6356 Langmuir 2005, 21, 6356-6365

Adsorption of Organic Matter at Mineral/Water Interfaces.

6. Effect of Inner-Sphere versus Outer-Sphere Adsorption
on Colloidal Stability
Stephen B. Johnson,† Gordon E. Brown, Jr.,†,‡ Thomas W. Healy,§ and
Peter J. Scales*,§
Surface & Aqueous Geochemistry Group, Department of Geological & Environmental Sciences,
Stanford University, Stanford, California 94305-2115, Stanford Synchrotron Radiation
Laboratory, SLAC, 2575 Sand Hill Road, MS 69, Menlo Park, California 94025, and
Particulate Fluids Processing Centre, Department of Chemical and Biomolecular Engineering,
The University of Melbourne, Victoria 3010, Australia

Received December 2, 2004. In Final Form: March 29, 2005

The effects of the adsorption modes of several low molecular weight (LMW) organic anions (maleate,
oxalate, and citrate) on the colloidal stability of corundum-water suspensions have been examined using
electrokinetic and shear yield stress (τy) measurements over a broad range of pH conditions and LMW
organic anion concentrations. Consistent with previous studies, increasing concentrations of maleate,
oxalate, and citrate progressively shift the electrokinetic isoelectric point and pH of the maximum shear
yield stress (τy,max) to more acidic conditions. Due to its predominant electrostatic driving force for adsorption,
outer-spherically adsorbed maleate possesses a very limited ability to charge reverse the corundum-water
interface or bind to the negatively charged corundum surface. By contrast, inner-spherically adsorbed
oxalate and citrate can significantly charge reverse the corundum-water interface, with the extent of
charge reversal being related to the relative binding strengths of the oxalate and citrate anions. Adsorbed
maleate, oxalate, and citrate generate steric barriers to interparticle approach, leading to substantial
reductions in the magnitude of τy,max at low to intermediate concentrations of those LMW anions. At the
highest anion concentrations investigated, however, increases in τy,max are observed, and can be attributed
to the formation of bridging Al(III)-organic surface precipitates, as suggested by in situ attenuated total
reflectance Fourier transform infrared spectroscopic measurements of corundum-oxalate suspensions at
high oxalate concentrations. The extent of precipitate formation is greatest for the corundum-oxalate
system due to the strong dissolution-enhancing properties of the inner-spherically adsorbed oxalate anion
(i.e., its ability to generate enhanced concentrations of dissolved Al(III) which can then participate in
precipitate formation). The effects of the LMW organic anion adsorption modes on both the forms of the
measured τy versus pH data, and the ability to quantitatively compare τy and ζ potential data measured
at different corundum concentrations, are also discussed.

1. Introduction workers have demonstrated that LMW anions that bind

Low molecular weight (LMW) organic and inorganic
anions are generally considered to bind to the surfaces of
(oxyhydr)oxide minerals through one of two fundamental
adsorption modes: inner-sphere adsorption, in which one
or more direct chemical bonds are formed between anionic
functional group(s) and metal cation(s) in the mineral
surface, and outer-sphere adsorption, in which no direct
bonds are formed, and the anion is instead held at the
mineral surface through electrostatic and/or hydrogen-
bonding forces. The mode of anion adsorption has a
significant influence on a number of the physicochemical
properties of the mineral surface. For example, outer-
sphere surface complexes are generally more susceptible
to desorption in the presence of competitive ligands, and
therefore often (but not always1) possess a strong depen-
dence on solution conditions such as ionic strength.2 The
nature of the adsorption mode is also of considerable
importance when considering the dissolution behavior of
(oxyhydr)oxide particles. For example, Stumm and co-
* To whom correspondence should be addressed. Phone: +61 3
83446480. Fax: +61 3 83446233. E-mail: peterjs@unimelb.edu.au.
† Stanford University.
‡ SLAC.
§ The University of Melbourne.
(1) Johnson, B. B.; Sjoberg, S.; Persson, P. Langmuir 2004, 20, 823.
(2) Stumm, W.; Morgan, J. J. Aquatic Chemistry: Chemical Equilibria
and Rates in Natural Waters; John Wiley and Sons: New York, 1996.
in an inner-sphere, mononuclear, bidentate manner can
dramatically enhance the dissolution kinetics of a variety
of (oxyhydr)oxide minerals by polarizing bridging metal-
oxygen bonds in the mineral substrate.3-7 In contrast,
LMW anions that adsorb to form inner-sphere, binuclear,
bidentate complexes tend to inhibit mineral dissolution8-10
due to the high activation energies associated with
simultaneous detachment of two metal cations from the
mineral surface. Similarly, outer-spherically adsorbed
LMW anions can inhibit mineral dissolution through steric
blocking of access to dissolution-active surface sites for
dissolution-promoting species such as protons.11
(3) Furrer, G.; Stumm, W. Geochim. Cosmochim. Acta 1986, 50, 1847.
(4) Zinder, B.; Furrer, G.; Stumm, W. Geochim. Cosmochim. Acta
1986, 50, 1861.
(5) Stumm, W.; Furrer, G. The dissolution of oxides and aluminum
silicates; examples of surface-coordination-controlled kinetics. In Aquatic
Surface Chemistry; Stumm, W., Ed.; Wiley-Interscience: New York,
1987; p 197.
(6) Stumm, W. Adv. Chem. Ser. 1995, 244, 1.
(7) Stumm, W. Colloids Surf., A 1997, 120, 143.
(8) Bondietti, G.; Sinniger, J.; Stumm, W. Colloids Surf., A 1993, 79,
157.
(9) Biber, M. V.; Afonso, M. D.; Stumm, W. Geochim. Cosmochim.
Acta 1994, 58, 1999.
(10) Eick, M. J.; Peak, J. D.; Brady, W. D. Soil Sci. Soc. Am. J. 1999,
63, 1133.
(11) Johnson, S. B.; Yoon, T. H.; Kocar, B. D.; Brown Jr, G. E.
Langmuir 2004, 20, 4996.

10.1021/la047030q CCC: $30.25 © 2005 American Chemical Society

Published on Web 06/04/2005
Organic Matter Adsorption at Mineral/Water Interfaces
In addition to the above processes, the adsorption of
LMW anions is known to have a significant effect on
properties affecting the colloidal stability of mineral
(oxyhydr)oxide suspensions. Adsorbed LMW anions com-
monly affect colloidal stability in two ways: first, by
modifying the effective interfacial charge,12-16 so alter-
ing the nature of the electrical double layer interac-
tion between the sorbate particles,17 and, second, by
generating a short-range steric barrier to interparticle
approach,12,16,18,19 thus effectively truncating the short-
range strength of the attractive van der Waals force.
Similar effects have been reported in the presence of sorbed
macromolecular organic matter20-26 and in combination
(where they are collectively referred to as electrosteric
effects) can have a dramatic impact on the colloidal
behavior exhibited by mineral particles in the environ-
ment. For example, Lowry et al.27 and Slowey et al.28 have
demonstrated that the presence of common LMW organic
anions such as malonate, oxalate, and citrate can sig-
nificantly enhance the stability (and therefore the un-
desirable transport) of mercury- and arsenic-bearing
mineral nanoparticles. Adsorbed organic matter can also
act to physically stabilize particles in natural waters,29,30
while the stability-enhancing characteristics of a common
LMW organic anion, citrate, have recently been investi-
gated in the context of remediating aquifer sediments
containing heavy metal contaminants.31 Similarly, in an
industrial context, the enhancement of colloidal stability
that can be imparted by adsorbed LMW organic anions
has led to species such as citrate being investigated for
use as dispersants in the aqueous-based formulation of
advanced ceramic components.13,32,33
While a significant number of studies have now ad-
dressed the effects of LMW anion adsorption on colloidal
stability, none to our knowledge have yet attempted to
distinguish between the relative impacts of inner-spheri-
cally versus outer-spherically adsorbed LMW anions. Such
differences in adsorption mode are anticipated to be of
potential importance in a number of contexts. For example,
(12) Leong, Y. K.; Scales, P. J.; Healy, T. W.; Boger, D. V.; Buscall,
R. J. Chem. Soc., Faraday Trans. 1993, 89, 2473.
(13) Hidber, P. C.; Graule, T. J.; Gauckler, L. J. J. Am. Ceram. Soc.
