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\ Printed in the United Statts of America. Actable from National Technical Information Service U.S. Department of Commerce 5286 Port Royal Road. Springfield, Virginia 22161 Price: Printed Copy $7.75; Microfiche $2.25 0MK.4111 UC4-CH lili
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FEMUAKY 1976
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NOLffN«Aft.TS¥*TfMS 1 I Matlrsh&akXcxiofPlNinm I II I TwSrfmDt*aMm.wH*r4kKSSarfiKCs»»MSNl 1 II. t (w«c.. 114 tifrvtsof Ox>ys> «m me ti|ii*fcniiii n 1 AOlCOiS SYSTEMS ANPCCOrnCtMAlEl«aCY 2 I A^wStiKiH 12 211 1Vlftffih iii I* 4. OKMBniY0FnUmUUMUIfLBSN1S 4.1 Dmi—ama of d»IMf-Wj^< • 4J9 EltCtfOA BaaawaffM EMCinCS Ml ActMMM. nuCAKMMBML. HMflBaWR. 4.9 Ainaaiiwi Sow Qrait Suaiia» of a* 4/Le»et a the Actaade Sewn 38 4.10 TarCaMfwaiaa 0»yaai Systrai 40 4.11 TrawlH i iia 0«»aanae» aal fjxyadftdts 40 4.12 Uaduaar Acaadt Hydrowda 41 4.13 Bccmmrmmi&tKWnMm&bmitivnm\<>tOmmmt:f,Es m*atwil*t 41 4.14 Effect of Ti ay* i lit oa a* SdfLaaarsccacc of SrCl, Doped «i* •**Cm 417 Searca for Palo aan Ftaoreeuau 44 5. fMVWtCNKESTM tHtMBHV 5.1 Traaams w Fata-Oxyarft-Oroar Sysanas fteacnoa of Of ID) AIOHB tri* CF,C1: 45 Water ObdWrprd from PowerPbatCniifcaj Syswaa 46 5J Claaariiy crfSatfaradaAiawadiMt . 46 *. si^ARATioi^cmxmntY 6 I SpectroplKwoaatnc Studai of SotoeowCowuaa»|ltwlin>*.ir«t •laternb 4* 6.1.1 Pfcotocamatry of Aiawnas Fwnuaaai Soatiow 4ft 6.1.2 Catawstry of Faaoa Prodacts a Carbon Dnudr «9 6.2 Macroporoas todies Fdkd ank Oxides and Salfafcs at Ad»rbeais 49 6.3 •raerktitio* of rVMograpluc Wastes 50 6.4 Aajnn tatfciaar Adatrptka of Inmatmm EJoaeati froa TMoadfrte Sototioas 51 65 Advanced Filtration Aapataticasof Energy Sajaifkatce S2 6.6 taaVltaotaioa Separaonm 55 6.7 New Separations Apmis 55 V 7. KUClEAftOKMSntY 7 1 OKMr^^emtt mi LX*MfUamRcMmm a( tiamtm2*9nS -- S? 7 2 XJta> Uemm6cj»mmm4 Deem ftapen^ of kmitofei of L»\ ILMTW 5* 7J SVK*CTB and Attnapttd X*ay Mrntjfcoition of Onmem 106 Uang *ehohjpeI%,Un> $9 74 AFjaT^tTn^panAwMUyfbrShon-liMrilieOTy-BaMMNwMcs r»o4u4j(Oiur to 75 Mr»»M—ioT*eBa:iwC^ 2*Slatesm,T,Hf SO 7.27 Low-Intensity tela Transition in the Decay of **Tc f I 728 "'NdDrcay and the °* Ft Ground SU!« Spin H2 729 Decay of "'Pb 82 7.30 Pnmordial Radinelemeni and Cosmoarnk Radioetetneni Distributions in Luna* Samples from Descartes and Tauras-litirow 63 a OaCANCOEMBTVYCATALYSS. AND COAL RESEAKll si Kfgiiii — M.if*c44tniM •. MOfYSKAL UutMaMKV 9 1 Sniflet EXCMIOB Traasfa few Poh f Afc> Boun d Dvr * 77** 93 9.2 Tfceurt of Eidttd-Siaie iMeracHnns m hwkab Ayrpia 94 M. OKMKAtniVSCS 10.1 Structural Otessstrx 9« 10 I I Computer Simulation of lupwdSuduw 96 10 I 2 Amorphous S»M Water . 9s 10 13 Seutroa fttTrjcoon Stmhe* of Tfctf Hydratesof Fmijphntimtjtit Acid 97 10.1 4 Terror) Structural Mtereaccs benwm Mtcrohral Sermr Proteases and me Paacreatit Serme Eaiymes 98 10 1.5 Aa AtjEbrat/ Meamd for AaaK/mf Latae Rearrangement Seunxk* of Isomeric Mokvm>v 98 10.16 The Crystal and M-decufar Structure of aV Compiei of Plalmum Dbwfcdc mm the Puner of Pnaiii*.m laceume 99 10.1 7 A Neutron Diffraction Sv»t, ofuW I I Molecular Cnmpk* .if 7.7X8Jmacyanoi|uuiiwlunrfnav wr* p-Terpheavl 100 10.1 8 The Structure ofSaxitoxm A Test of Impcoiul Method* fat $-*mc me flttK ProMem 101 10.1 9 Strangr New Orfpmc Conductors The TetratlmifBlvaknc Halogen Complexes IOC 10.1.10 Xrufron Structural Sntdin RcbktJ to 0*m«w: Reactions 103 10.2 Atomic and Molecular C OJRMORS 105 10.2 1 Crossed Molrcular bam 5tua^ of the Reactinas of UF» wi* Alum Atoms 105 10.22 Surface Reac lints and tanpatmn of UF» I Oh 10.2.3 Hyper- and Pi*ar Cnamtdm* ofChargr-Sufe Selected 27.5-MrV Oxygen Ions iaSihvr 106 10.2.4 Electron Emission from Fast Oxygen and Copper lam Energjng from Tkin Gold Crystals m Channeled and Random Directions 107 •0.2.5 Crossed Molecular Beam Studies of Excited Atom Reactions 108 I© 3 mx*mmr mi tUmffmmmcy Smxtnmcam MUM Ckemmtn. mi UmmmmOmmutty . I0» 10.3.1 UtctnmSrmttnmmetSmixiailimiiiDvnm. Ffcr-*»vm **•** 109 10 3 2 SJecrai Spa ttemmmoe 5taak* oOJfctrrocydbc Kompamma m immto IMHMJ raoMnrss Ifc-fVfiBMi aiLMfcoKyhc Aai 110 !0.3 3 EkKtriwi Sf fcwaact Sifc n of ,V-HneracydK COHMNNJMH « bands Dana* K«4v* rVnaaKCa*wyi*eAaaNB Ill 10.3.4 T«Meafe»*rH,OCOCrl.-fl: Smew Ill 10.3 5 atoaaar FMMM • me RaawHas of Aaa* MI Iwaade kaStaM»*» 112 111 Uectf«iAea»^BcbsnnrofCo«r4eiAc«^#kiOTrMri^^lKti«Kw SnKw 114 112 Oe*t*m^*w0kmer»du4Bc4Sm*iUt£tHmr IIS 11.3 fchxUfdieaiial Hwrno at SwMwk Retmw 116 114 rm^lm)Kmftoatamd\mwi+rxke*+t4Bccuc4n 116 11 5 MeclrodKmcal Recover* a* RrdaL'.afc hmpM. MntaMs frOK Al|f IWII StUtJMB I |7 12 TaKRNALGEr*BUTOK0F|]YDft0GEN ll« 13. SURFACE CHEMISTRY 13 I A4-mrf*ft«i of a* Anaraied j*d Injdntrd Laax Fwc*SJWJII 121 13 2 hnei»;t*mt4(i4*c*wt6LMmtManendi Rented RewfoU* Ap.*> II 121 13 3 The hMesKtmn .-.'Sorted Wjier wi* Laaar fmniSmrpte 12001) 122 13 4 TheRc*cti.ia.lfV>rlKdWater»MliCr<«K!V.>lcMcM«KTA 122 13 5 Hraf aflMmcnNWofZirct«wiiiOudea(Ele<3'edTe«perMMO 122 I3A lafrarcd Speclrji Slate* ofiaieracliomoaOuar Surfaces . . 122 riMJCATIONS. PATENTS. LECTURES. AND fAfERS •RESENTED AT NEETRvGS 125 SUmEMENTAllY ACTTVmES 144 ORGANIZATION HURT 153 Preface Tbs mum** Kfurt B a MNMMY of tat rcscMca camimae4 m the Cat—jin Dnm Jan* the period MM 2.. 1*74 fHoarii V*caa*T 1. 1975. Farther jafnnatww itptimg work • lb* nrioas pr-jfna» OH be ofcijt J ftam die Ktfneaces offc> ooatactaa; airiM aKbors oe tat Dram Daectoc. I. MChen-Salt Svsteim II WOLIBlSALlUEACimrwOGkAn At steady stale, then, the producUua of the first parent m a chasn war equal the decay rale, where production rate (atoms, sun I - (UssiousinmNyieUriss/wl. A D Mmers D. Y. Vatmune decay rate = (Annijman of atoms preset). tdmui on Hatteftoy N surfaces m a lOQO-Mwiei The steady-state inventory of a species (number of MSMI was needed at order to design deposition atoms present | may then be found from exyrrssnenu tot nrvcst^gaOoa of iiBmnunnidiiLicd cor rosion and grass boundary crackmg. previously ob inventory = (fission rate x yield* X . served n the MSM To make such cstnwaies. it was necessar) to conwder the ovcral duptiatM of tcflu- When deposition from the fuel salt was calculated for a nun both as the piuwary sy sua: and nt the dram tank. parent of fdlurium. the tcnunum surface concentration Tie sources of leuwnum were taken as the direct tisaon was obtained by successively balancmg production and yield ut Kfluncm fn>m the fuel salt plus al ssjsuficani decay rates. The total inventory was then proportioned deca> chant yields. Cualnbatioa from various teflu- to the various surfaces of interest according to the laws num Hotopes were obtained fror steady-state rate and of mass transport. Fmatv then. TTTtw-ramf— calculations- The amimptiofts made in order to svnte a steady-state rate balance lor production tsnver.'ory Htraction going to a specific surface) vs decay of tellurium produced from direct fission and decay ot precursors have been described m detan.' ' atoms unit area on that surface . Two conditions were verified which alowed a simpli fied caicubfmn of the concentration of tellunum that The resulting expresaon for teuunum Jepostion on could deposit on any of the three types of surfaces the IfastcCoy N surfaces of the heat exchangers I with encountered in an MSMI metal, graphite, and bubble* equal slicking probabilities for boUi metal and graphre The first condition is thai both •*• residence tunes of surfaces and a low sticking probability lor bubbles) may teaunum and its precursors m the salt and the half-lives be written as of three species be long compared with the fuel salt circuit lime. This condition was shown to hold, assuring 10JOJSr* 0.012) mtcnr . that the contributions from fission yields in the cure are uniformly distributed throughout the primary system. with ' in effective full power years (EFFY). The first The second condition is that the residence time of term represents the deposition of stable tellurium teflurium and its precursors be short compared with the isotopes, and the second term represents the steady- half-lives of these species, assuring thai deposition state amount of radioactive tellurium isotopes at the occurs as fast as production and that the total inventory heat exchanger surfaces. Thus, in 30 EFPY. 9.105 b thus somewhere on a surface. This condition holds mg/cm2 of stable tellurium isotopes would deposit on fairly well. For very large tellurium particle sizes (1000 the HasteiToy N heat exchanger surfaces. In addition. A |. an error of less than Ti was estimated. This error 43.08 mg/cm2 of radioactive isotopes of tellurium becomes negligible, however, for tellurium particle sizes would have at one time contacted a Hastelloy N surface less than 100 A. (steady-state amount X time X 0.6931 /r,/2). Since 1 2 neither (he rate of diffusion of tellurium into Hastelloy Hastelloy N or its various modified alloys are exposed N nor the mechanism of any surface reaction is known, to tellurium vapor. the effect of the radioactive isotopes cannot *x accu Three consecutive test exposures of standard rately calculated. If. however, every atom of tellurium Hastelloy N were made for periods of 100. 100. and (stabte and radioactive) that ever contacts a Hartelloy N 200 hr respectively. Four tensile specimens, one sheet surface is assumed to react, a cumwhtwe exposure to sample, and one foil sample were exposed to tellurium the neat exchanger surfaces equivalent to about S2.I v apor at a tellurium diffusion rate to the specimens of mg/cm2 would occur in 30 EFPY. 0.048 mg/hr. With the temperature difference between Assuming that ail the tellurium adhering to bubbles solid tellurium and the specimens as the controlling arrives in the drain tank and is available for deposition variable, this particular diffusion rate was produced by on the Itastelloy N surfaces there, a cumulative ex holding the solid tellurium at 440"C when the speci posure equivalent to about 5 5 mg/cm2 (0.965 mg/cm2 mens were at 700°C. Visual inspection of the specimens stable tellurium isotopes + 4.57 mg/cm2 cumulative after the finn! 200-hr exposure revealed a uniform radioactive tellurium isotopes) would occur on the darkening of the entire surface are?. The weight data drain tank surface in 30 EFPY. This calculation assumes were inconsistent. Two specimens gained weight slightly a uniform distribution on the drain tank surface: and two lost weight. In addition, a gray deposit was however, it is suspected that a lugher concentration will observed on the inside of the quartz tube in a position > be found in a ring at the gas-liquid interface !evel that could have *>een as much as 5°C cooler than the around the drain tank. specimen temperature. Apparently, material had been One further estimate of the maximum exposure transported from the specimens to the qas.tz surface. attainable in the drain tank was made by increasing the X-ray diffraction analysis of this material, performed by bubble fraction to approximate the maximum permis 0. B. Gavin of the Metals ind Ceramics Division, sible void fraction in the core (1-2% void or 100.000 showed it to be NiTe0 7. No elemental tellurium was ft2 of bubble surface area) and assigning equal sticking detected. Since volatile nickel telluride species were probabilities to all surfaces. This calculation yieids a formed, material could well have been lost from the cumulative exposure to the drain tank of 166.1 mg/cm2 specimens during out gassing procedures prior to the of tellurium (29.0 mg/cm2 stable tellurium iso Te, exposure, in addition to the material lost to the topes + 137.1 mg/cm2 cumulative radioactive tellurium quartz during the exposure itself. This would explain isotopes) in 30 EFPY. In this case the tellurium the failure to record weight gains from tellurium exposure on the heat exchanger surface would be addition. 2 2 reduced to 9.7 mg/cm (1.70 mg/cm stable tellurium Various techniques were used to analyze the surfaces 2 isotopes-*-8.019 mg/cm cumulative radioactive tellu of the tensile and sheet specimen; X-ray diffraction, rium isotopes) again.performed by O. B. Cavin. identified NijTej and NiTe0.»» on the surface of the sheet specimen. Relative amounts of these species could not be obtained because I. V D. Kclmer* and l>. Y. Valentine. MSft Program their diffraction patterns overlap to a great extent. Semmmrn Prog Rep teh 2H. IV73. ORNL-5047. pp. 37-40. Auger spectroscopy, performed by C. L. White of the Metals and Ceramics Division, was used to examine the 1.1.2 Exposure of Metallurgical Samples first few atom layers on one of the tensile specimens. to Tellurium Vapor The elements chromium, oxygen, carbon, and possibly some tellurium were detected. The distribution of these A O. Kelmers D. Y. Valentine species along the length of the tensile specimens Investigation of 'he Hastelloy N surfaces in the MSRE appeared to be fairly uniform. The chromium and showed that ilie grain boundaries of this alloy had been oxygen are believed to result from a thin Cr20j surface selectively attacked and that intergranuiar cracking had coating which may have been present on the specimens occurred. It has subsequently been shown that tellu before the exposure began. The carbon is presumed to rium, produced as a fission product in the MSRE fuel arise from the diffusion of oil in the vacuum system. salt, induces such cracking. Currently, it is believed that The other two specimens were tensile tested by resistance to tellurium attack can be achieved by B. McNabb of the Metals and Ceramics Division and modifying the llistelloy N alloy. Experiments were examined for intergranuiar cracking. No loss of yield conducted1,3 to evaluate the extent of tellurium- strength or tensile strength was recorded. Under micro induced grain boundary cracking that occurs when scopic examination, however, extensive intergranuiar 3 V r4' ~> **' >. '* <* _V">;. ^ Fig. I.I. HasleBoy N specimen after tensile letting. Specimen has been cui in half and elrhcd to show grain boundaries, (a) Mapiifirafion 200x;(*) magnificat inn 33x. 4 cracking was visible over the entire surface of the 0<5hL-C*C- ra-HMJ specimens. The depth of the cracking ranged from 1 to TEMPCfUTURC (X) 5 mils, with most of the cracking occurring to a depth 800 ?SO TOO WO of about 2 mis. as shown in Fig. 1.1. : I 1 1 1 : Quantitative data on tellurium accretion to tensoe specimens cannot be obtained by this vapor deposition method because of die unanticipated formation of volatile nickel tctkirides- However, this methoJ is capable of producing teUurhun-induced intergranular cracking in the tensile specimens and appears to be a useful screening method to initially test HasteOoy N : \ modifications for alloys which do not crack. In view of this fact, other tests wiB be made in which tensile \\ specimens of three modified alloys will be exposed, \ > along with another set of standard Hastelioy N speci \ mens. 1. A. D. KdMrs and C. Y. Vakatinc. HSR hopmm Semmnmi hog. Rep. Aug SI. 1974. ORNL-SOII.pp. 22-23. \ 2. A. D. KdMcn and D. Y. Vakatme. MSR hognm Semmmu. hog. Rep. Feb. 2$. 1975. ORNL-5047. pp. 40-41. \ \ 113 Hydrogen Reduction t>i»iiuw of UF« \ Dissolved m Molten Fluoride Mixtures o LONG AND BLANKCNSHIP L 0. Gilpatrick UM.Toth $ GtP*TRICK WO TOTM A study of the equilibrium I0"7l I 1 I 1 1 i I UF4(d) + Ht H,(g) * UF,(d) • HF(g) 8.6 9.0 9.4 9.8 «0.2 fO.6 ff.O 11.4 to4//- no has been initiated using high-temperature spectroscopy Fja- 1.2. MniMMi «Mti»ts. <>* = (UF^WF«) (HF/ to reassess the redox chemistry of the fuel salt in a vSjK «s m* reciprocal of iijolti ttwpuif t foe H2 re- molten-salt breeder reactor. This chemistry is particu •actim of UF4 M LiF-M?} (66-J4 nwk *). larly important in minimizing corrosion, tritium con trol, and other equilibrium processes (e.g.. tellurium behavior) which can be affected hy the redox potential. over the previous study are in the ability to con Although the above equiltbrium has been studied tinuously monitor aO components of the equilibrium previously,1 the overall importance of the fuel salt and controllably reverse the equilibrium by changing chemistry and some discrepancies1 found in the wage the temperature or the composition of the HF-hydro of that earlier data warranted a closer study of the gen cover gas. equilibrium. Equilibrium quotients measured with LiF-BeFz The procedure involves sparging a small (approxi (66-34 mole '*>) as the solvent are given in Fig. 1.2. The mately 1 g) sample of molten salt that has a UF« effect of changes in solvent composition on the concentration of 0.038 to 0.13 mole/liter with hydro equilibrium is being investigated for other UF-BeFj gen gas at 5 50 to 850°C until partial reduction of UF4 mixtures as well as for the MSBR fuel salt solvent to L'Fj is observed. Then HF at a fixed partial pressure LiF-BeF,-ThF4 (72-16-J2 mole %). is added to the hydrogen gas stream to establish an equilibrium between the UFj and UF4 in solution and 1. G. Long and F. F. Mankenship. The Stability of VFj. the HF-hydrogen cover gas. A spectrophotometric ORNL-TM-2065 (November 1969). 2. L. M. Toth and L. O. Gilpatrick. The Equilibrium of Dilute measurement of the UF* and UF4 concentrations is combined with an analytically determined1 UFj Solutions Confined in Graphite. ORNL-TM-4056 l/2 (December 1972). HF/(Hj) ratio to yield the equilibrium quotient for 3. L. M. Toth and L. 0. Gilpa trick. MSR Program Semiannu a given set of conditions. The principal improvements hog. Rep. Feb. 29. 1975. ORNL-5047, p. 43. 5 1.1.4 Effects •fOsyfMwiarEqHikwM anomalously low UF,/UF4 ratios previously en of UF3-UF4 Molten Fluoride ttnlaiiinj countered, these recent results suggest that uranium carbides are more stable than uranium oxycarbides at temperatures below I000°C and strongly enforce the L. O. Gi-patrick R.M.Waller1 LM.Toth contention that trace amounts of oxygen in the MSBR During the investigation cf the UFj disproportkm- wffl not precipitate the fuel from the melt as uraunun ation equilibrium in moltenfluoride solutions. 1 it was oxycarbides. observed that the UF,/UF4 concentration ratio feffl to very low values yet stii behaved as if equiUbr run 1. Dcaaxd. conditions were being maintained. The accompanying 2. L St. Totfc»ILO.Gopatridt. TheEqmMhmmofDimu UF 5bfcn»u OmumrJ m Gnpkile. OKNL-TM-40S6 formation of U0 suggested that oxygen-containing } 2 t December 1972). impurities were responsible for the equilibrium shift, and it was speculated that uranium oxycarbide phases might form from uranium fluoride melts at 500 to 115 CViiiny of SodoMi Fhwroborate 800*C. If uranium-carbon-oxygen phases were more stable than the known uranium carbides, it could be LMaya possible to have equikbria with them and the UFj-UF 4 Hydrogen-containing species present in molten solutions: NaBF4-NaF mixtures can play an important role in managing the tritium produced in the operation of an <4x)UF, +(2x)C + Graphite capsule experiments were designed so that The system HB02-HjOBF4-H20 was characterized by constructing solubility diagrams at 25 and 60"C. The UO2 and UC: could be equilibrated in molten salt fluxes via the processes compounds H,OBF4 BF,-2H20, and HBF2(OH)2, which are components o( the system, were studied by proton and fluorine NMR spectroscopy. It was found <3x)UF4 • (jr)UC2 * (4rHJF, + (2x)C , that in the pure state these species undergo proton (*r)UF,*(2*)C*(I-x)UO, exchange between the undissociated and hydrouium ions and the anion. Furthermore, exchange of both **(3x)UF,*U(CJt.Ol.,),. protons and fluorine takes place in mixtures of these compounds. The NMR in this case is of limited value as The overall reaction would be the sum of the above an analytical tool, since no specific signal could be reactions: assigned with certainty to a particular species. However, the NMR was valuable in detecting these exchange jrliC, • (I - JC)UO, * U(C,.0, _xh . processes, which are an indication that these com pounds can participate in isotope exchange, thus The identification of uranium oxycarbide phases was providing a means for trapping tritium. Chemical sought without success by x-ray and petrographic analyses of these compounds in the pure state or as analyses after three-month equilibration periods. mixtures arc difficult to interpret, since the original Another type of experiment involved spectro- composition is altered upon dilution by hydrolysis. The photometric studies in which UFj-UF4 solutions were solubility diagram of the system HB02 H,OBF4-H20. exposed to dilute CO-argon mixtures in an attempt to Fig. 1.3, proved to be very useful in the interpretation produce uranium oxycarbides. Both of these ap of analyses, since it is possible to derive the original proaches showed that no uranium-carbon-oxygen molecular composition from the elemental analysis. The phases could be formed via the above mechanisms. diagram also provided information about the relative Although no satisfactory explanation exists for the stability of these compounds. 6 MN-.-DfcC n-WO H,OWF4 «tX .H) HSO,»t% H,0«t% H,BO, F» 1.3. SohHHy oT IS* qrMtM M02-H,(NF4-H20 at 2S*C. Determination of the oxide and hydroxide species A series of experiments was initiated to search for present in the melt at tow concentrations is a much alternate stable compounds in the system NaF-NaBF« - more difficult task, since the bulk of the fluoroborate BjO,. of which both Na2B2F*0 and Na,B,F,0, are will interfere. The compound NaBFjOH can be deter components. A selected number of compositions of the mined1 by making use of the OH' absorption in the above-mentioned system were examined: infrared region, but it has been found that the bands for oxide specie* are not specific and appear as broad signals in the region from 700 to 1400 cm ~'. where NaF NaBF4 »,o, there is considerable overlap of the sodium ftuoroborate bands. The use of x-ray powder diffractio n analysis is of I 2 1 2 1 1 limited value, since it cannot distinguish less than about J 1 2 S mole % of foreign species in fluoroborate. NMR is 4 2 2 also of limited use unless the species are in solution. 5 0 2 Thus the development of separation techniques or the finding of more sensitive spectroscopic means of de The procedure followed consisted in melting the mix tection is required. ture in a platinum container under a nitrogen stream at The compounds Na2B2F*0 and Na3B3FtOj. pos either 450 or 550°C. There were no significant weight sible oxygen-containing species in the melt, were lasses except for mixture S. which showed a weight loss examined by DTA and TCA. Both are thermally corresponding to the volatilization of one mole of BFj. unstable and do not show a sharp melting point: In addition to these mixtures. Na,B]FtOj. instead, they form glasses, and a crystalline phase Na2B2F«0, and a mixture composed of NaBF4 and segregates that is composed of NaF and NaBF4 in the NaBOi (2:1 ratio) were also examined. It was found case of Na3B,F»0 and of NaF in the case of that all these mixtures would form glasses: however, a NajBjFfO). This finding would tend to eliminate crystalline phase could be separated from all except the these compounds as possible oxygen-containing species 1:1:! mixture. Chemical analysis indicated, and later in the melt: however, this is not a definite conclusion, x-ray diffraction analysis confirmed, that the identity since NaBFjOH is also unstable as a pure compound and approximate quantity of the crystalline phase but does have limited stability in the melt. corresponded to the component (or components) in 7 excess of the ratio I: I: I. Chemical analysis also showed determined by using moitta NaBF4 as the reaction thai boric oxide or the metaborate was converted into a medium. Theequmbriam is compound containing B F bonds. , The following conclusions can be derived from these 4Na,CrJFM(c)*%N»IF4(d,«* I) experiments: (I) simple boron-oxygen-containing species, such as BJOJ or BO; ~. cannot be the oxygen- *Na,CrF»(c) + %BF,(g). (II containing species in mdten fluoroborate: any boron- oxygen species up to a certain concentration level will EquiibriuiA pressures of BF,, measured in the range contain fluorine as well: (2) fluoroboraie melts can 408 to S92°C over differing proportiom of Na,Cr,F,« contain relatively large amounts of oxide species with and NajCrF* in molten NaBF4. can he represented by out forming a separate solid phase: and (3) there are the equation indications that a compound containing NaF. NaBF4. and B20, in a molar ratio of 1:1:1 is especially stable. InrV , (atm)= I 910 - 9293/7T*K). (2) This would correspond to a compound with the By combining these data win rhernrachemical data for empirical formula Na2B)F50j. Further spectroscopic 3 4 4 evidence for this will be sought. NaF(c). - BFj(g). and NaBF4(#V* *« V**** stability (-6.3 kcal/mole) of CrF, ta Na,CrF* caa be demonstrated. In other words, for rhe two reactions 1. H. W. ROKMU ct aU The Derriopmrnt Sums of Molten-Stir Breeder Reactors. ORNL-4SI2 (Aagast 1972). pp. 3NaF(c> + CrF,(cl<»Na,CrF«(c). (3) 135 4*. 2. A. S. Meyer et aU AntL Chrm. Dm Anmu. hag. Hep. %NaF(c) • CrF,(c) - %Na,Cr,F, (c). (4) Sept. 30. 1972. ORNL-4S3S. p. 21. 4 AC*(3) - AG*(4> is 6.3 koa/mole at «W°K. This 1.1.6 ThermodyMnics of Corrosion Product greater stability explains why Cr(HI) precipitates from Fhrarides in Molten-Salt Reactor Coolants molten NaBF4-NaF as NajCrF* rather than at S. Cantor B F. Hitch Ni,Cr,F,«. The thermodynamics of reactions (3) and (4) with The primary purpose of this investigation is to AHIII) instead of Crflll) show . difference of -7.8 provide the thermochernical data necessary to predict, 7 kcal/mole at 800°K With AKIII) the free-energy define, and explain corrosion equilibria in molten change of a reaction analogous to reaction (3) is -22.5 fluoride coolants proposed for fission (molten-salt kcaVmole. Assuming mat -22.5 kcal/mok • abo me breeder! and fusion reactors. Several corrosion products ££?•• for reaction (3) and combiaiag das vabje with lake the form of double salts of NaF and die fluorides formation free energies of CrF,(c) (-225 ±5 of Cr(lll). N*H>. and Fefll). A secondary objective of 1 kcal/mole. adjusted from the remits of Tamka et ai. ) thii study is to correlate the thermodynamic informa 4 and of Naftc). we estimate that AC(««. for tion so as i.> be able to provide reliable estimates of Na,CrF*fc) equals 600 kcai/mote Ahbough this similar information for analogous compounds. value has an uncertainty of roughly ±8 kcai/mok. it is StaMity of Na,CrF* ami Na,Cr,F,«. When oxidants still useful for correlating other chemical mforrnation are introduced into eutectk NaBF4-NaF (the coolant on the formation of borides from NalF4 in structural specified in the conceptual t'esign' of the Molten-Sail afloys used in molten-salt reactors. Breeder Realtor), a sparsei, sohiMe green sail. fmnm*m**mHnbynK*m*md>mtUK - NajCrF*. is the characteristic corrosion product 4 NwFand rfcnniBiia jnnhfcrih— atafi. Ussng the free formed from alloys which contain chromium. Other energy of to natron of Na,Cr*(c) estimated above. M complex CiflHl sails. Na,Cf,F, and NaCrF*. might 4 can be shown that for the reaction also have been expected, since these compounds have been reported in the NaFCrFj phase diagram.2 (I *jr)Cr(c)* NaBF4(d)« 2NaF From the reaction of solid CrF, and molten NaBF4. we attempted to obtain the free energy of formation of -Na,CrF*(c)*Cr,B(c>. (5) NajCrF*: however. CrF, reacted completely, and the reaction yielded Na,Cr,FM as well as NajCrF*. The AGtf * 10 ken). In reaction (5) me exact vahie ofx relative stabilities of Na,CrF» and N>,CJFM were is unknown: however, the free energy of formation of t dV more stable rmiiaaaai borides (CrjB. Cr,i,) it aided and iron m contact wan metis cuataaHag NaF tu—and to be 22 kcal per gram-atom of bona.* in (sacfc as eatevac NaBF«-NaF» wil corrode u> lurm Mcket-fease aloys coataauag chroaaam |e.g.. Hastttu? NilIII and Fdll) watch reaady precrprtaie fr»mi die N(7* Cr> and Income! 600(15* Cr||. reaction (SI may me* as NaNiF* and NaFcf, The rate eaergKs «»f proceed even more uaa% to uV right because ate foratatua of *ese compound* between 700 and 875°K reaction were determined by Bamberger. Hitch, aad Baes." Their data were used to calculate oar taenaodyaamks C^MO+vWc.aBoy) * JrCifcatoy)* Ni,B (61 of thefoaVnring traction s at 298.15°K: is probably exothermic- Assnanng dm JC* of forma- NaPO+ MuFjIcl^NaNiFskl: 'Jou of NyB equals Aff* of formation.'* men AC?.. Aflf%, » 0.7 ± 1.4 kcnVmole. for reaction (6) is about -3 kcal per gram-atom of boron. AS%, = 4.9 caVlmok-'Kl: An investigation to determine boride formation m nickel base strucfral aloys is in progress, m dm Na*U) • FeF,(c> * NaFeF,(c>. experiment specimens of Hactettoy N and Incond 600 A«?„ = 0.3 • 14 kcal/mole. ant eipnTniiiai d witf». molten NaBF4-NaF (92-8 mole %) at 640°C- Speuwu-H are penodicaMy removed, washed AS?,, = 4.9 cal/(mole-°K). free of salt, and sufcuiit*ed for analysis to the Analytical Chemistry Division. The surface of each specimen is Thr endialpy tor these two reactions is very close to routinely analyzed by spark-source mass spectrometry zero; die uncertainty noted is that given for the free (SSMS) for boron and for sodium, the latter to verify energy of formation-" The only estimate used in mat NaSF«-NaF has been rufy removed. With alloys arriving at these values of the enthalpy and entropy was equarorated for periods up to 129 days, some boride that yCp for these two reactions is zero in rhe seems to form. Typical SSMS analysis shows iSOOppm temperature range 298 to 800°K- boron after 72 days of eqiatibratkxi for Inconet 600 For die analogous Mgf II) reaction. and between 30 and 2000 ppm for Hastdloy N; control rpecimeaf. mat is. unequiibrated coupons cut from the KaF(c)* MgFj(c) * NaMgF,(c). same metal sheet(s), contain about 10 pom boron by SSMS analysis. Alr%s = 0.1 ± 0.S kcal/mole. the data having been Ion mkroprobe analyses have also been performed on determined by aqueous solution calorimetry.11 The two specimens. By das method, boron wasfound t o be striking regularity in the enthalpies of these three distributed in small discrete particles on the surface of a reactions perhaps extends to other divalent metals of coupon of Incond 600 that had been equiibrated for roughly the same ionic radius. In the absence of 72 days and for which SSMS showed ISOOppm boron: experimental data on the enthalpy of formation of m analyzing this specimen for major constituents to a NaMeFj(c), a reasonable value may be obtained by depth of about 4000 atomic layers (~l urn), it was adding together the enthalpies of formation of NaFtc) found that chromium was almost completely depleted and MeFj(c) and assuming that £//%* = 0 for the from die first 200 layers away from die surface and was reaction partially depleted from up to 4000 atomic layers. A Hastetloy N specimen which had been found by SSMS NaRc)+ MeFj(c) - NaMeF,(c). to contain 80 ppm boron showed a low (reported as especially for Me = Zn, Co. and Mn. ft. r. CM. C. «!>•••• MHLA.M. 7)WB. FM# toe. at 550°C aar consistent with zero-order uanaaer- The •4.517 nut. 7. t *. tk.iaj.aV** Dam. I. 2211 ,I97M. tratioa. hydrogen flow me. and hydrogen paraal t. H. T*a*a. A. Tweife aat J- Miifriwi. A**M» |iiu»j«. The data yield a rate coastaat of 0 00135 Kmaakt r«toraa» 3S.11*1 fhiwa'j.aaa. hvftrma of toepm.*mj awaau. UCRL- la al nV tests the hydrogen ataaarjna was low SIM.HI97I). Kl*>. ntost of aae gas saapr> baaUed dkroagh riae la. aS.Ciii>in A.S. l>naii»in.ai>.KiaamiMii.aal melt. DHaocntioa of dw hydiugta awtecaae to yield N. A. Clafco*. mm / An Ohm. 4k431 In previous experimental studies of the reaction of platinum catalyst and die IFF* to yield UF4. or that hydrogen with UF, dissolved in fuel carrier salt. catalytic dtsproporoonatioa of UF5 was ocuirriag to yield some UF«, was precluded ia Che Jtcoad test ia LiF-BeF2ThF4 (72 l<-12 mole %). die hydrogen utdi- zation and die rate of reaction were found to be low-' which the U** conceatratioa was iactejstd to 4.14 wt A detailed investigatior> of die reaction % and exposed to die catalyst for 2!% ia uW absence of hydrogen. No U** reduction occurred. Fotowiag in troduction of hydrogen, the reduction again was aearty UF,(d> • % rMg) •* UF4(d) • HF(gi (I) complete in 30 mm. was carried out during this report period. In a typical Fnlowiag these tests, during cleanup of dae reactor, a experiment, a 200-g charge of fuel carrier salt phis discoloration and granular appearance were observed on about 1 to 4 wt % UF4 was placed in a gold reactor and die bottom of die gold finer and abo at dar sait-gas sparged with equimoUr K2-HF at 600°C for about 24 interface. Presumably, some of dae ulatinam had hr to remove any oxide contaminants present. Then die alloyed wrm or sintered to dae huer. A test was Aen stoichiometric amount of gaseous UF* was added at made to see whether das material had any catalytic 600°C to convert all the uranium to UF,. The activity. The results again showed complete reduction temperature was then adjusted to die desired reaction in less than 30 min and near stokbtometric hydrogen temperature, and the salt was sparged with hydrogen to utilization. This fortuitous result suggests that it war be reduce the UF$ to UF«. Samples of die salt were easy to take advantage of dae catalytic effect in withdrawn at intervals and subsequently analyzed for enajneering-scale apparatus by addiag ubtanaii to gold U5* and IT** content. Normally, the reducing gas flow components of the fuel leconstitation equipment. TV rate was 40 cc/min for the first 4 hr and. then. 120 catalyst increased the rate of redaction of UF, by cc/min for an additional 4 hr. The .educing gas was about rwo ordenof magmtudeand wW danperaat die either pure hydrogen or an argon-hydrogen mixture. design of srraller and simpler tngmeeiing apparatus. In the first series of tests, at S50°C. die rate of reduction followed zeroorder kinetics, hi which case I. N- R. Beanm aai L. is. Ferra* J. aaaa BhtcL Cnna> 3a* the rate of the reaction is independent of die concentra I2»5 (1974V tion of the reacting substance; dius -dn/dl = K. (2) where n is the number of moles of substance, I is the H. R. Bronstem F. A- Posey time in hours, and X is the rate constant. From the integrated form of Eq. (2). it follows that a plot of the Studies were continued on the development of porous number of moles of UF, reduced vs time should be and packed-bed electrode systems as contawsas. on linear and have a slope of*. Data from die experiments line monitors of rhe concentration of eJeclroactrve M MDVPI ad fiR- of |Muai and packed-bed electrodes faretertio- tbr ncovny of tace ananases of i firaa oAn •ypes of tflhoiii; '~* Hot pnority B gam lo of a device for bar stwdits oa MSM fad: od aaahty wnl be ieaa*i lununi of the parted bed electrode w» only aont 2.5 en9. an? at»-to* wring aae of a pfaay carbon rod for dertned et wna dse bed. A bag iijjilrw sled rod (not a ?