Colloids and Surfaces

A: Physicochemical and Engineering Aspects 180 (2001) 131 – 140

www.elsevier.nl/locate/colsurfa

Selective adsorption of dyes and other organic molecules to

kaolinite and oxide surfaces
Rodney G. Harris *, John D. Wells, Bruce B. Johnson
Colloid and En6ironmental Chemistry Laboratory, La Trobe Uni6ersity, P.O. Box 199, Bendigo, Vic. 3552, Australia

Received 10 April 2000; accepted 23 August 2000

Abstract

Adsorption of 23 organic molecules, including a number of polyaromatic dyes, from aqueous solution to kaolinite
and amorphous alumina was measured at pH 9. For 22 of the 23 solutes, adsorption was greater to kaolinite than
to alumina, and more than seven times as much was adsorbed to kaolinite for eight of the 23 adsorbates. Four dyes,
3,6-diaminoacridine, 9-aminoacridine, azure-A and safranin-O, were selected for further study, including an investiga-
tion of the effect of pH on adsorption, and measurement of adsorption to gibbsite (a-Al(OH)3) and silica at pH 9.
Strong preferential adsorption to kaolinite was observed over the whole pH range, and at pH 9 the dyes also adsorbed
much more to kaolinite than to gibbsite or silica. The basal spacing of kaolinite crystals, measured by X-ray
diffraction, did not change when 3,6-diaminoacridine was adsorbed, indicating that the dye molecules were not
intercalated between the crystalline layers. It is suggested that the negatively charged, flat silica faces of kaolinite
crystals may serve as templates for pi-stacking association of the positively-charged polyaromatic molecules. © 2001
Elsevier Science B.V. All rights reserved.

Keywords: Silica; Gibbsite; Alumina; Polyaromatic

1. Introduction industries [2]. Its presence in the soil, along with

The adsorptive properties of kaolinite and alu-
mina make them valuable materials both scientifi-
cally and commercially. Kaolinite has been
utilised in the removal of dyestuffs from waste
waters [1], to improve the surface quality of pa-
per, and in the ceramic, paint and pharmaceutical
* Corresponding author. Tel.: +61-3-54447222; fax: + 61-
3-54447476.
E-mail address: rharris@ironbark.bendigo.latrobe.edu.au
(R.G. Harris).
other aluminosilicates and oxides, is of ecological
importance as they are largely responsible for the
fate of agrochemicals and metal cations in soils
and ground water [3,4]. The bulk of the alumina
produced finds use in the manufacture of abra-
sives, ceramics and refractory materials as well as
the production of aluminium metal, and it is also
important as an adsorbent and a catalyst support
[5,6].
Apart from their obvious use as colouring
agents, dyes are often used to determine surface
area and cation exchange capacity of oxides and

