Journal of Mineralogical and dissolution

Silica Petrological Sciences,

catalyzed byVolume
NaOH 107, page 87 ─ 98, 2012 87

Silica dissolution catalyzed by NaOH: Reaction kinetics

and energy barriers simulated by
quantum mechanical strategies

Osamu Tamada*, Gerald V. Gibbs**, Monte B. Boisen Jr.***

and J. Donald Rimstidt**
*
Department of Bio-Environmental Sciences, Kyotogakuen University,
Sogabecho-Kameoka, Kyoto 621-8555, Japan
**
Department of Geological Sciences, Virginia Polytechnic Institute and
State University, Blacksburg, VA 24061, USA
***
Department of Mathematics, University of Idaho, Moscow, ID 83844-1103, USA

Quartz dissolves in Na+ solutions much faster than in pure water though the experimental activation energies are
essentially the same. To elucidate the mechanism, silica dissolution was simulated using Gaussian 03 software
at B3LYP/3-21G* initially and the B3LYP/6-311G(2d,p) levels, applied to a modeled silica Si4O6(OH)4 in the
presence of an NaOH molecule and up to five water molecules. Each water molecule was added one by one to
the system and approached the surface silicon in successive geometry optimizations. The atomic positions of
the sodium hydroxide, the water molecules and the surface SiO3(OH) moiety were varied to mimic the surface
reaction whereas the positions of the remaining Si3O3(OH)3 atoms were frozen to represent the bulk structure
throughout the geometry optimization.
   In the first step a single H2O molecule was added to the system [Si4O6(OH)4 + NaOH]. None of the Si-O bond-
ed interactions were ruptured by the intrusion of the water molecule but the surface Si was stabilized in the Q3Si site
(connected to three Si-O-Si bridges), being coordinated by five oxygen atoms. The energy barrier was 63 kJ/mol.
   In each of the second and third steps one more water molecule was introduced to the system. One Si-O
bonded interaction of the Si-O-Si bridges was ruptured to make Q2Si and Q1Si sites in the second and third
steps, respectively, and the energy barriers were low (22-29 kJ/mol).
In the fourth and fifth steps, the added water molecules were prevented by the sodium ion from reaching the last
Si-O-Si bridge, leaving the Si in the Q1Si site.
   The basis set was raised to the 6-311G(2d,p) level and applied to the 63 kJ/mol barrier found in the first
step to determine the maximum energy barrier in the series of reactions. The barrier increased to 88 kJ/mol (82
kJ/mol in enthalpy), which is still in the range of experimental activation energies of 46-96 kJ/mol.
In summary sodium works to stabilize the surface silicon in penta-coordination with the energy barrier, 82 kJ/
mol, resulting in longer Si-O distances and the weakening of the bonded interactions. This makes the Si-O rup-
ture easier and faster, which gives insight as to how the presence of alkali enhances silica dissolution.

Keywords: Sodium hydroxide, Gaussian 03, Activation energy, Geometry optimization, Alkali enhancement

