Kinetic and theoretical studies of the reactions acetylperoxy + nitrogen dioxide + M .dblarw. acetyl peroxynitrate + M between 248 and 393 K and between 30 and 760 torr

Bridier, Isabelle; Caralp, F.; Loirat, H.; Lesclaux, R.; Veyret, B.; Becker, K. H.; Reimer, A.; Zabel, F.

doi:10.1021/j100162a031

Cited by 122 publications

(112 citation statements)

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“…(1) and (2) to calculate PAN decay rates during the campaign using reaction rate constants reported by Bridier et al (1991) and DeMore et al (1997) and measured NO to NO ratios (Fig. 3).…”

Section: Pan Lifetimesmentioning

confidence: 99%

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Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Jacobi

Weller

Jones

et al. 2000

Atmospheric Environment

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Because investigations of PAN at higher southern latitudes are very scarce, we measured surface PAN concentrations for the "rst time in Antarctica. During the Photochemical Experiment at Neumayer (PEAN'99) campaign mean surface PAN mixing ratios of 13$7 pptv and maximum values of 48 pptv were found. When these PAN mixing ratios were compared to the sum of NO V and inorganic nitrate they were found to be equal or higher. Low ambient air temperatures and low PAN concentrations caused a slow homogeneous PAN decomposition rate of approximately 5;10\ pptv h\ . These slow decay rates were not su$cient to "rmly establish the simultaneously observed NO V concentrations. In addition, low concentration ratios of [HNO ]/[NO V ] imply that the photochemical production of NO V within the snow pack can in#uence surface NO V mixing ratios in Antarctica. Alternate measurements of PAN mixing ratios at two di!erent heights above the snow surface were performed to derive #uxes between the lower troposphere and the underlying snow pack using calculated friction velocities. Most of the concentration di!erences were below the precision of the measurements. Therefore, only an upper limit for the PAN #ux of $1;10 molecules m\ s\ without a predominant direction can be estimated. However, PAN #uxes below this limit can still in#uence both the transfer of nitrogen compounds between atmosphere and ice, and the PAN budget in higher southern latitudes.

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“…(1) and (2) to calculate PAN decay rates during the campaign using reaction rate constants reported by Bridier et al (1991) and DeMore et al (1997) and measured NO to NO ratios (Fig. 3).…”

Section: Pan Lifetimesmentioning

confidence: 99%

“…As a result, PAN in#uences the NO V balance, which in turn critically controls photochemical production and destruction of ozone in many regions of the troposphere (e.g. Carroll and Thompson, 1995).…”

Section: Introductionmentioning

confidence: 99%

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Jacobi

Weller

Jones

et al. 2000

Atmospheric Environment

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“…The equilibrium between peroxyacetyl radicals, NO 2 , and PAN (Reactions R4 and R5) is highly temperature-sensitive. Thus, the PAN lifetime changes from 30 min at 25 • C (Bridier et al, 1991) to 5.36 years at −26 • C (Kleindienst, 1994). Measurements of NO x species in the remote atmosphere have been made over the last 40 years.…”

Section: Introductionmentioning

confidence: 99%

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?

et al. 2016

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Abstract. Measurement of NO 2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO 2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NO x environments which have measured higher NO 2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O 3 , j NO 2 , etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured "compound X" that is able to convert NO to NO 2 selectively. Here we explore in the laboratory the interference on the photolytic NO 2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale (∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO 2 (HO 2 NO 2 , N 2 O 5 , CH 3 O 2 NO 2 , IONO 2 , BrONO 2 , higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO 2 measurements and (2) the NO 2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NO x concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO 2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO 2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

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“…Lennard-Jones collision parameters were the same as used by Bridier et al (1991). The NO 2 and -C-O-O moieties were treated as hindered rotors in the transition state.…”

Section: Photodissociation Quantum Yieldsmentioning

confidence: 99%

“…Reaction of PAN with OH is too slow to be of relevance (DeMore et al, 1997). Similar to other peroxy nitrates (Kirchner et al, 1999;Zabel, 1995), PAN has a low dissociation energy, D 0 (CH 3 C(O)OO-NO 2 )=9820±240 cm −1 (Bridier et al, 1991;Zabel, 1995), which falls between the 3ν CH (E≈8550 cm −1 ) and 4ν CH (E≈11 100 cm −1 ) vibrational states of the molecule. To evaluate the efficiency of near-IR photochemistry of PAN, knowledge of both the intensity of the CH stretching overtones and photodisssociation quantum yields are required.…”

Section: Introductionmentioning

confidence: 99%

Near-IR photodissociation of peroxy acetyl nitrate

et al. 2005

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Abstract. Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (J near−IR ≈3×10 −8 s −1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with J near−IR ≈10 −5 s −1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of freedom in PAN, which make 4ν CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2ν OH in PNA).

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Kinetic and theoretical studies of the reactions acetylperoxy + nitrogen dioxide + M .dblarw. acetyl peroxynitrate + M between 248 and 393 K and between 30 and 760 torr

Abstract: Kinetic and Theoretical Studies of the Reactions CH3C(0)02 + N02 + M *e CH3C(0)02N02 + M between 248 and 393 K and between 30 and 760 Torr

Cited by 122 publications

References 1 publication

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?

Near-IR photodissociation of peroxy acetyl nitrate

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Kinetic and theoretical studies of the reactions acetylperoxy + nitrogen dioxide + M .dblarw. acetyl peroxynitrate + M between 248 and 393 K and between 30 and 760 torr

Abstract: Kinetic and Theoretical Studies of the Reactions CH3C(0)02 + N02 + M *e CH3C(0)02N02 + M between 248 and 393 K and between 30 and 760 Torr

Cited by 122 publications

References 1 publication

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Interferences in photolytic NO&lt;sub&gt;2&lt;/sub&gt; measurements: explanation for an apparent missing oxidant?

Near-IR photodissociation of peroxy acetyl nitrate

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Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?