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215-220, 1995
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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.
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
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 ;
.S
-400
20 -
,200
0 % Adsorption
0 0 1 2 3 I
4 I
5 I
6 I
7 t
8 9’
PH
PH
In q = In qm - K’t2 (10)
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&)
Table 1. Thermodynamic parameters for the adsorption of dysprosium ions on activated charcoal
AG (kJ/mol)
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
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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