Home Physical Sciences A novel method for the determination of uranium and free acidity in nuclear fuel process samples by extraction spectrophotometry
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A novel method for the determination of uranium and free acidity in nuclear fuel process samples by extraction spectrophotometry

  • Raghbendra Thakur , Pranab K. Tarafder EMAIL logo and Raj Ranjan Jha
Published/Copyright: December 28, 2018

Abstract

A novel and useful extraction spectrophotometric method for the rapid determination of uranium and free acidity in nuclear fuel process samples using the reagent, 2,3-dihydroxynaphthalene as an extractant as well as color forming agent is described. Uranium at milligram level forms a yellowish- orange anionic complex with the ligand, 2,3-dihydroxynaphthalene over a pH range, 10–12. This anionic complex is easily extracted into ethylacetate as an ion-pair complex with cetyltrimethylammonium cation (CTA+). The absorbance of the ion-pair complex in ethylacetate is measured at 390 nm. The molar absorptivity and Sandell’s sensitivity of the system being 5.0×103 L·mol−1 cm−1 and 0.047 μg cm−2, respectively at 390 nm. This very reagent (2,3-dihydroxynaphthalene) also forms a yellowish-orange nitro product with free nitric acid (HNO3) in the presence of concentrated sulfuric acid. This nitro- product is easily extracted into the same solvent (ethylacetate) and absorbs maximum at 380 nm. The molar absorptivity (ε) and Sandell’s sensitivity of the system being 2.4×103 L·mol−1 cm−1 and 0.027 μg cm−2, respectively. By using the single chromophoric agent (2,3-dihydroxynaphthalene), both uranium and free acidity can be easily and reliably determined separately in the process solution. The relative standard deviations (RSD) are in the range, 0.5–2.0% and 1.5–2.0%, respectively for uranium and free nitric acid determinations. The method has been applied to nuclear fuel process solutions, and the results obtained have been found to be favorably comparable with those obtained from standard methods.

Acknowledgement

Authors are grateful to Director, Additional Directors, Regional Director/ER and Head Chemistry Group, AMD, for giving constant encouragement and inspiration as well as for providing facilities to carry out the research work. The authors are thankful to Director, AMD for giving permission to publish the work.

References

1. Sato, T.: The co-extraction of nitric acid and uranyl nitrate by tributyl phosphate. J. Inorg. Nucl. Chem. 9, 188 (1959).10.1016/0022-1902(59)80081-6Search in Google Scholar

2. Karpas, Z.: Analytical Chemistry of Uranium (Environmental, Forensic, Nuclear and Toxicological Applications) (2015). CRC Press, Taylor & Francis Group, Boka Raton, London, New York.10.1201/b17750Search in Google Scholar

3. Rathore, D. P. S.: Advances in technology for the measurement of uranium in diverse matrices. Talanta 77, 9 (2008).10.1016/j.talanta.2008.06.019Search in Google Scholar

4. Chitnis, R. T., Kulkarni, R. T., Reges, S. G., Mukherjee, A.: Volumetric method for the determination of uranium in the active process solutions. J. Radioanal. Nucl. Chem. 45(2), 331 (1978).10.1007/BF02519600Search in Google Scholar

5. Bickel, M.: The Davies-Gray titration for the assay of uranium in nuclear materials: a performance study. J. Nucl. Mater. 246(1), 30 (1997).10.1016/S0022-3115(97)00040-8Search in Google Scholar

6. Editorial staff: Technical Report on Analytical Techniques in Uranium Exploration and ore processing, Series No 341, Determination of Uranium (U3O8) in Uranium Mill Products and Ores by the Lead Reduction Method (1992). International Atomic Energy Agency, ISBN-92-0-103792-9, IAEA, Vienna, p. 125.Search in Google Scholar

7. Editorial staff: Vogel’s Textbook of Quantitative Chemical Analysis (1989). ELBS, Longman, England, 5th Ed., p. 471.Search in Google Scholar

8. Smith, W. B., Drewry, J.: Colorimetric determination of uranium in phosphate rock after extraction with alkyl acid phosphates. Analyst 86, 178 (1961).10.1039/an9618600178Search in Google Scholar

