Environ. Sci. Technol.
1994, 28, 763-760
An ZmSitu ATR-FTIR Study: The Surface Coordination of Salicylic Acid on
Aluminum and Iron( II I)Oxides
Madeleine V. Blber' and Werner Stumm
Institute for Water Resources and Water Pollution Control (EAWAG), Dubendorf, Switzerland, and Swiss Federal Institute of
Technology (ETH), Zurich, Switzerland
Information on the bonding of organic ligands to hydrous
metal oxide surfaces, necessary to gain insight into the
mechanisms of surface reactivity, was extracted using
attenuated total reflection-Fourier transform infrared
spectroscopy. Various ligands were investigated in-situ
on the surface of &A1203 in water. Keeping the study of
structure with respect to surface reactivity in the fore-
ground, we report here specifically on the model ligand
salicylate, which we also examined on the surfaces of other
oxides, including corundum, hematite, lepidocrocite, and
goethite. Because the direct ligand-metal bond vibrations
absorb in the same region as the metal-oxygen vibrations
in the bulk oxide, evidence of bonding was obtained by
observing changes in the spectrum of the ligand itself.
Results show that salicylate does not bond identically on
all metal oxide surfaces. In the cases examined, the
chemical composition of the metal oxide, as opposed to
the morphology, determined the structure of the ligand
surface complex.
Introduction
Substances adsorbed to metal (hydr)oxides are known
to change the properties and reactivity of the surface. The
interactions and chemical reactions occurring at the solid-
water interface have major implications for the dissolution
kinetics of the metal oxides. In doing so, they provide
important controlling mechanisms for corrosion and its
prevention, passivity, and for geochemical processes
such as weathering, sedimentation, and soil formation.
The focus of this work is to elucidate the structure of
surface complexes on metal oxides in aqueous systems as
they relate t o the reactivity of the oxides toward
dissolution. Ligands such as complex-forming anions and
weak acids have been shown to form surface complexes on
hydrous oxides by replacing hydroxo groups on the surface
(1-3). It is generally assumed that the formation of inner-
sphere surface complexes, especially in the chelated
(mononuclear) form, facilitates the detachment of the
metal ion from the surface lattice ( 4 ) , whereas the
formation of outer-sphere complexes has little or no effect
on the dissolution rate of the oxide. It has been shown
that the enhancement of dissolution by various ligands
containing bidentate oxygen donor atoms is surface
controlled. A relative inhibition of dissolution, on the other
hand, has been demonstrated under suitable conditions
by ligands such as CrOP, phosphate, borate, and benzoate,
which are believed to form binuclear surface complexes
(see Figure 1).
The motivation for this study, therefore, comes from
previous work in the laboratory of the authors. Most
* Address correspondence to the author at her current address:
Dept. of Analytical Chemistry, University of Geneva, 30 quai
E.-Ansermet, 1211 Geneva 4, Switzerland.
0013-936X/94/0928-0763$04.50/0 0 1994 Amerlcan Chemical Society
15 T
...i
0 A/ , *
0.0 0.5 1.0 1.5 2.0 2.5 3.0
qs[IO e moles m- 1'
Figure 1. Effect of salicylate on the dlssolutlon rate of b-AIpOa, pH 5.
The rate is proportional to the surface concentrationof the sailcylate.
(Data from ref 4.) The horizontal line at 2 X 10-g mol m2h-' gives the
dissolutionrate for the absence of salicylate at pH 5. Inset: Adsorption
isotherm, surface density of salicylatevs free concentratlonof salicylate
in solution, pH 5. (data from ref 2.)
evidence that ligands form surface complexes appears in
the form of adsorption isotherms. Investigations using
magnetic resonance methods (5) have also supplied
additional information. Recently, however, new spectro-
scopic methods using extended X-ray absorption fine
structure (EXAFS) have been of value (6). (For a general
review, see ref 7.) Many ligands alone, upon specific
adsorption, increase the otherwise very slow rate of
dissolution of metal (hydr)oxides at a particular pH value
of the solution. In systems where dissolution is fast due
to another ligand, on the other hand, their effects are
varied. Some of the ligands are able to slow the dissolution
considerably, whereas others are not. Previously, the
structure of various complexes has often been suggested
indirectly on the basis of kinetic behavior. It is desirable,
however, that such structures, in particular inner-sphere
versus outer-sphere, be confirmed by direct evidence from
spectroscopic methods.