1996, 79, 1857.
(14) Hidber, P. C.; Graule, T. J.; Gauckler, L. J. J. Eur. Ceram. Soc.
1997, 17, 239.
(15) Yao, H. L.; Yeh, H. H. Langmuir 1996, 12, 2989.
(16) Johnson, S. B. The Relationship Between the Surface Chemistry
and the Shear Yield Stress of Mineral Suspensions. Ph.D. Thesis, The
University of Melbourne, Melbourne, Australia, 1998.
(17) Hunter, R. J. Foundations of Colloid Science, 2nd ed.; Oxford
University Press: Oxford, U.K., 2001.
(18) Leong, Y. K.; Boger, D. V.; Scales, P. J.; Healy, T. W.; Buscall,
R. J. Chem. Soc., Chem. Commun. 1993, 639.
(19) Biggs, S.; Mulvaney, P.; Zukoski, C. F.; Grieser, F. J. Am. Chem.
Soc. 1994, 116, 9150.
(20) Davis, J. A. Geochim. Cosmochim. Acta 1982, 46, 2381.
(21) Tipping, E.; Higgins, D. C. Colloids Surf. 1982, 5, 85.
(22) O’Melia, C. R. Colloids Surf. 1989, 39, 255.
(23) Tiller, C. L.; O’Melia, C. R. Colloids Surf., A 1993, 73, 89.
(24) Amirbahman, A.; Olson, T. M. Colloids Surf., A 1995, 95, 249.
(25) Killmann, E.; Adolph, H. Colloid Polym. Sci. 1995, 273, 1071.
(26) Mosley, L. M.; Hunter, K. A.; Ducker, W. A. Environ. Sci. Technol.
2003, 37, 3303.
(27) Lowry, G. V.; Shaw, S.; Kim, C. S.; Rytuba, J. J.; Brown, G. E.,
Jr. Environ. Sci. Technol., in press.
(28) Slowey, A. J.; Johnson, S. B.; Rytuba, J. J.; Brown, G. E., Jr.
Environ. Sci. Technol., in press.
(29) Ali, W.; O’Melia, C. R.; Edzwald, J. K. Water Sci. Technol. 1985,
17, 701.
(30) Weilenmann, U.; O’Melia, C. R.; Stumm, W. Limnol. Oceanogr.
1989, 34, 1.
(31) Johnson, C. R.; Hellerich, L. A.; Nikolaidis, N. P.; Gschwend, P.
M. Ground Water 2001, 39, 895.
(32) Sacks, M. D.; Tseng, T. Y. J. Am. Ceram. Soc. 1983, 66, 242.
(33) Luther, E. P.; Yanez, J. A.; Franks, G. V.; Lange, F. F.; Pearson,
D. S. J. Am. Ceram. Soc. 1995, 78, 1495.
Langmuir, Vol. 21, No. 14, 2005 6357
as outer-spherically adsorbed anions are often held at
positively charged surfaces by electrostatic means, the
extent of their adsorption is likely to have a strong
dependence on the interfacial potential. As a result, anions
that tend to adsorb in an outer-sphere manner may have
a limited ability to charge reverse mineral surfaces (due
to the electrostatic repulsion that will exist between like-
charged interfaces and anions), a factor that will affect
the nature of the electrical double layer interaction
between adsorbate particles. In contrast, inner-spherically
adsorbed anions are unlikely to exhibit such behavior (at
least to the same extent) due to the presence of a significant
chemical (nonelectrostatic) contribution to the adsorption
free energy. The dissolution-enhancing properties of
anions adsorbed in an inner-sphere, mononuclear, bi-
dentate manner may also impact the colloidal stability of
mineral suspensions in two manners: first, by markedly
increasing the ionic strength through the production of
significant concentrations of dissolved metal cations, an
effect that decreases the effective interfacial potential and
so alters the strength of the electrical double layer
interaction between adsorbate particles,34-37 and, second,
by driving the dissolution of sufficiently high concentra-
tions of metal cations from mineral surfaces to allow the
formation of metal-organic precipitates which, should
they bridge between particles, will generate an additional
attractive interparticle force. A reduction in the suspension
stability will then result. Such bridging precipitates are
likely to be formed to a lesser extent (if at all) in the
presence of outer-spherically adsorbed anions due to the
dissolution-inhibiting effect these anions can exhibit under
acidic solution conditions.11
The purpose of the present study is to examine the effects
of outer-sphere versus inner-sphere adsorption of LMW
organic anions on the colloidal stability of a model mineral
suspension. To this end, two common LMW organic anions,
maleate and oxalate, and a model mineral substrate,
corundum (R-Al2O3), were selected for study. Several
recent studies have demonstrated that maleate adsorbs
in a predominantly outer-sphere manner to aluminum
(oxyhydr)oxide particles, including corundum.11,38 In
contrast, provided a sufficiently long equilibration period
is allowed,39 oxalate will adsorb to aluminum (oxyhydr)-
oxides, including corundum, primarily in an inner-sphere,
mononuclear, bidentate fashion.39-41 As a result, the use
of maleate and oxalate, both of which are simple dicar-
boxylate LMW anions, allows the effects of outer-sphere
and inner-sphere adsorption, respectively, to be probed.
Corundum was selected for study due to its well-
understood electrokinetic,13,14,36,42 dissolution,11,41,43,44 and
rheological16,37,42 properties.
In the present study, the properties affecting the
colloidal stability of model corundum suspensions have
(34) Wiese, G. R.; Healy, T. W. J. Colloid Interface Sci. 1975, 51, 427.
(35) Larson, I.; Drummond, C. J.; Chan, D. Y. C.; Grieser, F. J. Am.
Chem. Soc. 1993, 115, 11885.
(36) Johnson, S. B.; Scales, P. J.; Healy, T. W. Langmuir 1999, 15,
2836.
(37) Johnson, S. B.; Franks, G. V.; Scales, P. J.; Healy, T. W. Langmuir
1999, 15, 2844.
(38) Rosenqvist, J.; Axe, K.; Sjoberg, S.; Persson, P. Colloids Surf.,
A 2003, 220, 91.
(39) Axe, K.; Persson, P. Geochim. Cosmochim. Acta 2001, 65, 4481.
(40) Yoon, T. H.; Johnson, S. B.; Musgrave, C. B.; Brown, G. E., Jr.
Geochim. Cosmochim. Acta 2004, 68, 4505.
(41) Johnson, S. B.; Yoon, T. H.; Slowey, A. J.; Brown, G. E., Jr.
Langmuir 2004, 20, 11480.
(42) Johnson, S. B.; Russell, A. S.; Scales, P. J. Colloids Surf., A
1998, 141, 119.
(43) Carroll-Webb, S. A.; Walther, J. V. Geochim. Cosmochim. Acta
1988, 52, 2609.
(44) Samson, S. D.; Stillings, L. L.; Eggleston, C. M. Geochim.
Cosmochim. Acta 2000, 64, 3471.