INTRODUCTION bonded interaction is key to interpreting many important

geological and geochemical processes. For example, rock
Understanding the interaction of water with the Si-O strength is affected by hydrolytic weakening (e.g., Tullis
and Yund, 1980, 1989). The full range of water-rock in-
doi:10.2465/jmps.110909 teractions found in magma generation and evolution
O. Tamada, tamada@t02.mbox.media.kyoto-u.ac.jp Corresponding (Burnham 1997), metamorphism (Spear, 1993), wall rock
author
G.V. Gibbs, ggibbs@vt.edu
alteration (Reed, 1997) and chemical weathering (White
M.B. Boisen, boisen@uidaho.edu and Brantley, 1995) involve the reaction of water with
J.D. Rimstidt, jdr02@vt.edu Si-O bonded interactions. In the waters in the natural en-
 88 O. Tamada, G.V. Gibbs, M.B. Boisen Jr. and J.D. Rimstidt
vironment, alkali ions are commonly present and play an
important role in water-rock interactions. It is, therefore,
of great value to investigate the interaction of Si-O bonds
and water in the presence of alkali ions.
Numerous experimental studies of the kinetics of sil-
ica dissolution reactions, reviewed by Dove and Rimstidt
(1994), provide base-line information about the nature of
the silica- water interaction. In these studies the activation
energies for quartz dissolution were estimated to be
roughly 75 kJ/mol (18 kcal/mol) although there is a large
scatter (46-96 kJ/mol) around this value (Table 1). It is
well known that silica dissolution is endothermic reaction
(Iler, 1979) and that the presence of alkali cations like Na
and K enhances the dissolution rate. For example, Dove
and Crerar (1990) determined the quartz dissolution rates
at near-neutral pH in the solutions with as little as 0.05
molal NaCl or KCl concentrations at the hydrothermal
conditions of 100 °C to 300 °C, and found that the rate is
enhanced by a factor of 33. In spite of the alkali enhance-
Table 1. Experimental and calculated activation energies (Ea, kJ/
mol) for silica dissolution
Note; (Qn → Qm ) indicates the rupture of Si-O-Si bridges con-
nected to Si atom from n bridges to m bridges.
ment, the activation energies in the presence of alkali cat-
ions (71.2 kJ/mol for NaCl and 71.5 kJ/mol for KCl) are
reported by them to be the same as that in the deionized
solution (71.3 kJ/mol). Thus, the activation energies so far
reported are in the same range as for silica dissolution in
deionized water. The reason for the alkali enhancement is
still unclear.
On the other hand, theoretical tools of computational
chemistry, such as molecular dynamics and molecular or-
bital geometry optimization strategies, enabled the model-
ing of surface reactions at the atomic level (Lasaga, 1995;
Felipe et al., 2001). In an earlier study, Lasaga and Gibbs
(1990) pointed out that the reaction, H2O + ≡Si-O-Si≡ →
2 ≡Si-O-H, is an elementary step in the hydrolysis pro-
cess occurring at the surface of silicate. Subsequent stud-
ies have been carried out in an attempt to clarify the silica
dissolution kinetics (Xiao and Lasaga, 1994, 1996; Walsh
et al., 2000; Criscenti et al., 2006; Nangia and Garrison,
2008, 2009).
Several studies have simulated the hydrolysis of sili-
ca surfaces using molecular dynamics strategies (Cheng
et al., 2002; Du et al., 2003; Rignanese et al., 2004; Ma et
al., 2005). These studies indicate that the attack of water
at the defect sites on a silica surface lowers the energy
barrier and that the reactions are catalyzed by a coopera-
tive transfer of hydrogen atoms contributed by the water
molecules.
Pelmenschikov et al. (2000) considered the resis-
tance of the bulk structure to the activated surface and
found that the activation energy decreases as the “con-
nectedness” of the target Si decreases from Q4Si (con-
nected via four bridging oxygen atoms to four adjacent Si
atoms) to Q2Si (connected via two bridging oxygen atoms
to two adjacent Si atom). They concluded, in a later study
(Pelmenschikov et al., 2001), that the experimental acti-
vation energy correlates with the cleavage of the last Si-
O-Si bonded interaction in Q1Si. Cypryk and Apeloig
(2002) reported that the protonation of the siloxane oxy-
gen, assisted by the cooperative hydrogen transfer, was
the most important factor in reducing the activation ener-
gy barrier. Recently Wallace et al. (2010) investigated the
ability of M(II) aqua ions (Mg2+, Ca2+) to promote the hy-
drolysis of Si-O bonded interactions.
In these computational efforts we find some features
such as the calculated activation energies are generally
higher by roughly 40-80 kJ/mol than the experimental
ones as shown in Table 1. It is also suggested that they are
reduced by the “connectedness” (Pelmenschikov et al.,
2000), that the addition of water molecules to the dissolu-
tion system reduces the activation energy (Cypryk and
Apeloig, 2002) and that the high and low pH values en-
hance the dissolution rate as indicated in the study of the
 Silica dissolution catalyzed by NaOH
protonated, neutral and deprotonated species (Nangia and
Garrison, 2008, 2009).
The Na enhancement of the experimental silica dis-
solution rate is markedly observed in solutions from neu-
tral to high pH (Dove, 1995). The enhanced rate curve ex-
tends smoothly from high to very high pH, which
suggests that Na enhances dissolution even in solutions
with very high pH. Consequently, we use the sodium hy-
droxide molecule for modeling the system of silica in ba-
sic solution and for simplifying the system.
Sverjensky (2005) used a theoretical framework to
predict surface charges on oxides in 1:1 (M+;L−) electro-
lytes salt solutions and found that on high dielectric con-
stant solids, such as rutile, the alkali cations predominant-
ly adsorb close to the surface as inner-sphere complexes
but on most other oxides, including silica, they predomi-
nantly adsorb further away as outer-sphere complexes.
This means that most adsorbed sodium ions on a silica
surface are present as outer-sphere complexes. However,
Sverjensky’s model implies that even though the concen-
tration of adsorbed alkali cations present as inner-sphere
complexes is small there is an equilibrium between inner-
and outer-sphere cations so that some inner-sphere com-
plexes are present on silica surfaces. Wallace et al. (2010)
investigated the effect of both inner- and outer-sphere
complexes of Mg2+ and Ca2+ on the hydrolysis of Si-O
bonded interactions and found that the height of the hy-
drolysis barrier is significantly lower for the inner-sphere
site. They concluded that, despite their documented abun-
dance at the silica-water interface, outer-sphere surface
complexes are not likely participants in the Si-O bonded
dissociation mechanism. Taking these points into account,
we designed a simulation model, which considers the ef-
fect of sodium ions adsorbed on silica surfaces as inner-
sphere complexes because they appear to be the species
most likely responsible for the observed increase in disso-
lution rates.
In this study, we examine the attack of multiple wa-
ter molecules on a neutral silica surface in the presence of
an NaOH molecule. In this dissolution simulation, the
strategy is to have each water molecule approach the sili-
ca model Si4O6(OH)4, step by step producing the opti-
mized geometry at each step, thereby moving along the
energy valley.
The objective of this simulation is to find what are
likely to be the intermediate structures and the values of
the intermediate energies in a series of reactions. In this
way, we are able to obtain insight into the dissolution pro-
cess that is not possible to observe in experiments, and,
therefore, to promote our understanding of silica dissolu-
tion catalyzed by sodium hydroxide.
Besides our primary goal of clarifying the dissolu-
89
tion kinetics in the presence of sodium hydroxide, the
second goal is to address how the calculated activation
energies relate to the experimental ones for silica dissolu-
tion with sodium hydroxide.
COMPUTATION AND RESULTS
Gaussian 03 (Frisch et al., 2003) and Xtaldraw (Bartel-
mehs et al., 1993) were used for the ab initio calculations
and crystal structure drawings, respectively.
At the silica-water interface, the silica surface is hy-
droxylated with the major part of the surface consisting of
silanol in which the surface silicon is in the Q3Si site
(connected to three Si-O-Si bridges and a silanol) (Iler,
1979; Parks, 1984). On this basis, the silica was modeled
as a hydrogen clad, Si4O6(OH)4 molecule which was ge-
ometry optimized at the B3LYP/6-311G(2d,p) level, as-
suming S4 point symmetry. The resulting configuration is
composed of four silicate tetrahedra corner sharing each
others. This molecule is used to model the silica surface
and the matrix by considering it in two parts, one variable
surface SiO3(OH) moiety that is flexible so that it can re-
spond to the water attack and three frozen inner tetrahedra
Si3O3(OH)3 matrix used to model the bulk structure.
First step
The oxygen atoms of a water molecule and a sodium hy-
droxide were initially placed 4.3 Å and 3.5 Å respectively
from the target surface silicon Sit atom as shown in Figure
1. The atomic positions of each of the atoms in the
SitO3(OH) moiety, the sodium hydroxide and the water
molecule were free to move during the geometry optimi-
zation with the constraint that the Sit-Ow distance r (Ow:
the water’s oxygen) was fixed at 4.3 Å. As indicated
above, the remaining Si3O3(OH)3 atoms associated with
the interior of the silica model were frozen at their initial-
ly optimized positions. The geometry optimization of the
system was completed at the B3LYP/3-21G* level. After
the optimization, the Sit-Ow distance r was decreased by
the value Δr, and as before, the positions of the atoms in
the SitO3(OH) moiety, sodium hydroxide and the water
molecule were again relaxed during the energy optimiza-
tion. This strategy was continued with a progressive
shortening of the Sit-Ow distance from 4.3 to 1.55 Å. A
graph of the total energies was obtained along the poten-
tial surface valley of the Sit-Ow pathway as displayed by
the curve in Figure 2.
The total energy increased from a distance of 3.4 to
2.3 Å with the slope of the energy curve progressively in-
creasing with decreasing distance. From this energy curve
and the geometries, estimates of the adsorption state and
 90 O. Tamada, G.V. Gibbs, M.B. Boisen Jr. and J.D. Rimstidt