There have been numerous studies done on the ad-
sorption of ligands onto mineral surfaces using conven-
tional infrared spectroscopy, and the amount of data
available in the literature is quite copious. For the most
part, however, the methods used for obtaining these data
required dry samples, thus precluding the in-situ inves-
tigation of surface interactions. The surface species and,
consequently, their characteristic infrared absorption
frequencies are affected by the presence of a surrounding
medium. Nonetheless, data from conventional IR tech-
niques have still provided insight into adsorption mech-
anisms, and information on the possible surface structures
of phosphate, sulfate, and various organic ligands on iron
and other (hydrloxides has been obtained through the
works of Parfitt, Atkinson, Busca, Lorenzelli, Rochester,
McBride, and others (8-15).
Environ. Sci. Technol., Vol. 28, No. 5, lQ94 769
 The introduction of attenuated total reflection-Fourier
transform infrared spectroscopy (ATR-FTIR), however,
broadened the possibilities for the investigation of sub-
stances in aqueous environments. Tejedor-Tejedor and
Anderson (1) took advantage of this new technology to
develop a technique that allows the in-situ investigation
of interfacial species at the mineral oxide-water interface.
ATR-FTIR in its current form is best suited for simple
chemical substances with distinctly different functional
groups which give clear absorption spectra. Salicylate is
such a substance, as its two functionalgroups, a carboxylic
and a phenolic OH group, are distinguishable in the IR
spectrum.
The purpose of the present study was to determine
spectroscopically if a ligand such as salicylate forms an
inner-sphere surface complex (as opposed to an outer-
sphere complex, which hardly affects the surface reactiv-
ity), to find out if the surface structure is the same on
various hydrous metal oxides, and, if not, to further
determine whether it is the morphology or the chemical
composition that is the critical factor in determining the
type of surface complex formed. We have investigated
numerous carboxylicacid ligands on the surface of hydrous
6-A1203(16);however,here we report on salicylicacid only.
Experimental Section
Materials. All solutions and suspensionswere prepared
using doubly-distilled deionized water and analytical-grade
reagents. The 6-A1203used in this study was the Degussa
Type C aluminum oxide, found in other studies to have
a zero point of charge of 6.5 (17) and a BET surface area
of 100 m2/g (18). The goethite (a-FeOOH) and lepi-
docrocite (7-FeOOH) had surface areas of 89 and 165 m2/
g, respectively. The hematite, commercially available from
Fluka, AG, and designated as a-Fe203, had a surface area
of 7.2 m2/g. The corundum (a-Ale03)was obtained from
Aldrich and had a surface area of 7.0 m2/g,while the Condea
Puralox-230aluminum oxide was determined to be 7-A1203
with a surface area of 273 m2/g.
Sample Preparation. The suspensions were prepared
by diluting a portion of a stock 1M solution of NaC104,
adding the appropriate ligand, and then adding the solid
oxide. The pH was adjusted by the addition of 0.1 M
HC104 or, if necessary, small amounts of 0.1 or 1M NaOH.
The suspension was continuously stirred, and pH was
maintained with a pH stat system. A minimum of 2 h was
left for adsorption. Samples were prepared by centrifuging
an aliquot of the suspension. Part of the supernatant was
filtered through a 0.1-pm cellulosenitrate membrane filter
and then used as a reference. The remaining unfiltered
supernatant was then returned to the original aliquot to
resuspend the solid. The resulting suspension had a
concentration of 60-95 g/L solid oxide, with a few cases
of 120 or 300 g/L.
Homogeneous solutions were also prepared at an ionic
strength of 0.1 mol/L of NaC104. The pH was adjusted
with 0.1 or 1 M HC104 or NaOH. Reference samples
without ligand were prepared and adjusted to the correct
pH in the same manner.
ATR-FTIR Spectroscopy. The ATR-FTIR spectros-
copy was performed on a BioRad FTS-45 spectrometer
equipped with an internalTGS thermal detector, a purging
molecular sieve air dryer and an auxiliary air supply. The
ATR accessoryconsisted of a 3.2-mL stainless steel sample
764 Envlron. Scl. Technol., Vol. 28, No. 5, 1994
boat with a ZnSe crystal of square cross-section. A single-
beam background spectrum of 2000 scans was recorded
with the empty sample boat in place, and this spectrum
was stored in the background file. Reference and sample
spectra were recorded in absorbance mode and were
automaticallyratioed to the single-beam background most
recently entered in the background file. The absorbance
spectrum is produced by computing the logarithm (base
10) of the ratio of the background spectrum to the sample
spectrum: A = loglo(background/sample) Each reference
and corresponding sample were scanned 2000 times.
