Journal of Nuclear Energy Science & Power Generation TechnologyISSN: 2325-9809

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Research Article, J Nucl Ene Sci Power Generat Technol Vol: 2 Issue: 2

Performance Based Characterization of Nuclear and Non-Nuclear Grade Anion Exchange Resins Indion 102 and Indion-860 by Application of Radio Analytical Technique

Singare PU*
Department of Chemistry, Bhavan’s College, Munshi Nagar, Andheri (West), Mumbai 400 058, India
Corresponding author : Singare PU
Department of Chemistry, Bhavan’s College, Munshi Nagar, Andheri (West), Mumbai 400 058, India
Tel: + 91 2226256451/ 52; Fax: + 91 22 26256453
E-mail: [email protected]
Received: March 25, 2013 Accepted: July 10, 2013 Published: July 18, 2013
Citation: Singare PU (2013) Performance Based Characterization of Nuclear and Non-Nuclear Grade Anion Exchange Resins Indion -102 and Indion-860 by Application of Radio Analytical Technique. J Nucl Ene Sci Power Generat Technol 2:2. doi:10.4172/2325-9809.1000111

Abstract

Performance Based Characterization of Nuclear and Non-Nuclear Grade Anion Exchange Resins Indion 102 and Indion-860 by Application of Radio Analytical Technique

The present study deals with the application of 131 I and 82 Br radioactive tracer isotopes to evaluate the performance of Indion-102 (nuclear grade) and Indion-860 (non-nuclear grade) ion exchange resins. The major parameters studied for evaluation were specific reaction rate (min-1 ), percentage and amount of ions exchanged (mmol). It was observed that for both the resins under identical experimental conditions, iodide ions exchange take place at faster rate as compared to that of bromide ions which was related to the extent of solvation. It was observed that at a constant temperature of 35.0 °C, as the concentration of spiked iodide ion solution increases 0.001 M to 0.004 M, the percentage of iodide ions exchanged increases from 63.8% to 68.8% for Indion-102 resins; while for Indion-860 resins it increases from 51.1% to 52.6%. Similarly for 0.002 M spiked iodide ion solution, with rise in temperature from 30.0 °C to 45.0 °C, it is observed that the percentage of iodide ions exchanged decreases from 66.1% to 64.0% using Indion-102 resins; while for Indion-860 resins it decreases from 52.4% to 49.8%. The study reveals that for both the resins there exist a strong linear correlation between amount of ions exchanged and concentration of ionic solution, as well as between amount of ions exchanged and temperature of exchanging medium. In general based on radiotracer applications it was observed that Indion-102 resins show superior performance than Indion-860 resins under identical operational parameters.

Keywords: Radiotracers; 131I; 82Br; Radio analytical technique; Ion exchange resins; Characterization; Specific reaction rate; Nuclear grade resins; Indion-102; Indion-860.

Keywords

Radiotracers; 131I; 82Br; Radio analytical technique; Ion exchange resins; Characterization; Specific reaction rate; Nuclear grade resins; Indion-102; Indion-860.

Introduction

Radioisotopes are widely used as tracers in analytical chemistry. This is due to the sensitivity and simplicity of the method involved. Many elements have multiple oxidation states and in the investigations involving tracers, the oxidation state of the tracer must be ensured to be the same as that of the element in the bulk. Industrial applications of radioisotopes ensure good quality products and bring down the cost of manufacture by ways of sensitive non-destructive testing and efficient in-process control. The efficiency of several devices in a wastewater treatment plant (primary and secondary clarifiers, aeration tank) is investigated by means of radiotracers [1]. Radioisotopes are also employed in certain manufacturing processes to induce desired chemical reactions [2]. Thus radioisotopes have become a useful tool and almost every branch of industry uses them [2]. The radioisotopes in suitable physical and chemical forms are introduced in systems under study. By monitoring the radioactivity both continuously or after sampling (depending on the nature of study), the movement, adsorption, retention etc. of the tracer and in turn, of the bulk matter under investigation, can be followed. Radiotracer methodology is described extensively in the literature [3-5]. Generally in most of these applications the radioisotopes preferred are gamma emitters having half-life compatible with the duration of studies; also the amount of radioactivity used varies depending on the nature of application.
Considering the extensive technological application of radioactive tracers, in the present investigation, attempts are made to apply the tracer technique for performance evaluation of Indion-102 (nuclear grade) and Indion-860 (non-nuclear grade) ion exchange resins which are widely used in nuclear and chemical processing industries for removal of radionuclide, for cleaning and decontamination processes as well as in water treatment.