6358 Langmuir, Vol. 21, No. 14, 2005
been examined over a broad range of maleate and oxalate
concentrations and solution pH conditions. The electrical
properties of the corundum-water interface have been
probed using electrokinetic (electroacoustic) means over
a range of different corundum volume fractions, φ (φ )
0.02-0.25). The shear yield stresses of the corresponding
concentrated (φ ) 0.25) suspensions were then measured
as an indicator of the net interparticle force at each pH
condition examined. Analogous results obtained for an
additional LMW organic ligand, citrate (which strongly
adsorbs to corundum in an inner-sphere manner13), are
also presented for the purpose of comparison. In selected
cases, in situ attenuated total reflectance Fourier trans-
form infrared (ATR-FTIR) measurements have addition-
ally been undertaken to probe for the existence of metal-
organic precipitates. The results serve to demonstrate
some novel differences in colloidal stability promoted by
outer-spherically versus inner-spherically adsorbed LMW
organic ligands.
2. Experimental Section
2.1. Materials. A well-characterized, high-purity (>99.99%)
AKP-30 corundum with a BET surface area of 7 m2/g, a mean
particle diameter of 0.30 µm, and a density of 3.97 g/cm3 was
obtained from Sumitomo Chemical Co., Japan. It was used as
received. Maleic acid, oxalic acid, citric acid, crystalline aluminum
oxalate, KNO3, and KCl were obtained from a variety of suppliers,
and were of reagent grade or higher. Milli-Q grade water
(resistivity 18.2 MΩ cm at 25 °C) was used in all experiments.
All suspensions were prepared by briefly ultrasonicating the
aqueous corundum-organic mixtures using a Branson model
450 digital sonifier equipped with a 1.3 cm horn. The sonifier
was operated at a frequency of 20 kHz, and the power output was
maintained at 50% of the limiting power (350 W). The maximum
suspension volume ultrasonicated at any one time was ap-
proximately 90 cm3. Following ultrasonication, all suspensions
were allowed to stand for several hours prior to measurement.
For electroacoustic and shear yield stress measurements, a
background electrolyte of 0.01 M KNO3 was utilized, and the pH
was adjusted using small volumes of 1-5 M HNO3 and KOH.
The concentrations of organic anions utilized were selected to
allow comparison with previously published measurements of
maleate, oxalate, and citrate adsorption on corundum.11,13,41
All electroacoustic and shear yield stress experiments were
undertaken with the pH progressing from acidic to more basic
conditions. For ATR-FTIR measurements, a background elec-
trolyte of 0.01 M HCl was instead utilized to avoid spectral
complications introduced by the FTIR response of the nitrate
anion. In the latter cases, the suspension pH was instead adjusted
using 1-5 M HCl and KOH solutions.
2.2. Electroacoustic Measurements. All electroacoustic
measurements were performed using an AcoustoSizer instrument
(Colloidal Dynamics, Warwick, Australia). The AcoustoSizer
measurement cell consists of a sample-holding vessel of volume
∼400 cm3, a variable-speed stirrer, built-in pH and conductivity
probes, a dual titrator syringe module for acid and base additions,
and a heat exchange thermocouple for maintenance of a preset
suspension temperature. The AcoustoSizer utilizes two parallel
plate electrodes embedded in opposite walls of the measurement
cell to generate pulsed alternating electric fields in the megahertz
frequency domain. Upon application of an ac voltage pulse,
charged particles are induced to oscillate with a velocity
dependent upon their charge and size, and the frequency of the
applied voltage. Such particle oscillations produce pressure
changes at the suspension boundaries, a phenomenon referred
to as the electrokinetic sonic amplitude (ESA) effect. The
AcoustoSizer utilizes a combination of glass rods and piezoelectric
transducers to quantify the ESA signal.45 The ESA signal can
then be related to the particle-averaged complex dynamic
mobility, 〈µD〉, and in turn the electrokinetic ζ potential, by the
theory of O’Brien and co-workers.46-48
(45) Hunter, R. J. Colloids Surf., A 1998, 141, 37.
(46) O’Brien, R. W. J. Fluid Mech. 1990, 212, 81.
Johnson et al.
In this study, electroacoustic measurements were generally
performed at φ ) 0.02, although for comparison, several systems
containing substantially higher solids volume fractions (φ ) 0.25)
were also examined. A temperature of 25 οC and a constant
stirring speed of 500 rpm were used in all experiments.
Calculations of particle-averaged ζ potentials from the net ESA
responses were performed using the AcoustoSizer software (DOS
version 1.26).
2.3. Shear Yield Stress Measurements. Shear yield stress
(τy) measurements were performed on concentrated particulate
suspensions using the vane technique of Keentok, Nguyen, and
Boger.49-51 Experimentally, the shear yield stress apparatus
consists of a small four-bladed vane attached to the spring-driving
motor of a Haake RV-3 viscometer. The vane is immersed in a
concentrated colloidal suspension of interest, with the spring
then being wound up at a low and constant rate. As a result, the
spring torque is increased without perceptible movement of the
vane, with the maximum observed torque corresponding to the
moment of yielding. The maximum torque can then be related
to τy using the shear yield stress theory of Nguyen and Boger.51
In this study, an MK-500 driving head and a stainless steel
vane with dimensions Hv ) 30.17 mm and Dv ) 25.02 mm and
a blade thickness of 0.55 mm were used for all τy measurements.
Shear yield stress experiments were performed at the ambient
temperature (23-24 °C), and using a rate of spring rotation of
0.2 rpm (a condition at which the measured shear yield stress
is expected to be independent of the speed of rotation50,52).
2.4. Attenuated Total Reflectance Fourier Transform
Infrared Measurements. ATR-FTIR measurements of oxalate
and maleate adsorbed to corundum were performed in situ on
wet corundum-oxalate and corundum-maleate pastes using a
Nicolet NEXUS 470 FTIR spectrometer equipped with a deu-
terated triglycine sulfate (DTGS) detector, a horizontal attenu-
ated total reflectance attachment, and a germanium crystal. Data
collection and spectral calculations were performed using OMNIC
software (version 6.0a, Nicolet Instrument Corp.). A total of 500
scans (with a spectral resolution of 4 cm-1) were performed and
averaged for each sample.
Wet pastes for ATR-FTIR analysis were obtained by centri-
fuging aqueous corundum-oxalate or corundum-maleate sus-
pensions (see section 2.1) at a centrifugal force of ∼10000g for
20 min in a Beckman Avanti 30 benchtop centrifuge. The
supernatant liquids were then decanted and passed through 20
nm syringe filters (Whatman Anotop 25 Plus) to remove any
residual corundum particles. The concentrated wet pastes were
applied directly to the germanium crystal. To hinder evaporation
during ATR-FTIR measurements, a small volume of the corre-
sponding filtered supernatant was placed on top of each paste
and the sample-holding region was sealed with a lid.
To obtain the ATR-FTIR signals from surface-associated
oxalate and maleate species alone, it was first necessary to
eliminate the strong infrared absorbance of water. This was
achieved by measuring the ATR-FTIR spectrum of each filtered
supernatant, and subtracting this from the ATR-FTIR spectrum
measured for the corresponding corundum-oxalate or corundum-
maleate wet paste. In addition, the hydrated corundum surface
itself was also found to possess a significant ATR-FTIR response.
For each wet paste, the latter unwanted spectral contribution
was removed by measuring the spectrum of a corundum-KCl
paste at an equivalent pH condition, and then subtracting this
from the ATR-FTIR spectrum measured for each corundum-
oxalate or corundum-maleate paste, as described elsewhere.11,41
3. Results and Discussion
3.1. Electrokinetic Studies of LMW Organic An-
ions Adsorbed on Corundum. The ζ potential proper-
ties of corundum are shown as a function of maleate
(47) O’Brien, R. W. J. Fluid Mech. 1988, 190, 71.