Spectra. In order to facilitate peak identification,
spectra of the ligand are first collected above and below
its pK1 value of 2.8. The species covered in this range are
the fully protonated form below the pK1 and the singly
deprotonated form in which the carboxylic group loses its
hydrogen. Appearance and disappearance of peaks, as
well as peak shifts, are the results of changes in bonding,
i.e., changes in speciation or the formation of a strong
interaction with the surface. A spectrum was then
obtained of the metal-ligand complex in homogeneous
solution, followed by the spectrum of the ligand at the
oxide-aqueous solution interface. Evidence of bonding is
found by observing changes in the spectrum of the ligand
itself, because the direct ligand-metal bond vibrations of
a surface complex absorb in the same region as the metal-
oxygen vibrations of the bulk oxide. The interpretation
and tentative peak assignments were carried out with the
help of literature data (19-28), especially those of Yost et
al. (26).
The spectra were generally dominated by the strong
absorbance of water. In order to obtain a useful spectrum
of the substance of interest, a reference spectrum must be
subtracted from the sample spectrum. The reference
contains everything the sample does except the substance
of interest. For example, to obtain a spectrum of salicylate
a t pH 5, the following procedure was used
(1)A reference sample of 0.1 M NaC104 at pH 5 is
prepared and scanned 2000 times.
(2) The solution is removed from the sample boat, leaving
the boat in place.
(3) A sample of salicylic acid in 0.1 M NaC104 at pH 5
is prepared. This sample is also scanned 2000 times.
(4) The reference spectrum is subtracted from the
sample spectrum using a subtraction factor of 1.000,which
for purposes of consistency was used in all cases. The
resultant spectrum contains, in theory, only the peaks due
to the salicylate.
A similar procedure is used to obtain interfacial spectra
of adsorbed species. Spectral subtraction of a supernatant
from a suspension results in a spectrum of the solid phase
and the interfacial region. Futther subtraction of a
spectrum of the solid phase (without adsorbate) yields a
spectrum of the interfacial region only. This spectral
subtraction can be optimized by using similar hydration
profiles of the solid with and without the ligand (sample
and reference). According to Yost et al. (26),the surface
hydration profiles can best be matched by using the same
conditions of pH and ionic strength, because salicylate
adsorption has little effect on surface hydration. It should
be noted that due to the extremely strong absorption of
water around 1640 cm-', the subtraction can still be
difficult in this region. A slight difference in surface
hydration, for instance, may cause too much of this peak
to be subtracted by the supernatant spectrum. In this

Flgure 2. Possiblesurface structuresfor salicylate inner-spheresurface
complexes.
area, therefore, occasionally an inconsistency such as a
negative peak may appear. The reproducibility of the
other peak shifts and shapes between different runs of the
same experiments, however, supports the validity of the
spectra.
The spectral data were transferred and converted to be
used on a Macintosh system. Using the Matlab program,
baseline corrections were carried out on all spectra so that
the average points in the spectral range of 2000-2010 and
3910-3920 cm-l were set to zero. The individual ligand
spectra were offset from each other so that they could be
easily distinguished. The interfacial spectra were generally
multiplied by a factor between 5 and 10, so that peaks
were clearly visible and could be compared to the ligand
spectra. As a result, the absorption scales for the
superimposed spectra are not the same; however, the
qualitative interpretation is not affected by this procedure.
Results and Discussion
This in-situ FTIR method has been used for the
qualitative characterizationof adsorption reactions in the
interfacial region of aqueous goethite (a-FeOOH) suspen-
sions (25-27). Salicylate in particular was investigated in
the goethite-water interfacial region by Zeltner et al. (23,
where a chelate surface structure was determined. In this
case each salicylate takes the place of two hydroxyl groups
attached to one surface iron atom (structure 2 of Figure
2). Further studies by Yost et al. confirmed the chelate
formation, involving a carboxylic and a phenolic oxygen
bound to a surface iron, for low surface coverages. At
higher surface coverages, this structure was found to coexist
with salicylate ions that are weakly bound in the double
layer. Tunesi and Anderson (28) studied the adsorption
of salicylate on titanium dioxide ceramic membranes and
found the same surface configuration as found on goethite
by Yost et al. (26).
