Minerals Engineering, Vol. 13, No. 5, pp.

527-540, 2000
Pergamon © 2000 Published by Elsevier Science Ltd
All rights reserved
0892-6875(00)00033-9 0892--6875/00/$ - see front matter

EFFECTS OF THE TEXTURAL AND SURFACE PROPERTIES OF

ACTIVATED CARBON ON THE ADSORPTION OF GOLD DI-CYANIDE

M.D. SEKE §, R.F. SANDENBERGH § and N.M. VEGTER t

§ Department of Materials Science and Metallurgical Engineering, University of Pretoria,

Pretoria 0002, South Africa. E-mail: mseke@postino.up.ac.za
I" Iscor Limited, PO Box 9229, Pretoria 0001, South Africa
(Received 9 December 1999; accepted 31 January 2000)

ABSTRACT

The influence of the surfacecondition of activated carbon on the adsorption of aurodicyanide was
investigated to gain a better understanding on the influence of the pore volume distribution and heat
treatment on t,~e adsorption capacity of the carbor~ Three activated carbons were heat-treated at
850 °C in nitrogen gas. Adsorption of gold di-cyanide on heat-treated carbon increased compared
to the untreated carbon. However, no drastic change in the pore volume was observed after heat
treatment of the activated carbon. Therefore, the combined effects of textural and surface properties
of the activated carbon are relevant for the equilibrium adsorption of gold di-cyanide.

In the second part of the paper one of the major assumptions in adsorption modelling onto activated
carbon based on aqueous surface chemistry principles is investigated; that of accounting for
electrostatic i~:teractions. The surface of activated carbon contains acidic and basic surface groups,
which influence the adsorption of gold di-cyanide from the aqueous solution. The surface charge
density that arises from ionisation of these surface groups in response to the solution pH and ionic
strength was evaluated by potentiometric titration. The surface potential based on the Gouy-
Chapman relationship for a fiat surface does not reflect a realistic picture of the potential
distribution ir~ride the microporous carbon as the size of the micropore is too small to allow such a
potential distr,ibution to develop. This currently forms the basis available adsorption models. It is
proposed that the overlapping of the potential fields inside the micropores could be handled by
using the Donnan potential. © 2000 Published by Elsevier Science Ltd. All rights reserved

Keywords
Activated carbon; mass balancing; hydrometallurgy

INTRODUCTION

The adsorption of gold di-cyanide onto activated carbon has been studied extensively and general
agreement has been found on the mechanism by which the gold adsorbs onto the activated carbon. Adams
and Fleming (1989), Adams (1990) and Jones et al. (1988) found that gold di-cyanide is adsorbed without
any chemical change from alkaline solution onto activated carbon. Furthermore, the graphite-like structure
of the activated carbon has been found to be one of the most important factors for the adsorption of gold
di-cyanide (Miller and Sibrell, 1991; and Ibrado and Fuerstenau, 1992). However, little consideration has
been given to the role of both textural and surface properties of the activated carbon.

527
528 M.D. Sekeet al.

The effect of the textural properties represented by the relationship between the pore size distribution
and the adsorption of ionic species has been investigated by Adams (1993) and by Newcombe et al.
(1996). They have presented compelling evidence that small ions or molecules such as gold cyanide
and 2-methylisoborneol adsorb mainly in the micropore volume.
The effect of surface properties as represented by the link between different functional groups and
adsorption of gold di-cyanide was investigated by Tsushida et al. (1985) and by Adams (1993).
Adams concluded that the correct structural characteristics alone were not sufficient to produce an
activated carbon with a high activity for the adsorption of the gold di-cyanide; indeed the presence of
certain functional groups, such as hydroxyl, carboxyl, and phenolic groups also plays an important
role.

Acidic and basic functional groups impart a polar character to the carbon surface by interaction with water
(L6on Y. L6on et al., 1992; Kinoshita, 1988; Corapcioglu and Huang, 1983 and 1987). Ionisation of these
surface groups depends strongly on the pH of the solution, and leads to a build up of a charged interface
between the activated carbon and the bulk of the solution. The formation of complexes occurs in addition
to simple ionisation of surface groups by the association/dissociation reaction of protons and hydroxyl ions
(Davis et al., 1978). It is assumed that I-I+ and OH- are potential determining ions only insofar as the
common method of definition of the surface charge is through the uptake or release of potential
determining ions at the surface (Davis and Leckie, 1978 and 1980). The electrostatic interactions between
the charged surface and the adsorbing ionic solute are determined by the ionic charge and by the
magnitude of the surface potential. The magnitude of the surface charge increases with the ionic strength
of the solution. Generally, the observed increase in adsorption of anions with decreasing pH has been
attributed to the decrease in negative charge of the adsorbent. This effect has been observed by a number
of investigators (Tsushida et al., 1985; and McDougall et al., 1980).

