Carbon 37 (1999) 477481

Point of zero charge and intrinsic equilibrium constants of

activated carbon cloth
S.K. Milonjic *, M.J. Polovina, B.V. Kaludierovic
B.M. Babic,
Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, Yugoslavia
The Vinca
Received 20 June 1997; accepted 30 July 1998

Abstract
Surface properties of cellulose-based activated carbon cloth were investigated. The point of zero charge was determined
by batch equilibrium method. Surface charge densities were obtained from potentiometric titrations. The site-binding model
was applied to calculate the intrinsic acidity constants. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: A. Activated carbon; Carbon cloth; D. Surface properties

1. Introduction
Activated carbon cloth (ACC) can be obtained by
carbonization and activation of previously impregnated
organic polymers, mostly of cellulose origin. Due to high
specific surface area and microporosity, ACC shows good
adsorptive properties both in the gaseous and the liquid
phase. Several investigators have used ACC to remove
organics and inorganics from aqueous solutions [16].
They have found that adsorption strongly depends on the
pH and concentration of solutions, nature of carbon
surface, and size and shape of pores in adsorbent. For
determination of surface properties numerous methods
were developed [7].
In order to continue the study of adsorption processes on
ACC, the point of zero charge and intrinsic equilibrium
constants of ACC were determined.

2. Experimental
The viscose rayon cloth (from the Viskoza Factory,
Loznica, Yugoslavia) was used as a carbon precursor. Cloth
was carbonized in a nitrogen flow and activated in carbondioxide flow at 8508C for 1 h. The impregnants, usually
applied prior to carbonization and activation, were mixtures of NH 4 Cl and ZnCl 2 . These additives produce
activated material with a low ash content. ACC samples
were washed in distilled water to remove traces of
*Corresponding author.
0008-6223 / 99 / $ see front matter
PII: S0008-6223( 98 )00216-4

chlorides and other soluble impurities. Samples were kept

in a desiccator until use.
The specific surface area of ACC was determined with
an ASAP 2400 (Micromeritics, USA). Before obtaining
adsorption or desorption isotherms, the ACC sample was
degassed at a temperature of 523 K to remove any
contaminants that may be present on the ACC surface.
Adsorption of nitrogen gas was performed at 77 K. The
values of specific surface areas obtained by BET (multipoint analysis), Langmuir and Single Point (at P/Po 5
0.1407) methods were 1125, 1392 and 1166 m 2 / g, respectively. The average pore radius was smaller than 1 nm (0.7
nm), with a total pore volume of 0.42 cm 3 / g. The data
agree well with those for a similar material reported by
Jayson et al. [3].
Batch equilibrium method for determination of the point
of zero charge (PZC) was proposed by one of the authors
[8]. Accordingly, the samples of ACC (0.2 g) were shaken
in PVC vials, for 24 h, with 40 ml of 0.01 or 0.1 mol / dm 3
KNO 3 , at different pH values. Initial pH values were
obtained by adding an amount of KOH or HNO 3 solution
(0.1 mol / dm 3 ), keeping the ionic strength constant. The
amount of H 1 or OH 2 ions adsorbed by ACC was
calculated from the difference between the initial and the
final concentration of H 1 or OH 2 ions.
Specific adsorption of counter ions was investigated
using 1310 25 mol / dm 3 solutions of Zn(NO 3 ) 2 or
YugosCd(NO 3 ) 2 of p.a. quality (product of PP Baric,
lavia).
Surface charge densities of ACC, in aqueous solutions
of KNO 3 , were determined by potentiometric titration. The

1999 Elsevier Science Ltd. All rights reserved.

478

B.M. Babic et al. / Carbon 37 (1999) 477 481

out at 29860.2 K. The difference in acid or base quantities, used to reach the same pH in solutions with ACC
and the blank, was taken to represent the association or
dissociation of H 1 ions from ACC surface.

3. Results and discussion

Fig. 1. Determination of pH PZC of ACC in KNO 3 solutions (pH i ,

initial value; pH f , final value).

titration started from pH corresponding to PZC of ACC.

