Finlayson-Pitts

Allen, H. C. Brauers, T. Finlayson-Pitts, B. J. Illustrating Deviations in the Beer-Lambert Law in an Instrumental Analysis Laboratory Measuring Atmospheric Pollutants by Differential Optical Absorption Spectrometry, /. Chem. 

CO to CO2 (e.g. Finlayson-Pitts and Pitts 1986). The role of HOj in any of these atmospheric cleansing and oxidant formation pathways is a catalytic one, but the generation of ozone is strongly dependent upon the nitric oxide concentration. 

Finlayson-Pitts, B.J. Pitts, J.N., 3x. Atmospheric Chemistry Fundamentals and Experimental Techniques-, John Wiley Sons New York 1986 589-600. 

Finlayson-Pitts, B. J. and Pitts, J. N. (1986). "Atmospheric Chemistry." Wiley, New York. 

Photochemistry plays a significant role in nitrogen s atmospheric chemistry by producing reactive species (such as OH radicals). These radicals are primarily responsible for all atmospheric oxidations. However, since the photochemistry of the atmosphere is quite complex, it will not be dealt with in detail here. For an in-depth review on tropospheric photochemistry, the reader is referred to Logan et al. (1981), Finlayson-Pitts and Pitts (1986), Crutzen and Gidel (1983) or Crutzen (1988). 

The extent to which this occurs depends on a number of issues (Finlayson-Pitts and Pitts 1997), including the reactivity of the hydrocarbon that is itself a function of many factors. It has been proposed that the possibility of ozone formation is best described by a reactivity index of incremental hydrocarbon reactivity (Carter and Atkinson 1987, 1989) that combines the rate of formation of O3 with that of the reduction in the concentration of NO. The method has been applied, for example, to oxygenate additives to automobile fuel (Japar et al. 1991), while both anthropogenic compounds and naturally occurring hydrocarbons may be reactive. 

Finlayson-Pitts B, J Pitts (1986) Atmospheric Chemistry. Wiley, New York. 

Finlayson-Pitts BJ, IN Pitts (1997) Tropospheric air pollution ozone, airborne toxics, polycyclic aromatic hydrocarbons, and particles. Science 276 1045-1052. 

B. J. Finlayson-Pitts and J. N. Pitts Jr., Chemistry of the Upper and Lower Atmosphere Theory, Experiments, and Applications, Academic Press, San Diego, California, 2000. 

Finlayson-Pitts,B.J. and Pitts, J.N.Jr., "Atmospheric Chemistry Fundamentals and Experimental Techniques",Wiley,New York,1986. 

Photolytic. A photooxidation rate constant of 6 x 10 " cm /molecule-sec at room temperature was reported for the vapor-phase reaction of benzene with OH radicals in air (Atkinson, 1985). The reported rate constant and half-life for the reaction of benzene and OH radicals in the atmosphere are 8.2 x 10 M/sec and 6.8 d, respectively (Mill, 1982). Major photooxidation products in air include nitrobenzene, nitrophenol, phenol, glyoxal, butanedial, formaldehyde, carbon dioxide, and carbon monoxide (Nojima et al., 1975 Finlayson-Pitts and Pitts, 1986). 

Chemical/Physical. Products identified from the reaction of toluene with nitric oxide and OH radicals include benzaldehyde, benzyl alcohol, 3-nitrotoluene, p-methylbenzoquinone, and o, m, and p-cresol (Kenley et ah, 1978). Gaseous toluene reacted with nitrate radicals in purified air forming the following products benzaldehyde, benzyl alcohol, benzyl nitrate, and 2-, 3-, and 4-nitro-toluene (Chiodini et al., 1993). Under atmospheric conditions, the gas-phase reaction with OH radicals and nitrogen oxides resulted in the formation of benzaldehyde, benzyl nitrate, 3-nitrotoluene, and o-, m-, and p-cresol (Finlayson-Pitts and Pitts, 1986 Atkinson, 1990). 

Finlayson-Pitts BJ, Pitts JN. Chemistry of the upper and lower atmosphere theory, experiments, and applications. San Diego (CA) Academic Press 2000. 

FIGURE 1.3 Diurnal variation of NO, N02, and total oxidant in Pasadena, California, on July 25, 1973 (adapted from Finlayson-Pitts and Pitts, 1977). 

Finlayson-Pitts, B. J., and J. N. Pitts, Jr., The Chemical Basis of Air Quality Kinetics and Mechanisms of Photochemical Air Pollution and Application to Control Strategies, Adv. Environ. Sci. Technol., 7, 76-162 (1977). 

In addition to the criteria pollutants, a wide variety of trace gaseous and particulate species are present in the polluted troposphere (Finlayson-Pitts and Pitts, 1997). Table 2.9 shows some of these gaseous noncriteria pollutants identified in photochemical air pollution and gives typical concentrations under conditions ranging from those in remote areas to severely polluted urban air (see also Chapter 11). 

