ORNL-1771 - Oak Ridge National Laboratory

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The data obtained are presented in Table 5.8, which gives the concentration of iron found in the filtrate, the ratio of the HF concentrations in the influent and effluent gases, and the equilibrium constants and corresponding activity coefficients for the FeF As is evident, the data in Table 5.8 2: are less precise than those obtained by the dynamic procedure. The lowered precision is probably due to the more complex apparatus and technique. How- ever, when the data are plotted (Fig. 5.8), the spread of the data is less than the estimated un- certainty in the AFO values. The agreement be- tween the values obtained by the two methods is remarkably good, TABLE 5.8. EPUlLlBRlUM DATA FOR THE REACTION FeF2 + H,+Fe' t 2HF AT 800°C IN MOLTEN NoF-ZrF4 (53-47 mole %) Concentration of of FeF, (ppm Fe) 912 223 915 7 40 360 185 160 27 5 Ratio of HF in Influent Gas P2HF to HF in Effluent Gas 0.79 0.9 1 1.02 0.98 1.00 0.93 0.9 1 0.99 0.40 1.08 2.09 2.12 1.71 1.89 2.14 3.12 YFf2F2 0.4 1 0.74 1.43 1.45 1.17 1.30 1.47 2.14 PERlOD fNDING SEPTfhlBER 10, 1954 at 150 to 200°C. An attempt to prepare AgF by reacting HF with AgCN was unsuccessful; most of the AgCN did not react. Several botches of anhydrous ZnF, were prepared by heating ZnF2.4H20 under HF at 600°C. The compound TeF4 was prepared by reacting Te and HNO, and reacting the resulting TeO, with aqueous H F to give Te02F2.H 20p which was thermally decomposed to yield Te02, HF, H20, and the product TeF,. The TeF, was collected in a condenser held at 130 to 140°C. Small quantities of Rb,CrF, and Li,RbCrF4 were prepared by heating the proper quantities of CrF3, RbF, and LiF in sealed capsules ai 900°C. The Rb,CrF, has properties approximating those of a corrosion product found in a rubidium-base fuel. The compound RbCrF, was prepared by heating CrF, and RbF at 800°C in a sealed capsule. Numerous batches of structural metal fuel- or coolant-type fluoride complexes were prepared. Among these (prepared by methods previously described) were: K,CrF,, K,Ni F, and KNi F,. The compounds NiF,, FeF,, and FeF2 were prepared in a high state of purity by hydrofluorination of the corresponding chlorides. FUNDAMENTAL CHEMISTRY OF FUSED SALTS EMF Measurements L. E. Topol Mater i a1 s Cherni s try Di vi s ion - Av 1.84 1.25 Additional measurements of decomposition potentials of KCI and of various chlorides in molten KCI at 850T were mude. Morganite (AI 0 ) ? 3 crucibles were employed with all the melts studied. Preparation of Various Fluorides Platinum and nickel were used as cathodes, and B. J. Sturm E. E. Ketchen the anodes were of nickel, carbon (graphite), Materials Chemistry Division chromium, and zirconium. The solutions of various chlorides in KCI were The simple structural metal fluorides have conprepared by melting 2 moles of KCI with 1 mole of tinued to be used extensively for numerous purthe anhydrous chloride in a sealed, evacuated poses. A limited interest also has been maintained quartz tube. More dilute solutions were prepared by in several of the complex fluorides formed by the adding appropriate quantities of KCI to the 33.3% interaction of alkali fluorides with structural metal KCI mixtures so obtained. The data obtained fluorides. Some effort also has been expended on recently are given in Table 5.9. the preparation of other simple fluorides, as well as The value of 1.5 v found upon electrolysis of KCI on the purification of small quantities of the strucwith an anode of electrolytic chromium agrees with tural metal fluorides. The identity and purity of the value previously reported for chromium-plated these fluorides have been established mainly by gold wire in an atmosphere of helium,20 The more chemical analysis supplemented by x-ray and petrorecent value of 1.27 v for electrolytic chromium in graphic data in some cases. - _I___ - __ The with an ratio Of T. E. Topol, ANP Quar. Pmg. Rep. MUF. 10, 1954, 0.98, was prepared by heating Ag,CB, mder HF <strong>ORNL</strong>-1692, p 63. 67