Salicylate in Solution. Salicylate differs from other
aromatic carboxylic acids in that it exhibits an anomalously
0 1M alumlnum perchlorate
0.025M BallCyllC BCld
0.1M NGD4
I
, ‘ Y
1800 1700 1600 1500 1400 1300 1200
wavenumber (cm.’)
Flgure 3. Ai1l1-saIicylatecomplex in homogeneous solutlon at pH 2.
0.007M sallcyllc acid
30 gll € 4 1 *Os
0.1M NaCD
t
1800 1700 1600 1500 1400 1300 1200
wavenumber (cm ’ )
Figure 4. Spectrum of interfacial sallcylate-Al2O3 surface Complex
at pH 5, compared to free salicylate in solutlon.
high pK2. The cause of this phenomenon is the intramo-
lecular hydrogen bond. The H of a hydroxy group involved
in a hydrogen bond is very strongly bound to the molecule,
making it more difficult to remove than in the nonchelated
form. This H bond is present in salicylic acid, but is
stronger in the anionic salicylate (29). The spectra of
salicylate in the solid phase have been mentioned elsewhere
(26). The spectra of salicylate in aqueous solution (see
Figure 3, spectra at pH = 2-5) at first glance appear to be
impervious to pH changes in the 2-5 range. A closer look,
however, indicates that there are indeed changesoccurring
which correspond to deprotonation at the pK1. Specif-
ically, one such change is visible at 1705 cm-l (Figure 4,
spectra at pH = 2-5). The absorption of a carbon-oxygen
double bond is expected at this wavenumber and, indeed,
can be found appearing as a shoulder shape at pH 2. This
is especially obvious when compared to the other spectra
at the higher pH values. In these other spectra, this
absorption is no longer expected because through the
deprotonation of the carboxyl group above the pK1, the
C=O bond gives way to two more or less equivalent
carbon-oxygen bonds.
The other specific change in the solution spectra with
increasing pH, one of the peaks key to this study, is due
to the phenolic functional group. In solution, this peak
is at 1244 cm-l at pH 2 and shifts to approximately 1252
cm-l at pH 5. As in Yost et al. (261, it is assigned to the
phenolic C-OH stretching vibration, although alternatively
one might argue that it is a C-0 stretching coupled with
the in-plane deformation of the phenolic OH group. The
slight shift with increasing pH may be due to the
Environ. Scl. Technol., Vol. 28, No. 5, 1994 765
 intramolecular hydrogen bond, which is stronger in the
anion than in the acid. A stronger hydrogen bond to the
carboxylate group lengthens (weakens) the 0-H bond in
the phenolic group. This in turn leaves more negative
charge on the oxygen, creating a stronger phenolic C-0
bond, thereby causing the absorption band to shift to
higher frequencies. According to Yost et al. (26),a phenol
peak found at 1240 cm-' will shift to 1270 cm-l when the
phenolic group deprotonates.
Aluminum and Salicylate in Solution. Figure 3
shows the spectrum of the aluminum-salicylate complex
in homogeneous solution compared to the spectra of the
ligand only in solution. The low pH of 2 for the metal-
ligand complex was necessary to avoid precipitates. The
log K1 for the aluminum-salicylate complex is given by
Sillen and Martell (30)(for 20 "C and I = 0.1)to be 12.9.
Considering the aluminum-salicylate concentration ratio
of 4:l in the system, the monosalicylate-A1 species is the
most likely complex to form. At pH 2,the salicylic acid's
carboxyl group is deprotonated, whereas the phenolic
group is not.
The general change in the overall spectrum of aluminum
and salicylate in homogeneous solution (monosalicylate-
Al"9 indicates that salicylate binds with aluminum in an
inner-sphere complex in solution. The presence of a band
assigned to the C=O vibration implies that only one of
the oxygen atoms of the carboxyl group is involved in
coordination. Accordingto Yost et al. (26),salicylate forms
a chelate structure with iron involving a carboxylic oxygen
as well as the phenolic group. This is evident in their
infrared spectrum because the phenolic OH band shifts
to lower frequencies. The shift to higher wavenumbers of
the phenolic OH vibration in our study with 6-Al203, on
the other hand, seems to indicate that, as opposed to the
iron system, this functional group is not directly involved
in the association with aluminum. The shift is probably
not large enough to indicate deprotonation; however, it
could be caused by stronger hydrogen bonding. Based on
these results, it is proposed that under the conditions of
our experiment (pH = 2,a1uminum:salicylateratio = 4:1),
salicylate coordinates with aluminum in solution in a
configuration which is monodentate.
