124 ACIDS AND BASES (1125) + (IIS.) (S' )= I x 10 2 mot/l.

(9.79)
equations 9.30 and 9.31. However, here we
rewrite the mass-action equations (9.32 aid 9.33) If all activity coefficients arc equal to one, we can
as follows substitute equations 9.77 and 9.78 into 9.79,
o b t a i n i n g : a -
1115 I _ 10-2"
(9.75) 1o1115-1+ itis-1 4 i6oltis-1
111,S1 111'1
= ) x 10'2 mol/L ( 9 . 1 1 b )
and:
I5;-J Iwo, which reduces to:
(9.76)

IIIS1.1111 II1HS1 = 1 x mol/L (9.81)

We see that the activity ratios of 111S 1/1112-S1
and 1521/11-1S- 1 depend on the activity of the
hydrogen ion. According to equation 9.75,
1115-1/11124=1.0when111'1= 7 mul/L. If
111+1>10'k.say then1HS-1/111,S1 =0.1.
which means that the activity of 1125 is 10 times
greater than the activity of 111S-1. Similarly. if
1/1 '1 < 10'20 say 10 IV. then IIISTIM = 10
and 111S-1 is 10 times greater than that of HAS
hviiknily. 1111 = 10-20 (pH = 7.0) is an impor-
tant boundary at which the abundances of HS
and HS- arc equal. 11$ dominates at pH < 7.0.
whereas I IS- dominates at pH > 7.0
Similar arguments, applied to equation 9.76,
indicate that pH = 12.9 is another boundary in
the system. At pH < 12.9 we find that HS"
more abundant than S2-, whereas at pH > 12.9
the sulfide ion (52') dominates Such relation-
ships occur in all weak acids and bases because
their dissociation into ions is controlled by the
pH of the environnwni.
the control of dissociation equilibria by the
p11 has an important consequence because it
means that we can identify the dominant ionsat dif-
ferent values of the pH. In order to demonstrate
how this works we fix the total amount of sulfur
bearing species in the solution at 10-2 mol/L and
calculate the activities of 11,S, HS-. and S2- as a
!unction of pH. At pH = 60 we obtain Irom equa-
tion 9.75:
kibulHS-1
100151 (9.77)
Ulm
and from equation 9.76:
152"I 10"121S1
.11 -
and hence 11-1S1 = 9.09 X 10- mo1/1.-From
equation 9.77 we determine that IH7S1 =
9.09 X mol/L and Irom 9.78 we have
IS21 a 1.14 x 10 10 mot/1..' Therefore. HS is the
meat abundant spccies at p11 = 6.0 and constitutes
90.9% of all S-bearing ions or molecules in the
solution. The bisulfate ion (I IS ) is next in abun-
dance with 9.09%, which leaves only 0.01% lot
SI-. When we repeat this calculation lot different
values of the pH. we generate three curves that
represent the changing abundances of 115, HS
and 52- in the solution. As expected, we see from
Figure 9.3 that 11,S dominates at pH < 7.0, that
HS' is the dominant ion for pH values from 7.0 to
12.9, and that SI- is dominant at pit > 12.9.
Although all of the tons or molecules are present
throughout the range of pH values, most of the Sin
the solution is associated with a particular species
except at the boundaries at winch the abundances
of Iwo species are equal.
9.6 Solubility of Amorphous Silica
The oxides of many metals react with water to
form bases and the oxides of nonmetals react with
water to form acids For exampk, CO2 reacts with
water to form carbonic acid:
CO2 + H20 ) Elf, (9.62)
and SO, forms hydrosulfurous acid:
' SO, + 1120*HiSO, (9.83)

I
10 (9.78) From the
MUSS balance: