نوع مقاله : مقاله پژوهشی

نویسندگان

1 پژوهشکده‌ی چرخه‌ی سوخت هسته‌ای، پژوهشگاه علوم و فنون هسته‌ای، سازمان انرژی اتمی ایران، صندوق پستی: 8486-11365، تهران ـ ایران

2 بخش مهندسی معدن، دانشکده‌ی صنعت و معدن زرند، دانشگاه شهید باهنر کرمان، صندوق پستی: 7616914111، کرمان ـ ایران

چکیده

استخراج ناپیوسته‌ی توریم برای تعیین استوکیومتری گونه‌های توریم (IV) استخراج شده به انجام رسید. تأثیر غلظت اسید، استخراج‌کننده و دما بر روی استخراج توریم بررسی شد. یافته‌ها نشان داد که سازوکار استخراج توریم در غلظت‌های پایین و بالای نیتریک اسید (به ترتیب، 1-mol L 001/0 و 1-mol L 8) از نوع حلال‌پوشی و در ناحیه‌ی غلظت‌ متوسط (1-mol L 1) از نوع تبادل کاتیونی است. با استفاده از روش تحلیل شیب، مشخص شد که گونه‌ی استخراج شده‌ی توریم به فاز آلی به صورت A.HA(3NO)2(OH)Th است. بررسی‌های ترمودینامیکی نشان داد که فرایند استخراج توریم (IV) خودبه‌خودی (° >G ) و گرمازا (° >H ) بوده و در آن بی‌نظمی کم می‌شود (° > S). مقدار انرژی فعال‌سازی واکنش استخراج توریم (IV) برابر با 46/17 کیلوژول بر مول محاسبه شد که نشان‌دهنده‌ی آن است که واکنش استخراج به وسیله‌ی فرایند نفوذ کنترل می‌شود.
 

کلیدواژه‌ها

عنوان مقاله [English]

Thermodynamics and mechanism of Th(IV) extraction from nitrate medium with cyanex 272 in kerosene

نویسندگان [English]

  • Saeid Alamdar milani 1
  • Mahmoud Eskandari nasab 2

چکیده [English]

Batch extraction investigation was carried out to elucidate the stochiometry of the extracted Th(IV) species. The effects of nitric acid concentration, extractant concentration and temperature were studied. The results showed that the extraction of thorium follows solvation mechanism in the low
(0.001 mol L-1) and high (8 mol L-1) nitric acid concentration, while the cation exchange mechanism dominates the middle acidic area (1 mol L-1). The extracted species was found to be Th(OH)2(NO3)A.HA on the basis of the slope analysis method. The results of the thermodynamic investigations indicated that the extraction process is spontaneous (G<0), exothermic (H<0), and less random in nature (S<0). The value of activation energy of the extraction reaction was calculated to be 17.46 kJ mol-1 which indicates that the extraction reaction is controlled by the diffusion process.
 

کلیدواژه‌ها [English]