6-Al203. The interfacial spectrum of salicylic acid and
6-A1203exhibits several peak shifts and changes compared
to the spectra of the free ligand in solution (see Figure 4).
The peaks in this spectrum at pH = 5 are tentatively
assigned as follows:
(a) The peak at 1708 cm-1 is assigned to the C=O
stretching vibration. This mode appears as a shoulder at
the same frequency for salicylic acid in solution.
(b) The peak at 1604 cm-l may be due to a u(C-C) ring
vibration, as found at 1620 cm-1 in the ligand spectra.
(c) Yost et al. (26) found a peak at 1568 cm-1, as was
found in this study, and assigned it to a u(C-C) ring
vibration which has shifted on adsorption.
(d) A peak appears at 1534 cm-l, which is present in
neither the ligand nor the metal-ligand spectra, is assigned
to the vas (COO-).
(e) The peaks at 1469 and 1454 cm-l were also found by
Yost et al. and assigned to C-C ring bands of the salicylate
surface complex (26). Kung and McBride assigned a band
at a similar wavenumber to a C=C ring stretching for
both mono- and disubstituted chlorophenols (11).
Arguably, several other bands might be expected in this
region, including a vas (COO-), an in-plane deformation of
766 Envlron. Scl. Technol., VoI. 28, No. 5, 1994
T
&AI 203
, PH 7
€ 4 1 ,03, p H 5
al
C goethite, PH 5
B goethlte, PH 7
P
a
1800 1700 1600 1500 1400 1300 1200
wavenumber (cm")
Figure 5. Comparison of surface salicylate complexes on &A1203 at
pH 7 and pH 5 with those on goethite.
part of the carboxylicgroup, and a coupled C-0 stretching.
Due to adsorption, this doublet is significantly narrower
and more intense than for salicylate in solution.
(0 The peak at 1381 cm-l is assigned to the u,(COO-)
vibration.
(g) The band at 1259 cm-l is assigned, as in Yost et al.,
to the C-0 stretching of the phenolic OH group. This
band has shifted slightly to higher wavenumbers from the
ligand spectrum, where it was near 1250 cm-l.
The interfacial spectrum of salicylate on 6-A1203at pH
7 fairly closely resembles that at pH 5 (see Figure 5). The
zero point of charge (zpc) of the aluminum oxide used was
found by Ibric (17) to be 6.5. The similarity of the spectra
at pH values of 5 and 7 confirms that the adsorption is
primarily the result of a chemicalreaction not electrostatics
(i.e., inner-sphere, not outer-sphere).
Some of the possibilities for the structure of a salicylate
surface complex are shown in Figure 2. According to Yost
et al. (26),adsorption of salicylate changes the ?r-electron
density of the benzene ring, thus altering the absorption
bands of its C-C vibrations. This explains the appearance
of the large peak at 1604 cm-l, also found by Yost et al.
(26)for the adsorption of salicylate onto goethite. In fact,
the peaks found in the 1650-1400 cm-l range in their study
are extremely close to those in this study. The only
difference found in this region is that the peak which is
found at 1534 cm-' for salicylate on aluminum oxide (this
study) is found at 1524cm-l on goethite (their study). The
peaks found in the region below 1400cm-1, however, differ
rather markedly. The u,(COO-) peak at 1381 cm-l on
aluminum oxide does not shift from the ligand spectrum,
whereas it shifts down to 1369 cm-l on goethite. Also of
significance is the phenolic C-OH peak, which on adsorp-
tion to aluminum oxide shifts to slightly higher wave-
numbers compared to the ligand spectrum, whereas on
goethite it shifts to lower wavenumbers. The shift of this
peak in the opposite direction on aluminum oxide from
goethite indicates that salicylate does not form the same
surface complex on the two mineral surfaces. Thus the
structures other than 2 of Figure 2 must be considered.
