O GOVERNMENT of INDIA ATOMIC ENERGY COMMISSION
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B.A.R.C-628 o GOVERNMENT OF INDIA ATOMIC ENERGY COMMISSION . RADIOCIiEMIStRY DIVISION ANNUAL PROGRESS REPORT FOR 1971 Edited by R. H. Iyer and M. V. Ramaniah Radiochemistry Division BHABHA ATOMIC RESEARCH CENTRE BOMBAY, INDIA 1972 B.A.R. C.-628 GOVERNMENT OF INDIA ATOMIC ENERGY COMMISSION < RADIOC HEMISTRY DIVISION ANNUAL PROGRESS REPORT FOR 1971 Edited by R. H. Iyer and M. V. Ramaniah Radiochemistry Division BHABHA ATOMIC RESEARCH CENTRE BOMBAY, INDIA 1972 IHTRODUCTIO The major highlights of the activities of the Hadiochemistry Division during the year 1971 were research and development work on the actinides and other radioelements and services like chemical, mass speetro- metric, x-ray and optical spectrographio analysis of plutonium and other radioactive materials and supply of special radioactive sources to various institutions inside and outside BAEC. As in previous years, research on the actinide elements centered around solution and radiation chemistry of Plutonium, study of various complexes using x-rayf e.p.r. therraograviraetrio, Mossbauer and optical spectrographie techniques and investigations of neutron induced fission. The development work on actinides included process chemistry of neptunium, preliminary studies on transpluton* ;«>. elements, setting v.p and operation of gamma-ray and neutron monitoring assemblies SOB the in-line analysis of fission products and plutoniuim respectively in Ssel reprocessing streams and the accurate analysis of plutonium in plutonius oxide samples and sintered FUO? pellets* In the chemical development worie on molten salt breeder reactor ooncept utilizing plutonium, the solubility of Plutonium trifluoride was determined in the ternary system and the binary system CONTENTS introduction SECTION 1 I SOLUTION AND BABIATION CHEMI3THI 1.1 Sol-rant Extraction Studies 1.1.1 Synergiatio extraction of uranyl Ion 1 1.1.2 Extraction of some txivalent lanthanides from thiocyamte by neutral organophOBphoroas extraotanfe* ft 1.1.3 Studies on the oomplexes of lantbanidea 12 111.4 Investigations on the chemistry of Pa(YIl) W 1.2 Studies in Radiation Chemistsy 1.2.1 Gamma radiolysis of plutonitto(lIl)/(lT) syatea In 0.8 N, 6 H and S N hydrochloric acid solutions t@ 1.2.2 Ganma radiolysis of plutonlum(lll) in adtric aoid solutions 25 1.2.3 EPR stadia8 of intermediates fcaned in xadiolytio and redcoc reactions in aqueous medium 29 1.2.4 Badlation chemistry of nitrio acid JO 1.2.5 Two phase radiolyaie and the effect of radiatiou on ffa* . diBtxihution coefficient of uraniwa and piatoniua 36 1.2*6 Slaeh photolysis of sulphanllanld* and ether p-suhstituted anilines 39 SECTION 2 t STHtrCTORAL STUDIES 2*1 Solid Complexes of Uranyl 0 -diketones with I>ea«r Chain Aliphatic Sulphoxides ' 44 2.2 Stability Correlations and Sterio Effects of Synergistia Complexes 45 2*3 X-ray Structural Studies Ill 2.3.1 Refinement; of the oryetal structure of uranyl oxalate 48 2.3.2 Qralato and aoetato complexes of aotiaides 51 2.5«3 Non-stoiehiometrio oxides of the lanthanides 55 2.3.4 Calibration of Mattler thermoanal^sec » 2*4 Mouebauer Studies 2*4*1 Moesbauer studies on some 58 145 2,4.2 Preparation of Pa g3 2.5 Fluorescence and Absorption Spectrum of Tb*+ Ion in laBr, Crystal g^ 2.6 Energy-tranafer Studies in Raxe Earth Chelates $$ 2.7 BPH Study of TC-"H" in UOgtHOjJgifiHgG Single Crystal 