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Carbon, Vol. 33, No. 2, pp.

215-220, 1995
Copyright 0 1995 Elsevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved
ooO8-6223/95 $9.50 + .OO

0008-6223(94)00135-9

ADSORPTION OF DYSPROSIUM IONS ON ACTIVATED


CHARCOAL FROM AQUEOUS SOLUTIONS

RIAZ QADEER and JAVED HANIF


Pakistan Institute of Nuclear Science and Technology, P.O. Box 13.56, Islamabad Pakistan

(Received 13 July 1994; accepted in revised form 4 October 1994)

Abstract-The adsorption of dysprosium ions onto activated charcoal from aqueous solution has been
investigated in relation to pertinent variables, such as shaking time, pH, concentration of dysprosium ions,
and temperature. The conditions leading to maximum adsorption have been established. The adsorption
of dysprosium ions obeys the Langmuir and the Dubinin-Radushkevich isotherm equations. Thermody-
namic quantities, namely AH and AS, have been calculated from the slopes and intercepts of plots of
In (Ko) versus l/T. The results indicate that the adsorption of dysprosium ions on activated charcoal is
an endothermic process. The influence of different cations and anions on the adsorption of dysprosium
ions has been examined. The adsorption of other metal ions on activated charcoal has been measured un-
der specified conditions to evaluate their selectivity. Approximately 98% of the dysprosium adsorbed on
the activated charcoal was recovered using 40 ml of 3M HNOs solution.
Key Words-Activated charcoal, dysprosium ions, adsorption, aqueous solution, selectivity, elution.

1. INTRODUCTION lybdenum[l l] and copper[l2] surfaces. No data are


available on its adsorption on activated charcoal.
Activated charcoal is a widely used material that is
well known for its adsorption properties. Activated
charcoals are non-hazardous, processed carbonaceous 2. EXPERIMENTAL
products having an intricate porous structure and a
large internal surface area that is contained predomi- 2.1 Chemicals
nantly within micropores. The adsorbent properties of The chemicals used in this study were dysprosium
activated charcoals are essentially attributed to their nitrate (Rare Earth Product, 99.999%) and a com-
large surface area, high degree of surface reactivity, mercial activated charcoal (M/S British Drug House,
universal adsorption effect, and favorable pore size BDH; item No. 33032). The B.E.T. surface area, de-
distribution. The latter makes their internal surface ac- termined by nitrogen adsorption, was found to be
cessible and enhances their adsorption rate without 980 m2/g. The porosity and pore volume were found
sacrificing their mechanical strength[ I]. Due to these to be 75.74% and 1.43 cm3/g, respectively, and aver-
properties, activated charcoals have found many ap- age particle size was 3.7 + 0.2 pm.
plications in industry for separation and purification
purposes, such as the removal of toxic and health- 2.2 Instruments
hazardous particles and ions from solutions. We have An energy dispersive X-ray fluorescence (EDXRF)
previously used activated charcoal for the adsorption spectrometer, XR-500 from Links System, U.K.,
of strontium[2], samarium[3], gadolinium[4], euro- equipped with an 860 analyzer, a Si(Li) detector and
pium[5], thorium[6], uranium[7], and cerium[8] ions an X-ray tube K5012 SV with tungsten anode, was
from aqueous solutions. The present work describes used for measuring the dysprosium ion concentration
our investigations of the adsorption of dysprosium in the solutions, with an error within 2.0%. A Heto-
ions on activated charcoal. The adsorption of dyspro- frig shaker from Heto Birkerod, Denmark, was used
sium ion on solids is important for its preconcentra- for the adsorption studies. The surface area of the
tion, because it has numerous applications in nuclear activated charcoal was determined using Quantasorb
and metallurgical industries. Due to its thermal neu- Sorption System (M/S Quanta Chrome Corporation,
tron adsorption cross-section (930b) and high melting N.Y.). An Autoscan- mercury porosimeter (M/S
point (1412”C), dysprosium along with special steel is Quantachrome Corporation, N.Y.) was used to mea-
used to make nuclear reactor control rods. Moreover, sure the pore volume and porosity of the activated
in combination with vanadium and other rare earth, charcoal. Sub Sieve Sizer-95 supplied by Fischer Sci-
dysprosium has been used in making laser materials. entific Company was used to carry out the particle size
Previously, a few reports have been published on the analysis of the activated charcoal.
adsorption of dysprosium ions on tungsten[9-lo], mo-
2.3 Procedure
Correspondence should be addressed to: Dr. Riaz Qadeer,
Adsorption measurements were carried out via a
Senior Scientific Officer, PINSTECH, P.O. Box No. 1356, batch technique at room temperature (22 + O.SOC), ex-
Islamabad Pakistan. cept where otherwise specified. Accordingly, 10 ml of