%. 1.4) coKscted the top of the rod and led dwnagh the lop of the lest which conid be evacuated or [ as woaiind. The melt flowed op ritrongb ** ccntrci tabe (F%> I4K fcuii the packed bed. aad uat a of vertical stofs into a overflow cfcaaber. la Pb> 1-4. awaaaiaifa °f' Reafts of Haeai jweep voJtaaattric carried oat a the prcseace of saal taawn of iron I aaxanry attorn faactioaed dM aad pwviuMify. ad to coast radian ad testing of any an weaoaatraad an? abeaat aaaarffy or ana prior to aV lesmnptwn of expert- araod of adyws. Ilonmt. the tots OR die proto its, la falae work. pnaannary type ctfl dwwed the aeed for awancatioa to die chnckoar ad cdaratkai wtt be carried oat again in to factilalc addition of kaowa UCI-kXI atactic mat the behavior of a wanber of i at varans abstvees to die adi aad to alow eJectroective abstaces bs> dandy been cstabhaed in optratiua ander vacana a inert sjarapnat oar hag avis inaaa. Experbantd aeaswwnents win then be periods of oar. Sabaawat effort wa denoted to atteapnrd on ar baaaa system ad oa other efectro- of die experiaeatd aaetbty. to anjaatan of active abstain Fotowanj acccssfat testing of the 11 pmcai cef assembly, we expect 10 design and con struct a similar, all-metal apparatus for use widi mtilten fluoride salts. 1. r. V r*»*y ami A- A- tJko. *cJqrr mmJ Amm'rm of Timer Cumlmmwmmn hug Kern. Oenomer 197J September »V. ORSL-MSt-r ATC-I I. pp. 144 SI. 2. IL I- Merer Ml.i rWy. Om Or 4am /•«*. Rep. Ifatr .V #•*#. ORNL-197*. pp. 105 t. J. H. R. Rmaona i-J K A. rNnej. Okrai. Oir y4wai rV*. AVji ¥*r J». /«74. OUNL-W4. pp. 109 II. Fig. 1.5. DKWoMpaaioww^eawwM ctMwaorwiMMiannni in •often UF-tcF2 <47-*J •"** ft) « 3MTC wife caveat 1.2 tWANStOKT AND THERMODYNAMICS IN mammy of 1.26 A/**1 at Utywmm matt. MOLTEN SALTS C L Valet1 J. Brainstem LiF concentrations, and the expected higher diffusion A genuine understanding of transport processes in coefficients are observed. The higher diffusion coeffi viscous high-temperature elevtroiytic systems is essen cients necessitate the use of faster scans, that is. higher tial in the development of nuclear reactors, high- currents, to avoid convection, as well as oscillographic tempcrature batteries, molten-salt catalysts, glasses, and recording of the chronopotentiograms. This, together membranes. Transpurt properties in such systems pro with the greater change of the diffusion coefficients vide needed tests of computer simulation studies such during the course of a chronopotentiogram, emphasizes as moieu. lar dynamics computations.3 the need for digital data collection to simplify analysis As part of a program aimed at characterizing high- of the chronopotentiograms. The results demonstrate temperature ionic conductors, we have previously also the desirability of analyzing the early portion of demonstrated that the interdiffusion coefficient and the chronopolentkjgram rather than attempting to relative electrical conductance in binary molten salt locate a transition time. However, at these concentra mixtures may be evaluated by analysis of chrono- tions, die transference number of Li* relative to f " is poientiograms (voltage response, as a function of time, known.4 simplifying the solution of the flux equations to the application of a constant electrolytic orrent). for the concentration-dependent diffusion coefficients. The method was applied to lithium fluoride beryllium A typical chronopotentiogram is shown in Fig. 1.5. fluoride mixtures containing S to 22 mole ** lithium Preliminary analysis of die results indicates values of 3 fluoride. and to some aluminum chloride-rich mix the mutual diffusion coefficient of about 10"* em'/sec tures of an alkali chloride with aluminum chloride. The with an activation energy of about 9 kcai/mole. evaluation of the transport coefficients is based on the Measurements hi the eutectk melt (53 mole % BeFj) solution of the electrochemical flux equations derived can be made over a broad temperature range and should with the aid of the thermodynamics of irreversible provide information on nudeatkm and phase separation processes. Current W 21 AQUEOUS SYSTEMS statistical. This model reduces to a form consistent with the observations I Table 2.1. Fig. 2.1) 2.1.1 TheHydFstyswwfCawini A Critical ^. - .**• • • • ** • -^* .. —*. *^^. KCVKWOI ISynvMrSB apCCSCSM intV3(aMBNy logA.,, =.4 •«(-). (3) C. F. Baes. Jr. R. E. Mesmer \ here r is the cation charge and d is the MO Our review of the literature of cation hydrolysis2 is interatomic distance. now essentially completed- For each cation we have Likewise, based on this model, a fairly uniform attempted to determine the important hydrolysis prod decrease in the logarithms of the successive stepwise ucts and their formation quotients (Qxr). defined in constants is expected. Except for the heavier alkali various aqueous media by metal cations, all cations seem to form one or more mononuclear hydrolysis products in the sequence 1 2 xMz*+rH 0"M «OH) Ur r J Qxy = (M,(OHL > >*| |H*| /|M-**| . this increment. Enthalpies for mononuclear hydrolysis reactions are not well known: however, they appear to have a linear and to estimate the formation constants (£xr) at zero ionic strength. Included are similar data on the solubil relationship with z/d. ity of oxides and hydroxides. A principal objective has SulaMaty of oxides and hydroxides. There is a been to discern the characteristics of hydrolysis reac striking correlation (Fig. 2.2) between the solubility of tions in solution that best explain the wide variety of the stable oxide, oxyhydroxide. or hydroxide of a behavior that is displayed. Some of the more important cation and the stability of the first hydrolysis product conclusions are summarized below. MOH"~' ** such that the equilibrium constants for the Mononuclear hydrolysis species. A model for the free reaction energy of formation of the species MOu(OH)T- {z u iCMi\, -*"*** offers some explanations of ob M(OH)z(c) • (z - I jit* * * .-MOrf ' * . (4) served trends. According to the model, [MOH*- |2 , »I0 5* AGVV.HT>_V _ 23RT ' '' (or the corresponding reactions for phases containing *Vo%Q-Vn\uWwir\ +{2u + v-\yotS5.S . (2) oxide) often are dose to 10* *. Half the observed values fall within 1.6 log units and 90% fall within 3 lot where the first term on tbs right is the sum of units of this value. This is a fairly narrow range when nonetectrostttk contributions from M, O, OH, and one considers the wide variation of A',, andA,|C. : OHj. the second term is a summation of the pahwise The value of the product K,, A',|0 corresponds to electrostatic interactions and includes a parameter for the concentrations of M-'* and MOH" ' >• when these the fraction of an electron to be assigned to the valence two species are present in equal amounts at equilibrium shefl of M (the degree of covaJency of bonds), the third with the solid phase. If the ratio (MOH" ' >*\I\W*\ term is a partition function that represents contribu is to be increased while rnsintatt'ng equilibrium with tions from structural homers, and the last two terms arc the solid phase, the concentration \W*\ must be 12 13 T*fc2-I. Tfct —1 «f •» MOW11''H nV'.C^.Sr*.*,* -22i>tO-5 IMt I fc*\ Ha*. ff^.Co*. **.<:•*. to*. «** Sc^.Ti*. V^.Cr*. Ft*, •fc^.d'*. to* Ce*. Til*. fc*\ if. Up*. »V Af'.TI* -iS*4 I lw» ii*m» 12.2 *Tkc awaM w Eq. <3>. 2.0 Ffc.2.1. Tit « kg ft, ,«•*!«••«« Hydroxide bridges Mm to he negative vahits of &zxy*/y. where isHy' is the smn of HUmiiaWr tor the formation of Marty all the pary- the sanies of the charges on the prodnct species in 14 73-I20S2 After conversion to the mote fraction scale of concen T 1 1 T trations -by addition of ((JC l)/»| leg S5.5}. this • onots • OXT-HnrORODOCS quantity generally has a narrow range of values for the o mOROMKS various porynuciear species of a given cation. Excluding the relatively unstable MjOH** species of Co2* and Ni~*. the deviation is generally less than 0.3 log unit. in general. 3Hxv/y is positive and in the range 4 11 kcal- For the species of a given cation, the values generally fall in a much narrower range, usually less than ±0.4 kcal- Since (l/r) log Kxv for such species is also fairly constant when corrected to the mole fraction scale, it follows that &Sxr/y is similarly a constant characteristic of the potynuctear species of a given cation. Moreover, from the values that are available it appears there is the following linear correlation between &Sxyly and z/d for the cation when the entropy change is expressed on the mole fraction scale: 1. Tim contribution n based on a renew begun as a spore-Tine protect of the authors. More recently, support has come m pan front the National Science foundation's RANN- EATC Program, the CoBcfc of Wiliam and Mary, the United States Atomic Energy Commission, and Energy Research 2nd MCWJM (4). The tee uwnpowfc to K, ,**„. « I0~* •- Development Admnustratioa. This summary is based on the coadndmg part of a four-part report (ORNL-NSF-EATC-3. Part I. January 1974: Part II. in press: Part III. December I974>. reaction (I) less the sum of the squares of the charges 2. C. F. Baes. Jr.. and R. E. Mesmer. Chrm. Diw Annu ftog Rrp May 20.1974. ORNL-4976. pp. 77-10. on the reactant species. This seerm to be a real restriction that greatly reduces the number of poly meric species that can form. Those that do form often 2 2.1.2 Transport Behavior of Concentrated hare AzJtj /y values either of zero or as dose to zero as is possible given the number and charge of the cations. Aqueous Electrolyte Sohttions The most favored configurations for pclynudear species A. L Bacarella J. Braunstein appear to be symmetrical ones. Most such structures that can be assembled from 2. 3,4, and 6 cations held The development of a number of energy resources, together by OH* ions with coordination numbers of 2 including the use of geothermal brines and the large-' or 3 are mduded in Table 2.2. These ibrmulas account scale production of hydrogen, requires an understand for the large majority of poh/nudear hydrolysis prod ing of the corrosion, thermodynamic, and transport ucts that have been reliably identified, and the indi behavior of concentrated aqueous electrolytes. We have 1 cated structures have been confirmed in a number of shown that large changes in the transport properties 2 i by diffraction studies of solutions and/or crystals, and thermodynamic properties are found as the water porynuckar species generally appear soon after content is reduced and the electrolyte concentration hydrolysis begins, perhaps is should not be surprising increases. These changes occur hi the concentration that there be correlation between their formation range important to geothetmal brines, water elec- trolyzers for hydrogen production, and some reaction constant KSJ and the first hydrolysis constant AT,,. 3 The most significant quantity appears to be the ratio steps in proposed thermochemical hydrogen cycles. In 4 i,y a previous study of the mechanism of corrosion of Kxy IKl,, which is the equilibrium constant for the copper-nickel alloys in more dilute brine environments, it was shown that the rate of corrosion was limited by the diffusion of oxygen to the alloy surface. Studies of MOH"-'>• *- M,(0H)/"->>* • (5) (' -;K very concentrated aqueous electrolytes are needed to 15 Svtoo Cum >M .c*OH" ItjOH' .Co*.!**. I Za>.C«*\Hf'\iV M,tOH>,(,X_2>* Cu*. $•*. UO,*. NfOj* 1*0,*. VO*. > M,(OH>) •e^.Hf** Sc'W'.U* IMOHV iti>.Co>.Mi>.caa M«nH>." Zr*.Tli« H,*q«*fcwKfcci(fctOH •*»*. oar entered am md muiti each <%e. M*<0H>.4 •e*.** M* octahedron with c%ht OfT I* POMS cuMcicd on faces. H.IOH),,*' M* ocfakeinm with 12 OH ' 12 RMS OmtCfCaJ 3 'Number of water molecules liberated by reaction (5> if the coordmafun acinbcf ream** constant. bridge the gap between theories of molten salts and of in excellent agreement with those reported pre aqueous electrolytes. viously.5'* The diffusion coefficient is seen to change Here we report the results of chronopotenlioinetric by more than three orders of magnitude over the rwge measurements of the diffusivity of CdJ* in hydrous of concentration and temperature studkd (Fig. 2 J). melts of Ca(NO)), at 35. 40. SO. 65. and 79°C and The viscosity data of Ambrus. Moyn'tan. and Macedo7 over a concentration range from iboot I to 17.V for demonstrate parallel behavior, as does the electrical each temperature, that is. at water contents between conductivity.*'' An analysis of these results shows that about 20 and 3 moles of wafer per mole of salt. The for R < 6 (where R is the mole ratio in moles of water diffusion coefficients D were determined from the Sand per mole of salt), the activation energy for diffusion is equation. D x l2T/nF2AiC2. for transition times r strongly temperature dependent and increases with ranging from about I to 6 sec. A summary of these decreasing temperature. Similar variations with concen results is presented in Fig. 2.3. The previously reported tration are found for the enthalpy of vaporization of results' at 50°C were confirmed in this more extended water and the free energy of association of CdBr* as a study. Where comparisons are available, our results are function of water con'ent.2 16 ONM.-DIK 74 tj«« by lowered temperature (i.e.. by reducing kinetic R (noies HjO/mole salt ) energy). At higher temperatures, if S0 is physically 20 K5 5 4 3 significant, it should be related to properties of a fluid molten salt. 1. A. U BaorcOa. D. Brown, and J. Braunslein. Chan. Dhr. Amu. Prog. Rep. May 20. 1974. ORNL-4976. p. 132. 2. H. Braunstein. J. Brainstem, and P. T. HanfcMV, / Phyi. Chem. 77. 190711973). 3. C. E. Bamberg-, and D. M. Richardson. Chrm. Techno!. Hit. Annu. Prog. Rep. Mar 31. 1974. ORNL-4966. p. 73. 4. A. L Bicarclla and J. C. Cries*./. Ekxmxhem. Stx. 120, 459(1973). 5. J. Brainstem. L. Orr. A. R. Alvarez-t-upes. and H. Brainstem./, lleilromel. Chen 15, 337 11968). 6. C. T. Moynihan and C. A. Antrtl. /. Phyt. Chem. 74. 736 (1970). 7. J. H. Ambrus. C. T. Moynihan. and P. B. Macedo. /. Elevlnxhem. Soe. 119. 192 Here. N0 is known as the zero mobility concentration. and a cell model at higher concentrations. Thus, an At lower temperatures the value of/V0 increases slowly electrolytic solution of any particular concent.ation is with increasing temperatures, similar to the observa treated as a mixture of these two models or structures, tions made by Angell for the conductivity and viscosity the contribution of each being weighted by a partition of these melts.*'' Our results at 79°C suggest a sharper function, nuch as the sum of contributions from two increase of N0. The measurements are being extended significant structures has been used to describe the to higher temperatures to determine whether this properties of liquids. behavior may characterize departure from the low- In combining the two-structure parameters for each temperature glass-forming regions. component electrolyte into a two-structure model for Much shorter transition times (r from. say. 0.1 to 0.6 mixtures, we have used the form of a simple equation sec rather than 1 to 6 sec) will be employed in order to previously developed3 for predicting the activity coef to minimize error from convective transport, which ficient of a component of an electrolyte mixture from becomes increasingly important at the higher tempera the activity coefficients of the individual components in tures. The importance of characterizing the temperature pure solution. The resulting two-structure expression is dependence of JV0 is that at low temperatures it is analogous to a glass transition temperature. That is, it represents the isothermal transformation of the solution into a glass by water removal (i.e . by increased ,< ,) /J , cohesiveness via increased charge density) rather than Citl\c " '/ + »l//' +C ///. (1) 17 where log >•, refers to the logarithm of the activity measured to 300°C) and to the prediction of the coefficient of the ith component in a mixture where the activity coefficient of each component in HCtNaCI- remaining electrolytes are indexed j"; S, is the Debye- MgCh mixtures to 55°. At nearly aD values of total Huckel limiting slope appropriate for component /. and ionic strength, composition, and temperature, predicted the remaining coefTicients (a0\f, B^, and Ci; are values cf the activity and osmotic coefficients were weighted averages computed from the corresponding within 1 to 2% of fitted observed values. terms for each single electrolyte. At the present time only the osmotic coefficients of When Eq. (I) is used to predict the activity coef HO, NaCI, MgClj, and MgS04 have been measured fidents of each component in a number of electrolyte accurately at elevated temperatures. If predictions are mixtures, it is found that the values are as dose to to be made of osmotic or activity coefficients for fitted-observed values as those predicted using more geothermal solutions, then the osrnotk coefficients of a elaborate treatments. Two important features of the few additional electrolytes Mill need to be measured at two-structure model should be noted: (I) only one elevated temperatures- The most important of these are adjustable parameter C is needed per component KCI and CaClz. In addition, the osmotic coefficients of electrolyte in a mixture, and (2) the values of the a and a few synthetic geothcrrnal solutions should be meas B parameters [Eq. (1)| are directly related to valence ured to provide a check on the accuracy of vahies type and hence appear to have direct physical origin, in predicted using our simple equations. contrast to the empirical constants associated with any model that retains the Debye-Huckel term at all 1. Summarized from The fftdklkm of Osmotic end Activity concentrations. Coefficients for electrolyte Nizam at Elemttd Tempentvm. ORNL-4999 (September 1974). 2- M. H. Uetzke and R- W. Stou(ploa./ Inort- Nucl. Chem. 1. Summarized from a paper accepted for p-jMkatkm m J. 3*. 1315(1974). Inarm. Mud. Chem. 3. M. H. Lirtzkc and R- W. Stouchton,/ Solution Chem. I, 2. M. H. Lieizkc. R. W. Stooghlon. and R. M. I uo». hoc. 299 H972). Sat. ActJ. Set. U.S.A. 59.39 < 19M|. 3. M. H. Derzkc and ft. W. Stoufhton./ Solution Chem. I. 299 < 1972). 2.1.5 lomzaaon Constant of Nitric Acid at rttgh Temperatum from Solubilities of Calcium Sulfate: 2.1.4 Prediction of Osmotic and Activity Activity Coefficients and IVniiodynamic Functions' Coefficients for Electrolyte Mixtures 2 at Elevated Temperatures' W. L. Marshall Ruth Susher M. H. Lietzke R. W. Stoughton Quantitative solubilities and extents of ionization in high-temperature water solutions of common salts and In fields such as geochemistry, desalination, and acids are of fundamental and applied interest to several utilization of geothermal energy, one encounters need fields: examples include geothermal energy, water desal for information on the thermodynamic properties of ination, natural oil-water solution systems in oil re aqueous electrolyte mixtures at elevated temperatures. covery, pressurized water reactor chemistry, crystal Direct measurements, particularly above 100°C. are growing, and basic chemistry. A sal: of particular difficult experimentally and very time-consuming. interest to desalination processes (where scale may Hence, it seems desirable to develop methods for form) and to geochemistry (because of the salt's predicting properties such as osmotic and activity abundance in nature) is calcium sulfate, which can also coefficients for electrolyte mixtures at elevated temper exist as either of the hydrates CaSO«-VJHJO and atures. Such values need not be of the highest possible CaSO* -2HjO. Moreover, the solubility of this salt (and accuracy: values accurate to I or 2% are entirely its hydrates) is sufficiently low that its solubility adequate for practical applications. relations in aqueous ionic solutions may be described In the present study we have demonstrated that conveniently by Debye-Huckel extended theory. Adher relatively simple expressions devised for predicting ence by CaS04 to this theory at high ionic strengths has csmotic2 and activity3 coefficient values for electrolyte been confirmed not only in the range 0 to I00°C (for mixtures at 25°C function equally well at elevated CaSO4'2H}0) (ref. 3) but also at temperatures ap temperatures. Because of the paucity of mixture data at proaching 374°C, the critical temperature for water.4-5 elevated temperatures we have restricted ourselves for This agreement is observed when a 1-1 »lt (e.g., NaCI. demonstration purposes to the prediction of the os NaNOj. or UNO;) is used to change the ionic strength motic coefficient of synthetic seawater (which has been of the solution.3"6 18 In this study, solubilities of anhydrous calcium sulfate and thermodynamic functions were calculated. Activity (anhydrite) in dilute and concentrated HNOj-H20 coefficients for both CaS04 and HNOj equilibria are solutions were obtained at temperatures from 100 to obtainable from the results. These activity coefficients C 3S0 C. and ionization quotients (ft,) for aqueous nitric may be used to .calculate solubilities ofCaS04 in other acid were calculated through a set of equations believed high-temperature mixed-electrolyte systems. The domi to represent die significant equilibria. In the calcula nant species present in the system studied were calcu tions, we used previously published ionization constants lated and are shown in Fig. 2.4 for both low and high 7 (Kz). of HS04~ son, solubility product constants(Ksp) temperatures. of CaS04 (refs. 3-6) to 350°C. and the variations of quotients (Crp) or products of activity coefficients with 1. Summary of paper to appear in J- Inorg .VIM7. iDhrm. ionic strength. (1975). By Debye-Hiickel extrapolations of Qm, ionization 2. Computer Science* Division of Union Carbide Corpora constants (A'„) of nitric acid were obtained. These tion. 3. W. L. Marshall and R. Slasher. J. ftrt Cfcrm. 70. 40IS constants agreed with some earlier values from Raman 11966). and reference* therein. spectra (Krawetz* at 0. 25. and 50Y) and electrical 4. C. C. Tempkton and J. C. Rodger*../. Ckem. tug. Data II. conductance (Noyes et al.* at 218 and 306*0. Values 536(1967). of Kn (in molar units) decreased from 45 a' 0°€ ; o 5. W. L. Marshall and R. Slasher. J. CVnt Thermodrn 5. about 0.0005 at 350*C. values 20 to 30 ti'.KS lower 189(1973). 6. W. L Marshall. R. Shiner, and K V. Jones.J. Cktm. ln than the ionization constants of I t salts at 350°C. The t £teM9. 187(1V64). 10 equation by Young. Maranville. and Smith for tnr 7. W. L. Marshall and K. V. Jones./ fftvi. CArm. 70. 4028 variation of KH with temperature was substantiated. (1966). o 0.2 0.4 3.6 0.8 0.2 0.4 0.6 08 MNOj . molality HNOj. molaliry so/: ** •~~1 1 L i i A —1 \ 0.2 04 0.6 0.8 ,20 200 300 HNOj . molality TEMPERATURE . *C Fig. 2.4. Dominant species in HNO,4i20 solutions. (Al 0 lo I m HNOj saturated by CaS04-2H20 al 25°C:(«» 0 to I m HNO, saturated by CaS04 at 200°C: (O 0 to I m HNOj saturated by CaS04 at 300*C: f/» I m HNOj from 0 to 400*C. saturated by CaS04-2H20at 25*C and by CaS()4 above ~40°C 19 8. A. A. Knwetz. Ihesu. linivcnity of CfckafO. II.. U-S-A. from the recent solubility studies in aqueous sulfuric |19SS». acid.' These extrapolations are shown in Fig. 2.6. 9. A. A- Noyrs, The Ettctncml ConaWririrr of Adorns Solubilities obtained at 200 to 3S0*C of magnesium Sototinms. Carnegielastitotioaof WashMgtoa.DC.pabikatiua sulfate monohydrate in aqueous sodium nitrate solu- No. 63119071. 10. T. F. YoMf. U F. Manirrtfr. ud H. M. Samh. "Raima Socctnl bnmiptiomof look EqaiBbra in Sofetioas of Suva* *•-11441 Ekcttotytei." dap. 4 in 7V Struclmr of Electrolytic Soki 1.4 noma. co. W. J. HUM. J. Witty aad Ckaaaaaa and Hall. New ' 1 ' 1 ' 1 ' I 1 [ 1 Yofk.l9S9. - Soto,. Solid - M9SQ,- HjO 200"C- 12 - 1 ) Cofculo'ctf Ftom Equilibrium Constants / : 2.1 A ExntranortalandCalcvialed o ^ I I Snioofned Tnanajh b 250" of Magnesium Satfrte * 10- l^aafs (Nifnc Acid and wUlti tfl > as / yxr W.L Marshall Ruth Slusher* fW^iORS Of %y J In earlier studies, high-temperafure sohibilities of H20 in 0 to 1 /n HN0j-H20 solutions at temperatures up to 350°C. and they were compared with experi mentally determined solubilities obtained in the study. Agreement between the experimental and independ s Ocbyc-Hiickei Slopes ently calculated values was good, as shown in Fig. 2.5, where the square root of HNOj molality arbitrarily is •K> J . L J 1 L J_ plotted to spread out the points. 01 0.2 0.3 0.4 0.5 0.6 The experimental solubilities, when treated by itera *T/(t +1.6/7) tive equations, and the resulting values of solubility F«. *•*• LofWimw of ate jotoMity ptoincu (Q^) of products extrapolated to zero ionic strength yielded Mn$0« -H30 in HNOj-HjO KHOIMM n a faacfio* of dW ionic values of Ksp essentially identical with those obtained alnnwdi it. in moMMy). 200 to JS0*C 20 fans and of magMsnun and calcium hydroxides in plotted against an extended Debye-Hackci equation, nitric add aided the interpretaiioas. extrapolation to zero ionk strength yielded a Mnhicompoaent systems of widely variafc sowbinty product constat (A' I. as shown ia F^g. 2.7 fans at both low and high temperatures are ; for NiS04-H.>0. Other sohnnwlies mterpreted in this in nature. The ability to predict phase behavior b highly manner were those for MgS04-H20. CaS04-2H:0. desirable, for example, in the assessment of very dilute CaSCV^HjO. CaS0«. Li.SO«. and Na:S04 in and concentrated geothermal solutions considered for H;S04-H20 sohuions and for MgSTVDjO. MSQ,- power production or nvnerai processing, in evaluations 0,0. and U2S04 in DJSCVDIO sohNions. With the for water desalination, and for bask imderstanding of exceptions of CaS04H»0 and CaS04-%H;0 snmatd these systems. only at 25 10 60'C and at I25°C. respectively. aB jjlunnwki of safcs were evahuHd at temperatures from 200 to 350 C Adherence 10 extended Debye-Hackel 1. s» in J. tmafg. Mmcl Cmrm theory was good and provided a method for calculating U975|. mean activity coefficients of the several separate salts m 2. CnfUi Sciences DWBJOW of V > CafMt Coipora- the acidk medm. Values of log A'v for each metal 3. R. UPBMMKM. U *- Yeans. w. L. Itahl. J sub** studied at 200 to 3S0°C are plotted aanmst IT Ohm. Tmrrmodjrm. 5. S9| < 19731.» (°K) ia Fig. ZS. from which ibermodynamic functions 4. M. H. Lirtzkc ami «L W. SinwjWIim. J. t*ri Cham. U. of sotammty were obtained. Il»3.1 IS*. I9M H9S9>:*4. 133. tl* II9M>. 5. H H. Uakc aaf R. W. Suntan. J. fkn Cmrm »]. I US 119591 "»\. 7*1 '< 91** * W L NnM au~E.V. hm. / Art. Cmrm. ML 402S 0- — II9M). 7. W. L Marwaf./ tea* V»rf Cfc-w aprnxitTjcw Sec:. 2.1.7 of ihs icpart. -2- t. M. H. liake jaw R. W. Seaacfcttm. / fmrs. Cmrm mi. 1190(1959). 225 9. w. U MantoU ana KthShunti.X **n* *wrf. Owm.. a pica (1975 y. tee Sect. 2.15 of Urn report -4- 2.1.7 Tlasmadynamk Fi at OT JCVCMi HCTaTal -~ -4- Q Salfuric and Deai Adds l' npto3SwV W. L Marshall z Metal sulfates in high-temperature aqueous solutions are unusual in showing retrograde solubilities with ~ -6- increasing temperature.2 Moreover, at temperatures above 200°C in neutral or bask solutions, several 2-2 cT-6- J 4 dissolved salts. MgS0«. NiS04. and CuS04* among others, hydrorytkalry precipitate metal hydroxides and -8<' hydroxysulfates. However, in moderately acidic high- -8-,-' temperature solutions, precipitation of hydroxides and hydroxysulfates is prevented, and the 2-2 metal sulfates Sotq. Solid; MiSQ, Hfi • (or metal sulfate hydrates) are stable saturating -8- Mj^-HpO ScJ'ns phases.*4 Oebve-Hikkri Slopes In this work, solutility products (Qtp) were calculated -10 from solubilities of several metal sulfates in aqueous 0> 02 0.3 04 05 06 07 solutions of sulfurk and deuterosulrurk acids at tem yr/(t»i6/D peratures up to 350°C together with second ionization Faj. 2.7. of quotients of the xids.**7 When isothermal values of log ir«04-H]Ovsa in"- • Qtp in solutions of widely varying molality of acid were M)H]S04-H20 209to350°C. 21 OHM.-oat <• anc 2.2 CeOVIaBaULBancV rX «C JK MO *» 250 2» SOO OmhiiaaJ moarcei are varioaay estaaeted as pro- vasaaj for the proaactjoa of MHvef. I|to200 cuecsvc atwkattwa of ajiipicaaliiel aater. hot ary rock, aad hot braves, aace dry sveaas icaoarces sachas are beiag cxptoaed M the Geysers are any rare. IV tedantopes for expfcanag aKk rcaoBvces rcaaaa aa- dntliiprd. however, aad. partkafarly for the bat briar i/r. *«r tered severe corroaaa mi scaatg aroafcaa.' Oae of » abca. whka is presort ai coacratrauoas m me nape tare of the geotopjeat fonaaboa of orifla. The sofcajil- The calcalarioas of luJataaj prodacts for several 1-2 iry of taaiiphuai sflica drew avis airh aeaeaaag tcatprratare. so ic leads to precipiUK or deposa wiih aad 2-2 axial saMale sabs in HjS0,-H2O awl DjSO^O nlMMt at teaKcratarcs of 200 to JSf/C feajtUM probable deletenoas effects on bea'-Uaasfef aad mar jdatwau to a DebyeJfacfcd exteadrd aad aaxhaaKai c*aapateat perfonaaace. *. perspective eaaaiioa ranker sapport the aaaKcatioa of rat sheor) oa the aapaitade of the probieai U sapptied by at b*> ttaratiataiu. With wt of the Drayr-Nfidtd esraawes' thai the aaka preapitr^oa postanal ia iHalkaaaaji. di—boas of activity aiefrkjcats of ram; varioas parts of a lOO-MWfe) f ofheraaJ pfaat is •ami a**** tan caa aow be mate. The vatats shoaVJ approxaaateJy oae toa per hoar. The aaaeveatly cova- pks cheaasuy of saaca precaatatwa is farther coai- W raVCfwl lO l^drotlHIMJI fEOCaatJMStfy M nfOK puaaaii by the extreaveh varied toaavwwtiuai eacoaa- SSCCaatCaraRT HI raWVaVSlaraaraVBC aBaSa^CaaaVCVaVlOrt tOIVllOaV teved ia atother*asl waters aa4 by the aaBcatioas froai espwratory ncta ancaajatsons that hyaroayaaaac coa- onn m rat ratare. We are mutfyim, aa tjuHiaa, 100-fpaitisaajaai loo p to prewiae a sw£*y for staayiag the foraorioa of ajhea I. Svi—o of nan to appear « •* **•* -*»W Chrm «l«75» over a period of years ia saaae water conoajoa stataes 1 A. annlk. //4iw»r/•% Chrm 2«7. 147«1941 >. with md wit boat poOataat aawjtavs sach as HjS. NHj. J. V. L NMM mi Rata Smmn.J. Chrm. Bug. An Ml 3S3<1*S>. aai SOj aad shoald be eojaaOy •aefat ia lias appbea- 4. W L MMimm. t.S.Cm.mi9mmmmmi.J. man, mxt. tioa. Tbjt loop has beea reaajearaVd aad pat throat* Chrm. J4.M9 pressure drop of 25 to 30 lb for its 4-in.-Jum. 24-in.4eep bed at I gpm* the available £>p acruss the pump is about 100 ps. so this arrangement should be satisfactory. The stator of the titanium canned-motor lO&gpm pump is cooled to protect the insulation of the •wuftngs: thus, the rotor and bearings operate at 50 to lOO'C. In order to prevea: sdica precipitation in this region it is necessary to flush the pump cavity with sftca-free feed solution. This is done by injection of the solution into the back of the pump with a Pubafeedet pump: extensive operation of sirdar loops with 1000- g/bter thorium oxide slurries showed that a purge rate of about I gph kept the oxide out of this region adequately. Such purge injection, of course, requires an equal removal of equilibrated silica-containing solution tVywr from the loop. This removal stream will be used to extend and augment the studies carried out in the system described below. The lO&gpm loop will be gpm) through a column Tiled with silica powder: designed to operate continuously for periods of five to initially we plan to use porous Vycor (Corning Glass ten days to provide for longer-term studies. Code 7930: 97% S02. 37 B,0,) to load the column. The bypass heat exchanger system shown in Fig. 2.9 Exploratory studies with some of this material f -325 is intended to provide for realistic flow conditions for mesh) in a l-cm-diam column at temperatures to 250°C the study of the effects of impingement, turbulence, gate reasonable agreement with literature data for and wall shear stress. Detailed design of this equipment amorphous silica solubility in water, as shown in Fig. will depend considerably on results obtained with the 2.10. Some of the data at about 240° C were obtained once-through and removal systems. Present ideas visual with only about a third of the silica left in the column, ize a segmented cool-down and reheat bypass system indicating saturation was achieved with a contact time with a flow of about I gpm. The segments of the of about 12 sec. The pressure drop through the column cool-down system will be individually cooled and using the -325 mesh powder was 90 to 100 psi at instrumented to follow heat-transfer changes indicative 245°C. We have ordered coarser material (-140 +200 of scaling. The segmented design will also permit mesh) for loading the loop column and calculate a borescope examination of deposits formed. 