The 2 nd International Conference

th
on Chemical Sciences Proceeding ISSN NO. 1410-8313
Yogyakarta, October 14-16 , 2010

REMOVAL OF AuCl4- FROM AQUEOUS SOLUTION THROUGH

REDUCTIVE ADSORPTION ON PEAT SOIL HUMIN
1, 1 1 1*
Shinta Rosalia Dewi *, Eko Sri Kunarti , Dwi Siswanta , Sri Juari Santosa ,
2
and Muefit Bahadir
1
Department of Chemistry, Universitas Gadjah Mada, Yogyakarta, Indonesia
2
Institute of Ecological Chemistry and Waste Analysis Faculty of Life Sciences,
Technische Universitact Braunschweig, Germany

* Corresponding author , Tel/fax: 0816-426-2984 / 0274-545188

ABSTRACT
-
Removal of AuCl4 from aqueous solution through adsorption and accompanied by
reduction on peat soil humin has been done. The effect of medium acidity on the reductive
adsorption as well as the kinetics and isotherm of the reductive adsorption were studied. The
reductive adsorption was optimum at pH 2 and best described by Langmuir model with the
capacity of 71.43 mg/g. The reductive adsorption fit well the kinetic model of first order
-1
reaching equilibrium with first order rate constant 0.001 min . Diffractogram of X-ray diffraction
(XRD) and photo-optical microscope confirmed the removal of gold as gold metal.

Keywords: gold, removal, reductive adsorption, humin

INTRODUCTION Based on the capability of humin to

adsorps metals, which due to the presence of -
he amount of electrical and electronic COOH and phenolic -OH functional group in

T wastes (printed circuit board (PCBs),

phone, computer, TV) are increasing
due the increase of those electrical and
humin, so in this study, removal of AuCl4
through reductive adsorption on peat soil
humin was examined.
-

electronic device production, which cause

serious damage to the environment because EXPERIMENTAL SECTION
of the hazardous content of metals such as
Mn, Fe, Ni, Cu, Zn, Sn, and Pb [1]. Meanwhile, Materials
they are also contain precious metal, such as Stock of 1000 ppm gold solution were
Ag, Au and Pd [2]. The purity of precious prepared by dissolving 1 g gold metal in a
metals in PCBs is more than 10 times higher minimum aquaregia (HCl/HNO3) solution, and
than that of their rich–content minerals [3], then diluted to 1 L using 0.1 mol/L HCl. HCl
whereas cellular phone contain 200 g Au per and NaOH were purchased from Merck and
ton of its scrap [4]. The increasing demand of used without purification.
electrical and electronic product which have
limited industrial raw materials and dangerous Instrumentation
waste on the environment, becomes one A pH meter (Horiba F-52) was used for
reason for the gold recovery. pH measurements. Shaker (Marius
Humic substances such as humin, Instrument) was used to shaking solution.
humic acid, and fulvic acid are relatively Spectrophotometer UV-visible (Shimadzu UV-
inexpensive and natural polymer that 1601) was used to determine the
-
environmentally benign. Previous study has concentration of AuCl4 Photo-optical
shown that humic acid which contains -COOH microscope (Ephitot+ Nikon D60) was used to
and phenolic -OH groups had the ability to observe the gold metal obtained. X-ray
remove gold ions through reductive adsorption diffractometer (XRD, Shimadzu 6000) was
in acid medium [5]. Humin, one fraction of used to determine the crystalline phases of
humic substances also contain -COOH and - gold metal.
OH functional groups and capable of binding
+ + 2+
various metals such as Cs , Sr , and Gd [6].

Shinta Rosalia Dewi, et al 111

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada
ISSN NO. 1410-8313 The 2 nd International Conference on Chemical Sciences Proceeding
th
Yogyakarta, October 14-16 , 2010

Procedure Kinetic adsorption

Preparation of peat soil humin The effect of contact time on the
-
Humin was isolated from peat soil removal of AuCl4 are shown in Figure 2. It is
collected from South Kalimantan. Isolation of clearly indicated that equilibrium was reached
humin was based on traditional alkali within 15 h contact time.
extraction, with 0.1 M NaOH and purified with
0.1M HCl/0.5M HF.

Reductive adsorption experiment

The batch reductive adsorption
experiment were performed in Polyetilen
bottles (0.010 g peat soil humin with 10 mL of
gold solution of known initial concentration)
shaked at desired temperature. Gold solution
was adjusted to pH 1.0 2.0, 3.0, 4.0, 5.0 and
6.0 by HCl or NaOH for the investigations of
the effect of pH. Kinetics of adsorption of
-
AuCl4 on humin was studied at various contact
time (5 min – 25 h). Isotherm adsorption of
-
AuCl4 on humin was studied at various
-
concentration (15-400 mg/L). The AuCl4
concentration was determined by
Spectrofotometer UV-Vis, and gold metal was
Figure 2. Effect of contact time on the removal of
confirmed by XRD and photo-optical -
AuCl4 onto humin from aqueous solution
microscope.