0927-7757/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 0 ) 0 0 7 4 7 - 0
132 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140
clays [7–9]. Other organic molecules have also
been used for these purposes [10], but the ease of
determining dye concentrations via spectrophoto-
metry makes their use more common.
Factors affecting the adsorption of organic
molecules to minerals include pH [11], tempera-
ture [12,13], the ionic strength of the suspension
[14], the structure and concentration of the ad-
sorbing molecule [4,11,13,15,16] and the structure
of the mineral [11,17,18].
Kaolinite is a 1:1 aluminosilicate consisting of
stacked pairs of tetrahedral silica sheets and octa-
hedral alumina sheets [19,20]. Each pair of sheets
is bound together through common oxygen
atoms, and successive pairs are held together by
hydrogen bonding between SiO and AlOH
groups. The resulting crystal has a silica face of
SiO2 tetrahedra, an alumina face carrying AlOH
groups, and edges which carry both SiOH and
AlOH sites. Under normal conditions kaolinite
does not swell because of the strong hydrogen
bonding between the 1:1 pairs [19,20]. Iso-
morphous substitution of Al3 + for Si4 + in the
silica layer leaves that face with a small perma-
nent negative charge, while the charge on the
alumina face and on the edges is pH-dependent.
The point of zero charge (pzc) of kaolinite is
approximately 4 – 4.7 [21,22]. The edge is consid-
ered to have a pzc of 6 – 7 [21] but this quantity is
difficult to determine accurately.
Alumina exists in a number of crystalline
forms, including cubic (g-Al2O3), monoclinic
(gibbsite, g-Al(OH)3), orthorhombic (diaspore, a-
AlO(OH) and boehmite, g-AlO(OH)) and rhom-
bohedral (corundum, a-Al2O3) [23]. Chemical
species
1
present at
1
the hydrated surface may be
+ −
OH2 or OH2 depending on the pH. Most
forms of alumina have a pzc of about 6.6–9.4
[24], but Hiemstra et al. [25] reported values as
high as 11, with 9.8 – 10 for gibbsite.
Silica has the general composition SiO2 and
consists of polymerised silicon tetrahedra (SiO44 − )
with a pzc of about 2 [26], although it has been
reported as high as 3.7 [24].
Many studies have been carried out on the
adsorption of dyes to kaolinite [1,2,8,12,13,27,28],
alumina [9,29], and other minerals
[4,7,9,15,16,30,31]. Ramiraj et al. [32] reported
that 3,6-diaminoacridine adsorbed more strongly
to kaolinite than to alumina, but few have com-
mented on differences in the specific adsorption to
diverse adsorbents.
The present study investigated the adsorption
of 23 aromatic adsorbates onto two adsorbents,
kaolinite and amorphous alumina, and then fur-
ther examined the adsorption of four of these
adsorbates onto two more adsorbents, gibbsite
and amorphous silica, in an attempt to gain a
better understanding of the adsorption processes.
A preliminary account has been published else-
where [33].
2. Experimental
2.1. Reagents
Milli-Q® reagent grade water (Millipore, Bed-
ford, USA) was used throughout. Dyes and other
organic adsorbates were of the highest grade
available; their structures are given in Fig. 1. All
other reagents were of analytical reagent grade
(AR). Adsorbate solutions were stored in borosili-
cate glass vessels.
2.2. Adsorbents
Table 1 gives details of the kaolinite, alumina,
gibbsite and silica adsorbents which were used in
this study without further treatment. Hysteresis in
the BET adsorption isotherm, determined with a
Micromeritics AP2000 instrument after out-
gassing at room temperature for 16 h, suggested
some porosity in the QAL alumina sample.
Adsorbents were characterised by X-ray diffrac-
tion and scanning electron microscopy. X-Ray
diffractograms were collected with a Philips
PW1710 X-ray diffractometer fitted with a copper
target. A 3.00-g aliquot of mineral sample and
2.00 g KNO3 were ground together in a mortar
and pestle, and the mixture was compressed to
form a disc for analysis. Scanning electron micro-
graphs of gold/palladium-coated adsorbent parti-
cles were recorded with a Cambridge S150
Scanning Electron Microscope.
 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140 133

2.3. Adsorption experiments
Glass reaction and storage vessels were soaked
overnight in 1:1 nitric acid and rinsed thoroughly
with Milli-Q water. Where necessary, mechanical
cleaning was used before acid washing. Orion
Ross Sure-Flow double junction combined pH
electrodes were calibrated with NBS standard
buffers (pH 4.01, 6.86 and 9.18).
Two series of experiments were performed. The
first set were batch experiments to determine the
relative amounts of organic solutes adsorbed to
the chosen adsorbents. These were carried out for
the 23 adsorbates onto kaolinite and alumina, and
also on gibbsite and silica for four chosen adsor-
bates. Kaolinite (82 m2 l − 1), alumina (150 m2
l − 1), gibbsite (1.4 m2 l − 1) or silica (173 m2 l − 1)
were suspended in a solution containing 1.0 mM
adsorbate and 10 mM KNO3, and the pH ad-
justed to 9. The tubes were capped, mixed vigor-
ously at hourly intervals for 5 h, left to stand
overnight, and then mixed again. Approximately
1 h after the final mixing each suspension was
centrifuged, and both the supernatant and the
original 1.0 mM adsorbate solution were diluted
with buffer (pH 9.18) to give absorbance values

Fig. 1. Structures of the organic adsorbates.