Two runs were carried out: (a) in the presence of ACC (0.5
g of ACC into 200 ml of 0.001, 0.01 or 0.1 mol / dm 3
KNO 3 ), (b) in the same electrolyte in the absence of ACC
(blank). A 0.1 mol / dm 3 solution of HNO 3 or NaOH was
used as a titrant in the pH range below or above that of
PZC, respectively. A dose of titrant, 0.050.5 ml, dependent on the solution pH and the electrolyte concentration,
was added successively every 10 min. During the titration,
solutions were stirred with a magnetic stirrer and purified
N 2 was bubbled through the system, preventing any CO 2
or O 2 adsorption from the air. Experiments were carried

Experimental results of the pH PZC determination are

illustrated in Fig. 1. They are given as pH values of filtered
solutions after equilibration (pH f ) with ACC as a function
of initial pH values (pH i ) of solution. It can be seen that
PZC of ACC, in KNO 3 aqueous solutions, is at pH57.0
(pH f level where common plateau is obtained). Determination of pH PZC in KNO 3 solutions of different concentrations gave the same results. This leads to the
conclusion that pH PZC is independent of the ionic strength
of KNO 3 solutions, i.e. that KNO 3 is an indifferent
electrolyte. To our knowledge, there is no report on pH PZC
value for ACC in the literature. Values of pH PZC for
granulated activated carbons with similar specific surface
area as that of our ACC sample, reported by various
authors, are listed in Table 1. For comparison, literature
values of the isoelectric point (pH IEP ) are also given.
Differences in data are a consequence of different precursors, way of preparation, impurities or methods for
determination. It should be noted that the pH PZC values,
reported by Huang [13], are in fact isoelectric points.
Namely, the reported pH PZC values, determined by some
electrokinetic methods, represent isoelectric points. Only in
the absence of specific adsorption of counter ions, pH PZC
is equal to pH IEP [14].
Determination of pH PZC in the presence of Zn 21 or
Cd 21 ions is presented in Fig. 2. The choice of these ions
was based especially on a possible ecological demand for
their removal from drinking and technical waste-water. It
is evident that the adsorption of Zn 21 and Cd 21 ions leads
to the lowering of pH PZC of ACC to the values 6.0 and 6.5,

Table 1
The point of zero charge and the isoelectric point for activated carbon cloth and various activated carbons
Commercial name

Specific surface area, m 2 / g

pH PZC

pH IEP

Reference

ACC
KETJEN BLACK
DARCO KB
NUCHAR WVW
FILTRASORB 400
DARCO HDB
NUCHAR SN
NORIT C
FILTRASORB 400
NUCHAR 722
DARCO
PITTSBURGH HGR
NUCHAR C-190-N

1125
950
1500
1215
1236
606650
14001800
10851380
10501200

890

7.0
9.85
4.25
7.25
10.4
7.45
5.35
2.29.0

2.2
3.0

1.44.9
7.10
5.70
6.15
6.70
4.75

This study
[9]
[9]
[10]
[10]
[11]
[11]
[12]
[13]
[13]
[13]
[13]
[13]

B.M. Babic et al. / Carbon 37 (1999) 477 481

479

Fig. 2. Decrease in pH PZC of ACC due to specific adsorption of

21
21
Zn and Cd ions.

Fig. 3. Surface charge densities of ACC in KNO 3 solutions as a

function of pH.

respectively. This is in accordance with the literature data

on the influence of specific adsorption of counter ions on
pH PZC and pH IEP [1416]. Specific adsorption of cations
shifts pH PZC and pH IEP toward lower and higher pH
values, respectively. However, specific adsorption of anions shifts pH PZC and pH IEP to the opposite directions
[1416]. Our results reveal an expected decrease in pH PZC
of ACC in the presence of Zn 21 and Cd 21 ions, confirming their specific adsorption.
The surface charge densities as a function of KNO 3
solution concentration and pH are presented in Fig. 3. If
we assume that H 1 and OH 2 are potential determining
ions for ACC, then surface charge (s 0 in mC / cm 2 ) can be
calculated from:

carbide and silicon metride), and are a characteristic of the

solidsolution interfaces for which H 1 and OH 2 are
potential determining ions.
It is well known that the most common functional
groups (containing oxygen) on the activated carbon surface
are carboxyl, lactonic, carbonyl, and phenolic. According
to Davis et al. [1719], the associationdissociation of
amphoteric surface groups on ACC can be defined by the
following equations: (a) in the pH range below pH PZC :
K int
1 a1

SOH 2 SOH 1 H S

(b) in the pH range above pH PZC

K int
a2

Dy ? M ? F ? 100
s0 5 ]]]]
S ? A ?V

(2)

SOH SO 2 1 H 1
S

(3)

