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Weathering reactions

We can consider many weathering reactions as acid-base reactions. Acidity in soils can
be generated from several sources. The main ones are:

Hydration of CO2 (yields carbonic acid): CO2 + H2O H2CO3

Organic decomposition to yield organic acids (R-COOH R-COO- + H+)
Sulfide oxidation to yield sulfuric acid (2FeS2+4H2O+7.5O2 4H2SO4+Fe2O3)
Atmospheric deposition of mineral acids such as H2SO4 and HNO3.

The hydrogen ion released by these acids can react with carbonate minerals (e.g.
CaCO3) or alumino-silicate minerals (feldspars, micas, clays .). Carbonate and silicate
weathering reactions can be considered separately:

For carbonates, we can write:

1) CaCO3 + H2 CO3 Ca++ + 2HCO3-

In this reaction carbonic acid (from CO2 and water) and calcium carbonate react
to form bicarbonate ion and calcium ion. The net reaction yields no H+, so the carbonic
acid has been neutralized by reaction with carbonate. It also yields no solid phases the
carbonate mineral undergoes complete dissolution. This sort of reaction is know as
congruent dissolution.

An example silicate reaction would be the reaction of potassium feldspar (a

primary mineral) to form kaolinite, a secondary mineral . The reaction of a primary
mineral to form a secondary mineral plus solutes is called incongruent dissolution.

2) 2KAlSi3O8(Kspar) + 2H+ + 9H2O Al2Si2O5(OH)4(kaol) + 4H4SiO4(aq) +2K+

If the source of acidity is CO2, we can write equivalently:

3) 2KAlSi3O8(Kspar) + 2CO2 + 11H2O Al2Si2O5(OH)4(kaol) + 4H4SiO4(aq) +2K+ + 2HCO3-

In the breakdown of K-feldspar, acidity is consumed. We can see that H+ is used

up and K+ is released to solution, a kind of ion exchange reaction. Also released to
solution is dissolved silica or silicic acid, written H4SiO4.

As a general observation, we can say that acids are neutralized (H+ consumed) by
weathering minerals. The reaction products are base cations (Na+, K+, Ca++, Mg++), and
if CO2 is the acid another product will be bicarbonate ion (HCO3-). In the case of
alumino-silicate weathering, silicic acid (a.k.a. dissolved silica) is released as well.
Secondary alumino-silicate minerals are typically clays, and have increased hydroxyl
and/or water content, relative to their primary precursors.

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Because of its low solubility in typical environments, aluminum is often largely
retained in the secondary mineral. It is sometimes a useful approximation to treat Al as a
conservative element, i.e. one that does not enter or leave the system of interest. We
can then normalize the other elements in a mineral to the Al content to examine net mass
transfer. For example, in reaction 2, we can write:

Table 1 Si/Al K/Al H/Al

K-feldspar 3 1 0
kaolinite 1 0 2

Since Al is neither gained nor lost in this reaction, it serves as an index element for the
others. The secondary kaolinite is depleted in Si and K relative to the primary mineral,
but enriched in H (as hydroxyl). Typically secondary clay minerals have increased molar
volumes (lower densities) than primary alumino-silicates.

An equilibrium constant for reaction #2 can be written

4):
+ 2 4

K'=
[K ] [H SiO ]
4 4
+ 2
[H ]
by taking the square root of both sides we can reduce it to
5)
!
[K+]
K = + [ H 4 SiO4 ]
2

[H ]
Taking logarithms, we can write
! " [K + ] %
6) logK = log$ + ' + 2log[H 4 SiO4 ]
# [H ] &

We can make a plot with log[H4SiO4] for the x axis and log([K+]/[H+]) for the y axis.
Then equation 6 has the form of a straight line y = mx + b with a slope m of -2 and a y
!
intercept of logK:

" [K + ] %
7) log$ + ' = (2log[H 4 SiO4 ] + logK
# [H ] &

The value of logK can be found in some tables of geochemical data, or calculated from
thermodynamic data for the Gibbs free energy of formation (Gf) of the reactants and
!
products:

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8) Greaction = Gf(products) - Gf(reactants)

!"G r0
9) log K =
2.303RT

The value of R = 8.3143 J-1mol-1K-1, so if the Gf data are given in kilojoules per mole
(kJ/mole) and the temperature is 25C (298.15 K), equation 9 can be simplified to:

10) logK = - Greaction/5.708 kJ mol-1.

