Preparation of Experiments: Addition and In Situ Production of Trace Gases and Oxidants in the Gas Phase

Preparation of the air mixture used in chamber experiments requires typically the injection of trace gases into a bath gas. In this chapter, recommenda-tions and standard protocols are given to achieve quantitative injections of gaseous, liquid or solid species. Various methods to produce ozone, nitrate radicals and hydroxyl radicals are discussed. Short-lived oxidants need to be produced during the experiment inside the chamber from pre-cursor species. Because highly reactive oxidants like hydroxyl radicals are challenging to detect an alternative method for the quantification of radical concentrations using trace molecules is described.

[1]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates , 2020, Atmospheric Chemistry and Physics.

[2]  A. Prévôt,et al.  Secondary organic aerosol formation from smoldering and flaming combustion of biomass: a box model parametrization based on volatility basis set , 2019, Atmospheric Chemistry and Physics.

[3]  D. Topping,et al.  Secondary organic aerosol reduced by mixture of atmospheric vapours , 2019, Nature.

[4]  J. Thornton,et al.  Quantitative constraints on autoxidation and dimer formation from direct probing of monoterpene-derived peroxy radical chemistry , 2018, Proceedings of the National Academy of Sciences.

[5]  P. Shepson,et al.  Nitrate radical oxidation of γ -terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields , 2017 .

[6]  T. Petäjä,et al.  New particle formation in the free troposphere: A question of chemistry and timing , 2016, Science.

[7]  P. Edwards,et al.  A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor , 2015 .

[8]  J. Thornton,et al.  Tropospheric Halogen Chemistry: Sources, Cycling, and Impacts , 2015, Chemical reviews.

[9]  T. Stavrakou,et al.  Hydroxyl radical recycling in isoprene oxidation driven by hydrogen bonding and hydrogen tunneling: the upgraded LIM1 mechanism. , 2014, The journal of physical chemistry. A.

[10]  H. Kjaergaard,et al.  A large source of low-volatility secondary organic aerosol , 2014, Nature.

[11]  Roderic L. Jones,et al.  Intercomparison of NO3 radical detection instruments in the atmosphere simulation chamber SAPHIR , 2013 .

[12]  D. Heard,et al.  Tropospheric OH and HO2 radicals: field measurements and model comparisons. , 2012, Chemical Society reviews.

[13]  T. Lohaus,et al.  Organic aerosol yields from α-pinene oxidation: bridging the gap between first-generation yields and aging chemistry. , 2012, Environmental science & technology.

[14]  B. Ghosh,et al.  Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm. , 2012, The Journal of chemical physics.

[15]  J. Doussin,et al.  An experimental study of the gas-phase reactions of NO3 radicals with a series of unsaturated aldehydes: trans-2-hexenal, trans-2-heptenal, and trans-2-octenal. , 2012, The journal of physical chemistry. A.

[16]  P. DeCarlo,et al.  OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber , 2011 .

[17]  J. Seinfeld,et al.  Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NO x conditions , 2011 .

[18]  P. Monks,et al.  Total radical yields from tropospheric ethene ozonolysis. , 2011, Physical chemistry chemical physics : PCCP.

[19]  N. Donahue,et al.  Effect of the OH Radical Scavenger Hydrogen Peroxide on Secondary Organic Aerosol Formation from α-Pinene Ozonolysis , 2011 .

[20]  J. Burkholder,et al.  (CH3)3COOH (tert-butyl hydroperoxide): OH reaction rate coefficients between 206 and 375 K and the OH photolysis quantum yield at 248 nm. , 2010, Physical chemistry chemical physics : PCCP.

[21]  H. Dorn,et al.  Technical Note: Formal blind intercomparison of OH measurements: results from the international campaign HOxComp , 2009 .

[22]  G. Marston,et al.  The Gas-Phase Ozonolysis of Unsaturated Volatile Organic Compounds in the Troposphere , 2008 .

[23]  G. Pietsch,et al.  On the Performance of Ozone Generators Working with Dielectric Barrier Discharges , 2006 .

