. 19 " . WV 1. 7171 2 24 TV * US 1471.1 IN4S 9 * . WARE + ." Ph. 1 - KUIN 1 LY . Mini .. IN 1 1 . .. .. . . i . 1 ", . - . . . . . ! . . . T LYK. . . ) 31 T : .. 1. . . . AWN . - . . . . . . . . . TY . " . . IT . : . . 1 , .' . 71.1 * ! . NITI , ? . 1 Y " ; Y " 2 . " ". ilia . hay 1. 2k TYY EKS? TA Wis + . . . 7.' A . Tin - .. .. SK 1 . irri . PI 1 L 'i .- ! i. :. , . . 1.2 * is, i . '. .!. ' ' . . ..? 2 . * , - IT 1 + ... .. . . . . .. . 1 . ? ., . N - . 1- ! i 1 ?! ? ' ! .. UT .. 73 LPA * UNCLASSIFIED ORNL .: . . 1 an RA 1 . . . - - . . - EVES . > 2 * .. I. CAT PAS STAY 69 V21 . Wr . .. . . . * :* "JULY RA. SD 403 . VY - XOX - 1.. ! ! . . ' 2 . ** i Air. 2 " AY ! LETON 2: A 4 .LU . IR . 1 . 11 ) - - день - д у - - - - - - - ..- -A - - DTIE-S - - .:> - - -:; - Oral Presentation - 15th CITCE Meeting, London, England September 23 OCT 5 1989 DIRECT SPECTROPHOTOMETRIC STUDTES OF REDOX REACTIONS D... MOLINEN FLUORIDE SAINS: ELECTROCHEMICAL IMPLICATIONS 4 . . - . 1 . . . J. P. Young Oak Ridge National Laboratory Oak Ridge, Tennessee MASTER I will first show a few slides to introduce you to the experimental techniques developed for handling corrosive molten fluoride salts for spectrophotometric study. FIRST SLIDE This 18 a cut-away drawing of the original high-temperature cell assembly. Of importance 18 simply to note that the sample, confined in a windowless container, 18 placed in the center of the heated portion of the furnace and light from a Cary recording spectrophotometer, model 14,, passes through the furnace by means of the light bean ports. NEXT SLIDE This is a photograph of the presently used furnace. It is an all nickel apparatus, so that the sample containing compartment is relatively free from possible hydrolytic contaminants. A sample 18 placed in the compartmented 11d in a dry box and then can be transferred to the cell assembly for subsequent melting without exposure to the atmosphere. By means of vacuum and helium gas the atmosphere inside the cell assembly 1o exchanged with hellum and the sample lovered into the heater portion of the assembly, prior to melting, by means of the quartz rod shown. Research sponsored by the U. 8. Atomic Energy Commission wder contract with the Union Carbide Corporation. - LIOAI NOTICE - The report wwe mpendwm me e Omer s oned with Matthin the United mhome, who own , we murun way w e calatori Ai Mehme r pet, pontor Imutted, we hope the new. wwwroom, or m o re common in the report mey met water Antony www me on 1. A my w pod w towa , w how o manage torm wou d o e n , wo w process to more As wwwd o wn uporwa Owoco" moked my m. Menu w war m , wompleyou in modo commen, om het www wimptome e mire . O ttom, a w ww.trmation map , decomwa moto modulo W, rosto moment w mo . truet the own, e me te m iratur. 2 OF 2 ORNL P 3136 . . . EEEEEEEE - - L 1.25 14 .6 MICROCOPY RESOLUTION TEST CHART NATIONAL BUREAU OF STANDARDS - 1963 . . ' M U NITY YAPAYAT , 2 . ..: . . .- 9. 1 1. 1 . Loutit, J. F. 1964. The Biology o? Radiation-Induced Cancer. Annals of the New York Academy of Sciences, 114: Pp. 816-822. --:. - ... - .. . McClellan, R. O. 1966. Hematopoietic tissue neoplasms in animals administered 90Sr. (A preliminary report). Health Phys., 12: 1362–1365. . - --.- .. - .. . McClellan, R. O., and L. K. Bustad. 1964. Toxicity of Significant Radio- auclides in Large Animals. Annals of the New York Academy of Science, 3: 973-811. .. - . . . . . . . McEndy, D. P., M. C. Boon, and J. Furth. 1942. Induction of Leukemia in Mice by Methylcholanthrene and X-rays. Journal of the National Cancer Institute, 3: 227-247. . - MacMahon, B. 1962. Prenatal X Ray Exposure and Childhood Cancer. Journal of the National Cancer Institute, 28: 1173-1191. MacMahon, B., and G. B. Hutchinson. 1964. Prenatal X-Ray and Childhood Cancer: A review. Acta Unio International 1s Contra Cancrum, 20: 1172-1174. Maisin, J., P. Maldague, A. Dunjic, and H. 