215
216 R. QADEER and J. HANIF

dysprosium-containing solutions of known concentra- ing variation in percentage adsorption and in the dis-
tion were shaken with about 0.1 g of dry activated tribution coefficient (KD) with shaking time. It is
charcoal in 250-ml reagent glass bottles for a given clear that, under the conditions chosen, the adsorp-
time period. The solutions were then filtered through tion of dysprosium ions is rapid in its initial stages,
Whatman filter paper No. 40 (circular, 14.0 cm). The and that gradually the process slows down and sub-
first 2-3 ml portion of the filtrate was rejected because sequently attains a constant value after about 60 min-
of the adsorption of dysprosium ions on the filter pa- utes (i.e., when adsorption equilibrium is established).
per. The concentration of dysprosium ions with mear- For this reason, a shaking time of 60 minutes was se-
ing filtrate was determined by means of the EDXRF lected for all subsequent experiments.
spectrometer and was corrected for losses due to ad- The adsorption rate constants for the two stages of
sorption on the walls of the glass bottles by running dysprosium ion uptake on activated charcoal are de-
blank experiments (i.e., without activated charcoal termined using the eqn[l3]:
added). The percentage adsorption and distribution
coefficient (K,,) were computed using the following [l - F(t)] = Ale+” + AzepkZf (3)
equations:
where F( t ) is the fraction of dysprosium ions adsorbed
(C; - (7) x loo at time t on activated charcoal, k, and k2 are the rate
% Adsorption = (1) constants for the first (I) and second (II) stages of ad-
G
sorption, respectively, and Ai and AZ are constants.
and Plots of In [ 1 - F( t )] versus t for dysprosium ion ad-
sorption on activated charcoal are given in Fig. 2. The
c, - C, v values of k, , kZ, A, and A2 obtained from these curves
Distribution coefficient (Ko) = ___ x -M (2) are 9.22 x 10p2/min, 6.24 x 10-4/min, 0.15, and 0.36,
C, respectively.
The influence of pH on the adsorption of dyspro-
where C, and C’ denote the initial and final concen-
sium ions onto activated charcoal was studied with the
tration of dysprosium ions in the solution, respectively.
dysprosium ion concentration, shaking time, and
In eqn (2), V is the volume of the solution and M is
amount of activated charcoal fixed at 2.0 g/l, 60 min-
the amount of the activated charcoal used.
utes, and 0.1 g, respectively. Figure 3 shows the influ-
ence of pH on the adsorption of dysprosium ions on
3. RESULTS AND DISCUSSION activated charcoal. The percentage adsorption and the
distribution coefficient (KD) increase with increasing
Preliminary investigations were conducted to ascer- pH up to a value of 4 and then start to decrease. Max-
tain the time required to reach an equilibrium between imum adsorption occurs at a pH of 4 and, hence, a
dysprosium ions and the activated charcoal. This ex- buffer with a pH of 4 (Fluka, item No. 82560) was
ploratory work involved shaking 10 ml of a solution used in all subsequent experiments.
containing 2.0 g/l of dysprosium (pH = 3.66) with The behaviour of dysprosium ions in aqueous so-
0.1 g dry activated charcoal for different intervals of lution is a complex phenomenon, in the sense that
time from 2 to 120 minutes. Figure 1 shows the result- dysprosium ions may be present as ions exhibiting

loo
l-----725o pS 2; 4;
t (mini
6; ;O 14” 12;

-lC
20 40 60 80 100 120

Shaking time (mini

Fig. 1. Adsorption of dysprosium on activated charcoal as Fig. 2. Plot of In [ 1 - F(t)] versus t for dysprosium ion ad-
a function of shaking time. sorption on activated charcoal.
Adsorption of dysprosium ions 217

