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July 16, 2007 17:42 00951

Surface Review and Letters, Vol. 14, No. 3 (2007) 461469

c World Scientic Publishing Company




Department of Chemistry, University of Karachi, Karachi 75270, Pakistan

Fuel Research Centre, PCSIR Karachi, Karachi 75280, Pakistan
Received 7 February 2007
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Although particle size and its measurement are intuitively familiar to particle technologists, the
concept of point of zero charge (pzc) is less widely understood and applied. This is unfortunate
since it is at least as fundamentally important as particle size in determining the behavior of
particulate materials, especially those with sizes in the colloidal range below a micrometer. pzc
is related to the charge on the surface of the particle and strongly depends on the pH of the
material; so it inuences a wide range of properties of colloidal materials, such as their stability,
interaction with electrolytes, suspension rheology, and ion exchange capacity.
The pH dependence of surface charges was quantied for four dierent adsorbentaqueous
solution interfaces. The points of zero charge were determined for activated charcoal, gran-
ite sand, lakhra coal, and ground corn cob materials using three methods: (1) the pH drift
method, measuring pH where the adsorbent behaves as a neutral specie; (2) potentiometric
titration, measuring the adsorption of H+ and OH on surfaces in solutions of varying ionic
strengths; (3) direct assessment of the surface charge via nonspecic ion adsorption as a func-
s s
tion of pH. The intrinsic acidity constants for acid and base equilibria, pKa1 and pKa2 , were
also calculated. Lakhra coal was found to have the lowest pzc value among all other adsorbents
studied owing to the presence of a large amount of humus material. The results were used to
explain general connections among points of zero charges, cation exchange capacity, and base
saturation % of adsorbents.

Keywords: Points of zero charge; adsorbent; cationic exchange capacity; surface charge density;
solidliquid interface.

1. Introduction The surface charge development process is char-

acterized by an important interfacial parameter,
When adsorbents are suspended in an aqueous elec-
commonly known as point of zero charge (pzc). The
trolyte solution, surface electrical charge develops
concept of pzc was born during the studies of the oc-
from the dissociation of the surface hydroxyl groups
culation of hydrophobic colloids.2 In the rst remark-
and complexation of the background electrolyte ions. able series of papers published in Croatica Chemica
H+ and OH are considered to be the potential- Acta, Stumm et al.3 invoked the pzc to express the
determining ions.1 Thus, depending on pH of the acidbase reactions of hydroxyl groups on the surface
solution and concentration of the electrolyte, these of oxide minerals. Nearly 30 years after their pioneer
surfaces can behave as cation exchangers having net work, the prediction of the surface charge properties
negative charge, or anion exchangers bearing positive of amphoteric adsorbents through chemical models of
charge or neutral species having no charge. the particlewater interface has become a hot topic

July 16, 2007 17:42 00951

462 M. Nasiruddin Khan & A. Sarwar

in aqueous environmental chemistry.48 Although where IS and OS are the surface densities of
Sposito9 and Appel et al.10 clearly explained the rig- the inner-sphere and outer-sphere complex charges,
orous proofs of generic properties of surface charge, respectively, and equal to the net total surface charge
on the basis of results they established and used gen- of the ions, other than H+ or OH , that have formed
eral connections among several points of zero charge inner-sphere and outer-sphere complexes with the
(PZCs) such as point of zero salt eect (pzse), point surface functional groups. If P is nonzero (the par-
of zero net proton charge (pznpc), point of zero net ticle posseses charge), it must be balanced by the
charge (pznc), and conventional point of zero charge charge of ions adsorbed in the diuse layer D .
(pzc). Mostly, authors used pzc as a general term
P = D ,
for all types of PZCs.11,12 Lyklema postulates that
only protons contribute to the surface charge and or
hence pzc and pznpc are identical.13 In addition, sev- P + D = 0, (2)
eral workers reported points of zero charge as a tool so
for the determination of chemical properties of soil
0 + H + IS + OS + D = 0. (3)
samples and mineral oxides or hydroxides by apply-
Surf. Rev. Lett. 2007.14:461-469. Downloaded from