Experimental

Materials
Ion exchange resin Indion-102 is a nuclear grade strong base anion exchange resin in hydroxide form, while Indion-860 is an industrial grade weak base anion exchange resin in chloride form (both supplied by Ion Exchange India Ltd., Mumbai). Details regarding the properties of the resins used are given in Table 1.
Table 1: Properties of ion exchange resins.
The radioisotope 131I; 82Br used in the present experimental work was obtained from Board of Radiation and Isotope Technology (BRIT), Mumbai. Details regarding the isotopes used in the present experimental work are given in Table 2.
Table 2: Properties of 131I and 82Br tracer isotopes [6].
Analytical grade salts of silver nitrate, potassium iodide and potassium bromide supplied by S D Fine Chem. Ltd., India were used for the study. All the solutions were prepared in double distilled deionised water.
Conditioning of ion exchange resins
The resins were converted separately in to iodide/bromide form by treatment with 10% KI/KBr solution in a conditioning column at the flow rate as 1 mL/min. The resins were then washed with double distilled water, until the washings were free from iodide/bromide ions as tested by AgNO3 solution. These resins in bromide and iodide form were then dried separately over P2O5 in desiccators at room temperature.
Study on kinetics of iodide ion-isotopic exchange reaction
In a stoppered bottle 250 mL (V) of 0.001 M iodide ion solution was spiked with diluted 131I radioactive solution using a micro syringe, such that 1.0 mL of spiked solution has a radioactivity of around 15,000 cpm (counts per minute) when measured with γ-ray spectrometer having NaI (Tl) scintillation detector. Since only about 50-100 μL of the radioactive iodide ion solution was required to spike the solution, its iodide ion concentration will remain unchanged, which was further confirmed by potentiometer titration against AgNO3 solution. The above spiked solution of known initial activity (Ai) was kept in a thermostat adjusted to 35.0 °C. The swelled and conditioned dry ion exchange resins in iodide form weighing exactly 1.000 g (m) were transferred quickly into this spiked solution which was vigorously stirred by using mechanical stirrer and the activity in cpm of 1.0 mL of solution was measured. The solution was transferred back to the same bottle containing spiked solution after measuring activity. The iodide ion-isotopic exchange reaction can be represented as:
        (1)
Here R-I represents ion exchange resin in iodide form; I*-(aq.) represents aqueous iodide ion solution spiked with 131I radiotracer isotope.
The activity of solution was measured at a fixed interval of every 2.0 min. The final activity (Af) of the solution was also measured after 3h which was sufficient time to attain the equilibrium [7-11]. The activity measured at various time intervals was corrected for background counts.
Similar experiments were carried out by equilibrating separately 1.000 g of ion exchange resin in iodide form with spiked iodide ion solution of four different concentrations ranging up to 0.004 M at a constant temperature of 35.0 °C. The experimental sets were also repeated in the temperature range of 30.0 °C to 45.0 °C by using 0.002 M ionic solution which was kept constant.
Study on kinetics of bromide ion-isotopic exchange reaction
The experiment was also performed to study the kinetics of bromide ion- isotopic exchange reaction by equilibrating 1.000 g of ion exchange resin in bromide form with spiked bromide ion solution in the same concentration and temperature range as above. The 82Br radioactive tracer isotope was used to spike the bromide ion solution for which the same procedure as explained above was followed. The bromide ion-isotopic exchange reaction can be represented as:
        (2)
Here R-Br represents ion exchange resin in bromide form; Br*-(aq.) represents aqueous bromide ion solution spiked with 82Br radiotracer isotope.