the total energy decreased until a distance of 1.8 Å was

obtained. The product geometry was also optimized relax-
ing Sit-Ow distance as shown in Figure 3 together with the
geometries of adsorption and transition states. Note that
the five-fold coordinated silicon atom is sitting at the sta-
ble Q3Si site in the minimum energy configuration. The
sodium atom is connected to one of the three bridging ox-
ygen atoms, an oxygen originated from the NaOH mole-
cule and the water’s oxygen. As a result, the sodium atom
weakens the Si-O bonded interactions around the surface
Si and the Si-O distances are elongated from ~ 1.65 Å to
~ 1.75 Å, which are suitable bond lengths for a five-fold
coordinated silicon. In previous works, there has been no
report that the sodium stabilizes the silicon in the five-
fold coordination in the neutral surface condition.
Figure 1. The initial geometry for the first step. The modeled silica In order to highlight the role of sodium hydroxide in
Si4O6(OH)4, an NaOH molecule and a water molecule are shown
silica dissolution the same calculations were performed
in theTamada
figure. The
et al.bold line
Fig.separates
1 the surface part of
SitO3(OH) moiety, H2O and NaOH molecules from the matrix setting the model without sodium hydroxide (the model is
part of Si3O3(OH)3. The atoms in the surface portion are all acti- the same as above but the NaOH molecule is replaced by
vated and those in the matrix are all frozen throughout the opti- a water molecule HOH, in which each hydrogen is placed
mizations. about 1 Å from the water oxygen). A graph of the total
energies and the geometries of adsorption and transition
-2216. + states, and product are shown in Figures 4 and 5, respec-
‐0.495 tively. In this case the activation energy from the adsorp-
Transition
tion state to the transition one is fairly high (112 kJ/mol)
‐0.500
and one of three Si-O-Si bonded interactions is ruptured
to make Q2Si site as shown in the product. This illustrates
e)
Energy((Hartree