(48) O’Brien, R. W.; Cannon, D. W.; Rowlands, W. N. J. Colloid
Interface Sci. 1995, 173, 406.
(49) Keentok, M. Rheol. Acta 1982, 21, 325.
(50) Nguyen, Q. D.; Boger, D. V. J. Rheol. 1983, 27, 321.
(51) Nguyen, Q. D.; Boger, D. V. J. Rheol. 1985, 29, 335.
(52) Liddell, P. V.; Boger, D. V. J. Non-Newtonian Fluid Mech. 1996,
63, 235.
Organic Matter Adsorption at Mineral/Water Interfaces
Figure 1. Variation of the ζ-potential of corundum as a function
of maleate concentration (Γ) and pH. The corundum volume
fraction was 0.02, and the background electrolyte concentration
was 0.01 M KNO3 in all cases. Key: b, Γ ) 0 µmol/m2; O, Γ )
0.36 µmol/m2; 2, Γ ) 0.71 µmol/m2; 4, Γ ) 1.4 µmol/m2; [, Γ
) 3.6 µmol/m2; ], Γ ) 7.1 µmol/m2; 1, Γ ) 14 µmol/m2.
concentration and solution pH in Figure 1. The background
electrolyte concentration is 0.01 M KNO3 in all cases. In
the absence of maleate, Figure 1 shows that the isoelectric
point (iep) of the bare corundum surface is 9.4, in good
agreement with values in the vicinity of 9 previously
reported for corundum powders dispersed in aqueous
media.13,14,36,42,53,54 Figure 1 also shows that the position
of the iep systematically decreases as a function of
increasing maleate concentration, reaching a value of 5.8
at the highest maleate concentration examined (Γ ) 14
µmol/m2, where Γ is defined as the total (i.e., adsorbed +
free) concentration of maleate normalized by the corundum
surface area). In addition, at pH < 10, the measured ζ
potential data at each pH condition are observed to
progressively decrease as the concentration of maleate
rises. Such results are driven by the significant surface
association of maleate (primarily in its fully deprotonated
form, Mal2-) that has previously been observed by Johnson
et al.11 on the positively charged corundum surface.
Maleate adsorbs at aluminum (oxyhydr)oxide surfaces,
including corundum, predominantly as an outer-sphere
complex.11,38 As a result, the adsorption of maleate is
expected to be largely governed by its electrostatic
interactions with the corundum surface. This expectation
is borne out in Figure 1, where at pH conditions above the
iep of bare corundum (i.e., pH > 9.4), the measured ζ
potential is relatively insensitive to maleate concentration.
Such results are consistent with the very low extent of
maleate adsorption measured by Johnson et al.11 at pH
> 9.5, and indicate that anionic maleate is unable to adsorb
to the negatively charged corundum surface to a significant
extent. Similar electrokinetic results have previously been
reported for the interaction of maleate with δ-Al2O3.15
Figure 1 also demonstrates that, at pH < 9.4, maleate is
able to charge reverse the corundum surface to only a
small extent, even at the highest maleate concentrations
examined. The latter result can again be attributed to the
low affinity of maleate anions for like-charged mineral-
water interfaces. Similar results have previously been
reported for the interaction of sulfate (which adsorbs to
(oxyhydr)oxide surfaces in an outer-sphere manner at all
but quite acidic conditions55) with corundum.16
Figure 2 shows the ζ potential properties of corundum
as a function of oxalate concentration and pH. As was the
(53) Franks, G. V.; Meagher, L. Colloids Surf., A 2003, 214, 99.
(54) Kosmulski, M. J. Colloid Interface Sci. 2004, 275, 214.
(55) Wijnja, H.; Schulthess, C. P. J. Colloid Interface Sci. 2000, 229,
286.
Langmuir, Vol. 21, No. 14, 2005 6359
Figure 2. Variation of the ζ-potential of corundum as a function
of oxalate concentration (Γ) and pH. The corundum volume
fraction was 0.02, and the background electrolyte concentration
was 0.01 M KNO3 in all cases. Key: b, Γ ) 0 µmol/m2; O, Γ )
0.36 µmol/m2; 2, Γ ) 0.71 µmol/m2; 4, Γ ) 1.4 µmol/m2; [, Γ
) 3.6 µmol/m2; ], Γ ) 7.1 µmol/m2.
case for corundum in the presence of maleate, Figure 2
demonstrates that the position of the iep of corundum
decreases markedly as a function of increasing oxalate
concentration. Except at very short reaction times, oxalate
adsorbs to aluminum (oxyhydr)oxide minerals including
corundum41 in a predominantly inner-sphere manner to
form bidentate, mononuclear surface complexes with
surface Al(III) cations.39,40 As a result, in addition to an
electrostatic attraction between the oxalate anion and the
positively charged corundum surface, a significant chemi-
cal component of the adsorption energy will exist as a
result of the direct surface Al(III)-oxalate bonds that are
formed. As a consequence of this chemical component,
Figure 2 shows that oxalate is able to charge reverse the
corundum surface to a significantly greater extent than
maleate, with ζ potentials as low as -34 mV being observed
at pH 7.1 and the highest oxalate concentration examined
(Γ ) 7.1 µmol/m2). Interestingly, however, Figure 2 also
shows that the ζ potential versus pH behavior observed
at pH g 11 is relatively insensitive to oxalate concentra-
tion. The latter finding is in accordance with the recent
adsorption study of Johnson et al.,41 which demonstrated
that the extent of oxalate adsorption on corundum is very
low above the iep of the bare corundum surface (i.e., the
surface in the absence of oxalate). The latter finding may
indicate that the unfavorable electrostatic repulsion that
exists between oxalate anions and the corundum surface
under such high pH conditions is sufficient to overcome
the chemical component of adsorption. Alternatively, it
may be a function of a different outer-sphere binding mode
dominating adsorbed oxalate speciation in the vicinity of
the iep of the bare surface.
The electrokinetic behavior exhibited in Figure 2 can
be contrasted with that obtained in the presence of a more
strongly binding LMW ligand, citrate, as shown in Figure
3. In agreement with past electrokinetic studies of aqueous
corundum-citrate systems,13,14,33 Figure 3 shows that both
the corundum iep and the corundum ζ potentials measured
at each pH condition are significantly reduced as the citrate
concentration is raised. Past in situ studies have dem-
onstrated that citrate adsorbs to (oxyhydr)oxide minerals,
including corundum,13 in a predominantly inner-sphere
manner involving one or two of the citrate carboxyl
groups.56 The citrate R-hydroxyl group also participates
in the formation of inner-spherically adsorbed citrate
(56) Lackovic, K.; Angove, M. J.; Wells, J. D.; Johnson, B. B. J. Colloid
Interface Sci. 2003, 257, 31.
6360 Langmuir, Vol. 21, No. 14, 2005 Johnson et al.

Figure 3. Variation of the ζ-potential of corundum as a function
of citrate concentration (Γ) and pH. The corundum volume
fraction was 0.02, and the background electrolyte concentration
was 0.01 M KNO3 in all cases. Key: b, Γ ) 0 µmol/m2; O, Γ )
0.071 µmol/m2; 2, Γ ) 0.14 µmol/m2; 4, Γ ) 0.36 µmol/m2; [,
Γ ) 0.71 µmol/m2; ], Γ ) 1.4 µmol/m2; 1, Γ ) 3.6 µmol/m2.
Figure 4. Variation of the ζ potential of corundum versus pH
at a maleate concentration, Γ, of 3.6 µmol/m2 and a background
electrolyte concentration of 0.01 M KNO3. This concentration
of maleate corresponds to the τy versus pH curve at which τy,max
is at its minimum value. Key: b, φ ) 0.02; O, φ ) 0.25.