23 n-MM* • HEATMK EuBUSvT NaS ;EL£we»TMa2 HCATMC Euwcprr mii F»X1I The l-cm-dum cohimn system was put together using solutions. TV research is in support of the govern available stainless steel componenu and was therefore mental, industrial, and academic efforts to not compatible with the use of brine solutions because geothermal energy from the various sources of stress-corrosion cracking susceptibility. However, tered in the western U.S. Specifically, we an conduct results obtained with water and nitrate solutions indi ing potentiometric. isopiestic. conductance, calorimet- cated that such a system would provide data both ric. and theocetical-nwdeiing studies on the properties intrinacaUy useful and also useful in the design of the of the brines and their interactions with minerals which test systems for the 100-gpm loop facility. A system occur most prominently. with a large. SO: column, better temperature and flow Wwrafion of water in NaCI somtioas. We initiated control, and compatibility with brines has been de our geothermai program with experiments to determine signed and is under construction. The system, shown the salt effect in NaCI media - those most relevant to schematically in Fig. 2.11. consists of a preheater. a geothermal waters - because the ionization of water had salurator column, and an oil-bath intermediate cooler been extensively determined' only in KCI media at high which will cool the solution to the temperature (50 to temperatures. Measurements in 1 m and 3 m NaCI were 125*0 to be studied in the quartz-tube test section. made from 50 to 300°C in the stirred hydrogen-elec Temperature, flashing, and gross brine composition will trode concentration cell. The difference flog C^JVIJCI be the initial variables of interest. - Hog Qirhcci ***** f,om abou' 00' M 30° to about 0.09 (/ = 1 m) and to about 0.16 (/ = 3 m) at 300°C near the saturation vapor pressure. The quantity Q'K I. Abstract of VS. Gcofefkal Survey report, m Ckem. Eng tepresents the apparent ionization quotient for water. S2H9l.69iScpt. 15.19751. 1. Federal Fnerry AdmoiBiratinn. ftoject Independence These data in NaCI (Table 2.3) can be fitted within Btuepnnt Final Ttsk Force Report, (ieothemal Energy. I'.S. twice the estimated standard error with an expression Government Pnnfmc Office. WadimctiNi. DC. November of the type 1974 ). I). W Shannon. Economic Impact of Corrosion and Scaling FrttNrms m ticothrrmal Energy Systems, report \o%Q[ -\ogK*a>JiH\ *y/T) + M (l> BNWL-1 MA (January I975i. 4. CM. C; Brown el A.. I'ml Operations. Wiley and Son*. New York. 1950 where a is two times the Debye-Hiickel slope and b varies with temperature and ionic strength as a function with four parameters. Figure 2.12 shows the tempera 2.2.2 Physical Chemistry of ture dependence of log (TH'^OH '• lnc cufm *me Geotherrnal Sohitiom calculated from the derived parameters, and the points are the experimental observations. The systematic bias R ¥.. Mcsmer R. H. Busey of the calculated curve for I m NaCI results from he The objective of this program is to provide physical- inclusion and heavy weighting of the data of Harned chemical information of several kinds on geotheimal and Mannweikr3 at low temperatures. 24 M. ti aaopanaa* kf tf^o**^ "X«n " t» ! •"* IJT44 I ••» 25 il 25 o I J. 7251* law 25 « IJ*S»i 3*» 25* I20W KIM 5«» U2I« >0» $«0 I2*»0I I Ml 50J» l> |0Ji 500 II «? ll» 1000 l2«o l« n II IJ» law I SUA ii m 5 0» 1500 10 412 I ttt 200* 10 5 J* ifln 206.0 18241 100 2500 I0M00 Ja» 2500 •04J im 2050 0.5*2 3JW 2*5 0 *Ctff*c<-aaa* iat ihr O»UHUM—i <4 btdMpraI p*f*» «50I 0 709 f"l' .*«x*<4aMli VjkK% •Il t«t> or •nffufcanjiwi, O00C-O0S. 75-«093 cavenag brood vanafioas of coaaswntaaH. atforaniioa •*> these species cat be obtaaW- That far. poteattoaKfnc Mratiua e*pcraaeais am 0.OS. 0.022. 0DI. aad 0.005 01S* IV H 300010 J0D ppm S*>: 1 have been made at temperatures of 200. ISO. aad 100 C. The cell representation showing the mini ceU sohitiun B I wNatl I i*\Hl HVP om$ nirtw ViSrftaOHi, fl H- 0 02 m NjOtl A sohHion coatamaig I 01 NaCI and either 0.1 m or 0.4 01 HO was mjected into the nghf side of the cell and the eojuiibrium potential determined after each incre ment. 300 At 200 T the sofciiiun with the highest Sri IV1 concentration precipitates sdica at about 0 = 0.5 \n a F*. 2.12. V; the average charge per sucon atom, or the average mm*imS*\ number of OH' ions bound to each SHOHu complex |. At 150 f. precipitation begins at about n - 0.7 and 0.6 in solutions with "»SlllV| - 0.05 and0.02 respectively. Wmiatkm and anKatcrizafam of sikk acid. Equilib- At these two highest temperatures the data uMhcate the num data on Sri IV) m solution are important because presence of very liltk. if any. poiysiikaie species. At of the relatively high concentrations which are some I00C. however, the 0.05 and 0.02 m SrilVi sol'iiions times encountered in brines and the prominence of precipitate at about n - 0.7 and 0.4. respectively, and silicate chemistry ,n geothermal systems. Presently it indicate the presence of polysrikaie species. Approxi appears that the behavior of dissolved silica is very mate values of pKx ft»r the ionization of silick acid in I complex at low temperatures.3 Large polymers occur in m NaCI are XI. XJ. and X.6 at 200. 150. and 100 C solutions of moderate concentration of Sit IV) under respectively. More precise values will be available when some conditions, but in relatively bask solutions a more detailed analysis of the data is completed smaller species occur, principally SJOfOH)/ and Preliminary data at 60 C give pK, % X 9 and indicate 1 Si40.(0H». . r-rom potentiomelrk measurements that pnlysilkates are present even in 001 01 Si(IV) » nvaiauas More 4MS me rcqwrea' for mi mtkym far tht Where tvtcMttauaa occurs fioai sniatioas CQBUMBJ species prcseat • these sokMiuas. The MUMI of •fiiif*' the nn«m SfOHk. mi SOiOHV. *e cheaajtuy saanortaaj fam icacior tedaaukJgv B concerned »i* ! Innetks of variousreactions dm probaMy aril occar • drve^—taratal ad : taaanreactor*. Th e aunaaea»eaL kaadfeag. aad recycle of iiiii—i B m . proMem dm MM be solved if coatroaed nViwoaathaireactors (CTRsI air lo brcoaaereaaWe. large anaaiiiiir of tntuaai wdlbe pjudaced. recycled, andconsumed •• an uprnnam CTR. and laiiiuaare aid regabnoas wul demand auauaamrelease o f tntaaa from lb* faennry; dm B. a connoted amatory of int—i per CTR B • •a'aiory. la order lo lanjanm the tiiinan inventory aad auaaaur ore release of intanu. njanWnemd chemical dau aad coadnaons ate feqawjed ai several areas of research (l| BK sohnmfcy of irilaaa m dar various potential blanket HUlerub- (2| dre darraajdyuaaucs aad bueacs retired lo da?removal aa drecovery of tntiam fiuai various potential Wanfcet amena—. |3l corrosive properties of the Uaaket aMenah. |4| miaaa peraaabaaaes of the construcuoa anteiiab. aad «5| ways i«» aaawde tntaam ptnueafioa through tbe coastrncoon amenak. especnly rime Ibf sieaai generator*. Tart prueram B •vriiM,itanj there subjects, aad experimental pnunnes are set accoraaae i«» the keadmr CTR desajas and concept*. The program benefits from an _M 3.1 EQUUMUA IN HYDROCEN-«OTO*C- Meawremenb of die eqadriwaaR pressures of rac CTR-SLANKETSYSTEMS hydrogen isotopes (pressures X) I ion) m oV U-LiH-H;. U L_M>:.aad U-LiT-T; system* at 7001.. T .iT-" . . t __T ,0Mf C "i* mrt- Mode «*•> fact*** m bond C. M. Regan J. T. BeH adnata less dun 0.1 hare beea conipleied Tar data Meialic IrdMan is presently the most proamac «,I"B*> *»* *« S**"** Kiatwidup. V* = *VV blanket material for CTRs «condary choices include •*«* ',«»«** *«»* «* ««* hydr.asrn »*-:..Y, B molten Li:BeF« IFUBEI. hduant-aluiaaNRi aUoy^. *« "** «"w«»« "t" hydropea Botope at Ac lupad aad some solid hthaan U20. LIAIOL and U,SiO, Equdajna beitreen these «"«»i» obtwwl 'TaWe 3 I) hare been exprrued » a materials a»d tntrom ai temperatures at the 500 to function «* Wrnretature jcoKdmc I.. I000°C ranee are bemt studied to aid m the develop ment of tritium management methods and selection of die best blanket material for CTRs. }mKt-b mT'* III Tcaarnnae r fiorr"2 rnolrfncmn) .. _____5__— -- ptC*f*_fC IHWTI * n riy*sni Dcvtenwn Thnww 700 31 41 57 M* 4* am 5* ?* t* 1*4 2117 «o »j 112 1X1 *SO 750 toot) IJ7 •to i«n 26 27 VJhto •« b hit h\4rufm. iritenmm. mi inborn are *» *4?. v 515. Md V 226 rrtpexnveh Respective vafcan •« « a* «s242. 5*44 m& 50*5. Tile wawKMb f<« the hydropm aid A •in— sysaeatt aKJaard rive IVrdstoaM ^•Mtiaii-piwiHMe pbseaa reasue. aAWii defiaes the rwu-hqwd pkw cnexateace repna Several *\i 'k*r ptaieaa preuw*. hit bydrojea aad dona— •"Ci .°K. with the Sitwm oatwts at TaMe 3.1 Al of 527 10' W » 10" 44 V 10 -*J Irydruora mi dtawn—» d* 1027 10" 4.9 y 10" 14 * !•" data.1'4 ao KfaaMe data were 527 !•' •J « 10" «w«y 10" 1027 0.9 » 10" |j»y 10" The for Ufl LHh aHovs (or aaac the riktnaa) faaciinas for H:. Dj- Tj. Ul. U>. a*ri UT pwe* by Hw. Fin aaiaa. mi Beckett * TVr CTR cakatated eqaaawwaa ooastaats a* paca m Table 3.2. can a lower The averaf* eadufe* duafrs are 5J. 4J6. mi 4J •lory. Wemraaaniri fccal note tor the reaitjoag aasrivaif bydroara. dea- LiAl at 500*C The I > SKVCHS vdUrViDf. dats ••? Smctti CQHHJBI VB 1 1 raaae The pmjecied partial maamt of T* to be 1.9 fill )X 10* torr ' at. fracUoa aa coatroled rimanaaaJm reactors u buweui 10"* at kmmmoam am rite anowH of MM dkat mi 10" atau Coavhaaa/. darie vahan wafc dar vapor COtPfJ Of V9CV Hi 0*W f JtffffiaWflWjV- StkT BVJVEBJVJKVJ mnmm of MM aari the eoariamaai cnmais fjvea of tnriMi ia LiAl «m less precnt The m TaUe 3.2. we tare cakaiated the coaceatiaaoas of iidobdinu rawjed frw 0.01 to 7 pp» at 400 to UT expected at CTR nperabag naaliim (TaUe 3J». 600*C and conespoadMc trioan partial ymwu of These data aaVjit that da- coaceairataoa at UT ia dar ai4 to 0.52 ton. Another alloy. l>li(lS-S5 at. %). has beta sMsaaed vapor phase May exceed rile T: coaceatrattoa. A aosvspectroaietrk aaarysti of the vapor phase above a as a sotvcM for extracnaf tritiMi from sMitm-srii Iroaaaa falwaa^drsriraidi at 4S0^o7S4rr showed btsafcet ameriah. We atfcMpted to neasue the sota- bftNy of trinni ia this may mi coactarird dm die UH F«I4KTROK. We mi Ww* have observed die LaD Mbsbdrty is kss thaa 0.1 ppb at 500 to 700*C aad tntiiMi pamai pressBres of 10'' to 10"' torr. There aari U: D spears a> rive U-La>I>2 system- These rente draMasirate (he coaapkruty of die vapor phase M die fore, the tritwan soMMjr>- at the alloy is too low for MMMR hydrofjnMtotope systems and aaajtratt die die swjested process to be practical- •nporuNce of farther mass^pectromef nc aaalvsei at me vapor phases. I f Vrfccta* f. H. VMOCVMMT. MHI J Ckm7l.|*)3 L*p'V;njp = um0< OnMrn*. «*W 7>*»Jb- Aww tSAEC itvcn KAPt IM7 (1*5*1 • la?,) for 3. a M. MtCnckt* mi D H. I CnnalJI p 151 » 7M Trnptrslvpt OKoaai 5riw Asm r 527 MO 0.314 o.:3« 0.213 5 L Knr. A- V Fiiiiii. awl C « •eckrii. Miaf G« *27 400 0.219 Oil 7 J 0.157 TIJIH—WJIVJ—» faMraun «*ai hMojt F.xthmtr Frntcmm far 727 1000 O.I«4 0.133 0.123 Hv+Hr*. OtwKnSn. W IVmaW. SBS NOMO- 027 1100 0.129 0.100 0.101 snrk20 3.2 PERMEATION OF MATERIALS BY with different water concentrations and at different mrmocEN ISOTOPES temperatures wdl begin soon. J.TBHi F.J.Smith J. D. Redman R. A. Strehlow 3J rOSSULE REDOX BUFFERS FOR FLUE BLANKETS The permeatioa of tntiMB duoagh dean nnab and rhrough aKtaJs under saaatated sKam-geaerator condi C. E. Bamberger 0. M. Richardson J. T. Bell tions B being investigated. These studies ate essential because very low release rates wal be required for The nuclear transmutation of lidiium in a CTR trruam from fusion (and festua) reactor systems aad blanket of FLIBE A laoed-botope tedaaqae aad da- associated appa smce it rs more soluble than T: The T; TF ratio ratus have been developed for measuring the permea- theoreficaffY can be controlled with a suitable reduc- uua of trifana dtfowgh metals aader sanataied *u-mt- tant. preferably one dissolved m the FLIBE The generator conditions. The feed or upstream gas is H> -Ar redactaat and its oxidized counterpart are called the <4-WH LMauaaag about 2 ppm Tj aad B at a pressure redox couple. The retirements for dW couple are: < 11 of 1 arm. A tabe-type metal or ahoy sample is the couple at low concentrations must quickly equdi- positioned m a furnace so dot the downstream side can braKwidiTi and TF when dK T* FT ratio is high, f 2) be swept whh argon or with argon coutammg water the couple must be stable dKrmalfy and to radiation, vapor at a pressure less dtaa I aim. The T; permeation and (31 the couple must be compatible with const ruc •s meaiaied first with ae argon sweep gats aad then tion materials Based on these requirements and on the with the argon-water sweep jets. After water is added to free energies of formation for metal fluorides, several die sweep gas. dK downstream side of die sample redox couples have been considered- S>«ne of the began to oxidize, aad the effect of dK oxidr film on reported thermodynamic data were quite uncertain, so dk impedance ;o tritium permeation is observed These the most attractive redox couples were tested experi- KcJaaqaes and apparatus were proven satisfactory by mer-taly. measuring the tritium penreation dirough nickel at AvaaaUe dKrmodynatfuc data mdicaicd that the temperatures between 636 and 4|0'K. The tnuum CetlllHlV) couple could be a suitable redox butler, permeabdiiy diroufh dean nickel. DKt. at a function of therefore, thrs was the first couple to be tested temperature was determined to be experimentally Solid C'eFi was exposed to HI at temperatures to 1000'K. and the gss phase was moni- , ,/2 2 lored for H; to <,etec< ihe reaction \nDKt [ccfNTP>-rrwn-mm"-t«>rr" -an" | = 0«?0b r»360T ' . CeF, *HF-feF« *'/:H: Hi and the activation energy for permeation was de- termined lobe 12 6: 04 kcai'mole. The effect of in After the experiment, the solid residue was anal\/ed for oxide film on impedmg dK permeation of tntium CeF* Hydrogen partial pressures gr.-ater than 10 "* atsi tfuough Incoioy MO has been observed m a lohg-terrr. would havi been delated, and fdlV) levels ereatcr expenmeni In this experiment, which lasted five than 50 ppm would have been observed However, we months, the permeabilitv was measured as a function of found no evidence that reaction til had occurred. The experiment was repeated using LiBeF-i saturated with tune at 650*C. The icmperalure. the composition of : the feed gas. and dK water partial pressure in the sweep CeFi and with HF bubbling through the meit Again, ps were held constant. The results showed that the no Hi or CeF., was delected The HF pressure. O.I* aim. and the maximum hydrogen pressure. 10 ' jtm. permeabdiiy of lz rapidly decreased over the first 24 hr and dowry decreased thereafter. The total effect was were used lo calculate a minimum SG "f 3 I ' ..rf mole f- r reaction f l> This minimum Mi and the Af» of to decrease the permeahdiry by a factor of 300 over a r 176-day period There was no indication thai the formation f«w HF We conclude from ihe above results that the sidered from a background in surface chemistry. L'p to CeilllMiV) redox couple rs not a suitable buffer for the> pumt. the effort has dealt enr.rely with existing reducing TF to T; in a CTR blanket composed of information, eidier from ORMAK operation or from FLIBE. the literature. the free energy change for the reaction The interchanges between "he plasma and the con taining donee involve two classes ci material, fuel and l CrF. • HF-CrF, * '2Hz (2) impurities. With the fuel, the interchanges result in a rapid decrease in density u> the first millisecond itt a calculated from NBS data is 9.4 kcal mole Also. some shot folowed by a more gradual return to die plasma oi unpublished data indicate the solubility of CrF) in hydrogen held up from previous shots. Both of these FUSE to be greater than 043 mote characterise thei;i sufficiently well to predfci the E. II Taylor corresponding behavior m target or different CTR This sqtvey has involved about a one-half-year study 4-vices. Up ;<> this point it has only been possible to of the mterchanre of molecule between the gas phase make a beginning, a summary of the principal relevant of ORMAK (the plasma, during a shot) and the ramus <>bservaiions on ORMAK. a number of working hy smks f>« such molecules m the device < manly surfaces) potheses, and the collection of applicable chemical The study wa* undertaken because it appeared that the information. From this beginning, however, it should be problems of recycle (as the interchanges described possible to plan work ih.1 will bring about the desired above are generally' termed) could profitably be con understanding. 4. Chemistry of Transuranium Element* 4.1 DETERMINATION OF THE HALF-WAVE the nobelium activity in the solution phase were made AMALGAMATION POTENTIAL OF NOBELIUM before and after electrolysis. By repeating the experi (ELEMENT 102) ment at various electrode potentials (maintained con stant by use of a potentiostat). the half-wave amalgama R. E. Meyer P. F. Dittner tion potential was determined to be -1.85 ± 0.1 V vs W.J. McDowell1 R.J. SiKa the saturated calomel electrode, as shown in Fig. 4.1. J. R. Tarrant The half-wave potential is estimated by taking the The half-wave amalgamation potential of nobeUum. midpoint of the final drop in the ratio. The lower ratios element 102. has been determined for the reaction at intermediate potentials for the runs with tetra- No2**2e-~-»No(amalgam). The nobelium isotope methylammonium chloride can be explained by an 255No. with half-life of 223 sec. was produced a few adsorption phenomenon. By combining this measure 3 hundred atoms at a time by the reaction ment with the systematics of Nugent. we may estimate 2 J*'Cfl(,2C,a2»)255No at the Oak Ridge Isochronous the standard potential for the No-No * couple to be Cyclotron (URIC). The nobelium activity was caught - 2.6 V vs the standard hydrogen potential. Thus, by on an anodized aluminum dak and transferred pneu making use of only a few cyclotron-produced atoms, a matically to the laboratory, where it was washed into a fundamental and important thermodynamic property small electrolysis cell with the solvent (0.1 M tetra- of nobelium was estimated. methylanunonium chloride or 0.1 M NH4CI) and etectroh/zcd into a mercury cathode. Comparisons of 1. Chemical Technology Dhr-son. OWtL- DWC. 75-7850 2. L. J. Nager.«.X Inarg. Sucl. Chem. 37.1767 (1975>. 1.4 4.2 PREPARATION AND STUDIES OF SOME ACTINIDE METALS1 R. G. Haire M. C. Noe'2 J. R. Peterson3 Our studies of actinide metals were continued during this report period. The major interest has been in the transpiutonium metals, but the metallic state of other actinides or lanthanides has been studied when it could contribute to an understanding of the actinide metals. The interest in the actinide metals is twofold: (I) to determine the basic nature of the metals (crystal structure, phase relationships, etc.) and (2) to use the metals in obtaining basic thermodynamic data for these elements. Recently, a de'.ailed study of californium metal was undertaken. Some of the initial efforts were done in collaboration with the Los Alamos Scientific -1.0 -1.2 -1.4 -1.6 -1.8 -2.0 Laboratory. This work is a logical extension of studies POTENTIAL , V r* SCE performed at ORNL on berkelium4"6 and curium7 metals. f'%. 4.1. Rstoof of nobetntm activities in sohjtim plotted n •offatiaL First run (»). 0.1 11 tctramcthybmmonium chloride; Methods have been developed to prepare and analyze wcond run (•». 0.I M (emmethybmmonium chloride; second submicrogram as well as milligram quantities of the tun < >. t> ] M NH4CI. actinide metals. Ine particular method used and the 30 31 quantity of the «. tinkle metai prepared are determined melting point (900°C) (ref. 9) exhibited an fee struc by the availability of material, the properties of the ture with an average lattice parameter (room tempera metal (vapor pressure, melting point, etc.). and the ture) of S.7S A. Iras form is the divalent (expanded) subsequent use of the metal. The higher volatility of fee phase of californium metal. When the reduction was californium (as compared with americium, curium, and carried out at lower temperatures (600 to 725°C). the berkdium metals), together with the relative scarcity of samples exhibited another fee structure, whose average 24*Cf. complicates the preparation of this metal. lattice parameter (room temperature) was 4.94 A. This Former work on californium metal* ~' ° was done by structure is the higher-vaknt (collapsed) fee form of volatilizing californium metal from CfzOj-lanthanum californium metal. With two samples, a lower reduction metal mixtures and condensing the californium on temperature was used (600°C) followed by a 20-mtn various supporting materials (carbon films, quartz annealing in situ at 550* C in 1 atm of helium. The fibers, etc.). The deposits were then analyzed by diffraction data obtained from these two samples electron and x-ray diffraction. The aim of recent work snowed : mixture of the collapsed fee form and the has been to obtain vacuum-distilled metal free of any dhcp structure. supporting material via the oxide reduction process and Several of the californium samples were subjected to to prepare californium metal by the reduction of CfFj various annealing treatments. Samples of californium with lithium metal vapor. In the latter method, the metal exhibiting the collapsed or the expanded fee form preparative system'' has a very low total heat capacity, were stored in liquid nitrogen for one month, but no which allows for rapid attainment of thermal equi transformation could be detected by subsequent x-ray librium. With this system, reasonable yields of califor analysis at room temperature. When a cahfomium nium metal can be obtained, despite the high volatility sample exhibiting the high-temperature, expanded fee of californium metal. The more recent californium form was annealed in the preparation crucible for a few metal products, made by both preparative techniques, minutes at 600°C and then slowly cooled to room have been analyzed with standard x-ray powder meth temperature, it was found to have partially transformed ods after sealing the californium metal samples in into an fee structure with a parameter of 4.98 A. When quartz capillaries under vacuum or helium atmosphere. a californium sample exhibiting the collapsed fee Based on studies made to date, it appears that structure was subjected to another high-temperature californium metal is more complicated and interesting (!000°C) reduction step followed by rapid quenching, than previously studied transplutonium metals in that it the californium product was found to exhibit the exhibits two different metallic valences. Two phases of expanded fee form together with the material having an californium metal (for the higher valence or collapsed fee parameter of 4.98 A. This latter material st;:c) have oeen established which compare with the (a0 ' 4.98 A) was observed in the presence of the metallic phases known for americium. curium, and expanded fee form, whereas the collapsed fee form berkelium metals. The crystal parameters for these two (a0 ~ *-94 A) iias never been observed in coexistence metallic phases are as follows: (I) dhcp. a0 - 3.384 A with the expanded fee form. This additional structure J , and c0 = 11.040 A;' ••• (2) fee. a0 • 4.94 A.' These (a0 - 4.98 A) might represent a defect structure of parameters agree with values extrapolated from the californium metal. other actiniae metals, providing an additional degree of Recent work on einsteinium metal has confirmed confidence that these structures do represent califor previous results.* and the data indicate that einsteinium nium metal. The earlier report' of the divalent or metal is divalent, exhibiting an fee phase similar to that expanded form of californium metal (fee, a„ - S.743 A) observed for the divalent or expanded form of califor has been confirmed.12 In addition, there is some nium metal. Studies on einsteinium metal f*~ve been evidence for the existence of a hexagonal phase of limited to submicrogram and microgram quantities on a divalent californium metal,10 but this phase has not semiannual basis, due to its short half-life and limited been observed in californium metal samples prepared by availability. the fluoride-reduction technique. Additional studies of californium, einsteinium, and Efforts were made to determine the temperature other selected actmide metals will be made. Larger relationship of the different forms of californium metal quantities of californium inetal will permit meaningful from the conditions under which each was obtained and purity analyses to be made, provide inetal for selected also by interconverting the forms by various annealing thermodynamic studies, and allow a more detailed treatments. examination of the different forms and their tempera All the metal samples prepared by reduction of the ture and pressure relationships. A more complete trifluoride at temperatures from about 72S°C up to the understanding of the californium metal system (the 32 effects of impurities, temperature, etc.) should aid in soon as very pure, well-characterized samples of berk;- interpreting the limited amount of data that can be iium metal become available. obtained from elemental einsteinium. I. Supported in part by North 'ubauc Treaty Oryaaization Research Grant So. 5*5 aad by ERDA contract 1. Supported in put by ERDA contract AT-t40-l>4447 with AT-440-1 >-4447 with the Univc.-*ity of Tennessee. KaonaV. the l'ar*crsity of Tennessee. KaoxvaV. 2- Institute of Radfocheaustry. Uamrstty of Uecc. Bihjinm. 2. PosfdMtoral Research Associate. Department of Chem- 3. Coasaltaat. Department of Hnjairtry. University of BOy. Uamrsiqr of Tt— f mi. Kaovriate: present IMR» Tennessee. Kaox.«dk. Framatome. 77/S1 Rae 4B HUB. 92403 Coorbevuie. FMCC. 4. Gn-hutc stadeat. Department of CV--in"» ''diversity of 3. Consultant, Department of Chcaastry. University of Tennessee. Kaotvafe: present address: t_i Naval Nndear Tennessee. KaowaV PonJCt School, WalhraatKS Drrtsnn. BambrvJcc. Md. 21905 4. J. R. Peterson. J. A. Fahey. and R. D. kaybarz./ Inert. 5- Postdoctoral Research Associate. Department of Chem Smcl. Chan. 33 334S (1971). istry. University of Trnntiirr. KaovaV. present address, 5. I. A. Fahey. J. R_ Peterson, and R- D. Baybarz. /ic»j- Framatomc. 77/tl Rne dm Mans. 92403 Coarbcwae. France .Vnrf. Ohm Lett. «, 101 (1972). 6. J. racer. J. R. Peterson. J. N. Stevenson. M. Nue. aad *. J. Facer. J. R. Peterson. J. N. Stevenson. M. C. Noe. aad R. G. Haire./ Imorr Anrf Ckem 37. 1725 < 1975). R. G. Hanx.V Inorg. XmeL Chrm. 37.172$ I197S). 7. J. R. Peterson et al.. VS. Energy Research aad Deidop- meai Adaaatstrarion docaavrai No. 0RO4447-006 4.4 SffiCTROSCOPIC AND X-RAY H 973-74). p. 12. S. Ckem. Tcautol Dn Anmi. Prof. Rep. Mar. 31. 1974. DIFFRACTION STUDIES OF ORNL-4966,p. IS. HNSTHMUM-253 •ROWDCS' 9. R. G. Haire aad R. D. Riybxrz. J. tnarj. \ucl Ckem. 3». 2 1295 |1974). R. L Fellows R.G. Haire 10. R. G. Haire and L. B. Asprcy. "On the Canfonaum Metal J.P.Young* M.C.Noe4 System"/HOT MaeL Chem. Lett., in pics. J. R. Peterson* 11. J. N. Stevenson aad J. R. Peterson. Mkrockem. J. 20. 2IJM975). We have nated previously* the apparent dilemma in 12. M. Nor and J. R. Peterson. "Preparation aad Study of the interpretation of our spectroscopic data on the Elemental Califonuam-249." r>oc. 4th Int. Trunsp/utonwm einsteinium bromides vs the work of Carnal! et al.7 LUm. Symp.. Baden-Baden. Germany. September 1975. Recent spectroscopic and x-ray diffraction studies at both room and elevated temperatures have resolved the question of the oxidation state of einsteinium in the 4.3 HEAT OF SOLUTION OF BERKEUUM product resulting from hydrobrominalion of the METAL1 oxide. Although several einsteinium-solution absorption 7 2 4 spectra have been published. '' our data are the first J. Fuger J.N.Stevenson 3 obtained from an einsteinium compound in the solid J. R. Peterson M.C.Noe* state. In addition, we have obtained the first x-ray R.G. Haire powder diffraction pattern of an einsteinium compound A second effort to determine the heat of solution of at ambient temperature. berkeiium metal was made at the end of the last Several different einsteinium bromide samples, pre progress report period. The data have been compiled, pared by hydrobromination of the oxide, have been analyzed, and published,6 and the results are summa studied. Two different oxide preparation techniques rized here. These are the first htat-of-solution data have been employed: (1) calcination in oxygen of an availabk for the transcurium metals. einsteinium-loaded activated charcoal chip and (2) Five measurements of the heat of solution were made calcination in oxygen of an einsteinium oxalate precipi on berkeiium metal samples as large as 0.5 mg each. An tate. The oxides prepared by method I were apparently average value of -576x 25 kJ/mole was obtained for contaminated to a degree sufficient to prevent complete the i*3t of solution of the double hexagonal closest enough conversion to the bromide for good optical packed fori;, of the metal in I M HC1 at 298.15°K. The transparency. Therefore, these samples were heated to error limits iepcri.y! above reflect (he uncertainties in elevated temperatures, where the pure einsteinium the purity of the berkeiium metal and not the precision bromide sublimed out of the bulk sample and. con of the calorimetric measurements. Plans call for re densed on the walls of the capillary containing the ducing the present uncertainty u\ me value reported as sample. The oxides prepared by method 2 were 33 cunvtf ted essentially compicicU to the bromides: how .». B. B. C uiuuMckun. I. R Peter**. R. D Baybon. and ever, the handling of these oxides was more difficult. T.( Parsons./we .Vac/. (Vm Leu 3. 519119*7». To date, we have also studied several hydrogen-reduced 9 D. K tn)tu. B. B- Cuarunckun. T. C. Parsons, and J. R. Peierson./Nurz .V«rl Chem. Leu 5. 245 (rl/z - 20.5 days) causes severe darkening of the film. ments in a variety of valence states was begun because OH spectral and x-ray diffraction data obtained from these compounds can serve as models for the behavior the hydrobrominated oxides at ambient temperature of heavy elements if released into the natural environ confsrm the presence oi Es* or EsBr*. NO charge ment. The humk materials which result from de transfer lEs** - EsJ* I or /-«/ absorption bands were composition oi plants are distributed across the land recorded at wavelengths down to 400 nm. although a surface and are suspended in natural waters. They are detailed analysis of the spectral data is yet to be done. chemically characterized as containing organic polymers On one powder pattern. IS lines AlClj-type monoclink structure expected for tsBr3 .' * (o-hydroxybenzoic acid) as a simple model and used it The derived lattice parameters \a = 7.27(2) A. for study of the bonding to actinides. b= 12.59(3) A, c = 6.81(2) A. and 5. Consultant. Department of Chemistry. University of was deduced to be UOJ(C7H30,)3'3HJO by com Tennessee. Knoxville. parison of its crystal data with published values.3 The 6. i. R. Peterson. "Physical-Chemical Studies of Transura complex with Th(IV) has not been analyzed as yet. nium F.lementJ." p. 4 in vol. I of ftoc. 10th Rare Earth Res. Crystallographic data are given in Table 4.1. Cimf. Carefree. Ariz.. 1973. 7. W. T. Carnall. D. Cohen. P. R. Fields. R. i. Sjoblom. and A single-crystal \-ray diffraction analysis of the R. V. Barnes./ Chem. Phvs 59.1785 (1973). structure of SrmTirlsOjb'HjO was performed. The 34 TaMr4.l. Setae* aiAt fciAi IAI Jldeel SaCTH,0]),-H:0 15-641 • 752 24.202 113.3 4 AIMCTHJOJIJ-HIO 1343 •.79 24 23 MS 4 IOIICTH50,»;-JH:0 HextftMat 1669 6.92 12 ••w n-ttt fif. 4.2. A jKunuppit iipuunHlii)« of part of Ike crystjf MUBH—L of SMCTHJOJIJ-HJO. AH aemm aiiacfced to the IIHUIMHII atom are oxygen and thoir lump Ihr one awnbrr are rctaied by crystal symmetry. TV atom bbrM W n ike oxyprn atom of a water mokcakr. 32 nonhydrogen atoms of the unit cell were found, and hydrogen bonds are also likely to be present, but direct their positions and anisotropic thermal parameters were evidence for them is not available. refined to high precision (RF - 0.037). The parameters A conclusion from these results which may be of isomorphous Am(C7HsOj)j-H20 were also refined tentatively applied to humtc materials is that such using x-ray diffiaction data, but to somewhat less trivalent metal ions as Am** should be extensively precision. The results for the two compounds are so bonded to them and that carhoxyi and hydroxyl groups similar that the following discussion applies to both. should both be effective in holding the metal ions. A portion of the structure is illustrated in Fig. 4.2, which shows one metal ion and the six salicylate ions 1. D. S. Gamble and M. Schnitzcr. in Trtcr Metals and and one ws'.er molecule which are bonded to it. Each Metal-Organic Interactions in Natural Water*, cd. t.C. Singer. metal ion is coordinated by nine oxygen atoms arranged Ann Arbor Science PuW Inc.. Ann Arbor. Mich. (1972). p. as a trigonal prism capped on its rectangular faces - a 265 ff. common arrangement of oxygen atoms around an ion 2. V. Amirthalinghain and V. V. Fadmanhaban. Anal. Chrm. 31.622(1959). of this radius (095 to 0.98 A). What is of interest is the source of these nine ligands. A single salicylate ion with 4.6 EFFECT OF SECONDARY BONDS ON THE its hydroxy I and carboxyl groups has three oxygen STRENGTH OF 0=Np=0 BONDS atoms available for complex formation. Monodentate or bidenlate bonding between metal and salicylate can J. H. Burns C. Musikas' thus occur in several possible combinations. Nearly all The Peroxide Ligand and Np(VI) appear in this structure. The net effect is that all the metal ions are linked together by sharing of salicylate The Np(V>Np(VI)-peroxide system is one of con ions in a continuous three-dimensional network. Many siderable complexity and has been studied in some IS rV' r* 4J. •T pan av- af N^NpfMOih-Wia Al oxycea detail by spectrophotoraetry and potentiuwetry. we strength, it is also influenced by the equatorial bonding have identified the crystalline precipitate from aHahne to the neptimhim atom and by the attraction of th» solution with excess peroxide to be Na^NpOzfO:))* oxygen atom by the two sodium atoms with winch it is 9H:0 and have carried out a single-crystal structure shared. By comparison with another structure in which determination and refinement. This work has provided these secondary bonds are unchanged, it is possMe to the first direct measurement of the (0=Np=K))** examine the effect on the bonding of changing just the geometry, although it has been estimated many times. acthude element, for example, from NpfVI) (S/1) to In order to provide a sound basis for comparison with U(VI) (5/*) Our results, from the study of (0=11=0)** in the same crystalline environment, we Nx.U02(Oi)j-9H20. are thus: all of the distances also refined the structural parameters of isomorphous mentioned above are not significantly different from Na4U0:(0I),-°H,0 using the same fechnicfies. This those in the neptunyl compound, and the U=0 (uranyl) uranyl compound had been studied earlier3 but without bond length is 1.8S2 A. His small difference (about sufficient precision to be useful to us. 0.01 A) between these uranyl and neptunyl bond A portion of the structure is portrayed in Fig. 4.3. lengths may be attributed to the actiniae contraction with the more interesting parts emphasized by bolder alone. 