‐0.505
a clear difference from the process with sodium hydroxide
‐0.510
0 510 63 kJ/mol where the Si atom is stabilized in a five-fold coordination
and in Q3Si site. The silicon atom is never stabilized in
‐0.515 higher coordinations than four without sodium hydroxide
Product and this is apparently the role that sodium plays in silica-
‐0.520
water interactions.
‐0.525
Adsorption Second step
‐0.530
0 530
1.5 2.0 2.5 3.0 3.5 4.0 4.5 A second water molecule was added to the product geom-
Sit-Ow distance (Å) etry obtained in the first step and the same strategy as in
Figure 2. A graph of the total energies calculated at the B3LYP/3- the first step was applied. That is, the atomic positions of
Tamada et al.     Fig. 2
21G* level versus the distance r of the water oxygen Ow to the surface SitO3(OH) moiety, sodium hydroxide and two wa-
target silicon atom Sit in the first step. At each point the geometry ter molecules were free to move during the geometry op-
was optimized under the constraint of a fixed r distance. The ad-
timization. The distance between the target Si and the ox-
sorption state, transition state and product were optimized with
the distance constraint removed, starting from the geometries op- ygen Ow of the added water molecule were fixed and the
timized under the constraint. geometry was optimized. In this way the optimizations
were performed step by step with each step decreasing the
Sit-Ow distance along the energy valley of Sit-Ow pathway.
the transition state were found. The actual modeled ad- The energy curve is shown in Figure 6. The energy gener-
sorption and transition states were found by taking the ge- ally decreases with decreasing distance from 4.0 Å to 2.0
ometries of the estimated states and optimizing these re- Å (although there is a hump around 3 Å), goes up to a
laxing the Sit-Ow distance. The resulting values are plotted sharp peak at 1.8 Å and falls down to a minimum at 1.7 Å.
in Figure 2. The energy difference between these states From the geometries of these constrained optimizations
was 63 kJ/mol. As the Sit-Ow distance further decreased, the adsorption state, reactant, transition state and product
 Silica dissolution catalyzed by NaOH 91

Adsorption Transition state Adsorption Transition state

H 2O Product H2O
H2O
H 2O
Product

Ow

Sit in Q3Si
Figure 5.
Tamada et The
al. geometries
Fig. 5 of the adsorption state (r = 3.6 Å), transi-
Ow tion state (r = 1.9 Å) and product (r = 1.7 Å) in the reactions
where the NaOH molecule was replaced by a water molecule
H2O. The product is characterized by the rupture of one of three
N
Na Si-Obr bonded interactions to make a Q2Si site keeping the four-
Figure 3. The geometries of the adsorption state (r = 3.4 Å), transi- fold coordination of Si.
Tamada et al.     Fig. 3
tion state (r = 2.3 Å) and product (r = 1.8 Å) in the first step. The
product is characterized by the five-fold coordinated silicon -2292. +
atom. ‐0.525

-2055. + ‐0.530 Transition

ee)

‐0.660
T
Transition
iti
gy(Hartre

‐0.670 ‐0.535
Hartree))

112 kJ/mol
Energ

‐0.680
Adsorption
‐0.540
Energy(H

‐0.690
22 kJ/mol

‐0.545
‐0.700
0.700 Reactant
E

Product
‐0.710
‐0.550
Product
Adsorption
1.5 2.0 2.5 3.0 3.5 4.0 4.5
‐0.720
1.5 2.0 2.5 3.0 3.5 4.0 4.5
Sit-Ow distance (Å)
Sit-Ow distance (Å) Figure 6. A graph of the total energies calculated at the B3LYP/3-
21G* level versus the distance r of the water oxygen Ow to the
Figure 4. A graph of the total energies for the system Si4O6(OH)4 +
2H2O without sodium hydroxide, calculated at the B3LYP/3- Tamada et al.     Fig. 6
target silicon atom Sit in the second step. At each point the geom-
Tamada
etry was optimized under the constraint of a fixed r distance. The
21G* level versus the et al. Fig.
distance r of 4the water oxygen Ow to the
adsorption state (r = 3.5 Å), reactant (r = 2.0 Å), transition state (r
target silicon atom Sit. At each point the geometry was optimized
= 1.8 Å) and product (r = 1.7 Å) were optimized without the dis-
under the constraint of a fixed r distance. The adsorption state,
tance constraint, starting from the geometries optimized under
transition state and product were optimized with the distance
the constraint.
constraint removed, starting from the geometries optimized un-
der the constraint.

energies. It is reasonable that this low activation energy

were successfully obtained at the distances of 3.5, 2.0, 1.8 results from the weakening of the Si-O bonded interac-
and 1.7 Å, respectively. The energy difference between tion associated with the five-fold coordination of silicon.
the reactant at 2.0 Å and the transition state at 1.8 Å is 22 The geometries of these states are shown in Figure 7. The
kJ/mol, a value far lower than the experimental activation added water molecule approaches the target silicon and
 92 O. Tamada, G.V. Gibbs, M.B. Boisen Jr. and J.D. Rimstidt

Adsorption Reactant -2368. +

0 545
‐0.545

gy(Hartrree)
H 2O ‐0.550
H 2O
29 kJ/mol
‐0.555 22 kJ/mol

Energ
Transition Fi t max.
First
‐0.560

‐0.565
0 565

Transition state Product TTamada et al. 