Results and Discussion

Comparative study of ion-isotopic exchange reactions
In the present investigation it was observed that due to the rapid ion-isotopic exchange reaction taking place, the activity of solution decreases rapidly initially, then due to the slow exchange the activity of the solution decreases slowly and finally remains nearly constant, thereby giving a composite curve (Figure 1). The specific reaction rates (k) of rapid ion-isotopic exchange reactions were calculated by resolving this composite curve. The amount of iodide / bromide ions exchanged (mmol) on the resin were obtained from the initial and final activity of solution and the amount of exchangeable ions in 250 mL of solution. From the amount of ions exchanged on the resin (mmol) and the specific reaction rates (min-1), the initial rate of ion exchanged (mmol/min) was calculated [7-11].
Figure 1: Kinetics of Ion-Isotopic Exchange Reactions. Amount of ion exchange resin = 1.000 g, Concentration of labeled exchangeable ionic solution = 0.002M, Volume of labeled ionic solution = 250 mL, Temperature = 35.0 °C.
Because of larger solvated size of bromide ions as compared to that of iodide ions, it was observed that the exchange of bromide ions occurs at the slower rate than that of iodide ions [7]. Hence under identical experimental conditions, the values of specific reaction rate (min-1), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) are calculated to be lower for bromide ionisotopic exchange reaction than that for iodide ion-isotopic exchange reaction as summarized in Tables 3 and 4. For both bromide and iodide ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in ionic concentration from 0.001M to 0.004M (Table 3). However, with rise in temperature from 30.0 °C to 45.0 °C, the specific reaction rate was observed to decrease (Table 4). Thus in case of Indion-102 at 35.0°C when the ionic concentration increases from 0.001M to 0.004M, the specific reaction rate values for iodide ion-isotopic exchange increases from 0.247 to 0.277 min-1, while for bromide ion-isotopic exchange the values increases from 0.199 to 0.229 min-1. Similarly in case of Indion-860, under identical experimental conditions, the values for iodide ion-isotopic exchange increases from 0.171 to 0.198 min-1, while for bromide ion-isotopic exchange the values increases from 0.119 to 0.142 min-1. The observed increase in values of specific reaction rate with increase in ionic concentration was due to decrease in swelling pressure of the resins. Similar results are reported previously for iodide ion-isotopic exchange reactions using Indion-810 resins in which the specific reaction rate values increases from 0.090 to 0.133 min-1 under identical experimental conditions [12]. However when concentration of ionic solution is kept constant at 0.002 M and temperature is raised from 30.0 °C to 45.0 °C, in case of Indion-102 the specific reaction rate values for iodide ion-isotopic exchange decreases from 0.261 to 0.248 min-1, while for bromide ion-isotopic exchange the values decreases from 0.215 to 0.199 min-1. Similarly in case of Indion-860, under identical experimental conditions, the specific reaction rate values for iodide ion-isotopic exchange decreases from 0.190 to 0.163 min-1, while for bromide ion-isotopic exchange the values decreases from 0.136 to 0.109 min-1. Here it is expected that due to rise in temperature the swelling pressure of the resins increases resulting in decrease in values of specific reaction rate. The results obtained here are similar to that reported previously for iodide ion-isotopic exchange reactions using Indion-810 resins in which the specific reaction rate values decreases from 0.121 to 0.084 min-1 under identical experimental conditions [12]. From the results, it appears that iodide ions exchange at the faster rate as compared to that of bromide ions which was related to the extent of solvation (Tables 3 and 4).
Table 3: Concentration effect on Ion-Isotopic Exchange Reactions.
Table 4: Temperature effect on Ion-Isotopic Exchange Reactions.
From the knowledge of Ai, Af, volume of the exchangeable ionic solution (V) and mass of ion exchange resin (m), the Kd value was calculated by the equation
         (3)