Vegter and Sandenbergh (1997) have demonstrated strong qualitative correspondence between the
adsorption behaviour of gold di-cyanide-activated carbon and organic-activated carbon systems. MOiler et
al. (1980), Derylo-Marczewska (1993), and Seco et al. (1997) have successfully modelled equilibrium
adsorption behaviour of these organic-aqueous-activated carbons systems. These models incorporate
aqueous surface chemistry effects such as chemical and electrostatic interactions on the adsorption
equilibrium. To account for the electrostatic interactions an estimation of the surface potential is needed.
This was obtained by assuming that the Gouy-Chapman or the triple layer models of the double layer for
flat surfaces could be used to obtain a relationship between surface charge and surface potential (MOiler et
a/, 1980; Derylo-Marczewska, 1993; and Seco et al., 1997). The isotherm equation for the adsorption from
solution is then derived by combining the mass balance of the number of adsorption sites with the
adsorption equilibrium constant. All these workers have found good agreement between the model
predictions and the experimental data, despite some detail differences in the assumed electrical double
layer models.

This paper presents the results of our research on the effect of micropore volume and surface properties on
the gold adsorption capacity of activated carbon. Firstly, the influence of the heat treatment of activated
carbon, which improves the gold adsorption capacity, is discussed. Secondly, the limitations of the
incorporation of the Gouy-Chapman or triple layer models as part of the adsorption isotherm models based
on aqueous surface chemistry principles is investigated. This might have a direct bearing on the validity of
future attempts to model the equilibrium adsorption of gold di-cyanide onto a microporous activated
carbon from aqueous solution by these models.

EXPERIMENTAL

Materials and sample preparation

Three commercial activated carbons, ANK10, ANK11 and WCM 006 were supplied by NCP (Germiston,
South Africa). Carbons ANK10 and ANK11 were made from coconut shells. Carbon WCM 006 is a coal
based activated carbon with a tridisperse pore structure, enabling it to be used in a wide range of liquid
phase applications such as removal of taste and colour from potable water and industrial waste water.
Table 1 gives some properties of these activated carbons. Before use, the carbon samples were screened to
minus 1.7 ram, followed by ultrasonic washing with distilled water for half an hour. The carbon was then
 EtTeetsoftexturaland surfacepropertiesof activatedcarbonon adsorptionof golddi-cyanide 529

boiled in distilled water for about two hours and rinsed repeatedly with distilled water. Finally, it was oven
dried at 110 °C far three days, and stored in a dessieator containing silica gel. The potassium gold di-
cyanide was supplied by Johnson Matthey (Pty) Limited. 0.1M HC1 and KOH titrisol solutions were
supplied by Merck, and all solutions were made up with distilled water.

TABLE 1 Designation and properties of as-received activated carbons

Desigxmtion Source Particle size (mm) % moisture % Ash % Carbon

ANK10 Coconut shell 1.18-2.36 1-4 2-4 89.0
ANK11 Coconut shell 1.18-2.36 1-4 2-4 86.2
WCM 006 Coal 0.42-1.68 2 5 86.7
Particle size, moisture, and ash content ~rovided by supplier.
Carbon content measured by the University of Pretoria (Department of Earth Sciences).

Heat-treatment of activated carbon

Carbons usually acquire a basic character after high temperature (above 700 °C) heat treatment in an inert
atmosphere (Kinc,shita, 1988). The basicity of the carbon follows from the increase in the point of zero
charge and/or isoelectric point value of the activated carbon (L6on Y. L6on, 1992). In an attempt to change
the textural properties and to remove some surface functional groups of the carbon, 10 g samples of the
carbons ANK10 and 11 were placed inside a quartz tube within a preheated furnace and heated to 850 °C
in a flow of commercial nitrogen. After 10 minutes of heat treatment at 850 °C, the activated carbon was
moved to a cooler part of the furnace and cooled to room temperature. The heat-treated carbon samples
were then stored in sealed bottles. The same treatment was repeated for 15, 20, 25 and 30 minutes. The
influence of the heat treatment on the basicity of the carbon was measured by contacting 1 g of activated
carbon with 50 rnl of distilled water for 24 hours, and measuring the pH of the slurry with a combined
Orion triode electrode and an Orion 420 pH meter.

Pore volume and surface area analysis

Pore volume and surface area measurements were performed at Mintek (South Africa). They were
determined from adsorption/desorption measurements with nitrogen at 77 K. The total surface area was
calculated by using the BET and Langmuir isotherms of nitrogen at liquid temperature. The Accelerated
Surface Area and Porosimetry System ASAP 2000 was used. The samples were degassed for about 25
minutes until a vacuum below 25 ~tm Hg was obtained. Prior to analysis, samples were further degassed at
liquid nitrogen temperature to a vacuum below 5 ~tm Hg, before dosing with nitrogen. The mesopore and
macropore data were determined by mercury intrusion using the Qauntachrome Autoscan Mercury
Porosimetry System. Samples were inserted into the cell and degassed at room temperature for 15 minutes
until a vacuum below 50 ~tm Hg was reached. They were then filled with mercury at 137.9 kPa, and
mounted onto the Autoscan Porosimeter, where they were intruded with mercury to 413.7 kPa. The
diameter of the pore was calculated by using the mercury contact angle of 140°.

Gold adsorption onto activated carbon

0.25g samples of the different carbons were contacted with 250 ml of 0.1 M KC1 containing approximately
300 mg/L of gold as KAu(CN)2. The initial solution pH was neutral and no further pH monitoring was
performed. The glass bottles were shaken at room temperature (18-20 °C) for four days using a table
shaker. Samples of the solution were analysed for gold by an atomic absorption spectrometer (AAS). The
solutions were diluted in order to operate within the linear range of absorption for gold. The amount of
gold adsorbed on carbon was calculated from the difference in the initial and final gold concentrations in
solution.

