Info

2. Use the structure-reactivity relationship approach to calculate the rate constants for the reactions of OH with the following compounds and calculate the percentage difference from the recommended values in Table 6.2: (a) ethane, (b) n-butane, (c) 2-methylpen-tane, (d) 2,2-dimethylpentane, (e) 2,2,3-trimethyl-butane, (f) n-nonane, (g) n-decane.

3. Use the structure-reactivity relationship approach to calculate the rate constants for the reactions of N03 with the following compounds and calculate the percentage difference from the recommended values in Table 6.3: (a) n-butane, (b) 2-methylbutane, (c) n-hexane, (d) 2,3-dimethylbutane, (e) n-octane, (f) n-non-ane.

4. Two of the products of the OH reaction with limonene that have been observed are the following:

Show mechanisms that would form these products.

5. The OH-C2H2 reaction is not quite at the high-pressure limit at 1 atm. The OH-acetylene reaction occurs by addition of the OH to the triple bond. For the reaction at 300 K, k{) = 5.0 X 10~3° cm6 mole-cule~2 s~\ K = 9.0 X MT13 cm3 molecule-1 s~\ and Fc = 0.62. (a) Calculate and plot the rate constant as a function of pressure up to 3000 Torr at 300 K. (b) What is the rate constant at 760 Torr and 300 K? How much different is this from the high-pressure limiting value?

6. Develop a mechanism for the photooxidation of diethyl ether in the presence of NOx that explains why Eberhard et al. (1993) observed ethyl formate, ethyl acetate, and acetaldehyde as products.

7. Calculate the lifetimes of PPN with respect to thermal decomposition at temperatures of — 30, 32, 70, and 120°F, respectively, assuming there is sufficient NO present to prevent the back reaction with N02 to regenerate PPN.

8. (a) ft is pointed out in the text that the effective rate of decomposition of PAN depends on how much NO is present, relative to N02, to prevent the back reaction to regenerate PAN. Show that the lifetime of PAN with respect to its thermal decomposition as a function of the NO and N02 concentration and the rate constants k75, k_15, and k7H is given by r = (l/k_75)(l + &75[N02]/fc78[N0]). Assume that the acetylperoxy radical is in a steady state and that reactions 75, -75, and 78 represent the entire reaction system, (b) Calculate the lifetimes with respect to the thermal decomposition of PAN at 25°C at ratios of [N0]/[N02] of fO, 1, and O.f, respectively.

9. Use the rate constants provided in this chapter to show whether or not the reaction of NOz with a-phel-landrene could compete with the OH, 03, and N03 reactions for the removal of this compound from the atmosphere.

10. The OH radical has been observed to be formed in a dark reaction when isoprene, high concentrations of N02, and NO are present. Postulate a mechanism for this OH generation.

11. Show that Eq. (G), which indicates that the peroxy radical concentration should vary with the square root of the 03 photolysis rate, can be derived from Eqs. (B)-(F).

12. Ferronato et al. (1998) have reported HCHO, CHOCH2OH, and CH3COCH3 as major products of the reaction of the biogenically emitted 2-methyl-3-buten-2-ol with OH in air. Develop a likely mechanism for the formation of these products.

13. (a) Calculate and plot the rate constant for the H02 self-reaction as a function of relative humidity at 298 K in increments of 10% from 0 to 100% at 1 atm pressure, (b) By what factor will the rate constant for H02 self-reaction change from the surface at a pressure of f atm, temperature of 298 K, and 50% RH to the lower stratosphere, assuming a pressure of fOO Torr, a temperature of 220 K, and a water vapor mixing ratio of 5 ppm?

14. Assess the atmospheric fates of 1-pcntcnc by answering the following questions:

(a) What are the potentially important tropospheric oxidants you have to consider, and what are typical concentrations of each oxidant under moderately polluted conditions?

(b) Calculate the lifetime of the organic with respect to each of the oxidants in (a). If the rate constant(s) you need are not available, estimate them based on those for analogous compounds.

(c) Show the mechanism of reaction of the organic with each of the important oxidants, following through to stable products in each case. Be sure to consider all possibilities. Be sure to consider all possible fates of reactive intermediates, and when some can be ruled out, state so explicitly.

(d) Suppose the oxidation occurs in a remote area where [NO] is close to 0. Trace the mechanism of the OH reaction through to one stable product under these conditions.

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