ing geochemistry principles.1419 Despite the impor- The surface charge balance requires that the intrinsic
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tance of charge properties to sorption of ionic and charge of the soil particles, in , including that result-
neutral solutes for the above-mentioned materials, ing from both isomorphic substitutions (permanent
PZCs have not been investigated for other adsor- charge, 0 ) and proton adsorption (variable charge,
bents in detail. The present paper is an attempt to H ) must be balanced by the adsorption from the
describe the properties of adsorbents based on the solution of the background cation and anion.20
concept of surface charge balance. A thorough under-
in = 0 + H = q. (4)
standing of points of zero charge enables researchers
to select adsorbents for their specic applications. The net charge of ions, q, adsorbed into surface
complexes and the diuse ion swarm is given by
2. Experimental q = (q + q ) = IS + OS + D , (5)
2.1. Background where q + and q refer to the adsorbed cation and
In solution, the presence of a net charge on a particle anion charge, respectively, on the porous surface. The
aects the distribution of ions surrounding it, result- presence of the porous surface into the colloidal par-
ing in an increase in the concentration of counterions. ticles signicantly alters the specic surface area of
The region over which this inuence extends is called the solid phase. However, the extent to which the
the electrical double layer. Conventionally, this layer chemical reactivity (e.g., surface acidity, ion anity)
is thought of as existing as two separate regions: an is aected is not known for most of the adsorbents.
inner region of strongly bound ions known as the In the present work, the adsorbents of dissimilar
stern layer and an outer region of loosely associated surfaces were used to measure their surface charge
ions called the diuse layer. properties in an aqueous electrolyte solution. The
The surface charge on a particle is classied into objective is to assess the extent to which the surface
three operational categories: (i) structural, denoted of the porous adsorbent aects the particle surface
by 0 ; (ii) adsorbed proton, denoted by H ; and (iii) charge and the background ion adsorption.
adsorbed ion, denoted by q + q q, where
q + and q refer to the adsorbed cation and anion, 2.2. Materials and method
respectively, excluding H+ and OH bound in sur-
Analytical-grade reagents were used without further
face complexes.20
purication. Deionized water was used throughout
A net total particle surface charge, P (in units
the work. All the solutions were prepared in Pyrex
of moles of charge per kilogram of solid, molc kg1 ),
glass vessels and stored at 4 C. An Orion 710 pH
is the sum of four components9 :
meter with a combined glass electrode and AAS (PE-
P 0 + H + IS + OS , (1) 3030 B) were used for potentiometric studies and
July 16, 2007 17:42 00951

Determination of Points of Zero Charge of Natural and Treated Adsorbents 463

metal ion determination, respectively. The estima- determine the pzse values for all adsorbents. Two
tion of Cl in the sample solutions was made using parallel experiments were conducted, each with air-
a chloride ion selective electrode on Auto Chem- dried adsorbent material (1 g) with 35 ml of 0.0001
istry 900 (Orion). The electrode was calibrated at 1.00 M NaCl as supporting electrolyte solution. One
the same ionic strength as the experiment. A Volac suspension was titrated with an acid (0.05 M HCl)
ULTRA micropipette (1001000 L), model R680/E, and the other with a base (0.05 M NaOH). The cip
was used for acid base addition. All experiments for was determined by plotting curves between the vol-
charge determination were carried out under ambi- ume of the acid and the base added against the pH of
ent laboratory conditions (temperature = 25 2 C). the solution at dierent ionic strengths. The pH value
The pH dependent surface charge was determined at the cip was taken as the pzse. It is the pH value
by potentiometric acid base titration under a CO2 at which surface positive and negative charges associ-
free atmosphere. Before the titration, the suspen- ated with protonation/deprotonation equilibria just
sions containing adsorbents were stirred and bubbled balanced in the presence of nonreactive electrolyte.
with puried nitrogen for an hour. The other two additional points of zero charge
Four dierent adsorbents were selected for the that have to commence are pznpc and pznc.
Surf. Rev. Lett. 2007.14:461-469. Downloaded from