Since on deprotonation this particular vibration shifts to
much higher wavenumbers,the shift to lower wavenumbers
on goethite is indicative of coordination to the surface.
This group is not directly coordinated to 6-Al203. On
6-A1203the upward shift is not large enough to signify
deprotonation; however, it could conceivably be caused
by an increase in the strength of the intramolecular

t
t , ,
1800 1700 1800 1500 1400 1300 1200
wavenumber (cm")
Figure 6, Comparison of surface sallcylate complexes on hematite
and corundum at pH 5.
hydrogen bond. This would lengthen the O-H bond,
thereby shortening the phenolic C-0. It could conceivably
be due to a free aluminum ion replacing the hydrogen
bond between the oxygens of the phenolic and carboxyl
groups, as would be the case in 8 in Figure 2. Another
possibility is a complete breaking of the H bond, thereby
making the OH group less constrained and freer to vibrate
(which may occur in 1,5, or 6 of Figure 2). There may also
be more than one type of interfacial salicylate. One might
be monodentate with respect to the carboxylgroup, thereby
accounting for the C=O vibration band (1 or 10 of Figure
2), and the other might be bidentate with respect to this
group (as 5, 6, or 7 of Figure 2), thus decreasing the
separation value between the antisymmetric and sym-
metric stretching absorption frequencies compared to the
free ligand. Finally, a very likely structure is a mono-
dentate coordination with respect to the carboxyl group,
with a hydrogen bond associating the phenolic OH group
with a deprotonated surface hydroxyl group. This hy-
drogen bond would thereby create a pseudochelate of the
molecule on the surface as described by 10 in Figure 2. It
would, however, necessarily be weaker than the intra-
molecular hydrogen bond present in the anionic salicylate
in solution.
If the various surface species present are the same at
pH 7 as at pH 5, there is clearly a shift in their proportions.
The more dominant species at pH 7 is most likely in a
monodentate configuration with respect to the carboxyl
group. If the interpretation of Yost et al. (26) for the
phenolic OH band is correct, then this hydroxyl functional
group of salicylate is not directly involved in a chelating
surface structure in this system. Based on these results,
the dominant surface structure of salicylate on 6-Al203
both at pH 5 and at pH 7 is not the same as that formed
on goethite.
cu-AlzO3. The interfacial spectrum of salicylate on
corundum ((Y-Alz03) was recorded a t pH 5 in order to
compare the adsorption on a mineral of the same chemical
composition but different morphological structure from
6-Alz03. Evidence of peaks is found in the same areas as
for 6-A1203 at pH 5, with the phenolic OH peak at 1254
cm-l (see Figure 6). The absence of a shift downwards
compared to the ligand spectrum again indicates that the
phenolic OH functional group is not involved in the surface
complex on this mineral surface in the same way as on
goethite. Therefore in all likelihood salicylate on corun-
dum does not form a chelating five-membered ring. Based
pH 5
y-AI 203,
lepldocrocite
PH 7
lepldocrocite
1800 1700 1600 1500 1400 1300 1200
wavenumber (cm" )
Flgure 7. Comparison of surface salicylate complexes on y-AlpOs at
pH 7 and pH 5 with those on lepldocrocite.
on the interfacial spectrum, the most plausible structure
for this system is a monodentate coordination through a
carboxylate oxygen to a surface aluminum atom (i.e.,
possibly 1, 8,or 10 of Figure 2).
yA1203. The salicylate-mineral interfacial region was
also investigated for y-A1203at both pH 5 and pH 7 (see
Figure 7). At pH 5, the region below 1650 cm-I shows
clear peaks, located in the same positions as for 6-A1203.
The peak assignments and interpretation therefore remain
the same, and it is presumed that the same surface
structure is formed by salicylate on both of these minerals
at pH 5.
At pH 7, the peak positions are similar to those at pH
5. Again, the phenolic OH band has shifted to higher
wavenumbers (to 1261 cm-l) compared to the ligand
spectrum, presumably indicating that this group is not
directly coordinated to an aluminum surface atom. Based
on the spectra, it is concluded that the same type of surface
complex is formed on this mineral at both pH 5 and pH
7.
