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Reactive Polymers, 16 (1991/1992) 261-269

Elsevier Science Publishers B.V., Amsterdam

261

KINETICS OF ISOTOPIC EXCHANGE AND MECHANISM OF SORPTION OF Co(II) ON HYDROUS STANNIC OXIDE
NASR Z. MISAK, EL-SAID I. SHABANA, ETIDAL M. MIKHAIL and HUSSEIN F. GHONEIMY

Nuclear Chemistry Department, Atomic Energy Authority, Atomic Energy Post 13759, Cairo (Egypt)
(Received December 13, 1990; accepted in revised form August 30, 1991)

Equilibrium measurements o f sorption o f Co 2 + from acidic chloride solutions on hydrous stannic oxide show that this sorption is accompanied by the release of an equivalent amount o f H +. Besides, Co 2 and C I - seem to be sorbed on separate sites on the oxide surface. The study o f isotopic exchange kinetics in 0.05-0.1 M Co 2 solutions proves a chemical control mechanism for the reaction that can mainly be represented by two processes. The rate constant of the slow process, whose contribution becomes quite small in the oxide heated at 400C, decreases with the increase o f the capacity. Keywords: stannic oxide, isotopic exchange, kinetics, cobalt(II), sorption

INTRODUCTION Alkali and alkaline earth cations are reported [1-7] to be generally sorbed by hydrous oxides by a simple equivalent exchange with surface H . This exchange is particle diffusion controlled at solution concentrations > 0.01 M [3,8-12]. For complexing cations, the situation is still ambiguous. A similar mechanism was reported for sorption of Cu(II) on hydrous thoria and titania [13] and of uranyl ions on stannic oxide [14]. However, for sorption of Th 4+ on tin oxide [14] and of UO 2+ and Th 4 on zirconia [15], strong complexation with surface oxygen, leading to chemically controlled kinetics, and a release of an equivalent amount of H +

were suggested. Dzombak and Morel [16] describe sorption of Cu(II) on ferric oxide by one or two second-order reactions implying chemical control. Though many studies [13-15,17-19] claim the release of equivalent H + on sorption of complexing cations by hydrous oxides, others show no release of H + [20,21], release of less than the equivalent amount [22-25], and release of more than the equivalent amount [25]. In the last case, multiple hydrolysis and multidentate bonding can be assumed. Even for the same oxide and sorbed cation, there are contradictory results [18,19,23]. Exchange with structural ions was claimed as an additional process in the sorption of Co(II) and Zn(II) by MnO2 [4]. Besides, A13+ was

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262 claimed to be sorbed on hydrous SnO 2 by coprecipitation rather than by ion exchange and the oxide washed thoroughly with 0.1 M H N O 3 (to remove carbonate impurity formed by absorption of CO 2 during precipitation and washing with ammonia) followed by distilled water, till the washings had a pH of 5, were used. The sorption of cobalt was followed by counting the y-activity of both solid (after washing with a small amount of alcohol) and solution, using the scintillation assembly Nuclear Enterprises, UK, with ST6 scaler-timer. The initial and final concentrations of CI- in solution were determined by titration with standard silver nitrate. Besides, the initial C1- concentration was estimated from the initial known amounts of CoC12 and HCI used. The initial H concentration was known from the added amount of HCI and was also determined by calculation, from the value of the initial pH (measured with an Orion research pH meter with an accuracy of +0.01 pH units) with activity coefficcients taken into consideration by the use of standard solutions. The final H concentration was determined from the final pH value and at relatively high acidities by titration with alkali.

[5].
Equilibria and kinetics of isotopic exchange of Co 2+ on hydrous stannic oxide are investigated here.

EXPERIMENTAL

Preparation of hydrous stannic oxide


A 0.1 M SnCI 4 solution was prepared by adding liquid stannic chloride of high purity to the requisite amount of distilled water. Hydrous stannic oxide (a-stannic acid) [5,26] was then precipitated from the 0.1 M SnC14 solution by adding 0.1 M NH4OH. The precipitate was washed with water by decantation to remove sorbed ions. After several days of such washing, the precipitate did not settle and was difficult to separate by filteration because it passed through the filter paper. Therefore, it was separated by centrifugation. Washing with dilute ammonia (which removes CI- effectively) was also unsuccessful because it again did not settle and passed through the filter paper. The solid was then dried at 50C, and could be washed with dilute ammonia until free of CI- (no C1- was detected in the washings) without any difficulty. It was washed further with distilled water until the p H of the washings became about 5, redired at 50C, sieved to different sizes, and stored over saturated NH4CI solution. Portions of the solid were heated at 200 and 400C before sieving and storage.