2 lines, within experimental error, the NpOj * group Ife Catenate Upmd ad NpfVl) (shown nearly perpendicular to the drawing plane) is linear (179.1°). and the two Np=0 bond lengths are The effect on the O^Np=0 bonds of changing the equal and have the average value of 1.838 A. Three compkxing bgand was examined by detennination of bidentate peroxide ions are attached to the neptunium the structure of IC«NpOj(COj)j by single-crystal x-ray atom in the NpOj 2* equatorial plane. In this plane the diffraction methods. This compound was chosen be Np-0 bond lengths range from 2.27 to 2.31 A, and the cause the CO}2' ions were expected to form bidentate internal peroxide bonds have the normal value of bonds around the equator of the NpOj2* group and 1.49010.007 A. Two of the sodium atoms are achieve a geometry very similar to that of the peroxide- octahedrally surrounded by water molecules, and the bonded compound. Yet the complexing should be 2 other two share some water oxygen atoms and some weaker with CO,*" than with 02 ~, and there should be other oxygen atoms to achieve six- and sevenfold less influence on the neptunyl bonds. coordinations respectively. In Fig. 4.4 the relevant part of the crystal structure is Although the length of the Np=0 (neptunyl) bond is pictured: the Np02'* group is oriented similarly to the primarily determined by atomic sizes and bond one in Fig. 4.3 for ease of comparison. The atomic 36 t*v :»; -» «-» F«. 4.4. SlWliajil *•»•* *tpM«ll r of Kj.NfO^tCOi); A rsofuM »i> tuMncrjpfcK un pn«-t rhruwch the i aw • a wcitkal *wm»». 2aw.-3«& ^1- -M J F%. 4.5. Snnoaiook. diwit of pan of ifce met • of KaNfO;(C:HtO:)i-2H30. AH al»in* Jlljifcol l« nrp 2 environment of the NpO: * is as expected. There are compound obtained. BaNpO:(C:H_,0:),-25l:0. was six carbonate oxygen atoms forming a nearly planar ascertained by determination of its crystal structure, a hexagon about the equator at Np 0 distances of 2.42 part of which is portrayed in Fig. 4.5. It can be seen to 2.44 A. These longer bonds, as compared with the that the local environment of the Np( V) is quite similar peroxide complex, reflect the weaker complexing abil to that in the carbonate and peroxide compounds 2 ity of CO* ' ions. Each neptunyl oxygen atom is shared discussed above. The equatorial plane of the NpO;* with four potassium atoms but at greater distances than group contains a hexagon of oxygen atoms belonging to the sodium atoms in the peroxide complex. thre; acetate ions bonded to the neptunium in The net effect of the weaker secondary bonds is to bidentate fashion. The lengths of these secondary bonds allow stronger neptunyl bonding, and considerable range from 2.52 to 2.58 A. The O Np-0 group is shortening of the Np=0 bonds is observed. Crystal linear with Np=0 bond lengths of 1.808 A. This larger symmetry dictates a linear group with identical bond value as compared with that in the carbonate com lengths, these are measured to be 1.776 A. pound reflects the fact that Np(V) is larger than NjKVI). The Acetate Ugand and NpfV) By use of acetate as a lipnd we were able to grow 1. Guett scientist from C.K.A.. Fonlcnay-aux-Rntes. I rancc larg; crystals containing the Np(V ion: attempts with 2. f. Mufttat.7. Chim. Phys. 71.197 (1974). cartonate were unsuccessful. The composition of the 3. N. W. Akock.y. CVm. Sir. A. 1588 4.7 NEPTUNIUM M-SEJUESX KAYS expressed • inratm rues, natural level' rauJtipiet structure, the -V-series x rays of 1 M. O. Krause were measured. The neptimnun M x rays As part of our program aimed at the determination of measured previously: in fact, m the artmide scries..11 \ rays have bee* studied only m unrium. protactinium, electronic level structure and of atomic dynanncs as and wanium- As m a previous study' of the .V * rays of uranium, we used the PAX method1 tpnotocicctrua i«oV spectrometry for the analysis of x rays J to measure the pronanent lines of the series. About 100 to ISO wg of neptunium was eJectrodeposated on a siver-plated. water-cooled copper anode and was hrjmbndtd with a 12-mA beam of 15-fceV electrons. The resulting x rays were transmitted through an 8*m beryllinai nindon into an atmosphere of either eeoo or argon. Those pbotoekcirons ejected from the Is sheD were Aspersed in an electron energy analyzer operated at a resolution of 4f/f< 0.153. where E is the energy of the photoelectron. Energies, bine widths, and retain? ener gies of the x rays were determined. The absolute energies were obtained in reference to the la, and L&x lines of silver, and the natural widths were obtained by an unfolding procedure that took into account' the contributions to the measured width from the spectrometer window and the converter level. Figure 4.6 shows the Ma, 2 doublet as an example, and Table 4.2 summarizes the data -20 -10 0 10 Af. REL»TWC EXKGV (tvi Fie, 4J6. The tpfjww Ma x-fiy hue resolved ml© the a, and 03 lompomnts and latrDHe strectmc. rontons of the 1. O. Keski-Rahkoncn and M. O. Kraiue.Mvs. Fern 9. SI. diapam iines are Voi^i function*. Resolution ai'/f" - 0.1 fX? for 261(1974). the photoclectrons ejected from the Ij shell of neon. 2. MO. Knusc.fftvx. Fern. 9. SI. 2S1 (1974). TaMr 4.2. Characteristics of piunwunt M x rays of neprwMin) Line Knerey teV> FWHM (eV> Relative intensity .V5.V70I 3260.7 «s-v6aj 3249.4(4) 6.3(8) Wj-Vrfi 2579.1(8) 11.4(9) 4.1(5) MtJV^ 3434.2(2) 4.7(4) 58.0(2.5) «*v2f2 2521.6(1.2) 1 O.CHI.5) 2.8(6) w>viT (3690)* 6.5(1.0) "Reference A* /.<», = 3150.97(3) eV and A*/.», » 2984.34(2)eV. Tentative assignment. 4 J ELECTION electron bnaSug energies of the —-»-=<*e elenKats. we (band a amubcr of dtacoaunauies whew pVxtiag ANDEMRBNAM -aF|4/| as a rant linn of Z; in particwlar. we observed an Jonge at the ha¥-tnVd 5/ shriL which gave a M.O. •tG.Hane J.H.05 in the ^l4/> vakac on going front awmwn s of the JML -V. O. and P electrons The buahng energies «4/> and the splitting -irVt4/) were nrtrrnanrd by the pbotoekctrun method, wang (for which no previous deter- oar 15-cni electrostatic election-energy analyzer and had been mane) • order to , iinmhii a table ' i fla i rrp IT rhr n irnnw man i Iniajli i amor kwb for the aconite elenvan^ The either by ekvtrovVepusioun from both by phofjehctnjn nd isopropyl alcohol solaiions or by vapor AT* x ays. and it i of the atetats- These raaulu were generany analyzed as received from the above procedures: surface Lm% mtiLfi x rays, to eject the fla finrttimwif frirj mdjiti with oxidation of the nwranr deposits often rcsalted from O.IS* RXMM was ascd for —lit the deter- of the rinmlrj io air. In many cases. treatment was carried ont on the f he energy levels of aaarocnan and was eapapped warn to prodnce either the oxide or fluoride (in . oxyflaoride). Typkaly. seven analyses (bat not less than three) were node for each element. The iifr hinftwig nfihi nwjiiiiiu I—JIIM T—jili i ifciih ranged from about I wj of 25,Es to up to 50 **g of splitting of d*e acthnmn Af doublet in a sample of Ac 0, (Fig. 4.7) serves as an example of the spin-orbit "••u were parified hy ion exchange trrhniquri and : efcctrowEposwed oa a abanrnm fad. hi the case of 0WH.OWS. 73-3731 phrtoninm. ctcdhM ijmplti were abo obtained by • i • • • i • •—• * i • • i f i vapor deposition of the nwtal. Sauajncs were Hammed as prepared and abo as oxides, which were obtained by heating the deposited material in air between 800 and lOOtfC. Data2 are presently being analyzed and win be incorporated in an atonic energy-level table in the near future. 1. M. O. Knnc aa4 F. WaiUcaaucr. m Electron Sftt- mncopy cd. D. A. Shaky. NonMtofead. Aamcnoai. 1972. p. 759. 2. To be pabfaned. 4.9 ANOMALOUSSfll^ORWTSrUlTINCOF THE 4/LEVEL IN THE ACT1NIDE SEMES M.O.Krause J. R.Peterson' R. C. Haire J. Oliver O. Keski-Rahkonen2 •8««V«- According to the theory of atomic structure, even in its sophisticated version, namely, the rdativistk 3 J_J, Hartree-Fock model. the spin-orbit splitting of a level 320 310 300 increases smoothly with atomic number Z. For ex EHQ ( om;*s* ateervjj for dsr 3c&as± by I to 2 eV bat left A£f4/) cjauninly the Jfau same. For rwiimpjlr. 3E{A/) dnHercd by only 0.2± QL2 fruoi thc-lin, . x-tay auaMrt.wInd eV for AcFj and AL.O, and by 0J102 eV for the the same spectroaKter is the PAX node.4 The resales averaged front al data ate pfotied m F%. 4 _S with the to the theoretical tetatmsuc Hamee-Fock predictions, as shift), tins other type of < gmen by the differences of the tiyaialaii of the 4/ the detansof the • • 3 stmctn-e. ~ The observed stractarc of .1£|4/) is electron attraction between ate 4/and wf: mwiwjmft of the stnacTare foaad by by Vander Sins and Nugent* for the energy differences 4/ electrons. The mf electrons < as for some actimdes. or | IF = *f(5/*6tf7j) «T<5/»"' 7s> It showM be .lfl4/) a sanaer for of the singly iowurd jet nude atones aad for other efcetrons in the ground state than for I properties associated with the peripheral electrons. This and that ^rT(4/> for the ughl and the fact that the number of 4/electrons electrons tans below the theoretical constant through the scries sapors! that the 4r?(4/) for the heavier miniii I hesa the theorctt- •J£|4/) spatting reflects the pttiphtijl electronic strac- cai curve. tare. Tics phenomenon differs from the so-cafxd The onestkm natmaly arises whether or not samnr chenacal shift (which correlates with the average charge discoatmwtics coald be obscned with other doublets, of an atom within a compound) in that it docs not shift sach as the Ad or Sd levels, which are Htety to interact the Afif2 and 4/?/2 levels by the same amount. It was strongly with the 5/ electrons. With regard to the 5d found that the chemical shift between the oxides and level, we find a 5rfs/I photoune considerably broad the fluorides of the actmides shifted both 4/~ levels ened by multiplet splitting and a 5di/2 photoiine that seems to have "flowed apart," presumably by very strong multiple! spiriting into several widely spaced CMML-OK.7S STS9* components. The difference. «&£(Scf). therefore remains -i—i—i—i—i—r i 'I ! ~! ! I I indeterminate, but the data demonstrate that the •CTiMOES interaction of the 54 electrons with the outer electrons zt>- A4f depends strongly on /'. Regarding the Ad level, the presence of discontinuities in AE(Ad) could not be \ 20 demonstrated for tics widely spiced doublet since we do not have a complete set of these data for 'he entire • !• - series. Finally, it should be noted that the 4/ doublet can readily be used for identification of an actinide by zo photoekctron spectrometry since it has a large photo- iocLz'.K-r ••••: -• .. iv~ the cui._aorly raed magnesium Ka and ammcuim A'a enesgr r X £ 10 • THIS • Of.SCl.AUX d»TJ) 1. Consultant. Department of Chemistry, University of Tennessee. Knoxvil*. 2. Present address. laboratory of Physics. Helsinki University of Technology. 02150 Otaniemi. Finland. -JL-JL I L_L_1 I 1 I I I J I 1 L_ 3. J. P Vaehux.At. DuuNuel. Dttm Tibia 12. 311 (1973). *C Th «* UNfftiAmCMttCfEsftKMMItoLr 4. M. O. Krausf.Myr. Fam % SI. 281 (1974). ELEMENT 5. C. K. Jdrccnscn.M?/. Miyt. 5. 271 (1962). F* 4A. The win-orbit jpbrtmj of the 4/ k*d for the 6. K. I_ Vandn Shris and L. J. Nugent./ Opt. Sot. Am. 64. •lementr as dctemMed by die pbofoclecfron Method. 687(1974). 4.M HE CAUHMVaUMOXVGEN SYSTBI of sapentractMw ban hie ikv latter tanas auaaj yaU aa tec-ate pattern The lots of aV saperstnacfarc R. C Have R t Taacotte' aaes analts fruai me aaonler m aV sysaoa. Several ol' the actaaar fteaiHMS ant kaowa in form AaaaaerolaV cajrfaaawm oxak • aapl .aarhcaa; both untered aad dBorarard aned^akwce oxaks it* have oxygea-io-aaetal raaus btiwwta t.S and -0 •1 air or o»ygea ifwoianiui, lat aahnat inaaerafaaei Eacher arffracOua rradai of ascragraai oaaMMar* of' •» shown *at admouaal oxabuoa of the caaf maami cahfomaaa oxafes showed riwi cabforanaa coaM be had uccamrd. ftned on lattice yaramihu cunevted for rahanac damage. aV * CIO, 7| Atomic oxygen or higher oxyarn pressures 411 TlUNSrTirrONHJmOXYSULrAT£S (100 anal were retaured for the preparation of oxides A.NDOXYSULFiDES abow dtis composition. Oxides of die MO,.7,4 compo R.GKaire i A. Fahcy" sition (MTO)2) haw been previously established for some of the lanthamdr elements (Ce. Ft. Tb). curium, The oxysulfates (M.0:S04» and the -txysuifides and bcrkeaum. (M:0:Si are kmiwn f CfO, fc7: lattice parameters varied from 10.830 A to for handling transplutonium elements. 10.790 A. The rhombohedrai structure corresponded to The oxysulfates and oxysulfides can be pr*rpa.<-v, CfO, 7,4 and was shown to be isostructural with the by thermally decomposing the sulfate salts other lanthanide and aciinide oxides of this composi (Mj(SO«), XhjO) or by calcining "loaded" r> wex 50 tion. The lattice parameters for the CfO, 7,4 rhombo resin beads (sulforiic acid-type resin) in different atmos hedrai structure were determined to be a„ = 6.596 A pheres. The oxysulfates are obtained .n air. and the and a - 9ft .40*. which compare with values for oxysulfides arc best prepared in hydrogen-argon atmos TbO,.7,4 of an = 6.509 A and a = 99.31*. The pheres. The actual product o»,;ained depends on the apparent fee patterns probably represent poorly crystal atmosphere, temperature. t>iJ duration of the calcina lized bcc or rhombohedrai structures, since the absence tion: both the oxyo.'i.'ales and oxy sulfides aie con- 41 wrned to auies at elevated araaarraiares m an oxyaca- Tar SOS '"Pa 50* '"Sai Irydnaude cry** «jiKtiaaag jhiwpacw. <"~S» is the daajMer of "Pat) haw beer an* For d*r faaduMtV aad t nvafeat actnadr cksaeats. dk oxysatfates exhanf a* ordaafoadac sraMnetty. wan of dkar amiuLrirtdi by electron aatwmnpy has •Ur dk oxysahSdes have trajaaal raaaanry at (•Wnaanat tfanaW' naaaaaaaT n4^aaaiaa**> tfavaaaa aaan* an*4P* •BrranaarnnTna'nBn. am contrast to dk laajilrti detuncooa of-*'Aa*OHh jimp ••* wall dK '•Thaiiai coaawjaads revealed aad 2«*CadOHb crystals i ahoat S <• ii—fci aad ahoat 1 day Kiau. natty. Lattice Parana M,IJ derwed from dk siinctare of ike QMwMjm. la aa effort to locate dkse >"ra,.'"s*i crystals stored m Miami were CSKB- aosmuas panniery. several atsnaats were aade to anly dK saae x dK par nam u caValavd far rhe Ahanaah single crystals arte art iibtaand. x-ray data saataraaa co«aoaads. Tlas resali woatd be expected if front the pohroystaKae taarJunnlr oxysalfate were dK '"Sai .injur replaced dK '"Par »ciw card to rehae atoaac pauiuons m dK oxysalfate »n itdnai asaienal aad if dK crystals were assaard to straciare. and tats inforntatjoa was ased to asssfa be aaaffocted by dK beta tadrauaa. X-ray rxanHnano* awhrrr to the traasphHuaaan oxysrifate x-ray data. of dK '"Pnv'^Sai crystals dot were stored * dK The ftsaits of dK study shear dm the rnvateat acfaade sobd state (x-ray capdbsks) inauittd about 159 oxysaffates aad oxy-saffides form two rsostracfaral expansion at oae paraajrter (#,. hexagonal P6, 'm series dui are pitapat jhh aidi dK cumipiTdHm, syaaartry) after aboat % half-bfc. A apuikaat loss of laadiaa 4.12 LANTHANID£ ACTIWDC HYDROXIDtS i. brpartmeni of Chemnuy. Bavtor Unneniiy. Waco. Tex. R. 0 Haire W. 0 Miibgan1 2. Chem Trdmal On. Anmt *of Rep Mtr 31. 1974. ORNL-4966. p. 19. Several years ago. comparative studies were done ov ine Chemical Technology Division on die crystal structure and morphology of the lanthanide and actiniae hydroxides. Part of the interest in these 4.13 ELECTRON PARAMAGNETIC RXSONANCE hydroxides arose because the colloidal nature of the BWESTICATIONS OF DIVALENT material produced 3 behavior contrary to that expected "'EilNSrO, ANOHBF] solely from the classical volubility products. Later, 1 L. A. Boatner' C. B. Finch efforts were made to examine the self-irradiation 2 4 R W. Reynolds M. M. Abraham damage in the hydroxide mkrocrystais. and l47Prr trihydroxide crystals were made in order to differen The electron paramagnetic resonance (EPR) spectrum tiate between the effects of self-irradiation by alpha and of 25,Es2* (5/" electronic configuration) has been 2 ,47 beta emitters. The Pm (/•/ =» 2.6 years, beta observed in the cubic single-crystal hosts BaF2 and emitter) has resided in these crystals for one half-life, SrClj. The spectrum obtained at about 24 GHz and a and the crystals were recently examined and compared temperature of 4.2°K exhibited it well-resolved eight- with damage in crystals of AmfOfl), and CmfOH),. line hyperfine pattern (/ = \) for 25,Es2* in both host 42 414 EFFECT OF TOaPEftATUBE OK THE SElf-UNVCSCENCE OF S*CI: DOPED WITH M*C- 0* : *' E* OKSEKVATM* OF HOST DEFECT I C • FMch' J P Y. f ertani artnaade-wa duped crystals, when trokh aaneaftec and heated. haae heen observed io hanr a dmerea; man—. iiu>ia:e dtaa whew atn ate c-joird. appears dut awnnB radfcMwaaaesccnt •eew auar on crystals a* nooaiien^eraauies or Wow. bni not a* elevated temptntmun As part M a atarral sndy of she properties of tnch duped crystals. BV idf w—njcewce of StCK frsstab di^ed w*h r*4C« or :,,Es was studied at 77 to 700'K m the from 300 to TOO ML TWO types <»f M*. Tnecwnt-hnr arptrftBC parieni « «• (• tfcr / * spectra- dipindnig oa sample temperatafc. ip»rfM/E*. were observed toe either dopant The spectra seen a* teaperatMes of 77 to 300* K correspund to a predomi nant bhje. and me spectra seen at 500 ... 700'K correspond to a preducnaiant yeBuw-orange en:iss»ia crystals: Fig. 4.9 shews the spectrum -.Atatned wrth the Tht lumincjcmce mtenaty at 500 to 700*K remams SrCij crystal. The magnetic Add positions of the vebbceh constant with time, suggesting the passable observed transitions were independent of the magnetic appbcation ot' this material a* a raJiottHoow Jrdtt field onentatron. but line width anisotropics were source. present The EfR spectrum of J**Es> was described by the spin Haauttonian I - Metal* and Ceramic* Ittnmm. X'WiHf + M* 2. Analytical Cfceamlry Dniiinn. with 5' = '/, and / = 7, and with * = 5*25(6). A = 0.121M<3> cm"1 for the BaF; h«»st and ft * b.65)*3). A = 0.13*2(2) cm"' for SrCI2 The significant difference between the measured g values for the two hosts 4.15 SOLUTION MKY0CAL0RJMETRY OF indicates that the fcs2* ground state is a (*» doublet in TRANSURANIUM ELEMENTS AND COMPOUNDS' BaF i and a T? doublet in SrCI . Although * similar 1 1 4 2 R L. Fellows D L. Raschetta J. R. Peters** change in ground states between BaF} and SrClj has been observed for the rare-earth analog of Es1* (Ho2* The development of a solution microcalorimetcr with a 4/" electronic configuration), a corresponding facility that is suited to he special needs of experi effect is not necessarily expected for Es1* in view of the mentation with transuranium elements and compounds known importance of intermediate-coupling effects in has proceeded during this past year to the point where the actinide series. The observation of such a cor we now have a working instrument. Our design goals respondence provides an additional example of the continue to be to have a calorimeter that will achieve increasing "rare-eanh-likc" behavior of the actinides 0.1% precision with submiiligram quantities of samples. with increasing atomic number. To date, the operating characteristics of the calori meter have been determined only for the system in a preliminary configuration, which includes a tantalum cup with a gold-plated brass lid. Using the NBS standard 1. Ecole Poly technique Federate dc Lausanne, l-aboraioire de certification material Tm (tris(hydroxymethyl)amino- Phywque Experimental. CH 1007 Lausanne. Switzerland. 2. Advanced Technolory Center. P O Box 6144. Dallas.Tex meihane| in the exothermic reaction with HCI. an 3. Metal* and Ceramic* Division. average {N - 6) reaction heat was de'ermined to be 4. Solid State Division. 245.53 t 1.45 J/g. This should be compared with the 43 accepted >fiS » aaajaras lu fcaWe N T«o dimaaamau of aat km -f »«awna «f •e* dar semce brats aoueaary to cam oat a aade dun— atrial • 9 Jf HTi > O005 JV Na-SaF. baac •afATfltW VJW 47«a9Ca«vCaaKaBaajV^B> ataVar •fBCaTUaaa aaaaaa«Ta^» a9aa aTaaaavv vaided "5?.JS aad ?I3 25 U a»*V- as >w|«< tvars of saaaats, aadaaaaa; amfcea safes, aad bas be** aa* dar 25-year->44 banana* calac of ?S? U aaak * •ard im baac r^aaw i. -W several wstfv A aanuoe I* OUWXM mfe J Fanw* aad L PL *W» ~ aw* a fowMac am arralcaaaa of Bar pauead* accepted far KF-HF band aad HF naxr bs beo iroaard. ?57Uw4e«atae Kaaa^BBak^BBafaa' ^aaaal aaaattal dSjBaMaBBBCaaC^Bt*7 II & •"aBBBBBaaWaf aV^lh Saajt nV ins aad daarnaa cipcraarats sirtc per- a Trilai aiadnid a>rr iatn.tmdc asaaabK MC ama; fanned, rite . dm—t7cr has bom a»ahfird « order Co oai eaxMndMUcal saalan waaai dar fieaaue. aa to Moeane a* lehahdHy aad wmwrt Another sens cl n.aanijtanu of aaarwuaafceh 2»/C Tbrteraacc ba s Tns •eacuua beat tin—mwi nmi aV taataaaa Al-O, ataafoav «BKJI laauait that, aaaf oar aeady acquired laagsica icatti. an aurnabh pkg. abaJi coaiaan a porous Tcfloa fdo* •racOnn beats as sanal as 20 meal should be swiftcmi separator. Srddil AI2Os aawluas arc located at MT aieasurcaKats t» 01% pteceana. A reactioa beat of opposite cads of tar wortuaj coatpartnKat. Swce no this maoMfudc wuald correspond to 30 tag of an orda: Toltamcf nc snaaes ba«e been earned out on die actaudc metal with a heat of suhiiioa of 62* kj mole KF-HF soheat »ste*V- it has been necessarv i«> dunc- len/e die ebrvtrncaeniecat befcannr 2 4 2 platinum electrode, we have observed a nonreversible J. P Young C. Musikas cathodic wave that is seer on the return scan from the R L. Fellows' J. R. Peterson* anodic limn at platinum. The magnitude i>f this wave The hxkground and experimental approach of this appears lo be a function of exposure of the solvent project have been discussed previously.* Currently, we medium to water. The wave cannot be the direct result are reevaluating hydroxide melts as solvents for hign of any ca'hodic process involving an oxide species: but. oxidation states of the actinides. It is believed that rather, it may be the result of an insoluble oxidi/ed solubility can be improved if the solvent consists of the platinum product, involving oxide, which is subse heavier alkali hydroxides. quently rcd'iced. A 3-ft glove b.>x has been modified for use with a We have not been able to use a glassy carbon electrode Cary spectrophotometer, model I4H. An appendage on in molten KF-HF. Il appears to be insulated from the 44 mdt. Attempts have been made to improve the electri potential plutonium spills and dispersion in the environ cal junction of the glassy carbon with the metal ment. Development of an analytical technique that electrical lead-in by the appikation of silver paint, but would be sensitive both to very low concentrations and the problem is still present. Amorphous carbon eiec- to different oxidation states of plutonium would thus tiodes do not appear to be insulated in the melt. be most welcome. Fluorescence techniques are known Although graphite electrodes seem stable to fluorine to fulfill these criteria, so a preliminary study of evolution by voltammetry, they were decomposed to plutonium fluorescence in aqueous solutions was initi powder in the presence of C1F3, which we have used in ated. the purification of some KF-HF salt samples prior to There are only two reports of plutonium fluorescence mei:ing. There is some indication that copper electrodes in the literature, both dealing with Pu-doped crys become blocked when used anodkally. but the mecha tals.5' These reports indicated that iluorescence of nism is not understood at present. Pu3* anu Pu4* was observed in the near infrared (1.78 Spectrally. KF-HF melts seem ideally suited as a to 1.98 u) and that Pu3* fluorescence was observed in transparent solvent from 220 to 1900 nm. It was the visible region (500 to 600 nm). observed, however, in the experiment in which graphite All fluorescence data were obtained with an Aminco- was destroyed by CIF}. that the subsequent melt Bowman spectrophotofluorometer (No. 4-8202). using became orjjque it 1380 nm. This absorption may be a xenon lamp for excitation between 200 and 800 nm. caused by some product that is formed by the reaction Instrument sensitivity was established using a TTA of CIFj with the solvent salt, graphite, or other complex of eutopium(lll). whose fluorescence was unknown reactant. The electrochemical and spectral detected at concentrations down to I0"1' M. behavior of the solvent system now seems to be A stock solution of Pu** was prepared from sufficiently understood that meaningful studies can be I4,Pu0i. Portions of this Pu**-HN0j solution were ui dertaken with lanthanide-actinide solute species treated chemically to produce aqueous solutions in which plutonium existed as Pu3*. Pu**. Pu5*. and Pu7*. Acidic solutions of Pu3*. Pu4*. Pu5*. and Pu** and 1 1. Supported in part by ERDA conln.i AT-(40-! M447 with basic solutions of Pu** and Pu * exhibited no detectable the University of Tennessee. KnoxviDc- fluorescence at room temperature in the 200- to800-nm 2. Analytical Chemistry Division. wavelength region. Instrumental requirements have lim 3. Postdoctoral research associate. University of Tennessee. ited the studies to this wavelength region. However. KnoxviDe. TTA solutions of Pu** were found to fluoresce in 4. Visiting scientist from Centre deludes Nucieaires de Fontenay-aux-Roses, France. tensely in the vicinity of 550 nm. Further investigation 5. Consultant, Department of Chemistry. University of Ten has indicated that the fluorescence is due to the nessee, Knoxville. oxidized form of TTA and not :o Pu**. The possible 6. Chem. Drr Annu. Prog Hep. May 20. 1974. ORNL4976. analytical usefulness of the relation between the TTA p. 55. fluorescence and the quantity of Pu** initially present in solution is being considered. 4.1 "* SEARCH FOR PLUTONIUM FLUORESCENCE1 M. A. Lyster2 R. L. Fellows3 J. P. Young4 t. Supported in part by KRDA contract AT-(40-IH447 with the University »f Tennessee. Knoxville. One of the most important properties that must be 1. Albion College senior: participant in the Great Lakes determined in order to predict actiniae behavior is the College* Association Oak Ridge Science Semester, fall 1974. oxidation state of tne elemental ion in various com 3. Postdoctoral research associate. University of Tennessee. pounds. Compared with the lanthanides. the actinides Knoxville. demonstrate much greater variability of their oxidation 4. Analytical Chemistry Division. state; A fundamental question of current importance is 5. B. B. Cunningham, D. M. Gruen. J. (i. Conway, and R. D. McLaughlin./ Chem. Phyt 24. 1275 (1956). the behavior of plutonium in very dilute solutions 6. R. McLaughlin, R. White. N. Edeistein. and J. G.Conway. (about 10"' M). This question is of concern because or / Chem. Phyt 48. 967 M96«). 5. Environmental Chemistry SI TRANSIENTS IN FREON-OXYGEKOZONE the flash, followed by a first-order loss with tlf2 % 200 SYSTEMS: REACTION OF ATOMS WITH CF2 CI j absorber (O3). since the 03 dissociated by the flash is rapidl re-formed as the 0f'£>) atoms . re deactivated C.J.Hochanadel by Oj and the Of*/) atoms then combine with O?. The Reaction* in this system are of considerable current added Freon competes for the Of'/)) atoms and causes interest in upper-atmosphere chemistry. The protective a net loss of O3 (the rapid loss shown in Fig. S.I). A plot of [0,|/A[Oj| vs (0,]/ICF Cl l. which is ozone layer, normally at a steady-state concentration, 2 2 could be depleted by reaction of a species (such as NO indicated by the kinetic equation, gave a straight line with a ratio of slope to intercept of Jt{0 + from the supersonic transport or an atomic bomb 2 0CD)}[k[CF Cl +0C/))} = 0.13. Taking *{0 • explosion, or CI or Br from photolysis of Freon or 2 t 2 OCDi}=4.4$ X 10'° M-' sec'1 (ref. 1). *{CF,G + other halocarbon) sither directly with O3 or with 2 l Of'D) atoms (which are normally produced by solar Of 'D)} = 3.4 X 10 * M*' sec"'. Measurements were photolysis of O3). thereby pi eventing re-formation of maoV for three different ozone concentrations at i0 i/[FreonJ n'.ios ranging from 05 to 40. Reaction Oj. We have reported previously on extensive studie* of 2 of Of D) with CF CI produces CF C1 and ao. The sensitization snd inhibition of ozone formation both in 2 2 2 pulse radiolysis and in flash photolysis. The reaction of GO is known to absotb in the same region as O3. bur it was shown that CF2G does not. The ^[03J values Of'ZJ) atoms with CF2G2 has now been studied by were obtained from the measured change in optical flash-photolyzinc 03 in the presence of 02 and CFJCIJ A typical oscillogram in Fig. S.I shows loss of density and the known extinction coefficients for O3 absorption occurring on two different time scales and CIO at 2480 A. The pseudo-first-order decay shown in Fig. S.I was assumed to be due to reaction of CFC1 during the early part of the reaction. There is instanta 2 neous loss of absorption, whkh occurs mostly during with Oj; the second-order rate constant was 4.6 X 10* M~' sec'1. The known rate constant for reaction of GO with O3 (ref. 2) indicates that it is too slow to account for this decay. Reactions on a longer time scale 0»NL - 0*C. 75 - 400S become very complex and involve several GO, species and many elementary reactions in the overall mecha nism. Under steady photolysis by the analytical lamp, for example, the absorption at 2480 A (initially only by z o 27 — O3) decays by a chain reaction in about 1S sec (with no m Freon present the decay of O3 in this time is * o negligible). Even though the overall h,vchanisni in this IO Jo ze system is very complex, these preliminary measure 5X merits indicate that the initial stages are sufficiently simple to allow relatively direct evaluation of two es— important rate constants. The reaction of CFJCIJ with 1 Of /)) atoms is fast, the reaction of CF2CI radicals with O3 is somewhat slower than the analogous reaction of 200 mtcro»tcand» G atoms with 03. Fig. S.I. Typical osaflogram showing a decrease i DOH on flash photolysis of Oj in the pnsmce of CF3CI3 and O3. The instantaneous decrease is caused by reaction of CF2CI2 1. Review by R. J. Cvetanovk. Can J. Chem. 52, I4S2 with Of *0) atoms, and che longer, first-order, decrease is caused fl974> by reaction of the CF2CI radical with O3. 2. R T. Watson. N.B.S. report NBS IR 74-516. June 1974. 45 46 5.2 A UrWTK MODEL FOR PREDICTING place. Eventually the model will be incorporated into a THE COMPOSITION OF CHLORINATED WATER large unified transport program. DISCHARGED FROM POWER PLANT In addition to developing the kinetic program we will COOLING SYSTEMS modify an existing program for calculating the equilib rium concentrations of species present in chlorinated M. H. Uetzke water. As additional reactions are added to the kinetic model. the> will also be incorporated into the equilib Chlorine is commonly added to cooling water at rium program. In this way we will be able to assess at power stations to prevent slime formation in the any time the extent to which the kinetic model has cooling towers. Depending on the source, natural water approached equilibrium conditions. used for such cooling purposes contains a variety of impurities, both organic and inorganic. In addition to bacteria, algae, spores, and viruses, there will usually be traces of organic amines, other organic compounds, S3 CHEMISTRY OF SULFUR IN 1 ammonia (or ammonium ion), traces of heavy metals, THE ATMOSPHERE and various anions. Chlorine added to this water is C. F. Baes. Jr. J. T. Holdeman2 rapidly hydrolyzed to yield equimolar quantities of W.M.Culkowski1 hypochlorous acid and hydrochloric acid. The hypo- chlorous acid dissociates into hydrogen ions and Industrially produced sulfur enters the atmosphere in hypochlorite ions, the extent of dissociation being a reactive forms, primarily SOj and SO), that should not be function of both pH and temperature. Both the treated as inert pollutants for purposes of modeling. hypochlorous acid and the hypochlorite ion are power Since June of 1974 an effort has been under way to ful chlorinating agents. They will react rapidly, for describe the equilibrium and kinetic aspects of sulfur example, *r.t'.i ammonia or ammonium ions to produce chemistry in a form suitable for inclusion in the chloramines and with organic amines to produce transport model (ATM) being developed at ORNL.