Evaluation of a High-Purity and High-Stability Continuous Generation System for Nitrous Acid

Febo, A.; Perrino, Cinzia; Gherardi, M.; Sparapani, R.

doi:10.1021/es00009a035

Cited by 105 publications

(161 citation statements)

References 11 publications

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“…Gaseous HONO was produced by the reaction of gaseous HCl with solid NaNO 2 in a continuously stirred tank reactor (Figure 3), as suggested by the recent work of Febo et al 19 Consistent with this work, it was found that a temperature of 50°C produced maximum yield. Adjustments were made as needed to keep the reactor in the range of 50 ( 0.5°C.…”

Section: Experimental Approach and Data Reductionsupporting

confidence: 76%

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Tichenor¹,

Graham²,

Yamada³

et al. 2000

J. Phys. Chem. A

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Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C 2 Cl 4 (k 1 ) over an extended temperature range at 740 ( 10 Torr in a He bath gas. These absolute rate measurements were conducted using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The lower temperature values for k 1 are within (2σ of previous data using different techniques. The overall slope of our Arrhenius plot varies slightly from previously reported values. Agreement within our own data holds up to ∼720 K, but reliable measurement beyond this temperature was hampered by apparent thermal decomposition of our OH source (HONO). An Arrhenius fit to the data yielded the expression k 1 (T) ) (1.68 ( 0.25) × 10 -12 exp(-764.2 ( 79.1/T), whereas a three-parameter Arrhenius fit yielded the expression k 1 (T) ) (1.93 ( 0.20) × 10 -22 (T) 3.2 exp(660.8 ( 54.6/T), where k is in units of cm 3 molecule -1 s -1 . This work shows some deviation from previous low-temperature data. We propose that surface absorption influenced previously measured rate constants. Significant absorption was evident at low temperatures, and an experimental technique was developed to negate this effect. The predicted mechanisms were conceptualized using ab initio calculations to define the activated complex and transient intermediates, and thus predict the most likely path and products. Quantum RRK analysis yielded no overall pressure dependence. Model predictions indicate that trichloroethenol formation via Cl elimination dominates up to temperatures of 2000 K. At flame temperatures, the analysis also predicts increased formation of trichloroacetyl chloride with hydrogen elimination and back reaction to the original reactants.

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Section: Experimental Approach and Data Reductionsupporting

confidence: 76%

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Tichenor¹,

Graham²,

Yamada³

et al. 2000

J. Phys. Chem. A

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“…24 However, the desired concentration of HONO was produced by the reaction of NaNO2 with water vapor 26 in this study. Specifically, humidified zero air was introduced into a glass chamber (7.5-cm inner diameter and 24-cm length).…”

Section: Preparation Of Gaseous Hono and No2mentioning

confidence: 87%

“…In this study, simultaneous measurements of HONO using IBBCEAS and a chemiluminescence NOx analyzer with a molybdenum reducing catalyst (Mo converter) was carried out. Because the NOx analyzer with a Mo converter can measure HONO concentrations in the absence of any other nitrogen compounds, 14,24 comparisons between these two different measurement techniques can be used to validate measurements of HONO using IBBCEAS. Because NO2 and HONO coexist in ambient air, the simultaneous measurement of the mixtures of HONO and NO2 gases was undertaken.…”

Section: Introductionmentioning

confidence: 99%

Validation of in situ Measurements of Atmospheric Nitrous Acid Using Incoherent Broadband Cavity-enhanced Absorption Spectroscopy

Nakashima

Sadanaga

2017

ANAL. SCI.

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Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) is a useful technique for measuring trace gaseous species in the atmosphere. Recently, IBBCEAS was used to measure concentrations of nitrous acid (HONO) in the troposphere to resolve controversies related to its formation and loss. Here, measurements of HONO and a mixture of HONO and NO2 using IBBCEAS were validated by comparing them with those obtained with a NOx analyzer. Good agreement was found between these methods, given their respective experimental uncertainties. The detection limit of our IBBCEAS instrument was 0.2 ppbv, with a signal-to-noise ratio of 1, and a 5-min integration time.

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“…The inlet was overflowed with this gas combination for more than 8 h. NH 3(g) and HONO (g) were produced from a permeation device housed in a temperature-controlled oven [e.g., Markovic et al, 2012], with HONO (g) being generated at 50% relative humidity in a NaNO 2(s) -packed tubing fed with HCl (g) from a permeation device according to the method of Febo et al [1995]. A maximum breakthrough of 4% of gas phase HONO (g) to the particle channel was observed at the highest examined HONO (g) mixing ratio of 2 ppbv, which is above the maximum HONO (g) observed in this study.…”

Section: Aim-ic Hono Collection Efficiencymentioning

confidence: 99%

Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA, during CalNex 2010

et al. 2014

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Measurements of HONO (g) were validated to be free of known interferences for wet chemical instrumentation. The accumulation of nitrite into particulate matter was found to be enhanced when gaseous mixing ratios of HONO (g) were highest. Reactive uptake of HONO (g) on to lofted dust and the ground surface, forming a reservoir, is a potential mechanism to explain these observations. The AIM-IC HONO (g) measurements were parameterized in a chemical model to calculate the ground surface daytime HONO (g) source strength at 4.5 m above the surface, found to be on the order of 1.27 ppb h À1, to determine the relative importance of a surface reservoir. If all deposited nighttime HONO (g) is reemitted the following day, up to 30% of the daytime HONO (g) source at CalNex-SJV may be accounted for. The observations of HONO (g) and NO 2 À (p) in Bakersfield, during CalNex, suggest a surface sink and source of HONO (g) . Extension of currently accepted unknown daytime HONO (g) source reactions to include a potential surface HONO (g) reservoir should therefore be sound, but quantitation of the relative contributions of each surface source toward daytime HONO (g) production remains to be resolved.

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Evaluation of a High-Purity and High-Stability Continuous Generation System for Nitrous Acid

Cited by 105 publications

References 11 publications

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Validation of in situ Measurements of Atmospheric Nitrous Acid Using Incoherent Broadband Cavity-enhanced Absorption Spectroscopy

Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA, during CalNex 2010

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