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Reactor Centrum Nederland RCN H-lfS REACTOR CENTRUM NEDERLAND RCX-186 INVESTIGATION'S ON' l'RAN>L CHLORIDE, ITS HYDRATES, AND BAL;I" SALTS by G. Prins RCN does not assume any liabili;;' with respect to the use of, or for damages resulting from the use of any information, apparatus, method or process disclosed in this document. is: >?:'': as o. t><?~ifi, Vr i"verr\ity \T.'J '.•'••:":• Petten, May 1973. St'MMARY 'ibis report describes the preparation and an inwst: .-at io:. physieo-cheniical properties ot uranyl .-hlorivie, its i.y.-.r .*.•. 01 its basic sales. The Methods lor Lhe synthesis ot l'i'.,i\,, l'U .i!L , .'t; ,i , .U'.vi i; li«vo beer. critically reviewed in Chapter Li and L:U: :::a:<> ru been careiulLy checked. In order to obtain more information on phase rv latienshiy :- uranyl chloride - water system, the system I'O - \iC\ - •• ,i been investigated (Chapter III;. Five solubility rogi.ns :. round with the corresponding solid phases ."i>,i:i ..JH.O, l\> ,•.i. : i .•: . 2UO.HCl.4H.vO, 4U0 .HCl ÖH,Ü, and L'O .2ri,0. One oi the throe basie salts, 4U0 .HCL.8H ,0, is tsetastable. This compound has no. heen described before. Since the basic salt ro,(OH)C1.2H,0 is congruently soluhle, it ran '.-.- prepared easily. Vibrational spectra of U0oJio, its hydrates, l'0,<oh)C1.2H,u, i'i',. Jt-,i>. and lour other uranyl compounds have been obtained (Chapt.r l\'). !:;.• interpretation of these spectra has heen restricted to a discussion ot the stretching frequencies of the uranyl group. In most cases the data are in accordance with the model, obtained already trom X-ray and neutron diffraction, of a linear, symmetric, and unperturbed urany! ion. Moreover, in anhydrous L'O^Cl., and in the basic salt I'O.. (t»H;r.! .-ii ,0 or _(U0p) (0H).,Cl?(H.,0)/_ a strong coupling between the vibrations OJ two uranyl groups has been observed, combined with a slight a.syr::n>-'. ry in the uranyl group itself. The thermal stability of UO ,Cl , and ,l.\v;i .H ,o has been investigated (Chapter V). I'O CI. decomposes on heating into l"u., via the i nt<r::.ili.,t •• oxychloride (U0„) Cl . The latter compound, which has rmf i n described before, contains l'(V) and l'(Vl). t'O..CL ..I! ,<) shows a transi'i ;i point and then loses water to give anhydrous I'd ,'.1 . The thermal decomposition of the basic salt ('n^f r)fi)C 1 . ..'jj n c.i'.v.'. i'.<- hitherto unknown hemihydrate of this salt and ultimately a ::.i xtur.- < = • the orthorhombic UO phase and tiie hexagonal '"'", piiast (<,•,.•;,>• r '.' I,.. ïiiü heats ui formation ot L'O,(.:!., and its hydrates have been redetermined i-iilut i;;it'Li' Li-:Liiy by means on tne heats of solution in hydrochloric acid, usin^; Lht? known ht>at ot formation of ",-L'ü as a reference {Chapter VII). In the sanse way th£ heat of formation of HO-(OH)CI . 2H 0 has been o'a taint'd. The heat content ot anhydrous UO CI., has been measured in the temperature range I 19 to 423 C, using a (diphenyl ether) drop calorimeter (uhapter VII). The results can be described by the heat content function: HT ~ H'^a = 22.93T + 5.662 x 10~3T2 + 0.4643 x loV' - 7494 (298 - 700 °K; cal/mole) I-. citï u -J'.M-.IL" 'nig'ii-tüEiperaturü thermodynamic data for anhydrous L:0.,CI , ut tricii to measure the equilibrium constants of the reactions: UÜ2Cl,(sj - Uu/s) + Cl2(g) and LU2Ll2(g) Z UO^s) +• Cl2(g) but this proved to be impossible because of the occurrence of side reactions (Chapter VIII). However, the equilibrium constant of the reaction: U308(s) + 3Cl2(g) r 3U02Cl2(g) + 02(g) could be measured in the temperature range 862 to 1054 C, using the entrainment method (Chapter VIII). The standard free energy change o£ this reaction is: ;£° = 142 300 + 1600 - (67.8 + 1.3)T (cal) Finally, a summary of the thermodynamic data for anhydrous UO Cl„ (published values and own results) has been given (Chapter IX). CONTENTS INTRODICTIQN References THE PREPARATION! OF URANYL CHLORIDE AND ITS HYURATES 11.1. Anhydrous uranyl chloride Experimental 11.2. Uranyl chloride monohydrate Experimental 11.3. Uranyl chloride trihydrate Experimental 11.4. Conclusion References THE SYSTEM URANIUM TRIOXIDE-HYDROGEN CHLORIDE-WATER AT 25 °C III.1 , Introduction 111.2, Experimental 111.3. Results and discussion References SPECTROSCOPIC INVESTIGATIONS OB URANYL CHLORIDE AND RELATED COMPOUNDS IV.1. Introduction IV.2. Experimental IV. 3. uo2ci2 IV.4. U0 C1 H 2 2' 2° IV.5. U02C12.3H20 IV. 6. [(U02)2(OH)2C12(H20)J IV.7. UOj.211 0 IV.8. U02CN03)2.6H20 IV.9. UO2(CH3CO0)2.2H20 IV.10. cs2uo2ci4 IV. 11, Zn(U02)2(CH3CO0)6.7H2O IV.12. Summary References THE THEÜMAL SIAÜILII'V Ut' f^^Yl. OtiU'-U:^ .