134 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140
Table 1
Adsorbents used in adsorption studies
Mineral Supplier BET surface area
(m2 g−1)
Acid washed Ajax Chemicals, 14.73 9 0.06
kaolinite Sydney
QAL aluminaa CRLb 67.690.1
Alcoa C.31 CRLb 0.3239 0.013
gibbsite
Precipitated LabChem 155 9 1
silica
a
QAL alumina is a Bayer precipitated alumina.
b
Comalco Research Laboratories (Melbourne, Australia).
less than 1.0. The absorbances of the solutions
were measured with a Varian DMS-80 UV-Visible
spectrophotometer at the wavelengths given in
Table 2.
The second set of experiments investigated the
effect of pH on the adsorption of selected dyes on
both kaolinite and alumina. Suspensions contain-
ing either kaolinite (10 m2 l − 1), or alumina (41 m2
l − 1) in 135 ml of 10 mM KNO3 were equilibrated
for 16 h. HNO3 (1 M) was added to the alumina
suspensions to lower the pH to approximately 4.5;
no pH adjustment was needed for the kaolinite
suspensions as the natural pH of these suspen-
sions was about 4.5.
Sufficient adsorbate stock solution was added
to the suspension to give a total adsorbate con-
centration of 0.1 mM, and the suspension was
allowed to equilibrate for 30 min. A sample was
taken and centrifuged, and the pH of the remain-
ing suspension was then raised by approximately
0.5 by the addition of KOH. The suspension was
allowed to re-equilibrate for 15 – 20 min before a
further sample was taken. This process was re-
peated until the pH of the suspension was greater
than 12.
After the samples were centrifuged, the super-
natants were diluted at least 1:2 with pH 9.18
NBS buffer and the solute concentrations esti-
mated spectrophotometrically. The amount of dye
adsorbed was estimated from the ratio of the
absorbance of the supernatant to that of the 1.0
mM adsorbate solution. Separate calibration
curves showed that Beer’s Law was obeyed by the
adsorbates under the conditions used in this
study.
3. Results
3.1. Adsorbents
X-Ray diffraction patterns of the mineral sam-
ples were compared with JCPDS reference files
[34]. The QAL alumina was almost entirely amor-
phous, with a small amount of corundum evident,
but Alcoa C.31 gibbsite and Ajax kaolinite were
both highly crystalline, giving diffractograms typi-
cal for these minerals. The diffractogram for the
silica sample showed no evidence of crystallinity.
The basal (d(001)) spacing of the kaolinite was
7.17 A, . The same spacing was observed for a
kaolinite sample to which 3,6-diaminoacridine
was adsorbed at a loading of 1.1 mmol m − 2.
Scanning electron micrographs of the kaolinite
sample revealed typical hexagonal plate-like
kaolinite crystals of roughly uniform size and
shape, approximately 1.5–2 mm across and about
0.2 mm thick. The gibbsite crystals were also
uniform in size and shape, being approximately
cubic with edges about 8 mm long. The silica
particles were roughly spherical with a diameter
of about 2 mm, and the particles of QAL alumina
were irregular in shape, with most particles about
1 mm across.
3.2. Batch adsorption experiments
A series of batch experiments was conducted to
assess the relative adsorption of 23 organic solutes
to alumina and kaolinite. These experiments were
conducted at pH 9, chosen on the basis of prelim-
inary results for the variation of adsorption with
pH.
The results of the batch experiments are shown
in Fig. 2 and Table 2 as amount of solute ad-
sorbed per unit surface area. With the exception
of 3-aminoquinoline, all of the solutes adsorbed
more to kaolinite than to alumina. Eight of them
showed substantial selectivity, with at least seven
times as much adsorbing to kaolinite as to alu-
mina. For five adsorbates (3,6-diaminoacridine,
 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140 135