present work: (i) granite sand, (ii) activated char- The pznpc is the pH value where H equals zero.
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coal (Merck), (iii) lakhra coal; a famous coal mine in The balance of net surface charge (Eq. (3)) can be
Pakistan; and (iv) ground corn cob. expressed by
According to the standard denitions of points
of zero charge listed in Table 1, pzc is traditionally o + IS + OS + D = 0. (6)
dened as the pH value where one or more compo-
Therefore, by Eq. (4), it is the pH value where q
nents of the surface charge vanishes (D = 0) at a
equals o . The Stumm model23 is the most straight-
specied temperature, pressure, and aqueous solu-
forward method to determine the pznpc by measur-
tion composition.9 The pzc was determined by the
ing q as a function of pH and then locating the
pH drift method, recently used for the determina-
pH value at which q = 0 . This model marks out
tion of the pzc of the wheat-residue-derived black
the presence of surface charges on solids, which are
carbon.21 The pH of the 0.01 M NaCl was adjusted
the result from the acidbase reaction. Thus, consid-
to a value between 2 and 10 using 0.5 M HCl or 0.5 M
ering solids as containing functional surface groups
NaOH. An adsorbent (0.5 g) was added to 20 ml of
expressed as a generic binding site, SOH,
the pH adjusted solution in a capped vial and equi-
librated for 24 h. The nal pH was measured and SOH  SO + H+ (7)
plotted against the initial pH. The pH at which the
curve crosses the pHinitial = pHfinal line was taken as SOH+
2  SOH + H
the pzc.
The point of zero salt eect (pzse) is the com- the corresponding acidity constants are
mon intersection point (cip) of several H versus pH [H+ ]{ SO }
curves, each determined at xed ionic strength of the Ka1 = , (9)
{ SOH}
electrolyte background.9 The potentiometric titra-
tion method of Vanloon and Duy22 was used to s [H+ ]{ SOH}
Ka2 = , (10)
{ SOH+ 2}

where [ ] is the solution species concentration in mol

Table 1. Denitions of some points of zero charge.
L1 and { } is the solid surface species concentra-
Symbol Name Dening equation tion in mol g1 . Considering the solid surface elec-
troneutrality and the denition of pznpc in Table 1
pzc Point of zero charge D = 0
(H = 0), another relation is obtain from Eqs. (9)
pznpc Point of zero net H = 0
proton charge and (10)
pzse Point of zero salt eect (H /I)T = 0 s s
pKa1 + pKa2
pznc Point of zero net charge in = 0 pznpc = . (11)
July 16, 2007 17:42 00951

464 M. Nasiruddin Khan & A. Sarwar

The surface charge of a solid, q in units mol g1 , acidity constants were obtained by taking intercept
corresponds to of the plot showing the following relation11 :

q = {SOH+ pKas = pKa(int)

+ q. (19)
2 } {SO }. (12)
The values of the pznpc for dierent adsorbents were
For each point of the titration,
calculated according to Eq. (11).
Ca Cb + [OH ] [H+ ] The pznc is the pH when the nonspecic surface
qH qOH = , (13)
m adsorption of anions and cations is equivalent. Posi-
tive and negative charges were estimated by the mea-
where Ca and Cb are the concentrations (mol L1 )
surement of Na+ and Cl as a function of pH and
of the added acid and base, respectively, [H+ ] and
ionic strength (I). The method of Marcano-Martinez
[OH ] are the molar proton and hydroxide ion con-
and McBride25 modied by Appel10 was used. Air-
centrations, and m is the mass of the solid in g.
dried samples of 2.0 g were placed in pre-weighed
For HCl or NaOH addition, qH and qOH can be
30 ml polyethylene centrifuge tubes to which 20.0 ml
expressed as
of 1.0 M NaCl was added. The samples were shaken
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Ca [H+ ] for 1.0 h and centrifuged, with the supernatant being

qH = , (14)
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m discarded. A 0.5 M NaCl soluction (20 ml) was then