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A Acute and chronic leukemia in irradiated spondylitics, in relation to age at first exposure (Dəll, 1962) A Acute and chronic leukemia, chronic lymphatic type excluded, in England and Wales, in relation to age (Doll, 1962). O Acute granulocytic leukemia in survivors exposed within to A-bomb radiation within 1500 meters at Hiroshima and Nagasaki, in relation to age at exposure (Brill, Tomonager, and Heyssel, 1962). * Acute granulocytic leukemia in Japan, Kinki district, in relation to age (Wakisaka, 1958). . ...... TY . . ......... . - .. . --- FIGURE 2. Annual incidence of leukemia, all types, in relation to radiation dose. ... O Nagasaki A-bomb survivors (Brill et al. 1962). Hiroshima A-bomb survivors (Brill et al., 1982), with revision of dose estimates as par J. A. Auxior, personal communication). A Irradiated spondylitics, radiation exposure expressed in mean doce (R) to spinal marrow (Court Brown and Doll, 1957), -- . .. - :. . Fig. 3. Incidence of thymic lymphomas in relation to dose and dose rate of x- and : Y-Irradiation. Shaded symbols, C57BL mice (Kaplan and Brown, 1952); open symbols, RF mice (Upton et al., 1966). Osingle, brief irradiation, 7 to 25 r./min. V four exposures at 1-day intervals A four exposures at 8-day intervals Diten exposures at 30-day intervais, Osemicontinuous exposure at 0.5 mr./min. SI FIGURE 4. Dose-incidence relation for granulocytic leukemia in wholo-body-irradiated RF male mico, as influenced by protraction or irradiation. (All mice were 8-10 weeks old at start of irradiation.) O. Single, acute exposure to X rays at 50-100 rads/inin.. .A Daily exposura to Cool gamma rays at 0.0006 rads/min. A Daily exposure to .. fast neutrons at 0.0006-0.006 rads/min. (A.C. Upton, J. W. Conklin, and i n 1.4.. Randolph, Unpublished data): W 11 - - . ., * ' . · " T.. . . . . .. . . . T .-' , 2 .. , - : * 7 -. :T . . . . . l. 1. 4 1: FIGURE 5. Average probability of dying with a malignant none tumor as a function of isotope dose in mice (from Finkel, 1959). . . . . . . . " : - . - . - " FIGURE 6. Incidence of thyroid cancer in humans, expressed in percentage of exposed, in relation to thyroid dose (fxom Beach and Dolphin, 1962). . ' - .1.- - . . 2 ...: . . : . . Z :,: FIGURE 7. Incidence of thyroid tur:ors in male Long-Evans rats injected with various doses of 1131 (from Mole, 19586, after Lindsay, Potter, and Chaikoff, 1957, and Potter et al., 1960). O Foliicular adenoma. Alevolar carcinoma. A Papillary and follicular carcinoma. ; - -- - - 1. - 1. ' : - . . . FIGURE 8. Annual incidence of respiratory cancer among uranium miners in relation to duration of occupational exposure (from Wagoner et al., 1965). - . . . 1 . i *. - - - .. L . ." . . . . . . . . -. .. . . p . .. 1 . . : : 11 . . . . ..... .... . . . ..... . ... . il .... . . . . . . . . . "-- . - - . . . . . . ' -. . .. ... - .... . .. . .. .. . ... . .. .. ... ... .... .... . .. . . .. . . . . . . . .... .... . . - - - . . . 11.. . ....... - .... . . .. .,' ; -, . . . .. .: - . . . ..:.. - - :. . . . . . . .7. TIT. * T.' " -.. .. . - . .. : Il - ANNUAL INCIDENCE PER MILLION PERSON-YEARS AT RISK I! - . SX :- 10,000 : : --.- -.. . . . + . . . . . . . - : : 1 . 1 .. . . - -- ; .. :. : . . . . 1 . - . .' . :: . . - . i. ' L ACUTE GRANULOCYTIC .; '. '. LEUKEMIA ACUTE GRANULOCYTIC . . . .. . . . " . L. .. ! J -'... . ' ' • 20 . . 1. . . . - '. . .. : . . .*... . : '.' ; ' ' . -' :ii:. : : LYMPHATIC EXCLUDED LEUKEMIA, CHRONIC : '. . . 1 : 1 - - . .. AGE (years) 30 : . . " il " " .. * :: ::. , 1:" . ' " '. ' 4 A : ... . . 40 Hiroshima and Nagasaki, < 1500 m AND CHRONIC LEUKEMIA, ACUTE I . , 1. . Japan, Kinki District .... .... . . ..... .. : ... . ... : . . .. :.'. England and Wales . . . .. - !" . . . I ! . I. . . 50 FIG.? 60 . Spondylitics Irradiated . 1.: , -:. .: . 4 - . 1. ii P Mi ! - :-. . " .. • . ... +. . . . - . ..,1. . T .... .' **.. . . 1** ic. Pui! ar 1. ini ... - . + + + 1 1" .... A . . . . .'- - . 2." . . . *1*1 1 1 . ! '. L . . . 1.' P * . . . ... . .. ..... . . : 4 V .: :,:!... : n i. - '. . î . . _31. ". . 2 .. .1-. . . . . . . .". : : I ,!; 1."... .... . : : . . - . : . . i . n .. . . . - P . . , ... . 17.!: 7 ... iii-** ..;::- . .-!- - . . ! . , .: - - -- *' . . - - 1 -- . .1..," 4 7. RO . 5 Y * ' VI 1 :14:13 7 - . -. . Tiim 1 .. - . . - . . 5 ', - ? 1.5"- , " vi r .11 A ' - --- - + 1- 45 RISTOV . : T', k : 'wi . : : !: ". . . . . ... -. -. .'