Surface charge and surface potential determination

The surface charpe density of one activated carbon (ANK11) was determined by potentiometric titration.
This was done by titrating a suspension of the activated carbon in an electrolyte solution of a given
concentration by known additions ofI-I+ and OH- ions. The relative surface charge, Qs, was calculated from
530 M.D. Seke et al.

the difference in volumes oftitrant needed to establish a certain pH in the presence of the activated carbon
as compared to a blank (same solution but without the activated carbon):

Q s = F [(V.COsun,.- (V.C) bl~]/g (1)

where F is Faraday's constant, V is the volume of titrant added, C is its molar concentration and g is the
mass of the activated carbon in the suspension. The relative values of the surface charge density expressed
per gram of activated carbon were made absolute by referring them to the point of zero charge (pzc) of the
activated carbon. The absolute values of surface charge density can be calculated from the following
equation:

CSo= Qs / SBET
(2)

where Oo (coulomb/m 2) is the surface charge density, SBET (m2/g) is the specific surface area of the
activated carbon as obtained fi'om nitrogen gas adsorption. The surface potential, V, was calculated from
data of the surface charge density, Oo, using the Gouy-Chapman relationship (SUmma, 1992):

CSo-- (8RTsso C x 103)nasinh(z~F/2RT) (3)

where s is the dielectric constant of water (78.5 at 25 °C), to is the permittivity of free space (8.854 x 10 -12
C V - l m -1 or C2j-lm-1), C is the molar concentration of the electrolyte, and z the ionic charge. Equation (3)
has been used primarily for the evaluation of the surface potential on flat surfaces.

The activated carbon ANK11 was washed as described earlier. Titration experiments were carried out in
two glass vessels of 1L each. The vessels were sealed, and pure nitrogen was bubbled through the solution
to avoid the possible absorption of CO2 from air into the solution. The temperature of the solution was kept
at 25 °C by immersing the titration vessel in'a water bath. Two samples were prepared for each set of
experiments by suspending 10 g of activated carbon in 500 ml of 0.1 M KC1 solution. The suspensions
were stirred at 240 rpm overnight by a flat 4-blade paddle. After this initial equilibrium the pH of the
solution was measured. One sample was directly titrated by adding 1 ml increments of 0.1 M HC1. The
activated carbon was removed from the second sample and the clear supernatant received the same titration
procedure as the first sample. The procedure was repeated on other samples prepared with different ionic
strengths (0.01 M KC1), and the solution pH was measured after each addition of acid (0.1 M HCI). The
maximum time interval between subsequent additions was set at 150 minutes, and pH measurements were
performed using a Kyoto 400 potentiometric automatic titrator. The titration curves were recorded as a
function of the potential and measured potential values were converted to pH values by means of a
calibration done before the experiment. Kinetic experiments of gold di-cyanide adsorption on ANKI 1 were
performed in an attempt to determine the acceptable time to be used between subsequent additions of the
titrant. 3g of activated carbon ANK11 was contacted with 600 ml of gold solution (136 ppm gold). The
suspension was stirred at 200 rpm and the adsorption temperature was set at 30 °C. Figure 1 shows that two
hours were enough for the adsorption of almost 90 and 98% of gold onto activated carbon at 0.1M KOH
and 0.1M KC1 respectively. It must be pointed out that this is not the true equilibrium time for the
adsorption of the gold di-cyanide onto activated carbon. The long period needed to reach equilibrium has
always been explained by the time needed for the micropore diffusion of the adsorbate.

RESULTS AND DISCUSSION

Surface area, pore volume distribution, and immersion pH

Figure 2 presents the results of the BET surface area and micropore volume of carbon samples as a
function of the heat treatment time at 850°C. The surface area of the activated carbon ANK11 did not
change following the heat treatment. The BET surface area was in the order of 1000 m2/g for all ANK11
samples. However, in contrast to this a decrease of about 20% in surface area was observed with the
activated carbon ANK10 heat-treated for 30 minutes compared to the starting material. The results of pore
volume measurements show that no drastic change was recorded in the pore volume. All heat-treated
 Effectsof textural and surfacepropertiesof activatedcarbonon adsorptionof golddi-cyanide 531

carbon samples presented a pore volume distribution similar to that of the starting material. It should be
mentioned that due to the insufficiency of data in the BET plot of some samples, the porosimeter could not
calculate the micropore volume and surface area of these samples even after a second attempt of analysis.
This is one of the problems in micropore measurements by adsorption/desorption using the ASAP 2000
porosimeter. Our results are in good agreement with those of Men~ndez et al. 0996) where a sample of
Norit C-granular activated carbon was held at 950 °C for 3 hours in the presence of nitrogen and hydrogen;
and then at 650 and 800 °C in hydrogen atmosphere (Table 2). Table 2 shows that the heat treatment used
did no affect the textural properties of the carbons, even after holding them in the furnace for 3 hours. In
the light of these results, we can postulate that no further significant change in the pore volume distribution
can be expected after the activation of the pyrolysed starting material.