  • Thorium
  • Solvent extraction
  • Cyanex ‌272
  • Mechanism
  • Thermodynamics
[1] T.S. Anirudhan, S. Rijith, A.R. Tharun, Adsorptive removal of thorium(IV) from aqueous solutions using poly(methacrylic acid)-grafted chitosan/bentonite composite matrix: Process design and equilibrium studies. Colloids and Surfaces A: Physico-chemical and Engineering Aspects, 368 (2010) 13-22.
[2] International Atomic Energy Agency, Thorium Fuel Cycles: Potential Benefits and challenges, Vienna, Australia (2005) 5-20.
[3] R. Meera, Synergistic solvent extraction of thorium(IV) and uranium(VI) with R-Diketones in presence of oxo-donors, Ph.D. thesis, India, Chap. 1 (2004) 1-5.
[4] J.E. Crawford, Thorium mineral facts and problems, U.S Bur. Mines Bull (1956) 556.
[5] F. Habashi, Texbook of Hydrometallurgy, Department of mining and metallurgy, Laval University, Quebec city, Canada (1993) 430-440.
[6] E.K. Hyde, The Radiochemistry of Thorium, Lawrence Radiation Laboratory, University of California, Berkeley, California, (1960) 7-27.
[7] F.L. Cathbert, Thorium production technology, National Lead Compony of Ohio, United State of Amearica, (1958) 104-120.
[8] Fathi Habashi, Handbook of Extractive Hydrometallurgy, Vol. III, Newyork, (1997) 1660-1665.
[9] K.H. Soldenhoff, Proceeding of the International Solvent Extraction Conferences (ISECʹ96), March 19-23, Australia 1 (1996) 469.
[10] V.C. Adya, N.C. Hon, T.R. Bangia, M.D. Sastry: ISAS National Symposium on Analytical Techniques for Safety and Sufficiency of National Resources/Products, Feb. 20-22, India (1997).
[11] S.D. Dogmane, R.K. Single, D.D. Baajapi,: National Symposium on Nuclear and Radiochemistry, Feb. 7–10, India (2001).
[12] S.I. El-Dessouky, N.E. El-Hefny, J.A. Daoud, H.F. Aly, Liquid–liquid extraction of uranium, neodymium and chromium from thiocyanate medium by Cyanex 921, Arab. J. Nucl. Sci. Appl., 36(1) (2003) 17-26.
[13] M.P. Jensen, A.H. Bond, Influence of aggregation on the extraction of trivalent lanthanide and actinide cations by purified Cyanex 272, Cyanex 301, and Cyanex 302, Radiochim. acta 90 (2002) 205.
[14] P.D. Clark, A. Cole, M.H. Fox, Proceedings of the International Soluent Extraction Conference (ISEC’93), Sep. 9-15, New York, England 1 (1993) 175.
[15] P.S. Mansingh, V. Chakravortty, K.C. Dash, Solvent Extraction of Thorium(IV) by Cyanex 272/Cyanex 302/Cyanex 301/PC-88A and their Binary Mixtures with TBP/DOSO from aq. HNO3 and H2SO4 Media, Radiochim. Acta, 73(3) (1996) 139.
[16] M.L.P. Reddy, T.R. Ramamohan, S.K. Sahu, P. Thakur, V. Chakravortty, Mixed-ligand chelate extraction of thorium(IV) and uranium(VI) with thenoyltrifluroacetone and various imidazoles, Radiochim. Acta, 88 (2000) 405-410.
[17] B. Gupta, P. Malik, A. Deep, Extraction of uranium, thorium and lanthanides using Cyanex 923: Their separations and recovery from monazite. Journal of Radio analytical and Nuclear Chemistry, 251 (2002) 451-456.
[18] N.E. El-Hefny, J.A. Daoud, Extraction and separation of thorium(IV) and praseodymium (III) with Cyanex 301 and Cyanex 302 from nitrate medium, J. Radioanal. Nucl. Chem. 261 (2004) 357-363.
[19] M. Karve, C. Gaur, Liquid-liquid extraction of Th(IV) with Cyanex 302, Department of Chemistry, University of Mumbai, Vidyanagari, Mumbai 400 098, India, Journal of Radioanalytical and Nuclear Chemistry, 270 (2) (2006) 461-464.
[20] M. Eskandari Nasab, A. Sam, S. Alamdar Milani, Determination of optimum process conditions for solvent extraction of thorium using Taguchi method, J Radioanal Nucl Chem 287 (2011) 239–245.
[21] S.A. Milani, M. Eskandari Nasab, Extractive Separation of Thorium, Uranium and Rare Earths from Nitrate Medium by Cyanex 272, J. of Nuclear Sci. and Tech. 63 (2013) 24-34.
[22] S.A. Milani, B. Maraghe Mianji, A.A. Abhari, Successive Uranium and Thorium separation from leach liquor of ore deposit of 5th Anomaly of Saghand by solvent extraction, J. of Nuclear Sci. and Tech. 66 (2014) 33-46.
[23] C. Moulin, B. Amekraz, S. Hubert, V. Moulin, Study of thorium hydrolysis species by electrospray-ionization mass spectrometry, Analytica Chimica Acta, 441 (2001) 269-279.
[24] J. Bjerrum, Metal Amine Formation in Aqueous Solutions: Theory of the reversible step reactions, DISS, Copenhagen (1941).
[25] C. Ekberg, Y. Albinsson, M.J. Comarmond, P.L. Brown, Studies on the Complexation Behavior of Thorium(IV). 1. Hydrolysis Equilibria, J. Solution Chem., 29 (1) (2000) 63-86.
[26] S. Gueu, B. Yao, K. Adouby, G. Ado, Kinetics and thermodynamics study of lead adsorption on to activated carbons from coconut and seed hull of the plam tree, Int. J. Env. Sci. Tech., 4 (2007) 11-17.
[27] P.D. Blundy, The determination of chromium by a solvent-extraction method, Analyst, 83 (1958) 555-558.
[28] P.R. Danesi, R. Chirizia, The kinetics of metal solvent extraction, Crit. Rev.Anal. Chem., 10 (1980) 1–126.
[29] P.R. Densi, International Atomic Energy Agency, Vienna, Austria (2008) 203-208.