.'.. .- -. .' 1. . W ! ! "! m .. ' ii . .. . . . . .... ... . id .: . .:' - "...: . . .. - ! . - . .. .. .. III' I. . 1651x N y .. . .. . " , " . . 2 >. : 15,694 1- - ' . . i: - . . . . .... . .:.,.. ' '. ' . .. . !! . . - .' .: ' : Y .' - . ? . i .. * 1.- . . 1400- . : . . I I 1. . . . . ." ". . . ; 1.. .. .-. . --- .:: . . . . . . . :! T'. . - - - . ?11 :- 5 :: . T 1. . : . ., : .: .... : : . - . .- ". .. . - : i .. . : . . 1 . . . i . . . T . . . .. . . . . . . . !. :: -. - .." .. ANNUAL INCIDENCE PER MILLION PERSON-YEARS AT RISK : . . 3 -- ' 1 .' . ' r T . . ::: . .. :: . .. "* - ... ' . ... . . :., ::- . . . ... . . . . . . t . ! . ... . .' ' . .' - . .'. .-- 1.1 -.-.- - - . - - - .. . - - . . 1 ... ... .le : - I. . - - - . ! *** .- .- -. ." 2.1 iti!.is . , 1 . . " .. . - . w. . .. .*: - : : . ' Ti 400 600 800 .. . 1000 1200 FIG. 2 -' ' "I .. .:: DOSE (R or rads) .. 2. - -- . 12. Ind . - ..:: : . L . 5. .." .. . '. T i . . .' i ' ? * 7111 ".' .. --- " UL. -.-- ** * L . Lil . . ..... ...... ..... . . . , . * 4. ill - Wik , W .- -- * 1. . . . : . .. . . .. 1. . . . . .' .' .'. . . , - . " ... ..., • "- , -. I' . ' ' I : 1.1 :::.- .. n! .. - . . . . . '.. . . . : i 1 . . . : . . . i- ! : ! . . . '. . T * -- . -... ' . - ii I , s. . . .!. , . F - . •. 1. . . ::. · . ' i . . - .. . t . - -. .: 17175 - Ww. - : .. . . .:.: ' . :: : . . ..:.:.- :: e . 3 T . . : * i = - ... -: . I .:. : -1..*: temi; : .. " . . . . . ' - . 100 . - . . . . - , in " . 7 - TO .. > . - m . . . + T 1... "... . 'Y '. ." . . 1 . . 1. . 1.. i ;.:.: 1-. .:. Wii : 1 . ,'. . . - 7 ..1:. .1. -'' . -:. . ! .. L . 1. . . 1 ! .". . : . .: 1 :.. - - . - . 14. - . 1 -. ..:* - . L .. - * * . - : FINAL INCIDENCE (%) - . . : . . 1 . i . 1 : E + . .* ". : ..: - , -- . .. . . . ". P . 1:1 2010-07- bol-o--2--------01 1 . . 200 1000 .. .... .. ........... ...... . ... .... - IL Inul. - .. 400 600 800 TOTAL RADIATION (R) . - .. . . -- ..... .', : . ... - FIG.8 ... IT: '. ... . *' . 1 - * - - - . .. ii' .. . 4.:. , 1 . .... . .. 'ļ" I . - ..... 5 . . . I . . . .. ... " 1" ' . r . . . . . 11 T - ?! J' " 15 .... illy? ! . rin ? ! 1 - -! . . ". " ; " . :? + I.. I ' OF . . ti - ". .. i : ... . . N i . : . '. - - i .., 1.'. :-.. T . , . "..: . i . '. . i . .. . . . . .. Y * . . .. '. . . * . . . - - 1 • IS • ' .'. + 1 j *. **** 19.1 2...!! - . : i. - j .. 11 ?. . d. . 1. ..: ERW . .- . . . . . .. . - --. i571.2. ' . . .: " F..... . . ' - ... II . . 6. ". : . 1 . ' . *. . .. . I T ' .. .!! !.. . . . . '. ! . 15697 . * - ... - ' , . .. " W . ... . ... .. Tei - • .' . … ... … …. … . .. . . . . = Li. * . n i ' . . ! !" . it , . i - . - 1 TIT: .... ... .' : T ...amitindones . 1 . - - . i . . * - . - ia . - . .: Tv : ! . : : " 1", 1 :: ".' 1 .. - .. - . . in. : I. .. : - - " -- . .. | -:. ... . 1 r .. i .... INCIDENCE (%) . . . . .. . . . ;, . . . Ain .. i -! . . !: .. . ... .- -. . . . .. ... Til . . i ... 1 . . .." 1 : : ; : -: . ::.. ? - . . .. . . 100 . 200 300 400 DOSE (rads) . -' 500 600 AG. 4 7 : - . '. : .4 ' ' 7 " ... . .... i . W .-.. .. - - 1.. . I . ." . . IT. .. . ? .. . TH . ;" . - ! ..- : . T. - w 216 .. .. ...... ... .. .- - I .- 4. 1 1 1. - - Hili . ..:- - .. ...... ..--- ... - -- - - - 11 -...+. Ai 11 1 11. .ir , . ?:3 ,!.. . . : ... ! : . . . . . . - . : . . : : 7 - ',,. . 1. : . .. - ...!! ! ii :: .....' - : 1... . . . ... . - . .! - " i . ...-.- . .. 1. S 1 . . 17" .- ', . 1 1.. .. YFIR TMLWYR - " * ! mitte H mih YA . : . ..:- *.*; ...".'; . .. ... NA . .... '. .. . . . 11. 7, :1. - *. 7 in : .7. . .. 1 .. ... .. . ? 1 . 1. ' " L ..... .... : . IT "__ y ... - I I . r.1 . 1,7' . '*.* . : . 1 ". . . 1: -... : iii ... - . .. . :::::: . ',''iti 111-. 1. 27::-. . ...' :. 1.1 . . :- 5. . I . - 1. : .. . ::: . . . . - . . . . . . :-;- -- . - . . vs. . . - 11,460 R . . ir , . .. , . . 11. ! - " ' ' 1 ..:::. : - . - :-. " . - .. . - : - . . . - gyi . . . . . . . " . . . . - - .- - ir 1. "* ..: . :: - ' .. 4 FI -.. - . HF; . . . . .. . - :: .. - - : . - " .. . " . Ts is . . P.., 1 PROBABILITY (2) .. . - . . ... : :. -. . . . . . :- wa .- ' . .-.. . 11 , : - . . . 