Kinetics of CH₂OO reactions with SO₂, NO₂, NO, H₂O and CH₃CHO as a function of pressure

Kinetics of CH₂OO Criegee intermediate reactions with SO₂, NO₂, NO, H₂O and CH₃CHO and CH₂I radical reactions with NO₂ are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH₂I₂–O₂–N₂ gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO₂, direct detection of CH₂OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH₂OO + SO₂ and CH₂OO + NO₂ are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10‾¹¹ cm³ s‾¹ (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10‾¹² cm³ s‾¹ (measured between 25 and 300 Torr), respectively. The rate coefficient for CH₂OO + CH₃CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10−13 cm³ s‾¹ and 9 × 10−17 cm³ s‾¹ are placed on the rate coefficients for CH₂OO + NO and CH₂OO + H₂O, respectively. The upper limit for the rate coefficient for CH₂OO + H₂O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH₂OO chemistry

An instrument to measure fast gas phase radical kinetics at hight temperatures and pressures

Fast radical reactions are central to the chemistry of planetary atmospheres and combustion systems. Laser-induced fluorescence is a highly sensitive and selective technique that can be used to monitor a number of radical species in kinetics experiments, but is typically limited to low pressure systems owing to quenching of fluorescent states at higher pressures. The design and characterisation of an instrument is reported using laser-induced fluorescence detection to monitor fast radical kinetics (up to 25,000 s-1) at high temperatures and pressures by sampling from a high pressure reaction region to a low pressure detection region. Kinetics have been characterised at temperatures reaching 740 K and pressures up to 2 atm, with expected maximum operational conditions of up to ~ 900 K and ~ 5 atm. The distance between the point of sampling from the high pressure region and the point of probing within the low pressure region is critical to the measurement of fast kinetics. The instrumentation described in this work can be applied to the measurement of kinetics relevant to atmospheric and combustion chemistry

OH yields from the CH3CO+O-2 reaction using an internal standard

Laser flash photolysis of CH3C(O)OH at 248 nm was used to create equal zero time yields of CH3CO and OH. The absolute OH yield from the CH3CO + O2 (+M) reaction was determined by following the OH temporal profile using the zero time OH concentration as an internal standard. The OH yield from CH3CO + O2 (+M) was observed to decrease with increasing pressure with an extrapolated zero pressure yield close to unity (1.1 ± 0.2, quoted uncertainties correspond to 95% confidence limits). The results are in quantitative agreement with those obtained from 248 nm acetone photolysis in the presence of O2

Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction

The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH+O2 (Reaction R5a), CH3C(O)OH+O3 (Reaction R5b), CH3+CO2+OH+O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293±2)K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37±0.10, α(R5b) =0.12±0.04 and α(R5c) =0.51±0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) =(2.4±0.4)×10-11 cm3 molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5% in OH concentrations in tropical rainforest areas and increases of up to 10% at altitudes of 6-8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx

An intercomparison of CH3O2 measurements by Fluorescence Assay by Gas Expansion and Cavity Ring–Down Spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