[OH ] Cb added to the tubes, with the sample pH being
qOH = . (15) adjusted with HCl or NaOH to span the expected
points of zero net charge. This was followed by 1.0 h
Since the solid is considered an amphoteric com-
of shaking, centrifugation, and supernatant removal.
pound, the total concentration of surface species,
The 0.5 M NaCl wash and pH adjustments were per-
{S}tot , corresponds to
formed two more times, with shaking times of 1.0 h.
{S}tot = { SOH} + { SO } + { SOH+
2 }. (16) The rigorous washing procedure was carried out to
ensure exchange sites were saturated with Na+ and
Surface acidity constants were calculated as follows: Cl . Five washes were then performed with 20 ml
When pH > pzc, the solution in contact with the of 0.01, and 0.001 M NaCl, with pH readjustment
basal oxygen surface contains excess hydroxyls. SO and shaking for 1.0 h between each washing. This was
species will dominate the surface, and the particle done to determine the eect of varying ionic strength
surface will then exhibit cation exchange capacity; on retention of ions. After the nal washing, equi-
so qOH = { SO } and Eq. (9) becomes librium pH of the supernatant was measured. The
supernatants were discarded and samples weighed to
s qOH [H+ ]
Ka1 = , (17) compensate for any entrained NaCl solution. Sam-
{S}tot qOH
ples were then washed with 20 ml aliquots of 0.5 M
but if pH < pzc, the solution in contact with the NH4 NO3 to displace Na+ and Cl ions. Extracts
basal oxygen surface contains excess protons. SOH+
2 were combined and ltered and stored in a refrigera-
species will dominate the surface, and the particle tor prior to analysis. Concentrations of Na+ and Cl
surface will then exhibit an anion exchange capac- were measured by AAS and ion meter, respectively.
ity; so qH = { SOH+ 2 } and Eq. (10) becomes The values of the pznc at dierent ionic strengths
were obtained from the adsorbed cation or anion (qNa
s ({S}tot qH )[H+ ]
Ka2 = . (18) or qCl ) vs. the pH curve.
The cation exchange capacity and base satura-
The value of {S}tot represents the total concentra- tion % were calculated using the standard method22
tion of the protonable surface sites, but in practice involving extraction by aqueous ammonium chloride
is often an adjustable parameter. Here, and follow- at a concentration of 1.0 mol/l with pH adjusted to
ing the previous observations, it is taken as equal 4.5. The adsorbent (1.0 g) was extracted with 100 ml
to cation exchange capacity (CEC), a very useful of ammonium chloride solution in order to displace
approximation.24 Successive pKas corresponding to the exchange cations from the adsorbent. After l-
each qvalue were calculated and plotted. Intrinsic tering, the principal cations calcium, magnesium,
July 16, 2007 17:42 00951

Determination of Points of Zero Charge of Natural and Treated Adsorbents 465

potassium, and sodium were determined by ame 12

atomic absorption spectroscopy. The hydronium ion
was determined by titration against standard sodium
hydroxide. The CEC was calculated by taking sum
of all individual cations in cmol(+) kg1 .

Final pH
The percent base saturation oers the percent- 6
age of the exchangeable sites occupied by the basic
cations. The base saturation % was calculated using 4
the following formula:

Base saturation 0
number of exchange sites occupied 0 2 4 6 8 10 12
by all cations (except H) Initial pH
= 100.
total number of exchangeable sites (a)
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3. Results and Discussion ++ +- --

- + +
++ -+ --
The points of zero charge PZCs for the chosen ++
- +- --
adsorbents are given in Table 2. At the pzc there ++ - +
-+ --
is no surface charge to be neutralized by ions in ++ - +- --
++ + +
the diuse swarm, and any adsorbed ions that -+ --
++ +- --
exist must be bound in surface complexes. The - +
++ -+ - --
pzc of all adsorbents studied is below 7, show-
K1 K2
ing the existence of perfect charge balance in the OH2+ OH O-
acidic the region among the equilibrated ions in
an aqueous solution (Fig. 1). Titration curves at (i) pH < pzc (ii) pH = pzc (iii) pH > pzc
Anion exchanger Neutral specie Cation exchanger
varying ionic strength (I) illustrated the impact
on the thickness of the diuse double layer as a (b)
function of salt concentration. More charges devel- Fig. 1. (a) pzc of adsorbents by pH drift method: ()
oped on the surface, and the adsorption of protons lakhra coal, () corn cob, () activated charcoal, ()
increased at low pH, whereas desorption of protons granite sand. (b) A visual representation of protona-
occurred at high pH. Activated charcoal (Fig. 2(a)) tion/deprotonation on the surface of adsorbent.

Table 2. Points of zero charge of adsorbents.