9. Currah, J. E., Beamish, F. E.: Colorimetric determination of uranium with thiocyanate. Anal. Chem. 19, 609 (1947).10.1021/ac60008a006Search in Google Scholar

10. Rizvi, G. H.: Potassium ferrocyanide as a spectrophotometric reagent for the determination of uranium. J. Radioanal. Nucl. Chem. 125(2), 333 (1988).10.1007/BF02041691Search in Google Scholar

11. Koppikar, K. S., Gajankush, K. B.: Spectrophotometric determination of uranium using 8-quinolinol. Rep. At. E.C. India, AEET-225 (1965), p. 17.Search in Google Scholar

12. Tarafder, P. K., Ramanaiah, G. V., Chaudhuri, M. K.: Guaiacol as a new reagent for the spectrophotometric determination of uranium. J. Radioanal. Nucl. Chem. 154(5), 331 (1991).10.1007/BF02165489Search in Google Scholar

13. Lazo, P., Cullaz, A., Dogiani, S., Lubonja, F.: Determination of uranium by spectrophotometric method with Arsenazo-III. Asian J. Chem. 12, 732 (2000).Search in Google Scholar

14. Orabi, A. H.: Determination of uranium after separation using solvent extraction from slightly nitric acid solution and spectrophotometric determination of free acidity in uranyl nitrate solutions. J. Radiat. Res. Appl. Sci. 6, 1 (2013).10.1016/j.jrras.2013.09.001Search in Google Scholar

15. Avivar, J., Ferrer, L., Casas, M., Cerda, V.: Automated determination of uranium(VI) at ultra-trace levels, exploiting flow techniques and spectrophotometric detection using a liquid waveguide capillary cell. Anal. Bioanal. Chem. 397, 871 (2010).10.1007/s00216-010-3600-4Search in Google Scholar PubMed

16. Moulin, C., Decambox, P., Mauchien, P.: Direct uranium (VI) and nitrate determinations in nuclear reprocessing by Time-Resolved Laser-Induced Fluorescence. Anal. Chem. 68, 3204 (1996).10.1021/ac9602579Search in Google Scholar

17. Savage, D. J.: Research and development topics in Analytical Chemistry. Proc. Soc. Anal. Chem. 11, 266 (1974).10.1039/sa9741100264Search in Google Scholar

18. Scargill, D., Waterman, M. J., Kuruez, A. S., Hitton, T. E.: Rapid titrimetric determination of free acidity in proess samples of uranyl nitrate. Report AERE-M 3823, Atomic Energy Research Establishment (1984). Harwell, Oxon.Search in Google Scholar

19. Damien, N., Cauchetier, P.: A method for the determination of free acidity in concentrated solutions of plutonium (IV). Anal. Chim. Acta 41, 483 (1968).10.1016/S0003-2670(01)80431-1Search in Google Scholar

20. Mayankutty, P. C., Ravi, S., Nadkarni, M. N.: Determination of free acidity in uranyl nitrate solutions. J. Radioanal. Nucl. Chem. 68, 145 (1982).10.1007/BF02517616Search in Google Scholar

21. Rodden, C. J.: Analytical Chemistry of the Manhattan Project, NNES VIII-1 (1950). New York, p. 214.Search in Google Scholar

22. Baumann, E. W., Torrey, B. H.: Determination of free acid by standard addition with potassium thiocyanate as complexant. Anal. Chem. 56, 682 (1984).10.1021/ac00268a021Search in Google Scholar

23. Arhland, S.: New methods for the determination of free acid in the presence of large amounts of uranyl salt. Acta Chem. Scand. 14, 2035 (1960).10.3891/acta.chem.scand.14-2035Search in Google Scholar

24. Marckzenco, Z.: Separation and Spectrophotometric Determination of Elements (1986). Horwood, Chichester, p. 609.Search in Google Scholar

25. Fujimori, H., Matsui, T., Suzuki, K.: Simultaneous determination of uranium and HNO3 concentrations in solution by Laser-Induced Fluorescence Spectroscopy. J. Sci. Technol. 25(10), 798 (1988).10.1080/18811248.1988.9735927Search in Google Scholar

