Some Photochemical Reactions of O3 in the Gas Phase

Katakis, D.; Taube, Henry

doi:10.1063/1.1732521

Cited by 88 publications

(32 citation statements)

References 11 publications

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“…Milligan & Jacox (179) reexamined the C03 molecule produced by vacuum uv photolysis of solid CO2• Their findings confirmed the results of previous investigators (180,181). Pyrolysis con ditions were adj usted to maximize the BH3 output as monitored by mass spectroscopy.…”

Section: Studies Of Special Interestssupporting

confidence: 61%

Infrared Spectroscopy

Ewing¹

1972

Annu. Rev. Phys. Chem.

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The past several reviews (1-3) presented in the Annual Review of Physical Chemistry entitled "Vibrational Spectroscopy" have included discussion of both Raman and infrared techniques. The present review is then somewhat unique since only infrared spectroscopy is to be considered. The recent de velopment of tunable infrared sources and the new techniques of nonlinear absorption that provide extraordinarily high resolution spectra justify re stricting the topic of this review to infrared spectroscopy alone since important new directions in this field are being mapped. Furthermore a new emphasis on determining intermolecular forces of molecules by infrared spectroscopy seems to be forming.The topics selected in this review reflect the author's own subjective view of what is interesting and exciting in the field. It is hoped that the reader will find what is presented here a fair presentation of at least some of the new trends in infrared spectroscopy. INSTRUMENTATION 2Hadamard transform spectroscopy.-There is considerable interest in developing cheap and efficient infrared spectrometers for the quantitative detection of specific components of industrial and atmospheric samples. The recently developed Hadamard Transform Spectrometer (HTS) (4, 5) offers several advantages over conventional dispersive spectrometers, filter spectrom eters (6), and Michelson interferometers. A conventional scanning instrument is very slow and has highly restricted throughput. Although the Michelson interferometer uses available signal power more efficiently, much of the data collected have no information content of analytical interest. Filter spectrophotometers and dispersive instruments equipped with multiple detectors require expensive repetitious electronics and are highly susceptible to internal drift.Consider the determination of the intensities on N spectral elements cor responding to characteristic absorption features of each component of interest. Instead of measuring the intensity of each spectral element separately, the HTS concept involves simultaneously measuring a combination of several of

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Section: Studies Of Special Interestssupporting

confidence: 61%

Infrared Spectroscopy

Ewing¹

1972

Annu. Rev. Phys. Chem.

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“…Finally, the CO 2 is passed through a glass U‐trap at dry‐ice temperature (−78°C) to remove remaining traces of water. Heating the O 3 and CO 2 mixture above 200°C might cause isotope exchange between O 3 and CO 2 , but it does not cause a problem for our purpose which is to prepare 17 O‐enriched CO 2 .…”

Section: Methodsmentioning

confidence: 99%

Determination of the triple oxygen and carbon isotopic composition of CO₂ from atomic ion fragments formed in the ion source of the 253 Ultra high‐resolution isotope ratio mass spectrometer

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Hofmann

Paul

et al. 2019

Rapid Comm Mass Spectrometry

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Rationale Determination of δ17O values directly from CO2 with traditional gas source isotope ratio mass spectrometry is not possible due to isobaric interference of 13C16O16O on 12C17O16O. The methods developed so far use either chemical conversion or isotope equilibration to determine the δ17O value of CO2. In addition, δ13C measurements require correction for the interference from 12C17O16O on 13C16O16O since it is not possible to resolve the two isotopologues. Methods We present a technique to determine the δ17O, δ18O and δ13C values of CO2 from the fragment ions that are formed upon electron ionization in the ion source of the Thermo Scientific 253 Ultra high‐resolution isotope ratio mass spectrometer (hereafter 253 Ultra). The new technique is compared with the CO2‐O2 exchange method and the 17O‐correction algorithm for δ17O and δ13C values, respectively. Results The scale contractions for δ13C and δ18O values are slightly larger for fragment ion measurements than for molecular ion measurements. The δ17O and Δ17O values of CO2 can be measured on the 17O+ fragment with an internal error that is a factor 1–2 above the counting statistics limit. The ultimate precision depends on the signal intensity and on the total time that the 17O+ beam is monitored; a precision of 14 ppm (parts per million) (standard error of the mean) was achieved in 20 hours at the University of Göttingen. The Δ17O measurements with the O‐fragment method agree with the CO2‐O2 exchange method over a range of Δ17O values of −0.3 to +0.7‰. Conclusions Isotope measurements on atom fragment ions of CO2 can be used as an alternative method to determine the carbon and oxygen isotopic composition of CO2 without chemical processing or corrections for mass interferences.

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“…[1][2][3][4] In view of radiation-induced degradation of oxygen-bearing molecules such as ozone or carbon dioxide, ionizing radiation from the solar wind can liberate oxygen atoms in their electronic ground ( 3 P) or first electronically excited state ( 1 D), both with a significant amount of excess kinetic energy. It was suggested that these atoms reacted with carbon dioxide molecules either in the gas phase [5][6][7] or in the solid state [8][9][10] to form a carbon trioxide intermediate(s) [Eq. (1)].…”

Section: Introductionmentioning

confidence: 99%

“…The oxygen atoms can react with adjacent carbon dioxide molecules in the ice, thereby forming carbon trioxide. The pathway to the C 2v isomer is experimentally known [5,6,[8][9][10] [Equation (3)]. …”

mentioning

confidence: 99%

Identification of the D_3h Isomer of Carbon Trioxide (CO₃) and Its Implications for Atmospheric Chemistry

2006

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The CO3 molecule is considered an important reaction intermediate in the atmospheres of Earth and Mars for quenching electronically excited oxygen atoms and in contributing to the anomalous 18O isotope enrichment. The geometry of the CO3 intermediate plays an important role in explaining these effects; however, only the cyclic (C(2v)) isomer has been experimentally confirmed so far. Here, we report on the first spectroscopic detection of the acyclic (D(3h)) isomer of carbon trioxide (12C16O3) via its nu1 and nu2 vibrational modes centered around 1165 cm(-1) under matrix isolation conditions; the identification of the 12C18O3, 13C16O3, 13C18O3, 16O12C18O2, and 18O12C16O2 isotopomers of the acyclic isomer confirms the assignments.

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Some Photochemical Reactions of O3 in the Gas Phase

Cited by 88 publications

References 11 publications

Infrared Spectroscopy

Infrared Spectroscopy

Determination of the triple oxygen and carbon isotopic composition of CO₂ from atomic ion fragments formed in the ion source of the 253 Ultra high‐resolution isotope ratio mass spectrometer

Identification of the D_3h Isomer of Carbon Trioxide (CO₃) and Its Implications for Atmospheric Chemistry

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Some Photochemical Reactions of O3 in the Gas Phase

Cited by 88 publications

References 11 publications

Infrared Spectroscopy

Infrared Spectroscopy

Determination of the triple oxygen and carbon isotopic composition of CO2 from atomic ion fragments formed in the ion source of the 253 Ultra high‐resolution isotope ratio mass spectrometer

Identification of the D3h Isomer of Carbon Trioxide (CO3) and Its Implications for Atmospheric Chemistry

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Determination of the triple oxygen and carbon isotopic composition of CO₂ from atomic ion fragments formed in the ion source of the 253 Ultra high‐resolution isotope ratio mass spectrometer

Identification of the D_3h Isomer of Carbon Trioxide (CO₃) and Its Implications for Atmospheric Chemistry