10 1000 · 100 INJECTED DOSE (NO/NO) ... ..: - FIG. 85 • Hii .:'; . - . +1, 394 - . .. • 'TTE. ' - ...... ....... .... . .......... . ........ ..... ". '' -- ' i' ..' - - - - 1 - ...Tadindo".- .-.. - ... ... .. . - - - - - - - - 1 .- - .- -..-.. .... - 1 --................. . . - - - . . .. . . . . .. ---- 1: . I ! i " T: + !!' :LI. ul.." . - . . : . . .. . : . . . . . . ! I ,. . ! .. . 12:72 I is !: .. . , , : . .. : TTT - . . . I' ll . .. . " Y . ! " ; " pl: Yah, : .. . . .. . . si, 1:#ic . . - - - * ' -" : . .... . . r: ". . . i : . '. . . : . ..- - . " . . . . . * . : ..: 5 ::: ... " . E ine 1 !''. '" ?'. .. ... . I :, - . TE . *... BR ... . , ih 2 - ....., .** - - LEV. .. with .. : . * . I... , ST . + . . . * ..: . . 4. 7 . . . + . . ." 1: * '... : : .1. . ' . ....i . . .. - " . ..- *** . . : I .:! - I- 1 + . " 1 :,:. ::..ie . 1 . ili - . 1 .. ... " ." . . T . :"; ...' . , . : . 1 " L . IT: . -.. . . . . 1..- . ..... . I. ' 1. . - . . . . .. 1.. ! . . .. . . .... . . :.' . . ... . : - . .. . . . . - - . . . . . . :. :* : . "-.-. i. ... . " !. :,:. "TI. ... ... + . . . I. . . . PERCENTAGE INCIDENCE OF MALIGNANT THYROID TUMCURS ". ri - "--:" . .. ' '. ' 1:ni . . . . . . . . " 1. ., - - ..' - - - :. I ... - . . . . 1. , .. 1. . . . .-. .- 1 . : ::: 1' . . . .. . . . . - 200 . : . . - 'T .', ' . " " - - - ... . " 1 300. . . . . - . '. - - . J 1.1 i . . - ... - - - ... 20 THYROID DOSE, RAD 300 600 OOOOO - . . : - .. !- .i . . i FIG. 36 700.000 . .- .. : : . : - . . - .: - . . .- -.- *: - - - - -- .--. - '3 - - - - .. - ... - -- - . . . - - - - . . - --. * -? ::.. Ini - - * . - * * ,-- -- - ' . ? 3.. . ". - . . . ' . ^ - ' .' . " . iii i ii. .. . . .ii 1 - " ! :- : . .. : ,, - . - - . 400 .. 7 . .- -. 1.. - 7 . , . . . . . FIG. JO7 . .... 2 . L . : :in; . . ! . 2 . 300 1 . .:.:.:.:.. :. : : .'. 5+ .- : - ;s. ; -. * - * 5 ,-. . V ..... ... .... . . . : . waarin 200 [131–DOSE (uc) .. . .. !::.". .' .-. 2 1 1. : . " - 00 . .. ? ^. R r .. :- - . ? !- :* • A-A ... .. ... ... . .. .. . . . . .. .. . . . . . . . . . . . .. - - - . . . .. .-- . - . ., . _ ... . . . ... ... . . . - - . - - - - ... ... . .. .. ..... . - - .- -.. ' . . . . 1 Looi F08 20- . T :. .: .- INCIDENCE (%) .. ... . : ... ,. :- .. -- . :. : . 1'. .. :.* - -* . :. - :: ::. .:. . .. . .. :." . . 19 11. I ". '! " . .. . . ... .. . . . ..ALI.. . Ni. h r / - r.- ' GUA ............... MLANKLIN W.. WW ,. W . WWW . TW . Her * : *" . , * . . . p .. . .. ..... . ? .' . 1. .. ." .. . 1 .- .12 . T !! . ...... . . i ; .'. . . ... 7. , ' , i ' W 2. .. ... . .."," . . . .: .: www ! " . .... ......! i :, . . . :: , ." . ". i I'ATE L ' viii . . " ? * !.. 3 -. .'. .. .. . . ! " 15696-22 . . - .. - . . i .-. . . . :. -:- " . -. :. ':.. 7. . 1: ' : . .' --. 1. .' .'. " . .., .. : -. . . . . . . . . . . . " . - . . . . " - . : 7, 7 :. :. . :'. . - ' ' . . .. . . - I + 1 INCIDENCE, STANDARDIZED FOR AGE INCIDENCE, STANDARDIZED FOR AGE AND CIGARETTE CONSUMPTION 5:17 T - . - . :. ".. . i r ' ..! .. .. : : . - : . ....... ' - Enis 1: .. US . ' Sweet T E L. :.. ... . .. .. .. . - ';' ;' '. . . ANNUAL INCIDENCE OF RESPIRATORY CANCER /10,000 MINERS ..':. . + ' : 1 : - : ?.. " 7 '" ' - LINK .. . ii . . . .. .. . ..: - :D : .' . -- .. . . . - : .. ... " i - -. 11 . .. 1 . . . ... . 2760 CUMULATIVE WORKING LEVEL MONTHS :- #.- ..... . . .+. . I ' ' "" ."' - - " : "/" -" '" ' ' "" ' .'"'. 1 . - - . . . FIG. 48 LC u 17 .. - . . - . - - :!... . . .: . ::. . '1' :: .:: :. . 77. - ! WWW . ... . ......!!! . " - - . --.**. * * INN E W * * -* .1... ' ' ' ","? RE I "W : M. L., ..ther *** * WET r hayopate . # . 'L'. SYRIA ... ... - ''TRI : : :? :;' :- ? 4.. - 15 42LA"!! . .: TV : . , . * . :. *) . . : -. END 21 .. . . . . . . ... . . .:.1 . . . ... : : : . . . : . . . . ... . .. .. . .... .... .. . . . .. i niew _AN . . .......... -- .. ... .. .. . DATE FILMED 8 / 21 /67 .: . . 2 : . . 1 . . .. . ' :.: .,! .. RES ... MR. . . . n ! : . . . : ..' S I . . . . . : ... :: . 