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ABOUT URANIUM DETERMINATIONS in the Last Few ABOUT URANIUM DETERMINATIONS İhsan TOPALOĞLU and Nilüfer BAYÇIN Maden Tetkik ve Arama Enstitüstü, Ankara ABSTRACT. — The most important methods in connection with uranium analyses published up to date will be briefly outlined in this article. Here each method is not taken separately. Instead, methods applied by various authors in the separation of uranium from its associated elements — Such as extraction, precipitation, electrolysis, column chromatography, separation by means of ion exchangers — and the determination proper — such as gravimetric, volumetric, coloriroetric and spectro — photometric, fluorometric, electrometric and radiometric — are discussed as a whole. Of these methods those which were actually put to test and their degree of precision checked up, using standard specimens, are discussed in detail. INTRODUCTION the determinations, and then this is fol- In the last few years, due to the rapid lowed by the determination proper. For development observed in the means for the uranium separation, either an extrac- putting to good use the atomic energy, tion method or one using precipitation, analysis of radioactive minerals— espe- electrolysis, column chromatography or cially the determination of elements Ura- ion exchangers is applied. As for the nium and Thorium—won a wide interest. determination, any one of the methods The physical and chemical analyses of that can be specified as gravimetric, these elements have, in pace with the mar- volumetric, colorimetric and spectro - ked development in this field in general, photometric, fluorometric, electronic or displayed considerable progress. Exten- radioactive may be chosen. sive work is being eagerly carried on and In all methods, in order to decompose the results regularly published. This the ore containing uranium, the sample article is written with the purpose of is treated with HNO3 or some mixtures briefly reviewing the current literature of acids such as (HNO3+HC1O4), (HNO8 on the methods of uranium analysis, + HF), (HN03 + HG104 + H2SO4+ considered particularly important, and HF) in given proportions. Those which to describe those among them which are not dissolved in acids are rendered are actually applied in our Institute. soluble by means of special mixtures like ( NaOH+Na2O2 ), (NaOH+NaNO3), PART I (Na2O2+Na2CO3). URANIUM DETERMINATION METHODS Separation of Uranium Various methods have been devised for the determination of uranium. In 1. Extraction methods. general, first step in any method is to This is based on the fact that some free the uranium from its associated ele- uranium salts are more readily decom- ments, interfering with the precision of posed in certain organic solvents than 44 İhsan TOPALOĞLU, Nilüfer BAYÇIN in an aqueous solution of a given com- an ethyl acetate extraction have been position. The organic solution which , jointly used. In case the amount of U3 8 comes in contact with the one contain- exceeds 0.05 gr. in a solution of the ori- ing the uranium, either continuously or ginal sample, the tri-butyl phosphate gradually, after a while absorbs all of separation is dispensed with (12). the uranium. This is followed by ,evapor- According to a different method, the ation, of by destruction, of the organic extraction of uranium is done by first matter leaving uranium salt. adding sulfo-cyanide and then tin (II) One of the methods used to recover chloride in a medium of hydrochloric uranium from low-grade ores is the ether acid, followed by further addition, extraction method. In this method the within a given range of acidity (pH), of solution containing uranium is first dibutoxytetraethylene glycol plus tin acidified by adding nitric acid and, af- (II) chloride. As the latest publications ter being saturated with ammonium have shown a penta-ether to give a nitrate, is subjected to ether extraction purer product and do this more quickly in an extractor (1, 2, 3). An other method than tri-butyl phosphate, this latter may consists of ethyl acetate extraction from preferably be substituted (13, 14). nitric acid solutions having a high con- Apart from these, based on the fact centration of or being saturated with alu- that the complex substance obtained by minum nitrate (4, 5, 6, 7, 8). This method uranium (VI) with 8-hydroxykinoline is of separation for uranium is widely soluble in organise solutions, uranium is used and often applied prior to calori- extracted, within a given pH range, metric, spectro - photometric and flu- using 8 - kinolinol (oxine) and its deri- orometric determinations. Some authors vatives (such as di-chloro-oxine and di- prefer to apply ether acetate extraction bromo-oxine) and chloroform. The deter- method after adding hot aluminum mination of uranium follows using nitrate to the solution containing nitric spectro-photometry (21, 15, 16). acid or heating the solution to the boil- An other method, similar to the one ing point (9, 10, 11). In order to free above, is the cupferron or chloroform the uranium— obtained with either of extraction in a medium of sulfuric acid these two methods — from its organic or perchloric