Kinetics of isotopic exchange


Samples of known particle sizes were saturated with C o 2+ by repeated equilibration with CoC12 at 100 c m 3 / g for about 2 weeks in a thermostated shaker adjusted to 25 + IC until the p H of the equilibrating solution remained constant. Usually, the equilibrium pH was somewhat lower than the initial pH, which is probably because C1- ions sorbed at the early stages of equilibration (higher acidity due to higher Co 2+ sorption) are very sluggishly removed at the lower acidity in the later states. The removal of CI- lowers the solution pH since it occurs through sorption of O H - from solution. The kinetics of isotopic exchange was followed by contacting, at 25 + IC, 0.06 g of the Co-saturated sample with 6 cm 3 of the

Equilibrium measurements
0.01 N CoC12 solutions, to which 6Co and known amounts of standardized HC1 were added, were equilibrated for 48 h at 20 + IC in a thermostated shaker with hydrous stannic oxide dried at 50C. The original oxide

263

solution used in sample saturation after adding 6Co to it. After shaking for a predetermined time, the solid and the liquid were immediately separated by filtration. The extent of isotopic exchange was followed by counting the y-activity of both the solid and liquid. In addition, the pH of the solution was measured and it was assumed that it always remained at the value of the equilibrium saturation solution. The amount of cobalt in the solid (capacity in m e q / g ) was determined from separate experiments in which the saturation solutions contained 6Co. The activity of both solution and solid was measured after each equilibration, until saturation was attained. Besides, this capacity was determined by the isotopic dilution method. The capacity was found to be independent of particle size. From duplicates of equilibria and kinetic experiments, the results were found to be reproducible to _+3%.

RESULTS AND DISCUSSION

The results of equilibrium measurements are given in Table 1. The calculated final pH given in this table is that obtained by considTABLE 1

ering the change in the initial H + concentration due to a release of an equivalent amount of H + on sorption of Co 2+ (2 H + per Co 2) and of O H - due to sorption of CI- ( O H - per CI-). Activity coefficients are ignored in the calculation of this pH. Hence, the values obtained are expected to be somewhat lower than the actual values. Table 1 shows that with the original material, no H is released on Co 2+ sorption. Some of the initially present H + may even disappear. With the acid-treated material, H is released. However, the mole ratio H + / C o 2+ comes very close, becomes or equal, to 2 only at relatively high acidities. At the latter acidities, the calculated final pH comes close to the experimental value. One may assume that the acid treatment of the oxide removes or reduces carbonate impurity in the oxide. The presence of such an impurity will partially or completely consume the acid released due to the exchange sorption of Co 2+. Actually, carbonate ions were found in solution on washing the oxide with ammonia. Since in our calculation of the H + / C o 2+ ratio we assumed the release of equivalent amounts of H and O H - due to sorption of Co 2 and CI-, respectively, the value of 2 for this ratio means that either this assumption

Equilibria measurements for sorption of cobalt and chloride ions from 0.01 N CoC12 on original and acid treated hydrous stannic oxide (37.5 cm3/g) under different conditions Sample Initial pH Co 2+ sorbed (mM/g) 0.059 0.056 0.048 0.047 0.043 0.041 0.035 0.026 0.017 0.016 CI- sorbed (mM/g) 0.007 0.008 0.018 0.024 0.025 0.025 0.027 0.049 0.075 0.080 pH Final 4.08 4.00 2.98 2.77 2.72 2.69 2.66 2.38 2.25 2.13 Calculated 2.50 2.44 2.67 2.65 2.62 2.58 2.53 2.33 2.22 2.14 H + / C o 2+ (mol/mol) 0.023
-a

Original Acid treated

3.73 3.15 4.17 3.45 3.16 2.99 2.78 2.36 2.18 2.07

1.28 1.68 1.7(} 1.64 1.42 1.92 1.98 2.06

Calculation shows that no H is released and that some of the H + initially present disappears.

264 is true, or that cobalt is sorbed as Co 2 with the release of one H and uptake of one CIfor electroneutrality of the surface, or as CoC1 +, or as C o O H . The latter two assumptions may be excluded on the basis of the relatively low p H and C1- concentrations used in the present work. If Co 2 is sorbed with the release of one H , as previously suggested for stannic oxide [24], the fact that one C1- must be sorbed by the solid to make it electrically neutral means that in the cation exchange sites, the sorption of CI- should be equal to that of Co 2 (in m M / g ) . If, moreover, C1- is sorbed on anion exchange sites, CI- sorption is increased. Table 1 shows that at the relatively high equilibrium p H values, the sorption of CI- is always less than that of Co 2. At pH values >i 4, where Co 2 sorption is high (original material), C1- is practically not sorbed. One may, therefore, deduce that two H are released for each Co 2 sorbed and that C1and Co 2+ are sorbed at separate sites on the hydrous tin oxide surface. The latter conclusion is in agreement with the fact that C1sorption increases with the decrease of pH, whereas the reverse is true for Co 2. with H in the oxide, is available for isotopic exchange. The kinetic curves (not shown here) which express F as a function of time t, where F is the fractional attainment of equilibrium at time t, have shown that particle size has no effect on the rate of approach to equilibrium. This excludes film or particle diffusion control of the rate of the exchange process. Besides, these curves show that at comparable capacities, the increase of solution concentration increases the rate of approach to equilibrium. This excludes particle diffusion as a slow rate-controlling step. The exchange rate is therefore chemically controlled. For Na [27,28] and Cs [29] isotopic exchange in stannic oxide, particle diffusion is rate controlling. This shows that Co 2 is interacting much more strongly than Na or Cs with the oxide surface. For chemically controlled isotopic exchange reactions, McKay's equation (for homogeneous reactions) [30] acquires the following form in the case of heterogeneous exchange [31]: ln(1-F)=