S. No. Adsorbents pzse pznc [NaCl] (mol L ) pzc pznpc

1 Granite sand 3.60, 8.23 0.01 6.20 6.86

9.40 1.00 6.85
2 Corn cob 3.10 4.55 0.01 4.40 4.61
0.10 4.26
1.00 3.89
3 Activated charcoal 6.36 5.85 0.0001 5.79
0.01 5.34 5.62
1.00 6.01
4 Lakhra coal 4.50 2.22 0.01 3.10 2.78
0.10 2.67
1.00 2.44
July 16, 2007 17:42 00951

466 M. Nasiruddin Khan & A. Sarwar




5 3.2
NaCl 1.0M
1.0 M NaCl
NaCl 0.1M
3 0.01 M NaCl NaCl 0.01M
0.001 M NaCl
3 1 1 3 5
4 2 0 2 4
Acid Vol./ ml Base Acid Vol. / ml Base

(a) (b)
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10 12

8 10

6 8


4 6

1.0 M NaCl NaCl 1.0M

2 0.1 M NaCl 4 NaCl 0.01M
0.01 M NaCl

0 2
4 2 0 2 5 3 1 1 3 5
Acid Vol. / ml Base Acid Vol. / ml Base
(c) (d)

Fig. 2. pzse of dierent adsorbents: (a) activated charcoal, (b) lakhra coal, (c) corn cob, and (d) granite sand.

followed the usual trend, i.e., at higher electrolyte consumed in dissolution reactions instead of gener-
concentration higher pH results before the pzse.10 ating the surface charge.
This behavior explained the compression of the Corn cob (Fig. 2(c)) has shown a increasing gap
double layer at high ionic strength and eectively between the titration lines after the pzse due to
reduced the thickness of the double layer. The pres- diminished buering capacity of the material which
ence of these counterions in high concentration near was manifested via a relatively small increase in vol-
the colloid surface helps to reduce the surface poten- ume resulting in large change in pH. Generally soil
tial more rapidly. samples have the pzse from 2 to 4.7 Granite sand is
The cross over of ionic strength curves for an exception. It yielded two intersection points at pH
lakhra coal (Fig. 2(b)) showed an opposite trend, 3.60 and 9.40, respectively (Fig. 2(d)). This behavior
i.e., at lower electrolyte concentration higher pH showed the dual anity of granite sand for adsorp-
results before the pzse. It is possible that at lower tion/desorption processes in both acidic and basic
ionic strength values protons were predominantly regions.
July 16, 2007 17:42 00951

Determination of Points of Zero Charge of Natural and Treated Adsorbents 467

3000 2500


qNa or qCl (mmolc kg-1)

qNa or qCl (mmolc kg -1)


2000 1500

1500 1000

Na 500 Na
Cl Cl

500 0
5 6 7 2 2.1 2.2 2.3 2.4

pH pH

(a) (b)
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qNa or qCl (mmolc kg -1)

qNa or qCl (mmolc kg -1)



2000 100
Cl Na
3 4 5 6 7 0
7.2 7.7 8.2 8.7
pH pH

(c) (d)

Fig. 3. pznc of dierent adsorbents: (a) activated charcoal, (b) lakhra coal, (c) corn cob, and (d) granite sand.

The pznc values of lakhra coal, corn cob, and acti- of the fact that H = 0 at the pznpc. It follows that
vated charcoal were in the acidic region, while granite 0 will be a negative quantity. In this work, the pznpc
sand showed in the basic region (Fig. 3). It was due was found to be slightly greater than the pznc for
to the fact that the pznc values of humus materials activated charcoal and lakhra coal; this result was
are below 4, and they tend to increase toward the an immediate indication that a slight negative struc-
basic region as the geochemical weathering of soil or tural charge exists onto the surface of the sample.
sediment increases.9 Lakhra coal was found to have While an opposite behavior was observed for corn
the lowest pznc among all other adsorbents owing to cob and granite sand, i.e., H as a negative quantity,
the presence of a large amount of humus material. and 0 as a positive quantity.
The values of pznpc are given in Table 2, accord- The approximate equality between the pzc and
ing to Eq. (11) by taking intercept from Fig. 4. the pznpc for granite sand realized the validity of
Several predictions for the behavior of adsorbents equation
can be made on the basis of PZCs values. Consider
the relationship between the pznpc and the pznc as 0 + IS + OS = 0.
a rst application. At the pznc, Eq. (4) reduced to
0 + H = 0 (Table 1). This equation explains that if Since this special case was quite unlikely for soil
pznpc > pznc, H must have a positive sign because samples, it can be achieved approximately for
July 16, 2007 17:42 00951