Simultaneous measurements of CH3O2 radical concentrations have been performed using two different methods in the Leeds HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) chamber at 295 K and in 80 mbar of a mixture of 3 : 1 He : O2 and 100 mbar or 1000 mbar of synthetic air. The first detection method consisted of the indirect detection of CH3O2 using the conversion of CH3O2 into CH3O by excess NO with subsequent detection of CH3O by fluorescence assay by gas expansion (FAGE). The FAGE instrument was calibrated for CH3O2 in two ways. In the first method, a known concentration of CH3O2 was generated using the 185 nm photolysis of water vapour in synthetic air at atmospheric pressure followed by the conversion of the generated OH radicals to CH3O2 by reaction with CH4 / O2. This calibration can be used for experiments performed in HIRAC at 1000 mbar in air. In the second method, calibration was achieved by generating a near steady-state of CH3O2 and then switching off the photolysis lamps within HIRAC and monitoring the subsequent decay of CH3O2 which was controlled via its self-reaction, and analysing the decay using second order kinetics. This calibration could be used for experiments performed at all pressures. In the second detection method, CH3O2 has been measured directly using Cavity Ring-Down Spectroscopy (CRDS) using the absorption at 7487.98 cm-1 in the A <– X (ν12) band with the optical path along the ~1.4 m chamber diameter. Analysis of the second-order kinetic decays of CH3O2 by self-reaction monitored by CRDS has been used for the determination of the CH3O2 absorption cross section at 7487.98 cm-1, both at 100 mbar of air and at 80 mbar of a 3 : 1 He : O2 mixture, from which σCH3O2 = (1.49 ± 0.19) × 10–20 cm2 molecule-1 was determined for both pressures. The absorption spectrum of CH3O2 between 7486 and 7491 cm-1 did not change shape when the total pressure was increased to 1000 mbar, from which we determined that σCH3O2 is independent of pressure over the pressure range 100–1000 mbar in air. CH3O2 was generated in HIRAC using either the photolysis of Cl2 with UV black lamps in the presence of CH4 and O2 or the photolysis of acetone at 254 nm in the presence of O2. At 1000 mbar of synthetic air the correlation plot of [CH3O2]FAGE against [CH3O2]CRDS gave a gradient of 1.10 ± 0.02. At 100 mbar of synthetic air the gradient of the FAGE – CRDS correlation plot had a gradient of 1.06 ± 0.01 and at 80 mbar of 3 : 1 He : O2 mixture the correlation plot gradient was 0.91 ± 0.02. These results provide a validation of the FAGE method to determine concentrations of CH3O2

Design of and initial results from a highly instrumented reactor for atmospheric chemistry (HIRAC)

International audienceThe design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; and NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and measurements of the blacklamp flux have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response under a range of atmospheric conditions

Kinetics of the Reactions of Hydroxyl Radicals with Furan and its Alkylated Derivatives 2-Methyl Furan and 2,5-Dimethyl Furan

Furans are promising second generation biofuels with comparable energy densities to conventional fossil fuels. Combustion of furans is initiated and controlled to a large part by reactions with OH radicals, the kinetics of which are critical to understand the processes occurring under conditions relevant to low-temperature combustion. The reactions of OH radicals with furan (OH + F, R1), 2-methyl furan (OH + 2-MF, R2), and 2,5-dimethyl furan (OH + 2,5-DMF, R3) have been studied in this work over the temperature range 294 to 668 K at pressures between 5 mbar and 10 bar using laser flash photolysis coupled with laser-induced fluorescence (LIF) spectroscopy to generate and monitor OH radicals under pseudo-first-order conditions. Measurements at p ≤ 200 mbar were made in N2, using H2O2 or (CH3)3COOH radical precursors, while those at p ≥ 2 bar were made in He, using HNO3 as the radical precursor. The kinetics of the reactions R1-R3 were observed to display a negative dependence on temperature over the range investigated, indicating the dominance of addition reactions under such conditions, with no significant dependence on pressure observed. Master equation calculations are in good agreement with the observed kinetics, and a combined parameterisation of addition channels and abstraction channels for R1-R3 is provided on the basis of this work and previous shock tube measurements at higher temperatures. This work significantly extends the temperature range previously investigated for R1 and represents the first temperature-dependent measurements of R2 and R3 at temperatures relevant for atmospheric chemistry and low-temperature combustion

Unimolecular decomposition kinetics of the stabilised Criegee intermediates CH₂OO and CD₂OO