-k(n a+nb)t

(1)

Kinetics of isotopic exchange


The different oxide samples used in these experiments were saturated with Co 2+ at different p H values from 0.05 M CoCI 2. In one case, 0.1 M CoCI 2 was used with the oxide dried at 50C, and it was found that the capacity at pH 3.54 is equal to 0.51 m e q / g . The oxide dried at 50C was found to have capacities of 0.41, 0.32, 0.22 and 0.13 m e q / g at p H 3.71, 3.54, 2.63 and 2.19, respectively. The oxide dried at 200 and 400C has capacities of 0.24 and 0.22 m e q / g , respectively, at p H 3.54. The capacity determined by the analysis of the saturation solutions and by the isotopic dilution m e t h o d were practically equal. This shows that the cobalt, sorbed by exchange

where k is the rate constant, F is the fractionnal attainment of equilibrium as given above, n a is the number of moles of the exchanging species in the solid, and n b is that number in the liquid. The application of eqn. (1) to the isotopic exchanges occurring under different conditions is given in Figs. 1 and 2. These show that in all cases the exchanges are complex ones, involving more than one process. Besides, it is seen (Fig. 2) that, as was deduced from the original kinetic curves, the exchange rates are independent of particle size and that at comparable capacities (0.41 and 0.51 m e q / g from 0.05 and 0.1 M COC12, respectively) the rate is higher at the higher solution concentration (Fig. 1). To analyse the curves in Figs. 1 and 2, the straight lines corresponding to the last (slow) process were extrapolated in several in-

265 stances to zero time to obtain the equilibrium fraction of exchange (or capacity) corresponding to the first fast process (or processes) and, besides, the F values (at different times) corresponding only to this process (or processes). Equation (1) was then applied to these F values. The results of this application (Fig. 3) show that straight lines are obtained. However, these lines do not cut the ordinate at zero time, showing that there is a still faster process (which we shall call the fastest process) preceding the fast one represented by the straight lines in Fig. 3. By also extrapolating these lines and with the known total capacity we obtain the capacities corresponding to the slow, fast and fastest processes. The rate constants (k) of the fast and slow processes, and the capacity values for the different processes are given for the various conditions in Table 2. Table 2 shows at the 0.0! ~k'~ _
-0.5 -

heating temperatures of 50 and 200C, the contribution of the fastest process constitutes only a very small fraction of the total capacity. The capacity is much lower for the sample heated at 200C. However, the contributions of the fast and slow processes are almost equal to those of the sample dried at 50C. U n d e r the same conditions of pH (3.54) and concentration (0.05 M), these contributions are about 27 and 71%, respectively, for the oxide dried at 50C, and 24 and 71%, respectively, for that heated at 200C. The capacity of the oxide heated at 400C is little different from that of the oxide heated at 200C. However, for the former heating temperature, the capacity for the fastest process is much higher (about 20% of total capacity) and the slow process (about 9%) is largely reduced. The decrease of capacity on heating must be due to removal of exchange sites (OH

o &

0~41 0 32 0.51

meq/g 1 5M meq/g~0oO meq / g 0o10M

-1.0

I 4

I 8

I 12

~ 16

I 20

I 2/.

l 28

I 32

I 36

Ti m e hr Fig. 1. Kinetics of isotopic exchange of Co 2+ from 0.05 and 0.1 M CoC| 2 on hydrous stannic oxide dried at 50C, with different capacities and average particle diameter 225/zm.

266

' ~

s~."--~

22s.

~0 "c 0.32 m ~ ,

15-

-2.(3
0

~ t.

I 8

I 12

I 16

I 20 Time~hr

I 2/,

I 28

l 32

I 36

I 40

Fig. 2. Kinetics of isotopic exchange of Co 2+ from 0.05 M CoC12 on hydrous stannic oxide of two particle diameters, and different capacities at different heating temperatures.

