J. Phys. Chem.

B 2002, 106, 2937-2945 2937

Evidence of the Existence of Three Types of Species at the Quartz-Aqueous Solution

Interface at pH 0-10: XPS Surface Group Quantification and Surface Complexation
Modeling

Y. Duval,† J. A. Mielczarski,*,† O. S. Pokrovsky,‡ E. Mielczarski,† and J. J. Ehrhardt§

Laboratoire “EnVironnement et Minéralurgie”, UMR 7569 CNRS, INPL-ENSG, B.P. 40,
54501 VandoeuVre-lès-Nancy, France, Laboratoire de Géochimie, UPS-CRNS (UMR5563),
314000 Toulouse, France, and Laboratoire de Chimie Physique et Microbiologie pour l’EnVironnement,
UMR 9992-CNRS, 54600 Villers-lès-Nancy, France
ReceiVed: July 23, 2001; In Final Form: NoVember 26, 2001

The surface composition of a quartz surface reacted with various aqueous solutions of pH 0-10 was
qualitatively and quantitatively evaluated using X-ray photoelectron spectroscopy (XPS). The positions and
intensities of the recorded Si 2p and O 1s lines change depending on solution conditions. The O 1s line,
where the position varies more significantly, was analyzed in detail showing three components corresponding
to three surface species: >SiOH2+, >SiOH0, and >SiO- (where > represents the bulk quartz). The changes
in the Si 2p spectra support these findings. The atomic ratio between the surface oxygen and silicon atoms
was found to be 1.8. These data allow proposing a two-step deprotonation model of the quartz surface where
two surface oxygen atoms are bonded to one silicon surface atom and where the most deprotonated surface
sites show the SiO- configuration. Physisorbed water in the amount of around 10% of the monolayer was
also found on all samples under spectroscopic investigation. The density of the >SiO- group increases
significantly with an increase of pH, whereas the surface concentration of the >SiOH2+ group is the highest
at pH 0. The maximum of the neutral >SiOH0 group is observed at pH 6. These results indicate immediately
the validity of a 2-pK model of protonation of quartz/electrolyte interface versus a 1-pK model. The 2-pK
surface capacitance model of the electric double layer having pK1 ) - 1.0 and pK2 ) 4.0 was derived from
the XPS data. The new surface stability constants allow a quantitative description of quartz surface charge
and dissolution kinetics in neutral to alkaline solutions and explicitly account for an increase of quartz
dissolution rate at pH < 2 due to significant increase of the concentration of the >SiOH2+ surface species.
These results provide, for the first time, direct atomic level spectroscopic evidence of the validity of the
chemical surface speciation approach, notably the existence of the charged >SiOH2+ and >SiO- species at
the quartz surface and their relative densities in acidic and alkaline solutions.

Introduction silicates depend on their unique surface properties, which rely

on the nature and density of surface specific groups.
The natural abundance of quartz and its important techno-
At present there are two principal models applied to describe
logical applications stimulated, both in the past and present
ionization at oxide-water interfaces. The most common is a
times, a collection of vast amounts of experimental information
2-pK model that assumes two consecutive protonations:26
and modeling results aimed at characterization of quartz surface
chemistry and reactivity in aqueous solutions. In particular,
numerous studies have been devoted to measuring quartz and >MeOH0 + H+ ) >MeOH2+ (1)
amorphous silica surface charge and ζ potentials,1-4 dissolution
kinetics,5-12 and infrared spectroscopic observations of surface >MeOH0 - H+ ) >MeO- (2)
groups.13-18 This allowed extraction of a rigorous picture of
the SiO2/H2O interface and formulation of various mechanistic/ Here the intrinsic stability constants are given by
thermodynamic models describing quartz reactivity and charging
behavior in aqueous solutions19 as well as ab initio calculations
of silica interactions with water.20,21 Moreover, because of its K1 )
{>MeOH2+}
{>MeOH0}aH+
exp ( -Ψ0F
2.3RT)
relatively simple surface chemistry, quartz is often used as a

( )
model compound for testing various physicochemical models
for metal oxide/solution interfaces and mineral surfaces (see, {>MeO-}aH+ -Ψ0F
K2 ) exp
for example, refs 22-25). Many applications of quartz and {>MeOH } 0 2.3RT