-'.... I i'S Hi'URATES Ui V- l. Anhydrous l'0,i:L, '-> 7 Svxp e r i rw n t a I Kesuit* ;nui ji^iiissijn 51 V.2. l"0,v.l.,.H,v1 V.' Experimental hO Results and discussion oO V.j. UO C1,-3H(0 b-+ References 65 THE THERMAL STABILITY OF BASIL l'RA^L CHLORIDE 66 VI.!, Introduction 66 VI.2. Experimental 68 VI.3. Results and discussion 7Ü References 76 THERMODYNAMIC PROPERTIES OF THE URAN'YL CHLORIDES 7 7 VII. 1. The Ueats of forsmion of t07Cl?, ffl^l^.SO, UO C1,.3H 0, and UO^(0H)C1.2H?0 77 Introduction 77 Experimental 77 Results 80 Discussion 83 VII. 2. The high-temperature heat content of anhydrous uranyl chloride 87 Introduction 87 Experimental 88 Results 89 Discussion 92 Preferences 94 Mfil VIII. HIGH-TEMPERATURE THERMODYNAMIC PROPERTIES OF URASYL CHLORIDE: THE EQUILIBRIUM U (sJ + 3C1 Cg) T 3°8 2 3U02Cl2(g) + 02<g) 96 VIII.1. Introduction 96 VIII.2. Method of investigation and apparatus 97 VIII.3. Experimental 100 VIII.4. Results 103 VIII,5. Discussion 107 References 109 IX. SURVEY OF THE THERMODYNAMIC PROPERTIES OF ANHYDROUS URANYL CHLORIDE 110 IX.1. Gaseous U0 CI 110 ix.2. solid uo2ci2 in IX.3. The thermodynamic f mictions of UQ Cl?(s) and UO.n ,(>ï Ü3 References 1 15 Chanter I INTRODUCTION l.l. History of the element uranium (1) Long before uranium was recognized as a new element, some of its minerals had been described in the literature; pitchblende as early as 1365- These minerals were supposed to contain copper, iron, lead, silver, tungsten, or zinc. In 1789 Klaproth demonstrated that the main constituent of pitchblende was «in unknown metal, which he named uranium after the planet Uranus, discover­ ed eight years before by Herschel. Klaproth and others believed to have prepared the free element by reduction of various uranium compounds with carbon or hydrogen, but in 1842 Pëligot (-) showed that the product so obtained was only a lower oxide, known after­ wards as uranium dioxide. Piligot succeeded in preparing the metal by re­ duction of uranium tetrachloride with potassium. The most important method in use nowadays is by reduction of uranium tetrafluoride with magnesium or calcium (3). Before the Second World War the element uranium found only limited applica­ tions. It was used for the manufacture of pigments in glass and ceramics industries, and also in steel alloys. The present importance of uranium in the field of nuclear energy is well-known. The other industrial applications of the element have come to an end. Aim of the p resent investigation There is a growing interest in chlc-rination techniques in uranium technology. Trie most important chlorination products encountered in the various processes are uranium tetrachloride, UC1,, and uranvl chloride, UO CI . 4 ' Z / The commercial uranium reserves of the world could be greatly increased if chfcner processing of low-grade ores would be possible. A potential method is extraction by chlorination (4). In this procedure the ore is roasted and the metal oxides formed are converted into chlorides or oxychlorides o by gaseous chlorine at temperatures from about 30Ü to h+0'j C, w.iereas the gangue is not attacked under these conditions. Most of the chlorination products are volatile and are carried off by the gas stream. At 1000 - References 1100 C the U-jO in the roasted ore is converted into uranyl chloride, volatile in that temperature range. By making use of the different 1. F. Kirchheir&er, Daa Dran und seine GeschichEe, Stuttgart, volatilization temperatures, a fractionation of the various metals E. Schweizerbart'sche Verlagsbuchhandlung (1963). in the ore is often possible. The extraction, besides the uranium, 2. E. Péligot, Ann. chim. phys. (3} 5^ (1842) 5. of the main ore constituents in an almost pure state is an advantage 3. W.D. Wilkinson, Uranium Metallurgy, Vol. I: Uranium Process that can make the exploitation of low-grade uranium ores economically Metallurgy. New York, London, Interscience Publishers (1962). feasible. 4. "J. Kangro, Zeitschrift für Erzbergbau und Metallhüttenwesen \6_ An alternative method for the manufacture of uranium dioxide - the (1963) 107, 328, most important nuclear fuel in use at present - consists in the electrolysis of a molten salt solution of uranyl chloride (5,6,7). 5. R.S. tfilks, J. Nucl. Mat. T_ (1962) 157. The salt bath may consist of an alkali chloride solvent salt, for 6. F.A. Scott and L.K. Mudge, J. Nucl. Mat. 9_ (1963) 245. instance LiCl-KCl eutectic, into which the uranyl chloride haa been 7.
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