d l
‐0.570
Fig. 7 Reactant
Adsorption
Product
‐0.575
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Sit-Ow distance (Å)

Ow
Ow
Sit in Q2Si Figure 8. A graph of the total energies calculated at B3LYP/3-21G*
level versus the distance r of the water oxygen Ow to the target
silicon atom SiTamada et al.       Fig. 8
t in the third step. At each point the geometry was

Na optimized under the constraint of a fixed r distance. The adsorp-

Figure 7. The geometries of the adsorption state (r = 3.5 Å), reac-
tant (r = 2.0 Å), transition state (r = 1.8 Å) and product (r = 1.7 Å)
in the second step. This step is characterized by the rupture of
one of the three Si-O-Si bridges, making the Q2Si site.
makes a bonded interaction with the silicon momentarily
to form a six-fold coordinated silicon intermediate. It at-
tacks one of the three bridging oxygen atoms, transferring
a hydrogen to it in the transition state. As a result, the
bridging oxygen moves from the Si atom, which consti-
tutes the rupture of Si-Obr bonded interaction, leading to
the formation of Q2Si site. At the end of this step, the so-
dium atom has caused a weakening of the Si-O bonded
interactions, connected to the three oxygen atoms around
the target silicon resulting in the five-fold coordinated sil-
icon atom as shown in the product geometry.
Third step
A third water molecule was added to the product geome-
try obtained in the second step and the same strategy as in
the previous steps was performed. The energy curve is
shown in Figure 8. As the Si-Ow distance goes from 4.7 Å
to 3.5 Å , the energy decreases. The energy increases as
the distance decreases from 3.5 Å to around 2.7 Å. Then,
it decreases to a minimum at 2.0 Å, again increases to a
sharp peak at 1.74 Å and then drops down to a minimum
at 1.73 Å. From the geometries of these constrained opti-
mizations the adsorption state, the first maximum (com-
putationally a transition state), the reactant, the transition
state and the product were successfully obtained at the
distances 3.5, 2.7, 2.0, 1.74 and 1.72 Å, respectively. The
tion state (r = 3.5 Å), first maximum (r = 2.7 Å), reactant (r = 2.0
Å), transition state (r = 1.74 Å) and product (r = 1.72 Å) were
optimized without the distance constraint, starting from the ge-
ometries optimized under the constraint.
energy difference between the adsorption state at 3.5 Å
and the first maximum at 2.7 Å is 29 kJ/mol and that be-
tween the reactant at 2.0 Å and the transition state at 1.74
Å is 22 kJ/mol. Both of them are far below the experi-
mental activation energies. It is clear that these low acti-
vation energies result from the weakening of Si-O bonded
interaction associated with the five-fold coordination of
silicon. The geometries of these states are shown in Fig-
ure 9. After the added water molecule has passed through
the distance of the first maximum as it approaches the tar-
get silicon atom, it attacks one of the two Si-O-Si bridg-
ing oxygen atoms yielding a hydrogen to that oxygen just
before the transition state as shown in the figure at r = 1.8
Å, at which time the target silicon is instantaneously coor-
dinated with six oxygen atoms. As a result the bridging
oxygen moves from the Si atom rupturing the Si-O bond-
ed interaction, which leads to the formation of a Q1Si site.
After this has occurred, the target silicon atom is only
connected with the inner matrix by the last Si-O-Si bridg-
ing oxygen and is still coordinated by five oxygen atoms
as shown in the product geometry.
Fourth and fifth steps
In each of the fourth and fifth steps one additional water
molecule was added. But these additional water molecules
were prevented by the sodium atom from reaching the last
Si-O-Si bridge. It is possible that, after the sodium atom
is saturated with water molecules, the next one might suc-
 Silica dissolution catalyzed by NaOH 93

Adsorption First maximum Reactant

H 2O
H 2O

H 2O

Before Si‐O rupture at  1.80 Å Transition state Product

Figure 9. The geometries of the ad-

sorption state (r = 3.5 Å), first max-
imum (r = 2.7 Å), reactant (r = 2.0
Å), the point just before Si-O rup-
ture (r = 1.8 Å), transition state (r =
1.74 Å) and product (r = 1.72 Å) in
H 2O Ow Sit in Q1Si Ow the third step. This step is charac-
terized by the rupture of one of two
Si-O-Si bridges, making the Q1Si
Na site.