* Corresponding author. E-mail: jerzy.mielczarski@ensg.inpl-nancy.fr. where {>i} stands for surface species concentration, ai is the
Fax: (33) 3 83 59 62 55. activity in solution, Ψ is the electrostatic potential of the surface
† INPL-ENSG.
‡ UPS-CRNS (UMR5563). plane, F is the Faraday constant, R represents the gas constant,
§ UMR 9992-CNRS. and T is the temperature.
10.1021/jp012818s CCC: $22.00 © 2002 American Chemical Society
Published on Web 02/20/2002
2938 J. Phys. Chem. B, Vol. 106, No. 11, 2002
There are three primary types of surface species responsible
for quartz surface electric charge, dissolution, and adsorption/
desorption properties, and two of them are produced from neutral
silanol species >SiOH0, which undergo protonation and depro-
tonation in acidic and basic solutions. It is not correct to assume
these reactions as consecutive ones where both hydrogen ions
are bounded to the same single oxygen atom. In this case the
difference between the consecutive pK values has to be larger
than 10, which is not observed experimentally. Therefore, other
surface reactions were proposed27 where two oxygen atoms are
bonded to each metal atom:
>[Me(OH2)2]+ ) >Me(OH2)OH + H+
>Me(OH2)OH ) >[Me(OH)2]- + H+
In this case it is considered, as a basic unit of a 2-pK model,
two neighboring oxygen atoms coordinated to a different metal
center. This assumption explains the small splitting of the two
pK values derived from experimental results.
As a simpler explanation, a single protonation step, a 1-pK
model, can be considered for which a surface reaction can be
described:
>[MeOH2] +1/2 ) >[MeOH] -1/2 + H+
As was concluded from theoretical consideration,27 in most cases
the 1-pK model provides a sufficiently accurate description of
the proton titration of surface groups, whereas the 2-pK model
can describe all titration data. The proton titration measurements,
similarly as electrokinetic ones, give macroscopic information.
They cannot deliver direct information about the real composi-
tion and structure of surface groups.
Of these three surface species listed for the classical 2-pK
model, only the >SiOH0 has been directly observed on quartz
or silica surface using spectroscopic (mostly infrared-based)
techniques. The other two surface species have been conven-
tionally postulated, as for other simple oxides, to describe the
surface ionization and resulting charging behavior. The physical
meaning of the >SiOH2+ and >SiO- species has not been yet
well established because of lack of any spectroscopic observa-
tions of these species.7 In this paper we attempted, for the first
time, to relate the XPS spectroscopic observation of the surface
atomic composition of quartz after its contact with aqueous
solutions of different pHs to the corresponding change in quartz
surface speciation and to propose surface complexation model.
It should be underlined that spectral evidence for the presence
of the three surface groups was found even though the
spectroscopic XPS study was performed under high-vacuum
conditions and held at these conditions for a few hours. The
existence of the >SiOH2+ and >SiO- surface species inferred
from this approach allows us to propose the 2-pK model and
explain the quartz surface charge and dissolution rate variations
with pH both in acid and alkaline solutions.
Background
Surface Complexation Modeling of Quartz. The acid-base
properties of quartz and silica surfaces have been extensively
investigated. The intrinsic stability constants of reactions 1 and
2 are fairly well-known. They were inferred from surface charge
data obtained by surface titration of solid powders in various
electrolyte solutions. It is important to note, however, that most
of the available information concerns amorphous silica/solution
interfaces and there are only a few titrations2,3,28,29 and electro-
Duval et al.
kinetic studies3,4 for quartz. The pK values for quartz proposed
in the literature22,30 are in the following ranges: pK1 ) 3.0 (
1.0 and pK2 ) 7.0 ( 1.0 for reactions 1 and 2, respectively.
These values are valid for constant capacitance model (CCM)
of the electric double layer (EDL) with a capacitance of 1 F/m2.
They allow one to calculate the isoelectric point for quartz, i.e.,
pH of the solution in which the electrophoretic mobility or
streaming potential (ζ potential) of quartz equals zero. The range
of pHiep values reported in the literature, from 0.5 to 3.5,26 is in
agreement with value 2.0 predicted from the model. As a first
approximation, we use this model in our surface speciation
calculation for quartz as the CCM is the simplest EDL model.
This model was used successfully for a number of various types
of solids in aqueous solutions.32 The density of quartz sites
depends on the type of crystal plane developed. We used the
value 8 sites/nm2, which is the average for 001 and 101 planes
and is widely used in surface complexation modeling.22,23
The MINTEQA2 computer program33 was used to calculate
the equilibrium species and surface speciation equilibriums in
the system SiO2(s)-H2O-HNO3-KOH system. This program
combines surface equilibriums, homogeneous solution equilib-
riums, and mass balance calculation. The set of equations
obtained is solved by iteration using the Newton-Raphson
method. The activity coefficients of free aqueous ions were
calculated by means of the Davies equation.
Previous Spectroscopic Studies of Quartz and Silica
Surfaces. For over last 50 years, a significant amount of
information on the surface chemical groups of quartz and silica-
water interface has been collected using IR spectroscopy.
Unfortunately, the majority of these spectroscopic data describe
transformation surface of OH groups during heating of silica
or quartz sample to very high temperature, up to 1000 °C.
Several steps of surface dehydration are clearly identified;
however, there is no detail information available on the surface
group presence in room temperature. The total concentration
of OH groups on fully hydroxylated surface of silica does not
depend on their origins and specific surface areas being a
physicochemical constant: 4.9 OH groups/nm2 as determined