140 ~ ,////

120
Supporting electrolyte
100 • 0.1 M KCI
A

E
et
• 0.1 M KOH
Q.
¢- ~7 0.033 M CaCIz
o
80

.E 60
"o
O

40

20

0 120 240 360 2000 3000 4000 5000 6000

Time (min)

Fig. 1 Adsorption of gold di-cyanide onto activated carbon ANK11. Adsorption conditions: 3g activated
carbon ANK11,600 ml gold solution, 200 rpm, 30 °C, Co = 136 ppm Au.

TABLE 2 Summary of textural, chemical and electrochemical properties of as-received and

surface-treated carbons (Men6ndez et al., 1996)

Activated carbon 'NORIT-C (fi'omwood)

Heat treatment temperature (°C) 0 950 950 800 650
Heat treatment atmosphere Nitrogen Hydrogen Hydrogen Hydrogen
Carbon content (1%) 82.3 94.2 99.0 97.0 94.8
Hydrogen content (%) 2.3 0.6 0.4 0.9 1.6
Oxygen content (%) 15.1 4.6 0.3 1.2 3.1
Point of zero charge 2.5 5.2 9.0 7.5 6.3
Isoelectric point 2.6 3.5 4.9 4.5 4.4
BET surface area ~m2/gl 1378 1257 1241 1028 1224
Micropore volume (cm3/g) 0.31 0.37 0.34 0.30 0.30
Mesopore volume (cm3/g) 0.55 0.50 0.49 0.40 0.55
532 M.D. Seke et al.

10

9 /
/o
-1-
¢X I
e-" I
O ~// 0 ANK11
'~ 8
E • ANKIO
(
mE
7

I I I I I I
0 5 10 15 20 25 30 35
1200

1000 •.... _o__~__g__~_-o

E
m 800
==
m
600
8
¢/) 400
I-
w
m 200

0' I 1 I I I

0 5 10 15 20 25 30 35
0,8 Micropore diameter: <1.8 nm
Mesopore diameter: 1.8-30 nm
0.7 Macropore diameter: >30 nm
0.6-
E° 0.5 - Mtcropores
N~
E 0.4 "~ L. . . . . . . O.... -O--'O
0.3-, Macropores .,
o ~,o -
o 0.2 ,
r. . . . ~--a--e--~-~
. . . .

0.1-
Mesopores~¢"
0.0 I I I I I I

0 5 10 15 20 25 30 35
Heat treatment time (min)

Fig.2 Effect of heat treatment time on the immersion pH, surface area, and pore volume of carbon
samples.

Thermal treatment is known to be one of the commonlyused techniques employed for the activation of
carbons electrodes (Kinoshita, 1988). The reported results of Men6ndez et al. (I992) shows that the point
of zero charge and the isoelectric point of carbon samples increased after heat treatment in the presence of
nitrogen or hydrogen gas, giving to the carbon samples a basic character (Table 2). This could be explained
by the removal of oxygen functional groups from the activated carbon during the heat treatment process.
The evidence of this removal is shown by the decrease in hydrogen and oxygen content as presented in
 Effeclsof textural and surfacepropertiesof activatedcarbonon adsorptionof golddi-cyanide 533

Table 2. Therefore, measuring the point of zero charge, oxygen and hydrogen content of our heat-treated
carbon samples was found to be out of the scope of this study. Although no titration or electrophoresis
measurements were performed on our heat-treated carbon samples in order to follow the change in the
point of zero charge and isoelectric point, the immersion pH was measured. Figure 2 shows the change in
solution pH measured after immersion of the heat-treated carbon samples in distilled water for 24 hours.
An increase in pH with heat treatment was observed for all samples, and all pH values were higher than 9
after heat treatment.

Gold adsorption capacity of activated carbon

Gold adsorption capacity of three different activated carbons (WCM 006, ANK10 and 11) have been
investigated before heat treatment and the results are presented in Figure 3a. These results indicate that
coconut shell based carbons ANK10 and ANK11 have a higher gold capacity than the coal based carbon
WCM 006. The difference in gold capacity is probably due to the higher pore volume (> 0.4 cm3/g) that is
found in the carbons ANK10 and ANK11. The carbon WCM 006 has a micropore volume of 0.30 cm3/g,
which could be to a certain extent responsible of the poor gold adsorption capacity. Even the adsorption
capacity calculated per unit surface area showed that the carbon with high micropore volume adsorbs more
gold than the one with less micropore volume. This argument is supported by the results of Adams (1993)
that are reported in Table 3. As shown in Table 3 and Figure 3b, an increase in gold adsorption with the
micropore volume is observed. Adams (1993) explained the marked correlation between gold di-cyanide
adsorption density and micropore volume on the basis of the dimension between the micropore (< 2 urn)
and the gold di-cyanide ion (0.19 nm). Norit G 210 is an activated carbon from coconut shell, while
carbons A, B and C are based on coal, peat and wood respectively. Although the surface areas of all these
commercial carbons were very similar, no correlation was found between the surface area and the gold
adsorption capacity. Newcombe et al. (1996) also showecl Rat the adsorption of a small molecule such as
2-methylisoborneol, which is responsible for musty odours in water, is strongly influenced by the
micropores of the activated carbon. In the light of these findings, we believe that the micropore volume of
the activated carbon is an important parameter for the adsorption of gold di-cyanide.

