), CF4 (0.047), C2F6 (0.11), and SF6 (0.045). It has been assumed that collision-induced intersystem crossover in excited singlet ketene makes an insignificant contribution to the observed quenching effects, but it has not been possible to verify this assumption experimentally. The mechanism of collision-induced electronic relaxation of singlet methylene is discussed in the light of the results.


1998 ◽  
Vol 62 (1-2) ◽  
pp. 89-101 ◽  
Author(s):  
Willer H. Pos ◽  
Daniel D. Riemer ◽  
Rod G. Zika

2012 ◽  
Vol 9 (6) ◽  
pp. 6947-6985 ◽  
Author(s):  
H. E. Reader ◽  
W. L. Miller

Abstract. The photochemical oxidation of oceanic dissolved organic carbon (DOC) to carbon monoxide (CO) and carbon dioxide (CO2) has been estimated to be a significant process with global photoproduction transforming petagrams of DOC to inorganic carbon annually. To further quantify the importance of these two photoproducts in coastal DOC cycling, 38 paired apparent quantum yield (AQY) spectra for CO and CO2 were determined at three locations along the coast of Georgia, USA over the course of one year. The AQY spectra for CO2 were considerably more varied than CO. CO AQY spectra exhibited a seasonal shift in spectrally integrated (260 nm–490 nm) AQY from higher efficiencies in the fall to less efficient photoproduction in the summer. While full-spectrum photoproduction rates for both products showed positive correlation with pre-irradiation UV-B sample absorption (i.e. chromophoric dissolved organic matter, CDOM) as expected, we found no correlation between AQY and CDOM for either product at any site. Molecular size, approximated with pre-irradiation spectral slope coefficients, and aromatic content, approximated by the specific ultraviolet absorption of the pre-irradiated samples, were also not correlated with AQY in either data set. The ratios of CO2 to CO photoproduction determined using both an AQY model and direct production comparisons were 23.2 ± 12.5 and 22.5 ± 9.0, respectively. Combined, both products represent a loss of 2.2 to 2.6 % of the DOC delivered to the estuaries and inner shelf of the South Atlantic Bight yearly, and 5 to 6 % of the total annual degassing of CO2 to the atmosphere. This result suggests that direct photochemical production of CO and CO2 is a small, yet significant contributor to both DOC cycling and CO2 gas exchange in this coastal system.


2018 ◽  
Vol 18 (2) ◽  
pp. 1363-1378 ◽  
Author(s):  
Wu Sun ◽  
Linda M. J. Kooijmans ◽  
Kadmiel Maseyk ◽  
Huilin Chen ◽  
Ivan Mammarella ◽  
...  

Abstract. Soil is a major contributor to the biosphere–atmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify terrestrial photosynthesis based on the coupled leaf uptake of COS and CO2, but such use requires separating soil COS flux, which is unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is a significant natural sink that influences the tropospheric CO budget. In the boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain poorly understood. We measured hourly soil fluxes of COS, CO, and CO2 over the 2015 late growing season (July to November) in a Scots pine forest in Hyytiälä, Finland. The soil acted as a net sink of COS and CO, with average uptake rates around 3 pmol m−2 s−1 for COS and 1 nmol m−2 s−1 for CO. Soil respiration showed seasonal dynamics controlled by soil temperature, peaking at around 4 µmol m−2 s−1 in late August and September and dropping to 1–2 µmol m−2 s−1 in October. In contrast, seasonal variations of COS and CO fluxes were weak and mainly driven by soil moisture changes through diffusion limitation. COS and CO fluxes did not appear to respond to temperature variation, although they both correlated well with soil respiration in specific temperature bins. However, COS : CO2 and CO : CO2 flux ratios increased with temperature, suggesting possible shifts in active COS- and CO-consuming microbial groups. Our results show that soil COS and CO fluxes do not have strong variations over the late growing season in this boreal forest and can be represented with the fluxes during the photosynthetically most active period. Well-characterized and relatively invariant soil COS fluxes strengthen the case for using COS as a photosynthetic tracer in boreal forests.


1968 ◽  
Vol 46 (16) ◽  
pp. 2693-2697 ◽  
Author(s):  
R. Payette ◽  
M. Bertrand ◽  
Y. Rousseau

The mercury-photosensitized decomposition of dimethyl ether has been studied at room temperature and at pressures ranging from 10 to 200 Torr.The formation of an excited dimethyl ether (DME) molecule has been verified by following the rates of formation of methane, ethane, and carbon monoxide with various ether pressures.The study of the variation of the quantum yield of molecular hydrogen formation with absorbed light intensity at high ether pressures has shown that the primary process involves the dissociation of ether molecules into hydrogen atoms and methoxy methyl radicals:[Formula: see text]The results presented in this paper indicate that the excited DME molecule can originate in a radical recombination between hydrogen atoms and methoxy methyl radicals.


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