by the deuterium-exchange method,17,34 which is also in
agreement with tritium exchange results (4.6 sites/nm2 34). NMR
studies of amorphous silica powders indicate that approximately
47% of surface hydroxyl groups are geminal (i.e., H-bonded
Si(OH)2 groups) and the remaining 53% are single silanol.36
The deprotonation reaction2 has been investigated by Marshall
et al.,37 who deduced, in good agreement with SCM, a pK2 )
7.2 from infrared spectroscopic studies noting OH stretching
vibrations induced in the presence of organic compounds
(acetone, phenols) of different acidities. To what extend these
findings for amorphous silica may serve as a guide to under-
standing the surface chemistry of quartz is still a matter of
debate. For example, in contrast to observations on silica, Gallei
and Parks15 reported the existence of two sharp bands (at 3649
and 3627 cm-1) on the quartz surface dried at 110 °C. They
assigned these bands to two different OH sites on the surface.
However, Koretsky et al.,18 using DRIFT spectroscopy, were
not able to detect any surface groups besides terminal silanol
groups at a single type of surface site (band at 3745 cm-1).
The only spectroscopic evidence for the ionization of silanol
groups on quartz surfaces has been recently obtained by Du et
al.,38 who reported, using infrared-visible sum-frequency
generation, that the water molecules interact with a quartz
surface via two opposing forces: hydrogen bonding with silanol
groups at neutral to acid pH and electrostatic interaction with
charged >SiO- species at pH g 10. However, no quantitative
XPS Surface Group Quantification and Modeling
TABLE 1: Detected Impurities in Quartz
impurity amt (ppm) impurity amt (ppm)
Na+ <10 Al3+ <30
Li+ <3 Fe3+ <10
correlation between the intensities of these interactions and
chemical speciation at the quartz surface in aqueous solutions
has been attempted in this study. Overall, the spectroscopic
observations of quartz surfaces in aqueous solutions are rather
limited and do not allow, for the present time, to test rigorously
the existing SCM.
Experimental Section
Materials. Synthetic polycrystalline quartz of highest purity
was procured from Neyco Co. The detected impurities are listed
in Table 1. A slab sample with dimensions of 10 × 9 mm2 was
cut and polished using emery paper and increasingly smaller
sizes of alumina powder (to 0.03 µm) and washed with acetone
and water in an ultrasonic bath. No aluminum presence on the
surface was detected by XPS indicating total removal of
polishing material from the quartz surface. Milli-Q water (18
MΩ cm) and analytical grade reagents were used throughout
the experiments.
Interaction with Water. The quartz sample was contacted
with aqueous solutions at different pH’s immediately after
polishing. Solution pH was adjusted by adding HNO3 or KOH.
As a result, the ionic strength of solution varied from 1 M (in
1 M HNO3) to 10-4 M KOH, at pH 0-10, respectively. The
changes in the surface composition after 5 min of contact with
water were studied by XPS immediately after the sample
emerged from solution. If necessary, the surface of mineral
samples was quickly blotted to remove excess of water before
the spectroscopic analysis. After 30 min contact with water,
almost exactly the same results were produced.
XPS Analysis. The XPS technique has been widely used to
probe surface composition of minerals such as silicates,39,40
oxides,41 sulfides,42 and carbonates.43 The depth of analysis can
be derived from the electrons’ inelastic mean free path (IMFP)
and knowledge of the analysis geometry. The determined IMFP
for SiO2 at a kinetic energy 1150 eV (Mg anode) for the Si 2p
line is 2.1 nm.44 For the O 1s signal (kinetic energy 720 eV)
the electron escape depth is 1.6 nm. Hence, the recorded spectra
of quartz will carry out information only from the first few
outermost atomic layers.
The X-ray photoelectron spectra were obtained with a
multidetection electron energy analyzer (VSW FAT mode
CL150). The nonmonochromatized magnesium radiation sources
(1253.6 eV) operated at 15 kV and 10 mA were employed. The
XPS resolution was between 0.9 and 1.0 eV determined by the
use of gold standard. The operating pressure of the spectrometer
analyzer chamber was close to 10-8 mbar. The measurement
was performed with a takeoff angle close to 90°. A very high
charge, between 4 and 5 eV, was observed. The carbon C 1s
line with a position at 284.6 eV was used as reference to correct
the charging effect. The most characteristic peaks O 1s, Si 2p,
C 1s, and K 2p were recorded in narrow ranges of binding
energy to obtain a good signal/noise ratio and resolution required
for an optimal spectral manipulation. No N 1s line was detected
in the recorded spectra of quartz after any treatment in solution.
The recorded lines were fitted using a curve-fitting program
with a Gaussian/Lorentian or pure Gaussian peak shape.
To compare the spectra of quartz samples reacted in different
solutions, all experimental and measurement conditions were
precisely reproduced from experiment to experiment. It was
J. Phys. Chem. B, Vol. 106, No. 11, 2002 2939
Figure 1. XPS O 1s lines of quartz samples conditioning in water at
pH from 0 to 10. The area below line A represents the subtracted
intensity of bulk oxygen (Si-O-Si) and some part of the >SiOH0
surface groups.
TABLE 2: Binding Energy of the Recorded XPS Lines
pH Si 2p O 1s C 1s K 2p
0 103.20 532.40 284.60 nd
2 103.10 532.25 284.60 nd
4 103.10 532.20 284.60 nd
6 103.05 532.10 284.60 nd
8 102.75 531.95 284.60 nd
10 102.85 532.05 284.60 293.20
found that the exposition of the quartz sample to high vacuum
from the standard 30 min to 5 h does not change notably the
intensity and shape of the recorder major lines. This indicates
a good stability of the surface groups produced originally in
water solution even under high-vacuum conditions and after
exposition to X-ray beam. Hence, though spectroscopic studies
are not performed in situ, they can provide direct information
about the type and amount of the surface hydration groups of
quartz, which are closely related to those produced in solution
conditions.
Results and Discussion