74 SSCTIQR 5 1 NUCLEAR CHEMISTRY 5*1 Eadiochemical Studies on Fission 3*1.1 Be coil ranges and kinetio energy distribution in the reactor neutron fission of 23'Hp 80 3.1.2 Becoil ranges of isobar pairs iu tbs thermal neutron fission of ^-*tf & 3 >1 "3 Studies on highly asymmetrlo binary fission t Fission of natural uranium with reaotor neutxons • Sf 3.2 mission Studies using Solid-state Track Deteotors 3.2*1 Total fLsaion cross section for th» thermal and 14 MeV neutron induced fission of 231 Pa 94 3*2.2 Mass and angular distritution in Mission using correlated fission track technique 95 3*2*3 Analysis of angular distributioo data at 15*9 BeT $B 3*2*4 Thermal neutron flu>x , distributioj n at the thermal 102 3«3 ilaaion Studies using ilass Spaotecmgtrie Steebniqa© 106 3*4. - Calibration of a <fe(Li) Detector 106 iT 3»5 EUotrodeposition of Aotinides 3*5.1 ELeotrodeposition studies with 244Ca 107 3*5.2 KLeotrodeposition of piotaotiniun 112 3*5*3 Mechanism of electrodeposition of aoSinide* 113 3.6 Computer Programme for Analysis of Oe(ll) Gamma-ray Spectra 115 SSCTIOH 4 t FBOOESS CHEHI3THT 4*1 Process Chemistry Oi Feptuniun 117 4*2 In-line Analysis of Fuel Bsprooarsing Streaas 123 4.2.1 In-line monitoring of fission products 124 4*2*2 Heutrca monitoring for plratocj.um 331 4*4.43 ^-raIransplatoniuy Huoxesoenom Elemente Analysis s of Aotinide Blemeafcs 132 in Solution 136 SECTION 5 t REACTOR CHMISTHY 5.1 Chemical Development Work on Molten Salt Breeder Beaotor Concept c - ^ 5.1*1 Preparation of pure Thl1. and I1F 141 5.1*2 Solubility of^ PuFj In l^^Fg^B^ m^t«^s 142 5.1 »3 SoluTsilHy of PtiFj in LiF-IMP. nixtux«s 14i5 5.1.4 Impendence of solubility of PuF, on the salt ooapoeition 146 SSCTIOH 6 s AMLTfTlCAt CHEMISTRY iMD MISCELLANEOUS SiSKVICSS 6.1 Mass Speetrometry ISO 6.1.1 Analytical eerricea : 150 Isotope dilution method for input accountability in a reprocess ire plant 151 Fuel burn-up measurements 152 Determination of "^tJ content of Natural and Depleted Uranium Samples by Fission Track Method 154 Analysis of FuO. fos Auditing 159 Emission Bpeotzoscopy Analysis of some common impurities in high purity selenium 159 New Badiochemical Methods for the Separation of Cu and Heavy Bare Earth Elements from Fission Products 67 fiadiochemical separation of 'Cu activity 16? Eadiodhemlcal separation of heavier rare earths 168 Supply of Radioactive Sources I73 Eftdioohemistry Laboratory at the Reactor Research Centre 173 SECTIQH 7 j INSTRUME3ITATI0N 7.1 Fabrication of a Scanning Spectrometer 174 7«2 A Low Geometry Alpha Counter 177 Summary 180 List a£ Publications During 1971 186 LIST OF TABLES Table 1 » Extraction of La(III), Eu(III), tu(lIX) and Am(lIX) by TOPO, TBPO and TBP 8 Table 2 * Dissociation constants of Uganda 14 +5 Table 3 * Stability constants of Sm oomplezes (by least squares) 16 Table 4 * Ganina radiolysis of plutonium(lll)/(iv) system In 0.8 N HG1 t Yields of plutonium(xv) and ^O 1Q Table 5 * Spectrophotometric measurements on solutions irradiated by gamma ray in the presence of oxygen. 