11 ! ! .. PLIS .... NEXT SLIDE We have developed several types of windowless sample holders, this 18 one of them (called a captive liquid cell). Liquid 16 maintained in the plane of the smaller holes in the cell and light passes through the lower, larger, holes for spectral study. The cell 16 attached to a holder which 18 cemented to a quartz rod. As explained in the last slide, the sample bolder then can be manipulated from outside the cell assembly. In all experiments reported today the sample container was made from Cu except where noted. If anyone desires more information as to the apparatus and techniques, please contact me after the meeting and I will be glad to discuss the various aspects with you. Since the data acquired from these techniques will be of interest to more people, however, I will proceed to a discussion of results. .- . .. NEXT SLIDE www... ..... Shown here are the solvents which we have used in our various spectro- photometric studies along with the composition of the mixtures where appli- cable and also the melting points. Although not listed on the slide, we have performed some studies in other solvents such as L1-KC1, pure Lidl and other materials which are liquid at temperatures above 100°c. My remarks today will be limited essentially to a discussion of results which were obtained by the use of the first three solvents. The alkali fluoride eutectic 18 a useful solvent for fundamental research. The next solvent 11sted will be the coolant salt for the soon to be completed Molten Salt Reactor Experiment which will be operated at Oak Ridge National Laboratory. The third salt listed 18 the fuel solvent for the same reactor. In the reactor this solvent viu - . .- *.. -3. ? contain about 0.9 mole per cent uranium tetrafluoride. NEXT SLIDE It has been found that a number of metals are reactive to the molten eutectic WF-NaF-. In fact, this technique bas proven to be an ideal way to prepare solution so trivalent uraniw. A summary of the studies we have undertaken of this nature 18 given here along with the T for the reaction at 1000% as written per atom of alkali metal produced. The positive is lead one to infer that these reactions proceed by the volatilization of the alkali metalo formed with the corresponding oxddation of the active metal to some ion with possibly reduced activity. The alkali metal vapors are easily identified by the characteristic resonance absorption spectra which can be seen in the hellum gas surrounding the liquid sample. Although it can be seen that Li metal vapor 18 not seen, there is some evidence that l :. . -* , .' perhaps the ability of lithium metal to alloy might also be a driving force in this and other reactions to be discussed in reference to the BeF2 solvents. The free energy changes. given were estimated by considering the free energy of formation given by Classner for the reactants and products in their proper physical state extrapolated to the desired temperature. Experimentally the reactions were studied at ca 800%. The resultant oxidized metal ion in each case 18: none in the case of iron, probably Cr(II) and then Cr(III), U(III), U(IV), Zr(IV), Mg(II), Y(III) and L1(I). In the chlorides the only one of the three were found to react was Сa going to divalent Ca. Under the present experimental conditions, chromi um appears to be the least active metal that wili be oxidized by contact with the alkali fluoride cutectic. It 16 not known, a yet, way the resonance absorption spectra of the wall metal vapors are not observed in this case. A spectrum corresponding to that expected for Cr(II) 1. seen tho. Although botih Na and K vapors vere . . . E N TITY WWWWWWWWWWWWWWW.Yanmar -- 4. identified as the result of the reaction of Zr metal, the melt remained colorless. From this, it is inferred that Zr 18 oddized dørectly to Zx(IV). This conclusion 18 in line with the electrochemical findings of D. L. Manning for the polarographic study of Zr in fluoride melts. NEXT SLIDE Considering the spectrophotometric observation of the reaction of U ard. UF, with LiF-NaF-Kr these reactions can be written. It has not been possible to determine, spectrophotometrically, which of the reactions IIa or IIb occur; possibli botih occur. The overall effect of these reactions, however, is that lower valent uranium will be oxidized to U(IV) in this solvent under the experimental conditions of this study. A reaction of small amounts of prin the sample with vº should also have been shown. NEXT SLIDE Since it is known that alkali metals are generated by the reaction of active metals with LiF-NaF-KF and since alkali metals are believed to form colored solutions with their respective molten halides, it was of interest to . prepare these solutions and obtain their spectra. Since spectrophotometric .