complexes, and significantly enhances the inner-sphere

binding strength of citrate, as evidenced by the substan-
tially stronger adsorption of citrate compared with tri-
carballylate (the analogous tricarboxylate anion, but
lacking an R-hydroxyl group).13 The R-hydroxyl group is
believed to act as a “supporting” electron donor group in
concert with the adjacent citrate carboxyl group,57 and
results in a substantial chemical component to the
adsorption energy. This effect is evidenced in Figure 3,
where citrate is shown to be able to charge reverse the
corundum surface to a substantially greater extent than
even oxalate, consistent with its very strong inner-sphere
adsorption strength and higher (-3) anionic charge. Figure
3 also shows that the presence of citrate has a significant
impact on the ζ potential properties of corundum at all Figure 5. Variation of the ζ potential of corundum versus pH
but the highest pH conditions examined (pH 12). The latter at an oxalate concentration, Γ, of 1.4 µmol/m2 and a background
electrolyte concentration of 0.01 M KNO3. This concentration
finding indicates that the large chemical component of of oxalate corresponds to the τy versus pH curve at which τy,max
the adsorption free energy allows citrate to remain is at its minimum value. Key: b, φ ) 0.02; O, φ ) 0.25.
adsorbed to corundum even at pH conditions significantly
higher than the iep of the bare corundum surface, in
agreement with the previous macroscopic adsorption data
of Hidber et al.13,14
The effects of the different adsorption modes and
strengths of maleate, oxalate, and citrate on the surface
charging properties of corundum are further demonstrated
in Figures 4-6, respectively, where the ζ potential
properties of corundum are shown as a function of pH at
two significantly different solids concentrations (φ ) 0.02
and 0.25). The higher solids concentration shown was
chosen to allow later comparison with relevant shear yield
stress data (see section 3.2). The organic anion concentra-
tions shown were selected to minimize τy,max (see section
3.2) for each corundum-organic anion system at φ ) 0.25,
so allowing measurements of ζ to be practical across the Figure 6. Variation of the ζ potential of corundum versus pH
entire pH range of interest. at a citrate concentration, Γ, of 1.4 µmol/m2 and a background
The predominant outer-sphere mode of adsorption of electrolyte concentration of 0.01 M KNO3. This concentration
maleate means that its affinity for the corundum surface of citrate corresponds to the τy versus pH curve at which τy,max
is driven by nonchemical (electrostatic) considerations, is at its minimum value. Key: b, φ ) 0.02; O, φ ) 0.25.
so its adsorption should demonstrate a significant de-
pendence on corundum concentration. As shown in Figure higher solution ionic strength generated by nonadsorbed
4 , the result is a substantially lower iep (iepφ)0.02 - iepφ)0.25 maleate at φ ) 0.25.
) 2.9), and a higher extent of charge reversal at pH < 10, The significant chemical adsorption component associ-
being measured at φ ) 0.25 than at φ ) 0.02, corresponding ated with inner-sphere adsorption of oxalate (and so its
to a higher extent of maleate adsorption. By contrast, the stronger intrinsic surface association) is expected to lead
lower magnitude ζ potential data measured for φ ) 0.25 to its adsorption (and its electrokinetic) properties,
than for φ ) 0.02 at pH > 10 is a function of the much demonstrating a weaker dependence upon the corundum
concentration. This is borne out in Figure 5, where the ζ
(57) Strathmann, T. J.; Myneni, S. C. B. Geochim. Cosmochim. Acta potential properties of corundum in the presence of oxalate
2004, 68, 3441. are shown at φ ) 0.02 and 0.25. The iep measured at φ
Organic Matter Adsorption at Mineral/Water Interfaces
Figure 7. Variation of the shear yield stress (τy) of corundum
as a function of maleate concentration (Γ) and pH. The corundum
volume fraction was 0.25, and the background electrolyte
concentration was 0.01 M KNO3 in all cases. Key: b, Γ ) 0
µmol/m2; O, Γ ) 0.36 µmol/m2; 2, Γ ) 0.71 µmol/m2; 4, Γ ) 1.4
µmol/m2; [, Γ ) 3.6 µmol/m2; ], Γ ) 7.1 µmol/m2; 1, Γ ) 14
µmol/m2.
) 0.25 is slightly lower than that obtained at φ ) 0.02,
although the magnitude of this iep shift ()0.3) is far
smaller than was observed for maleate, and may be
accounted for by the pH suspension effect (see the
discussion below). At pH < 10.5, ζ potentials measured
at φ ) 0.25 lie consistently below those found at φ ) 0.02
(indicative of a higher degree of oxalate adsorption at φ
) 0.25), but again, the magnitudes of these ζ potential
differences are significantly less than observed in Figure
4. The lower magnitude ζ potentials obtained at φ ) 0.25
than at φ ) 0.02 at pH > 10.5 can be attributed once more
to the substantially greater ionic strength that arises due
to nonadsorbed oxalate at the higher corundum concen-
tration.
The effects of corundum concentration on its ζ potential
properties measured in the presence of the inner-spheri-
cally adsorbed citrate anion are shown in Figure 6. In this
case, with citrate possessing a very strong chemical
association with the surface, the electrokinetic properties
are shown to possess only a very minor dependence upon
the corundum concentration, with the ζ potential versus
pH curves being effectively shifted to more acidic pH by
0.4-0.6 units. Such changes may be due to a slightly higher
adsorption of citrate at φ ) 0.25 than at φ ) 0.02, but are
more likely to be accounted for by the pH suspension effect.
The latter effect occurs as a result of the modification of
H+ and OH- mobilities (and so the measured pH) induced
by the presence of electrical double layers surrounding
colloidal particles in aqueous solution.58 Its influence is
therefore expected to increase as a function of rising
corundum concentration, and will lead to slightly different
experimental pH values being measured under equivalent
solution conditions at φ ) 0.02 and 0.25, consistent with
the data of Figure 6.
The correlation between the electrokinetic and stability
behavior of corundum-LMW organic anion suspensions,
and the effects of different corundum concentrations on
this relationship, is further examined in the following
section.
3.2. Shear Yield Stress Studies of Concentrated
Corundum-LMW Organic Anion Suspensions. The
shear yield stress properties of several corundum-
maleate, corundum-oxalate, and corundum-citrate sus-
pensions at φ ) 0.25 are shown as a function of both LMW
organic concentration and suspension pH in Figures 7-9,
(58) Lyklema, J. Fundamentals of Interface and Colloid Science;
Academic Press: London, 1991; Vol. 1.
Langmuir, Vol. 21, No. 14, 2005 6361
Figure 8. Variation of the shear yield stress (τy) of corundum
as a function of oxalate concentration (Γ) and pH. The corundum
volume fraction was 0.25, and the background electrolyte
concentration was 0.01 M KNO3 in all cases. Key: b, Γ ) 0
µmol/m2; O, Γ ) 0.36 µmol/m2; 2, Γ ) 0.71 µmol/m2; 4, Γ ) 1.4
µmol/m2; [, Γ ) 3.6 µmol/m2; ], Γ ) 7.1 µmol/m2.
Figure 9. Variation of the shear yield stress (τy) of corundum
as a function of citrate concentration (Γ) and pH. The corundum
volume fraction was 0.25, and the background electrolyte
concentration was 0.01 M KNO3 in all cases. Key: b, Γ ) 0
µmol/m2; O, Γ ) 0.071 µmol/m2; 2, Γ ) 0.14 µmol/m2; 4, Γ ) 0.36
µmol/m2; [, Γ ) 0.71 µmol/m2; ], Γ ) 1.4 µmol/m2; 1, Γ ) 3.6
µmol/m2.
respectively. The background electrolyte concentration is
0.01 M KNO3 in all cases. In the absence of LMW anions,
the τy versus pH curves measured for aqueous corundum
suspensions fall into an approximately parabolic form,
with the position of the maximum shear yield stress, τy,max
()9.0 ( 0.1) lying in close proximity to the electrokinetic
iep of the bare corundum surface ()9.4; see Figures 1-3).