RESULTS AND DISCUSSION The observed data were fitted with the
first order of Santosa kinetic model, reaction is
Effect of pH given as [7]:
-
Effect of pH on the removal of AuCl4
(Figure. 1) showed that the removal was
optimum at pH 2 (acid medium). In that pH,
functional groups of humin should be
protonated and have positively partial charged,
-
and species of AuCl4 at pH 2 was dominant. -
-
The removal of AuCl4 on humin is due to the where CA is the concentration of AuCl4
positively charged surface of humin and it species in solution (mol/L), CA0 is initial
-
interacts with negatively charged species of concentration of AuCl4 species (mol/L), t is
-
AuCl4 by electrostatic attraction. contact time (min), k and K are adsorption rate
-1
constant (min ) and adsorption equilibrium
constant (L/mol), respectively. They could be
determined from slope and intercepts of linear
plot of

. versus of .

A plot of as

function of as shown in Figure 3., resulted

linear relationship with correlation coefficient
2
(R ) of 0.960. From the slope and intercept,
the value of k and K were evaluated as 0.001
-1
min and 16,401 L/mol, respectively.
-
Figure 1. Effect of pH on the removal of AuCl4 onto
humin from aqueous solution

112 Shinta Rosalia Dewi, et al

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada
The 2 nd International Conference
th
on Chemical Sciences Proceeding ISSN NO. 1410-8313
Yogyakarta, October 14-16 , 2010

0.990. From the slope of this curve, the

-
maximum loading capacity of humin for AuCl4
was evaluated as 71.43 mg/g while the value
of KL was evaluated from the intercept as
0.068 L/mg.
XRD analyses of humin were perform
-
after the removal of AuCl4 . The XRD
diffractogram confirmed the formation of gold
metal during the removal (Figure 5.) with sharp
o
peaks at 2 values of 38; 44; 64; and 77 ,
that corresponding to gold metal as observed
by Nakajima et al. [8].

Figure 3. Relationship between ln(Co/Ca)/Ca and

t/Ca

Adsorption isotherm
Figure 4. shows the removal isotherm of
- -
AuCl4 in acid medium. The removal of AuCl4
-
increased with increasing of AuCl4 equilibrium
concentrations in low concentration regions
and plateaus were observed at high
concentration regions exhibiting a Langmuir
type adsorption. The removal data was then
fitted with the following Langmuir equation:
Figure 5. X-ray diffraction pattern of humin taken
Ce/qe = (1/qm) Ce + (1/K.qm) after the removal of AuCl4
-

where qe is the amount adsorbed at

equilibrium (mg/g) and Ce is the equilibrium
concentration in solution (mg/L), qm and KL are Figure 6. shows the photo-optical
Langmuir isotherm constant which are related microscope of humin after the removal of
-
to maximum adsorption capacity and AuCl4 . This figure shows that the black
equilibrium constant, respectively, were patches are humin, while bright patches are
determined from slope and intercepts of linear aggregate of gold metal as the reduction
-
plots of Ce/qe versus Ce. product of AuCl4 .

Figure 4. Relationship between Ce/qe and Ce

Figure 6. Photo-optical microscope image of gold

As shown in Figure 4, the plot is lying on
2 aggregates formed during removal of
a linear line with a correlation factor (R ) of -
AuCl4 on humin (200x magnification)

Shinta Rosalia Dewi, et al 113

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada
ISSN NO. 1410-8313
-
Thus, the removal of AuCl4 proceeds
through adsorption on humin and then
followed by reduction to gold metal by phenolic
-OH of humin, as presented in the following
reaction:
- 0
AuCl4 + 3Ar-OH  Au + 3Ar=O + 3H +4Cl
where, Ar (aryl) is aromatic chain of humin.
CONCLUSION
Humin, one fraction of peat soil
contained -COOH and phenolic -OH groups
- -
and had capability for removal of AuCl4
through adsorption and followed by reduction.
-
Reductive adsorption of AuCl4 from solution
was optimum in acid medium (pH 2). Removal
-
of AuCl4 on humin fitted well the first order of
Santosa kinetic model and Langmuir Isotherm
-1
with rate constant of 0.001 min and maximum
capacity of 71,43 mg/g, respectively.
-
Reduction of AuCl4 to gold metal occurred
because of phenolic -OH in humin was
oxidated. The presence of gold metal has
been shown by the appearance of four peaks
o
at 2 of 38; 44; 64; and 77 in the
diffractogram of XRD and by the photo-optical
microscope.
114
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada
The 2 nd International Conference on Chemical Sciences Proceeding
th
Yogyakarta, October 14-16 , 2010
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Shinta Rosalia Dewi, et al