Qualitative Approach to the Surface Composition of
Quartz Contacted with Aqueous Solution at Different pH’s.
The XPS results obtained for quartz samples conditioned in
water at pH from 0 to 10 are presented in Table 2. The spectra
recorded directly after conditioning in water (Figure 1) show
that the composition of the outermost layer of quartz strongly
depends on the pH of solution. The position of a broad O 1s
line is shifted gradually with an increase of pH from 532.4 eV
at pH 0 to 532.0 eV at pH 8. The chemical shift to lower binding
energy (BE) indicates changes in the close environment of the
surface oxygen from more positive to more electronegative. At
pH 10, the position of the oxygen line shifts to 532.1 eV
suggesting a more positive surface oxygen environment than
at pH 8. Similar variation of the position of the silicon Si 2p
line is observed; this will be discussed in detail later.
The observed shifts of the line positions are not very large;
therefore, the experiments were repeated at least three times to
determine an experimental reproducibility, which is within 0.05
eV. The total intensities of the recorded lines vary somewhat
from sample to sample, and the reason for this stems from
difficult to control the differences in a carbon contamination
level. The carbon contamination forms the outermost layer and
screens the original signal from quartz surface. For this reason
the quantitative evaluation (see next section) of the surface
groups on quartz were performed from the experimental spectra
showing a similar carbon contamination level, i.e., at the C 1s/
Si 2p ratio 0.4 ( 0.1.
The recorded O 1s broad line carries out signals from oxygen
atoms involved in the formation of the different surface groups
2940 J. Phys. Chem. B, Vol. 106, No. 11, 2002
and the bulk Si-O-Si oxygen. The bulk oxygen component
could represent about 60% of the total oxygen intensity and
obviously is the same for all samples prepared at different pH’s.
This dominating bulk oxygen signal overlaps the surface oxygen
signals; therefore, the background subtraction and peak decon-
volution (see the next section) are necessary before any
quantitative evaluation based on the recorded spectra is per-
formed. The surface oxygen atoms, which are involved in the
formation of different surface species, could show BE from 534
to 530 eV.
According to the current view of quartz surface speciation,
three types of surface oxygen can be distinguished:26 (i) oxygen
with a positive environment, OH2+; (ii) oxygen with a neutral
environment, OH0; (iii) oxygen with a negative environment,
O-. These three surface oxygen types are expected to show lines
at similar BE to that observed for adsorbed water (about 533.5
eV), hydroxides (about 532 eV), and oxides (about 530.5
eV).44-46
The >SiOH0 surface groups are in predominant amount. The
>SiOH0 component of the O 1s line can be, similarly as the
bulk Si-O-Si oxygen component, the same for all quartz
samples under investigation. The largest differences between
the samples under investigation are expected at the lowest and
highest pH. At pH 0, the highest surface density of the SiOH2+
surface groups is predicted. The observed position of the oxygen
line, at the highest BE, is in agreement with this forecast.
Between pH 4 and 8 the negative charge of quartz surface
increases. This is visible as a shift of the position of oxygen
line to the lowest BE at pH 8. At pH 10 and higher, two
important experimental observations were made: (i) Potassium
ions are observed at the quartz surface (Table 2). (ii) A more
positive oxygen environment is observed at pH 10 than at pH
8 (a shift of the O 1s line to higher BE at pH 10 in comparison
to pH 8 (Figure 1)). These observations indicate that at pH 8 a
maximum amount of the free >SiO- groups is present. At
higher pH, after crossing some negative surface charge, the free
>SiO- groups attract counterions from solution (K+) and their
negativity is reduced.
This discussion indicates that the major features predicted
from surface speciation model for quartz contacted with aqueous
solution can be derived from the recorded XPS spectra. These
spectra are recorded in high vacuum at temperature 25 °C. At
similar conditions, by the use of the mass spectrometric thermal
analysis in conjunction with the temperature-programmed
desorption, less than a monolayer of physisorbed water was
determined on amorphous silica surface.34 Close inspection of
the experimental O 1s spectra obtained for quartz at different
pH (Figure 1) does not suggest the presence of a monolayer of
physisorbed water as the top layer in ultrahigh vacuum. If the
adsorbed water is present in monolayer quantity, we should be
able to see an O 1s component at the position about 533.5 eV
for all samples under investigation. This suggests that the
amount of physisorbed water on quartz surface groups is only
a small part of monolayer and the majority of the water
molecules are probably adsorbed on charged sites as the
>SiOH2+ and >SiO-, which is in agreement with recent results
of Du38 et al. and Rudzinski et al..24 The low level of
physisorbed water allows determining the density of the surface-
charged groups OH2+ and O- with appropriate precision.
Quantitative Approach to the Surface Composition of
Quartz Contacted with Aqueous Solutions at Different pH’s.
For appropriate quantitative evaluation of the surface species,
especially the charged ones, the background subtraction and peak
deconvolution have to be performed on the O 1s experimental
Duval et al.
Figure 2. XPS O 1s lines for each pH after subtraction of line A shown
in Figure 1.
TABLE 3: Relative Intensities of the Recorded XPS Lines
Si 2p O 1s C 1s K 2p
0 1.00 1.85 0.26 nd
2 1.00 1.84 0.46 nd
4 1.00 1.86 0.34 nd
6 1.00 1.86 0.30 nd
8 1.00 1.95 0.52 nd
10 1.00 1.85 0.53 0.01
spectra. At first, the bulk oxygen Si-O-Si component and the
oxygen component from the surface OH0 groups, at least those
having the same position in the XPS spectra for all quartz
samples, should be subtracted. To perform this subtraction the
appropriate references are required. Unfortunately, there are no
available precise references of the bulk quartz oxygen, as well