- 1200
60 -

-1000

.E 3
._ 60_
z -800 ;

P‘: 40- - 600 ,o

.S
-400

20 -
,200
0 % Adsorption

0 0 1 2 3 I
4 I
5 I
6 I
7 t
8 9’

PH

Fig. 3. Influence of pH on the adsorption of dysprosium 0


ions on activated charcoal. 4 5 6 7 a 9 10 11

PH

Fig. 4. Distribution of various hydrolyzed species of dyspro-


different compositions and different degrees of activ- sium ions in solution against pH.
ity. Therefore, it is necessary to ascertain the nature
of dysprosium ions in solution in order to understand
their adsorption behaviour towards activated charcoal.
The percentages of hydrolyzed species of dysprosium competitive adsorption of H30+ and Dy3+ ions var-
ions at a total dysprosium concentration of 2.0 g/l ies in accordance with the acidity of the solutions. As
were calculated from the following equilibria and their the pH of solution increases from 1 to 4, the adsorp-
respective hydrolysis constants[ 121: _ tion of H30+ ions decreases, and that of Dy3+ ions
goes up. Above a pH of 4, the Dy3+ ions start to get
Dy3+ + H,O = Dy(OH)*+ + H+, hydrolyzed, resulting in the formation of hydroxide
ions such as Dy(OH)‘+, DY (OH):, DY (OH)!, and
K I = l@.O (4) Dy(OH),. These hydroxide ions are weakly adsorbed
as compared to Dy 3f ions; therefore, the adsorption
Dy(OH)*+ + Hz0 + Dy(OH); + H+,
of dysprosium starts decreasing above pH 5 and up
K2 = 1O-8.2 (5) to 8. Above a pH of 8, the adsorption process could
not be followed because of the formation of insolu-
Dy(OH): + Hz0 = Dy(OH); + H+, ble dysprosium complexes in aqueous solution.
The adsorption of dysprosium ions on the activated
K3 = 1O-8.5 (6) charcoal was studied as a function of total dysprosium
ion concentration in the range of 1 .O to 7.0 g/l on a
Dy(OH), + H,O = Dy(OH), + H+,
buffer solution at pH = 4. The results, depicted in
K = lo-IO.3 Fig. 5, show that the percentage adsorption and the
4 (7)
distribution coefficient (KD) decreased as the dyspro-
The percentages of all ionic species, namely Dy3+, sium ion concentration increased, thereby indicating
DY (OH) *+, Dy(OH):, Dy(OH)$ and Dy(OH), at dif- that energetically less favourable sites become involved
ferent pH values, have been estimated and are plotted in the adsorption process with increasing dysprosium
versus pH in Fig. 4. It is evident from this figure that concentration. The data concerning the dependence of
at a pH between 1 and 4 the predominant species is the extent of adsorption on the dysprosium concen-
Dy3+. At a pH of 5, the species Dy(OH)*+ has a value tration were subjected to examination by means of the
of 0.037% but, at a pH of 8, it has a maximum value Freundlich, Langmuir, and Dubinin-Radushkevich
of 11.3%. However, above a pH of 8, its value starts (D-R) isotherm equations. The Freundlich equation
decreasing. Dy(OH): is calculated at a pH of 5 to was used in the form:
be < 1 .O%, having a maximum value at a pH of 8
(14.65%) and then decreasing to 1.49% at a pH of 10. q = AC”” 03)
Whereas the species Dy(OH)i is insignificant at a pH
of 6, its extent is 71.28% at a pH of 9 and 63.60% at where q is the amount of dysprosium ions adsorbed
a pH of 10. At pH values below 8, Dy(OH), is neg- per gram of the activated charcoal, C is the equilib-
ligibly small; however, its percentage at a pH of 10 is rium concentration of dysprosium ions in solution,
33.40%. Based on the above calculations, it is con- and A and n are constants that can be related to the
cluded that from a pH of 1 to 4, the Dy3+ ions exist strength of the adsorptive bond and the adsorption
as such in aqueous solutions. In this pH range, the bond distribution, respectively. The Freundlich plot
218 R. QADEER and J. HANIF

The linearized D-R isotherm equation[l5] is:

