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E XAMPLE 6.20 E FFECT OF SO 2 O XIDATION ON THE pH OF AN O PEN S YSTEM
(A QUEOUS D ROPLET ) THAT C ONTAINS HNO 3 ,NH 3 ,H 2 O 2 ,
AND O 3
Consider an aqueous droplet with HNO 3 ,NH 3 ,H 2 O 2 ,O 3 , and SO 2 as the main
constituents. The following initial conditions ( t = 0) were chosen by Seinfeld and
Pandis(2005):[S(IV)] total = 5 ppb,[HNO 3 ] total = 1 ppb,[NH 3 ] total = 5 ppb,[O 3 ] total
= 5 ppb, [H 2 O 2 ] total = 1 ppb, [S(VI)] t = 0 = 0, and water content = 10 6 .
For an open system, we can assume that the partial pressures of the different species
remain constant. As S(IV) gets oxidized to S(VI), the new species of interest will com-
prise SO 2
4
and HSO 4 . We shall indicate [ S(VI) ]=[ SO 2
]+[ HSO 4 ]+[ H 2 SO 4 ] aq .
4
The electroneutrality equation is
H + +
NH 4
HSO 3
+ 2 SO 2 3
+ 2 SO 2 4
HSO 4
NO 3 .
= OH +
+
+
6.2
6.0
5.8
Open system
5.6
5.4
5.2
Closed system
5.0
4.8
4.6
0
10
20
30
40
50
60
Time, min
FIGURE 6.37 pH as a function of time for both open and closed systems. The condi-
tions for the simulation are [S(IV)] total = 5 ppb, [NH 3 ] total = 5 ppb, [HNO 3 ] total =
1 ppb, [O 3 ] total = 5 ppb, [H 2 O 2 ] total = 1 ppb, θ = 10 6 ,pH o = 6.17. (Reprinted
from Seinfeld, J.H. and Pandis, S.N. 1998. Atmospheric Chemistry and Physics ,
p. 390. NewYork: Wiley. With permission.)
continued
 
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