9-aminoacridine, azure-A, safranin-O and fluores-
cein) the adsorption to kaolinite was about 20
times the amount adsorbed to alumina. Fluores-
cein was not used for further study because it
adsorbed much less to both adsorbates than did
the other four molecules.
Fig. 3 and Table 3 compare the adsorption of
the four selected dyes from aqueous solution to
kaolinite, QAL alumina, gibbsite and silica at pH
9 by the batch method. Adsorption to gibbsite
and silica was of similar magnitude for all four
dyes but the amount adsorbed to QAL alumina
was approximately half of that found for silica
and gibbsite. The quantity adsorbed to kaolinite
was 6–20 times greater than that for any of the
oxides.
The adsorption of some dyes to kaolinite was
so great that the supernatant solutions were al-
most colourless, and in some cases the colour of
the adsorbed dye was distinctly different from
that of the original solution. In particular aqueous
azure-A solutions were blue, but azure-A ad-
sorbed to kaolinite was purple.
3.3. pH dependence of adsorption
Adsorption of the selected adsorbates onto
kaolinite and alumina was measured as a function
of pH. The data in Fig. 4 show that adsorption
was only slightly pH-dependent, and the selectiv-
ity for adsorption to kaolinite over alumina per-
sisted over the whole pH range investigated. Only

Table 2
Adsorbate removed from solution by QAL alumina and kaolinite, pKa of adsorbate and wavelength used for spectrophotometry

Adsorbate Quantity adsorbed (mmol m−2) pKa l (nm)

Kaolinite QAL Alumina

Tropaeolin-O 10.8 5.29 436

Safranin-O 10.4 0.55 11.0a 518
Ethidium bromide 10.4 3.67 476
Neutral red 10.1 3.37 454
Azure-A 8.80 0.45 10.6a 622
3,6-Diamino acridine 7.18 0.34 9.5a, 9.65b, 9.7f 443
Methylene blue 7.01 0.88 \12f 664
Acridine 6.42 0.88 5.6c,d, 5.58d 388
Alizarin 6.27 3.78 453
Eosin yellowish 5.77 3.27 514
9-Amino acridine 4.85 0.02 9.9a, 9.99b,e, 10.0f 400
Crystal violet 4.27 0.31 589
Malachite green 2.94 1.82 615
8-Amino quinoline 2.18 0.35 4.0d,f 245
Quinoline 2.07 0.35 4.9c,f, 4.90d 276
Alizarin red S 1.70 1.25 450
Pyridine 1.34 0.69 5.3c, 5.22d, 5.19d, 5.2f 256
Fluorescein 0.91 0.00 490
Cresol red 0.86 0.48 572
Remazol brilliant blue-R 0.72 0.22 587
Indole 0.33 0.20 269
Aniline 0.25 0.14 4.6c, 4.606d, 4.60d, 4.6f 279
3-Amino quinoline 0 0.59 4.9c, 5.0f 374