In q = In qm - K’t2 (10)

where E = R T ln( 1 + l/C), K’ is the constant related


to the adsorption energy (mo12/kJ2), R is the gas con-
stant, and T is the absolute temperature. The quantities
q, qm, and C have their previously defined meanings.
A straight line is obtained upon plotting In q versus e2
as shown in Fig. 6(c), indicating that dysprosium ion
adsorption onto activated charcoal also obeys the D-R
isotherm equation. Values of qm and K’ calculated
from the intercept and the slope of the plot were 0.29
01 2 3 4 5 6 7 8 (g/g) and 0.0247 (mo12/kJ2), respectively.
Concentration of dysprosium (g/l) The influence of temperature on the adsorption of
dysprosium ions was also investigated. For such stud-
Fig. 5. Effect of dysprosium ion concentration on its adsorp- ies, the dysprosium concentration in the solutions used
tion onto activated charcoal. were 2.0, 3.0, 4.0, 5.0, and 6.0 g/l and the tempera-
ture was varied from 10°C to 60°C in 10°C steps while
other parameters were kept constant. Figure 7 shows
that KD values increase with increasing temperature.
of log q versus log C shown in Fig. 6(a) demonstrates The thermodynamic quantities AH, AS and AC of
the non-validity of the equation over the whole range dysprosium ion adsorption were calculated from the
of dysprosium ion concentration studied here. KD values using the following relations:
The Langmuir equation was applied in the form:

c (11)
-_= L+C
4 Kqm qm
and
where C and q have been already defined, qm is a
measure of the monolayer capacity, and K is a con- AG=AH-TAS (12)
stant related to the heat of adsorption. A straight line
was obtained by plotting C/q against C, Fig. 6(b), in- The values of AH and AS were computed from the
dicating the conformity of the data to the Langmuir slopes and intercepts of the linear variation of In KD
equation in the whole concentration range. Values of with the reciprocal of temperature, Fig. 8, and are
constants qm and K from the slope and intercept of given in Table 1 along with the values of AC deter-
the plot in Fig. 6(b) were 0.294 (g/g) and 8.94 (l/g), mined from eqn (12). The positive values of AH show
respectively. that the adsorption of dysprosium ions on activated

iogc
-1.5 -1.0 -0.5 0 0.5 1.0
-0.2 I I I 16
I

- 12
=:
,"
"
m 1
s-
2m \
D
s
,"
-4 " Dy soln. cont. (g/l 1
02.0 03.0 r4.0 -
05.0 n 6.0
10 I I I I I I I , I
0 1 2 3 4 5O
10 20 30 40 50
c (g /II
Temperature&)

Fig. 6. (a) Freundlich, (b) Langmuir, and (c) D-R isotherm


plots for the adsorption of dysprosium ions onto activated Fig. 7. Effect of temperature on the adsorption of dyspro-
charcoal. sium ions on activated charcoal.
Adsorption of dysprosium ions 219

Table 1. Thermodynamic parameters for the adsorption of dysprosium ions on activated charcoal
AG (kJ/mol)

(kJ%ol) (kJ/dtzmol) 283 293 303 313 323

2.0 58.11 0.26 -15.47 -18.07 -20.67 -23.27 -25.87


3.0 28.71 0.15 -13.74 -15.24 -16.74 -18.24 -19.74
4.0 24.23 0.13 -12.56 -13.86 -15.16 -16.46 -17.76
5.0 19.98 0.11 -11.15 -12.25 -13.35 -14.45 -15.55
6.0 13.68 0.08 -8.96 -9.76 -10.56 -11.36 -12.16