-.- . . .. studies of molten fluoride salts are done in windowless containers, Na or K cannot be added directly to the solution as they would immediately distill out of the melt. It was found that a solution believed to be K and/or Na in LiF-NaF-KF could be prepared, however, by the reaction of an excess amount of Mg or Y with the eutectic. The resultant blue solution exhibits one broad absorption peak as shown here, with a maximum at 615 m. The resonance absorption spectra of the alkali metals are seen in the gas phase surrounding the solution. Since L1 18 not s volatile as the other alkali metala, solu- tions of Li in the eutectic could be made by direct additons of this metal to the melt. However, as indicated by free energy considerations, is ge ! ► N . UN ? C . ) ! . .1 " .. Law EN M 1, TA MVN *** -5. * . 1 - ann - .. - *1 ! - H -- - - unstable in such a system and would be oxidized by the other alkall metal fluorides. This was precisely the experimental case. The same blue solution was formed when lº vas added to the solvent. This points up one of the conclusions I wish to make in the presentation. One must be sure of the compatibility in the experimental system which they are investigating. It has been brought to my attention in published and mpublished results that pertaps such considerations are not made. In the work that was carried out with LiF-NaF-KF reactions were seen which were not favored thermodynamically and others were seen which one might not expect to be favored thermodynamically, but which are favored. NEXT SLIDE To demonstrate that Liº will be compatible with some systems I'U sku this slide of the spectrum of L1° 10 molten L10. These materials are extremely corrosive and this spectra was obtained with the melt contained 10: à molybdenum captive liquid cell. Again, compatibility of materials murt be considered in experiments. If this experiment 18 carried out in platinut ware, the solution remains colorless. After the experiment the li chia be found alloyed with the platinum. This is perhaps an obvious example of incompati. bility, but one must be careful to avoid more subtle examples either with respect to reactants added or with respect to products formed. NEXT SLIDE 'I'U show this slide as added information for the present. This is a plot of the increase in absorbance of a strong U(III) absorption peak in the reaction of vº with LF-NaF-KT". These data suggest that this reaction 1. in some way autocatalytic. NEXT SLIDE Turning to tho Lir-BoT, and Lir-Bef2-25T solvents, these following reactions have been observed and in some cases studied. This work 16 st111 . b mimpi melombang -60 progressing, but this will give you an idea of the reactions that can occur. Uranium has been observed to reduce U(IV) to U(III); beryllium metal has been observed to reduce U(IV) to U(III) and in other experiments in which the sur. face of a piece of beryllium metal, in contact with melts which contain U and Zr, has been analyzed by X-ray diffraction zirconium metal and uranium metal (as an alloy with Zr) has been found. Iu experiments designed to produce Zr(III) in such melts by the reaction Zrº with Zr(IV), 20 colored dissolved species has been observed. From this evidence lt 18 concluded that Zrº will not react with the solvent and also that a rather obvious way to prepare solutions of Zr(III) 18 of no value. The blotted out portion of this slide porported to show that tº does not react with solvent. This has not been verified in practice. Since the thermo- dynamic values for the various products and reactants involved are still open to question, a case could be made for the reaction of uranium with either Zr or Be ions to form U(III). It 18 also quite possible that Uº 18 simply reacting with impurity metal ions in solution, Fe, Ni, Cr, to form