TABLE 3 Gold adsorption activities, chemical and textural properties of commercial activated
carbons after 24 hours (Adams, 1993)

Carbon desigrnation Carbon G210 Carbon A Carbon B Carbon C

Source Coconut shell Peat Coal Wood
Carbon content (%) 92.5 89.2 85.4 69.4
Hydrogen content (%) 0.9 0.8 0.9 3.4
Oxygen content (%) 1.7 3.0 5.3 4.6
BET Surface area (mZ/g) 1000 1160 1160 1200
Total pore voltune (cm 3/g) 0.6509 0.7238 0.7511 1.7634
Micropore volttrne (cm3/g) 0.3916 0.3711 0.3691 0.1926
Gold ads No additives 16.4 22.7 20.4 7.8
activity (%) 0.033M CaCI2 32.7 33.4 31.6 22.0
0.1 M HCI 79.4 80.1 74.9 23.0
Adsorption conditions: volume of solution, 100 ml; mass of carbon, 0.1 g; initial gold in solution, 300
rag~L; contact tim,,., 24h.

The influence Of heat treatment on the gold adsorption capacity of the activated carbon is shown in Figure
4. For almost the same volume of micropores and approximately the same total surface area, the heat-
treated carbons displayed an increase in gold capacity. These results are indicative of the affinity between
the surface properties of the carbon and the gold di-cyanide anion. It is believed that some functional
groups have been removed from the carbon surface during the heat treatment, leading to an improvement
in the affinity of the gold di-cyanide for the carbon surface. However, no strong evidence can be given in
terms of the nature of the functional groups removed or created during the heating process. Men6ndez and
co-workers (19961) concluded that heat treatment of the carbon in a nitrogen atmosphere is effective in
removing oxygen-containing surface groups from the carbon (Table 2). Furthermore, basic properties were
found on the carbon after heat treatment. These basic properties are more favourable for gold di=cyanide
534 M.D. Seke et al.

adsorption because they shift the pzc of the activated carbon towards more alkaline values, which would
favour the adsorption of the gold di-cyanide anion at the higher pH values that are typically used in
practice.

0.60 0.60

0
E 0.55 Microvorevolume(cma/g) -0.55
E WCMO06:0.30 / j ~ ( ~ E
,-I

.~' 0.50 ANKIO:0.40 ,4 0.50

"O ANKII: 0.42 to
e-
(3.
0.45 0.45
t,- t-
.o
0
2" 0.40
tO
____./ - 0.40
O

0
to

t~ 0.35 - 0.35 "o

m
O O
O (.9
0.30 I I I I I 0.30
0.15 0.20 0.25 0.30 0.35 0.40 0.45
Micropore volume (cm3/g)
1.4

~
A

1.2 0 0.033M CaCI=

~
E : 0.1MHCI ~
v 1.0
O (b)
m
0..
0.8

.o_
= 0.6
EL

0
o
to
0.4

•a 0.2
0
.71ti'-.
0.0 I I I I I

0.15 0.20 0.25 0.30 0.35 0.40 0.45

Micropore volume (cm3/g)

Fig.3 Adsorption of gold onto activated carbon as a function of micropore volume. (a) this study, and
(b) after Adams (1993).

Surface titration of activated carbon

Figure 5 shows the change of surface charge with solution pH at different ionic strengths. It can be seen
that the surface charge varies between 10 mC/m2 and -10 mC/m2 in the range of the experimental pH
values. Figure 5 shows that the point of zero charge for the carbon ANK 11 was situated at a pH of 7.1
when 2.5 hours were allowed between subsequent additions of the titrant. For pH values lower than 7.1 the
surface of the carbon ANK 11 will be positively charged, and for the pH values higher than 7.1 the surface
will be negatively charged. At pH 7.1, the adsorption of positive ions should be balanced by the adsorption
of negative ions. The surface potential was calculated from the surface charge data using the Gouy-
Chapman relationship between the surface charge and the surface potential. The change in surface
potential with pH is plotted in Figure 6. These results are in agreement with the reported results of MUller
and co-workers (1980).
 Effect~of textural and surfacepropertiesof activatedcarbonon adsorptionof golddi-cyanid¢ 535

0.70

0.65
• ...1 O
• ANK10
O ANK11
060

~o 0.55
"O

o03 0.50 I I I I I I

0 5 10 15 20 25 30 35
Heat treatment time (min)
0.80

~0.75 •

, 0.70

-o 0.65

0,60
o.55
~0.50 I I I J i I I
0 5 10 15 20 25 30 35
Heat treatment time (rain)

Fig.4 Gold adsorption and gold adsorption density of activated carbons ANKI0 and 11 as a function,
of heat treatment time at 850 °C.

0.015
• 0.1 M KCI
A 0.01 M KCI
E 0.010
=7.1
0.005
t~
"8 0.000
8
10g of ANK11
-0.005
• 500 ml solution
2.5h Equilibration time
-0.010 I I I I

4 5 6 7 8 9
pH

Fig.5 Effect of the pH on the surface charge ofANK11 at different ionic strengths after 2.5 hours
between subsequent additions of the titrant.
536 M.D. Seke et al.

40
..... 3 0 -
> /k 0.01 MKCI
E 20- • 0.1M KCI

¢- 10-

o
-10 -

-20
CO
-30 -

-40 I I I I

4 5 6 7 8 9

pH
Fig.6 Effect of solution pH on the surface potential ofANK11 at 0.1 and 0.01M KCI.