The latter finding is consistent with the concept that a
maximum in the shear yield stress (i.e., a minimum in the
physical stability of the corundum particles) arises when
the repulsive electrical double layer force between the
particles is minimized.37,42,59 Under such circumstances,
the net interparticle force is dominated by strongly
attractive van der Waals interactions. The slightly lower
pH value of τy,max compared with the electrokinetic iep
can be attributed to the pH suspension effect,58 and is a
function of the higher solids concentration used in τy
measurements (φ ) 0.25) compared with that used in
determining the iep of bare corundum (φ ) 0.02).
Figures 7-9 also show that, as the concentrations of
maleate, oxalate, and citrate are increased, the position
of τy,max progressively shifts to lower pH, in qualitative
agreement with the downward shifts in the iep observed
as a function of increasing maleate, oxalate, and citrate
(59) Scales, P. J.; Johnson, S. B.; Healy, T. W.; Kapur, P. C. AIChE
J. 1998, 44, 538.
6362 Langmuir, Vol. 21, No. 14, 2005
Figure 10. Comparison of the changes in the electrokinetic
iep (obtained at φ ) 0.02) and changes in the pH of τy,max
(measured at φ ) 0.25) measured for aqueous corundum-
organic acid suspensions as a function of various LMW organic
anion concentrations. Data for maleate, oxalate, and citrate
are from Figures 1-3 and 4-6, while data for malate and lactate
are from ref 16. Key: b, maleate; O, oxalate; 2, citrate; 4, malate;
[, lactate.
concentrations in Figures 1-3. A quantitative comparison
between the pH positions of τy,max and the iep data obtained
from Figures 1-3 is shown in Figure 10, and demonstrates
that while the pH of τy,max and iep data are in close
correlation for inner-spherically adsorbed oxalate and
citrate, substantial deviations are apparent for maleate.
The latter findings are presumably due to the different
corundum concentrations utilized in the electrokinetic (φ
) 0.02) and τy (φ ) 0.25) measurements, which evidently
has little effect on adsorbates with a strong chemical
component of adsorption, but significantly affects results
obtained for LMW organic adsorbates instead adsorbed
in an outer-sphere manner. Similar findings are obtained
for corundum particles suspended in aqueous solution in
the presence of other LMW organic anions. For example,
Figure 10 shows that similar to the corundum-oxalate
and corundum-citrate data, the pH of τy,max and iep data
obtained in the presence of malate are closely correlated.
This finding is understandable given that malate strongly
adsorbs to corundum to an extent comparable with that
of citrate,14 and via an adsorption mode that (on the basis
of ATR-FTIR observations of its complexation to metal
cations in solution57) is expected to be predominantly inner-
sphere in nature. By contrast, the pH of τy,max data obtained
in the presence of lactate exhibit significant deviations
from the corresponding iep data (Figure 10). The latter
finding is not surprising given that lactate adsorbs
comparatively weakly to mineral (oxyhydr)oxides such as
corundum14 in a combination of weak inner-sphere and
outer-sphere adsorption modes.60,61 By contrast, a com-
parison of the pH of τy,max and iep data instead obtained
at φ ) 0.25 demonstrates close correlations for all organic
anions examined in Figure 10 (see Table 1). In combina-
tion, the data of Figure 10 indicate that a quantitative
comparison of electrokinetic data (typically obtained at
low φ) and rheological data (obtained at higher φ) obtained
for aqueous mineral-LMW organic anion systems only
appears reasonable in the case of strongly inner-spheri-
cally bound LMW organic anions.
Figures 7-9 further demonstrate that the magnitude
of τy,max initially decreases as a function of increasing
maleate, oxalate, and citrate concentrations, reaching a
(60) Filius, J. D.; Hiemstra, T.; Van Riemsdijk, W. H. J. Colloid
Interface Sci. 1997, 195, 368.
(61) Ha, J.; Johnson, S. B.; Brown, G. E., Jr., Manuscript in
preparation.
Johnson et al.
Table 1. Electrokinetic Isoelectric Points Obtained at O
) 0.020 and O ) 0.250 and the pH Positions of the
Maximum Shear Yield Stresses Obtained at O ) 0.250 for
Various Corundum-LMW Organic Anion Suspensionsa
LMW organic Γ iep iep pH(τy,max)
anion (µmol/m2) (φ ) 0.02) (φ ) 0.25) (φ ) 0.25)
citrate 1.4 5.3 4.8 5.1
malate 1.4 7.0 6.6 6.6
lactate 7.1 8.9 7.8 7.7
maleate 3.6 8.3 5.4 5.7
oxalate 1.4 7.5 7.2 7.0
a Maleate, oxalate, and citrate data are based on Figures 1-9,
while malate and lactate data are from ref 16. Values of Γ were
selected to allow direct comparison of electrokinetic and rheological
data obtained under conditions where τy,max is at its minimum
value.16
minimum value at Γ ) 1.4 µmol/m2 for both oxalate and
citrate, and Γ ) 3.6-7.1 µmol/m2 for maleate. Similar
observations have previously been reported by Leong et
al.,12,18 and are attributable to the finite sizes of the strongly
adsorbed LMW organic anions on (oxyhydr)oxide surfaces.
As a result, in this case, the adsorbed maleate, oxalate,
and citrate anions generate short-range steric barriers to
interparticle approach, so truncating the strength of the
strongly attractive van der Waals attraction, and leading
to an increase in the physical stability of the suspended
corundum particles (i.e., a decrease in τy,max). The minimum
values of τy,max observed in Figures 7-9 decrease in the
order oxalate > maleate > citrate, implying that the size
of the steric barrier imposed in the vicinity of the iep follows
the reverse order. Such findings are consistent with the
relative sizes of (and so the size of the steric barriers
presented by) the maleate, oxalate, and citrate anions
(i.e., citrate > maleate > oxalate).16 Further details
regarding the effects of adsorbed organic anions on the
magnitude of τy,max are given in the studies of Leong et
al.12,18
Interestingly, Figures 7-9 show that, at the highest
maleate, oxalate, and citrate concentrations examined,
increases in τy,max are observed compared with its mag-
nitude at intermediate concentrations of those LMW
anions. Several possible explanations exist for these
findings. First, a rise in the magnitude of τy,max at the
maleate, oxalate, and citrate concentrations examined
could be consistent with a lower extent of adsorption of
the LMW anions at low pH, leading to a decrease in the
size of the effective steric barriers presented by the
maleate, oxalate, and citrate species. Such an explanation
is particularly applicable to inner-spherically adsorbed
oxalate, which acts to significantly increase the dissolution
kinetics of aluminum (oxyhydr)oxide materials3,40 includ-
ing corundum,41 leading to the generation of substantial
dissolved Al(III) concentrations in solution. As oxalate
forms a range of stable complexes with Al(III) in solution,62
dissolved Al(III) can then strongly compete with the
corundum surface for oxalate, leading to a decreased extent
of oxalate adsorption under low pH conditions, as has
been recently demonstrated by Johnson et al.41 An Al-
(III)-induced reduction in the extent of oxalate adsorption
compared with that obtained at intermediate oxalate
concentrations would, however, be expected to lead to a
corresponding upward shift in the iep and pH position of
τy,max at the highest oxalate concentration examined (Γ )
7.1 µmol/m2), an expectation that is clearly inconsistent
with the data of Figures 2 and 8 (where shifts to lower pH
are instead observed). Similarly, substantial downward
(62) Sjoberg, S.; Ohman, L. O. J. Chem. Soc., Dalton Trans. 1985,
2665.