* ^chlorinated amines. The rates of these reactions are At the usual low m^cntrations of S02 in the abo functions of both pH and temperature. The treated atmosphere (typically 10'* atin). it reacts with water cooling water containing the chloramines and unreacted only if condensed water already is present, producing chlorine is eventually returned to the biosphere. the dissolved species H*. SOj(aq). HSO,*. and SO,2-. Although the toxic nature of chloramines has long In contrast. SOj reacts vigorously and completely with been recognized, it has only been within the last few either gaseous or liquid water to produce acid droplets 2 years that national attention has been focused on the containing the additional species HS04" and S04 '. problem. For example, a massive fish kill in the cooling These droplets can be partially or completely neutral waters of a large generating station on the shore of ized by atmospheric NH}. the end product being solid Saginaw Bay has been attributed to a lethal concentra particles of (NH,)iSO« or. if the relative humidity tion of residual chlorine in the water, whether the exceeds about 80%, droplets of ammonium sulfate. chloramines or other chlorinated compounds will have a A computer program has been written which - given long-term toxic effect on man is at present unknown. In the toul concentrations of SflV), SfVI), NH,. and any event it is now necessary to take cognizance of this COj. along with the relative humidity and the tempera problem in assessing the impact of power-generating ture - calculates the amount and composition of stations on the environment. aerosol and the equilibrium partial pressures of the We are in the process of developing a kinetic model gases. Such a detailed calculation is made possible by for predicting the composition of chlorinated water the availability of accurate thermodynamic data5 for all discharged from power plant cooling systems. As a the species involved. The calculation also includes start, this model will contain two rate equations: one estimates of the activity coefficients of the aqueous for the reaction of hypochlorous acid with ammonia ions* needed to correct for the nonideal behavior of the and the other for the reaction of hypochlorous acid solutions involved and to estimate the aqueous vapor with an organic amine. The two simultaneous differen pressure. tial equations will be solved numerically to give the The program next calculated the rate of oxidation of composition of the water as a function of time. Other S(IV) to SfVI) in the atmosphere, which can occur by rate equations will later be added to the model to several mechanisms. Recently. Castleman et al.7 and account for other reactions that are known to take Davis and Klauber* have concluded that the most rapid 47 reaction involving a gaseous oxidant is that with the OH serosa! and the partial pressure of SOj in a power plant radical: plume as a function of the distance downwind from the source. S02(g) +OH-•products. 1. Wort perfonued foe the Ecology and Analysis of Trace Coataauunts (EATO Program supported by the National Science Foandxien. This work was previously described in ORNL-NSF-EATC-11 (December 1974). pp. 22-24. With concentrations of OH radical (an intermediate in 2. Member of Computer Sciences Division. other reactions) in the range 0.1 X 10T to 6 X I07 3. Atmospheric Tuibahnu and Diffmion Laboratory molecules/cm3 (0.4 X 10"'3 to 24 X 10',J atm)* the lATDD.Oak Ridge. Tenn half time of reaction of SOj should be in the range of 4. If. T. Mnfc and M. Reeves. A MNthStmree Atmospheric Transport Model foe Deposition of Trmce Conummnmts. 16 days to 7 hr. Of the reactions that occur in solution, ORNL-NSF-EATC-2 from (I) known solatntitics of (NHahSOt in H1OH1S04.(2> known osmotic coeflicients of HjSO* and of 6.1 SPECTROPHOTOMETRIC STUDIES OF The photochemical reductions of PuOjJ" to PuO/ SOLUTIONS CONTAINING RADIOACTIVE and of Pu** to PuJ* by light (2500 to 4000 A) and MATERIALS ethanol have been observed, and respective quantum yields of 0.02 and 0.03 were determined. The photo These fundamental studies have concentrated on chemical reactions are probably similar to the well- expected problems in reactor and fuel cycle develop z known photochemical reduction of UOj *. and we have ment. Results from the studies of aqueous solutions of written the reactions as actinides. especially those containing plutonium. are important in reactor fuel preparation and processing, PuOj 2* + ethanol • light - Pu0 * waste management, and the terrestrial or environmental 2 cycles for actinides. Results from studies of the + acetaldehyde+H* (I) interactions of iodine, water, and other impurities in liquid and gaseous phases of carbon dioxide are and important in development of the KALC process1 for cleaning the off-gases from HTGR fuel reprocessing. Pu** • ethanol + light -*• Pu3* These latter studies are also applicable to the off-gas • acetaldehyde + H*. (21 cleanup for LMFBR fuel reprocessing, because the only Almost any organic compound will serve as the re difference between the two processes is that the ductant in the photochemical reduction of U0 2* and LMFBR process uses Freon rather than carbon dioxide as 3 probably of Pub,1* and Pu**. Therefore, it is likely the process medium. It is expected that the chemistry that photochemical reactions will change various plu of iodine and water in carbon dioxide should be similar tonium oxidation states in fuel recycle schemes and in to that in Freon. the environment, where there are huge amounts of organic compounds and of light. A reversible photochemical shift in the equilibrium 1. M. E. Whaitey. CalcuUtwns on the ferjormmtce of the for the disproportionation of Pu(IV), £4£CAo<- 3Pu** + 2Hj0 * 2PU** • PuOj2* • 4H*. (3) 6.1.1 Photocbemirtiy of Aqweous PhtOMMi Sototkm has Oeen observed. The equilibrium quotient for Eq (3) increased by a factor of IS when a solution was J.T.Bell HA. Friedman L.M.Toth irradiated with ultraviolet light (2500 to 4000 A) from The effects of light radiation on aqueous solutions of a 1000-W mercury arc lamp. When the lamp was turned plutonium have been examined as part of a continuing off, the dark-state equilibrium conditions were reestab program in actinide chemistry using spectroscopic lished. Changes in acidity from 0.4 to 20 N HCI04 had techniques. Although most aqueous redox .eactions of no observable effect on the magnitude of the reversible plutonium have been well characterized, there is little photoshifi in the equilibrium. information on the effects of light on the oxidation Light was observed to increase the rate and extent of states of plutonium or any of the other transuranium depotymerization of "freshly prepared" PuflV) poly elements. Aside from their fundamenul importance, mer in 0.S N HCXV A particular solution of fresh photochemical studies of aclinides are important to polymer in the dark depdymerized to 80% Pu** in 130 technologies for reprocessing nuclear fuels and for hr: a portion of the same solution was 99.9% depoly- environmental control. We have observed significant merized with four 1-hr intervals of iOumination during photochemical effects hi several aqueous plutonium an 80-hr period. The sample probably would have systems. depolymerized in 5 hr of continuous illumination. 48 49 "Aged** polymer is much more stable than "fresh** TmmmW ml I lmmm*wmmmmmfmm *«Im*4JVm*P'm*-m*m*ni amf mmmmmw> mm*tamm*Pml polyrner to reaction with acid, and the investigation is being extended to "aged" solutions of porymer. These studies are intended to include some structural studies ltUIC(*C) DqitVtf to determine the structural differences between "fresh" 29 22 and "aged" Pu(iV) porymer. The photochemical effects 25 52 have been published1 and discussed.2 19 10.0 15 143 iO 27.5 1. J T Bdl ind H. A Friedman. "Photochemical Reaction: 5 54X1 of Aqueous Plutonium Systems." / Inorg. Sud Ckrm.. m ptess. 0 (OX) 2. J. T. Bell. L. M. Totb. and H. A. Friedman. The 10 135 Photochemistry of Aqueous PratoniuM Systems," paper pte- 20 260 senled at the VIII International Conference on Photochemistry. 26 320 Edmonton. Canada. Ant. 7 13.1975. 'Defined as 6.1.2 Chenustry of Fission ftod»cts / specific absoibance of liquid \ , p, Dq*l )( — in Carbon Dioxide \ specific absorbance of vapor '\u] J. T. Bell S R.Buxton' mole fraction in liquid D.W. Fuller L.lf.Toth H. A. Friedman mole fraction in vapor Previous studies1*3 of the chemistry of some fission where products in liquid and gaseous carbon dioxide have l2 absotbance at 520 nm indicated that molecular iodine is not stable in carbon specific absorbance * dioxide, that water is associated with carbon dioxide in path length the vapor, and that water decreases the stability of and iodine in carbon dioxide solutions. These observations are important to the cleanup of the off-gas from HTGR p = density of CO2- fuel processing because of corrosion effects and the likely entrapment of iodine and tritium in the KALC not indicate such products and suggest, therefore, that process.4 the previous investigation was obscured by impurity We have shown that solutions of iodine in liquid reactions. We have observed corrosion of the type 304 carbon dioxide are indefinitely stable in stainless steel stainless sted absorption cell when both iodine and cells as long as the system is free of water and organic water are dissolved in the carbon dioxide. The cause of materials. We have prepared these stable solutions in the the corrosion is being investigated further. laboratory and have measured distribution coefficients for iodine between the carbon dioxide liquid and gas 1. ChemfcalTcduwtofy Dmsmn. phases from 26 to +30°C. These coefficients were 2. Chem. Technol Dn. Atom. frog. Rep. Mar. 31. 1974. calculated as the ratio of mole fractions, and they 0RNI.4966. p. 49. indicate that the lower temperatures favor iodine in the 3. R L. Haffman. "Moiecubr Interactions m Liquid Phase liquid phase (Table 6.1). Systems." Ph.D. dissertation. Memphis Slate Unn-ersny. August Association of water and carbon dioxide in the vapor 1974. 2 4. M. E. Whallcy. Cskulariom on the fierftrmmce of the phase has been suggested based on correlations of an KAlcrrocestO*m.4lS<*m*y 1973). absorption band at 18.800 A with changes in the carbon dioxide pressure. This analysis has been revised after showing that the observed 18.800-A band consists of 6 2 MAOtOPOROUS SOMES FILLED WITH two partially resolved bands, a water band and a carbon OXIDES AND SULFIDES AS ADSORBENTS* dioxide band. 3 F Nelson J S Gilbert K.A.Kraus Previous investigators* have suggested the formation of low-boiling products from reactions of iodine with We showed many years ago that certain hydrous carbon dioxide. Our results with dry carbon dioxide did oxides and insoluble sulfides have excellent and highly so selective ion exchange and general adsorption proper carbon, thus, surprisingly, is only partially available for ties. Although these characteristics have been confirmed adsorption and exchange in times typical for arnfl-scale amply in many laboratories, application of these mate- column operations. It is not clear why part of the zinc riab for practical processes has not been commensurate sulfide shows less favorable kinetics. Nevertheless, the with their promise and uniqueness. One of the reasons practical capacities which are attainable by the tech for the slowness in their commercial use may be the nique are similar to those one normally expects for difficulties encountered in preparing the materials in a organic ion exchange resins in more conventional form suitable for column operation while retaining the applications. The materials thus should be useful for a attractive kinetic properties of the mkrocrystalline variety of applications, particularity those involving materials that we normally prepare. Last year we removal of toxic transition elements from various reported that some of these difficulties might be aqueous streams. bypassed by utilizing the macroporous region of acti XAD-2 filled with ZnS showed similar characteristics, vated carbon for holding a typical hydrous oxide although it appears that its kinetic properties are (hydrous Fe2Oj). By this method, adsorbents of somewhit inferior ;o those of the filled activated reasonably high capacity and good adsorption kinetics carbons. could be prepared (they contain very finely divided hydrous oxide) while retaining the desirable hydraulic properties of the activated carbon particles. 1. Supported in pan by .he Naval Skip Research and We have continued preparation of new adsorbents Development Center. Annapolis. Md.. F »'. Lord. Technical utilizing this technique of filling activated carbons and Coordinator. extended the studies to adsorbents prepared by filling 2. Graduate student. Department of Environmental Engineer ing. Unhvnity of Tennessee. KnoxviUe the polystyrene-divinylbenzene copolymers XAD-I and XAD-2. With activated carbon (powdered activated carbon Aqua Nuchar A, Darco C-60, and granular 63 BENEF1C1AT1GNOF coconut charcoal) we have successfully prepared mate PHOTOGRAPHIC WASTES rials containing ZnS. CdS. and MnOj in addition to Fe,Oj. Most of the work with XAD-2 dealt with F. Nelson J.S. Gilbert' K A Kraus material filled with ZnS. With activated carbons, princi pal emphasis also was on ZnS-filled materials. A program was initiated, partially funded by the VS. 2 Although vaiious techniques have been employed to Navy. for exploring newer techniques for benefkiation incorporate the sulfides in these macroporous materials, of photographic wash waters. The objective of this work the most successful one at present seems to be based on is to remove contaminants from the waste and allow impregnation of the carbon with the acetates of the recycling of the water. For silver removal we examined. metals, followed by high-temperature evaporation and as part of this program, possible application of macro drying under vacuum. Conversion to the sulfide can porous bodies filled with sulfides, application of a then be easily achieved by passing gaseous H2S over macroporous quaternary amine anion exchanger, and columns of the carbons filled with acetates. With /jnc examination of a technique which combines oxidation sulfide, materials containing from I to 6 moles of ZnS of the complexing agents (thiosulfate and sulfite) with per kilogram of carbon were prepared. After washing axial filtration. Although this work is still in progress, a with water, the materials showed little tendency to lose few observations may be worthy of note at this time. (colloidal) sulfides during handling and column opera The activated carbons filled with ZnS. which showed tion. excellent adsorptive properties with dilute silver nitrate By this technique, carbons containing as much as 2.4 solutions, were less attractive when the solutions also moles of ZnS per liter of bed were prepared. In tests contained thiosulfate. There seemed to be a significant with 0.0S M Ag* solutions it was shown that $7% of decrease in uptake, and the system showed substantially the theoretical capacity was available for adsorption poorer kinetics than the thiosulfate-free system. during relatively short contact times. Effluent Ag* Adsorption of silver from dilute fixer solutions by the concentrations were usually Anion exchange, particularly of transition elements, from a variety of media has long been known to be an '0 - effective method for isolations and separations. Most of the existing techniques, however, are applicable only to concentrated electrolyte solutions. It appeared to us ^LL tOOO ISO0 that an anion exchange technique is needed by which t 2000 250C SCO dEO VOLUMES the usually toxic transition elements could be removed Fie. 6.1. Anion exchanfr of Actl) and Cdfll) m rfciowlfne. and concentrated from dilute electrolyte solutions. A Amberlite IRA-9IO(IOO-I70 mesh), room temperature, flow possibly attractive complexing agent which would be rate I to 2 cm/mm; 1.6 x 10'7 M NajSjOj 3 2 x 10~* M selective for many transition elements and which might NajSOj-3x 10 -J Mi acetic acid 52 Cadmium appears as a sharp band just ahead of silver tively !ax temperature limitations. Par! of an: interest breakthrough: the cadmium concentration, as expected, in aqueous wastes from the textile and (he krafi-pulping is very much larger than its initial concentration(C/C^ industry has derived from this characteristic. > I). For the elements mentioned, the 01 Jer of elution With textile wastes, the primary recent activity has in 2 X IO3 M S>0,:" is Zn. Cd. Cu * Ag. Hg. This been participation with the South Carolina manufac ehition order would not necessarily be the same at turers' organization and Gemson University in an different thiosulfate concentrations and ionic strengths, EPA-supported program of month-long tests at eight since the charges of the adsorbed complexes are not textile plants. The tests were carried out with our necessarily the same. mobile uni? (see Fig. 6.2). whose capabilities for A particularity attractive feature of this technique of dynamic membranes were augmented with a second removing transition elements from dilute solutions is loop for commercial membranes. Visits have been the fact that the adsorbed materials can. usually, be completed, and evaluation is under way. Filtrate pro rapidly eluted from the exchanger, permitting its reuse. duced from a wide variety of feeds has been of Most of the elements mentioned were removed ir very adequate quality for recycle, and concentrated streams, sharp bands of less than 4 c.v. with concentrated with appropriate additions to produce desired shades, ammonium nitrate - ammonia soluikms. have been reused in dyeing; a savings in chemicals, or at While application of these observations lo the re least waste disposal, can be realized by this pattern. A moval of the transition elements from thiosulfate new program, specifically directed at energy conserva solutions is obvious, we want to point out that the tion and chemical recovery by treating strrims from elements probably can abo be concentrated from waste m-plant point sources (in contrast to the jmbined streams or natural waters that originally are free of plant effluents emphasized previously), has been funded thiosulfates by adding a small amount of the complex - by EPA at Clemson. Among other advantages, this ing agent to the solutions before the anion exchange approach greatly enhances the possibilities of recovery of step. valuable chemicals. Our participation will be primarily as consultants. I. Y. Marcus. 4r« Arm. Srm/ II.6I9H957). Most recent work on pulp-mill wastes has been aimed at extending the advantages in dynamic ultrafiltration membranes mentioned in last year's report. Since fouling is perhaps the major barrier lo adoption oi 6S ADVANCED FILTRATION APPLICATIONS membrane processes, the identification of membrane Of ENERGY SIGNIFICANCE formers of low flux decline is of particular importance. R.E. Minium A.J.Shor G.E.Moore We have carried out an extended (est with one of the C. G- Westmoreland Neva Harrison W. G. Sisson1 more promising, hydrous zirconium! IV )-silicon| IV) J. S. Johnson. Jr. oxide, on a 19-tube bundle of Selas ceramic lubes with krafi bleach-plant effluent (Fig. 6.3). Limits on availa Our objective is evaluation of Water Research Pro bility precluded continual introduction of fresh feed, gram developments for use in conservation of energy but ai intervals between periods of recycle of filtrate to and in production or conversion of fuels, including the feed tank, some filtrate was discharged and made up treatment of polluted streams generated. These meth with equivalent volumes .->f ihe original shipped-in ods originated in desalination and abatement research effluent (see water recovery record). Color and total for other agencies over the past decade, and they organic carbon (TOT) removals Were good, and chloride involve filtration of substances varying from particu was rejected to only a minor extent desirable lates to dissolved sails (hyperfiltraiion or reverse os behavior for this «r>pinalion. since this ion B not mosis), the unifying (heme being movement of the wanted in the concentrate when n is sent to the sohition being filtered relative to the tillering surface. :n chemical recovery system for disposal. After fou.- dissipate concentration polarization and to retard fom- months of operation, flux was still about 45 gal' ft1 per day. A dye-waste ultrafiltration earned out during an When hot solutions are generated in industrial pro interruption reduced flux, but w*hing with a sodium cesses and must be punned before discharge, significant carbonate solution for a short time restored it. energy savings may be realized by Muring them at We mention other activities briefly. One involved temperature and recycling the hot filtrate. Dynamic preliminary hyperfiltration tests of solutions mimicking membranes are particularly attractive, because of rela coal conversion process streams. Rejections of TOC S3 PHOTO 32SO-M F» * J. WMtr Research Fragraai MoMr hyperfltratioa wmL At rajhl. operator collects filtrate from dyiuaacafly fonaed hydrous urconium(IV) oxide - polymerybtc Visitor holds saMpk of dye waste I O»*L-O«C n-ytx iLJ ,k '•Color i «ofe * •••*_. •TOC 80 <• • • »' 20B* . * Conducfivvfy i -i '*-—*"*-^-r»--«t » ^ .*_—. -_a-r, « _i i i_ f0r 55: 33010 - 1 1 1 1 . i • - • • i 1 til ±. 60 Lr*"* •• • • 4 20>r • 1 . • • • ' ti »00r -1 J 20 40 60 00 tOO 120 M0 OPERATING TIME (#n*> Ft>*J. timfiMnrtiMcf lideMMWkMKMl^wh* 2tW pa. 7 rps. pH %.$ to9.S. Arrows indicate A. dye waste tests.*, oka anta* «ndMW carbonate wash. 54 ranged around 90%. but fluxes were only about IS International Paper Company Mobile. Alabama, com gal/fr per day. Considerable progress toward practical plex. One. aimed piimarily at hypeifiltratiun of pulp outside-pressurized modules of Selas ceramic tubes washing liquors, b to be a modification of an earlier included satisfactory performance of 19-tube bundles in Water Research Program desalination pilot plant built the laboratory in the field tests with textile wastes. for the Office of Saline Water and operated at their Preliminary results with a 61-tube design (about 8 ft2 Rosweli. New Mexico, field station several years aeo. of membrane suffice pe two-bundle module) indicated The second wifl be a new ultrafiltration unit for that scale-up to this size may be feasible. In earlier evaluation of treatment of bleach-plant effluents. These work, hyperfitration with hydrous zirconium! IV) waste streams contribute a large fraction of the burdens oxide- polyacryiate membranes had produced filtrate of the kraft process on the aqueous environment. of good quality with laundry wastes:2 it now appears Work is under way here on both systems. Figure 6.4 that ultrafiltration with hydrous zirconium(IVVsili- gives an impression of the recent status of the hyper- confJV) membranes at relatively low pressure and filtration unit. Shipment of one or both to Mobile may circulation velocity may be adequate, at least with take place as early as the end of calendar 1975. and the simulated Navy shipboard wastes. It is also of interest test program is scheduled to last until spring 1977. that this waste composition seems efficacious in remov Besides our cooperative activities in the textile and ing some types of fouling from membrane surfaces. wood-pulping areas, we plan during the coming yea.' to A joint proposal from International Paper Company emphasize ultrafiltration at low pressures, in hopes of and us for pilot-plant test; on baft pulping wastes has increasing our understanding of fundamental processes been funded by EPA. Two units will be tested at the involved in dynamic membrane formation and fouling. H$.*A. 191$. 55 A practical motivation is the possibility of applications after Mean unwmj BOH of !fee •»•"•*"": I» ia£ cubvS wtuudc in removing hydrolyzcd aggregates of metal ions in front the process honor. Tho would be more than ample for a cood separation process if a way can be found to convert all of nuclear fuel processing. the cobalt to this species. Stability tests indicated that this ammjoo must take place divine the leaching step a the 1. ChemicalTechnology Pmsmn carbonato complexes once formed are difficult to convert to 2. R. E. Maun. J. S Johnson. Jr.. w. M. Schoficld. and the bexammme form. 0. K. Todd. "HyprrfdtraUuu of Laundry Wastes," Water J)A The tests abu indicated that nickel sorption by the Donex SO S.92I H974). resm B a strong function of pH. whereas sorption of the cobalt complexes b esseniialy independent of pH over a ra:her wide range, extending from ~pH It to 20. This phenomenon offers another potential method of separating these metal ions 64 HIGfi-RESOLUTrON SEPARATIONS1 F.J Hurst Major emphasis has now shifted to the separation of zirconium from hafnium. Initial studies have been in The use of ion exchange resins of very small panicle the sulfate system since the rt-nor constituent (haf size and high column pressures (termed "pressurized ion nium) in sulfate feed solutions is more strongly sorbed exchange") has been shown to have a number of by cation exchange resins. Two highly sensitive systems important advantages over conventional ion exchange in have been developed to continuously monitor tire some applications. It has been applied successfully in column effluent, one utilizes the colorimetric reagent analyzing body fluids, separating actinides, and puruy- arsenazo HI. and the other makes use of the fluori- ing 2,,U We have initiated studies to determine if metric reagent morin. exploitation of the unknie advantages of pressurized ion exchange might greatly broaden acceptance of ior. exchange m metal separations and other separations 1. Chem. U.+moi Da. Amm trot- Xep Mm. 31. 1974. processes. Initial consideration has been given to diffi 0RNL49*6. p. 27 cult hydrumetallurgicai separations such as the separa 2. F. J Hurst "Separation ri Co&J'. From Nickd in tion of nickel from cobalt, zirconium from hafnium, Ammonia-Ammonium Carbonzte Solution* Using Pressurized Ion Exchange." Hrdromrnlh^t* (in press). and niobium from tantalum. A paper2 describing the results of investigations on the separation of nickd from cobalt has been submitted 6.7 Nt^ SEPARATIONS AGENTS to the international journal HydrvmetaUvfy. The abstract follows: W. D. Arnold Hifh-resoraiion pressurued wo exchange has been wed OctvSphenylphosphoric acid (OPPA) is a com- *ucce*sf;Jly lo study and «crarate the varrm cobalt and nickel merceily available' mixture of mono- and diester acids cmnptexe* present in commercial ammonia ammonium car •Mi neutral impurities. It is the reagent of choice in a bonate solutions produced by ibe Caron prove** The teed process for recovering uranium from phosphoric arid3 honor used for most of the test* wa* nblamed from a user of , the commercial procrn. the sonitiofl had iprl«f 9.7 and »-a- and has shown potential for other appiications. We are about I 3 V m carbonate ttinp chromatographic clulinr. from tnumining this reagent with regard to separating and Dnwex 50W-XS115 25 nncroni ream with anHnonmm raAonare identifying the components of the commercial mixture soiutma*. three co>' alt specie* were separated from a 0.15 M diOPPA. the sotubdity loss of mono-OPPA at from I M HNO,. water, or | M Na:CO, were slightly an aqueous-to-orgaroc phase ratio of 1000/1 was 37 slower with I M THP in n-dodecane than with IM TBP mg/luer to "pure" 6 M H,P04. 19 mg liter to in n-dodecane. wet-process green acid (5.8 M H,P04).and 15 mg/liter to wet-process brown acid 16.1M H,P04 > There was no measurable loss of di-OPPA to the phosphoric acid I MoM Chrmwl Co. TO Box 26*83. R**ioo«d. Va solutions. The solubility of mono-OPPA in water at a 232*1 1/1 phase ratio was 4600 mgy liter, with no measurable 1 f. I H«rw ami D I Ctomc.fmi titf Ctum Ptnt Drvgn Drwftop 13.2S6 (My 19741 di-OPPA sohibility. In process use. a source of purified 3 Chrm TccMmtl Dtw Annu rYt>t Rep Mtr 31. !9?J. mono-OPPA would be needed to replace that lost t'-> ORNL4U3. p 5S aqueous solutions. * T H. SaMa* HI. Trulfcyl t*o*pluir% jnd DoAylpit.^ The relatively high distribution of tnbuty! phosphate phonic* M l'nmwn J*d Thncusi F.xlttctmi." ltd *'»jt to the aqueous phase is a disadvantage to its we for Ckem 51.4111959) processing radioactive feeds. The TBP dissolved in the 5 I. G Mnnfr. I.MFBR Fori Crdr SlmJirs Pmpett Report for Arm 1970. So 14. 0*NL TM 2*9*. p 17 aqueous phase undergoes chemical and radiolytic degra 6 WCMO«CIKIHK.II. Boty-WjrtrrC 7.1 DECAY PROKRTIES AND L X-RAY activity faced art SH Au) surface-barrier alpha and fission IDENTIFICATION OF ELEMENT "* 105 detector and r. «s viewed through the tape by an intrinsic germanium photon detector. P. F. Dinner R J Suva We measured the energies of the emitted alpha C. E- Bemts. Jr. R. L. Hahn 1 particles, fission fragmen a. and photons and deter DCHensJey JR. Tarrant mined the time from the end of irradiation associated L D Hunt with any individual even: and or the time between two As part of our continuing study of the identification events (such as alpha x-ray). During about 200.000 and properties of transfermium elements, we carried irradiation-counting cycles, we observed S50 alpha out an experiment to identify, by observation of events grouped into three peaks at 9.041. 9.074. and characteristic x rays, the atomic number of the pre 9.120 MeV. with relative intensities of 0.53. 0.28. and viously reported2 isotope :*°I05. We produced 0.19 respectively (see Fig. 7.1). and a halHife of 1.52 • I4*I05 in the :4*Cf("N.4n> reaction using 99-MeV 0.13 sec. which we ascribe to the decay ot 2** 105. In ,SN**" ions accelerated in the Oak Ridge Isochronous coincidence with these alpha events we saw about 150 Cyclotron (ORIC). After an energy loss of about 14 L x-ray events whose energies and relative intensities are MeV in the beryllium target-chamber window and in excellent agreement with the calculated values4-4 target backing, the ,5N ions iwJ an energy optimized (see Fig. 7.2) for the L x rays of lawrencium (Z - 103). for this reaction. The reaction products recoiling out of In order to establish a genetic linkage between the die }4*Cf target were transferred to our counting 3*°I05 and its daughter 25*Lr. whenever an alpha station via our new tape transfer system."1 The tape was event having an energy between 9.0 and 9.2 MeV advanced about every 3 sec so That the spot of collected occurred, the tape was stopped and the same spot was c»v ;»i "5 «oc» ALPHA ENERGY (M«V) TO 7 5 8 0 «S 9.0 tO.OOO *0J»_'***F m «• N I86 0M»V) ;*«• v*. (OIS-VSMC) «., "AT «ooo=- ""* mm- Tv* "•Hi; ««« *«- "-I04 s V f» 100 r- z o •°r 4000 «soc 5000 5100 CMIHHI^ Miitmn FIJ. 7.1. Atrka lyrcliww of actmfip praiu^ti mtitt1 CI* M mclioa at MO MeV. 57 58 viewed V the SKAu) detector for 35 sec in order to 1. Physics Dwiaoo. observe ih: alpha decay of the daughter. The spectrum 2. A- Ghiu-so. M. Nunno. K. Eskola. J. Harris, and f. Eskola. for this " xtended mode" corresponds in the energies Pkys. Rex. Lett. 24.1498 (1970). and the itf uive intensities of the alpha groups and in 3. Sec Sect. 7.4 of ch» report. half-life (».• Fig. 7.3) to the known properties7"1 of 4. C. C. Lu. F. B. Malik, and T. A. Carbon. Sud Phn. 2S*Lr. Thu vve have identified the atomic number of A 175.289 < 1971 >. -fc0105 on ;>-.; basis of the coincident L x-ray spec 5. J. H. Scofietd. Lawrence Lhennore Laboratory. Univ. of Cakf. report UCRL-51231 <1972K trum, and its i its number from the genetic linkage to 6. T. A. Carbon, private ootnmnqication of calcinated L x-ray 25 the *Lrdaugh:, ntcnsitKS. November 1974. 7. K. Eskofa. P. Eskola. M. Huron, and A. Chiono. fhrs. Her. C 4.632 (1971). 8. r. F. Dinner. C. E. Bonis. Jr.. R. I. Siva. R. L. Hahn. and OMNL-MG 75-«I«3 D. C. Henley, to be pobbsbed. ENERGY U*V> 15 30 25 35 7.2 X-RAY IDENTIFICATION AND DECAY ! ! L X-RAYS IZ-I03) -t PROFERTIFS OF ISOTOPES OF LAWRENCIUM C0INO0ENT «lTH ! « 20 - ALPHA EVENTS OF H C E. Bemis. Jr. D C HensJey' 2«°105 P. F. Dinner R L. Hahn ras I R.J.Sitva J.R.Tarrant L. D. Hunt II During the course of our experiment to identify element 105.2 and in a separate experiment where we bombarded a 24*Cf target with " B and then with '°B. we produced several isotopes of lawrencium. The • \m • ••» "I isotopes I$,Lr 2nd 2S7Lr were produced by the E -•• H 2*'Cf(,sNftjr/i) reaction, where x = 2 and 3 respec as tively. The same equipment as described in the 26° 105 J 1 200 300 400 500 article allowed us to determine the half-life, energies, CHANNEL NUMBER .aid relative intensities of the alpha groups of 2 s * Lr and 2 Fig. 7.2. L x-ray saectram in coincidence with alpha cmls *'' Lr (see Table 7.1). In addition, about 600 /.-series x hiring 9.0 ORNL-OWC, 75-4006 ALPHA ENERGY (MeV) 40 a00 8.20 8.40 8.60 8.80 g " i—|—i—r~7 'tu2* 23.6 ±75 sec £.»a27-a56MeV 4800 5000 5200 0 10 20 30 40 CHANNEL NUMBER TIME DIFFERENCE (sec) Fig. 7.3. Alpha spectrum and decay data of "extended mode." 59 Table 7.1. ExacMMMMesaMsoffc m ""-" "**"«=»'>m2S5guom»aS « Hatf-ife Alpha-part ide canty botope <«*> «>leV) r*) TkBWMk Rcf.3 This work Kef. 3 Taswoft Ref.3 J5*l 21J t 5.0 22tS S.429 t OJOU OJ02 401 10 -50 $.370 t CLOU 1.35! 0u02 Mt 10 -50 "•• 25.9 i 1.7 31 *3 U24tO025 M4*t0iT 2 4.2 t 1.1 3i2 1517*0015 •V52 tO02 19.1 2 IS 1913 *j»72 i 04)15 &4S tO02 13.3 11J 13 t 3 8-430 t O0I5 M3 t0u02 3t-3t2.9 34 t4 S-390±0i>l$ »J9 tOJtt IU>U 23t5 •JI«tO015 $J2 ±0J>2 «J±1.5 »'-2 I$7, OtM« -• OJT25 0u6 t l Utl 0J0I2 M7 tarn SS*4 SI t2 S-7% O0I3 Ml ttun 15 ± 4 191 2 4.3S tO» 4.2 t OM «-64« t OOIO •uM t 75-* identical with our earlier work on die x-ray identifica x-Mr ENEftGr (a*) tion of nobebum.1 The half-lives and aiyiu 3^rry K> 20 25 30 35 2S, no properties of *Lr and Lx are shown in TaMe 7.1. L X-«*rS IZ»tO«> Our results are in excellent agreement with previous CDMCCENT WITH 4 50 - *ITH VPM* EVENTS measurements and, in some cases, of higher precision. OF *5*L/ Further, the x-ray identification of ,5,Lr is the first unequivocal confirmation of the atomic number of lawrencium; earlier genetic linkage experiments are u fraught with uncertainty because the mendekvUim *> fO daughters either are not well characterized or do not a If undergo alpha decay. *> 5 !. Physics Division. 