The applicability of the Gouy-Chapman relationship for fiat surface to microporous substances such
as activated carbon

It is tempting to adopt their model for the adsorption of gold. However, one of the main assumptions of
these models is that the charge distribution decays away from a large fiat surface. In practice, activated
carbons with predominantly microporous structure are used in the gold industry. Evaluation of the double
layer thickness of a symmetrical 1-1 electrolyte shows that it decreases from about 10 to 1 nm with
increasing ionic strength of the solution from 0.001 to 0.1 M (Shawn, 1992). These ionic strengths
coincide with those of the gold industry. Hence, significant overlap of the potential distributions could be
expected inside the micropores. This presents a major challenge to factual corrections of the adsorption
models.

The calculated surface potential could be used in conjunction with a surface complexation model to
account for the electrostatic effect on the adsorption of gold di-cyanide onto activated carbon ANK11.
Although the surface complexation model might be thermodynamically applicable to microporous
activated carbons, it is not realistic to fit an electrical double layer into the micropore. Moreover, the
formation of surface complexes together with the adsorption of the background electrolyte makes the
structure of this double layer more complicated. Classical double layer models can be easily used for metal
oxide surfaces. However, for activated carbon the situation is more complex due to the pore-size
distribution that must be taken into account. Assuming that the charge is the same everywhere, the external
surface charge can be used to calculate the outer potential. This can be done on the basis of the Gouy-
Chapman electrical double layer. Generally, the inner surface potential will be different from the outer
surface potential. However, with the assumption that the outer and inner charges and surface chemistries
are the same, the inner surface potential must be the same as the outer surface potential. But the potential
decay will be different. Since adsorption on activated carbon occurs predominantly inside the porous body,
the inner potential must be known. Some authors (MUller et al., 1980; Derylo-Marczewska, 1993; and
Seco et al., 1997) have calculated the surface potential on activated carbon by using the Gouy-Chapman or
Stern-Gouy-Chapman electrical double layer models. In these works the pore walls were seen as two
planar plates separated by a distance d which is the width of the pore itself. In doing so, it is important to
make sure that the pore width should be at least twice the thickness of the double layer, otherwise
significant overlap of the double layers will occur and the Gouy-Chapman model will definitely not be
applicable. It is known that activated carbon used for gold adsorption contains mainly pores of size less
than 2 nm. Therefore, a Gouy-Chapman potential distribution inside a parallel plate model of the pore can
 Effects of textural and surfacepropertiesof activatedcarbonon adsorptionof gold di-cyanide 537

not be applicable due to the narrowness of the pore. It would be more realistic to consider the overlapping
of the potential inside the micropores and a Gouy-Chapman distribution potential outside the carbon
particle. A detailed investigation on the double layer of activated carbon electrodes is presented in the
literature (Milller and Kastening, 1994). They investigated on the electrolyte side of the capacitor to
improve further understanding of the nature of the capacity of activated carbon electrodes.

A simple model that considers the overlapping double layers is the Donnan gel model proposed by Koopal
(1996) and Benedetti et al. (1996). The model has been used for the prediction of metal ion binding to
natural organic substances such as humic acids. The binding of ions such as Ca 2+, Cd 2÷, Cu 2÷, Pb 2÷, and
A13÷ on humic substances is presented in the literature by Kinniburgh et al. (1999) and by Benebetti et al.
(1995), The Donnan model postulates the existence of a bulk solution phase and a gel phase (Donnan
phase). The particle charge is considered to be restrained in the particle volume by a hypothetical
membrane permeable to small ions only (Koopal, 1996). The Donnan phase volume or Donnan volume is
defined as the solution volume within the membrane. It is assumed that carboxylic and phenolic functional
groups are present on the gel surface and that the dissociation of these groups leads to a potential either at
the particle surface or inside the gel phase (Benedetti et al, 1996). The charge as a function of the pH can
be obtained from potentiometric proton titration of the adsorbent at a series of salt concentrations. For a
simple Donnan model, it may be assumed that at each charge the overall electroneutrality of the gel phase
is entirely preserved by the penetration of salt ions into the gel phase. The charge in the gel phase leads to a
single electrostatic Donnan potential that to a reasonable approximation is independent of the position in
the gel phase. Undler these conditions, the concentration of each ion i in the gel phase can be related to its
concentration C~ in the bulk by the Boltzmann factor (Koopal, 1996):

C~.D = Ciexp (-zi F ~!/d.D / RT) (4)

where ~,tD is the Donnan potential in volts and z~ is the ionic charge of i. The primary charge density in the
Donnan phase, P~,Dis related to the proton and hydroxyl ion uptake (Koopal, 1996):

Ps,D = F (Xn - XoH) / VD (5)

where Xi is the uptake of i in mol/kg, VD is the specific volume of the Donnan phase in m3/kg and fls,D is
expressed in C/m 3. In the absence of specific adsorption the charge density in the Donnan phase can be
equal to the diffuse Donnan charge, P0,D that can be expressed as a function of qJd,D in the presence of a
symmetrical indifterent electrolyte as:

- Pa.D -----2zCsFsinh(zF~d,D / RT) (6)

The calculated Donnan potential for the activated carbon ANK11 is plotted in Figure 7. The potential is
about 200 mV at pH 5 for an ionic strength of0.1M KCI. The Donnan potential calculated in this way is
10 times higher than the potential calculated from the Gouy-Chapman relationship for the same ionic
strength (Figure 6). A major difficulty with applying the two types of models is the estimation of the
surface area (for the Gouy Chapman model) or the Donnan volume (for the Donnan model). The BET
surface area that has been used for the charge density calculation with the Gouy Chapman model has no
physical significance for microporous sorbents. It is only a number that can be related to the total
adsorption capacilTy. However, it is believed that adsoption in the micropores is volume filling. In this
study, the total pore volume of the activated carbon ANK11 was considered as the Donnan volume. This
was measured by nitrogen adsorption as explained in the experimental procedure.