Gibbs free energy of formation data for some of the phases we will work with are in the
table below:

Table 2
phase formula Gf0,
kJ/mole
gibbsite Al(OH)3 -1151
kaolinite Al2Si2O5(OH)4 -3800
pyrophyllite Al2Si4O10(OH)2 -5275
muscovite KAl3Si3O10(OH)2 5606
K-feldspar KAlSi3O8 -3767
albite NaAlSi3O8 -3715
analcite NaAlSi2O6H2O -3090
Na-beidellite Na0.33Al2.33Si3.67O10(OH)2 -5382
K+ -283.27
Na+ -261.91
H4SiO4 -1316.6
H2O -237.13
Ca2+ -553.58
H+ 0

Data from J. I. Drever, 1997, The Geochemistry of Natural Waters, Prentice Hall

For reaction 2 (Kspar -> kaolinite) the Greaction is given by the products minus
reactants (with proper stoichiometric weighting), and will be:

11) Greaction = [-3800 + 2(-283.27) + 4(-1316.6)] - [2(-3767) + 2(0) + 9(237.13)]

= 35.23 kJ mol-1.

Using equation 9:

12) log KKspar-kaol = -35.23 kJ mol-1/(2.303 8.3143 kJ mol-1K-1 298.15 K) = -6.17

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Since K = K, from the properties of logarithms we have that

13) log K = log K/2 i.e. log K = -6.17/2 = -3.09

Note that, although we found it convenient to reduce the order of the equation 4 to
equation 5, we must still calculate Greaction according to the stoichiometry we have
written for equation 2. But, note also we could have equally well written equation 2 in an
alternative but still balanced fashion:

14) KAlSi3O8 + H+ + 4.5H2O 0.5Al2Si2O5(OH)4 + K+ + 2 H4SiO4

which would lead directly to the definition of K in equation 5. The two approaches are
equivalent and thermodynamically consistent.

Now we have numerical values for both the slope of this reaction line (-2) and its
y-intercept (-3.09) on a plot of log([K+]/[H+]) vs. log([H4SiO4]). What does this look
like? See Figure 1.

Follow the accompanying Powerpoint graphics with the equations below as we build the
stability relations for the system K-Al-Si-H2O.

In order to complete the system, we will consider the following phases and the
reactions between them: K-feldspar, kaolinite, muscovite and gibbsite. We will also
include opal (amorphous silica).

The next reaction we write is kaolinite to gibbsite:

15) Al2Si2O5(OH)4 (kaol) + 5H2O 2Al(OH)3 (gibb) + 2 H4SiO4

Unlike the K-spar reaction, this is not an acid-base reaction. Gibbsite is an end-product
of weathering, completely stripped of base cations, and silica, leaving only the highly
insoluble aluminum hydroxide. It is typically found in highly weathered tropical soils.

The equilibrium constant for this reaction is simply;

16) K(kaol-gibb) = [H4SiO4]2

From the data in Table 2, we can write

17) Greaction = [-3800 + 5(-237.13)] - [2(-1151) + 2(-1316.6)] = 50.45 kJ mol-1.

From equation 10 we obtain

18) log K(kaol-gibb) = -50.45 kJ mol-1/(5.708 kJ mol-1) = -8.8

19) K = K= [H4SiO4]

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20) log K = logK/2 = -4.4 (i.e has a numerical value of 10-4.4).

On the plot of log([K+]/[H+]) vs. log[H4SiO4], the equilibrium boundary appears as a

straight vertical line (i.e. undefined slope) with an x-intercept of 4.4 (Figure 2).

The next reaction we add is between muscovite and K-feldspar. Muscovite is a mica, and
can be a primary mineral. The mineral illite, a fine-grained clay is chemically and
structurally very similar to muscovite, and is commonly a secondary mineral. Here we
use the thermodynamic data for muscovite.

21) 3KAlSi3O8(Kspar) + 2H+ + 12H2O Kal3Si3O10(OH)2 (muscl) + 4H4SiO4(aq) +2K+

The equilibrium constant is

[K + ]2
22) K'= [H 4 SiO4 ]6
[H + ]2

[K + ]
23) K Kspar"musc = +
[H 4 SiO4 ]3
! [H ]

Using data from Table 2 we find that Grxn = 74.42 kJ mol-1, logK = -13.0, and
logKkspar-musc = -6.5. As for equation 7, we can write:
!
24) log([K+]/[H+]) = -3log[H4SiO4] + logKkspar-musc

Thus, on our chosen axes, the reaction boundary between K-spar and muscovite will
have a slope of 3 and a y-intercept of 6.5 (Figure 3). Because they have different
slopes, the K-spar - muscovite reaction boundary intercepts the K-spar - kaolinite line.
Thus, depending on both initial conditions and the reaction path, K-spar could react to
form either muscovite or kaolinite. As we complete the diagram we will be better able to
see which reaction is relevant for a given set of conditions.

Muscovite may also react to form gibbsite:

25) KAl3Si3O10(OH)2 (muscl) + H+ + 9H2O 3Al(OH)3 (gibb) + K+ + 3H4SiO4

The equilibrium constant is

[K + ]
26) K musc"gibb = [H 4 SiO4 ]3
[H + ]

and we obtain directly

! 27) log([K+]/[H+]) = -3log[H4SiO4] + logKmusc-gibb

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From table 2, the value of Grxn = 74.42 kJ mol-1, and logKmusc-gibb = -9.5. The
muscovite-gibbsite reaction boundary will plot as a line with a slope of 3 and an
intercept of 9.5, and is parallel to the K-spar-muscovite line (figure 4).