as of the surface SiOH0 groups. The following procedure was
developed to allow a proper subtraction of the strong oxygen
signals from bulk and the oxygen of preponderant surface OH0
groups.
The experimental O 1s lines for all investigated pH are plotted
in Figure 1. The intensities (areas) of the lines vary a little
because of some differences in carbon contamination levels
(Table 3). With the assumption that the total amount of the
available surface sites is constant, the intensities of the oxygen
lines were corrected to the same value by the use of the spectrum
at pH 0 as the reference. Then the common area for all
experimental lines located between the peaks representing results
for pH 0 and 8 (Figure 1, line A) was fitted by a Gaussian/
Lorentian peak shape. The peak A that is in the envelope of all
experimental lines represents the bulk quartz oxygen and the
significant part of the surface oxygen bonded as the surface
OH0 groups, corresponding to about 70% of the intensity of
each line. This peak was subtracted from the O 1s line for each
pH, and the resultant spectra after the subtraction are presented
in Figure 2. These lines show a semiisosbestic point that
indicates a transformation of at least one type of the surface
species to another.
The oxygen lines after subtraction (Figure 2) were decon-
voluted to three components related to the >SiOH2+, >SiOH0,
and >SiO- surface groups having positions at around 533, 532,
and 531 eV, respectively. The fitting accuracy was better than
0.998. The exact positions of the three components and their
relative intensity ratios are presented in Figures 3 and 4a. It
can be observed that the position of the SiOH0 surface groups
(the parts which were not subtracted as the common for all
samples) shifts gradually to lower BE with an increase of pH.
Moreover, a local minimum at pH 8 could be noticed. These
observations can be explained by assuming the interaction of
the SiO- groups with the SiOH0 groups through the formation
of hydrogen bonding. The increase of the amount of the SiO-
XPS Surface Group Quantification and Modeling
Figure 3. Binding energy of three surface species and their shift
depending on solution conditions (Gaussian/Lorentian band shape).
Figure 4. Relative surface density of three surface species obtained;
(a) directly from deconvolution of data presented in Figure 2; (b) after
correction of the amount of the >SiOH0 species (see text).
groups with an increase of pH (Figure 4a) causes more of the
neutral SiOH0 groups to be influenced by the negative SiO-
groups. They are exposed to a more electronegative environment
resulting in the observed shift of the SiOH0 position. The lowest
BE observed at pH 8 agrees with the highest concentration of
the SiO- groups. At pH 10 and higher, the potassium ions are
adsorbed on the >SiO- sites as counterions lowering the
negative charge of the >SiO- groups and in consequence also
that of the SiOH0 groups. Similar lowering of BE is observed
(Figure 3) for the >SiO- component at pH 8, which supports
the proposed explanation.
The band assigned to the >SiOH2+ groups shows almost a
constant position at 533.2 eV (Figure 3). The intensity of this
J. Phys. Chem. B, Vol. 106, No. 11, 2002 2941
Figure 5. Schematic representation of quartz surface structure: (a)
atomically smooth surface; (b) real surface of quartz after contact with
aqueous solution.
band decreases sharply with pH increasing from 0 to 4 (Figure
4a) and then reaches a value around of 8% for higher pH. This
observation suggests that the band component at 533.2 eV
represents two surface species, i.e., the OH2+ surface groups
and adsorbed water. The band position above 533 eV is
characteristic for adsorbed water.45 Hence, we can conclude that
the quartz under high-vacuum conditions and at room temper-
ature is still covered by nearly 10% of the adsorbed water
monolayer. The amount of the > SiOH2+ groups decreases from
around 30% at pH 0 to almost zero at pH 5. The amount of the
>SiO- groups increases gradually from 8% at pH 0 to 50% at
pH 10.
The amounts of the >SiOH0 groups presented in Figure 4a
are not absolute values because the significant and not precisely
known part of the OH0 signal (common for all quartz samples)
was subtracted together with the bulk Si-O-Si oxygen
intensity. Therefore, to obtain the real surface coverage by the
>SiOH0 groups at different pH, a constant value should be
added to each value of the >SiOH0 presented in Figure 4a. We
assumed the subtraction of the <SiOH0 intensity between 40
and 80% as the common for all quartz samples. Then we made
calculation of pK values for various amount of the SiOH0 surface
group on quartz. The best fitting was obtained (see next section)
with assumption that 60% of the intensity of the OH0 was
subtracted together with the bulk Si-O-Si oxygen. This
together allows us to determine the surface density of three
different surface groups, OH2+, OH0, and O-, and the adsorbed
water. The results after the <SiOH0 correction are presented in
Figure 4b. It should be underlined that the surface densities of
the charged surface groups are determined with appropriate
precision.
Assuming that the electron escape depth (IMFP) for the
produced oxygen surface species on quartz is the same as for
SiO2, i.e., 1.6 nm, it is possible to estimate the average thickness
of the surface layer. This rough estimation indicates the
formation of a 1.1 nm layer containing oxygen surface species.
This implies that the surface oxygen groups are formed not only
on silicon atoms of the first outermost well-defined atomic
smooth layer as it is represented often in the literature (Figure
5a). These results suggest that real surface structure is similar
to that presented in Figure 5b. Hence, the surface density of
the OH2+, OH0, and O- groups per surface silicon atom is much
higher than 1, which could explain the experimentally estimated
thickness of the surface species. Moreover, the macroscopic
surface roughness (sample prepared by polishing) favors the
increase of surface signal versus bulk quartz (Si-O-Si) signal.
2942 J. Phys. Chem. B, Vol. 106, No. 11, 2002 Duval et al.