a
R.G. Harris, unpublished data.
b
[38].
c
[39].
d
[40].
e
[41].
f
[42].
136 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140
Fig. 2. The amount of organic solute adsorbed to kaolinite (82
m2 l − 1) and alumina (150 m2 l − 1) at pH 9.2. Solute concen-
tration 0.001 M, background electrolyte 0.01 M KNO3. (‘Et
bromide’, ethidium bromide; ‘3,6-DAA’, 3,6-diaminoacridine;
‘meth blue’, methylene blue; ‘eosin y’, eosin yellowish; ‘9-AA’,
9-aminoacridine; ‘crystal v’, crystal violet; ‘malachite’, mala-
chite green; ‘8-aminoquin’, 8-aminoquinoline; ‘alizarin r S’,
alizarin red S; ‘rbb-R’, remazol brilliant blue R; ‘3-aminoquin’,
3-aminoquinoline).
one set of results for adsorption on alumina is
shown: the data for the other three solutes were
very similar and overlie these results. Adsorption
to kaolinite generally increased by 10 – 20% as pH
was increased from 4 to 10. However, above pH
10 the adsorption of azure-A continued to in-
crease while that of 9-aminoacridine decreased
dramatically.
4. Discussion
The large differences in the amounts of dye
adsorbed to kaolinite and to the oxides dictated
the use of unequal mineral surface areas for the
batch experiments. If equal surface areas were
used, either the amount of dye adsorbed by
kaolinite reduced the absorbance of the superna-
tant almost to zero, making quantification
difficult, or the oxides adsorbed so little dye that
the difference in absorbance of the supernatant
before and after adsorption was difficult to mea-
sure reliably.
Kaolinite and one of the oxides (gibbsite) were
crystalline, but the other oxides were amorphous.
The nitrogen adsorption data for QAL alumina
suggested that this amorphous adsorbent was
somewhat porous. Some of the pores accessible to
nitrogen molecules may have been too small to
admit the much larger dye molecules, and thus the
effective surface area available for dye adsorption
may have been overestimated. This would result
in an underestimation of the adsorption of dyes
(expressed as the amount adsorbed per unit sur-
face area), but it could not account for the great
difference between the adsorption of the dyes to
kaolinite and QAL alumina. Furthermore Fig. 3
shows that the dyes also adsorbed much less to
the crystalline alumina (gibbsite), the surface area
of which is well defined, than to kaolinite.
Fig. 3. Adsorption of organic solutes to four minerals. Condi-
tions as for Fig. 2: Surface areas of gibbsite (1.4 m2 l − 1) and
silica (173 m2 l − 1).
 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140 137

Table 3
Adsorption of dyes by four adsorbents

Adsorbate Quantity adsorbed (mmol m−2)

QAL Alumina Kaolinite Gibbsite Silica

Safranin-O 0.55 10.45 1.40 1.40

Azure-A 0.45 8.80 0.90 0.88
3,6-Diamino acridine 0.34 7.18 0.70 1.15
9-Amino acridine 0.02 4.85 0.80 0.40

The degree of specificity of the dyes 9- change, and therefore that intercalation did not
aminoacridine, 3,6-diaminoacridine, azure-A and occur.
safranin-O for kaolinite over the three oxides was The surfaces of the oxides carry ionisable hy-
remarkable. The dyes adsorbed preferentially to droxyl groups, which may be protonated or depro-
kaolinite over a wide pH range, in which the tonated according to pH. The edges of kaolinite
protonation of the surfaces (pzc ca. 9–10 for are believed to be chemically similar to the oxides,
alumina and gibbsite, 4 for kaolinite, 6 – 7 for the and may therefore be expected to interact with dye
kaolinite edge and 2 – 3 for silica), and of the dyes molecules in a similar way. On the other hand the
(pKa 9.5 for 3,6-diaminoacridine, 9.9 for 9- silica faces of kaolinite crystals are quite different;
aminoacridine, 10.6 for azure-A and 11.0 for they are large flat areas, characterised by SiOSi
safranin-O) varies significantly. structures, and carry a relatively small but perma-
These dyes comprise three conjugated aromatic nent negative charge, as a result of isomorphous
rings, making them quite rigid, flat and relatively substitution of Al(III) for Si(IV).
hydrophobic molecules. Molecules such as 3- and
8-aminoquinoline have structures very similar to
that of 9-aminoacridine, except they have only two
conjugated rings, making them less hydrophobic.
They adsorb to kaolin much less than 9-
aminoacridine does, suggesting the possibility that
the hydrophobic nature of the adsorbates was
important in the adsorption process. We return to
this point later on.