20 Gamma radiolysis of argon equilibrated Table 6 i plutonium(lV) solutions i Yields of plutonium(lll) 23 and Hadiolysis of oxygen equilibrated plutoniom( III) Table 7 » solutions in 0.8 H HNO, containing different concentrations of sulpnamio acid 24 Table 8 t Present G(HNO2) values compared with other published values 35 Table 9 * Ratio of rate constants —— from thermal studies 36 K1 Table 10 t Decrease in Q(HNOg) with dose 38 Bate constant -values of the reactions of substituted Table 11 t benzenes and anilines with eaq 42 Characteristic infrared stretching frequencies (en ) Table 12 t in the complexes UOg(fi dike tone )gS 47 Boni distances (1) and bond angles (•) 49 Table 13 » X-ray data yy Table 14 * BesultB of T.G.A. analysis 54 Table 15 t Ihermal deoomposition of rara earth ozalatea 56 Table 16 1 Table 17 * Hossbauer parameters 60 Table IB t Hossbauer parametesp of the ferrous and ferric iron 61 Table 19 * Ferric iron oontent as percentage of total Iron t Comparison of Mossbauer and chemical data 62 vl vli Page Table 20 s Absolute rats constants for quenching of fluorescence + 1 from the J?Da le^el of %5 .^p0 * 17,250 ear . Solvent I Acetone . 72 44 Table 21 » Spin Hamiltonlan constants foe TO ion 77 Table 22 » The recoil ranges and kinetio_energies in the reactor induced fission of 25"ijp 82 Tettae 23 * Fission yields for reactor neutron induced fission of natural uranium Table 24 f Anisotropy data for the 15.8 ifeY neutron induced fission of heavy elements 102 Table 25 * Thermal neutron flux in Apaara thermal column using S.8.T.J laxan 104 Table 26 t Counting efficiencies of Ga(Li) detector for different nuolides 108 Table 27 i Counting efficiencies of Ge(Li) detector for different nuclides 109 Table 28 i Extraction of.Np(v) 119 Table 29 * Extraction of neptunium 120 Table JO t Variation of S^ with HNO, concentration 122 able 31 * Variation of K£ with concentration of uranium 122 Table 32 t Analysis of two compenent mixtures using Nal(Tl) monitoring assembly 128 Table 33 i Analysis of three oomponest siixtures using Hal(Tl) monitoring assembly' 150 Table 34 t Energies of alpha particles from various plutonioa 2 isotopes and those of 4iAm (in MeV) 135 Table 35 « Solubility of PuPj in lIP-BeF2-ThF4 (71.6, 16.29 12.2 m/o) 144 Table 36 t Precision in uranium isotope ratio measurement using an.NBS standard sample -550 Table 37 * Bstemination of total plutonium in ths tank 153 Table 38 * "tf content of natural uranium and dspletee! uraniam samples 156 Battle 39 * U oonient in syntbexio mixtures of mtural + depleted uranium 157 Table 40 t Precision and accuracy of Hie date 162 Table 41 1 Equations for the working ourrea for different elements 163 Sable 42 I Line pairs and estimation range* 164 table 43 * Comparison of detection limits obtaimd by different methods 165 L I 3 T 0P FIGURES Figure 1 t Plot of log K and log K va pKD of the @ -dHcetone figure 2 t Plot of log K TS shift in the 8ynaaetrio stretching frequency of water of different donor hydrates Figure 3 « Plot of chemical shift va donor concentsaiis Figure 4 t Plot of chemical shift va log K Figure 5 Extraction of La(lll), Eu(lll), Lu(lll) and Ao(XIl) from thiocynmte by TOPO 9 Figure 6 i Absorption spectra of Hd(lll) and Er(lll) 10 Figure 7 e Formation curve 15 Figure 8 t Plot of ^T8 pH 17 Figure 9 t Badiolysis of deaerated and argon equilibrated Pu(lll) solutions - yields of Pu(l7) and Hg 21 Figure 10 t Badiolyais of oxygenated plutonium( III) solutions yields of plutonium(lT) and 25 Figure 11 t Badiolysis of plutonium(lll) in nitric aoid solutions - yields of plutonium(lT) and 26 Figure 12 i Effect of gamma radiation on EER spectrum of 0.05 M PeClj in 0,16 M HOI at 77°K JO Figure 15 s Test of competition for HHOg species between SA and HgOg in tiie radiolyels of nitric aoid 33 Figure 14 t Test of simple competition for HNO2 specie? .