U(III). Experimentally it has been shown that U(III) grows into such melts slowly.. Work 18 presently under way to determine the reaction mechanism. I have talked for some time without mentioning the normal spectrophotometric terms such as wavelength, molar absorptivity, etc. I assume that the audience 18 not here to hear about spectra per se. In this case I should mention, tho, that the U(III) spectrum in the near UV portion 18 extremely sensitive because of a high molar absorptivity (ca. 500). Putting it another way, one could easily see U(III) concentrations down to some 200 ppm and less. Thus on a molar basis or mole fraction basis in these melts a small amount of U(III) can be readily seen. . . I > 11 .. S .... . . . NEXT SLIDE This shows some data collected in a study at various temperatures for the reduction of U(IV) with Zrº. It can be seen that the data apparently fits a first order rate mechanism. Instead of log concentration of U(IV) being plotted you will note absorbance difference was plotted on the log scale. The U(IV) spectrum 18 very Insensitive. By assuming that the reaction written at the bottom 18 quantitative one can obtain a measure of the original U(IV) concentration of the melt by the absorbance of the U(III) when it grove to its maximum value, then at any time (t) the absorbance of U(IV), which 18 a measure of its concentration, 18 the final absorbance of the U(III) A. minus the absorbance of U(III) at that time [4] . The resulting plots are the result of such considerations. Rate constants have been calculated from these data of 0.042/min, 0.065/min and 0.10/min at 480°, 510°, and 540° C respectively. The proper plot of these data yield a straight line with a slope which gives the resultant energy of activation of 17 Kcal. This is a reasonable figure, but I know of no comparative data. It has been suggested that the original plots could also be explained on the basis of diffusion of the colored species [U( 111)] into the observed portion of the melt. Although I do not as yet have sufficient data to refute this argument, at times I have had opportunity to observe the dissolution of species in fluoride melts and such a linear plot cannot be made of the data. DONAL 2 i . .. . .:;-. - ;-* " .- . ... .i .. . NEXT SLIDE .. This data may well be better presented in the sessions on complex ions in fused salts, but the slide demonstrates the use that can be made of spectra in determining the coordination of dissolved ions in molten salts. This is a spectra of N1F2 in UF-NaF-KF at 500°C. The interpretation of this spectrum - . 2 ut : 1, . " Y. ME f . I t . .. YA .. IN . DATE . * 7 TV S Aur 15 im . SIL PY P OR . A4 -8. ^ Pit - - -- - - - - - . .. - - - was carried out with considerable cooperation of G. P. Smith of the Metals and Ceramics Division of Oak Ridge National Laboratory. The spectrum has been interpreted to have probable octahedral symwetry in the alkali fluoride melt. N1(II) has been studied in many melts, but I believe this is the first cate observed for this ion to have peaks of proper position and intensity for simple octahedral symmetry. LAST SLIDE The interpretation of this spectrum of FeF2 in the same alkall fluoride melt is much less precise. The most logical case to be made for this spectrum 18 that Fe(II) exists mainly in Op symmetry (causing large peak at 10,000 wave numbers) with a small fraction of the ions in T, symmetry (causing peak at Ca. 5400 wave numbers). More work of this kind will be carried out as time permits. - . . . --- . - - - - - - wimming porn korneav 4 - - - - - - < S - * .. ! . OC 377 . JUN ... 21 WAY. . AAN . . PISTE NA UNCLASSIFIED ORNL-DWG. 63-4526 . YES RO FORMATION OF ALKALI METALS BY REDUCTION OF ALKALI HALIDES MF + RO —RFn + Mº Temperature 1000°K Resonance Absorption AF Reaction / Equivalent Reduced Solvent Lines Observed LiF-NaF-KF None None Κ, Να K, Na K, NO Fe 56 K, NO LICI-KCI Κ, Να None None K ( Na impurity) ca i .. . .LA W . 11 1. 4W .4 B . 4 AL . 4 TEL - 153 RS 2 RICKS NON R 1 4:35 " . 15G - . . UNCLASSIFIED ORNL-DWG. 64.4219 6000 5500 1800 [Fe] -0.4 moles / liter 1600 1400 7500 WAVELENGTH, cm 10,000_ 1200 WAVELENGTH, my 1000 800 Spectrum of FeF, in Molten LiF-NaF-KF at 525°C. 600 25,000 400 ABSORBANCE -- imave D ::: IM- . . . : Dr . .. 