Tamada et al.            Fig. 9
cessfully attack the last bridging oxygen to cleave the -2228. +
‐0.480
bridge or the sodium atom might dissolve out into the so-
‐0.485
lution. At this time, the computation needed to explore
Transition
ee)

this is too large. ‐0.490

0 490
y(Hartre

‐0.495
Promotion of basis set and correction of energies
Energy

‐0.500 88 kJ/mol
kJ/ l
Product
‐0.505
The energy barriers are as low as 22-29 kJ/mol in the sec-
‐0.510
ond and third steps. The highest barrier occurs in the first
step. The basis set was raised from the 3-21G* to the ‐0.515 Adsorption

6-311G(2d,p) level and applied to the transition and ad- ‐0.520

sorption states to better determine the energy barrier. The
barrier appreciably increased from the 63 kJ/mol calculat-
ed with the less robust basis to 88 kJ/mol as shown in
Figure 10. This increase is consistent with the increase
that was reported by Nangia and Garrison (2008), associ-
ated with the promotion of the basis set from 6-31+G(d,p)
to MG3S. Here we performed the vibrational frequency
calculation at room temperature. It is difficult to correctly
estimate the zero-point vibrational energy since positions
of the matrix atoms were fixed in the optimization, but the
rough estimation is reasonable because the zero-point vi-
brational energy itself is small compared with the total
energy. It is also true that the matrix atoms are frozen
throughout the optimizations for the adsorption state and
the transition one, so that the effect on vibrational ener-
gies should be nearly equal. The energy difference for this
part might, therefore, be cancelled out. The correction
value used for the activation energy is 3 kJ/mol, so that
1.5 2.0 2.5 3.0 3.5 4.0
Sit-Ow distance (Å)
Figure 10. The total energies of adsorption state, transition state
and product re-optimized at the B3LYP/6-311G(2d,p) level start-
ing from their geometries in the first step. The energy barrier in-
Tamada et al.        Fig. 10
creased to 88 kJ/mol from the value of 63 kJ/mol calculated at
the B3LYP/3-21G* level.
the barrier is lowered to 85 kJ/mol. Not only zero point
energies (EZPE) of adsorption state and transition state,
thermal energies (Etherm), thermal enthalpies (Htherm), entro-
pies (S) and thermal free energies (Gtherm) are also estimat-
ed from the vibrational frequency calculation as listed in
Table 2. Activation energy in enthalpy (ΔH) reduced to 82
kJ/mol and that in free energy (ΔG) increased to 91 kJ/
mol. The experimental activation energy is best interpret-
ed as the enthalpy of activation (∆H), i.e. the difference
between the enthalpy of formation of the activated com-
 94 O. Tamada, G.V. Gibbs, M.B. Boisen Jr. and J.D. Rimstidt
Table 2. Activation energies Ea for the silica dissolution with
NaOH and without NaOH
Note; The systems in the first step, re-optimized at the B3LYP/6-
311G(2d,p) level.
Zero point energies (EZPE), thermal energies (Etherm), thermal en-
thalpies (Htherm), entropies (S) and thermal free energies (Gtherm) are
derived from the vibrational frequency calculation at room tem-
perature (25 °C).
plex and the enthalpy of formation of the reactants, so that
activation energy in enthalpy (ΔH) 82 kJ/mol, is hereafter
used for the comparison with the experimental one.
The same calculations were also applied to the pro-
cess without NaOH in the first step and the results are
listed in Table 2. The barrier appreciably increased from
the 112 kJ/mol calculated with the less robust basis to 150
kJ/mol in the same way as above. The activation energies
in enthalpy ∆H and in Gibbs free energy ∆G are 139 and
151 kJ/mol, respectively, which all demonstrates high bar-
riers when the sodium hydroxide is not introduced in the
system. The entropy term T∆S at the room temperature is
9 and 12 kJ/mol for the reactions with and without NaOH,
respectively. Their difference is 3 kJ/mol, which is mostly
negligible.
DISCUSSION
Penta-coordination of Si and reaction barriers
In the first step in which a water molecule and a sodium
hydroxide were introduced to the system, nothing drastic
like a ruptured Si-O bonded interaction occurred but the
process of moving a water molecule steadily toward a tar-
get silicon concluded with a five-fold coordinated silicon
atom. This is the consequence of the presence of a sodium
hydroxide. The connectedness of the Q3Si site doesn’t
change but the coordination number of the silicon atom
increases from four to five. The energy barrier of this re-
action is 63 kJ/mol in the B3LYP/3-21G* level. The dis-
tances between Si and coordinated oxygen atoms are
lengthened from about 1.65 Å to 1.75 Å associated with
the increase of coordination number, which induces the
weakening of Si-O bonded interactions. This weakening
suggests that the Si-O connections are susceptible to rup-
ture. It is also important to note that the product is at the
stable state having the minimum energy configuration as
shown in Figure 2.
In each of the second and third steps a water mole-
cule approached the five-fold coordinated silicon atom
and cleaved one of the weakened Si-Obr bonded interac-
tions in each step, with low energy barriers of 22-29 kJ/
mol (due to the increase in coordination number). In this
process, the Q3Si site changed to a Q2Si and then to a Q1Si
site.
Going back to the first goal of this study, the most
important factor of the dissolution kinetics in the presence
of sodium hydroxide is that sodium plays the role of
forming a five-fold coordinated silicon atom, finally keep-
ing the system at the energy minimum. This makes the
rupture of the Si-O bonded interactions easier and faster.
This result suggests that alkali ions like Li and K and al-
kali earth ions like Mg and Ca behave in the same way as
sodium. Thus, the weakening of the Si-O bonded interac-
tions resulting from the five-fold coordination should be a
clue as to the reason for the alkali or alkaline earth en-
hancement of the silica dissolution.
It is well known that the silicon atom is four-fold co-
ordinated by oxygen atoms in ambient condition. But co-
ordination numbers higher than four have been actually