468 M. Nasiruddin Khan & A. Sarwar


10 5



NaCl 1.0 M 6 2
NaCl 1.0 M
NaCl 0.01 M
NaCl 0.1 M
NaCl 0.001 M 1
4 NaCl 0.01 M

3 0
-0.009 -0.004 0.001 -0.009 -0.004 0.001
q / mol g -1
q / mol g
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(a) (b)

12 pKa1s
pKa1s 12



6 6

4 4 pKa2s
pKa2s NaCl 1.0M
NaCl 0.1M
NaCl 0.01M
NaCl 1.0 M 2 2
NaCl 0.01 M

0 0
-0.00025 -0.00005 0.00015 -0.003 -0.001 0.001
-1 -1
q / mol g q / mol g

(c) (d)

Fig. 4. pznpc of dierent adsorbents: (a) activated charcoal, (b) lakhra coal, (c) corn cob, and (d) granite sand.

reference soil minerals suspended in aqueous solu- activated charcoal < corn cob < lakhra coal, while
tions of 1:1 electrolytes as exemplied by the data an opposite order has been observed not only for
for Al2 O3 (8.75 and 8.5), birnessite (1.7 and 2.2), pznpc values but for pznc and pzc values (Table 2).
and corundum (9.1 and 9.1).9 This result referred The values of CEC and base saturation % for
granite sand to hold peculiar characteristics among adsorbents under study are listed in Table 3. CEC
all other soil adsorbents. and base saturation % of lakhra coal were found
Sposito has observed that additional cation to be higher than that of other adsorbents, owing
adsorption by any mechanism tends to decrease the to the presence of the organic matter provided a
pznpc and vice versa.9 Our results veried his nd- major source of negative electrostatic sites showing
ings and explained in the other way that CEC of is a strong correlation between CEC values, and the
adsorbents was in the following order: granite sand < amount of organic matter present in the adsorbent.
July 16, 2007 17:42 00951

Determination of Points of Zero Charge of Natural and Treated Adsorbents 469

Table 3. CEC and base saturation values of adsorbents. 2. H. R. Kruyt, Irreversible Systems, Colloid Science,
Vol. 1 (Elsevier, Amsterdam, 1952), p. 80.
Cation exchange
3. W. Stumm, C. P. Huang and S. R. Jenkins, Croat.
Capacity Base
Chem. Acta 42 (1970) 223.
S. No. Adsorbents cmol(+) kg1 saturation %
4. D. A. Sverjensky and N. Sahai, Geochim. Cos-
1 Granite sand 259.86 3.79 mochim. Acta 60 (1996) 3773.
2 Corn cob 315.76 4.99 5. A. R. Felmy and J. R. Rustad, Geochim.
3 Activated charcoal 283.86 1.36 Cosmochim. Acta 62 (1998) 25.
4 Lakhra coal 887.98 202.94 6. S. Goldberg, P. M. Huang, N. Senesi and J. Bue
(eds.), Structure and Surface Reactions of Soil Par-
ticles (Wiley, London, 1998), p. 377.
7. W.-G. Hou, Y.-L. Su, D.-J. Sun and C.-G. Zhang,
4. Conclusion Langmuir 17 (2001) 1885.
Four adsorbents were used to describe the dier- 8. A. L. Kraepiel, Klauskeller and F. M. Morel, Envi-
ence between points of zero charge, namely the ron. Sci. Technol. 32 (1998) 2829.
9. G. Sposito, The Surface Chemistry of Soils (Oxford
point of zero charge, the point of zero salt eect, University Press, New York, 1984), p. 81.
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zero net proton charge using the acid base titration Geoderma 113 (2003) 77.
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erogeneous nature, the reproducible surface charging Bollinger, J. Chem. Edu. 80(1) (2003) 76.
12. S. Mustafa, S. Tasleem and A. Naeem, J. Colloid
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were also applied for natural and treated solids with S. Komarneni, S. L. Brantley and J. Chorover,
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results suggest that the use of the titration method (2000) 40.
alone may be insucient for thorough surface charge 17. M. Kosmulski, J. Colloid Interf. Sci. 275 (2004) 214.
18. J. Ganor, J. Cama and V. Metz, J. Colloid Interf.
characterization. Proton titrations should be coupled
Sci. 264 (2003) 67.
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