9.
7 SUMMARY 127
a.000-pi,
11,50.
S. 7 a 0 in
pit
Figure 9.4 Solubility of amorphous SiO: expressed in
units of mg of SiO. per liter of pure water at 25T hared
on equal tom 9 R4 and 0.85. Note that 11,50, begins to
dissociate appreciably at about pH r 8.0 and that
11,510, becomes dominant at pH = 9.71. The second
chsuxiation (equation 9 R51 is negligible in the pH
range shown here and. at pl I = 10.0.11 increases the
solubility of amorphous Si(), by only 0.03%. saki(
and is derived primarily by chemical litailienng of the
common rock forming Al-silicate and silicate minmak
but may be preoptlated from saturated solutions as
gelatinous amorphous silica when the p) I decreases As
amorphous silica ages it recrystallizes to form opal A
and opal CT until it ultimately loins chalcedony. which
is a variety of quartz
Surprisingly. quartz is not an important source
of mbar acid in natural solution because it IS quite
insoluble The equilibrium constant of the reaction.
SiO. 4 211 : 0= 11,SiO,
Quartz
is K = 111"1. As a result. the activity of HiSi0,, in
a saturated solution in contact with quartz at 25t
is 9.76 % mol/L_ which is equivalent to
3.9 mg/L of Si, in solution.The concentrations of
Si in average river water and seawater (Table 4.7)
are 63 and 2.8 pg/g. respectively These concentra.
lions can be transformed into SiO, in milligrams
per liter by converting first
to micromolcs of Si and then to micrograms of SO..
For average river water-
6- X 60.0R x 10'
S i 0 - 13.9 mg/L (9.94)
- 28.086 x 10'
Therefore, average river water is supers/noted
with respect to quartz but is undersaturatcd with
respect to amorphous silica. However. quartz
does not precipitate from aqueous solutions
directly but forms only by recrystallization of
amorphous SiO. as discussed presiously.The com
centration of Si0 : , in seawater is 5.R mg/L
(assuming a density of 1.025 p./cm), which is
close to the solubility of quartz at 25'C. Seawater
has a lower concentration of SiO ) than river
11
water because certain organisms (sponges,
diatoms and radiolarians) form skeletons corn.
posed of opal A. When these organisms die. their
siliceous skeletons accumulate on the bottom of
the ocean and may ultimately form either elicit.
composed of crypiocrystalline quartz. or deposits
of diatomite (Cressman.1962:Wedepohl.1972).
The geochemistry of silica illustrates the point
that some reactions in nature are essentially sire.
,erosible. When NaCI dissolves in water the
reaction is reversible because the compound does
precipi tate from supersaturated solutions. When
amorphous silica dissolves in water. it can be made
to precipitate again, although with some difficulty.
However, when quartz dissolves in water at 251. to
form silicic acid, the reaction cannot be reversed at
the same temperature. We will encounter this phe-
nomenon again in Chapter 10 when we discuss the
solubility of minerals some of which form only by
crystallization of magma at elevated temperatures.
(9.93)
9.7 Summary
Chemical reactions have a natural tendency to
achieve a stale of equilibrium in which the rates of
the forward and backward reactions are equal.
As a result. the amounts of reactants and
products that coexist at equilibrium are invariant
with time. This observational evidence was
originally used to