26. Ahmed, M. K., Suryanarayana, D. S., Sabbarwal, K. N., Srinivasan, L.: Simultaneous determination of uranium and HNO3 concentrations in solution by Laser-Induced Fluorescence Spectroscopy. Anal. Chem. 57(12), 2358 (1985).10.1021/ac00289a043Search in Google Scholar

27. Shepherd, M. J. Jr., Rein, J. E.: Manual of Analytical Methods Used by the Control Laboratory at the Chemical Processing Plant (1955). U.S. Atomic Energy Commission Report, IDO-14316.Search in Google Scholar

28. Kolthoff, I. M., Elving, P. J. (eds.): Treatise on Analytical Chemistry, Part II (1962), Wiley, New York, vol. 9.Search in Google Scholar

29. Tarafder, P. K., Murugan, P., Kunkal, L., Rathore, D. P. S.: Extraction of uranium with 2,3 dihydroxynaphthalene and cetyltrimethylammonium bromide and its fluorimetric determination in silicate rocks. J. Radioanal. Nucl. Chem. 253, 135 (2002).10.1023/A:1015880904919Search in Google Scholar

30. Sillen, L. G.: Some Graphical methods for determining equilibrium constants II. On “curve-fitting” methods for two variable data. Acta Chem. Scand. 10, 186 (1956).10.3891/acta.chem.scand.10-0186Search in Google Scholar

31. Hotzbecher, Z., Divis, L., Kral, M., Sucha, L., Vlacil, F.: Handbook of Organic Reagents in Inorganic Analysis (1967). Ellis Horwood Limited, Chichester, p. 167.Search in Google Scholar

32. Gavazov, K. B., Delchev, V. B., Stefanova, T. S., Toncheva, T. K., Simitchieve, K. K.: Russ. Specific features of tetranitrotetrazolium blue chloride as an extraction reagent for iron(III). Russ. J. Gen. Chem. 86(5), 1167 (2016).10.1134/S1070363216050315Search in Google Scholar

33. Mondal, R. K., Tarafder, P. K.: Extractive spectrophotometric determination of titanium in silicate rocks, soils and columbite-tantalite minerals. Microchimica Acta 148, 327 (2004).10.1007/s00604-004-0272-9Search in Google Scholar

34. Tarafder, P. K., Mondal, R. K.: Micelle mediated extraction of iron and its determination in geological, geochemical, hydrogeochemical, biogeochemical and process solutions. Am. J. Anal. Chem. 3, 339 (2012).10.4236/ajac.2012.35046Search in Google Scholar

35. Hora, F. B., Webber, P. J.: A source of serious error in the determination of nitrates by the phenoldisulphonic acid method and its remedy. Analyst 85, 567 (1960).10.1039/an9608500567Search in Google Scholar

36. West, P. W., Ramchandran, T. P.: Spectrophotometric determination of nitrate using chromotropic acid. Anal. Chim. Acta 35, 317 (1966).10.1016/S0003-2670(01)81682-2Search in Google Scholar

37. Norwitz, G., Keliher, P. N.: Inorganic interferences in the 2,4 xylenol spectrophotometric method for nitrate and their elimination. Anal. Chim. Acta 98, 323 (1978).10.1016/S0003-2670(01)84061-7Search in Google Scholar

38. Andrews, D. W. W.: A sensitive method for determining nitrate in water with 2,6-xylenol. Analyst 89, 730 (1964).10.1039/an9648900730Search in Google Scholar

39. Osibanjo, D., Ajayi, S. O.: Rapid and sensitive spectrophotometric method for the determination of nitrate in rain water using, 3,4-xylenol. Analyst 105, 908 (1980).10.1039/an9800500908Search in Google Scholar

40. Jenkins, D., Medsker, L. L.: Brucine method for determination of nitrate in ocean, estuarine, and fresh waters. Anal. Chem. 36(3), 610 (1964).10.1021/ac60209a016Search in Google Scholar

41. Velghe, N., Claeys, A.: Rapid spectrophotometric determination of nitrate with phenol. Analyst 108, 1018 (1983).10.1039/an9830801018Search in Google Scholar

Received: 2018-04-01
Accepted: 2018-11-27
Published Online: 2018-12-28
Published in Print: 2019-03-26

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