FIGURE 3.4 Vibration-rotation spectrum of 0.18 Torr HCI at room temperature using a path length of 19.2 m. Resolution is 0.25 cmH. The rotational transitions are shown as (initial. /. final J) (from B. J. Finlayson-Pitts and S. N. Johnson, unpublished data). 

Ganske, J. A., H. N. Berko, and B. J. Finlayson-Pitts, Absorption Cross Sections for Gaseous C1N02 and Cl2 at 298 K Potential Organic Oxidant Source in the Marine Troposphere, J. Geophys. Res., 97, 7651-7656 (1992). 

FIGURE 5.5 Typical plot of OH resonance fluorescence intensity as a function of reaction time in the presence of increasing concentrations of CINO (in units of 1011 molecules cm 3) at 373 K (adapted from Finlayson-Pitts et at., 1986). 

Determination of OH relative rate constants for compounds that photolyze significantly in actinic radiation requires a nonphotolytic source of OH. Three such OH sources are H202-N02-C0 mixtures (Campbell et al., 1975, 1979 Audley et al., 1982), the thermal decomposition of H02N02 in the presence of NO (Barnes et al., 1982), and 03-hydrazine reactions (Tuazon et al., 1983) or 03 alkane reactions in the dark (Finlayson-Pitts et al., 1993). However, in these cases, the reactant must not react with 03, HOz, or H202, and care must be taken in interpreting the data since these systems have the potential of being rather complex. Indeed, the rate constants derived have not always agreed well with literature values. Until the... 

FIGURE 5.22 Typical uptake of gaseous HN03 by solid NaCl (monitored at m/e = 46) and increase in the gaseous HC1 product (monitored at in /e = 36) (adapted from Beichert and Finlayson-Pitts, 1996). 

For some typical examples of the applications of Knudsen cells to atmospheric reactions, see Quinlan et al. (1990), Fenter et al. (1994), Beichert and Finlayson-Pitts (1996), and De Haan and Finlayson-Pitts (1997). 

FIGURE 5.29 Schematic of DRIFTS apparatus (adapted from Vogt and Finlayson-Pitts, 1994). 

Alfassi, Z. B S. Padmaja, P. Neta, and R. E. Huie, Rate Constants for Reactions of NO, Radicals with Organic Compounds in Water and Acetonitrile, J. Phys. Chem., 97, 3780-3782 (1993). Allen, H. C., J. M. Laux, R. Vogt, B. J. Finlayson-Pitts, and J. C. Hemminger, Water-Induced Reorganization of Ultrathin Nitrate Films on NaCI—Implications for the Tropospheric Chemistry of Sea Salt Particles, J. Phys. Chem., 100, 6371-6375 (1996). Allen, H. C., D. E. Gragson, and G. L. Richmond, Molecular Structure and Adsorption of Dimethyl Sulfoxide at the Surface of Aqueous Solutions, J. Phys. Chem. B, 103, 660-666 (1999). Anthony, S. E R. T. Tisdale, R. S. Disselkamp, and M. A. Tolbert, FTIR Studies of Low Temperature Sulfuric Acid Aerosols, Geophys. Res. Lett., 22, 1105-1108 (1995). 

Beichert, P L. Wingen, J. Lee, R. Vogt, M. J. Ezell, M. Ragains, R. Neavyn, and B. J. Finlayson-Pitts, Rate Constants for the Reactions of Chlorine Atoms with Some Simple Alkanes at 298 K Measurement of a Self-Consistent Set Using both Absolute and Relative Rate Methods, J. Phys. Chem., 99, 13156-13162 (1995). 

De Haan, D. O., T. Brauers, K. Oum, J. Stutz, T. Nordmeyer, and B. J. Finlayson-Pitts, Heterogeneous Chemistry in the Troposphere Experimental Approaches and Applications to the Chemistry of Sea Salt Particles, Int. Rev. Phys. Chem., in press (1999). 

Finlayson-Pitts, B. J., S. K. Hernandez, and H. N. Berko, A New Dark Source of the Gaseous Hydroxyl Radical for Relative Rate Measurements, J. Phys. Chem., 97, 1172-1177 (1993). 

Langer, S., R. S. Pemberton, and B. J. Finlayson-Pitts, Diffuse Reflectance Infrared Studies of the Reaction of Synthetic Sea Salt Mixtures with N02 A Key Role for Hydrates in the Kinetics and Mechanism, J. Phys. Chem. A, 101, 1277-1286 (1997). 

Laux, J. M., J. C. Hemminger, and B. J. Finlayson-Pitts, X-ray Photoelectron Spectroscopic Studies of the Heterogeneous Reaction of Gaseous Nitric Acid with Sodium Chloride Kinetics and Contribution to the Chemistry of the Marine Troposphere, Geophys. Res. Let., 21, 1623-1626 (1994). 

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