Figure 8. XPS Si 2p lines for each pH after subtraction of the intensity

of bulk oxygen (-Si-O-Si-) and some part of the >SiOH0 surface
groups.
Figure 6. Binding energy of three surface species and their shift
depending on solution conditions (Gaussian band shape).
Quartz Surface Speciation Modeling. The presented XPS
results show clearly the presence of three different surface
groups >SiOH2+, >SiOH0, and >SiO-. This indicates im-
mediately that the 2-pK surface dissociation model has to be
applied to describe the quartz-water interface. Another impor-
tant observation is that the ratio between the surface oxygen
and silicon atoms is close to 2.0. As a result of these
spectroscopic studies, a two-step deprotonation model of quartz
surface can be proposed (Figure 9) where two surface oxygen

Figure 9. Two-step deprotonation model of quartz surface proposed

on the basis of this spectroscopic work.

atoms are bonded to one silicon surface atom and where the
Figure 7. Relative surface density of three surface species obtained most deprotonated surface sites show the SiO- configuration.
by deconvolution of data presented in Figure 1.
This model of surface protonation is a modification of the
proposition based on theoretical consideration with the assump-
It has to be underlined that the experimentally determined
tion of the two oxygen atoms coordinating metal center.27
amount of the surface SiOH2+ and SiO- groups is nearly equal
A relationship between the predicted, based on the commonly
at pH 2 (Figure 4), which is in a perfect agreement with a value
used SCM (pK1 ) 3.0, pK2 ) 7.0), and the measured in this
pHPZC reported for quartz.23,26
work concentration of the surface species for quartz is plotted
To verify how the results presented in Figures 3 and 4 are in Figure 10. The correlation is positive; i.e., there is a decrease
sensitive to modification of deconvolution parameters, the curve of the >SiOH0 concentration with increasing of pH, which is
fitting was also carried out with a pure Gaussian line shape. In accompanied by the increase in the >SiO- surface concentra-
this case, an additional fourth component at about 534 eV has tions. In contrast, the concentration of the >SiOH2+ surface
to be added to achieve a good fitting (above 0.998). The obtained species is strongly underestimated as the SCM predicts their
results are presented in Figures 6 and 7. They are very similar amount e0.7% at pH 0.
to those obtained with mixed Gaussian-Lorentian band shape. Adsorption of potassium counterions on quartz surface in
The fourth component at about 534 eV is assigned to adsorbed alkaline solutions can be described within a triple layer model
water, which represents nearly 10% of monolayer coverage. This
is in agreement with the reported strong adsorption of water on
>SiO- sites as was proven spectroscopically38 and from
calorimetric measurements.24
The second element that can provide information about
surface composition of quartz is silicon. The Si 2p lines obtained
at different pH’s show a much lower shift with a change of
solution pH than that recorded for O 1s lines. Nevertheless, the
tendency is identical for silicon and oxygen lines (Figures 8
and 2). The highest BE of the Si line is observed for a sample
treated in solution at pH 0, and the lowest BE, for a sample
prepared at pH 8. This observation indicates clearly the presence
of different surface Si sites, which are influenced by the surface
OH2+, OH0, and O- groups. It is important to note that atomic
ratio of the total surface oxygen (after subtraction of the bulk
Si-O-Si oxygen) to the total surface silicon (after subtraction Figure 10. Correlation between predicted and measured in this work
of the bulk silicon) is almost constant and about 1.8 for all quartz concentration of surface species for quartz. SCM calculation was
samples prepared in solution at 0-10 pH. This finding supports performed by assuming pK1 ) 3.0 and pK2 ) 7.0. Numbers at points
the surface structure presented in Figure 5b. indicate pH values.
XPS Surface Group Quantification and Modeling
Figure 11. Speciation at the quartz-solution interface as calculated
from the experimental data obtained from this work for the surface
complexation model by assuming constant capacitance of the electric
double layer and pK1 ) -1.0 and pK2 ) 4.0.
Figure 12. Correlation between predicted and measured in this work
concentration of surface species for quartz. SCM calculation was
performed by assuming pK1 ) -1.0 and pK2 ) 4.0. Numbers at points
indicate pH values.
of the electric double layer.30 According to this model, nearly
10-15% of surface sites at pH 10 are occupied by potassium
ions in the form of >SiO-K0 species decreasing the concentra-
tion of the negative >SiO- groups. This is in perfect agreement
with the presented XPS observations (Table 3).
In view of poor quantitative agreement between the measured
quartz surface group densities and those predicted from classic
SCM, we attempted to generate an alternative set of surface
stability constants for quartz to obtain a better agreement with
the XPS experimental data. The resulted new pK values for
quartz, assumings constant capacitance of the EDL C ) 1 F/m2,
are pK1 ) -1.0 and pK2 ) 4.0 (Figure 11). The new set of
surface constants within the CCM provides a perfect description
of XPS results for three surface species for full range of pH
from 0 to 10 as is illustrated in Figure 12. This SCM implies a
surface stability constant for the silanol deprotonation reaction,
pK2 ) 4, that is very different from the corresponding constant
for solution silica monomer dissociation, pK(aq) ) 9.8.26 This