5 2 2. See Sect. 7.1 of this report. 3. P. F. Diiner. C. E. Bonis, Jr.. D. C. Hcasky. R. J. Siva, and C. D. Goodman, fhys. Rew. Lett. 2*. 1037 (1971). «• • ••>- 4. K. Esfcoia. P. Eskoia. M. Norma, and A. Ghiorso. Phys. Rew.C4.632 (1971). 0.5 400 200 300 400 500 CHANNEL NUMBER 7 J SYNTHESIS AND ATTEMPTED X-RAY Fhj. 7.4. Prompt photon spectiMi cxMacidfnt wftfi alpha IDENTIFICATION OF ELEMENT 106 USING THE 3 amps aanjaed to Die Jecay of ls*Lr. The unique energy ISOTOPE " 106(tef. I) signature confirms the atomic number as Z - 101; thus the alpha-decay parent is confirmed to be Z - 103. C. E. Bemis. Jr. R. L. Hahn P. F. Dinner 0. L. Keller D.CHensky* JR. Tarrant dence with the alpha events of "*Lr (see Fig. 7.4). L. D. Hunt thus identifying the atomic number of l^wrencium as 103. The nuclide "3 106 was predicted* to be one of the In another experiment. ,5*Lr and 2,5Lr were pro most favorable candidates for the production and study duced via the a*»CfV 'B.4») and J4,CrV0B.4/i) reac of element 106. The partial alpha-decay half-life was tions respectively. The experimental apparatus used was estimated to be in the range 0.1 to 2.0 sec, and 60 competition via spontaneous fission branching decay Their reported alpha-particle energies, intensities, and was estimated to be less than about 25%. This nuclide half-lite for !4i I Ob are in excellent agreement wtfi our can be produced in die I4,CfT*0.4i») reaction with a values. predicted3 cross section of about 2 X I0~>4 cm:. I4J Our early attempts to produce 106 were mcon- 1. A aaf>t brief article has appealed m Mrx. Dtt. .-4ML > dusne. Recendy. using our newly developed tape hag. Rep. Dec. 31. 1974. ORNL-502S. p. 60. transport system for the rapid transport of nuclides 2- Payacs Oiiwa. produced in heavy-ion reactions* we initiated a long 3. R. D- Barton. C. t. Beau* Jr- P. F. Dntatt. E. EicMn. scries of experiments to produce **J 106 and provide C. D. Goodaaa. R. L Hah*. D. C. Hooky. O. L KcBer. M. L. Malory, aad R. I. Sava. Chern. Dim. Amu. Aor- Rep- May 20. an x-ray identification smdar to dial provided for /•7/. ORNIM70*. p. t.7. 217 2 104.' The nuclide " 106 was produced by bom 4. See Sect. 7.4 of the report. barding an isotopicany pure 635-jnj/cm2 target of 5. C. E. Bern*. Jr.. R. J. Sara. O. C Header. O. L. Keller. I4,Cf with 96-MeV '*0 tons. Reaction products Jr.. J. R. Tanaat. L. D. Hani. P. r. Dinner. R. !_ Haha. aad recoiing from die target were thcmulized in helium gas C. D. Goodaoa,/*>«. Ret. Leu. 31. 647 <1973). 4. C. D. GoodNKM. C. A. Laanaaa. D. C. Header. R. Kan. at about 1.3 atm. continualy pumped out of die aad E. W. Aadenoa. ltE£ Tram. NmL So. It. 323 H97II: dumber dirough a small orifice, and coBected on Mybr C. D. Goodana. ORNL-TM-394* (1972): D- C Headey. l£Ef tape in the transport assembly. Following a collection Trans. -V».i Set 20. 334 (1973). period of 2.0 sec. the active spot was rapidly moved to 7. A. Gkiorw cl al. l+n. Iter. Lett. 33. 1490 (1974). die detection station, and a new collection of reaction products was started. Approximately 250.000 2-sec irradiation and count 7.4 A FAST TAKTRANSfftMT ASSEMBLY ing cycles were performed for a total of 157 uA-hr FOR SHORT-UVEO HEAVY-ELEMENT (electrical; of integrated "0 beam (4.21 X I017 NUCLIDES PRODUCED AT ORK particle:). Alpha particles were detected using a surface- C. E. Bemis. Jr. J. R. Tarrant barrier detector, and the signals were processed together E. W Chandler' L D. Hunt with the time of occurrence of alpha events from the end of bombardment. Fission events occurring in this The synthesis, identification, and study of nuclides of detector were processed separately, as were alpha and die heaviest elements (Z Z 102) are severely limited fission events occurring in a second surface-barrier because production rates are often as low as about I detector located in an "off tape" position to assess the atom'hr: half-lives are extremely short, of the order of buildup of long-lived activities on the tape. Photons I sec: and these nuclides can only be produced in occurring in coincidence with events in the first heavy-ion-induced reactions with limited combinations detector were also processed, as well as die output of a of targets and projectiles. Product nuclei, recoiling out time-to-amplitude convene, that was used to record die of the target as a result of the heavy-ion reaction, are photon coincidence time (-10 joec < A/ < lOOpsec). often thermalized in helium gas and pumped through a The analog, logic, and digital signals characterizing a small orifice, from whence they are transported to a decay event (ten parameters) were processed and stored detector station, either by a small capillary tube in the using an on-line computer system.* helium gas stream or by being collected directly and Two new alpha groups (approximately 30 events) then transported mechanically to suitable detectors. were observed in the singles alpha-particle spectrum The use of a long capillary tube as a reaction-product with energies of 9.06 and 9.2S MeV. These alpha groups transport mechanism in conjunction with a helium-jet decayed with a half-lift.- of 0.74 i 0.23 sec. out system is often characterized by poor efficiency unfortunately, no photons, neither L nor K x rays, that (^50%) and long transport times and usually requires are characteristic of element 104 were observed in the addition of impurities such as sodium chloride, coincidence with these new alpha-particle groups. The carbon tetrachloride, or benzene to the helium gas. observation of characteristic dement 104 x rays hi These impurity additives can interfere with the subse coincidence with alpha particles would have been the quent detection process or be decomposed in the basis for an unequivocal identification of element 106. vicinity of the target by the intense heavy-ion beam Subsequent to the completion of our studies, a report passing through it. of the discovery of element 106 using the isotope In order to avoid these difficulties and yet provide 241106, but based on an identification method dif rapid efficient transport of these product nuclides to a ferent from ours, was published by A- Ghiorso et al.7 detection station located outside of the bombardment 61 •OCR! 3* OR!C. we hare dcrcksped ad coBstrvticU a tape trampon system. This system is niusirated sche matically m Fig. 7.5. Recoiling nuclei aie thermakzed in hdknn gas. pumped contmuaBy through a O.OI35-ro. orifice, and collected on Mylar tape. IVnodiraly. the tape is mowed to position the collection spo; between detectors located in a room at a distance of about 11 ft directly above die target assembly- Identical drive JKIHMJM. each consisting of a l-hp 3600«pm motor, an electro magnetic clutch, an electromagnetic brake, and a high-vacuum rotary feed-through are located both upstairs at the target assembly and at the detection station. A photodiode and light unit detect boles perforated at one side of rhe tape at O.lOOtn. intervals. TTL logic modules have been constructed to control die clutch and brake units and detection electronics and are programmed to move dr colection spot the required number of boles to locate the activity between die detectors. Transit time from gas jet to detectors is about 170 msec, and die positioning accuracy is ±0.150 in. A cutaway view of the system is shown in Fig 7.6. Alalia particles are detected using a specially con structed 20Omm2 silicon surface-barrier detector mat is located in the vacuum system and views the active spot with a detection efficiency of 40%. Coincident fig. 7.4. Cutaway view of the tape Unsnarl systan- photons are detected using a large-area intrinsic ger manium detector (10 cm2 area and 12 mm thick) located outside the vacuum system behind a 0.020 in beryllium window. The absolute photopeak detection efficiency is about 30% for pho'oos in die energy range 10 to 40 keV and b about 25% for photons in die transfermium Ka x-ray region (115 to 130 keV). The system has been used in studies of element 106 using the nuclide2*3106 and m die x-ray identification of element 105 with the nuclide 2**105. Reports on these studies are given elsewhere in this progress report.2 Subsequent additions to the system will include a multiple surface-barrier detector system to provide an "indirect mother-daughter" genetic linkage capability in our experiments. 1. Ffant and Equipment Dm»oo. 2. Sec Sects- 7.1 and 7.J of this report. 7.5 MEASUREMENT OF THE ELECTRON CAPTURE BRANCH OF THE DECAY OF25 * No R.J.Suva CE.Bernis.Jr. P. F. Dinner 0. C. Hensley' Fig. 73. Schematic oodme of On tape trnupwi system The granddaughter nuclide. 223-sec 2$5No. produced snowauj gsjs-fct jneiuMy tnd detector station. by the decay of the daughter nuclide "• 104 has been 62 used m the tdentmcarioa of *** 106 by its discoverers.2 us to measure the aiph? energy spectra from each Ilowevei. qualitative analysis lequiied the pustdaooa sample at a geometry of about 283. in '5S^of asubstaMiaidecay 0t3Mwh(about 50%)*u Thirty-two 10-mia bombardments were made. The efcctroa capture (EC), a mode of decay not observed in first 28 samples were counted for 40 mm each- During the iaranfkaboa experiments. We have produced dus period, al of the 2i5No and about 64% of die 2$5No m tte :**Ct,2C ..» react*- .nag ike :55 Md decay were detected- The last four samples were ' *C** beans at aa energy of 86 MeV accelerated at the counted tor about 48 hr. These laager counts enabled ORIC. After traversing a I-mi beiynw— vacuum us to measure the amount of 2,,Fm as well. From notation window and a 0.5-mi beryaMun urgrt back- these data, using an average value of 8.8 ± 0.9% for die •kg. the >3C* energy (about 73 HeV) Matched due alpha branch of IS,Hd.' we determine die EC branch maoummm in die excitation function for dus reaction. of 2 " No to be 38-6 i 2.5*. The mndjag reaction products were dvennahzed m a hehuui aoansphere and swept out of our recoil Lhunbrr and conWud on ahnuuaun catcher disks. The ahuni- 1. n^wDwam. 2. A. Cniwi. J. ML Mutate. J. R. Atoio. C. T. Afa—>. M. nuni catcher disks were periadkaty (about 10 mm) *=•».». and G. T- Scabaq> /*« **» Lett- 33. 14*0 41974 k transferred to Die laboratory via a pneumatic tube, and ..ML Firafc. I. Abaa*. It. F. tomes. R- K. SpMoa. jari a new catcher disk was positioned in the cotecuon E P. Hocomrz. Mmd fkff. A 154. 407 < l970»; T. SikkcfaNd. position. A. Gknrw. R. LKM. mi A. E- Lanfc./»nL Hex. * 14a. 277 2,5 I IMS): R. W. HofT. E. K. than. R. J. Dv*zrlu R. W. L««jttc4. In order to determine die EC branch of Ho. the •Ml J- F_ Ens. teaon l ^^B^A^A* . . n * •• • ^ •! *._ — ^ ,n— JI ^ 4aV^^ ^aV^ - - • ^* - - An identification h pm Mi by obw tying £-series x ray* *TmK\ anawail taVCaaaawOSS* lO COarabSaVflP taaasl Daw? PBaKQtam watch lotow tat appnniaatety 20K alpha tirmraiag probably involves ate Master of a brmtaamHu decay to tae 2*eniuad-baKlrotatioBalstateai1>xNo. aggregate from fat ,XC projectae to aw "*Pu Additional identification Information was abo expected nadeas.3-4 by tat observation of tat time-conelaicd dnect geaetic In oar cwW Ttudies at ORK, we have aatasured ank with dae tawn daagnter aadiar. 25INo. relative excitation fractions for the reactions **0 • Initial experiments aaag tat ,44Can"*0.4a) reac "*Pu and ,#Ne • "»Fu that lead to M*«M«Cf.Ta« tion were Muaccessnd because of poor recoil yields cross sections encountered ate comparable with dvose from tat target, aid oar major efforts were made Bsmg foaad win ' *C. Tans, we am begmmag recoi areas**- the M*C|,1C>| reaction, a less favorable traction meau widt ttt **0 team to compare w*h die recoi became the predicted cross section is only about data obtamed with ,2C and to est oar model of aae-fifta oi that for '*0 • ,44Cm. Approximately transferreactions raroVr. 200.000 bombardments usure dre tape oaamort as sembly* at bombardmcat-coaatjag-taue cycles or 1-5 1. layws Dwvwan. sec were performed. Tae predicted yield for "* 104 2. Vnowj aoewmt 6*m Ccwnc fitmla MirWwii. -jader our experiaxatal coadtanns was expected to be about oae alpha cowl per tour. V Chtm. Mr. Amm. /h» /Up. Imj2». 1974. OKNL-4974. No obviously arw alpha groups were rradCy apparent 4. •_ L Matat. r. F. DinaR. K. S. Tom. ami a L. KcSer. M>rx Hew. C la. 1M9 < 1974). m our spectntm in fat energy range 8.5 to 9.2 MeV. Tat simultaneous prodaction cf 4.83-sec "7104 from (be (,JC.4n) reaction mterfeivd with 4K L-x-ray 74 MEASUREMENT Of LffETMES OF STATES identification, and no definitive information coma be IN A DECOUPLED BAND M ***Vb derived from the time-correlated genetic bak aspect of E. Eicbkr U L. Riedingtr2 our experiments. ObrioasV. better experiments can be P P Hubert' RJStnrm1 I44 performed uswg the Cmt'*0.4«) reaction as we N. R Johnson M. W. Geklry4 original/ had planned- No interference from " 7104 is expected using this latter reaction. Our studies* of decoupled bands m odd-mas '*5Yb hare lent strong support to die rotation-anfament (decoupling) model of Stephens et al* These results 1. fttJPMLS DWUMMC 2. Gw N. Fkro*. p. 459 m wot. 2 of ftot (71. -v» «n>i tu*wgy • . w Theory Wok Rottnoa 'V-'V »M «7-» 1.40 : 0.I3 013 I.Jt 32Z2 lO-Jtl-O 1.4* t 0.14 1-17 1-29 *v-*'fc-1^v* 429.2 4? i 0-94 • 043 1-21 IOt '**Yb bieomes agree well with results obtained re The tact that there was roughly a constant and cently by BJchev et J.* and with the rotational model. unidirectional difference of about 10% between these experimental and the theoretical B\E1) values was a poini tfsoitKcoaorm to ITS. It isvery difficult to inngine l. NATO F that the rotational model tans for the tow-spin members of this rotational band. Perhaps this difference between experiment and theory suggests the posribihty of systematic errors in our measurements or m the analysis 4. Oak of the data. However, we cm find no evidence for this Uuwcvscy of Tts conchrrion. The possibility that the theoretical values DWMM. Lwracc ftulifcj liunu:mv. 5. L U Killeri. C. I. SnMk. P- H. Stcboa. E. Ekakr. with which we compared the experimental numbers are C. ft. Hajramm. 0. C Homer. N. IL Jghmaa. It. L. Rttiaso*. in error aba seems rather remote since the B{£2:2-*0) aad R. O- Sqrcr.An *«». £rrt 33,134*(1974) •awe used m our calculations was measured by Bemis et 6. F. S. SMftm, «- H- luwanai aai S. G. Nam*. Mn al.* to 1% accuracy and was later reproduced in £m.«4«.429(l973)i experiments by Baktash and Saladm* to the same 7. See Chtm. Dm. Amm. Ai*. Rep. Mrr 20 1974. OftNL- 497*.»». IS-2*. accuracy. ft. ft. ftodKv. ft. KJm*imiij. S. A. Kjnmnii. T. In an effort to gain further insight into these states KmmVna. E. Niagrnv, ana V. G. SMAMM. JINft report and to gain information on still higher members of the tS3I.».7.Daaaa 1 .Mr 7-3. ruMJBtf2) natal '1* *UT2> Tnnsttua TtpiP*t>& E*pcnaaM*-*tr*»xl EifaiMAlMqt t-* 6 24.2 tl. 7 2.93 ±0-20 0.97 ±0-07 10-» 8 io.; s o.7 2J7±0.2I 092±OJ07 12-MO 5 64 ±040 2.99 ±0.24 0.94 £a« lA-r',2 335 ±0.26 3.01 ±0 24 094±0JM 16 — 14 2.20 ±0.33 3 13 ±044 0*7 ±015 *A«n3(tIJOJM fruaiifl *T*c wws saed « <-*b fBihr •dc of the rirtinwK lbisawn attenuation of the angular distribution of pans rays absomtc vane, b emitted in flight as a result of strong byperfme fiehb- reasonably strong nwramr that the For further detais on both the experimental apparatus deviations between the results of our expen- used in these measurements and the considerations that menu4 and theory were go into the data analysis, see refs. 7-9. 2>2Th. indeed, behaves as a good rotor through Addrtionai measurements on the lifetimes of high- 16*. This study represents the most thorough test spin states in * ,JTh have been node by the method of applied to high-spin rotational states to date. Doppler-broadened bne shapes (DBLS). As was done for the RD measurements, the DBLS experiments were 1. Oak Ridgr Aaocatcd Lwncraoes Graduate FeBow from done both in the singles mode and in coincidence with ilie Uiiiwiuiy of TcMcwce;pnemu address: Pindar ChnunoT J DmsftM. Lawrence Berikeky Laboratory. Uamrnry of CahV the scattered projectile.' *Xe. forao. Berkeley. CahY. This method depends on the broadening of the 2. Max Kade Fooodatioo Fclow. Unmiwry of Marbarc. gamma-ray line shape, which occurs as a result of the Geranay. Doppkr shifts of the energies of the gamma rays that 3. Laarcacx Btiktky Laboratory. Uaitiury of Cjfcfonaa. are emitted before the recoiling 1J1Th ions come to Berkeley. Calif. rest in the thick target. The DBLS method is most 4. H. R John**. R. J. Stam. E. EicMa. M. V. G-dry. ft O. Sayer. N. C. '*•&*. C. D. (TKcBcy. mm D. C. Heuncy. useful for the measurement of short lifetimes (!0~*' to fkn. Dm. Amm. /H* Kep. Ore. 31.1973. ORNL-4937. •. 42; 14 I0' sec) not easily accessible by the recoil-distance Jhji. •?**»•-, "T pVCSw. technique. A beam of 623-MeV 'J* Xe ions was used to 5. C E- Beam. Jr.. F. %.. McGowaa. J. U C. For*. W. T. induce the Coulomb excitation in these experiments. Mtaer. 9. H. Stefan*, and R. L- Robanoa. tkyt Krw C$, 14*6 Electronic stopping powers of thorium for 1JITh n«73>. 6. C- Baku* and J. X. Sabdir. An He* C M. 113% ions were obtained by modifying the values of North- (1974) 1 cliffe and Schilling ° with a correction factor generated 7. E- EKMCT. N. R. Johnson. R. J. ton*, and E. W. 1 from the results of Ziegler and Clu. ' Nuclear stopping OmuRcT. Chrm On Amu hot Hep tftx 20. 1974. powers were obtained from a parameterization of the ORXL-4«74.p.lS. numerical results of Lindhard et al.'2 These stopping S. M. W. GaaJry »"d R. J. Stan*. Oxm Dn Anmt ftttf. powe.s indicate that the most energetic 1,JTh recoils K . 11. i. K. Zwel-r w. fc. OIB. At \ud DtU Ttbtn 13. 7.3. Within error limits, the data for the 8* and 10* ]Hd 463 119741. states are in agreement with our data laken on the 12. L. LMdhard. N. Sdarff. mi H E. Sduori. AT. Own. ORIf. but they are closer to the rotational limit in ftdm*. 5rM.. M>r Fn. Mn« 3). No. 14 (196 J) «e 7lw CQIXOMiCXniATlOHW '*-Dv P. r. ItBKfft » N R «- h E Ek*-*- »•„• ••»*!«•• IMf«ues for rhe 4' -' ^c »* nnbm of the pammisute u-m:^. t^ri oi '4IDy haw been itnrrmmci' *-> tr* [\>P?^ -ra« recod-dcstance i These kxi» *ere populated by uwJupli exottiwe frwduced by a 146j»-Mer 4#Ar»* bean at ?ae OWC The target was a 13-mgfcur foi enriched to The bask principk of (he ntiwrwmi is to record rays emitted from the recod nutleui in coinci- the backscaftercd heavy ions for different i distances between the target and the phmger. i rays emitted when the recod audeui is in fhght * Doppwr anrt Ti«4»7J4. of wnT4Mcawia|C2)«MaiM '*'»> , TraaMKimi Tl II «P»**» ExptriMCMal «ir2>«**» » H^2V»l£2>nM 2*-0* 2l50±2O* lOJt 0.01* I* 4*-2* 132 ±4 150*0.06 100 ±0.04 6* -M* 1*4+10 U710.09 O.WtO.06 S*-6* 4* to.3 1*4 ±0.11 0.95 ±0.07 'Awsjr 4 mean of m mtatmimentt; tec Unci Dm Sheen. ' * ' Of, to be poMnMcd. 9Nnfmahzcd lo miry. 67 l**« f*^J I f|tf •2k7]gktM, I Mi iHeVi **4* t>* !•*.»* I2*/»* Nc" 72* 140 2 0.07 •»±«L*7 CI* 127 « 0Jlt«L*3 0-*Tt**3 IC7it.ll |7S±«.t7 **JU 14*4 0*J±0I4 *93±*.|7 lit ±0 17 14»t«J» *TtKo«raql wmu i »CTC qlamtcei* rnr vTimfcri -4c utrtm*c mm* titummtC1.C* •win, daab Bl£2.•* -2*1= 51 T% 711 DERMtMAIIONPARAMETBBOFTHE 7.12 reSXM«TKi*?4*rV"Nr CHARGE MSntmmON AND THE wamiktummoft* 0P1KAL fOTENTlAL FOR SOME RARE-EARTH NUCLEI R L Ferguson It L Hah* F rVasonton' FEOumnW I Y.Let* J.XSaiadm' A. H. Snefl F. Hubert J HOUCH' JCrBrieu' C.Baktash' C£ Bans. Jr. FisnoR is prcdkied to compete favorably with omer 2 PH. Stetson' FK-MLCowan modes of de-excitation for compound under in afl n 1 W. T. Miner J L. C. Ford. Jr. regions when the angular mumentum of the system is : 1 R. L Robmsou W.Tuttle vaffkienrJy high.4 This predkiion has been confirmed Detancd analyses of the clastic and inelastic scattering for several heavy-ion reactions, and m some systems of alpha particles on the rare-eanh nuclides '**Sm. fission appears to dc in mini an upper limit on the cross 5 '*•&. ,4,Er. ,,lW. »•*•/. and ,,*W for modem section for complete fusion. Thus, characieri 3 of aipha-panide energies spanninf the region of the the fission process can now be determined o»w * wry nuckar4Touiomb inierference region have been per large range of mass, excitation energy, am* angntar formed The £2 and £4 transition moments and the momentum and can be 1 umpired with theoretical charge-deformation and optical-potential-deformation predictions to provide stringent tests of theor" parameters have been extracted from the data using a We have attempted to determine mass -- d kinetic- coupied-channe! analysis of both the sub-Coulomb and energy distributions for fission fragment'. -*d angular interference regions for the excitation of the 2 * and 4* correlaiions for fission of the rebmc very light ground-band rotational slates. Differences are observed compound nucleus formed in the :eac? Ni • ,aNe. between the charge-deformation parameters derived For this system, the fessibriy paramete 7 as defined by from a Coulomb excitation analysis of the sub-Coulomb the liquid-drop model, is 0 J5. a val-- . taBer than that energy data and the results of the coupled-channel at which the Busmaro-Gattone r-- < occurs for zero analysis o( the interference region. These differences angular momentum ixtc - 0 .**•* ' This value of 0J5 might be connected with inadequate model assumptions implies that the mass datt^r , —. n peaked at very in the optical-model analyses and in the model for the asymmetric division, in .«y . 1 • thepredominantly charge distribution used to exiracf the sub-Coulomb symmetric divisioA -A / .1 n heavier compound deformations, as well as with the relatively large nuclei. Unpublished - J*', <•, a phenornenological. experimental uncertainties associated with the sub- self-consisienl inwr.-v^ ^sanation predki lhat the Coulomb measurements. Ni • Ne sys.em with '. anus of angular momentum will tei"! to fission avymnK-tncsOy.7 In addition, a recent calculation using a modified liquid-drop model, 1. Vmrcmtyofftiufcoryli. 2. flivnn Dmnnn. which takes into account the lowering in the nuclear J. Univrnif y «f Trancum. macroscopic energy itue to the finite range of ihe eS ancirar face. pstdacfs a tiaailwiimd kmefac energy of Tatar 7jfc. 46 MeV for turn iaraonmg system * Anogf w«jl trapfc kactK *mt*c 4* MrV of a 70*f/cm2 natural nickel tarftt wvat 162-MeV :#Se** •omrromnKORIC Owr$*»ns*rface*anm FWHMinli umtfanwHwirjiiry m»i 25' defector. sswjiendmg as aerie of about J* and locaied4 ca from dat target, was fixed at a* angle of 49* to dtr beam. A second detector, which abo jwhteadtd aw awjk of 3* in me reacoou plane diirrmmrd by the 7.13 hV£AVY-MW-tMNXH>rVSMlNAia> beawi awd the first detector, was located 24 ca from FUSION OF MEM9J4IASS MUCLB' 7.13.1 "Caad^Ifelwm IS and 60* on *e opposite side of ite beam from the first detector. At every angle, pake Inagkts corre- F. Hard3 F. Fleasoctoa: RL L Icrgvun R. L_ Hahn •ector. as wef as to the dMeicaces m rimes of detecticc in the two detectors. wee rounded event by event oa *e have 'i rwrmwtd oar stiadks of Aswan and ramon ungnetic tape. Two other detectors iwtund the with >:C and 2*Ne ions mcafcat on targets ranging 3*He elasricany scattered from die target awd were used front ,,TAg to "'Ft. The objectives of these stadaes 2b wotwnjrre the separate raws. were discussed in a uauions a—al report1 and can be So tar. we have perfornnd oaJy a prelmuaary analysis swanttamed as toBows: I i I to determine the fraction of of these data. We have assumed that aB coincidences the total reaction enre section that s accounted for by reswhed froni a two-body breakop of the target-pkrs- fosran and fusion. 12) to detenrant whether the ob projectne fystcai and have deduced fragment masses served lowcrwjg of the fission barrier with increasing and total kmetac energies «sing the principles of angatar momentwn is adeooately desvimtd b> the ^^rfwann^pwwanwlitfwwi d^m wmrmmR ^unami umMvanm^nniffwaanWi mmw> Swrnwam watfwS* %rwkff routing liquid-drop model.* and 1?}to obtain valon •red the erode fragment tane-of-rnght mformatica for the faron barrier at zero angobr momentum for outward in the cxperiraeM. SOT have we used oar relatively bght ^rstems that can be compared with knowledge of both detection angle* to exdude al iheorefKx! prcdsctioas.* non-two-body bteafcups front the analysts. A dncusKOtt of some of our results can be found in Tbns. the results given a Table 7.6 must be regarded ref. 6. It was found that the lowering of the fission as tentative. In addition to uncertainties du to possible barrier wrth increasing angular momeitium can be systcnu °ic errors, sutittkal uncertainties are estimated desenbed semiooarriitatrveK with the routing-bquid- to be ±5 MeV and ±5 amu However, these mails drop model. The conclusion rs based on an anarysrs of appear to suppcrt the AcorcoVal predictions*-7 that our measured tacion excitation functions, using statis das very light system fusions asymmetrically. The tical-model nuciear evaporation calculations that in avenge total kinetic energy is in good agreement with clude fission competition and angubi-«nonKntiirn- the predicted value.* dependent fission bjrrieo.7 It was also found, however, that in order to ob;ain reliable values for frssiui barriers at zero angular momentum. :• is essential to know btHh 1. rnVSKS ftvtaoC the fission cross section o and the cross section for 2. CojmtUM. f 3. Vonnc »CK»6»' fro* Centre iT.rades Nackairei. production of evapcration residues aFR. We have measured excitation funciions for fission and for 4. F. Haul an* M. MM*, ton Hew C II, JOS«1974). evaporation residues for the systems l,7Ag • }*Ne, 5. H. H. Gaftwd. F. Rani. H. C. Briti. S. H. F.rkkifa. It. H. '"a • "Ne. and ,4,ft * "C: to date, we have Uoin. ma M. Wbm. p. 309 m Vol. II of »jmr< and completed the analysis for the fusion excitation func Otnmurj of Ftoton. 1973. IAEA. VKMM. 1974. t. J. R. Nix. LAS Ahnmi SCKIMITK Labontery report tions of all three systems and for the evaporation- 7 ,0 LA-DC-72-7<9M972). residue excitation function of the " Ag • Ne 7. R. V. Canon, print; commwwcarioa. system. S. K. T. R. Ds*ic*. S. F. Knomn. I. R. Six. and A. I. Stttk. l07 Since we have both oK and Oyn results for the Ag Lra Abmnc Sarnfifk Laboratory report LA4JR-7S-3 (1975). 10 J T 9. ¥. Plasl. R. I. Fcrjrason. F. PksnoMon. and H. V + Ne case (compound nucleus ' La>. we had hoped Sdnmn.rhys Hew C 7.1IM (1973). (o carry the analysis of the data to the point of 69 1ST. MOO 'ft* IZC systems! ope to abeam a i bonier of'"lb. I. A inmm»M iCyiWT gaWf> jpMJCWBnf ml rmWt MM9 jfMumL AM£ Jbp Dt€ 31. 1*7*. OBNL-542S. 2. UrioPiiw •• X fmyt Dm Ammx I** Mem DK 31. 1973. 0*SIL<«937. 4. S. Ota. F. Had. MM) «. J. S—atifa. 4M **V» C2. 5S7U974». de-excaadoa oi the < 5. H J toaui art J. •_ MM. PL 159 a «•*. I •«" Nc JW data pomt at 170 MeV ies below the 14E* *>••. Mvx Cam. rwii dWtoar. *»'.. predkied curve. Nix and Sieitr pvedkt deaf for Mo *W>. IAEA. Vinm. 1974. • >9#Mo. as the bombarding energy is ratted to; *- F. ft**, p. 107 un«t. 2 of />•• i vagr «/mr I 20 MeV atone the iutemcfm* barrier. ^ mmmM Cmfmmtt m Memttmmx Btfmvtm Cm {JmjmtmWr. Tern* Jmmr 19-14. 1974). mined by the dynimrn path m the entrance «M>. 1974. and as the energy n raited stii farther. •£» is 7. m\.Vtmw\wm\\.r*ak.t*j\ ft/* Lm 29.303 < 1972). M. determmed by utstauuBty toward fission. Thus our •MM J«J F. Thai. AUCC A .Vmtkmr £i CMV. results are as qjuatitative agreement with tfce Six-Setik USAEC K*>jrf C0O-3494-I0 INM I. 1973) calculation. If we consider the results at a bonmordang energy of 7.132 °ArmJuKrltail 2tt MeV. we have a value of 1230 mb for «»> * «r. MMm1 HCBm.' Our results also mdkate a value of about 200 mb for B H Erkkia1 R.L. Ferguson deep-mctastk or quasi-fisskMi events. If we add to this the cross section for transfer reactions of 510 mb H.H.Gutbrod* F.nasa" 1 obtained by Hm> ct al..* we can account for the total R.H. Stokes reaction cross section of 2095 mb to wen within In ae experiment compfen entary to that discussed experimental errors. above, we measured o> and *tn excitation functions The otK results of Gauvm et al.'* for argon for the system !MAg • 4>Ar (compound nucleus bombardments of antimony hive giver: rise to an ,4*Tb) at the Lawrence Berkeley Laboratory Super important discrepancy. Those authors found by a MLAC. Preliminary results are shown m Fig. 7 J The method invoking the measurement of postirradiation ofm values are given by circles, the squares represent alpha-particle radioactivities that, at 300 MeV. oER is the sum of oER * or. and the triangles give values for of the order of 1000 mb. This result would lead to the the total reaction cross section oR obtained from surprising conclusion that compound nuclei predicted eiattk-Kallcimg angular distribuiions by the l/-t-po»ni •o hav* no itstton barrier''' can survive de-excitation by method.' The dashed line is the prediclion for oEK fission. We have repeated the ofm measurements for from the slatisfkal-model calcubtions of BUna and 4*Ar • "'Sb by our direct method of counting Plasil' with rotating4iquid-drop-modcl fission barriers. recoiling evaporation-residue nuclei. We obtamed aFn It can be seen in Fig. 7A that above about 20C MeV. values of 490 and 500 mb. respectively. M bombarding measured and calculated aKR v*'-jes MC in excellent energies of 282 and 340 MeV. Recent preliminary 1 agreement with each other. Below 200 MeV. OfR B results from Orsay ' at 295 MeV are in agreement with probably determined by entrance-channel effects rather out results. The new Orsay data were obtamed by a 30 dawct cowaaar. aKflaod saaaar to oar*, aad the resale; reactME Mcreaacs jad the man »-t the proprctac of tef. 10 thns appear lo be aVPawfi =a error k * becoaaes cuaa>arablr warn that ot' aV 'ar^rt —iknx hkely dot errors m the assamed hnaihaig rafaos Macfc drscasaua of sach phranaaai j* cntraace- acciaaM fo dac discrepancy chaaael effects, frwtiua aad vtscosaiy m wadei. and lb haw abo obtaatrd «[( aad «( rentas for "Kt • ojaast-riBua has occarrcd m the receat taewiar* * •*Ca_ At 4*4 aad 604 MrV. the gnhaaa HJ vahars for Laa year.*-* we reported oa ** At aad "Knadaced •m arc HM> and 3*0 ma tmpu.iwtiy.awd dKvahses leacooas ^tadKd at ihe accelerator ALICE I Acceleta- for Of are 640 and 1160 am respectively These retake lear Laaeaare de Chaagcaaie Earrpel ai Orsay Oar rcsaht droaed Otat the de-cxcitaawa oi the coaapoaad DCS. h pnrtkatar. m the ffi case, the aagatar aadeas. '*'Ei|aad '**Ei». fonaed at the aweractioas dMid»«ii0Misextrea^fbr«ard-pcafced.s^rJBialarfe of *#Az •«* "*Sa<"*Sal aadot ,4la wah "*Ge feactaoa of the cross sectaoa appears at ancles not l7:Ge). JH depend oa as awde oi forantwa ai diiajo iat widi 0V iiM|aaiaiiati of the aaJepead- large extrapotatioa. cace hypothesis of cvaaMaad-aacleas fonaataoa aad decay The data froai ate kiyptoa aaaaced reactions aK o^aahtatively drttereu froai those ohtaaird waif! 1. f~tat*rtB*Bm*a-U.G***mi_t. fbaLILC. Ban. B- H. t*U».R. B. SIACI. aal M. Mm ». 3W wM. 2«< **Ai. or heater.'' was the cvnUi: 557 f 1974). of evaporation of x neutrons. tlm. ph>iled x U*t 12. fHfmmurf train oC wwffc ky B. tiorfrv. H. liamnm. D. compound nudei :##Po and :**Po iprenousiy deter Carna. Y. UBcvec. M. Lrfari. I-. ffaMl. jai X. Tartar*. aaaed at Orsay) We mite that Ihe measured F values Ores*. Frawr. tm for the two compound systems are quite different for any value of x. neutron emission being much more 7 14 CQmfKnJNMWa£US9EACTtONS nkery m s**Po than in :MPo. These results can be INDUCEDBY *• Ar WITH • "Djr. understood in terms of sialislical-model cakulatNms* '*#Dy,AHID"4Yh that lake into account the effects of angular momen turn on the competition between particle evaporation Y. LeBeycc' K S. Toih: and fission The calculaiicns. which are seen lo agree R. L Hahn R. E. Fppley* with the data, indicate that, at fixed excitation energy Nuclear reactions induced by very heavy ions have and angular momentum, fission is more probable al the 2,, 2 only recently begun to be explored as a few accelera expense of particle emission in Po relative to **Po. 4 tors, notably at Berkeley. Dubna WSS.R). and Orsay Detailed undemanding of such effects in *Ar re (France), have been abic lo accelerate ions such as actions is necessary for us lo interpret results to he **Ar. "Kr. and *"Xe to sufficiently high energies to obtained with even heavi.n ions, such as "Kr or initiate reactions. With such ions, we may expect to see "*Xt Our future experiments at SupcrHILAC will 10 qualitatively new effects in nuclear reaction mecha prod'ice the same compound nuclei as above. *Po ,,4 nisms, as ihe angular momentum brought ••» the and Ra. in the reactions of "Kr with "*Cd and 71 CK**L-0B6. 79-1277 715 MULTMUCLEON iTUNSFE* EEACT10NS WTTH4*ArKAMS R RL.Haha D Gardes* Y. dr>luras' Rmt1 Two classes of reactions reduced by heavy was row been extensively studied, compile-fusion readmits, m which the projects* and tarjet completely merge, aed transfer reactions, m which a smal rammer «f m>dcons are exchanged between projectile and target A third type of reaction that rs tegjnmag i«* teceive attention, especzaty now that beams of ve.y heavy ions are becoming a*at*aMe. mvotve* rauUiimdeon transfers, wherein a large number of andeons are exchanged by the coBnting partners Ow ooftaborafne mvestigaMons of such -omplex transfer reactions have continued at the acceleraior ALICE in Omy. France.1J Cross sections and recon properties of the alpha-enuituig nuclides "'Dy. 150Dy.and i4**Tb were determined in 4#Ar bombard meats of a large aureber of targets, from lanthanum to terbium, so that, by keeping the projectile and product nuclei the same and varying the identity of the target nucleus, we could survey a wide variety of transfer reactions. The measured cross sections obtained widi the 345678910 2*2 MeV 4,Ar beam are shown in Fig. 7.10. All points MM. NUMBER OF EMITTED NEUTRONS that involve the transfer of a constant (net) number of protons from projectile to target are connected by one 7.