Organic Matter Adsorption at Mineral/Water Interfaces
shifts of both the iep and pH position of τy,max are also
noted at the highest concentrations of maleate (Γ ) 14
µmol/m2) and citrate (Γ ) 3.6 µmol/m2) examined, again
being inconsistent with decreased extents of maleate and
citrate adsorption compared with those measured in the
vicinity of τy,max at lower total maleate and citrate
concentrations.
Instead, the increase in τy,max observed at the highest
maleate, oxalate, and citrate concentrations examined is
likely to be generated by the formation of Al(III)-organic
gel-like precipitates at the corundum surface. The forma-
tion of amorphous Al(III)-oxalate precipitates has been
previously observed down to pH 3.5 in bulk solution by
Masion et al.63 The formation of Al(III)-oxalate surface
precipitates is, however, likely to be possible at signifi-
cantly lower bulk pH conditions in this study due both to
the higher reactant concentrations present (with very
substantial Al(III) concentrations arising from the oxalate-
promoted dissolution of corundum) and to the positive
interfacial charge that exists at low pH, even at the highest
oxalate concentration examined (see Figure 2). The latter
factor can lead to the effective interfacial pH being
significantly higher than that in bulk solution,11 thus
promoting precipitate formation.
By way of example using data previously measured for
another common LMW ligand, phosphate, Goldshmid and
Rubin64 have demonstrated that, at an aluminum con-
centration of 10-3 M and phosphate concentrations in
excess of ca. 10-2.7 M, the critical pH above which
precipitation occurs, pHp, is approximately 3. At higher
Al(III) and phosphate concentrations (provided phosphate
is not in large excess), however, pHp moves to progressively
lower pH, i.e., favors the onset of precipitation under more
acidic conditions. In addition, Liu et al.65 have shown that,
even at moderate concentrations of short-chain phosphates
(Γ ) 1-4 µmol/m2, depending on the phosphate chain
length), gel-like amorphous Al-phosphate surface pre-
cipitates are formed on alumina particles dispersed under
acidic pH conditions (pH 2). Such Al(III)-phosphate gels
were observed to dramatically increase the viscosity of
the aqueous suspensions by bridging between neighboring
particles. As a result, at high phosphate concentrations
and low pH, the formation of bridging Al(III)-phosphate
surface precipitates on corundum is also expected, as has
been shown by the substantial increase in τy,max observed
at Γ(phosphate) ) 7.1 µmol/m2 by Johnson.16
Similar precipitation phenomena are likely to have
governed the increase in τy,max observed at low pH and the
highest maleate, oxalate, and citrate concentrations
examined in this study. A comparison of Figures 7-9
indicates that the increase in τy,max is most marked for
oxalate, a finding that is likely to be a function of the
strong dissolution-enhancing properties of the inner-
spherically adsorbed oxalate anion when it interacts with
aluminum (oxyhydr)oxide minerals.3,40,41 As a result, the
concentration of dissolved Al(III) available to participate
in the formation of bridging Al(III)-oxalate precipitates
will have been substantial, as demonstrated by ATR-FTIR
analyses of centrifuged suspension supernatants (not
shown), which showed the concentration of dissolved Al-
(III) to be sufficient to fully complex all nonadsorbed
oxalate at Γ ) 7.1 µmol/m2 and pH 2 (primarily as AlOx+
and AlOx2-, on the basis of a comparison with spectra
previously reported by Johnson et al.41). Unlike oxalate,
(63) Masion, A.; Thomas, F.; Bottero, J. Y.; Tchoubar, D.; Tekely, P.
J. Non-Cryst. Solids 1994, 171, 191.
(64) Goldshmid, T.; Rubin, A. J. Sep. Sci. Technol. 1988, 23, 2269.
(65) Liu, J.; Wang, L. Q.; Samuels, W. D.; Exarhos, G. J. J. Phys.
Chem. B 1997, 101, 8264.
Langmuir, Vol. 21, No. 14, 2005 6363
Figure 11. ATR-FTIR spectra obtained for (a) a corundum-
oxalate suspension paste at Γ ) 7.1 µmol/m2, pH 2, and φ ) 0.25
and (b) a crystalline aluminum oxalate powder. For ease of
comparison, both spectra have been normalized against their
maximum absorbances. Vertical lines represent the positions
of major absorption peaks previously reported for oxalate
adsorbed on corundum in a bidentate, mononuclear, inner-
sphere manner.40,41
Furrer and Stumm3 have demonstrated that citrate has
a very limited ability to enhance the dissolution kinetics
of aluminum (oxyhydr)oxide surfaces under quite acidic
(pH < 3) conditions. Furthermore, outer-spherically
adsorbed maleate can inhibit the dissolution of corundum
under acidic conditions.11 As a result, under acidic
conditions, substantially lower concentrations of dissolved
Al(III) will be produced, allowing the formation of sig-
nificantly lower quantities of Al(III)-citrate and Al(III)-
maleate precipitates. Such expectations are in good
agreement with the data of Figures 7-9, which show that
the increase in τy,max at high Γ is greatest for oxalate, but
relatively small for maleate and citrate, consistent with
the formation of substantially lower concentrations of
bridging Al(III)-organic gels.
Several attempts were made to directly confirm the
presence of Al(III)-organic precipitates at high Γ and low
pH using in situ ATR-FTIR spectroscopy. An example of
these results is shown in Figure 11, where the ATR-FTIR
spectrum collected for a corundum-oxalate suspension
at φ ) 0.25, Γ ) 7.1 µmol/m2, and pH 2 (i.e., in the vicinity
of τy,max for that system) is compared with that obtained
for a crystalline Al(III)-oxalate powder (Al2Ox3‚xH2O).
Also included in Figure 11 are four lines indicating the
positions of major experimental absorption peaks previ-
ously measured by Yoon et al.40 and Johnson et al.41 for
oxalate adsorbed to corundum in a bidentate, mono-
nuclear, inner-sphere manner.
An examination of Figure 11 shows that the spectrum
of the corundum-oxalate suspension exhibits significant
deviations from the spectrum of crystalline aluminum
oxalate. At 1580-1780 cm-1, a significantly broader series
of peaks are obtained for aluminum oxalate than for the
corundum-oxalate suspension, a finding that is attribut-
able to the spectral contribution from “structural” water
in the crystalline aluminum oxalate powder. This spectral
contribution could not be removed even after extended
heating at 120 °C, and therefore prevents an accurate
comparison of the crystalline aluminum oxalate and
corundum-oxalate suspension spectra in this spectral
region. At lower wavenumbers, however, a number of
additional spectral differences are apparent between the
crystalline aluminum oxalate and corundum-oxalate
spectra, namely, significant shifts in the positions of the
major peaks and the appearance of several additional
minor peaks in the crystalline aluminum oxalate spec-
trum. These differences suggest that any surface Al(III)-
6364 Langmuir, Vol. 21, No. 14, 2005
Figure 12. τy versus ζ2 data obtained for an aqueous
corundum-citrate suspension at Γ ) 1.4 µmol/m2 and φ ) 0.25.