is in contrast to amorphous silica that exhibits similar surface
and solution deprotonation reaction constants.22 It can be
explained by different arrangement of the >SiO- and >SiOH0
groups on quartz and amorphous silica. For silica, the low
packing density of the O(H) groups and the location of reactive
surface groups result in the formation of surface groups with
an arrangement similar to those existing in solution, such as
H4SiO4(aq), whereas the dense and crystalline structure of quartz
implies much shorter Si-O(H) distances and, consequently,
J. Phys. Chem. B, Vol. 106, No. 11, 2002 2943
Figure 13. Comparison of streaming potential (ζ potential) data for
quartz4 and surface charge difference obtained from XPS spectra (∆σ
) {>SiOH2+} - {>SiO-}) as a function of pH.
Figure 14. Rate of quartz dissolution in neutral and basic solutions (6
< pH < 12) as a function of deprotonated surface species concentration
determined in this work. The rate dissolution data are from ref 5. The
surface species concentrations were calculated using CCM with new
surface stability constants pK1 ) -1.0 and pK2 ) 4.0. Numbers at
points indicate pH values.
different silica energies for the formation of the surface and
solution species.
The derived from XPS data the new pK values were tested
against the available information for quartz surface properties
and its reactivity in an aqueous solution. Unfortunately, unlike
for amorphous silica, there is almost nil surface charge measure-
ment for highly a crystalline quartz surface similar to that used
in this study. We compared in Figure 13 streaming potential (ζ
potential) values for crystalline quartz measured by Cases4 with
the calculated values of surface charge ∆σ ) {>SiOH2+} -
{>SiO-} from the XPS study as a function of pH. Both ζ
potential and ∆σ depend on pH in a very similar way. Other
evidence for validity of the calculated pK values can be obtained
from the analysis of surface-controlled dissolution kinetics of
quartz. It has been widely argued5,19,20,36 that the dissolution
rate of quartz at pH g 7 is positively correlated with its surface
charge or the concentration of the >SiO- surface species. Using
the data of Brady and Walther5 as an example, we plotted in
Figure 14 the quartz dissolution rate at 6 < pH < 12 versus
surface concentration of the >SiO- species. The latter values
were calculated using the new pK values. In accord with
previous studies,46 a linear relationship is observed with a slope
close to 4. The reaction order of 4 with respect to surface density
of the >SiO- groups is in accord with surface coordination
model of Stumm47,48 for the dissolution of simple oxides; the
reaction order with respect to rate controlling species is being
related to the valence of the central cation.
One of the important results of this study is the quantitative
determination of positively charged >SiOH2+ species at pH
below 4. The new pK set shows that at pH 0 up to 16% of the
2944 J. Phys. Chem. B, Vol. 106, No. 11, 2002
Figure 15. Rate of quartz dissolution in acidic solutions (pH < 4)
plotted as a function of >SiOH2+ surface concentration. The dissolution
rate data are from ref 12, and the concentration of >SiOH2+ surface
species is calculated using CCM with pK1 ) -1.0 and pK2 ) 4.0.
Numbers at points indicate pH values.
surface can be occupied by >SiOH2+ species. This is the major
difference between the usual view of surface chemistry of quartz
and that derived from these XPS measurements. Positive surface
species on amorphous silica49,50 and natural quartz29 were
already detected by electrophoretic technique at pH < 2. Other
evidence of the presence of positive surface species comes from
studies of quartz dissolution kinetics5,10-12,29 that unambiguously
demonstrate the increase of the dissolution rate with decrease
of pH below 2. Wollast and Chou12 noted that, below pH 3,
dissolution rates might be proportional to the concentration of
the positively charged surface species, >SiOH2+, rates increas-
ing with decreasing pH as the concentration of the latter species
increased.
Within the surface coordination theory,47 a proton-promoted
dissolution rate is directly related to the concentration of
protonated surface groups; i.e.,
R ) k{>SiOH2+}
where k is the kinetic constant. We presented in Figure 15 a
relationship between the dissolution rate for quartz at pH <
4 12 and the concentration of the >SiOH2+ groups as calculated
using the new pK set. A linear relationship is observed with a
slope close to 1, which implies that, in acid solutions, the
protonation of one Si-O bond is large enough to form a surface
precursor complex for dissolution reaction.
In the search for thermodynamic relationships in ion adsorp-
tion at oxide/electrolyte systems, it was recently found51 that a
pK1 is proportional to PZC. Taking the PZC value of quartz
derived from Figure 13, the expected value of the pK1 is -1.5.
This value is in an excellent agreement with the pK1 ) -1.0
determined in this work and very far away from that reported
in the literature of pK1 ) 3.0 ( 1.0. This interesting theoretical
consideration51 also underlined other parameters such as the
presence of an inert electrolyte and temperature-related phe-
nomena to have significant effects on the protonation processes
of oxides in aqueous solution. These subjects are considered
for future work that could provide new interesting insights into
surface group formation on quartz and generally on oxides.
Conclusions
The XPS studies gave direct and on atomic scale information
about the surface groups present on quartz contacted with
aqueous solution at different pH. Though the spectroscopic
Duval et al.
