Atmospheric Chemistry of CHF2CHO:  Study of the IR and UV−Vis Absorption Cross Sections, Photolysis, and OH-, Cl-, and NO3-Initiated Oxidation

2005 ◽  
Vol 109 (16) ◽  
pp. 3652-3662 ◽  
Author(s):  
Stig R. Sellevåg ◽  
Yngve Stenstrøm ◽  
Trygve Helgaker ◽  
Claus J. Nielsen
2020 ◽  
Author(s):  
Thomas R. Lewis ◽  
Juan Carlos Gómez Martin ◽  
Mark A. Blitz ◽  
Carlos A. Cuevas ◽  
John M. C. Plane ◽  
...  

Abstract. Iodine oxides (IxOy) play an important role in the atmospheric chemistry of iodine. They are initiators of new particle formation events in the coastal and polar boundary layer and act as iodine reservoirs in tropospheric ozone-depleting chemical cycles. Despite the importance of the aforementioned processes, the photochemistry of these molecules has not been studied in detail previously. Here, we report the first determination of the absorption cross sections of IxOy, x = 2, 3, 5, y = 1–12 at λ = 355 nm by combining pulsed laser photolysis of I2/O3 gas mixtures in air with time-resolved photo-ionization time-of-flight mass spectrometry, using NO2 actinometry for signal calibration. The oxides selected for absorption cross section determinations are those presenting the strongest signals in the mass spectra, where signals containing 4 iodine atoms are absent. The method is validated by measuring the absorption cross section of IO at 355 nm, σ355 nm, IO = (1.2 ± 0.1) ×  10–18 cm2, which is found to be in good agreement with the most recent literature. The results obtained are: σ355 nm, I2O3 


2020 ◽  
Vol 20 (18) ◽  
pp. 10865-10887
Author(s):  
Thomas R. Lewis ◽  
Juan Carlos Gómez Martín ◽  
Mark A. Blitz ◽  
Carlos A. Cuevas ◽  
John M. C. Plane ◽  
...  

Abstract. Iodine oxides (IxOy) play an important role in the atmospheric chemistry of iodine. They are initiators of new particle formation events in the coastal and polar boundary layers and act as iodine reservoirs in tropospheric ozone-depleting chemical cycles. Despite the importance of the aforementioned processes, the photochemistry of these molecules has not been studied in detail previously. Here, we report the first determination of the absorption cross sections of IxOy, x=2, 3, 5, y=1–12 at λ=355 nm by combining pulsed laser photolysis of I2∕O3 gas mixtures in air with time-resolved photo-ionization time-of-flight mass spectrometry, using NO2 actinometry for signal calibration. The oxides selected for absorption cross-section determinations are those presenting the strongest signals in the mass spectra, where signals containing four iodine atoms are absent. The method is validated by measuring the absorption cross section of IO at 355 nm, σ355nm,IO= (1.2±0.1) ×10-18 cm2, which is found to be in good agreement with the most recent literature. The results obtained are σ355nm,I2O3<5×10-19 cm2 molec.−1, σ355nm,I2O4= (3.9±1.2)×10-18 cm2 molec.−1, σ355nm,I3O6= (6.1±1.6)×10-18 cm2 molec.−1, σ355nm,I3O7= (5.3±1.4)×10-18 cm2 molec.−1, and σ355nm,I5O12= (9.8±1.0)×10-18 cm2 molec.−1. Photodepletion at λ=532 nm was only observed for OIO, which enabled determination of upper limits for the absorption cross sections of IxOy at 532 nm using OIO as an actinometer. These measurements are supplemented with ab initio calculations of electronic spectra in order to estimate atmospheric photolysis rates J(IxOy). Our results confirm a high J(IxOy) scenario where IxOy is efficiently removed during daytime, implying enhanced iodine-driven ozone depletion and hindering iodine particle formation. Possible I2O3 and I2O4 photolysis products are discussed, including IO3, which may be a precursor to iodic acid (HIO3) in the presence of HO2.


2016 ◽  
Vol 120 (45) ◽  
pp. 9049-9062 ◽  
Author(s):  
Antonia G. Zogka ◽  
Abdelwahid Mellouki ◽  
Manolis N. Romanias ◽  
Yuri Bedjanian ◽  
Mahmoud Idir ◽  
...  

2015 ◽  
Vol 17 (48) ◽  
pp. 32539-32546 ◽  
Author(s):  
Elizabeth S. Foreman ◽  
Kara M. Kapnas ◽  
YiTien Jou ◽  
Jarosław Kalinowski ◽  
David Feng ◽  
...  

Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry.


2017 ◽  
Vol 121 (43) ◽  
pp. 8322-8331 ◽  
Author(s):  
María Antiñolo ◽  
Iván Bravo ◽  
Elena Jiménez ◽  
Bernabé Ballesteros ◽  
José Albaladejo

Author(s):  
Kelly Chance ◽  
Randall V. Martin

This chapter provides a broad overview of the spectroscopic principles required in order to perform quantitative spectroscopy of atmospheres. It couples the details of atmospheric spectroscopy with the radiative transfer processes and also with the assessment of rotational, vibrational, and electronic spectroscopic measurements of atmospheres. The principles apply from line-resolved measurements (chiefly microwave through infrared) through ultraviolet and visible measurements employing absorption cross sections developed from individual transitions. The chapter introduces Einstein coefficients before in turn discussing rotational spectroscopy, vibrational spectroscopy, nuclear spin, and electronic spectroscopy.


2021 ◽  
pp. 000370282199044
Author(s):  
Wubin Weng ◽  
Shen Li ◽  
Marcus Aldén ◽  
Zhongshan Li

Ammonia (NH3) is regarded as an important nitrogen oxides (NOx) precursor and also as an effective reductant for NOx removal in energy utilization through combustion, and it has recently become an attractive non-carbon alternative fuel. To have a better understanding of thermochemical properties of NH3, accurate in situ detection of NH3 in high temperature environments is desirable. Ultraviolet (UV) absorption spectroscopy is a feasible technique. To achieve quantitative measurements, spectrally resolved UV absorption cross-sections of NH3 in hot gas environments at different temperatures from 295 K to 590 K were experimentally measured for the first time. Based on the experimental results, vibrational constants of NH3 were determined and used for the calculation of the absorption cross-section of NH3 at high temperatures above 590 K using the PGOPHER software. The investigated UV spectra covered the range of wavelengths from 190 nm to 230 nm, where spectral structures of the [Formula: see text] transition of NH3 in the umbrella bending mode, v2, were recognized. The absorption cross-section was found to decrease at higher temperatures. For example, the absorption cross-section peak of the (6, 0) vibrational band of NH3 decreases from ∼2 × 10−17 to ∼0.5 × 10−17 cm2/molecule with the increase of temperature from 295 K to 1570 K. Using the obtained absorption cross-section, in situ nonintrusive quantification of NH3 in different hot gas environments was achieved with a detection limit varying from below 10 parts per million (ppm) to around 200 ppm as temperature increased from 295 K to 1570 K. The quantitative measurement was applied to an experimental investigation of NH3 combustion process. The concentrations of NH3 and nitric oxide (NO) in the post flame zone of NH3–methane (CH4)–air premixed flames at different equivalence ratios were measured.


Sign in / Sign up

Export Citation Format

Share Document