reported in glasses containing alkali oxide in the system
of Na2O-SiO2-P2O5 (Dupree et al., 1988, 1989) where the
proportion of six-coordinated silicon depends on the al-
kali content and cooling rate. However, six-coordinated
silicon atoms were not observed by NMR spectroscopy in
SiO2-P2O5 glasses without Na2O (Weeding et al., 1985).
After these reports a number of examples of six-coordi-
nated silicon atoms in SiO2-P2O5 glasses containing alkali
oxide have been reported. Recently Ide et al.(2007) stud-
ied R2O-SiO2-P2O5 (R = Li, Na, K) glasses and observed
six-coordinated silicon atoms in the XANES and XAFS
analyses and the fraction of six-coordinated silicon atoms
increased with increasing concentration of alkali oxide.
Thus, these experimental results support our computa-
tional result that alkali ions help to make silicon atoms be
coordinated by more than four oxygen atoms.
Wallace et al. (2010) investigated the ability of M(II)
aqua ions to promote the hydrolysis of Si-O bonded inter-
actions using the silica cluster model H8Si6O16 and ad-
 Silica dissolution catalyzed by NaOH
sorption complexes of Mg2+(6H2O) and Ca2+(6H2O). The
activation free energies are 178.9 (Mg) and 178.8 (Ca) kJ/
mol in the outer-sphere adsorption hydrolysis and 138.9
(Mg) and 156.4 (Ca) kJ/mol in the inner-sphere adsorp-
tion hydrolysis, which is clearly different from the experi-
mental activation energies and our energy barrier of 82
(Na) kJ/mol.
The second goal for the activation energy is fairly
well addressed in this study. The largest energy barrier is
not the energy to rupture the Si-O bonded interactions but
the energy to form the five-fold coordinated silicon atom
in the presence of sodium hydroxide. The barrier is 63 kJ/
mol in the 3-21G* level and 88 kJ/mol in the 6-311G(2d,p)
level. The value 88 kJ/mol (82 kJ/mol in enthalpy) is fair-
ly high compared with experimental values but is still in
the range of experimental ones of 46-96 kJ/mol. The en-
ergy barrier of the Si-O rupture for Q3Si to Q2Si was 22
kJ/mol and that for Q2Si to Q1Si was 22 or 29 kJ/mol in
this study, which does not indicate the special resistance
of the bulk structure as Pelmenschikov et al. (2000) re-
ported. This can be explained by the result that the Si-O
bonded interactions are already weakened by the five-fold
coordination of the silicon atom in the presence of sodium
hydroxide, so that the effects of bulk resistance are not
explicitly observed in this study.
Cypryk and Aleloig (2002) calculated the activation
energies for hydrolysis of siloxanes and siloxanols using
water clusters (H2O)n n = 1, 2, 3, 4 at B3LYP/6-311+G(2d,p)
level and found that the energies are reduced from 140 kJ/
mol to 74 kJ/mol as the number of water molecules in-
creases, assisted by the cooperative proton transfer from
the nucleophile to siloxane oxygen. This is the result in
cleaving an Si-O-Si bridge of connectedness (Q1 → Q0)
attacked by multiple water molecules. Although the situa-
tion is quite different from our case, their result leaves the
possibility of a reduction of the activation energy by the
attack of multiple water molecules (n>3) on one Si-O-Si
bridge, so that the present value 88 kJ/mol (82 kJ/mol in
enthalpy) should be the upper limit of the activation ener-
gy.
Dissolution associated with Pelmenschikov`s self-
healing effect
After the third step the target silicon is still five-fold coor-
dinated and left as a Q1Si. The fourth and fifth steps were
tried adding a water molecule in each case, but the trial
failed because the last Si-O-Si bridge formed a narrow
bottle neck connecting the surface group and the inner
bulk structure, and the sodium prevented the water mole-
cule from entering the bottle neck. In this situation two
scenarios seem plausible for the Q1Si rupture. The first
95
one is that the last Si-O-Si bridge is ruptured with the low
activation energy of 20-30 kJ/mol after the addition of
several more water molecules, since the target Si is still
coordinated by five oxygen atoms. The second scenario is
that the sodium ion dissolves out into the solution by the
addition of water molecules and the energy for the hydro-
lysis of last Si-O-Si bridge is the same as the energy in
the deionized water without alkali ions, which conforms
with the experimental result. This second scenario also
conforms with Pelmenschikov’s proposal. Pelmenschikov
et al. (2001) proposed the new mechanism based on the
self-healing effect of reactions which makes the preexpo-
nential factor extremely small and emphasized the impor-
tance that the measured activation energy is associated
with the hydrolysis of the last Si-O-Si bond of the Si at-
oms.
According to the second scenario our results are es-
sentially consistent with Pelmenshikov et al.’s “self-heal-
ing” model of silica dissolution and provide a plausible
explanation for why silica dissolution in the presence of
alkali and alkaline earth ions is 20 to 30 times faster than
in pure water even though the observed activation energy
is essentially the same for both cases. Dove and Crerar
(1990) showed that the dissolution rate of quartz in 0.05
m NaCl solutions is about 30 times faster than in pure wa-
ter even but activation energies for both cases are essen-
tially the same [Ea(NaCl) = 71.5 kJ/mol and Ea(pure wa-
ter) = 71.3 kJ/mol]. Similarly, Icenhower and Dove (2000)
reported that the dissolution rate of amorphous silica in
0.05 m NaCl solutions is about 20 times faster than it is in
pure water but the activation energies are nearly the same
[Ea(NaCl) = 74.5 kJ/mol and Ea(pure water) = 76.4 kJ/
mol]. Thus, it seems that Na produces a catalytic effect
even though it does not change the experimental activa-
tion energy. A reasonable explanation for this effect is that
Na does not catalyze the Q1 → Q0 detachment reaction,
which is the observable step for silica dissolution, but
rather it catalyzes prior bond breaking steps in the overall
dissolution process such that it increases the concentration
of Q1Si sites on the silica surface.
The release of dissolved Si from a silica surface in-
volves a chain reaction consisting of three bond breaking
steps:
 