This system corresponds to the concentration of citrate at which
the minimum value of τy,max is obtained. τy data are from Figure
9, while ζ potential data are derived from Figure 6 after slight
adjustment of the iep to exactly match the pH of τy,max (see
Table 1).
oxalate precipitate that is formed is not crystalline in
nature, a finding that is not surprising given that Al-
(III)-oxalate precipitates formed in bulk aqueous solution
tend to be amorphous.63 Significantly, small differences
in the peak positions of the corundum-oxalate suspension
from those of bidentate, mononuclear, inner-spherically
adsorbed oxalate, and the appearance of a new shoulder
in the vicinity of 1325 cm-1, are also evident in Figure 11,
and are in agreement with previous findings at low pH
by Johnson et al.41 Such findings suggest the presence of
additional minor inner-spherically adsorbed or precipi-
tated species. Given that the new peak positions are in
poor agreement with quantum chemical predictions for
other possible inner-sphere oxalate species,40 we therefore
attribute these minor spectral changes to the formation
of an amorphous surface Al(III)-oxalate precipitate,
consistent with the high Γ, low pH data of Figure 8.
Attempts to directly probe the formation of surface Al-
(III)-organic precipitates for other LMW organic anions
were also performed using ATR-FTIR spectroscopy (not
shown). In those cases, however, the spectra failed to reveal
significant new features that could be associated with the
formation of Al(III)-organic precipitates, presumably due
to the much lower anticipated concentrations of Al(III)-
organic precipitates formed (see the discussion above). As
a result, the very minor spectral contributions from the
precipitates were presumably swamped by those from
other major adsorbed species, leading to inconclusive ATR-
FTIR results being obtained.
Interestingly, an examination of Figures 7-9 reveals
that the forms of the τy versus pH curves measured are
quite distinct for the corundum-citrate system compared
with the corundum-maleate and corundum-oxalate
suspensions. The latter findings can be rationalized with
reference to the electrokinetic data of Figures 1-3 and
previous adsorption data measured for these organic
anions on corundum.11,13,41 In the case of citrate, ap-
proximately parabolic τy versus pH data are obtained. Such
behavior is consistent with the approximately linear τy
versus ζ2 data that are expected for systems in which the
mean interparticle separation is constant for conditions
where the net interparticle electrostatic interaction is
attractive.59 An example of the latter behavior is shown
in Figure 12, where τy data from Figure 9 and ζ2 data
derived from Figure 6 (i.e., at equivalent φ) are plotted at
the citrate concentration at which the minimum τy,max
value is obtained (Γ ) 1.4 µmol/m2). The linearity of the
Johnson et al.
τy versus ζ2 data is consistent with both the approximately
symmetrical ζ versus pH behavior that is observed within
ca. 2 pH units of the iep (Figure 3, i.e., where τy > 0 at Γ
) 1.4 µmol/m2) and a constant interparticle separation
when τy > 0. The latter requirement is in agreement with
the almost constant degree of citrate adsorption on
corundum observed by Hidber et al.13 at pH < 6 and an
almost equivalent citrate concentration (Γ ) 1.6 µmol/m2,
corresponding to 0.3 wt % citrate in that case). Interest-
ingly, a significantly lower ζ potential (31 mV) is required
to achieve dispersed conditions (i.e., τy ) 0) at Γ ) 1.4
µmol/m2 citrate than is needed in the absence of citrate
(ζ potential for dispersion 40-45 mV). The latter finding
is a function of the significant steric repulsion generated
by the adsorbed citrate anions.
A comparison of Figures 7-9 shows that the τy versus
pH behavior exhibited by corundum-maleate and co-
rundum-oxalate suspensions is significantly more com-
plex than is observed for corundum-citrate systems. At
low maleate and oxalate concentrations (Γ e 1.4 µmol/
m2), a broadening of the τy versus pH curves is observed,
most significantly on the basic side of the maximum shear
yield stress. Such behavior is (at least qualitatively)
consistent with the systematic lowering of the ζ potentials
observed as a function of increasing maleate and oxalate
concentrations in Figures 1 and 2, a process that reduces
the magnitude of the repulsive electrical double layer force.
At higher maleate and oxalate concentrations, Figures 7
and 8 show that the τy versus pH curves become bimodal
in nature, with the maximum shear yield stress occurring
at low pH, and a second peak being present in the pH
range of 9-11. These observations are consistent with a
decreasing extent of maleate and oxalate adsorption on
corundum as pH increases,11,41 with the τy versus pH
behavior being governed by that of the corundum-maleate
and corundum-oxalate interfaces under acidic pH condi-
tions, but approaching that of the bare corundum surface
at high pH conditions. The substantial changes in the
extent of maleate and oxalate adsorption are expected to
lead to significant changes in the net interparticle
separation in the pH regions where τy > 0. As a result, the
maleate τy versus ζ2 data of Figures 5 and 7 (Γ ) 3.6 µmol/
m2), and the oxalate τy versus ζ2 data of Figures 6 and 8
(Γ ) 1.4 µmol/m2) (i.e., at the maleate and oxalate
concentrations at which the minimum values of τy,max are
obtained), demonstrated nonlinear τy versus ζ2 behavior
(not shown).
At pH 11.5 in Figures 7 and 8, the greatest values of
τy are measured for the highest total maleate and oxalate
concentrations, a finding that is attributable to the
significantly greater ionic strength (generated by non-
adsorbed maleate and oxalate) at those conditions. This
increased ionic strength acts to reduce the repulsive
electrical double layer force, leading to enhanced values
of τy at high pH.37 Interestingly, at intermediate pH
conditions (7-8.5) and high oxalate concentrations (Γ g
3.6 µmol/m2), corundum-oxalate suspensions are fully
dispersed (τy ) 0), while at similar pH conditions and the
highest maleate concentrations examined (Γ g 7.1 µmol/
m2), net attractive interparticle networks persist (τy > 0).
The latter behavior can be attributed to the greater degree
of charge reversal (and so the larger electrical double layer
repulsion) that is generated by the inner-spherically
adsorbed oxalate species compared with that of the outer-
spherically absorbed maleate anion in this near-neutral
pH domain (see section 3.1).
Organic Matter Adsorption at Mineral/Water Interfaces
4. Conclusions
The effects of outer-spherically adsorbed maleate and
inner-spherically adsorbed oxalate and citrate on the
colloidal stability of corundum particles in aqueous media
have been examined as a function of pH and maleate,
oxalate, and citrate concentrations using electrokinetic
and shear yield stress measurements. ζ potential data
indicate that outer-spherically adsorbed maleate possesses
a very limited ability to charge reverse the corundum
surface, or affect the electrokinetic properties of corundum
above the iep of the bare surface. By contrast, inner-
spherically adsorbed oxalate and (to a greater extent)
citrate are capable of significant charge reversal of the
corundum surface. With its very substantial chemical
binding component, inner-spherically adsorbed citrate is
also able to adsorb to the corundum surface and affects
its ζ potential properties at pH conditions well above the
iep of bare corundum.
Consistent with the corresponding iep properties, shear
yield stress measurements show that the position of τy,max
is systematically moved to lower pH as a function of
increasing maleate, oxalate, and citrate concentrations.
Except at the highest concentrations examined, the
Langmuir, Vol. 21, No. 14, 2005 6365
magnitude of τy,max is also reduced as the concentrations
of maleate, oxalate, and citrate are raised, a finding that
is attributable to the steric barriers to interparticle
approach produced by these adsorbed species. By contrast,
at the highest maleate, oxalate, and citrate concentrations
investigated, an increase in the magnitude of τy,max is
observed, and can be attributed to the formation of gel-
like Al(III)-organic precipitates that bridge between
adjacent particles, resulting in an additional interparticle
attraction. The extent of this increase in τy,max is greatest
for oxalate due to its strong dissolution-enhancing prop-
erties, which allow increased concentrations of dissolved
Al(III) to be made available to participate in precipitate
formation. The forms of the τy versus pH data observed
for the corundum-maleate, corundum-oxalate, and
corundum-citrate suspensions can also be rationalized
with reference to the relative binding strengths, electro-
kinetic behavior, and (at least to some extent) the differing
adsorption modes of the maleate, oxalate, and citrate
anions.
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