[24]  J. Gal,et al.  Thermogravimetric calibration of permeation tubes used for the preparation of gas standards for air pollution analysis. , 2005, The Analyst.

[25]  Allen L Robinson,et al.  Critical factors determining the variation in SOA yields from terpene ozonolysis: a combined experimental and computational study. , 2005, Faraday discussions.

[26]  Franz Rohrer,et al.  Characterisation of the photolytic HONO-source in the atmosphere simulation chamber SAPHIR , 2004 .

[27]  J. Wenger,et al.  Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals with Dimethylphenols , 2004 .

[28]  R C Flagan,et al.  Secondary organic aerosol formation from cyclohexene ozonolysis: effect of OH scavenger and the role of radical chemistry. , 2004, Environmental science & technology.

[29]  P. Ziemann,et al.  Effects of Stabilized Criegee Intermediate and OH Radical Scavengers on Aerosol Formation from Reactions of β-Pinene with O 3 , 2003 .

[30]  G. Marston,et al.  OH Yields in the Gas-Phase Reactions of Ozone with Alkenes , 1999 .

[31]  Ian Barnes,et al.  Gas-phase absorption cross sections of 24 monocyclic aromatic hydrocarbons in the UV and IR spectral ranges , 1999 .

[32]  A. Ravishankara,et al.  Rate Coefficients for the Reaction of OH with HONO Between 298 and 373 K. , 1992 .

[33]  S. M. Aschmann,et al.  Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes , 1992 .

[34]  I. Barnes,et al.  Kinetics and products of the reactions of nitrate radical with monoalkenes, dialkenes, and monoterpenes , 1990 .

[35]  W. Carter,et al.  Kinetics of the gas‐phase reactions of NO3 radicals with a series of aromatics at 296 ± 2 K , 1984 .

[36]  A. Winer,et al.  Kinetics of the gas-phase reactions of nitrate radicals with a series of dialkenes, cycloalkenes, and monoterpenes at 295 .+-. 1 K. , 1984, Environmental science & technology.

[37]  W. Carter,et al.  An Experimental Protocol for the Determination of OH Radical Rate Constants with Organics Using Methyl Nitrite Photolysis as an OH Radical Source , 1981 .

[38]  P. Maker,et al.  An FTIR study of mechanisms for the HO radical initiated oxidation of C2H4 in the presence of NO: detection of glycolaldehyde , 1981 .

[39]  G. Takacs,et al.  Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate , 1980 .

[40]  A. Winer,et al.  Temperature dependence of the unimolecular decomposition of pernitric acid and its atmospheric implications , 1977 .

[41]  J. Heicklen,et al.  Photolysis of methyl nitrite , 1973 .

[42]  T. Nash Chemical Status of Nitrogen Dioxide at Low Aerial Concentration , 1968 .

[43]  Ian Barnes,et al.  Reactions of NO3 radicals with limonene and α-pinene: Product and SOA formation , 2006 .

[44]  B. d'Anna,et al.  Kinetic study of OH and NO3 radical reactions with 14 aliphatic aldehydes , 2001 .

[45]  L. Krasnoperov,et al.  Oxalyl ChlorideA Clean Source of Chlorine Atoms for Kinetic Studies , 2001 .

[46]  Bénédicte Picquet Etude cinetique et mecanistique de la photoxydation des acetates en atmosphere simulee , 2000 .

[47]  J. Burrows,et al.  The nitrate radical: Physics, chemistry, and the atmosphere , 1991 .

[48]  B. Finlayson‐Pitts,et al.  Atmospheric chemistry : fundamentals and experimental techniques , 1986 .

[49]  S. M. Aschmann,et al.  Kinetics of the gas phase reaction of Cl atoms with a series of organics at 296±2 K and atmospheric pressure , 1985 .

[50]  E. H. Fink,et al.  Reactivity studies of organic substances towards hydroxyl radicals under atmospheric conditions , 1982 .

[51]  R. Wayne,et al.  Kinetics and photochemistry of NO3. Part 1.—Absolute absorption cross-section , 1980 .

[52]  R. A. Cox The photolysis of nitrous acid in the presence of carbon monoxide and sulphur dioxide , 1974 .