4.1. Unique features of kaolinite

The layered structure of kaolinite is quite differ-

ent from that of the oxides. Ramiraj et al. [32]
assumed that the greater adsorption of 3,6-di-
aminoacridine to kaolinite than to alumina was
the result of intercalation of dye molecules into the
clay. However, kaolinite is not a swelling clay, and
although intercalation of some molecules (e.g.
urea and DMSO) has been reported [35], it is
unusual. Intercalation of dye molecules between
Fig. 4. Adsorption of four dyes to kaolinite (open symbols)
the crystalline sheets would cause the basal spac- and alumina (solid circles) at room temperature. Dye concen-
ing to increase, but the X-ray diffraction results tration 100 mM, background electrolyte 0.01 M KNO3, surface
showed clearly that the basal spacing did not areas: kaolinite 10 m2 l − 1, alumina 50 m2 l − 1.
138 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140
4.2. Adsorption sur6ey at pH 9.2
Except for tropaeolin-O, which adsorbed
strongly to both kaolinite and QAL alumina, the
first seven compounds in Fig. 2 have conjugated
aromatic ring systems, and are positively charged
at pH 9. The same is true of 9-aminoacridine and
crystal violet, both of which showed a strong
preference for adsorption to kaolinite. Com-
pounds which are uncharged or negatively
charged at pH 9 exhibited a much lower prefer-
ence for kaolinite surfaces.
It is likely that compounds which adsorb
strongly to both alumina and kaolinite do so at
the variable charge surfaces (i.e. they adsorb at
the edges of the kaolinite crystals), but the posi-
tively-charged aromatic compounds that adsorb
preferentially to kaolinite probably do so mainly
at the flat silica faces.
A common test used to determine whether ad-
sorption is due largely to electrostatic interactions
is to study adsorption at relatively high ionic
strength. Adsorbates held by electrostatic forces
tend to be displaced at high ionic strengths (i.e.
adsorption is reduced). Unfortunately the dyes
used in this investigation have very limited solu-
bility at high ionic strength, so the effect of in-
creasing ionic concentration could not be studied
in this case.
4.3. pH dependence of adsorption
It is clear from Fig. 4 that the strong preference
of the four dyes for the kaolinite surface persists
over a wide pH range, from conditions under
which the variable charge surfaces are positively
charged (up to about pH 6 or 7 for the edges of
the kaolinite crystals and up to about pH 9 for
alumina) to conditions under which they are nega-
tively charged. This observation reinforces the
notion that specificity for kaolinite is largely asso-
ciated with adsorption to the silica faces, pre-
sumably by hydrophobic or electrostatic forces.
Fig. 4 shows that adsorption of four dyes to
kaolinite was not strongly affected by pH, at least
in the range 4 – 10. Deprotonation of the dye
molecules at pH values above the pKa (e.g. 9.5 for
3,6-diaminoacridine, 9.9 for 9-aminoacridine, 10.6
for azure-A and 11.0 for safranin-O) will remove
the positive charge on the molecules, and may
account for the decrease in adsorption for 9-
aminoacridine above pH 10. However there was
no such decrease in adsorption for 3,6-di-
aminoacridine, while adsorption increased for
azure-A, possibly due to continuing positive
charge on the ternary amine.
4.4. Extent of surface co6erage
It is useful to estimate the extent to which the
kaolinite surface was covered by dye molecules.
The dimensions of 3,6-diaminoacridine are 12.6×
4.8×3.6 A, . For a monolayer of molecules lying
flat on a surface the adsorption density will be
about 2.8 mmol m − 2, but if the molecules were
stacked perpendicular to the surface the maxi-
mum adsorption density would be 3.7 mmol m − 2
if the long edges were against the surface or 9.6
mmol m − 2 if the short edges were against the
surface. The adsorption measured in our experi-
ments (4.9 mmol m − 2 for 9-aminoacridine, 7.2
mmol m − 2 for 3,6-diaminoacridine, 8.8 mmol m − 2
for azure-A and 10.5 mmol m − 2 for safranin-O)
was much higher than that estimated for flat
adsorption and similar to or greater than that
estimated for molecules stacked on the short
edges.
The experimental adsorption densities assume