charcoal is an endothermic process, a fact that is quite charcoal more effectively than the cations with smaller
contrary to the usual observations of adsorption exo- Z/r values.
thermicity. A possible explanation for the endothermic We have also examined the adsorption behaviour
heat of adsorption was given in our earlier communi- of dysprosium ions on activated charcoal in the pres-
cations[ 16,171. The values of AC are negative, as ex- ence of CH,COO-, S,O:-, I-, Br; Cl-, NO;, and
pected for a spontaneous process. The decrease in AC EDTA. The concentration of added anions and dys-
values with increasing temperature shows that the ad- prosium ions were fixed at 1.Og/l and 2.0 g/l, respec-
sorption of dysprosium ions on activated charcoal is tively. The results are shown in Table 3. The presence
more favourable at higher temperatures. Since the ad- of additional anions also induced a negative effect on
sorption process is endothermic, it follows that, un- dysprosium adsorption. The degree of reduction in the
der these conditions, the process becomes spontaneous adsorption of dysprosium ions in the presence of an-
because of a positive entropy change. ions was in the order EDTA > NO; > Cl- > Br- >
The effect of various cations such as Cs+, Na+, I- > S20:- > CH,COO-. It may be inferred that the
Li+, Sr’+, Ca2+, Zn2+, Co2+, Ce3+, Sc3+, and Cr3+ on affinity of the complexes of anions is low towards the
the adsorption of dysprosium ions on activated char- activated charcoal surface as compared to that of free
coal has also been examined. The concentration of Dy3+ ions.
added cations and dysprosium ions were fixed at 1.O The adsorption of other metal ions was measured
g/l and 2.0 g/l, respectively. The results of these in- under the optimum adsorption conditions employed
vestigations are given in Table 2. It is obvious from for dysprosium ions to check the selectivity of the ac-
this Table that the presence of additional cations in so- tivated charcoal for dysprosium ions. The results, pre-
lution reduces the adsorption of dysprosium ions on sented in Table 4, indicate that Eu, Sm, Er, U, La, Y,
activated charcoal. The adsorption of dysprosium is Ce, and Ba exhibit considerably higher values for the
lowered because these cations are coadsorbed along percentage adsorption and K,; hence, would be co-
with dysprosium ions. Table 2 also demonstrates that adsorbed beside dysprosium onto activated charcoal.
the cations with larger charge density (Z/r) values re- In contrast, Cr, Cd, Cs, Co, Ni, Zn, Mn, V, Sr, Cu,
duced the adsorption of dysprosium ions on activated and Rb are poorly adsorbed; hence, the separation of
dysprosium from these metals may be achieved. The
separation factor for dysprosium is large in the pres-
ence of Zn, Mn, V, Sr, Cu, and Rb because these met-
12 als have much lower KD values.
I I I I I
The feasibility of using activated charcoal for the
Dy soln.conc.(g/l) preconcentration/separation of dysprosium was as-
02.0 03.0 r4.0
05.0 m6.0
9

-a-
Table 2. Effect of different cations on the adsorption of
D dysprosium ions on activated charcoal
Y
+
Cations Z/r % Adsorption KD (ml/g)
6
Nil 91.90 1134.57
cs+ 0.5988 91.00 1011.11
Na+ 1.0309 90.00 900.00
Li+ 1.4706 88.50 769.57
Sr’+ 1.7857 86.30 629.93
3 l I I I I 2.0202 85.45 587.29
3.0 3.1 3.2 3.3 3.4 3.5 3.6 $1 2.7027 84.25 534.92
co>+ 2.7778 83.85 519.20
lo'/ T IK)
2.9013 80.50 412.82
$: 4.0984 77.65 347.43
Fig. 8. Plots of lnKD versus l/T for the adsorption of dys- Cr3+ 4.7619 74.95 299.20
prosium ions on activated charcoal.
220 R. QADEER and J. HANIF

Table 3. Effect of different anions on the adsorption of I , I , I I , t ( t -

dysprosium ions on activated charcoal 60 -

Anions % Adsorption KD (ml/g)

Nil 91.90 1134.51


CH,COO- 91.85 1127.00
s,o:- 88.45 765.80
I- 80.20 405.05
Br- 16.10 329.20
cl- 71.29 250.26
NO; 60.65 154.13
EDTA 49.28 97.04

sessed by elution studies. For such studies, a glass col-


A-A-
umn (30 cm x 0.7 cm i.d.) containing a known amount
0 10 20 30 40 50 60
of dry activated charcoal on a glass wool support was
used. The column was loaded with a solution contain- Volume of eluont (ml)

ing 2.0 g/l of dysprosium at a pH of 4 and kept for Fig. 9. Elution of dysprosium ions adsorbed onto activated
60 minutes. About 90% dysprosium was adsorbed on charcoal by means of 3M HNO,.
the activated charcoal. The elution of adsorbed dys-
prosium was carried out with 3M HN03 solution at
a flow rate of 1 .O ml/min. Figure 9 shows the elution
profile of dysprosium. About 98% of the adsorbed
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