By Murray J McEwan

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20 Absorption spectrum of S0 2 (after J . G . Calvert and J . N . Pitts, Jnr . , Photo­ chemistry, John Wiley & Sons Inc . , New York, 1 966). has so far defied more than a partial analysis. 2 0 Above 400 nm the bands consist of many sharp rotational lines ; below 370 nm the bands are generally diffuse because of predissociation. The theoretical dissociation limit is 399 nm. 8 nm; absorption cross sections in this region are typically 2 x 10 - 1 7 cm 2 • Photodissociation coefficient ( s - 1 ) Rate of photodissociation of methane by Lyman-ix, calculated by Nicolet, 1 6 as a function of altitude and solar zenith angle X· Fig.

19 Nakata, R. , Watanabe, K. and Matsunaga, F . , Sci. , Tokyo, 14, 54 (1965). , 'Molecular Spectra and Molecular Structure, III. Electronic Spectra of Polyatomic Molecules' . D. , 1966 . 21 Holt, R . , McLane, C. K . and Oldenberg, 0 . , J. chem. Phys. , 16, 225, 638 (1948). 1 Introduction In this chapter we consider the various techniques that can be used to obtain experimental information about the chemistry of the atmosphere. Investigation of the troposphere presents relatively few problems because the whole region is accessible to the experimenter, and the photochemical processes that occur are fairly easy to simulate in the laboratory.

32 N m - . 5 Fig. 3 Fig. 4 Photograph of the rocket nose cone of Narcisi5 showing the mass spectrometer and pump assembly incorporated in the rocket payload. (Kindly provided by Dr R. S. Narcisi, Air Force Cambridge Research Laboratories, Bedford, Mass. ) 42 EXPERIMENTAL METHODS unexpected peaks corresponding to mass numbers 19 and 37 . H20 (37) led to laboratory studies of the rates and equilibria of clustering reactions for water molecules and positive ions. A theory to account for the presence of these ion clusters was later proposed by Fehsenfeld and Ferguson6 , as discussed in Chapter 6 .

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