*. rviiiBij «r ni)in>u or x •imn. rxm. z curve. -JV4 is the mass difference between the product njfaitt *t*xaumm wt ti«i|imi HdH **f^ mi :Mn> tmmt4 m rkr rorlnw * **Ar TNk "'Or art nucleus and the laiget nucku*. The data dearly '*4Dv. PV>alt carrrtpiai i« rfcr praln a( rhr resprclne I Arjrm indicate that the probability Px of the transfer of x e%c«a.l«Ki fonciKHtv rateable* Tjiun were nbUMrd wsh j protons vznes with the overall mass balance of the ••ifcat e*af*Matmi cnaV rrri t» transfer and that, in general. >*r decreases as x increases. We also note that the total cros. sections for all ' **Te. lespectively. and :**Po in the reaction o( reactions in which more than three protons are cap ,,:Xe*nh**Zn. tured by the target is relatively small, about 60 mb relative to a total reaction cross section of about 2 b. 1. Iiniilul «Je K«>«*HK NuHewr bution, muhinucleon transfer reactions appear to occupy an intermediate position between quasi-elastic transfer reactions, in whicn detafis of the entrance channel are preserved by the final products, and compound-nucleus reactions, in which many entrance- channel properties are not retained during the approach to thermodynamic equilibrium. 1. Instrtutderliy^ueNacieaiie.Onay.lraace 2. Cham Oh Amm. hog. Rep. Mar 20. 1974. ORNL-497*. p 13. 3. R. Brabot. D. Gardes. R. L. Halm. Y. deMoras. and M. F. Rrret..V«ri toys. A 22S.«5 (1974). 4. A. C. Artukh. G. F. Griaacv. V. L. Mikbeev. V. V. Vofcov. and 1 Wiczynsfci..Ytrrf l+yi A 215.91 (1973). 5 L.C-Motetto.Nauonallfeen^c^tlKAnRwanClmaical Society. Atlantic City. N.J.. September 1974: L- G. Moreno. S. G. Thompson, et aL. Lawrence Berkeley Laboratory report LBL2J*6.p 51(1973) 7 1© HEAVT40N IftJLTINlXlXOr^TRANSFER REACTIONS TO THE CONTINUUM1 R L Harm F.FIasi.2 R. L. Ferguson F. Obenshain* Fn> 7.10. Variation of cipiiuninttl era* sections (caatab- F.Pteasonton2 A.H.Snell1 trve yields) n ike act MM pirn. &A = ^(observed aadcas) F. Hubert3 -4 (target). The solid Hoes ate drawn Co guide the eye through the data points that convspopd to the same number of protons. Using the ££*-£ counter-telescope system with a gas x, gained by the larger Squares correspond to residual nucleus ssl ls0 {4 counter (proportional counter or ionization chamber) Dy, circles to Dy. and triangles to *Dy. Fid symbols 4 are used for odd values and open symbols for even values of jr. for A£ developed for complete-fusion experiments, we The dotted line corresponding to Sp capture was interpolated have begun to study multinucleon transfers induced by between the Ap and 6p curves. heavy ions at the Oak Ridge Isochronous Cyclotron (ORIC). Such investigations are of interest because recent previous work (such as refs. 5-8) has demon reactions gives results that are consistent with th» strated that the characteristics of multinucleon transfers following description: The projectile and target undergo are qualitatively different from reactions involving a collision in which they remain in contact for only a either complete fusion or the transfer of only one or short time. The lifetime of this composite »ystem is two nucleons. One interpretation of such results* is long enough, however, for equilibrium to be established that in massive transfers a partial equilibration, or in its neutron/proton composition, so that the NjZ relaxation, takes place ir> the interacting system formed ratios of the intermediate nuclei that tesult from its by target and projectile. scission are equal to the ratio for the composi*e system. The advantage of using apsM counter in this wort, The kinetic energies of the two separating intcrmedisie is that its effective thickness can be varied easily by nuclei are characteristic of the Coulomb repulsion changing its gas pressure. Thus, energetic light frag between them. Thus, much of the kinetic energy ments from transfer reactions as well as fission products brought into the system by the projectile is transformed and low-energy complete-fusion products can be ob into excitation energy, with most of it being taken up served with the same counter telescope. by the heavy fragment that subsequently de-exciles by We have begun a systematic study of transfers using nuclear evaporation to become the observed final }0Ne as the projectile. We selected ,07Agas the initial nucleus. target because the complete-fusion4 and fission' re By such characteristics as asymmetric angular distri actions of 10Ne + l07Ag have already been investi butions and equilibrium in the neutron-proton distri gated. 5y studying transfer reactions as well, one may 73 expect to haw examined all of the major exit channels ,,7 I. R. L. Mac***. F ML Gets. J- Hafcpena. • T Rowberry. available in the "Ne + Ag system. Angular and H. W. Sdunin. R. W. Stoajatoa. am M. Tobias. Varf hat/mm. energy distributions of the light products from boron to «* 3 small, are considered to be several times the estimated We have modified our He neutron-multiplicity 1 uncertainties in the measuiement. However, the value counter to enhance its efficiency. The counter had a of v deduced from the neutron multiplicity distribution single-neutron efficiency of about 0.28 with a 0 appears to lie between l.S and 2.S (which is consistent -in.-diatn.24-ir.4ong sample cavi<> inside the 20 'He with that of 7i*U. i - 2.0). Further experiments are detectors and paraffin ~y..ix. In order to increase the planned to extract urati -m from these samples in order efficiency for detailed fission-energetics studies, we > to determine whether the let multiple-neutron emission installed 10 more He detect TS in a cylinder of rates persist in these samples. polyethylene inside the 9-in.-diam cavity. The poly ethylene cylinder has a 4-in.-diam sample cavity, and the detectors are halfway between the 4-in. and I. AnalyticalChrmntry Division. 2 See Sect 7.17 off hi* report. 9-in.diametcrs. End plugs can be inserted to give an opening of any desired length up to 20 in. (the length 7.19 NEUTItONMlAIIPIJCITIESIN of the sensitive portions of the detectors); currently the NATURAL SAMPLES length is 12 in. The single-neutron efficiency was 1 measured to be 0.47. with a thin }52Cf source in a J. Halperin J. M. Bird 1 fission chamber and gating on fission fragment pi (7.7. Nnrt •ft** Clock HMtcrofMrinphcibes ._. Weight Observe*) Conwcfcdr Mars) 2's 3's >4*s 2s 3's >4s 2J0 I4.S ISO t 1 0.4 0.1 -0J 23J> *J0 71 0 0.1 OJO 14.5 4.1 «7 I 0.1 0J>, OJO so,* 12.7 •J *7 3 0 0.1, 04, OJO 'OWNS per 4>y pc? (fee •Fi i to Nor* Pacific Ocean. i the tinde Pwiwm. UnJuaCjrtidi Corporation. of jnwphiMte4 from the Department of Geuiopcal 7 J* NEIjreONMULTnTUCiTIESm Sciences of Condi University (their entire supply); this FRACTIONS HON LEAD AND ZJRCOMUM rare natural iron-nickel atoy is thought by some ORE PROCESS**; geologists to come from the earth's core. We obtained a 1 large sample of spuufex-textured uftramafic volcanic J. Maty R. L. Ferguson rocks* from northeast Ontario; this outcropping is R. W. Stoughton J.I believed to come from a depth of some 300 km within The following samples from France were counted in the earth's mantle. Since some possMe superheavy 3 our neutron multiplicity counter: 2.1 kg of zircon ore. elements are predicted to be volatile, we examined IX) kg each of ZrOj and HrD, from this ore. 1.5 kg of some sftka gel from a Union Carbide Corporation Lmde PbS0„ from lead ore processing, and a thin sample Division plant in Hnntsvile. Alabama; this mate's! had sepauicd from leal ore (the latter sample was counted been used for sorbing and desorbtng gases and other in a pied ztoae so that only neutrons in coincidence volatile components in air. Some manganese nodules* with fission fragments were counted). We observed no from the North Pacific Ocean were counted. The results definitive results in the larger samples. While there are shown in Table 7.7. The values of dock time were appeared to be somewhat higher multipliciiies in the corrected for counter dead time (13%) due to an HfOj and PbS0 than in very pure samples, the anticoincidence mantle that reduced background re 4 apparent difference is very likely not significant. The sulting from reactions of cosmic-ray muons with de uranium content of the samples, and/or secondary ments of high Z (<£26). All counts were corrected for effects of density and sample size and shape on the the empty-counter background; in the case of the muon reactions with high-Z materials, b thought to be josephinite. the background was measured with 2 kg of sufficient to account for the observed multiplicities. iron in the counter. The thin sample was counted in our reviseri counter3 All samples showed negative results within our limits (jf'ciency * 0.47) several months after if reparation. of detection. During the first 32 days of counting, about 0.8 i 0.2 fission/day was observed with about 3.910.6 neutrons/ 1. Department of Geological Sciences. Cornell Unhersiiy. fission. After a few months the counting rate was about 2. Department of Geology. University of Toronto 3. Linde Division. Union Carbide Corp.. Tonawanda. NY. 0.4 fission/day with v * 3.5; these values remained 4. J. M. Bird and M. S. Weathers. "Josephinite. Specimens about the same for about six months more. There may from the Earth's Core?" submitted to firrrA timet. Sci leu.: have been a shorter- and ? longvr-lived componeni abo.Orem. t-ng. Newt. Apr. 22.1974. p. 30. present. The overall averages showed 0.44 t 0.06 5. DR. Fyke. A. I. Naldrett. and 0. R. Eckstrand. Oral. Sot. fission/day and v = 3.5410.35. the latter being close to Am Bull. $4,955(1973). 2 6. Courtesy of Norman Beecher and G. L. Hubred of the the value for " Cf. Kennccott Copper Corp.. Lexington. Mass.. and Sr^ldon Hall of There were also about 500 alpha particles per day Kennccott Explorations. San Diego. Calif. observed with a counting efficiency of about 0.4. While ?s the sample was too thick for any significant alpha In addition to demonstrating the production of nuclei energy resolution, the energies were consistent with that have mass wwm up to about 265 or higher by members of the natural thorium and uranium series. prompt muirjple-ne&troa capture, tins type of experi ment is valuable m testing two crucial theoretical predictions concerning heavy neutron-rich nuclei. The I. Fonaerir at liMitm 4c Hiyiint Hmtfhmr. tear. Fax; mam at SOCMC Apfhoma*. lac.. Mo Alto. Cain". first involves the rate at which the nuclear surface 2 R. L. stadrln. F. If. U» i Katpena. It T. Roarfccny. energy decreases with increasing neutron excess, and H. W. SdMMi. R. W. Stonffeum. ana M. Tabb». .V«rf hairmm. the second involves the sangte-paxtide effects associated Mr<*o* tOX 1*1.1972) with the short spontaneous-&ssioa half-lives m the 3. See Sect 7.|7orihitirpMi. region of Z* 95 and* * 165 to 175. A test of these two predictions is crucial in n*Jung more firm theoret 721 HOW ID DETECT THE HEAVIEST ical calculations on such important questions as the MAN-MADE BOTOTES' ukebhood of producing superheavy nucki either by H.W.Mddner2 JR. Nix3 muhipie-neutroa capture or m heavy-ion reactions. G. A. Cowan1 R. W. Stoughton Heavy elements up to ,s7Fm have been made in i. S mmmmy of a paper Jabwwttt 4 lo Injs. AVr.C. 2. Unw-iaty erfCaUfocwa ai San Diego. La Jona. thermonuclear explosions by prompt nwritipfc-neutron 3. Lot Ahwwi SaentilK Ufcontrfy. capture on uranium targets.4 Current nuclear-structure 4. C. A. Cowan, p. 291 in rYoc. Robert A. WHtk Famd. theory of heavy neutron-rich isotopes suggests dut Omf. Ckem. Ret.. *oL XUl.Thr TMMSWWWM* Btmain - 7ft* neutron capture on ^aiuum continues pan mass 257 HmdtUtw Ctnumm*. Maw*. Testa. 19*9. Robert A. Wek* with the consequent production of much heavier FoMMfatna. HocBfcM. Texas. 1970. 5. E.Ote^eu. E R.G«*i.H R.Bowni*.* C.JareeU R isotopes. The apparent limit of A = 257 observed in all ffaatcT. awl S. G. TbontfOM. p. 709 in vol. 2 of *wr. huComf exposures to date is therefore possibly due to the ftopertiet of Nmctei Far from tme Krgkm of Beta StakHty. relatively long tine required for recovery and mass Ley**. Swrtztrbml. 1970. CERN report 70-% 11970). analysis rf the products (about 8 hrl rather than to •A R. L. Mac***. F. M. daas. J. Hatperia. R. T Roaefcerry. intrinsic difficulties associated with producing heavier H. w. Sduant. R. W. Stoafhio*. ant M. Tobias. Nad. Imstrum. Mrrfc»0l«Z.I8Mi>72>- nuclei. Hence, conventional mass analysis, ever when 7 R L kbctlm J H.loid.HVmU.utattlKoibeny. combined with the most rapid recovery techniques, prinv ammmmiatioa; J. H. TocM. in Itatrumenmhcm mtd seems inadequate for the detection of possibly pro ConnonDn 4mm. *wjt Hep. Sept. I. 1974. ORNL-S032. m duced heav:rr species. pre». Obviously, we need some very early counting tech $. J R. Nix.flryi Uti. B Jt. I I19*9»- 9. H. W. Scnmut a*d V. Moid. Afe* fhyt. 4 IN, I <1972>. nique that would check characteristic spectral features 10. Sec Sect. 7.17 of this report. (tf, neutron multiplicities), for whxh we propose the use of a neutron-multiplicity counter.5"7 Such a tech nique should be possible because the average number of 7.22 MEASUREMENT OF THE NEUTRON FISSION neutrons r emitted per fission is predicted to increase CROSS SECTION FOR ,45Cm USING substantially for very heavy nuclei (eg., about 10 forZ T1ME-0F FUCHT TECHNIQUES * 114 and A * 298 compared with 2 for * * *U and 4 for C.F.Benus.Jr. N.W.Hili* ,,2Cf)*"* The usefulness of these neutron counters is J. W. T. Dabbs' S. Raman* restricted by the large size (about 100 sneer of their gates (highly moderated neutrons are detected by the We have developed a fast hemispherical-plate ioniza counters described in refs. 5 and 6) and their vulner tion chamber for the detection of fission fragments and ability to gamma background. The latter, in fact, have used the chamber to measure the fission cross excludes the counter described in ref. 5 for our section for 2**Cm in tiroe-of-flight experiments at the purposes. The 'He counter of tef. 6. on the other hand, Oak Ridge Electron Linear Accelerator (ORELA). appears to be the least gamma-sensitive instrument This ionization chamber uses the large difference in developed thus far. In addition, its * ri$nally low initial ionization density between alpha particles and efficiency has been improved from about 0JO to 0.47 fission fragments, together with the hemispherical-plate 10 by some modifications. Reference 7 involves a geometry, to limit the size of alpha pulses. Improved fast-neutron counter that might be useful for our performance over parallel-plate ionization chambers is purpose. realized, and, in the worst case, the alpha-to-fission 76 currcnt-pube ratio for dun samples does not exceed About 12 fission resonances below about 20 eV were 7I4. Thus, fission fragments may be detected in the observed in our experiments. This energy range is presence of intense atpha-partkie radioactivity if fast inaccessible to underground nuclear explosion experi current-pube amplifiers are used to reduce alpha pube- ments and is of interest in assessing the production and pfleup effects. Fission pube duration times of about 35 destruction of actiniae nuclides in fission power re to 40 nsec have been measured with this dumber using actors. Our data for the energy range 03 eV to about 2 a 252Cf source, and we expect adequate fission-alpha- MeV »;e currently being analyzed to yield cross sections particle pieup dbcrmination at alpha rates of about as a function of energy and resonance parameters. 10* per second. Experiments at less than 200 pulses per second are This chamber has been used inhialy in neutron- currently being performed to provide a 2,5U normali induced fission cross-section determinations for 2* 'Cm zation check at a neutron energy of 0.025 eV (2200 via tme-of-flighi at the ORELA. Approximately 30 ag m/sec). of nearly isotopicauy pure 245Cm (99.965%) was Experiments of this type are planned for 242Am, prepared using the Transuranium Research Laboratory 243Cm. 24*Cm, and 2,,Cf. Our experiments with isotope separator: a fraction of this material was 24'Cf using a different fission fragment detection eiectrodeposited onto a hemispherical target plate. A technique have been reported p evwusty.3 similar target plate of 2,5U was abo prepared, for use as an internal neutron flux monitor, and mounted 1. rnysics DNTBIMI. 245 adjacent to the Cm plates in the chamber. The 2. lam•intation and Coatrob Dnrinoa. chamber was located at a 93-m flight path station, and 3. C. E. Bens. Jr.. J. W. T. Dabte. C. D. James. N. W. HM. approximately 12 days of ORELA operation at 52 kW M. S. Moore, and A. N. EMn.Chtm. Dn. Anmu. frof. Rep. May and 800 pulses per second was carried out. A portion of 20.1974.0RNL4976. p. 36. our raw experimental fission data for 245Cm is shown hi Fig. 7.11 for the neutron energy range 0.3 to I IS eV. 7.23 THE NEUTRON CAPTURE CROSS SECTION OF "S TO 850 keV J. Halperin R. L. Macklin1 \ measurement of the conversion rate of 32S to J*S reUfive to other nuclides produced during nucleo synthesis provides a test of the adequacy of explosive carbon burning to explain the abundance of the rare and neutron-rich nuclide 3*S (140 pom in natural sulfur). A critical uncertainty in this conversion rate concerns the branching ratio in the decay of 34S (about 11.5 MeV above ground) by charged-partkle emission compared with gamma-ray deexcitation. This problem is being investigated in a collaborative effort.2 and this report is concerned only with the production path leading to "S. In view of the essential nonexistence of data for JJS(n,-y)3*S in the literature, measurements were carried out on the radiative capture neutron cross section of "S (0.76% in nature) at the Oak Ridge Electron Linear Accelerator (ORkLA) time-of flight facility. The energy region covered was from 25 to 850 keV, at which point the onset of gamma rays from inelastic neutron scattering would be expected. The 0.M measurement was carried out at 40 m, with 5-ns pulses, at a repetition rate of 1000 pulses per second. A 1.1-g Ft 7.11. AaortfcMofo* sample of "S (88.21% abundance) with an areal mm forM *Cm tor iwdwrMMvtMtollStV. density of 0.0132 atom/b was viewed by two total- For ampacity, only one oaf of every nine has been energy detectors utilizing on-line pulse-height weight- 77 This retailed • aa avenge detector response listed ap to S49 keV, i iadtutalfat of the paws* cascade from the of from a awekas'-4 aad proportional to rhe total 1 A 11 live a^amnua plot of the ' (j.e.. biadms energy plas center-of-anm aeatroa of resoaaaces observed in the intervzl from 13 energy). The aeatraa Ihu was measured with 05-aan- to 240 k*V ranyiti dot to dot enemy very few dack * U glass ia tiaasauBioa. The effective captaie cross sectioa uf ,3S w caergy is sbowa M Fnj. 7.12 for the faatc saaad Resonance parameters were extiacted from of observed resoaaaces vsiag aa antonutk *• fyjTt.1 rM fitting coapater code foMowedby an analysis CkeV) (eV) «eV) fokhag ia Poppter broadraam, jastiumurtal resohrtion. sdf-dikidaig.aadmortiplescattermrrTabk741imtlvt 1345 Oj0*7it040 4 107*20* energies of the observed resoaaaces, die captnrc 1742 0334 '0432 40.7 *9.7 strength gr r„ir , and the total widths as evahnted 2353 IJ03 t0455 44.1*93 y tot 31.79 0443 1(040 4 <15«V* from tbe resolvedresonances. Sem e 39 resonances are 52J0O 0J14I tO420 330*70" 5331 0351 (0433 240*50 5947 0474 it044 l 340*70 77.74 133 it04 S 400*100 •1.19 03* c044 500*120" VAs 0.77 t04S 240*50 UJ2 0.139 t©41 240*50 100.7 0.94 t04t 1500*300 1273 no no 030 c044 150*170 130.* 034 t044 300*40 133.1 042 t043 230*40 13* J 032 t047 150*30 151.2 044 it04 7 340*70 1474 147 tO-14 3300*400 i.jLiJL.j-t.. i 1774 035 tom 740*150 (•^"mvjwjnjw^ wvwp-www»w^Wfmwmi - 1944 I.U tO.10 710*140 tw m too 199.1 IJ09 t9.ll 700*140 2024 1130*200* X 152 tt.15 2I0J 030 t04S 310*40 2154 032 c045 <120eV* I- 221.2 0.73 i0.ll 1570*300* S 22»J 037 t04S 430*130 5 40 " I 2373 140 tO.I4 410*120 lUMmV'WNMU'VWO 25»4 130 t0.l2 400* SO* •U 2(0.2 041) t049 550*110 10 CO 2954 2J0S t0.14 410 * 120 290.2 152 10.16 790*140 300.7 130 t032 470*140 3355 0.70 t0.13 740*40 3474 134 t0.lt 400*00 ins 2.77 t047 1400*250 3913 344 t03f 1300*250 4253 143 t032 1700*300 4*54 3.11 1033 3300*500 US 85 5404 2.77 t040 IN*) 2300*400 Ma, 7.12. Tw erncare monoa „^ *We art mtebicd to W. 'I.Good foraBowawji "UniP% Aon 23 to 450 MV. The omn of gamma ays lo data. proa'accd by todastk neutron scat leant lakes pkwt jwt above Trn s-wave rejcawcw. / « 0, ware fcy 050 kcV. Energy rrwhiiion it iy©00 at 20 keV and Mb to obftpfw$ mttntntK* mil ey300at750kcV 7S ifiiwwn i arc Kissed and yields an average level TaUr?.9. s*Si HJHII nimmi spacing D of 9.1 ± 05 keV. The resonance integral (/ . e, dE/E) is calculated to be 33.415 JO nb. r r # s .fv, *-- »' 203.) 0 70 ±009 3.20* 048 tODt, 2 G F AadM^a^k.J Hatpna.ll L IfaddM.aaiW M 4.230 II ±0 2 Howatd. -KateoH "**.«,) aad "$(«.<>> Cross $n.tma*: •.230 0 09 ±0.03 Importance a the NadeosyMhew of the Rare Nucleus '*S.~ 6.2J0 045 ±0 2 J*nL/te»C 12. 1126(1975) 6.3*0 0070*002 3. *. L. Mackta Ml J. H. GMma*. »*». *e». IS9. 1007 9.120 04$ ±015 U967). 9.230 069 ±0.15 4. It. L. Macks* aad B. J. Aim. JVarf. Aomin Jfrmods 91. 9.«50 0 1* ±003 MS (1971). 11.100 0.79 ±01* 5 .Vrtrnm Ooa Srcnorn. casapikd by S. F. U^tabrJub 11.530 0 54 ±013 aad D. I. Garbex, Brookkavca Nalkani Laboratory eport BNL-325. M ed.. vol-1. Ttnowance Pannetcn" < 1973). ra> cascade following neutron capture. Experimental 7.24 THE NEUTRON CAP1T1KE CROSS SECTION details have been previously described.4 OF5*NiTO!3keV After correcting for the sample-independent back ground, largely due to radioactive impurities present in J. Halperin R. L. Macklin S. Raman' the "Ni preparation, the capture yield data for 4,Ni were normalized -o previously measured* capture areas In a high-flux reactor. **Ni formed by neutron in **Ni (the **Ni content of the current sample is 5, capture in natural nickel (683% Ni.<4<'»Ni) = 4J 79.5%). The capture cross section as a function of b) becomes a significant constituent of structural energy is shown in Fig 7.13- materials. The relatively large (#t,o) cross section in The large resonance seen in Fig. 7.13c at 203 eV **Ni. leading to the accumulatk.. of helium at grain dominates the thermal and near-thermal response and boundaries and the consequent swelling and premature clearly has implications for reactor design. The region failure of nickel-containing alloys in a reactor environ from 1300 to 13.000 eV is covered in Fig. 7.13a and ment, has excited special interest in this nuclide. It has 7.136. In Table 7.9. we list the energies and capture 2 been the subject of a collaborative effort at the areas of II resonances assigned to "Ni from these ORELA. where measurements are being carried out on measurements. Four of these resonances, at 3206. the total, (nja). and capture-gamma cross sections of 4230. 6370. and 9230 eV. have also been observed in s *Ni We are reporting here on the measurements of the the measurement of the total cross section by Raman. neutron capture-gamma cross section for **Ni. This Harvey. Hill, and Jurney * isotope is unstable but has a long half-life (7*i/2 = 8 X 10* yean for K capture). Measurements have been carried out or. a 3.136-g 5 sample containing 2.96 at. % *Ni at the 40-m station 1. Physics Division. of the ORELA time-of-flight facility. Here the gamma 2. S. A. Harvey. J. Halperin. N. W. Hill. R. 1.. Mackiin. S. rays emitted following neutron capture are viewed by Raman, and t. T. Jurney. "Total and Capture Cross Sections of two fluorocarbon liquid scintillator detectors placed **Ni for eV and keV Neutrons." Butt Am Hiyt. Soc 20. just outside of the neutron beam. These detectors II95(I975>. 3. R. L. Macklin and J. H. Gibbons, fftys Ret 159. 1007 provide a response proportional to the total energy of (1967). the impinging photon, in this case proportional to the 4. B. J. Allen. R. L. Micklin. R. R. Winters, and C. Y. Fu. binding energy of the target nucleus plus the center-of- toys Re* C$, 1504 (1973). mass energy of the interacting neutron. The measured 5. R. L. Macklin. I. Halpenn. V. G. Percy, and C. U pulse heights as a function of time are weighted and RiRDleur. private communication: tnin-sample areas were nor malized to values of jrr„ryr ol 0.642 and 0.610 eV for the stored via an on-line computer. The "G-weight" proce 13.34- and 13.66-keV resonances in 5*Ni respectively. dure used here* enables evaluation of detector response 6- S. Raman. I. Harvey. N. W. Hill and E. T. Jumey. toys in a manner independent of the details of the gamma- Di* Amu hot Rrp Dee U 1974. ORNL 5025. p. 110. 7* oat rs-tsm* 20 -• WN. (3OM so«( 15 it : 3«olX) (a) r- ; 10 s - • 3 •j^^^Bki.- "• - 13* ; i i * - z o a. OC •900 •700 2K» 2900 2900 3900 3700 «0C 4500 4900 (Ci 160 170 ISO (90 200 2K) 220 230 240 290 2C0 270 280 290 200 MEuTROH ENERGY (cV) F«. 7.13. Nnaaa «K«Mars'Ni(IJ«9x 10^* •»•/•>. 7.25 MEASUREMENT ON THE 22-eV DOUBLET "G-weight" formalism of Macklin and Gibbons. This IN THE "*Th(n,j)2iiTh REACTION' provides a measure of the cross section independent of 1 the debits of the gamma cascade accurate to about \°k. J. Halperin C. de Saussure 3 The incident neutron spectrum was measured in trans R. B. Perez1 R. L MacHin mission with a thin *Li glass displaced 0.4 m forward The 22-eV doublet in the 233TW«.y) reaction con in the beam. tributes about half the thin-sanple resonance capture Since the gamma width dominates in these two integral for 2,,Th. A discrepancy of some 15% in the resonances, the capture area predominantly provides a measured neutron width for the 23.439-eV resonance is measurement of the neutron width. Monte Carlo apparent among ssveral recent measurements.** In calculations evaluating the capture area of the reso view of the special interest in 2,,Th as the fertile nance at 23.439 eV (provisionally normalized to the nuclide in the a"U breeder, we have remeasured the better known 21.783-eV resonance) yield a measure of capture cross section with a relatively thin (0.0002375 gT„ - 3.72 ± 0.11 meV. This value is consistent with an atom/b) metal sample. unpublished ORNL value determined by I. A. Harvey1 The measurement was carried out at the 40-m of*r„ = 3.74±O.I5meV. flight path of the ORELA time-offlight facility. The capture gamma cascade was measured with non- 1. Bull Am. Phyi Sot 20,165 (1975). hydrogenous total-energy detectors making use of the 2. Neutron fTiyncs Dnwon. 80 3. ikpiai for CD transitions from pure ^-vibrational 4. .«MM Oat* Section BNL-325. 34 ed, 1 1 (2) J. H. Hamiton K. Kumar LVameli* A.V.Ramayya2 1 cast serious doubts on the generality of this interpreta P. E. Little N.R Johnson 1 tion. Aldushchenk^v and Voinova report in their Large dectric-monopoie-to-eiectnc-quadnipole (£0/ compilation several excited 0* and 2* states of die £2) transition strength ratios obsenred in deformed same nucleus with comparable Jf(£0/£2) values. A l7 nuclei arc often interpreted as the "signatures" of the particularly interesting case is *Hf. where-there are de-excitation of ^-vibrational states.1-5 This interpre not only three 0* states but also two 2* stales tation is based on the coMtctimnodel equation for the previously measured' with saniar X values ranging £0 transition matrix element:'-* from 0.1 to 05. Clearly, all of these stales are not ^-vibrational states. In an effort to gain a dearer understanding of these M£0) (0 states, we have performed careful internal-conversion- #N ciectron and gamma-ray studies as well as gamma- gamma angular correlation measurements* which yield where i and / are initial and final states of a nucleus. the E2I1HI admixture of the transitions. The latter /?# is its radius. Z is its charge, and 0 is the magnitude of measurements showed the presence of appreciable Ml quadmpole deformation. The nutrix element of Eq. (I) radiation in some of the transitions and. thus, are TaHe 7.10. Exa*ria«eatal£0/£2 tiwition sncnjtk ratios • ' 7*Hf The table gives the dimciHionless ratio where p is the reduced nuclear matrix demest: of an £0 transition and R0 is the nuclear radios Transition Galafher Nielsen Gizon Present i / f elal* etal* etal.c work 0, 0, 2, 0.IS ±004 018 ±0.04 x 0 155 ±0011 0.160 ±0.009 2, 2, 2, 0i4±004i' 1.34 ±018 156 ±015 0,0,2, 0.10 ±0.02 0 115 ±0007 0.066 ±0007 2, 2, 2, 0.12 t 005rf 0.67 ±007 0.76 ±0.04 04 0, 2, 0.53 ±0.16 0 38 ±9 08 0 52 ±003 0 50 ±002 0, 0, 2, 0.57 ±016 'Secret. 8. *See ref 10. fSeercf. II. No 4f| admixture was included in this 2—2 transition. SI absolutely necessary fir i tntamagful donmmibonof EOIEI ratios. Bbek. NmcL Iftys. 7*. I (19**). Our XiEOlEl) values for the five stttes already *. K. Uu, m The Bir*mwmym tir bmememm at mariner H>yaa. ed. W. D. Ill—• n • • Wnita IfciRiml. I • H11 li • • 1974. known, along with the value for a newly established* cm*.Illrpv>.55-llt- 0* state at 1772 keV. are given • Table 7.10. The 7. A.V. AMiii,aiafco» ami H. A. V In order to clarify this point, we compared the as NR,Tc04. Samples used for counting ranged in 2 measured X values with those expected on the basis of thickness from 8.1 to 37 mg/cm - Gamma-ray spectra single-proton transitions. The result is that, although were recorded with Ce(Li) detectors coupled to a the ^-vibrational X value represents an enhancement Nuclear Dau mode! ND4420 computer-based dau compared with y vibrations, it represents a substantial acquisition system. Computer programs for dau reduc rttankitkm compared with single-particle transitions. tion were chosen for their reliability in extracting The present investigation thus has led to the impor accurate peak areas and centroids from dau where the tant conclusion that although large X values may be peak-lo-background ratio is low (about 0.12 for the employed to rule out the possibility of pure y "Tc dau. due to an intense bremsttrahlvng continu vibrations, they should not be regarded as firm evidence um). for ^-vibrational slates. The energy of the gamma transition in "Tc was accurately determined as 89.601 0.05 keV. This value 1. A fad account of lh» work wat puMbhed recently: J. H. agrees with earlier measurements on the energy of the Hamilton. K. Kumar. L. Vamef. A. V. Ramayya, t. E. Little, first excited state in "Ru of 8936 ± 0.40 keV by Moss and N. It. Joh«KM,Myf K<* C10,1540(1974). and McDanieb1 and 89.6 ± 0 J keV by Antoneva et al * 2. Vanderbilf Lmvenity. NadrriHe. Tenn. By using 98.906 for the atomic weight of "Tc and J. J. O. Rasmiwn.iVur/ Mri 19. t5 (19*0). s (2.I4± 0.05) X 10 yean for its half-life, the intensity 4. J. H. Hamilton, W. H. Brantley. T. Kat.m. and E. F. Zaanjar. Inimtl Conwenkm hoteaes. ed. '/. H. Hamilton. of the 89.60-keV gamma ray was found to be (4.92 ± Academic New York. 19*6, p. 297. 0.45) X 10"* per disintegration, in good agreement S3 ORM.-OMG. 74-84.3A 5. S. RMU aad N. B.Coie. /*»« Rtw C 7. 1995 11973). tc 6. C. fc. Eagcftr aad J. D. Utaoa. Hin Rev C 9. 2JS8 43 (1974). £t4 « tQ*y 7M * "N4 DECAY AND THE ' 3*Pr GtvOUNDSTATESrm A 00012% B.H.Keteile A.R.Brosi' loa y • 15.8 The study of the decay properties of ' 3*Nd and the excited levels in ' 3*Pr has been completed.2 This work /g^-ioo% -8&60heV is part of a continuing effort to elucidate the charac teristics of nuclei which fall between the 82-neutron Of * 292.1 ±3i0keV closed-shell spherical region and the deformed region of lower neutron number. This 50.65-min activity was produced by the ' J»Ce(,HeJ/i»,,*Nd reaction on the ORIC. The total decay energy was calculated to be 2211 ± 25kcVi~rom 44RU the measured c/p" for transitions to the I49.2-keVIevd oi praseodymium. Energies and intensities of 30 gamma Fij.7.14. Record decay of"Tc. rays have been measured, and 17 gamma-gamma coin cidence pairs have been observed. The multipolarities of the three most intense transitions have been determined with the value of (6.5 ± IS) X 10"* reported by from conversion coefficient measurements. Based upon Legrand and Morel.1 The gamma peak area correlated this information a decay scheme has been constructed accurately with the mass of "Tc present in the showing the beta branching to 11 excited levels in samples. From the average measured mixing ratio 52 = ,3'Pr. Spin and parity assignments to nine levels have E2/MI = 2 J ± 0.0S the total internal conversion been made. Configuration assignments using Nilsson coefficient was calculated as 1.55 ± 0.10. The total orbitals have been made to the ground state and the decay intensity of the 89.60-fceV stale in "Ru. first two excited levels. These are consistent with a corrected for internal conversion, was deiermined as small prolate deformation for ' 3*Pr. Other levels are (1.25 ±0.10) X 10"* per disintegration. thought to be the result of weak coupling of the I* The resulting decay scheme of "Tc o presented in particle states with 2' core vibrational states. Fig. 7.14. The comparative half-life log/:« was calcu lated as 15.78 t 0.03. which is consistent with the few 1. Deceased. previously known cases* of second-forbidden unique 2. A. R. Brosi and B. H. Ketelk. .Vurl flra .4 245. 