that the whole of the surface is available for
adsorption. If, as we have suggested, dye adsorp-
tion is restricted to the flat silica faces of kaolinite,
the adsorption density on these faces must be
much greater, which suggests that multilayer ad-
sorption may occur.
In a study of the adsorption of safranin-O to
hydrophilic and hydrophobic (silanized) glass
powders, Atun and co-workers [36] found that the
maximum adsorption density on the hydrophilic
surface was three times that on the hydrophobic
surface, but at very low concentrations more dye
adsorbed to the hydrophobic surface. Quantita-
tive comparison of their data with ours is not
possible because the surface areas of the glass
powders were not reported.
It is known [37] that aminoacridines, and in
particular 9-aminoacridine and 3,6-di-
 R.G. Harris et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 180 (2001) 131–140
aminoacridine, form association complexes in the
presence of polyanions. Apparently, stacking of
the positively-charged flat aromatic rings of the
dye molecules is promoted by the presence of a
linear array of negative charges on a polyanion. It
is possible that the flat, negatively charged silica
face of kaolinite crystals can also act as templates
for the association of positively-charged polyaro-
matic dye molecules. Such a mechanism is consis-
tent with our observation that the molecules
which showed the highest preference for kaolinite
were those that had hydrophobic character and
were negatively charged.
Further to this point, azure-A underwent a
clearly visible colour change (from blue to purple)
on adsorption to kaolinite from aqueous solution.
It seems likely that this was due to either a
chemical change in the dye on adsorption, or the
formation of dye aggregates on the adsorbate
surface, or possibly a combination of the two.
Azure-A is purple in non-aqueous solutions, so
the colour change associated with the adsorption
of azure-A onto kaolinite indicates that the
kaolinite surface can act as a non-polar adsor-
bent, which may promote aggregation of the dye
molecules resulting in a change in the absorption
spectrum.
The use of dye adsorption to measure the sur-
face areas of mineral samples [7,9] assumes that
the dye used adsorbs equally well to all mineral
surfaces. Our data show that this is not the case.
The use of these methods can be justified only if
the adsorption characteristics of the particular dye
have been predetermined for each mineral to be
studied. Results obtained from mixed mineral
samples (including soils) are unlikely to be
reliable.
5. Conclusion
All but one of the 23 organic solutes studied
adsorbed more to kaolinite than to amorphous
alumina, and for five solutes the adsorption to
kaolinite was about 20 times greater than to alu-
mina. For the four dyes studied more extensively,
preferential adsorption to kaolinite persisted over
the pH range from 4 to 12, and their adsorption
139
to kaolinite was also much greater than that to
crystalline alumina (gibbsite) or to silica.
The strongest preference for kaolinite was
shown by polyaromatic molecules carrying amino
groups. Such solutes can associate by pi-stacking,
and could also interact with the permanent nega-
tive charges on the flat silica faces of the kaolinite
crystals. The extent of adsorption of the solutes to
the edges of kaolinite crystals is probably much
the same as that to the oxides, because the kaolin-
ite edges are structurally similar to the oxide
surfaces.
The fact that the basal spacing of the kaolinite
layers did not change on the adsorption of 3,6-di-
aminoacridine shows that the dye did not interca-
late into the clay crystals. It is therefore likely that
preferential adsorption of the polyaromatic dye
molecules to kaolinite occurs at the silica faces of
the crystals, which may act as templates for pi-
stacking association of the dye molecules.
The results in this paper show that the use of
dye adsorption to measure the surface areas or
cation exchange capacities of single or mixed min-
eral samples, including soils, is likely to yield
unreliable results, since the extent of adsorption is
critically dependent on the particular adsorbent–
adsorbate system.
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