Goethite. Our spectra of the 6-Al203-salicylate system
differed from those of Yost et al. (26) on the goethite-
salicylate system. For purposes of comparison, therefore,
salicylate on goethite was also used in this study. The
spectrum obtained (at pH 5 , using 0.007 M salicylate and
a final goethite concentration of approximately 90 g/L)
showed the same peak locations and shifts within spectral
resolution as those reported by Yost et al. (26). The
spectrum clearly differs from that of the aluminum system
(see Figure 5 ) .
The interfacial spectrum of salicylate on goethite at pH
7 was slightly different from that at pH 5. The deep valley
at 1600-1650 cm-l is due to spectral subtraction of the
water, which absorbs very strongly in this region. The
most obvious difference is the large shoulder which appears
near 1280 cm-l. There may be another interfacial species
at this pH in addition to the chelating five-membered ring.
The species are clearly different from those formed on
&A1203 at pH 7 (see Figure 5 ) .
For interpretation and band assignments of salicylate
on goethite, the reader is referred to Yost et al. (26).The
structure inferred from the spectra at pH 5 is a chelating
five-memberedring involvingone oxygen from the carboxyl
group, the phenolic oxygen, and one surface iron atom (2
of Figure 2).
Hematite and Lepidocrocite. The spectra of salicylate
on hematite (cu-FezO3)and lepidocrocite (y-FeOOH) were
Envlron. Scl. Technol., Vol. 28, No. 5, 7994 767
 recorded with the purpose of finding out if it is the
morphology or the chemical composition of a mineral
surface which determines the type of surface complex
formed. If the interfacial spectra for hematite are similar
to those for corundum, then the structural modification
of the mineraldetermines the type of inner-sphere complex
formed. If, however, the interfacial spectra for salicylate
on all the iron oxides are similar, yet different from those
for all the aluminum oxides,then the chemical composition
of the mineral phase is the important factor.
The interfacial spectrum of hematite and salicylate at
pH 5 looks quite different from that of its structural
counterpart, corundum (see Figure 6). Due to the
incomplete spectral subtraction of the water OH bending
band, the region around 1600cm-l is difficult to interpret.
The usually clearly sharp doublet near 1455and 1470cm-1
is certainly present; however, its peak at 1470 cm-l has
split. The v,(COO-) band is at 1380 cm-l, where it was in
solution. The most obvious difference lies again in the
phenolic OH band. For the hematite system, contrary to
corundum, it has shifted to lower wavenumbers (1241
cm-l). This downward shift was also found for the goethite
system, implying that chemical composition of the surface
determines the surface complex structure.
The lepidocrocite system, as with yAlzO3, was also
investigated at both pH values of 5 and 7 (see Figure 7).
The interfacial spectra for salicylate on lepidocrocite are
very similar at the two pH values. The peak positions
remain within a few wavenumbers for both cases. Most
notably, however, the phenolic OH band is located at 1232
cm-'. The downward shift of this band is even larger than
for the other iron oxides investigated. It clearly indicates
the involvement of this functional group in the inner-
sphere complex and thus a structure as 2 in Figure 2. This
reinforces the concept that chemical composition, as
opposed to morphology, determines the structure of the
surface complex.
Conclusions
We conclude this in-situ ATR-FTIRstudy by answering
the questions posed at the outset of this work. First of all,
as seen in the infrared spectra, the ligand salicylate does
coordinate directly with the surface of hydrous metal
oxides, thereby forming an inner-sphere surface complex.
Secondly, it can be inferred that salicylate does not form
the same surface complex on all oxides. The structure of
this surface complex is a mononuclear five-membered
chelate on the surface of goethite (2 of Figure 2), whereas
on the surface of aluminum oxide it is plausibly a six-
membered pseudochelate involving a hydrogen bond (10
of Figure 2). Finally, it is the chemical composition of the
metal oxide, as opposed to the morphology, which in the
case examined determines the structure of the ligand
surface complex.
The importance of this work lies in its quest to examine
surface reactivity from a structural point of view. Although
it has not provided the exact relationship between surface
complex structure and reactivity, it does provide a
necessary stepping stone in connecting the two.
768 Envlron. Scl. Technol., Vol. 28, No. 5, 1994
Acknowledgments
We are indebted to Dr. M. Isabel Tejedor-Tejedor and
Prof. Marc Anderson for invaluable advice and to Dr.
Stephan Hug for assistance with the spectra.
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Received for review December 22, 1992. Revised manuscript
received June 7, 1993. Accepted January 25, 1994.'
'Abstract published in Advance ACS Abstracts, March 1,1994.