Heumann et al. [13] in the study of chloride distribution coefficient on strongly basic anion exchange resin observed that the selectivity coefficient between halide ions increased at higher electrolyte concentrations. Adachi et al. [14] observed that the swelling pressure of the resin decreased at higher solute concentrations resulting in larger Kdvalues. The temperature dependence of Kd values on cation exchange resin was studied by Shuji et al. [15]; were they observed that the values of Kd increased with fall in temperature. The present experimental results also indicates that the Kd values for bromide and iodide ions increases with increase in ionic concentration of the external solution, however with rise in temperature the Kd values were found to decrease. Thus in case of Indion-102 at 35.0 °C when the ionic concentration increases from 0.001M to 0.004M, the log Kd values for iodide ions increases from 18.5 to 20.5, while for bromide ions the values increases from 13.6 to 15.5. Similarly in case of Indion-860, under identical experimental conditions, the log Kd values for iodide ions increases from 16.4 to 18.6, while for bromide ions the values increases from 11.6 to 13.4. Similar results were obtained previously in which the log Kd values for bromide ions were reported to increase from 4.00 to 5.08, 3.38 to 3.95 and 3.00 to 3.50 respectively for Indion-850, Indion FF-IP and Indion-860 resins when the concentration of bromide ions was increased from 0.005M to 0.100M at a constant temperature of 25.0 °C [16]. However when concentration of ionic solution is kept constant at 0.002 M and temperature is raised from 30.0 °C to 45.0 °C, in case of Indion-102 the log Kd values for iodide ions decreases from 20.0 to 17.9, while for bromide ions the values decreases from 14.5 to 13.0. Similarly in case of Indion-860, under identical experimental conditions, the log Kd values for iodide ions decreases from 17.9 to 16.0, while for bromide ions the values decreases from 12.3 to 11.0. Similar results were obtained previously in which the log Kd values for bromide ions were reported to decreases from 4.00 to 3.28, 3.38 to 2.81 and 3.00 to 2.54 for Indion-850, Indion FF-IP and Indion-860 resins respectively when the temperature was raised from 25.0 °C to 45.0 °C using 0.005M bromide ion solution [16]. It was also observed that the Kd values for iodide ion-isotopic exchange reaction were calculated to be higher than that for bromide ion-isotopic exchange reaction (Tables 3 and 4).
Comparative study of anion exchange resins
From the Tables 3 and 4, it is observed that for iodide ion-isotopic exchange reaction by using Indion-102 resin, the values of specific reaction rate (min-1), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log Kd were 0.254, 0.325, 0.082 and 19.2 respectively, which was higher than 0.180, 0.257, 0.046 and 17.2 respectively as that obtained by using Indion-860 resins under identical experimental conditions of 35.0 °C, 1.000 g of ion exchange resins and 0.002 M spiked iodide ion solution. The identical trend was observed for the two resins during bromide ion-isotopic exchange reaction.
From Table 3, it is observed that using Indion-102 resins, at a constant temperature of 35.0 °C, as the concentration of spiked iodide ion solution increases 0.001 M to 0.004 M, the percentage of iodide ions exchanged increases from 63.8% to 68.8%. While using Indion-860 resins under identical experimental conditions the percentage of iodide ions exchanged increases from 51.1% to 52.6%. Similarly in case of bromide ion-isotopic exchange reaction, the percentage of bromide ions exchanged increases from 52.7% to 60.8% using Indion-102 resin, while for Indion-860 resin it increases from 38.1% to 44.9%. The results obtained here agrees well with that reported previously for iodide ion-isotopic exchange reactions using Indion-810 resins in which the percentage of iodide ions exchanged increases from 29.40% to 42.25% under identical experimental conditions [12]. The increase in percentage of ions exchanged as observed here might be due to decrease in swelling pressure of the resin with rise in ionic concentration. The effect of ionic concentration on percentage of ions exchanged is graphically represented in Figure 2.
Figure 2: Variation in Percentage Ions Exchanged with Concentration of Labeled Ionic Solution Amount of ion exchange resin = 1.000 g, Volume of labeled ionic solution = 250 mL, Temperature = 35.0 °C.
From Table 4, it is observed that using Indion-102 resins, for 0.002 M spiked iodide ion solution, as the temperature increases 30.0 °C to 45.0 °C, the percentage of iodide ions exchanged decreases from 66.1% to 64.0%. While using Indion-860 resins under identical experimental conditions the percentage of iodide ions exchanged decreases from 52.4% to 49.8%. Similarly in case of bromide ion-isotopic exchange reaction, the percentage of bromide ions exchanged decreases from 57.7% to 52.7% using Indion-102 resin, while for Indion-860 resin it decreases from 43.12% to 35.1%. Here it is expected that due to rise in temperature the swelling pressure increases resulting in decrease in percentage of ions exchanged. The results obtained here are similar to that reported previously for iodide ion-isotopic exchange reactions using Indion-810 resins in which the percentage of iodide ions exchanged decreases from 38.70% to 27.60% under identical experimental conditions [12]. The effect of temperature on percentage of ions exchanged is graphically represented in Figure 3.
