K

V 5jss M HS03-111~5jss kä- + ^ rucn-i I 2(^0 + kn)

[S°3lss = [S05"]ss[HS03-] + ^TrAT'^ [S051ss (7.A.12)

The steady-state concentration of SO5 can be calculated directly from (7.A.13) and then one can calculate the concentrations of the other radicals using (7.A.10) to (7.A.12). Finally, the sulfate production rate by the above mechanism is given by

Ä^l = ¿6[S05-][HS03-] + ¿g[S04 ][HS03-] + 2£14[HS05 ][HS03-][H+] (7.A.14)

FIGURE 7.A.2 Estimated steady-state radical concentrations as a function of pH for a mixing ratio of S02(g) = 1 ppb and [OH(aq)] = 1x10 12 M at 298 K.

FIGURE 7.A.2 Estimated steady-state radical concentrations as a function of pH for a mixing ratio of S02(g) = 1 ppb and [OH(aq)] = 1x10 12 M at 298 K.

The steady-state concentrations of the various radicals and the sulfate production rate, for [OH(aq)] = 7.5 x 10"12M and = 1 ppb, as a function of pH are shown in Figures 7.A.2 and 7.A.3. Note that the rate increases with pH, due mainly to the increasing S(IV) solubility, but remains less than 0.2 pM s"1 for pH less than 5.

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