Studies on separation and purification of fission (99)Mo from neutron activated uranium aluminum alloy.

A new method has been developed for separation and purification of fission (99)Mo from neutron activated uranium-aluminum alloy. Alkali dissolution of the irradiated target (100mg) results in aluminum along with (99)Mo and a few fission products passing into solution, while most of the fission products, activation products and uranium remain undissolved. Subsequent purification steps involve precipitation of aluminum as Al(OH)3, iodine as AgI/AgIO3 and molybdenum as Mo-α-benzoin oxime. Ruthenium is separated by volatilization as RuO4 and final purification of (99)Mo was carried out using anion exchange method. The radiochemical yield of fission (99)Mo was found to be >80% and the purity of the product was in conformity with the international pharmacopoeia standards.

A new ion selective electrode for cesium (I) based on calix[4]arene-crown-6 compounds.

A polyvinylchloride (PVC) based liquid membrane ion selective electrode (ISE) for cesium has been developed. 25,27-Dihydroxycalix[4]arene-crown-6 (L1), 5,11,17,23-tetra-tert-butyl-25,27-dimethoxycalix[4]arene-crown-6 (L2) and 25,27-bis(1-octyloxy)calix[4]arene-crown-6 (L3) were investigated for their use as ionophores. The cation exchange resin DOWEX-50W was used to maintain low activity Cs+ in inner filling solution to improve the performance. The best response for cesium was observed with L3 along with optimized membrane constituents and composition. Excellent Nernstian response (56.6 mV/decade of Cs(I)) over the concentration range 10(-7) to 10(-2)M of Cs(I) was obtained with a fast response time of less than 10s. Detection limit for Cs(I) using the present ISE is 8.48×10(-8) M Cs(I). Separate solution method (SSM) was applied to ascertain the selectivity for Cs(I) over alkali, alkaline earth and transition metal ions. The response of ISE for Cs(I) was fairly constant over the pH range of 4-11. The lifetime of the electrode is 10 months which is the highest life for any membrane based Cs-ISE so far developed. The concentration of cesium ion in two simulated high level active waste streams was determined and results agreed well with those obtained independently employing AAS.

Ion selective electrode for cesium based on 5-(4'-nitrophenylazo)25,27-bis(2-propyloxy)26,28-dihydroxycalix[4]arene.

A polyvinylchloride (PVC) based liquid membrane ion selective electrode (ISE) for cesium was fabricated with 5-(4'-nitrophenylazo)25,27-bis(2-propyloxy)26,28-dihydroxycalix[4]arene as ionophore. Different membrane constituents were investigated to realise optimum performance of the ISE developed. Of the four plasticizers and two ion additives studied, the best response was observed with membrane having 2-nitro phenyl octyl ether (oNPOE) as plasticizer and potassium tetrakis (perchloro phenyl) borate (KTpClPB) as ion additive. Linear response over concentration range of 10(-5)-10(-1)M CsCl was obtained. The Nernstian slope of the response was 56 mV per decade for Cs with a response time less than 20s. Matched potential method has been applied to find out the selectivity for Cs over several ions like Rb(+), K(+), Na(+), NH(4)(+), Sr(2+), Ba(2+), Ca(2+), Mg(2+), Cu(2+), Pb(2+), Zn(2+), Ni(2+) and Ce(3+). The response of ISE for Cs(+) was fairly constant over the pH range of 3-11. The lifetime of the electrode is 9 months which is the longest life for any membrane-based Cs-ISE so far developed. The concentration of cesium in two simulated high level active waste streams was determined and results agreed well with those obtained independently employing atomic absorption spectrometry.

Simultaneous determination of trace amounts of borate, chloride and fluoride in nuclear fuels employing ion chromatography (IC) after their extraction by pyrohydrolysis.

An accurate and sensitive method based on the combination of pyrohydrolysis-ion chromatography (PH-IC) is proposed for the simultaneous separation and determination of boron as borate, chloride and fluoride in nuclear fuels such as U(3)O(8), (Pu,U)C and Pu-alloys. The determination is based on the initial pyrohydrolytic extraction of B, Cl and F from the samples as boric acid, HCl and HF, respectively, which are subsequently separated by ion chromatography (IC). The proposed method significantly improves the existing analytical methodology as it combines the determination of boron, a critical trace constituent in nuclear materials, along with F(-) and Cl(-) for chemical quality control measurements. Various experimental parameters were optimized to achieve maximum recoveries of the analytes during the pyrohydrolysis and to get better ion chromatographic (IC) separation of borate, F(-) and Cl(-) along with other anions such as CH(3)COO(-), NO(2)(-), NO(3)(-), Br(-), PO(4)(3-) and SO(4)(2-). Recoveries of more than 93% could be obtained for all the analytes in the sample (0.5-1.5 g) at 1200+/-25K and distilled with pre-heated steam at the flow rate of 0.3 mL/min. An isocratic elution with a mobile phase of 0.56 M d-mannitol in 6.5mM NaHCO(3) was used for the IC separation. The detection limits for B (as borate), F(-) and Cl(-) were 24, 13 and 25 microgL(-1), respectively. Precision of about 5% was achieved for determination of boron, Cl(-) and F(-) in the samples containing 1-5 ppm(w) of boron, and 10-25 ppm(w) of Cl and F. The method was validated with reference materials and successfully applied to the nuclear fuels. The methodology is easy to adapt on routine basis.

Ensuring complete absence of Ce(IV) and measurement of the stability constant of the fluoride complex of Ce(III).

Literature survey revealed a wide variation in the measured stability constant values of the aqueous fluoride complexes of trivalent cerium. This could be due to inadequate care for full conversion and maintenance of the oxidation state of cerium to trivalent state. In the present work quinhydrone has been used to ensure complete absence of Ce(IV) and the stability constant of CeF(2+) in 1 M NaClO(4) has been measured potentiometrically using a fluoride ion selective electrode. Log beta(1) obtained in this work was 2.936+/-0.024 and fitted well with the general trend of stability constants of the lanthanide (rare earths) fluorides in aqueous solution.