acid. In this method, in solvent, this latter is evaporated. contrast to the previous ones, uranium Again, prior to colorimetric and (VI) is left in the aqueous solution, fluorometric determinations, the tri-butyl while cupferrates of the associated ele- phoshate extraction method may be ap- ments pass into the organic solution. plied to solutions containing uranium This method of extraction is applied nitrate. In this method, in order to ob- either before (20, 87) or after (3, 17, 18, tain two better-defined phases than in 19) hydrogen sulfide group elements are one using only tri-butyl phosphate, separated; the advantage of the method tri-butyl, phosphate + methyl isobutyl being the possibility it offers for the ketone or tri-butyl phosphate + diethyl double cupferron extraction, as the ether or a 22 % solution of tri-butyl uranium may be of (IV) or (VI) valence phosphate in n-hexane must be used (12). (21,22). And this is based on the fact Lately, to extract uranium especially that in an acid medium cupferron and from ores or solutions where it exists in uranium (VI) do not give any preci- very small quantities, first a mixture of pitate, while uranium (IV) precipitates tri-butyl phosphase and n-hexane, then in the form of a cupferrate and decom- ABOUT URANIUM DETERMINATIONS 45 poses in an organic solvent. Usually, zinc amalgam and then treated with after such a separation, the determina- ammonium carbonate. During this pro- tion of uranium is made volumetrically. cess uranium (IV) carbonate is separa- ted as a precipitate while iron (II) 2. Precipitation methods. remains in the solution. This method These methods make possible only is suggested mostly for the purpose of group separations, due to the fact that a rapid volumetric or gravimetric deter- uranium does precipitate with certain mination of uranium in the presence anions and cathions. Of course, they of- of excessive iron (26). Similarly, the ten are to be subjected to subsequent ore is rendered soluble with the aid of separation using any one of the extrac- potassium bifluoride and hydrofluoric tion methods. acid and then treated with an excess Frequently, uranium is precipitated of tin (II) chloride. In this manner, from uranyl solutions, under the action fluorides of uranium (IV), thorium, of ammonium diuranate. This method rare earth metals and earth alkali pre- makes possible the separation of uranium cipitate and are separated. This method from certain anions and some cathions, is applied mainly to complex minerals, such as Cu (II), Ni (II), which give such as, samarskite, columbite-tantalite complex substances with alkali, alkali and titano-niobite (27). earth (metals) and ammonia, and is 3. Separation by electrolysis. only applied to solutions containing no fluor, carbonate, citrate or tartarate. Electrolysis is used as an other ap- Thus the uranium precipitate, partly proach to freeing uranium from the separated from heavy metals, is decom- elements which might have misleading posed in a special acid, subsequently to effects during a determination. The undergo further separation either by sample, put in a solution form for this electrolysis or ether extraction. In this purpose, is subsequently electrolyzed, method pyridine or hexa-methylene tet- often in a medium of sulfuric acid, ramine are also used in place of ammonia using a mercury cathod. Under these (23,24,1). conditions, iron, cobalt, nickel, cop- per, zinc, gallium, germanium, rho- In still another widely used method, dium, palladium, silver, cadmium, in- hydrogen sulfide is passed through an dium, tin, iridium, platinum, gold, mer- acid solution containing uranium. Thus, cury, thallium, chromium, molybdenum, after the heavy metallic sulfides are rhenium, bismuth, arsenic, selenium, disposed of, cupferron - chloroform ex- tellurium, lead and osmium accumulate traction is applied to the filtrate. on the mercury cathod. Along with Instead of passing hydrogen sulfide these, manganese, ruthenium and anti- gas, the solution is treated, in an acid mony are also partially separated. Fol- medium, by sodium sulfide or, as prac- lowing this, uranium, columbium (VI), ticed lately, by thioacetamide (17, 18). tantalum, tungsten, titanium, vanadium A variation of this consists of preci- and zirconium, which are left ,in the pitating uranium (VI) with certain solution, are subjected to extraction for other metals in the form of phosphates, separation (28, 29, 30, 31). followed by the cupferron - chloroform extraction (25). 4. Column chromatography. Apart from these, as a special case, In this method separation is done the sample solutipn is reduced with in a column. The sample acidified with 46 İhsan TOPALOĞLU, Nilüfer BAYÇIN nitric acid is passed through a column dures are: (a) Amberlite 1R-4B, Amber- of specific dimensions which contains lite IRA-400, Amberlite IRA-410, a certain amount of active cellulose. Of Dowex-1, Dowex 2 (as ion exchanger the elements, totally or partiaily ab- resins) and (b) Amberlite IR-100, Amber- sorbed in the cellulose, in direct rela- ite IR- 120 and Dowex-50 (as cathion tionship with their speed in the column, exchanger resins).
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