Info

Using these data and assuming a quantum yield of unity for the subsequent process forming methyl iso-cyanide

CH3NCS + hv -> CH3NC + S, estimate the photolysis rate constant and lifetime for this compound at a latitude of 40°N on July 1 two hours before noon.

4. The absorption spectra of bromine compounds are generally shifted toward longer wavelengths compared to those of chlorine compounds.

(a) Use the absorption cross sections for Cl2, BrCl, and Br2 in Table 4.30 to calculate the factors by which the photolysis rate increases for BrCl and Br2 compared to Cl2 at a solar zenith angle of 20° at the earth's surface on December f5.

(b) Do the same calculation for a solar zenith angle of 86°. Comment on possible reasons for any differences.

5. The absorption spectra of iodine compounds are generally shifted toward longer wavelengths compared to those of both bromine and chlorine compounds.

(a) Use the absorption cross sections for IO and BrO in Table 4.31 to calculate the factor by which the photolysis rate increases for IO compared to BrO at a solar zenith angle of 20° at the earth's surface on July 1. Assume quantum yields of unity.

(b) Do the same calculation for a solar zenith angle of 86°. Comment on possible reasons for the differences.

6. Burkholder and McKeen (1997) report, based on their measurements of the absorption cross sections for

200 220 240 260 280 300 320 340 360 380 X (nm)

FIGURE 4-46 Absorption spectra of some simple alkyl iodides (adapted from Roehl et ai, 1997).

S03 (Table 4.22), that photolysis of this compound will become important at higher altitudes, sufficiently so to compete with its reaction with water to form sulfuric acid. Compare the S03 photolysis rate for an overhead sun for an altitude of 0 km to its rate of hydrolysis assuming a collision-controlled value for the effective bimolecular rate constant of 10"10 cm3 molecule-1 s_1 and 50% RH at 298 K at the earth's surface.

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