(1)
where the overall rate of dissolution is
  r = k+1aH OCQ1 −k−1mH SiO (2)
2 4 4
If the solution is very dilute so mH SiO ≈ 0 and aH O =1, the
4 4 2
 96 O. Tamada, G.V. Gibbs, M.B. Boisen Jr. and J.D. Rimstidt
observed rate is simply a product of the forward rate con-
stant and the concentration of the Q1Si sites
  r = k+1CQ (3)
1
at steady state
 k+2CQ −k−2CQ =k+1CQ −k−1mH SiO (4)
2 1 1 4 4
the concentration of Q1Si sites depends on the concentra-
tion of Q2Si sites
(5)
   values. This is the example to report the lowest energy
The concentration of Q2Si sites depends on the concentra-
tion of Q3Si sites in a similar fashion. This chain of re-
versible elementary reaction steps would produce the
“self-healing” effect described by Pelmenschikov et al.
(2001), which means that the concentration of Q2Si and
Q1Si sites is controlled by a sequence of near equilibrium
reaction steps. This leads to the conclusion that the mea-
sured activation energy for silica dissolution simply re-
flects the Q1Si to H4SiO4 reaction and that the overall dis-
solution rate is low because the concentration of Q1Si
sites is low.
The model presented here shows that inner-sphere
sorption of Na causes a significant reduction of the activa-
tion energy barriers for the Q3Si to Q2Si and Q2Si to Q1Si
reactions. This in turn causes the rates of these reactions
to increase and increases the concentration of Q1Si sites,
which causes an increase in the overall reaction rate.
However, our model shows that the Q1Si to H4SiO4 reac-
tion does not occur as long as the Na remains on the sur-
face but we postulate that Na will eventually become hy-
drated and depart the surface leaving behind a Q1Si site as
indicated above in the second scenario, which then reacts
with a water molecule to produce H4SiO4. Because the
more abundant Q1Si sites produced by this Na-catalyzed
process are indistinguishable from Q1Si sites produced by
the water hydrolysis elementary steps in the absence of
Na, the observed rate is increased even though the ob-
served experimental activation energy for the Na-cata-
lyzed reaction is the same as for the reaction in pure wa-
ter.
This is the dissolution kinetics according to the
Pelmenschikov`s self-healing effect (Pelmenschikov et
al., 2000, 2001) and all of these discussions emphasizes
the importance for determining the kinetics and the ener-
gy of hydrolysis for the last Si-O-Si bridge.
CONCLUSIONS
It is found that the presence of sodium atoms plays a role
for the formation of five-fold coordinated silicon atoms in
the dissolution kinetics of silica, which induces the elon-
gation of the Si-O distances and the weakening of the
bonded interactions, making the Si-O rupture easier and
faster. Accordingly, the energy for the rupture of Si-O
bonded interactions becomes as low as 22-29 kJ/mol, but
the energy for forming the five-fold coordinated silicon
atom is substantially higher at 63 kJ/mol in 3-21G* level
and 88 kJ/mol (82 kJ/mol in enthalpy) in 6-311G(2d,p)
level, which is consistent with the range of experimental
barrier based on transition state theory for the Q3Si →
Q1Si hydrolysis in a neutral surface condition.
The calculations in this study, suggest a new under-
standing of the mechanism whereby an alkali cation en-
hances the silica dissolution rate. This is based on increas-
ing the coordination number of the silicon atom from four
to five. The process of the Si-O hydrolysis occurs as the
water molecule attacks the five-fold coordinated silicon
through the intermediate of six-fold coordinated Si. The
last rupture of Q1 to Q0 still remains for investigation.
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Manuscript received September 9, 2011
Manuscript accepted January 20, 2012
Published online April 7, 2012
Manuscript handled by Hiroki Okudera