Figure 3: Variation in Percentage Ions Exchanged with Temperature of Labeled Ionic Solution.
Amount of ion exchange resin = 1.000 g, Concentration of labeled exchangeable ionic solution = 0.002 M, Volume of labeled ionic solution = 250 mL, Amount of exchangeable ions in 250 mL labeled solution = 0.500 mmol
From Table 1 it is clear that the moisture content of Indion-102 is (<60%) which is higher than that of Indion-860 resins (54%). Here it seems that the difference in the moisture content might be responsible for difference in the performance of the two resins. The overall results indicate that under identical experimental conditions, as compared to Indion-860 resins, Indion-102 resins shows higher percentage of ions exchanged which might be due to the difference in moisture content of the two resins. Thus Indion-102 resins show superior performance than Indion-860 resins under identical operational parameters.
Statistical correlations
The results of present investigation show a strong linear correlation between amount of ions exchanged and concentration of ionic solution (Figures 4 and 5). In case of iodide ion-isotopic exchange reaction, the R2 values calculated were 0.999 for both Indion-102 and Indion-860 resins, while for bromide ion-isotopic exchange reaction, the values calculated were 0.998 for both the resins.
Figure 4: Correlation between concentration of iodide ion solution and amount of iodide ion exchanged.
Amount of ion exchange resin = 1.000 g, Volume of labeled ionic solution = 250 mL
Temperature = 35.0 ┬░C
Correlation coefficient (r) for Indion-860 = 0.9999
Correlation coefficient (r) for Indion-102 = 0.9996
Figure 5: Correlation between concentration of bromide ion solution and amount of bromide ion exchanged.
Amount of ion exchange resin = 1.000 g, Volume of labeled ionic solution = 250 mL,
Temperature = 35.0 °C
Correlation coefficient (r) for Indion-860 = 0.9993
Correlation coefficient (r) for Indion-102 =0.9994
Similar linear correlation exists between amount of ions exchanged and temperature of exchanging medium (Figures 6 and 7). In case of iodide ion-isotopic exchange reactions the values of R2 calculated for Indion-102 and Indion-860 resins were 0.959 and 0.968 respectively. Similarly in case of bromide ion-isotopic exchange reactions the values calculated were 0.952 and 0.998 respectively for both the resins.
Figure 6: Correlation between Temperature of exchanging medium and amount of iodide ion exchanged.
Amount of ion exchange resin = 1.000 g, Concentration of labeled exchangeable ionic solution = 0.002M, Volume of labeled ionic solution = 250 mL,
Amount of exchangeable ions in 250 mL labeled solution = 0.500 mmol.
Correlation coefficient (r) for Indion-860 = -0.9843
Correlation coefficient (r) for Indion-102 = -0.9795
Figure 7: Correlation between Temperature of exchanging medium and amount of bromide ion exchanged.
Amount of ion exchange resin = 1.000 g, Concentration of labeled exchangeable ionic solution = 0.002 M, Volume of labeled ionic solution = 250 mL,
Amount of exchangeable ions in 250 mL labeled solution = 0.500 mmol.
Correlation coefficient (r) for Indion-860 = -0.9992
Correlation coefficient (r) for Indion-102 = -0.9759

Conclusion

It is well known fact that the organic ion exchange resins are the wave of the present research and are considered as the material of next generation. As a result in present time, extensive work is reported in the literature on synthesis of new ion exchange materials and their characterization. Among the different characterization techniques, radio analytical technique using isotopes as a tracer serves as one of the effective technique particularly due to their non- destructive nature. As a result in the present research paper we have successfully demonstrated the application of radio tracer isotopes to evaluate the performance of Indion -102 (nuclear grade) and Indion-860 (nonnuclear grade) resins. The results also indicate that the radio tracer technique used in the present work can be used to standardize the operational process parameters for efficient performance of the resins in various unit processes. The same technique can be extended further for characterization of different industrial grade ion exchange resins, the results of which will be useful in the selection of those resins for stipulated industrial application.

Acknowledgment

The author is thankful to Professor Dr. R.S. Lokhande (Retired) for his valuable help and support by providing the required facilities for carrying out the experimental work in Radiochemistry Laboratory, Department of Chemistry, University of Mumbai, Vidyanagari, Mumbai -58.

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