Muscovite may also react to form kaolinite:

28) 2KAl3Si3O10(OH)2 (muscl) + 2H+ + 3H2O 3Al2Si2O5(OH)3 (gibb) + 2K+

The equilibrium constant is:

[K + ]2
29) K'=
[H + ]2

[K + ]
30) K musc"kaol =
! [H + ]

Following the usual procedure with data from Table 2, we obtain logKmusc-kaol = 3.8.
Since this reaction does not produce dissolved silica, the equilibrium line will have a
! of zero and a y-intercept of 3.8 (Figure 5).
slope

The preceding are all the reactions among the alumino-silicate phases we will consider in
this K-Al-Si-H2O system, but there is one additional phase that we will add to bound our
diagram. The precipitation or dissolution of amorphous silica (opal) is often rapid
enough that it provides an upper limit for silica solubility in natural systems. The
reaction may be written:

31) SiO2(amorph) + 2H2O H4SiO4

32) Kopal = [H4SiO4]

Because of variation in both the composition and structure of this phase there is some
uncertainty in the thermodynamic data, or at least how a given laboratory experiment can
be applied to real systems. Recent experimental data give a logKopal value near 2.7, so
reaction 31 will have an undefined (vertical) slope and an x-intercept of 2.7 on our
diagram (Figure 6). Ordinarily, we do not expect to see dissolved silica (H4SiO4)
concentrations above 10-2.7 M at 25 C (equivalent to ca. 2000 molar), as they should be
limited by the solubility of amorphous silica.

Now we have a complete diagram, but it is useful to resize the axes to focus on the
environmentally relevant portion (Figure 7). [K+]/[H+] ratios in natural waters are usually
> 1, so we set the lower limit of the y-axis to zero (log(1)). The upper limit for silicic
acid is given by opal saturation, so we set the x-axis maximum to 2. The lower limit of
the x-axis and upper limit of the y-axis are simply chosen to cover almost all likely
compositional ranges.

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The next task is to sort out which are the stable phases and reaction boundaries (Figure
8). Starting in the upper right hand corner, the stable phase is K-feldspar. The stability
field of K-feldpsar is bounded by the reaction with muscovite when log([K+]/[H+]) > 3.8,
and with kaolinite below this value. Assuming log([K+]/[H+]) > 3.8, at the boundary K-
feldspar will react to form muscovite. Moving further to the right into the muscovite
field implies that K-spar is no longer stable, so the extension of the K-spar-kaolinite
reaction line into the muscovite stability field is called a metastable boundary. Since
neither kaolinite nor K-spar are stable in the muscovite field, the reaction between them
is not favored, and could only occur if some kinetic inhibition prevented muscovite from
forming.

At lower values of log([K+][H+]) < 3.8, muscovite is not stable. The reaction muscovite
kaolinite occurs at log([K+][H+]) = 3.8. Once muscovite or kaolinite react to form
gibbsite, the extension of the muscovite-kaolinite line to the left of the diagram into the
gibbsite field is no longer stable. Similarly, beginning from the lower left gibbsite field,
for log([K+][H+]) < 3.8, increasing [H4SiO4] causes the reaction to form kaolinite before
equilibrium with muscovite is reached. So, the extension of the muscovite-gibbsite line
into the kaolinite field is another metastable boundary, sometimes termed a metastable
extension. To reiterate, metastable boundaries are not the stable or equilibrium
boundaries we predict. However, in the absence of the true stable phase (typically
because it is too slow to form), they may be relevant.

A final cleaned up diagram is presented in Figure 9. We can use this diagram to

understand equilibrium sates and reaction paths.

Returning to the question of kinetic inhibition of the formation of a phase, we can

consider a reaction very similar to that between opal and water: quartz and water.
reaction may be written:

33) SiO2(qtz) + 2H2O H4SiO4

34) Kqtz = [H4SiO4]

Quartz is a nearly ubiquitous phase, but is very slow to precipitate below about 70 C, so
determining its solubility at low temperature has been surprisingly difficult. Recent work
gives a logKqtz value of 3.8, so, like opal, reaction 33 will have an undefined (vertical)
slope but an x-intercept of 3.8 on our diagram (Figure 10). If weathering solutions
were in true equilibrium with quartz, we would not expect to see dissolved silica (H4SiO4)
concentrations above 10-3.8 M at 25 C (equivalent to ca. 180 molar). However, it is not
uncommon to see measured values well above 180 M in low temperature solutions (i.e.
supersaturation with respect to quartz), because the rate of quartz precipitation is so slow.
Nevertheless can be helpful to draw the quartz saturation line on our diagram, because it
is a useful reference point.