ANP QUARTERLY PROGRESS REPORT q0-2 5 10-~ 1 O2 0 _. -- CALCUL ArED tROM FREE-ENERGY DATA (BREWER) AFo FOR FeF2= 65 4 'I kcol FXPtRlMCNTAL DATA ----- OFo FOR FeF, = 68 0 kcol CALCUC4TLD FROM FREE-ENERGY DATA (GI ASSNER) 2 5 .I o3 2 CONCEN.rRATlON FeF2 (ppm Fe++) UNCLASSIFIED 0 RNL- LR-- DW G 29 2 B 5 1 o4 Fig, 5.8. Equilibrium Concentration for the Reduction of FeF, by H, in )41aF-ZrF4 (53-47 mole %) at 800°C (Obtained by Equilibration Method). a hydrogen atmosphere may indicate that a hydrogen Current-voltage measurements indicate the first electrode is formed. reaction to be predominant. The Eo of 0.4 v for the The reaction of UCI, with zirconium metal n~iy reaction of UCI, with a chromium anode, that is, be ascribed to the following equations: 2UCI, t 3Cr - 3CrCI, t 2U , 2UC1, + 3Zr - 3ZrC1, I- 21J, !IFo = -10 kcal, Eo (theoretical) = 0,90 v, and 4UCI, I 3Zr - SZrCI, + 4U, AFo - 1-130 kcal, 68 seems to indicate strong complexing 3f the CrCl 2. There seems, from studies by other groups, to be
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Contract No. W-7405-eng-26 AIRCRAFT
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1. G. M. Adamson 2. R. G. Affel 3.
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197-198. Powerplant Laboratory (WAD
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FOREWORD This quarterly progress re
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PART II . MATERIALS RESEARCH 5 . CH
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Remote Metallography ..............
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ANP QUARTERLY PROGRE.S.5 REPORT ver
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AMP QUARTERLY PROGRESS REPORT A dev
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part I REACTOR THEORY, COMPONENT DE
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AMP QUARTERLY PROGRESS REPORT After
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ANP QUARTERLY PROGRESS REPORT the A
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ANP QUARTERLY PROGRESS REPORT 67 g
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ANP QUARTERLY PROGRESS REPORr Devel
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ANP QUARTERLY PROGRESS REPORT UNCL
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ANP QUARTERLY PROGRESS REPORi UNCLA
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ANP QUARTERLY PROGRESS REPORT lncon
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ANP QUARTERLY PROGRESS REPORT Fig.
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ANP QUARTERLY PROGRESS R€PORT 450
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ANP QUARTERLY PROGRESS REPORT TABLE
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132 ANP
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ANP QUr4RTERLY PROGRESS REPORT Addi
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ANP QUARTERLY PROGRESS REPORT mater
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ANP QUARTERLY PROGRESS REPORT Fig.
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ANP QUARTERLY PROGRESS REPORT oxide
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ANP QUARTERLY PROGRESS REPORT 10. A
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ANP QUARTERLY PROGRESS REPORT Oxide
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ANP QUARTERLY PROGRESS REPORT and U
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zirconium or aluminum complex, or l
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11. SHIELDING ANALYSIS J. E. Faulkn
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form in terms of the Spence functio
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these integral 5 become Let and the
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PERIOD ENDING SEPTEMBER IO, 7954 Al
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0 20 40 60 80 IO0 120 140 160 I, Di
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... Two configurations, a single du
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The thermal-neutron flux (Fig. 13.2
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E-7 1 O6 I 5 - - L I ___- 2 f o5 2
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TIME (rnin) PERIOD ENDING SEPTEMBER
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. - ., . ....._____... - PERiOD END
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io3 5 .--w 2 _J U 0 0 >- " 2 2 40 t
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PERIOD ENDING SEPTEMBER 10, 1954 Fi
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part IV APPENDIX
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REPORT NO. ~~-54-a-10 C F-54-6-4 CF
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