(1)

where Dy (cm 3 ) is the difference between the titrant

volumes, used for the solution with ACC, and the blank at
given pH values, M is the molarity of the titrant, F is the
Faraday constant (96 500 C), S is the specific surface area
of ACC (m 2 / g), A (g / dm 3 ) is the amount of ACC used for
titration, and V (cm 3 ) is the volume of KNO 3 solution.
It is evident (Fig. 3) that the surface charge density
curves for counterions (K 1 and NO 2
3 ) are not symmetrical
with respect to pH PZC . This fact indicates different complexation strengths of these ions. Shapes of the s 0 vs. pH
curves (Fig. 3) are similar to those of activated carbons
[10], inorganic oxides [14], and nonoxide ceramics (silicon

2
where SOH 1
denote positive, neutral, and
2 , SOH, and SO
negative sites on the surface of ACC, respectively.
int
The intrinsic surface ionization constants, K int
a1 and K a2
can be calculated from:

pK int
a1 5 pH 1 log[a1 /(1 2 a1 )] 1 ec0 / 2.3kT

(4)

pK int
a2 5 pH 2 log[a2 /(1 2 a2 )] 1 ec0 / 2.3kT

(5)

where a 1 and a 2 denote fraction of charge sites (a 1 5s 0 /

Ns for the positive, and a 2 5 2s 0 /Ns for the negative
surface), c 0 is the mean potential of the surface charge
plane, and k is the Boltzmann constant. The fraction of
charged sites was calculated assuming that the total

480

B.M. Babic et al. / Carbon 37 (1999) 477 481

amount of surface groups Ns 55 groups / nm 2 (or expressed

int
in charge units 80 mC / cm 2 ). Numerical pK a1
value can be
obtained from the dependence pQ a1 5pH1log(a 1 /(12
a 1 )) versus degree of surface ionization, a 1 . By extrapolating pQ a1 to the zero a 1 value, i.e. to the surface
charge s 0 50 and surface potential c 0 50 (absence of
specific sorption), the intrinsic acidity constant, pK int
a1 , is
obtained. Similarly, the pK int
a2 value can be obtained from
the dependence pQ a2 5pH2log(a 2 /(12a 2 )) versus degree of surface ionization, a 2 . By extrapolating pQ a2 to
the zero a 2 value and surface potential c 0 50, the intrinsic
acidity constant, pK int
a2 , is obtained. The double-extrapolation technique proposed by James et al. [20] was used to
int
calculate pK int
a1 and pK a2 . Obtained results are presented in
Fig. 4a and b. Two extrapolation routes lead to the values:
int
pK int
a1 51.9 and pK a2 511.5.
Since s 0 50 at pH PZC , the concentrations of SOH 1
2 and
SO 2 are equal and Eq. (2) and Eq. (3) can be used to
int
express pH PZC in terms of K int
a1 and K a2 alone:
int
pH PZC 5 0.5(pK int
a1 1 pK a2 )

(6)

int
int
Introducing the values obtained for pK a1
and pK a2
in
Eq. (6), pH PZC 56.7 is obtained, which is in good agreement with the one determined by batch equilibrium
method. Unfortunately, we did not find the literature data
int
on ACC pK int
a1 and pK a2 . To our knowledge, there are only
a few papers [10,13,2123] devoted to the determination
of acidity constants of activated carbons. Huang et al.
[10,13] used a method developed by Huang and Stumm
int
[24] to evaluate the pK int
a1 and pK a2 of activated carbon by
alkalimetric titration. They used various commercially
available activated carbons (Nuchar, Filtrasorb, and
Darco), some of them are given in Table 1, and obtained
int
the values 2.68.8 and 5.512.3 for pK int
a1 and pK a2 ,
respectively. Corapcioglu and Huang [10] concluded that
no correlation can be deduced from the surface chemical
composition and acidity of the investigated activated
carbons. Matsumura et al. [21] determined the surface
acidity of various commercial activated carbons by neutralization with an excess of NaOH, followed by back titration
with strong acid. They reported 27 and 711 for pK int
a1
int
and pK a2
, respectively. Schwarz et al. [22,23] evaluated
the surface acidity of several activated carbons using the
Boehm and potentiometric titration methods. From the
potentiometric titration, the pKa distributions were calculated and the surface density of acidic groups was assessed.
int
On the basis of the obtained pK int
a1 and pK a2 values for
ACC we can conclude that carboxyl or phenolic functional
groups, whose acidic constants have similar values, are
present on the surface of ACC. These results were
compared with those obtained by other methods for ACC
surface characterization [25]. X-ray photoelectron spectroscopy and selective neutralization method show that
phenol and carboxyl groups are dominant on the surface of
ACC, but a difference in the specific groups ratio was

Fig. 4. Variation of (a) pQ a1 and (b) pQ a2 values with fractional

surface charge and KNO 3 electrolyte concentration. Solid lines
represent experimental data while dashed lines and filled circles
are the extrapolated ones.