However, the Donnan volume of humic acids is estimated by viscometric measurements (De Wit et al.,
1993). This volur, ae has been found to decrease with increasing ionic strength due to the swelling and
shrinking of humic acids, The Donnan volume of activated carbon is assumed to remain insensitive to the
change in salt concentration and pH of the solution. This might be explained by the fact that activated
carbon does not shrink like humic acids. The total pore volume measured by nitrogen adsorption can be a
fn'st estimation for the Donnan volume of activated carbon, but it is possible that in the wet state the pore
volume is different from that in the dry state. These complications can explain the high value of surface
potential calculate~d on the basis of the Donnan model. Although the Gouy-Chapman and Dorman models
have been succe:~sfully used to predict the equilibrium adsorption of ionic species onto permeable
538 M.D. S e k e etal.

adsorbents, their choice for microporous activated carbons should be a matter of fundamental reasons
rather than practical. More experimental work is needed to establish the magnitude of the Donnan potential
of activated carbon over a wide range of pH values. In our personal communication with Benedetti we
have come to know that progress has been made on the determination of the Donnan volume of activated
carbon. Unpublished work of Benedetti has revealed that the Donnan volume of activated carbon does not
change with salt concentration. We strongly believe that a general agreement on the evaluation of surface
potential must be found for optimal use of the surface complexation model in predicting the equilibrium
adsorption of gold di-cyanide onto activated carbon. The application of the calculated surface potential to
the surface complexation model in order to predict the equilibrium adsorption of gold onto activated
carbons is beyond the scope of this work. Parallel to this study, a phenomenological modelling of the
equilibrium adsorption of gold di-cyanide onto iron oxide is being developed by Benedetti.

250
O-co--.q>_ o
200
150
100

t,,,..,
50
0
0

t-
-50
•
0
0.1 M KCl
0.01M KCI
1,,
t-
O -100
r~
-150
-200
-250 I I I
"q:%o-n
I

4 5 6 7 8 9
pH

Fig.7 Donnan potential for ANK11 as a function ofpH at 0.1 and 0.01M KCI.

CONCLUSION

Heat treatment of the activated carbon in a nitrogen atmosphere enhanced the gold adsorption capacity by
changing some surface properties of the activated carbon. No drastic change of the pore size distribution
occurred during the heat treatment of the activated carbon. Micropore volume has been found to affect the
uptake of the gold di-cyanide onto the activated carbon. The distribution of the surface potential inside a
microporous carbon cannot be described reliably by the Gouy-Chapman or Stem theories of the electrical
double layer. The size of the pores gives the Donnan model the fundamental advantage of being applicable
in the case of microporous activated carbon, because it takes into account the overlapping of the potential
inside the microporous activated carbon.

ACKNOWLEDGEMENTS

The authors would like to thank Mintek (Council for Mineral and Technology) for funding this project. The
contribution of Professor Luuk Koopal of the Wageningen Agricultural University (Netherlands) is
acknowledged. The comments and suggestions of Dr. Mike Adams are greatly appreciated. Gratitude is
extended to Mr. M. Rakwena and Mrs K. Hayman of Mintek for performing the pore size distribution
analysis.
 Effect..;of textural and surfacepropertiesof activatedcarbonon adsorptionof golddi-cyanide 539