Decomposition kinetics of stabilised CH2OO and CD2OO Criegee intermediates have been investigated as a function of temperature (450–650 K) and pressure (2–350 Torr) using flash photolysis coupled with time-resolved cavity-enhanced broadband UV absorption spectroscopy. Decomposition of CD2OO was observed to be faster than CH2OO under equivalent conditions. Production of OH radicals following CH2OO decomposition was also monitored using flash photolysis with laser-induced fluorescence (LIF), with results indicating direct production of OH in the v = 0 and v = 1 states in low yields. Master equation calculations performed using the Master Equation Solver for Multi-Energy well Reactions (MESMER) enabled fitting of the barriers for the decomposition of CH2OO and CD2OO to the experimental data. Parameterisations of the decomposition rate coefficients, calculated by MESMER, are provided for use in atmospheric models and implications of the results are discussed. For CH2OO, the MESMER fits require an increase in the calculated barrier height from 78.2 kJ mol−1 to 81.8 kJ mol−1 using a temperature-dependent exponential down model for collisional energy transfer with 〈ΔE〉down = 32.6(T/298 K)1.7 cm−1 in He. The low- and high-pressure limit rate coefficients are k1,0 = 3.2 × 10−4(T/298)−5.81exp(−12 770/T) cm3 s−1 and k1,∞ = 1.4 × 1013(T/298)0.06exp(−10 010/T) s−1, with median uncertainty of ∼12% over the range of experimental conditions used here. Extrapolation to atmospheric conditions yields k1(298 K, 760 Torr) = 1.1+1.5−1.1 × 10−3 s−1. For CD2OO, MESMER calculations result in 〈ΔE〉down = 39.6(T/298 K)1.3 cm−1 in He and a small decrease in the calculated barrier to decomposition from 81.0 kJ mol−1 to 80.1 kJ mol−1. The fitted rate coefficients for CD2OO are k2,0 = 5.2 × 10−5(T/298)−5.28exp(−11 610/T) cm3 s−1 and k2,∞ = 1.2 × 1013(T/298)0.06exp(−9800/T) s−1, with overall error of ∼6% over the present range of temperature and pressure. The extrapolated k2(298 K, 760 Torr) = 5.5+9.2−5.5 × 10−3 s−1. The master equation calculations for CH2OO indicate decomposition yields of 63.7% for H2 + CO2, 36.0% for H2O + CO and 0.3% for OH + HCO with no significant dependence on temperature between 400 and 1200 K or pressure between 1 and 3000 Torr

On-line solid phase microextraction derivatization for the sensitive determination of multi-oxygenated volatile compounds in air

Multi-oxygenated volatile organic compounds are important markers of air pollution and precursors of ozone and secondary aerosols in both polluted and remote environments. Herein, their accurate determination was enhanced. The approach was based on an automated system for active sampling and on-fibre derivatization coupled with the gas chromatography–mass spectrometry (GC–MS) technique. The method capability was determined for different compound families, such as aldehydes, ketones, α-dicarbonyls, hydroxy-aldehydes, hydroxy-ketones, and carboxylic acids. A good accuracy (<7 %) was demonstrated from the results compared to Fourier-transform infrared spectroscopy (FTIR). Limits of detection (LODs) of 6–100 pptV were achieved with a time resolution lower than 20 min. The developed method was successfully applied to the determination of multi-oxygenated compounds in air samples collected during an intercomparison campaign (EUROCHAMP-2020 project). Also, its capability and accuracy for atmospheric monitoring was demonstrated in an isoprene ozonolysis experiment. Both were carried out in the high-volume outdoor atmospheric simulation chambers (EUPHORE, 200 m3). In summary, our developed technique offers near-real-time monitoring with direct sampling, which is an advantage in terms of handling and labour time for a proper quantification of trace levels of atmospheric multi-oxygenated compounds

A newly developed tool for intra-tracheal temperature and humidity assessment in laryngectomized individuals: the Airway Climate Explorer (ACE)

The aim of this study is to develop a postlaryngectomy airway climate explorer (ACE) for assessment of intratracheal temperature and humidity and of influence of heat and moisture exchangers (HMEs). Engineering goals were within-device condensation prevention and fast response time characteristics. The ACE consists of a small diameter, heated air-sampling catheter connected to a heated sensor house, containing a humidity sensor. Air is sucked through the catheter by a controlled-flow pump. Validation was performed in a climate chamber using a calibrated reference sensor and in a two-flow system. Additionally, the analyser was tested in vivo. Over the clinically relevant range of humidity values (5–42 mg H2O/l air) the sensor output highly correlates with the reference sensor readings (R2 > 0.99). The 1–1/e response times are all <0.5 s. A first in vivo pilot measurement was successful. The newly developed, verified, fast-responding ACE is suitable for postlaryngectomy airway climate assessment