studies are performed under high-vacuum conditions, the
recorded spectra present clear evidence of the formation of three
type surface species: > SiOH2+; >SiOH0; >SiO-. This
indicates that a 2-pK model has to be applied to describe surface
phenomena at the quartz-solution interface. The two-step
deprotonation model of quartz surface is proposed where two
surface oxygen atoms are bonded to one silicon surface atom
and where the most deprotonated surface site shows the >SiO-
configuration. Physisorbed water in the amount of nearly 10%
of monolayer coverage was also found on all spectroscopically
investigated samples. The relative concentrations of the surface
species were determined in relationship to the solution condi-
tions. On the basis of the experimental results, a new pK set
for the quartz-solution interface is proposed for a wide pH
range from 0 to 10. This allows, for the first time, to explain
the increase of quartz dissolution rate with decreasing of pH
below 2 due to positive >SiOH2+ surface charged groups. The
new calculated pK set is also consistent with existing experi-
mental data on negative surface charge >SiO- species at pH
> 6 and the related dissolution rate.
Acknowledgment. Part of this work was supported by the
European Community (Project BRPR6CT98-0619). The techni-
cal assistance of Jacques Lambert is appreciated.
References and Notes
(1) Bolt, G. H. J. Phys. Chem. 1957, 61, 1166.
(2) Ahmed, S. M. A. Can. J. Chem. 1966, 44, 1663.
(3) Li, H.; de Bruyn, P. Surf. Sci. 1986, 5, 203.
(4) Cases, J. M. Les phénomènes physico-chimiques à l’interface. Ph.D.
Thesis, INPL, Nancy, France, 1967.
(5) Brady, P. V.; Walther, J. V. Chem. Geol. 1990, 82, 253.
(6) House, W. A.; Orr, D. R. J. Chem. Soc., Faraday Trans. 1992, 88,
233.
(7) Dove, P. Am. J. Sci. 1994, 294, 665.
(8) Dove, P.; Nix, C. J. Geochim. Cosmochim. Acta 1997, 61, 3329.
(9) Dove, P. Geochim. Cosmochim. Acta 1999, 63, 3715.
(10) Knauss, K. G.; Wolery, T. J. Geochim. Cosmochim. Acta 1988,
52, 43.
(11) Bennet, P. C. Geochim. Cosmochim. Acta 1991, 55, 1781.
(12) Wollast, R.; Chou, L. In Physical and Chemical Weathering in
Geochemical Cycles; Lerman, A., Meybeck, M., Eds.; NATO ASI Series
No. 251; Reidel: Dordrecht, The Netherlands, 1988; p 11.
(13) Anderson, J. H.; Wickersheim, K. A. Surf. Sci. 1964, 2, 252.
(14) Morrow, B. A.; Cody, I. A. J. Phys. Chem. 1976, 80, 1995.
(15) Gallei, E.; Parks, G. A. J. Colloid Interface Sci. 1972, 38, 650.
(16) Morrow, B. A.; Cody, I. A. J. Phys. Chem. 1975, 79, 761.
(17) Zhuravlev, L. T. Langmuir 1987, 3, 316-318.
(18) Koretsky, C. M.; Sverjensky, D. A.; Salisbury, J. W.; D’Aria, D.
M. Geochim. Cosmochim. Acta 1997, 61, 2193.
(19) Xiao, Y.; Lasaga, A. C. Geochim. Cosmochim. Acta 1996, 60, 2283.
(20) Koudriachova, M. V.; Beckers, J. V. L.; de Leeuw, S. W. Comput.
Mater. Sci. 2001, 20, 381.
(21) Ugliengo, P.; Saunders: V.; Garrone, E. J. Phys. Chem. 1990, 94,
2260.
(22) Hiemstra, T.; Van Riemsdijk, W. H. J. Colloid Interface Sci. 1989,
133, 105.
(23) Hiemstra, T.; Van Riemsdijk, W. H. J. Colloid Interface Sci. 1990,
136, 132.
(24) Rudzinski, W.; Charmas, R.; Piasecki, W.; Prelot, B.; Thomas, F.;
Villieras, F.; Cases, J. M. Langmuir 1999, 15, 5977.
(25) Rudzinski, W.; Charmas, R.; Partyka, S.; Thomas, F.; Bottero, J.
Y. Langmuir 1992, 8, 1154.
(26) Iller, P. K. The chemistry of Silica; J. Wiley & Sons: New York,
1979.
(27) Borkovec, M. Langmuir 1997, 13, 2608.
(28) Riese, A. C. Adsorption of radium and thorium onto quartz and
kaolinite: A comparison of solution/surface equilibriums models. Ph.D.
Dissertation, Colorado School of Mines, 1982.
(29) Cadore, E. Mécanismes de dissolution du quartz dans les solutions
naturelles. Etude expérimentale et modélisation. Ph.D. Dissertation, Uni-
versité Paul Sabatier, Toulouse France, 1995.
(30) Sahai, N.; Sverjensky, D. A. Geochim. Cosmochim. Acta 1997, 61,
2801.
XPS Surface Group Quantification and Modeling
(31) Sverjensky, D. A.; Sahai, N. Geochim. Cosmochim. Acta 1996, 60,
3773.
(32) Lutzenkirchen, J. J. Colloid Interface Sci. 1999, 217, 8.
(33) Allison, J. D.; Brown, D. S.; Novo-Gradac, K. J. MINTEAQA2/
PRODEFA2, A geochemical assessment model for enVironmental systems:
Version 3.0 user’s manual; U.S. EPA: Athens, GA, 1991.
(34) Zhuravlev, L. T. Colloids Surf., A 2000, 173, 1.
(35) Yates, D. E.; Greiser, F.; Cooper, R.; Healy, T. W. Aust. J. Chem.
1977, 30, 1655.
(36) Chuang, I.-S., Maciel, G. E. J. Am. Chem. Soc. 1996, 118, 401.
(37) Marshall, K.; Ridgewell, G. L.; Rochester, C. H.; Simpson, J. J.
Chem. Ind. (London) 1974, 19, 775.
(38) Du, Q.; Freysz, E.; Shen, R. Y. Phys. ReV. Lett. 1994, 72, 238.
(39) Liu, P., Kendelewicz, T., Brown, G. E. Jr., Nelson, E. J., Chambers,
S. A. Surf. Sci. 1998, 417, 53-65.
(40) Okada, K., Kameshima, Y., Yasumori, A. J. Am. Ceram. Soc. 1998,
81, 1970.
J. Phys. Chem. B, Vol. 106, No. 11, 2002 2945
(41) Muir, I. J., Bancroft, G. M., Shotyk, W., Nesbitt, H. W. Geochim.
Cosmochim. Acta 1990, 54, 2247.
(42) Mielczarski, J. A.; Cases, J. M.; Alnot, M.; Ehrhardt, J. J. Langmuir
1996, 12, 2519.
(43) Stipp, S. L. S.; Hochella, M. F., Jr. Geochim. Cosmochim. Acta
1991, 55, 1723.
(44) Hochella, M. F., Jr.; Carim, A. H. Surf. Sci. 1988, 197, L260.
(45) Thiel, P. A.; Madey, T. E. Surf. Sci. Rep. 1987, 7, 211-385.
(46) Guy, C.; Schott, J. Chem. Geol. 1989, 78, 181.
(47) Stumm, W. Chemistry of the Solid-Water Interface; J. Wiley &
Sons: New York, 1992.
(48) Stumm, W.; Wollast, R. ReV. Geophys. 1990, 28, 53.
(49) Kosmulski, M. J. Colloid Interface Sci. 1998, 208, 543.
(50) Gunko, V. M.; Zarko, V. I.; Leboda, R.; Chibowski, E. AdV. Colloid
Interface Sci. 2001, 91, 1.
(51) Rudzinski, W.; Charmas, R.; Piasecki, W. Langmuir 1999, 15,
8553.