REFERENCES

Adams, M.D., 1990. The mechanism of adsorption of aurocyanide onto activated carbon, 1. Relation
between the effect of oxygen and ionic strength. Hydrometallurgy, 25: 171-184.
Adams, M.D., 1993. Influence of the surface chemistry and structure of activated carbon on the adsorption
of aurocyanide. Paper presented at the )(VIII International Mineral Processing Congress 23-28 May
1993. Sydney (Australia), 1175-1187.
Adams, M.D. and Fleming, C.A., 1989. The mechanism of adsorption of aurocyanide onto activated
carbon. Metall. Trans. B, 20B: 315-325.
Benedetti, M.F., van Riemsdijk, W.H., and Koopal, L.K., 1996. Humic substances considered as a
heterogeneous Donnan gel phase. Environ. Sci. Technol., 30:1805-1813.
Benedetti, M.F., Milne, C.J., Kinniburgh, D.G., van Riemdijk, W.H., and Koopal, L.K., 1995. Metal
binding to humic substances: Application of the Non-Ideal Competitive Adsorption model. Environ. Sci.
Technol., 29, 446-457.
Corapcioglu, M.O. and Huang, C.P., 1983. The surface acidity and characterization of some commercial
activated carbons. Carbon, 25(4): 569-578.
Corapcioglu, M.O. and Huang, C.P., 1987. The adsorption of heavy metals onto hydrous activated carbon.
Water Resources, 21 (9): 1031-1044.
Davis, J.A., James,, R.O. and Leckie, J.O., 1978. Surface ionization and complexation at the oxide/water
interface. 1. Computation of electrical double layer properties in simple electrolytes. J. Colloid Interf.
Sci., 63(3): 480-499.
Davis, J.A. and Leckie, J.O., 1978. Surface ionization and complexation at the oxide/water interface. II
Surface properties of amorphous iron oxyhydroxide and adsorption of metals ions. d. Colloid Interf. Sci.,
67(1): 90-107.
Davis, J.A. and Leckie, J.O., 1980. Surface ionization and complexation at the oxide/water interface. 3.
Adsorption of anions, d. Colloid Interf Sci., 74(1): 32-43.
De Wit, J.C.M, van Riemdijk, W.H., and Koopal, L.K., 1993. Proton binding to humic substances. 1.
Electrostatic effi~cts. Envron. ScL Technol. 27(10): 2005-2014.
Derylo-Marczewska, A., 1993. Analysis of the adsorption equilibrium for the system dilute aqueous
solution of dissociating organic substance-activated carbon. Langmuir, 9: 2344-2350.
Ibrado, A.S. and Fuerstenau, D.W., 1992. Effect of the structure of carbon adsorbents on the adsorption of
gold cyanide. ~vdrometallurgy, 30: 243-256.
Jones, W. G., Klauber, C. and Linge, H. G., 1989. The adsorption of aurocyanide onto activated carbon.
World Gold 89, Aus. IMM and SME-AIME, pp. 278-281.
Kinniburgh, D.G., van Riemdijk, W.H., Koopal, L.K., Borkovec, M., Benedetti, M.F., and Avena,
M.J.,1999. Ion binding to natural organic matter: Competition, heterogeneity, stoichiometry and
thermodynamic consistency. Colloids and Surfaces A: Physicochem. Eng. Aspects. 151: 147-166.
Kinoshita, K., 1988. Carbon: Electrochemical and Physicochemical Properties. John Wiley, NewYork
(USA). p. 533.
Koopal, L.K., 1996. Ion adsorption on mineral oxide surfaces. In: A. Dabrowski and V.A.
Tertykh(Editors), Adsorption on new and modified inorganic sorbents. Studies in Surface Science and
Catalysis, 99, pp. 757-796.
L6on Y. L6on, C.A., Solar, J.M., Calemma, V. and Radovic, L.R., 1992. Evidence for the protonation of
basal plane sites on carbon. Carbon, 30 (5): 797-811.
McDougall, G.J., Hancock, R.D., Wellingtron, O.L., and Copperthwaite. R.G., 1980. The mechanism of
adsorption of gold cyanide on activated carbon. J. S. Aft. Inst. Min. Metall., 80: 344-356.
Miller, J.D. and Sibrell, P.L., 1991. The nature of gold adsorption from cyanide solutions by carbon. In:
D.R. Gaskell (Editor), EPD Congrress '91, Min. Metals and Mater Soc. AIME, Warrendale, PA (USA),
pp. 647-663.
Men6ndez, J.A, Phillips, J., Xia, B. and Radovic, R., 1996. On the modification and characterization of
chemical propel~ies of activated carbon: In the search of carbons with stable basic properties. Langmuir,
12: 4404-4410.
Mtlller, M. and Kastening, B., 1994. The double layer of activated carbon electrodes. Part.1. The
contribution ofiions in the pores, d. Electroanal. Chem., 374: 149-158.
MOiler, G., Radke, C.J. and Prausnitz, J.M., 1980. Adsorption of weak organic electrolytes f~om aqueous
solution on activated carbon. Effect ofpH. d. Phys. Chem., 84: 369-376.
540 M.D. Sekeet al.

Newcombe, G., Donati, M., Drikas, M. and Hayes, R., 1996. Adsorption onto activated carbon:
electrostatic and non-electrostatic interactions. Water Supply, 14(2): 129-144.
Seco, A., Marzal, P., and Galbaldon, C., 1997. Adsorption of heavy metals from aqueous solutions onto
activated carbon in single Cu and Ni systems and in binary Cu-Ni, Cu-Cd and Cu-Zn systems. J. Chem.
Tech. Biotech., 68: 23-30.
Shawn, D.J., 1992. Introduction to Colloid andSurface Chemistry. Fourth edition, Butterworth Heinemann,
London (U.K), p. 306.
Stumm, W., 1992. Chemistry of the Solid-Water Interface: Processes at the Mineral-Water and
Particle-Water Interface in Natural Systems. John Wiley & Sons, New York (USA), p.428.
Tsuchida, N., Ruane, M. and Muir, D.M., 1985. Studies on the mechanism of gold adsorption on carbon.
In: L.F. Haughton (Editor). Mintek 50. Proc. Int. Conf. on Mineral Science and Technology, Council for
Mineral Technology, Randburg (South Africa), pp. 647-656.
Vegter, N.M. and Sandenbergh, R.F., 1997. Adsorption mechanism of gold di-cyanide onto activated
carbon. World Gold 97, Aus. IMM and SME-AIME, pp. 115-127.

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