4. * L ' . : ! . . . :, , ,,, --- Sen * * Ye ci - . t . i ! ,1 1:14 . I. .? . * . : LALA'rs . * tas ÅRSRAPISx600 PS . : BY WYR : YYY -- UNCLASSIFIED ORNL-DWG 63-99 - - 0 - o o 5000 30,000 10,000 15,000 20,000 25,000 v (cm') Spectrum of NiF2 in LiF-NaF-KF at 500 °C. . - - tu. - UNCLASSIFIED ORNL-DWG. 64-7210 - UNCLASSIFIED ORNL DWG. 64-7211 - YA Solvent: LiF-BeF -ZrF4 rii REACTIONS 9 Ya When • Y . 4 ti - . preso o t . . \ 480°C ABSORBANCE (Q, UF3 - ,UF;) . . .. . U° + 30F4F4UF 1/4 Zº + UF4 — Upg + 1/4 ZFA > UF2 + 1/2 BeF2 1/2 6° + UF, C Be° + 1/2 ZIF → 1/2 Zº + Bef, Zº + SOLVENT —— NR U° + SOLVENT —NR * 510°C . . . - SA Wir 11. . 540°C . N 991.. . . 10 20 30 40 50 TIME, min Loss of UF4 by the Reaction UF4 + 1/4 Zrº - UF3 + 1/4 ZrFq. w 1- AYA TF . Y2 S 14 721 .-.,. I . . . - - Sony EST . N 1 7 T. y i . ... 1.SYL .. a " - . . 14 . L UNCLASSIFIED ORNL-DWG. 63-4123 ISO::1 . KAS Y ABSORBANCE . LS . . AY . . t RS24. DEN -9, * st : .. 300 500 700 900 1000 1300 WAVELENGTH, ημ Spectrum of Liº in Molten Lici at 650°C. UNCLASSIFIED ORNL-LR-DWG. 76809A ABSORBANCE 0 500 -1000 1500 WAVELENGTH, MM Tentative Spectrum of (Na, K ?) in LiF-NaF-KF; Mg + LiF-NaF-KF at 525°C. . -.-- Sii .- INTL . UNCLASSIFIED ORNL-LR-DWG. 76813 MH se. - - . FA SP : 1 2S ----2--0 ws L . : . S . U(MI), moles/liter x 10+2 . .v 13 1 A . : . , .. 1 rist * . ANA EST TY 1X RU) RE AR ' TA TEMPERATURE: 525°C SLOPE - 2.4 x 10-2 MER NA Si TEN To WY Jin VES Cor SC is LAN ASS 50 100 150 TIME, min Growth of U(III) in LiF-NaF-KF by the Reaction 1/3 U° + MF → 1/3 2 Wax C * Y 327 * XXX > SO 1 AC T atau A TU .. . .. : UNCLASSIFIED ORNL-LR-DWG. 76943 € IMF + ſuº → į UF3 + Mº Ia MF + UF3 → UF4 + Mº DID 4UF3 → V° + 3UF4 III HF + UFz → UF4 + H2 ) UNCLASSIFIED ORNL-LR-DWG. 59366 SAMPLE PORT- LID WATER INLET AND OUTLET LID RETAINER SCREW TOP PLATE PORTS FOR INERT GAS, ETC. ELECTRIC LEADS SHUTTER NOTCH HEATER PLATES SKE - - AR INSULATING BLOCK QUARTZ WINDOW " . LIGHT BEAM PORTS S CAVITY FOR MgO CELLS ESSERE VESICIOS WATER JACKET INSULATION POSITIONING SCREWS FOR FURNACE High Temperature Cell Assembly. . . . UNCLASSIFIED ORNL DWG. 64.7212 MOLTEN FLUORIDE SOLVENTS .. -, mole % 46.5 – 11.5 – 42.0 67 – 33 65 – 31 - 4 50 - 50 m.p. °C 454 454 LiF - NaF – KF LiF - BeF2 LIF - BeF 2 – ZrF2 NaF – ZrF4 450 512 Lif 844 NaF 985 KF 856 RbF 760 683 19 2. ? 1. .. Luna 9 . - x Te. VE . RE: with 1.RS ». R : ' A - +428 UK 17.2 ' MT . .. Rt 97 ROY 7 12 ATA ST DAT " P 54 10 . . . ** - fore .. . . . .- . . . -3 VRK . 1 SNL A. , 7 no 24 AMA - in ** Many RET . ... 12. . i' . 9. * 2 h2 . . . . T 27. POLINO W SYS ? S2 AL TT 17 > 22 . W . X . W . 3 " I SULATING CHAMBER . . . E -1 . be 26 22. YA W SL .. 1 26 1. . . 1. 19 1 :45 D EN! 1 WINDOW 22 IT 2 SM1 · W YC 1996 UTA. ' 11., 1 : T US . ! R Vi . . . c I! . T! . 1 + 2X2 .im me 2 !. . 1 47 SUU . :. 1 , N . metode 1 KEL .* 14 RTVA. . 4 COTTOM PLATE Y ...'' i. .. ** PIW 4 2 , us 2 . . P. Si '. 17, 22.. . . . ,. XT: 5 IN! 20 . ! . Joy SP . 12. . A * 1 . . W 1 . . ' s VES 12. . . INCH . TAR . ...) ! 11 ! . - 1. DATE FILMED 2 / 24 65 5 . 3 LEGAL NOTICE - This report was prepared as an account of Government sponsored work. Neither the United States, nor the Commission, nor any person acting on behalf of the Commission: A. Makes any warranty or representation, expressed or implied, with respect to the accu- racy, completoness, or usefulness of the information contained in this report, or that the uso of any information, apparatus, mothod, or proceso disclosed in this roport may not infringe privately owned rights; or B. Asnumer any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus, mothod, or process disclosed in this report. A, used in the abovo, "person acting on behalf of the Commission" Includes any on- ployee or contractor of the Cummission, or omployce of such contractor, to the extent that such employee or contractor of the Commission, or omployee of such contractor prepares, disseminates, or provides access to, any information pursuant to his employment or contract with the Commission, or his employmort with such contractor. . . END