B.M. Babic et al. / Carbon 37 (1999) 477 481

noted. Complexity of the ACC surface requires further

investigation and application of additional methods.
The relative acidity of surface functional groups can be
expressed by DpK5pKa2 2pKa1 . Davis et al. [17] have
reported that DpK values among oxides do not vary
greatly. For oxides such as TiO 2 , g-Al 2 O 3 and a-FeOOH,
DpK is equal to 6, while for SiO 2 it is 8. The DpK value
for our ACC sample is 9.6, indicating lower acidity of the
surface groups compared to the acidity of hydroxylic
groups of the stated oxides.

4. Conclusion
The point of zero charge for ACC in KNO 3 solutions,
determined by batch equilibrium method, is at pH57. In
the presence of zinc and cadmium ions, pH PZC decreases
due to specific adsorption of these ions. Using the surface
charge data, obtained by a potentiometric titration method,
int
the intrinsic equilibration constants pK int
a1 and pK a2 were
calculated to be 1.9 and 11.5, respectively.

References
[1] Jayson GG, Lawless TA, Fairhurst D. J Colloid Interface Sci
1982;86(2):397.
[2] Jayson GG, Sangster JA, Thompson G, Wilkinson MC.
Carbon 1987;25(4):523.
[3] Jayson GG, Sangster JA, Thompson G, Wilkinson MC.
Carbon 1993;31(3):487.
[4] Gaylor JDS, Maggs FAP, Park GB, Smith EM. In: Proceedings of 29th Alliance for Engineering in Medicine and
Biology (ACEMB). Boston, 1976:171.
[5] Brown PN, Jayson GG, Thompson G, Wilkinson MC. J
Colloid Interface Sci 1987;116(1):211.
[6] Freeman JJ, Gimblett FGR, Gray AC, Kenny MB, Roberts
RA, Sing KSW. In: Proceedings of 4th International Carbon
Conference.
Baden-Baden:
Deutsche
Keramishe
Gesellschaft, 1986:321.

481

[7] Radovic LJR. Hemijska Industrija (Chemical Industry) Belgrade 1996;50(6):225.

MV. Thermochim Acta
[8] Milonjic SK, Ruvarac ALJ, Susic
1975;11(3):261.
[9] Arico AS, Antonucci V, Minutoli M, Giordano N. Carbon
1989;27(3):337.
[10] Corapcioglu MO, Huang CP. Carbon 1987;25(4):569.
[11] Reed BE, Matsumoto MR. Sep Sci Technol 1993;28(13
14):2179.
[12] Menendez JA, Illan-Gomez MJ, Leon y Leon CA, Radovic
LJR. Carbon 1995;33(11):1655.
[13] Huang CP. In: Cheremisinoff PN, Ellerbusch F, editors.
Carbon adsorption handbook. Ann Arbor: Ann Arbor Science, 1978:281.

[14] Kallay N, Hlady V, Jednacak-Biscan

J, Milonjic S. In:
Rossiter BW, Beatzold RC, editors. Investigation of surfaces
and interfaces part A, physical methods of chemistry
series, vol. IXA, 2nd ed. New York, 1993:73.
[15] Milonjic SK. Sorption processes on colloidal silica interface.
Ph.D. Thesis, University of Belgrade, Belgrade, Yugoslavia,
1981.
[16] Breeuwsma A, Lyklema J. Discuss Faraday Soc
1971;52:324.
[17] Davis JA, James RO, Leckie JO. J Colloid Interface Sci
1978;63(3):480.
[18] Davis JA, Leckie JO. J Colloid Interface Sci 1978;67(1):90.
[19] Davis JA, Leckie JO. J Colloid Interface Sci 1980;74(1):32.
[20] James RO, Davis JA, Leckie JO. J Colloid Interface Sci
1978;65(2):331.
[21] Matsumura Y, Hagiwara S, Takahashi L. Carbon
1976;14(3):163.
[22] Bandosz TJ, Jagiello J, Schwarz JA. Langmuir
1996;12(26):6480.
[23] Contescu A, Contescu C, Putyera K, Schwarz JA. Carbon
1997;35(1):83.
[24] Huang CP, Stumm W. J Colloid Interface Sci
1973;43(2):409.
[25] Polovina M, Babic B, Kaluderovic B, Dekanski A. Carbon
1997;35(8):1047.