TABLE 2 Rate constants and capacities corresponding to the different processes involved in the isotopic exchange of Co 2+ in hydrous stannic oxide Heating temp. (C) Solution conc. (M) Total cap. (meq/g) Fastest process Capacity (meq/g) 0.011 0.011 0.013 0.05 Fast process Capacity (meq/g) 0.11 0.08 0.06 0.15 Rate constant (mo1-1 s -1) 0.33 0.31 0.38 0.32 Slow process Capacity (meq/g) 0.29 0.22 0.11 0.04 0.38 0.17 0.02 Rate constant (mo1-1 s -1) 0.044 0.050 0.053 0.064 0.028 0.047 0.048

0.50 0.05

0.10 200 400 0.05 0.05

0.41 0.32 0.22 0.13 0.51 0.24 0.22

267

groups and H 2 0 molecules [32]). It is noteworthy here that previously prepared a- and fl-stannic acids dried at 50C had comparable water contents (19.7 and 16.4%, respectively). At 200C, these values become 8.7 and 6.7%, respectively, whereas at 400C, they are 2.1 and 2.0, respectively. The sites for the fastest process may probably be H3 O+ (strong acid sites) accompanying, according to the particle hydrate model of England et al. [33], the stannic oxide particles. The capacity for this process (about 0.011 m e q / g ) is in agreement with Na capacities ( < 0.02 m e q / g ) previously found for a- and /3-stannic acids at pH ~<4 (27). At 200C, the weight loss does not alter the porous texture [32]. The capacity for the

fastest process remains about the same (Table 2), and one may assume that these sites are almost not affected. The sites corresponding to the fast and slow processes decrease considerably and by almost the same proportion. At 400C, the microporous texture is completely transformed into a mesoporous one with a smaller surface and higher porosity [32]. A change in the surface structure may occur. This is accompanied by an increase of average acidity, in agreement with previous results for a-stannic acid [32]. Table 2 shows that for the sample dried at 50C, the capacity for both the fast and fastest processes changes little with the change of total capacity, i.e., with equilibrium pH. The increase of the total capacity is therefore

0.0

o ",

O.t.1 0.13 O. 2/-. 0.22

meq/g .... " "

50C

2 0 0 C /-.0 O C

-0.2 n

-0.4

LI_
I

-0.6

-0.8

-1.0

1.2-

-1.4.

,
0

I 1

,
Time,

I 2
hr

I 3

Fig. 3. Plots of the fast process in the isotopic exchange of Co2+ from 0.05 M foE12 on hydrous stannic oxide of particle size 225/xm at different capacities and heating temperatures.

268

associated mainly with the slow process. This may lend support to the supposition that the fastest process involves the strongly acidic H2 O+ sites. It shows that the fast process sites are also relatively strongly acidic and are more acidic than the slow process sites. The k value for the slow process decreases with capacity. This may possibly be due to the involvement of sites of lower acidity and stronger binding. Table 2 shows also that in all cases, The sorption of Co(II) and hydrous stannic oxide can be represented by two main processes. REFERENCES
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269 26 M. Lepatey, J. Sautereau and J.-M. Bloch, Etude des propriEtEs physicochimiques de composes hydroxylEs de l'Etain(IV): Les acides stanniques, C.R. Acad. Sc. Paris, Ser. C, 273 (1971) 755. 27 E.I. Shabana, Ion exchange characteristics of hydrous tin oxide, Ph.D. Thesis, Ain Shams University, Cairo (1987). 28 N.Z. Misak, N.Sh. Petro and E.I. Shabana, On the behaviour of hydrous stannic oxide as an ion exchanger: Effect of aging and kinetics of exchange, Colloids Surf., 55 (1991) 289. 29 E.I. Shabana and N.Z. Misak, Self-diffusion and trace component diffusion and trace component diffusion of cesium ion in hydrous stannic oxide, Solid State Ionics, 44 (1990) 41. 30 H.A.C. McKay, Kinetics of exchange reactions, Nature, 142 (1938) 997. 31 K.H. Lieser, P. Gutlich and I. Rosenbaum, Kinetics and mechanism of heterogeneous exchange reactions on the surface of ionic crystals, Proc. Symp. Exchange Reactions, Brookhaven National Laboratory, Upton, NY, 31 May-4 June, 1965; Exchange Reactions, International Atomic Energy Agency, Vienna, (1965) 375. 32 N.Sh. Petro, I.M. E1-Naggar, E.I. Shabana and Nasr Z. Misak, On the behaviour of hydrous tin oxide as an ion exchanger: Structural features, porous texture, capacity and apparent p K values, Colloids Surf., 49 (1990) 219. 33 W.A. England, M.G. Cross, A. Hamnett, P.J. Wiseman and J.B. Goodenough, Fast proton conduction in ion-exchange compounds, Solid State Ionics, 1 (1980) 231.