243 beta transitions. (1975). While this work was in progress. Engelke and Ullman6 carried out a study of "Tc decay by beta-gamma 7.29 DECAY OF "JPb(ref. I) coincidence spectrometry. They verified the assignment of the low-energy gamma ray as discussed, measured the L.L.Collins2 H. K Carter3 gamma energy as 89.5 ± 0.2 keV. and estimated the G. D. O'Kelley R. L. Mlekodaj3 intensity of the weak beta transition as (1.2 ± 0.4) X L. L. Ricdinger3 J.W.Wood4 I0'5 per disintegration, all in excellent agreement with C. R. Bingham3 R. W. Fink4 the work reported here. A. C. Schmidt1 E. F. Zpnjar5 E. J. Spejewski3 J H. Hamilton* i*s 1. Oak Ridge Associated Universities. Present address: Texas Levels in Tl have been studied through the State Technical Institute. Waco. Tex. 76705. radioactive decay of 16-min "5Pb The activity was 2. J. Legrand and J. Morel. Ptiyt R'v C 8.366 (1973). produced in (' *0, xn) reactions on a natural tungsten 3. G. A. Moss and D. K. McDaniels. fhyi Rew. 1*2, 1087 target and continuously sepaiated using the UNISOR (1967). 4. N. M. Antoneva. K. P. Grigorev. and L. F. ftniasnva. /;r isotope separator on line to the ORIC. The activity was Akml. Nmik SSR. Str Fii. 34,865 (1970). deposited on a metallized Mylar tape, which was 83 periodically moved to various counting stations. The By contrast. n,;l and h 3/2 states are raptdry changing conversion electrons and gamma rays from the decay of with neutron number. These sutes are intruders from '*5fb were detected in the singles and coincidence above the Z = 82 shell-model gap and are not expected, modes, and their spectra were stored in a computer. at fust thought, to occur at low excitation- As The single, gamma-ray spectra were recorded m the explained by Newton et al.,7 these states drop, partly as multiscale mode, so the half-lives of the gamma-ray a result of parting energy when the 81st proton is peaks could be determined from the data. Our work has promoted into these levels and partly as a result of a led to a level scheme of "fTI containing transitions slightly oblate core deformation. between 21 sutes. Of special interest is the nature of sutes bunt on The motivation to undertake these experiments was a these high-/ orbiub. We have observed a very extensive desire to leam more of the properties of single-proton set of levels in the A,/2 structure. The yrast members of states, and the structures built on them, m the region this band are / = 11/2", 13/2", 15/2", and 17/2". In immcdiaiety below the Z = 82 closed proton shell. addition, two side bands are observed, one possibly of Figure 7.15 shows the trend of these proton states as a spins 5/2". 7/2 ". 9/2 ,11/2 *. 13/2". the other possibly function of neutron number. Low-spin states of "5TI 13/2". 15/2". These non-yras* levels can probably be are populated in the decay of the ground state in explained by the calculations of Meyer-tei-Venn,' • "5Pb. although we have not yet been able to measure who used a uiaxial rotor model. The energy sparing* the half-life of the ground state directly. Th? d3/J and are rather well reproduced if the asymmetry parameter dif3 excited sutes suy relatively consunt in energy y is set equal to 37°. These bands provide one of the 7 relative to the S|/Z ground states of thallium isotopes IKS! demonstrations to date of the importance of (Z = 81), a trend found also in gold nuclei (Z = 79). The triaxial shapes in nuclei. hlt/2 state is heavily populated in gold nuclei* but had not been seen in thallium nuclei before our work. It S ,3 1. Expanded abstract of a paper presented at the KnoxriBe, occurs at 1361 keV in " T1 and at 1319 keV in ' T1. , Term., mediae of the American Physical Society, lune If 18. known from UNISOR work* or* the decay of '• Pb. I975:»W/ Am 1+vs Soc 20.830 (1975). 2. University of Tennessee, KnovviDr. 3. UNISOR consortium. 0»«K.-3«6. TS-IJ»3 4. Georgia Institute of Technology. 5. Loucvna State University. 6. Vanderbut University. 1. For supplementary information on these nuclei, see J. O. Newton, K. S. Stephens, and R. M. Diamond, Nuci. Phys. A 236,225(1974). 8. E. F. Zganjar et al. (UNISOR consortium), fkys. Lett., in press. 9. A. Kohler, L. L. Riedingcr. C. R. Bingham, et al. (UNISOR). private cornmumcairon. 10. J. Meyer-ter-Vehn,yVur/ Hiyt.. to be published. 7JO MUMORDlALIUDWEI^MElvTAND COSMOGENIC RADIOELEMENT DISTRIBUTIONS IN LUNAR SAMPLES FROM DESCARTES AND TAURUS-UTTROW1 -2 G. D. O'Kelley J. S. Eldridge3 K.J.Northcutt1 JL £ *' *' »' •. Our previous studies4 •' on the distributions of the mn mn mu mu mn ' primordial radioelemenls potassium, thorium, and ura nium and of cosmogenic radionuclides in material from Fa> 7.15. Symmatjq of proton nam in thamimn troupe* of Apollo 16 and 17 have been extended to include a total odd num. Data fron. the literature and from recent work by the UNISOR consortium. For most level* are shown the spin, of 12 samples from additional locations and with a parity, and energy in kcV. greater range of properties. 84 Prenomiy. we showed4 that the potassium, thorium, The concentrations of cosmugenic radionuclides re and uranium contents of 11 soib from eigh; tMnpan^ flect the general trends due to chemical composition stations at Descartes were strikingly sjccdar. with observed earlier'*-5 for Apollo 16 and 17 materials- The average concentrations of 940. 1.95. and 034 pom for surface samples from Apollo 17 agam showed the potassium, thorium, and uranium respe .livery. Sample effects of the intense proton-accelerating flare of 63501. collected in the North Ray Crater ejecta August 1972. Samples which appear to be unsaturated blanket, showed anomalous potassium, thorium, and in their concentrations of S*AI. either due to partial uranium contents which were about 22% below the burial or to recent exposure, are: 65785. a rake sample: average- We have now examined shadowed sods 63320 67115:70315. 72155. a subsurface sample:and 74245. and 63340. from the same locality, and find them to be apparently buried near the orange soil at Shorty Crater even lower in primordial radkxiement content than the Shadowed soib 63320 and 63340 were collected average (about 31% lower). inskk a hole at the south end of Shadow Rock. 4 Two rare anorthositic rocks from the Apollo 16 rake Comparison with our measurements on ihe concen 2 J collection were analyzed: 65785. a spine! troctobte. tration of 2.6-year Na in exposed surface soil 63501. and 606 !S. a melt rock. Electron mkroprobe analyses* taken 15 m from Shadow Rock, suggests that 63320 of small samples fron these inhomogeneous rocks and 63340 were only 60 to 80% shielded from solar yielded potassium concentrations which differ consi cosmic-ray bombardment. Concentrations of 0.74 X 2 derably from the accurate whole-rock values measured 10* -year *Al in these soils also suggest that the top here. Additionally, we note that 60618 is unique m our layer (63320) and the soil below (63340) were slightly suite of Apollo 16 samples in that it shows the lowest mixed during sampling operations and that Shadow thorium-to-uranium ratio (2.25) that we have observed Rock fell into its present position only 2.000.000 to in Apollo 16 materials, althcjgh the potasshim-to- 3.000.000 years ago. uanium ratio is similar to that of other Apollo 16 samples. Among the Apollo 17 samples was 70315. a coarse 1. Research carried oo< under Union Carbide'* contract with grained basalt probably ejected from 50 to 90 m depth the VS. Atomic Energy Commission through interagency in Sherlock Crater. The potassium, thorium, and ura agreement with the National Aeionautics and Space Admini nium concentrations of 70315 are low and are similar stration. to those of other Apollo 17 coarse basalts.5 Adjacent 2. Summary of a paper acciited for publication in Proc f>th soil 70321 is medium gray, representative of the dark lunar Sri. Conf. vol. 2. to be published December ! 975. 3. Analytical Chemistry Division. mantle at Taurus-Littrow. and resembles in primordial 5 4. J. S. VUnift. C. D. O'Kelley. and K. J. !Wlhniu. in element content other dark soils. such as those Proc 4th Lunar Sri. Conf. (irothim. Cosmochint. Aria. Suppl. collected near Steno Crater. 4. vol. 2. p. 2115. Perpmon. New York. 1973. Surface soil 72161 was collected in a dark valley door 5. ). S. Fldridre. C. D. O'Keiley. and K. J. Northern!, in area adjacent to the litht-mantling detritus from the Proc Slh Lunar Sri. Conf. Ocochim. Cosmnchtm. Acta. Suppl. 5. vol. 2. p. 2139. Perjamon. New York. 1974. South Massif. However, the primordial radioelement 6. F. Dowty. K. Keil, aiwi M. Prinz. in Pruc 5in Lunar Sri concentrations in 72161 most closely resemble the Conf.. (iforhim. Cosmochtm. Acta. Suppl. 5. vol. I. p. 431. concentrations we found in North Massif soils.5 rVrnamon, New York. 1974. 8. Organic Chemistry, Catalysis, and Coal Research 8.1 REAMANGEKBiTOFTHE Meerwein rearrangement occurs with solvent attack at 44MMOADAMAOTYL CATION the back side of the new ion. Any front-side attack would result in some deuterium at the 11 position: no V. F. Raaen C. J. Coffins B. M. Benjamin deuterium was observed in that position. Of the 17 to The diamondoid molecule adamantine is found in 18% deuterium unaccounted for. a small amount coal and in aromatic fractions of petroleum: the closely appears to be in the 4 position, resulting from hydride related homoadamantane is less weO known. The shift, and m the 3 position, the product of hydride shift labeled 4-homoadamantyl cation is reported to undergo followed by w'agner-Meerwein rearrangement. rearrangement1 that would lead to label scrambling. In Sohrolysis of homoadamantyM-tosylate in buffered order to determine the consequences of this rearrange (sodhim trifluoroacetate) trifluoroacetk add produces ment we have synthesized 4-homoadamantane by ring homoadarnantan-4-trifluoroacetate and homoadaman- expansion (CH2N2 in alkali) from 2-adamantone. The tan-2-frifluofoacctate in a 3:1 ratio. These esters, and ketone was converted to the Sdt- and 85 >-*«•• (MML-OaC. M-10497 , itia*».«M Mr Mr c£L 2a. ^«• '»%•• - °a*t «•• • 1 . F>> U. SjmAiiii —1 jali»ljji»TT*>-2 F*> «-l- SjaMiii «T 2-«>«A»1-2<*' ij>la»wM|H^ 2-«X»4 • I 2k =- S* ^ St* ^^0 *0 0 I I- (II KO*c o 1*1 5t» S.tn J / I l~ I H0*C A<0 A 0 Ffe. M. *iofOMd McckMnm for Ac fonmtfM of At Fif. S.2. Product* from At sntvntyfto of 2-mrAjrl-2-{d>- ufcjtmd pmdacts from Ac «oln>ry*ii of <*)-t-*mto 64i alcohol, where the deuterium is 50% era and 50% using very highly p irified chemical constituents could emh: produce crystals which were approximately 3 cm long and suitabt; for neutron scattering studies. Neutron scattering experiments are being carried out by H. A. Mook of the Solid State Division. Future plans m this area are to prepare TTF-d4-TCNQ for further neutron scattering experiments. In the search for conducting organic charge-transfer D(50%) complexes. TTF-halogen complexes were prepared and studied. It was possible to grow the crystalline TTF- 54-Dimethyl-2-exo-aorboniyt-6^i akohol rodine and -bromine complexes by diffusion of the respective components in acetonitrik solution con This deuterium distribution is consistent with a mecha tained in an invert ."d U-tube. The TTF-iodine complex nism which allows cation equilibration (or a nondasa- was found to exist in two distinct polymorphs, a 1 cal ion > after the initial 6,2-H shift. chunky orthorhombic form and a needle monoclinic form. Conductance measurements by R. J. Warmack (Health Physics Division) show both polymorphs to be 1. Oak Mpe Associated Unnenilin FeBow from the Mm- good conductors along one axis, and approximately mnir of Tennessee. K*ox*M>. Th» wet ion a a portion of the comparable to TTF-TCNQ (about 300 A'1 cm'1). In Ifc.P. dmcttoitoi. of w. W. Schmidt. following the conductance of the monoclinic form vs 2. C D. Sargent. The 2-Nofbanqrl Cabuo," chap. 24. pp. 1099 1200 M Cmbommm hms. vol 3. G. A- Oh* ami P. v. R. temperature, an interesting hysteresis effect was ob ScMeycr. «*.. Wiry-lnleriarnce. New York. 1972. served. The crystal structures of the TTF-iodine com 3. C. I Cottars and C. f Haute*. J Am. Chrn Sot 91. plexes are unusual, and C. K- Johnson (Chemistry ?I94(I969>. Dhision) has determined preliminary crystaUograpfuc 4. <; A. Obh. A M. White. J. R. 0e Member. A.Commons. parameters on both the orthorhombic and monoclinic mdC Y. Lm./ Am Chrm Sot 92.4*27 (1970) forms. The TTF-bromine complex is also a good conductor, and its physical and structural properties are under 8.3 SYNTHESIS OF ORGANIC CONDUCTORS investigation Future plans include a study of 8.5 NUCLEAR MAGNETIC o o it * c c RESONANCE LABORATORY tC^H,) ^-CMC-OU"J • Cw,-0»^CO »VV r** •*•*• *' " O-C-O^CH, B. M. Benjamin L. L. Brown C. J. Collins A modern NMR laboratory was established to meet increasing needs at ORNL. Persons desiring to use NMR CMjO^ -C = C -COOCM, in their research ?re encouraged to contact one of us to discuss possible application?. A Varian XL-100 NMR spectrometer with Nkolet fast Fourier transform has been installed, tested, some defects found and elimi nated, and is now in operaring condition. With the OWC=C-C00N =^' C-j-CHc-CMjlUMk* equipment in its present configuration, we are capable IV V of obtaining ' H and ' 3C spectra in internal !H lock mode or in external ' *F lock mode. The two modes of operation permit research samples or routine samples to be mn in almost any convenient solvent is long as the solvent spectrum does not interfere wifti the sample spectrum. The following is a list cf die kinds of problems wv can study using our present NMR capabilities: (I) identifi cation of compounds. (2) elucidation of organic struc The reactions were repeated, with the exception 'hat tures. (3) investigations of the course of reactions or in the last step LxAlD4 was used at the reducing ages' processes. (4) quantitative analysis of certain mixtures. to give (5) ratios of aromatic to aliphatic hydrogens. (6) conformational and configurational analysis. (7) ex C-J-CSC-CHJCO^ON change and other time-dependent effects. (*) kinetics of VU-01 certain reactions. (9) spin lattice relaxation times. (10) molecular rearrangements. (II) deuterium and "C labeling experimenM. and (12) isotope position substi In each step of the sequence of reactions. NMR was tution. The data gathering technique depends on the used to ensure that the product desired was obtained, kind of problem being investiptcd. Samples are gen to determine purify of the product, and to confirm the erally not destroyed, and their size is of minor position and degree of deuterium substitution. importance. It is possible to obtain spectra of com Alcohols VII and Vll-d, were separately converted pounds in solution ranging in concentrations from to the trifluoromef hybulfonale esters, which were then greater than 100 mg/ml to less than I mg/ml. sotvolyzed in trifluoroacetk acid. The product. 2-meth- The NMR equipment is being used to investigate a ylcyclobuianone from the deuteraled esier. was found variety of problems: die skeletal rearrangement of the to contain an equal amount of deuterium in the 3 and 4 homoadamantyi cation (with V. F. Raaen); the homo- positions, using the integrated NMR spectrum. From •» dot dst «• wnyf cyeJo- I of dar ds—nary of cod As d* renal of afttMirn/ 10 No 6 for wkt fir* itifcn A \ were noted O.ISgofcaialysi| ~ Ikgof of *a* range 177 u> 2*7 —H 50un avei. TW catab/M was contanaed m 32-t mi—it naceralnanr carbon W2*?.hydrogen.5.1*5. <%•«.» wbmg and pbeed m a I wxronra iMT.ioJte I 2*i. V«nwtwas..indud• of an to 200 cc —n INTPI a m—lf Heel die * a |iri—i-of JawOhg/an* and of •» to 05 *Ta labont SO was watn cMkjBUMtnr extracted waaa bot. dry pyrnhnr of from 0.1 k>?0»gof The fratwnn of wavn< extracted aa nan way was 35**" into a byOmyn —n what* curiaatt hydrogen saatair * a tonunriatioa winch can be varied A nrass spectrometer n n»d to nwasnrc bodi oat hydroges wdftdr concenwataon and dsr extent of •V pnAK«Mb •catena' afforded ** dark-brown ran—a fracw«n far whsvh war raw» at abstatk to dw.cn for ten pinposti mrrerpuwded w wetght howdy jumuth. hydrogen* *a» I 7* The canom fractions, snaceveiocJtirsofO I to 10. which arc io be Mabaxted io tnrdsrt JH—id tatat- to •nitnn. bwtane. and hydro- MI. were ***** wader argon i«» protect dim from dar cowaawons ejnntnycd m dut »\\ftn stwly. Sance bntadMne v an mwrmewnie m die redwction and does not affect war nanwjactnmy.it was I. %. S l*».«tm jao L. A. Harm CMtM. selected at a naodel consponnd HI a stndy of dar catalytic acimry of cubah murybdau as a f— itiun of dw gat pbase nwfnr actmry as an by tbe HtHtj rado The Mdfnr atman ward m dsestwiy wereabovt 10'* »7 CHEMBTHY Of TW REMOVAL Of to 10 " fa IHJS fractions of 10 : !o 10**1 HETEItOATOMS FROM COAL Tbe rcwltt of dnt ttwdy m Table SI. R A SireNow L. L JofuMim which awt» die ratio of to bwantr as a I of ibe hydrogen of ibe hydrogen. In JH coal conversion pnvetsfi it B necessary to remove the organicafy bound beterualums. sulfur, nitrogen and »*ygen Both catalytic and noncatatyiK *JTC. processes hare been stnaYrd widely bat bmh lands of processes are far from being completely undmioud. HjS ''WMTJIM m H» —^-.» Catalytic processes mchsdr bydrodesasferuation and ivntafWI hydrodenitration Xoncautytic processes mcfode hajji- temperature organic reactions invokmg either transfer M •J of hydrogen from a donor sohreni or direct reaction » «• with hydrogen Became of Ibe importance ol catalytic J» 2.7 Jl hydrodesulfuri/ation. it was chosen as ihe nuiial area 2J» 5S 0.9 for study m ihn program 7* 0.7 0.9 The effect of catalyst conditioning on the trhximty •5 0J5 0J0 «»f J commercial hydrosulfun/alion reaction wa» ad 115 04 dressed fwl Although n t\ well established that ioao -1^ «• % ptoauaaora' aaaajaaa. m *tmmy lot biff rraW vwfnjM Mb J •nanu*' ••* *r Mrtak Ml :m jpprjrt to nai jl jbua* 100 past H:$ * Cruaa DMMUM J « Ijnm of *r 1'HHMII .< hxjfoaja Tla» a pNiauH> aW to %urptaai ikmaztct i%tw« of birar Ji kara afcfaxr* i*;«atari «t Mritahai Mm «•! tbr tc .ataK*t* mill H:$ mi kytropra ••* thr puarhlr p*d p>o0)» fa.MjUa' RrjktwaK wex %tmt4 »at m J aajl >4 a>aaj dan* react**** k> chafactrrt/r the dUK« a» arf a» i»» rrtatr the aafjcr doMn to pa* ottyw KraraAy J» J» aatul hyai ajta pin a*r «f jhoai I"»< pa ahach a> ja oain ot aiaajataar haM» Oua 4kjc Una ThrvjUhlK aMh «»f»yi)!awiccviw. aal •A KtMIIUWiOFIfW0TKC»TWC car hyaViajra >ahua rj*»> »j% jhuai dui irajaanl i«« CATALYSIS WITM « ATEB V ARM ihr i A $ D»oriun C t SfcMih Thrtr rrarfit «boa lb* ..cnjai i4 ibr J.HIK kauri v> tiran arc fat\ JA jtuvr j» arji anatvaUr Ai;f I. %a Thr mofvii <*rvnV4 hrrr I«MU> at r^pkirjiury aaporljai fcjtarc «t ihr a«t»,«% Mran t* Out ihr> hj»r vitMbn of moiirn sd\ »y»i«r* » mdyu* for ihr matrh toarr vapor pr»warr\ ihaa arjl AJ;fl» jad. nnihrw of forb from «:•«! The n»rtiiBjii<«j». which brawr. cja hr wir4 JI htsJkrr maaruiarr% when- ha** ima bem trinwuHil. wrw «:nn«m»eJ with *r prtahxl >rW» jrr bahrr ja4 dkr Nvoarn •«* ihr brji hviiniprmiiiw of coal to pmimce hahi knekmiihnm •4 react**) r» m*ar fjmrjhlr A anakv drgrrr >4 j*d with ihr hv4ri^mj«>«i of carbnn miMMnMV kiaiifoi <*rf ibrf't ( * pnnlaci iiilwkalaaj a praaaaV Sludm of ihr hydmprrutfwM of coal weir cjnwv "Ml m h> coniroNaM; ihr Vent* jvafcn -4 ihr tail nail •I \ wwtl bar •»! ..afaJvffc. fe\«**. j Rt>it<« vrft medium *-«aki he mod :•• *..<«mn<«i«i' \IA-4tcb <«c <>•*> »•! ent\ VI«JJ iR t|Wfr At% «a>. Ar »er\ ;jfflr brj! • •? ffa.tfe«l«B»<«if <<»i*.j( n»4r in thjf ptiBkCo jiv» rcqwto ^•«iljk.l "nctxvn j u4id Ar .. jw ••? sacAaBjftxnt V-mlasc vtuAfv ^t»an*4 Ajt v*. uni jnd j ttfei caiaiv «( w<«4 ..*jit <$r \ \ \ •2 me prodacrd e a faw».fwMi of teraprTataftt. parawr. In otjer !•• auf» tbe aaportjat paraa*rter> m aad aW aviv Quo elhtdropra tocarboa mmmnate m atrtbaw itr — ILIIII—l|L a vuMpatff propa* has atrteflieav bcea wnttea to saaaiate tbr opentiua «* a ictonaet l» oran to MI HBp.li At effect of tadmHnoi TW prognai coaasts of tx> parts Hi a fceeV irmfxiatare 11200 to 1*00 FI MKM. aV teed K» •mm to*awaa«e a tibjaattoa reactor Tar pfupaai wtadi cctW) of a —lift of sieaai aad andiaat Mfc?» Eoy III to |3l MTtuwh tot par* jrt* of ••in yeaned oaAwn of ifpmit aad picssare. ipfiaaa^ ..iwaMnwi Oafjpat fiw« ate yurs*m aafc- aM I't a daft coanrnrr oprrataag at a loaer waarra- dn aV ciwap naina of tar rut f» J4 afccAn or tar le*. "50 F| Thr feed to a* daft ciawrrlrr not txfboa. ndid as Jjjaphile .* a- ""TJnH- catbna. cuaasts of tbr rut ten trnai aV bah-teaseratarc wfl pKopMate aatVr atr «petifk« •TiaM| coaa> •rat tor N aV daft oua»eiKt aV proaW-tMn or ooav h aU*M to *t autrna! Maun, hen effects bsatopra o iiMtabjt eabaaLxd •» the daft urataua JK abo coapMHI. aviaamr. both ^tiiutbh brats aad |L>| I'H abadi » tav»«c4 at tbr Wm*i tempcTMmre tbeewdialpj of reacnua. As M aV aw df jftii pruvru. iy mat aaaiKaaas The — ii -mi m iiaaaj, process m be m*ed •am be coatrUki as Tdiaar-tfeaai irtoiaaaf »> t*-ai tot ate proaacava «rf by4ropm froai atrtbaar p» The Aipnyon^iaaa • of aV carbua auaiua* 4nr> K»4 dMBical eqaafboa •mtwia' a •*» paves* arc paccncK ocoif hi aaia>>« fc> aW aufcmai Uaacrv brat et:c.i> ate suae as time iMi-id a ibe proaWuo* of jte ah«» conpaici. akJaaaa; al j>aia^l> beats amk tfce aytbrv treat c«b« amaouar mi byaropr*. wtp eatbalp> Aaapf t*nib » tbe Nionarr mi. m tbr daft ifcat tbe 6m reactm n camei oat K rir newer** oiacenei R<~arit> •^Maawd tr«an naaaac •brie p»»- dmvooa SAX das re»n*e react** .» eaanateraac. oaatt waart a tanen »f op«r»fMW voadmom anil be beat wast be mppbrd to aV «%«•«• • orart to proiacc paHebci m a Mpaiaie report b>4r ipra troM mrtbaae Hrace tte anbav-neaai cetoraaar. process prw.Jc* a •K*taal tor stonay brat carrp dMaui> 9. Biophysical Chemistry •I SWCLETEXOTAllOKTBAMFBIHtOM rst\ poor baadaaj of torn anennnnci. r, , < 001 Saaahf km «aaaEs«4>, : anparraaV dua doc reaaaircd »•» seavttir the r.-im- air »btjanrd I 93 . fA.btc*Mra a>aam.ji onl—ua «•« aV ^wttoi »*jfc-. i-iaVf dun oc *M SO ban laVoat ISO A»» i* •*•*?*•* tfKtaui ntfaeuoua « j puaM .4 J>.-aur*.jt»w to bt anriaatoJ to danrt Fonan master to «V life okatMed ate anneal •* jar jikaaajayfc> M> 'A b* dwoaMajawcr m. m 2L 1 mttL M^matwnt- 10. Chnual Physics MLI SiaUC1UUL4 mu K.H. A.H. I • .|«T|I 4 % f (MM R.fh> *i « *iwir.i*?ii • X Sar ».Ji^»r ftk. ' f»r. 0*J» gam*. Mm tSfecmt aaa i* II. Xr« T-*. I*J* avataeof of C, =72 cai aapk'' *» ' wat ulnaiiica for *c saeaajc heal of aae aaaae!. The tataes ai aae MR> titan lor*" * lOTC nap fam C» *».• cat aeg ' oa* •Hie'1 to C» »«.4 cat note" acg *. Ike arff- tttmrnm cotfBcaan —i iiblaa*a ftowdie aa-aimk doae of dar aa?a» fiaw awaU: raw at niaar rang of IIK aaroclcv A vatae of O- 5.2 x I0'5 cm1'9c for he wry the MM coajaaars ocfl villi *c «aJae 0 « 4.5 x 10_* • dat laboratory.* The aaunaaaij at the coaauats •» jaM oara*. the mi—ifd aa- oaftrr (atKjCM. fir* i • die laboratory —jam—u, li • **ff |«5. saoafani kaooaj* dm iffawr aaa* odttr traaaaort aroperoes boaai. aaHjO caa be •Mateo' ai am I are very amative to anocaracas m the aoteaoal OK effects of tfractanl aaa din awl aarnaVr ON be faactna aa4 danefoee nm u a suaajeat am of dK atparaaed. Like aaaiy other aatenab. aaHjO s are- aered by vapor aaaoawaai oo a coM aaailiJle. Thai m V A. lbs. Aor XmL 4*m1 Jn. Mi •*,*•• I*'?• (M Imtail I Itav M 3m Sir SCO VakMHt S. A. tot. MliK Scwmc€ M*. 92711974* * * D Itorf it m* H. A Lm.; Am Cm-m. SR M. **s •!**;•. 7 r a toafctanfe. S- V Iter, JM* 1 * kn /. C*n* /fttt. 4JLI4»5il«7S> • $ *. bar. /i»Hfc*r Obvm Font*., m Tomn fcftratcr 1975.» It It IJ C. M. Irawii HALny of «• to* l«TK Ml 7TKI • a camjami attjO Wn of water aafjr-oyftjl 98 neutron diffraction studies of the three compounds electron density map of SGPB described the identifica H,P*'lI0«o-nH;O with n = 6. 29. and 2t. T.ie tion of the active site of the enzyme and two of the symmetry and lattice parameters of these substances are residues of the catalytic triad, namely, histidine 5? and summarized as follows: serine 195. The path of the polypeptide chain could not be followed with confidence at this resolution, although it = 6 » = » « = 2I there were clear indications of extended 0 structure in Sj*ee group frt3m Fdlm Kca the model Extension of the phasing of the reflections 7. 2 8 4 to 2-8 A minimum d spacing has been achieved with the a 12.1506(5) 23.272(5) 20.788(10) use of live heavy-atom derivatives and has revealed the b 13.086(3) complete path of the polypeptide chain with con c 18.879(5) comitant identification of the 185 amino a.;:4 resi&es present. Although the overall primary-structure homology Details of the hexahydratc structure were presented with the pancreatic enzymes a-chymotrypsin. etastase. in a p-Yvious report.2 and trypsin is slight, the tertiary-structure homology is The 29-hydrate has the anion arrangement deduced much greater: the conformation of two-thirds of the by Bradley and luingworth.3 but our data do not tit the polypeptide backbone is similar to that of the pan water locations which they describe. We have found creatic proteoses. The two disulfide bridges 42-58 and two kinds of disordered waters which account for 18 191-220 contribute importantly to these conforma molecules per formula unit. The remaining waters may tional homologies. There are. however, three major be so highly disordered that they are difficult to detect, regions which adopt a completely different tertiary and no evidence for the location of the acid protons has structure from the pancreatic enzymes. The microbial been found. A new neutron data set will be collected serine proteases are clearly more primitive than those of from a deuteiated sample. the mammalian pancreas, yet the tertiary-structural The formula and lattice parameters of the 2'-hydrate homology conclusively supports the case for divergent were reported b> Kraus.4 We have solved the structure, evolution of these two enzyme classes from a coninv.m and refinement is in progress. The phosphorus atoms ancestral gene. are located on the twofold axes. 4J. with r = 0.445. The anions have approximately the same geometry as 2 1. Thi« n an expanded abstract ••! J piper whmillcd In those described previously. and pscudo 4 axes make Mature \l.i>ndim\. ancles of 20.4 with the [I00| direction. Twelve kinds 2. Department of Hn>chcmiil,v I niverMty of Alberta. ot water molecules have been located which account for Kdmonlnn. Canada. the reported 21 molecules per formula unit. 3. P W. Coddini:. L. T. i. IX-lbacre. K. Ilayakawa. W. L. 11. Ilulvheon. M. N. (i. James, and L. Jura%k. ten J Hioclum 52. 208 11974). I Gr.idu.iK- student. Instit'it tic Phytiquc. l;nivcr«l< dc Liege 74. ORNI.-4976. 10.1.5 An Algebraic Method for Analyzing Large p. I4A. Rearrangement Networks of Isomeric Molecules 3. /*•->< K. .W. l.imJnn. Ser. A 157. 11 3 (1936). 4. /. Krislalfov.. Kristellgrom.. KrystattpHyv. Kristallchcm. C. K. Johnson J. Goodman1 94.256(1936). Suppose wc have a mole of molecular isomers, each of which is distinct from all others. How can we handle 10.1.4 Tertiary Structural Differences between such a system involving 6X I02'"" isomers? This prob Microbial Serine Proteases and the Pancreatic lem at first seems unmanageable and of little chemical Serine Enzymes1 interest, but the fact is that Avogadro's number is approximately 24!: thus certain organic molecules L. T. J. Dclbaerc2 W. L. B. llutchcon2 involving 24 substituent sites can produce an isomer M. N. G. James2 W. F. Thiessen network of tliis magnitude. Clearly, any attempt at This report describes the determination of the tertiary exhaustive enumeration is predestined to fail, because structure of the "B" protease from Strcpiomyccx contemporary computer systems arc capable of han griseus (S(iPB) by x-ray crystal-structure analysis at 2.8 dling arrays of only a few million discrete items at best. A resolution. An earlier report1 on the 4.5-A-resolulion An alternate approach is to invoke combinatorial group 99 theory1 of the type used by mathematicians working undergoes rapid dimerization to yield the cage-type mol with finite groups ecule ! J.S.7-tetramethyl-2.4.6^etratruaadamantane.2 We have written a PL/1 nonnumerical computer program ORPECRAN (Oak Ridge /Vrmutation Croup QftML-DWC. 79-4179 Analysis) based on an algorithm devised by Sims3 which allows us to store a canonical description for a permutation group in a space proportional to r3 rather than n! storage locations. The algorithm utilizes nested stabilizer subgroups with subgroup generators derived by Schrekr's method.1 The input to the program includes a description of the reactant isomer (i.e.. permutation character set base), a list of allowed rearrangement mechanisms (i.e., group generator permutations), and. optionally, a list of conceivable s s products to be tested. The output from the program is the total number of possible products (i*.. order of the The compiexing properties of this molecule for inorganic permutation group) and a yes-or-no answer as tc the species have only recently been investigated in the existence of a reaction path for each candidate product. extensive studies of Professor Lauren R. Wilson and his The algorithm also is capable of supplying one rear co-workers at Ohio Wesleyan University, who have rangement sequence connecting the reactant to any demonstrated the compiexing of Hgfll) Ag(l), Pd(III), accessible product, but this path is almost always much and Pt(ll) as chlorides, bromides, and iodides.3 longer than the shortest possible one. At present the The material for the present study was prepared in program is used mainly to verify that a path exists the laboratory of Prof. Wilson by reaction of PtG with before »arching for the she'test one with the 2 4 23 Ci H| S in ethanol and reaction of the resulting ORNOCAKE program. The 6X 10 -isomer problem 0 6 4 chloride compound with excess Nal. Well-formed, deep of the 24th-degree symmetric group described above orange-red polyhedral crystals resulted from diffusion can be analyzed in about 2 min of IBM 360/91 time of hexane into a solution of the compound in methyl with 200 K bytes of storage. Simpler systems like the 5 ene chloride. 80.000.000-isomer norbornyl rearrangement system*' require only a few seconds of computer time. X-ray examination established the space group to be P2XIJ with a= 14.243(1) A, r>= 15.073(1) A, 1. Oak Ridgr Associated Universities summer student c = 8.7696(5) A, & = 113.797(6)° (23°), density 273 trainee from Barnard College. New York, N.Y. observed by flotation, 2.75 calculated forZ = 4. The 2. W. Magnus. A. Karrass. and D. Solrtai. Combinatorial structure was ueduced from an E1 - 1 Patterson Group Theory: Presentation of Groups in Terms of Generators function prepared from 5029 symmetry-independent and Relations. Interscienct. New York. 1966. molybdenum Ka Bragg intensities, followed by Fourier 3. C. ('. Sims. p. 169 in Computational Problems in Abstract Alfehra. cd. J. Leech. Pcrranwn Press. New York. 1970; C. C. synthesis of the electron density and least-squares Sims. PTIK 2d Symp. Symbolic and Algebraic Manipulation. refinement of the parameters. The RF index for March 23 2$. 1971. las Angeles. California, ed. S. R. Petrkk. f8 > o(F*) at the present (incomplete) stage is 7.8%. p. 23. The structure contains the discrete molecules illus 4. C. K. Johnson and C. J. Collins, J. Am. CHtm. Soc. 96. trated in Fig. 10.2, with platinum coordinated to two 2514(1974). "adjacent" sulfur atoms of the cage. Bond distances and 5. C. J. Collins. C. K. Johnson, and V. F. Raa*n. / Am. Chem.S'x. 9*. 2524 (1974). angles and significant imermolecular contacts are listed in Tables 10.1-10.3. Of particular interest are (I) the lengthening of the C-S bonds involving complexed 10.1.6 The Crystal and Molecular Structure - sulfur over those involving "free" sulfur and (2) the of the Complex of Platinum Diiodide with the reduction or the S-C-S angle involving complexed Dimer of Dithioacetylacetone sulfurs (97.6°) compared with that involving free H. A. Levy J. R. Long' sulfurs(113°). Intermolecular distances are of normal values, with The sulfur analog of the well-known compiexing six I—S contacts per molecule at 3.97 to 4.00 A being agent acetylacetone has never been isolated, since it noteworthy. 100 TaWt 10. X rcoMarts<4jOOA Type Distance (At I...S 3.98.4.00.3.9/ t.-CHj 3.99 S...CHj 3.74.3.82 CHj -.CH, 3.89.3.75 1... CHj 3.99 1. Great Lakes Colleges Association student from Ohio Wedeyan Unr*oaty. autumn 1974. F«. 10.2. Tfe* stracMe of Ike OJ.5.7 2. Fromm a*d Zktsch. Bthchir 39, 3S99 (1906): Fratca H»MMttqfl-2.*M iriitfcinlimialwr) and Rraeodstroem. Ark Kemi. Mmertl Geol. 2M 10.1.7 A Nevtroa DiffinctiiM Stady J of the 1:1 MokcalarComflex of 7,7.8.8-Tetiacyaaogjaaoctaetlui Type NwiftCf Durance (A) Spread p-Terpaeayt' Pl4 2 2.59 0.00 G. C. Lisensky, C. K. Johnson H. A. Levy ft-S 2 2.30 0.02 C(I>S(2) 2 I.M* 0.002 Continued interest in organic compounds containing coysitt 2 IJ4« 0.02 C(5>-S<6> 2 1J0» 0.004 tetracyanoquinodimethane (TCNQ). some of which C<7>*6) 2 1.81* 0.01 show promise as electrical conductors, has prompted us C(IKt9) 2 1.55 0.03 to examine the structure of this molecule in various C(3>C(I0> I IJSJ 3 C(7KC(10) 1 1.54 environments. The 1:1 complex whose structure is COKCtU) 1 1.54 reported here, that with deuteratcd p-terphenyl. does CC7KC(14) t IJ» OOS not show electrical conductivity. The compound forms 134 CtlKdl) 2 dark red crystals, space group PI. with one molecule of *A*crattl.85A. each component in the unit cell of dimensions a = *Af«rapr 1.805 A. Note the disunion produced by oaordina- 8.0189(5}. b = 8.8927(5). c = 8.0264(5) A and o = tkm with platinum. 96.413(3). 0 - 95.861(9). y - 102.800(7)°. The structure was solved by fitting the transform of terphenyl ORNL-Ow*. 75-10916 Y (•) OR ORNL OM» 75-10915 06 isolating a crystalline substance from ethanolic HCI solutions of saxitoxin- The crystals are orthorhombk, space group/"2, 2,2,, with* = 9.213(2),b = 11.837(3). c = 18 573(7) A and Z = 4 Chemical analysis indicates a formula of C1H15N7O4CI1, which suggests the inclusion of a mole of ethanol per mole of toxin. A set of intensity data (copper ATo radiation, 29 < 100°) was F» I0J. Mofccnhr strecfe and diwusinni io—d for ») collected by one of us (J. B.) on a Syntex Pi TCNQ and (»)p hrghenjl awtende*. Note the dose agreement diffractometer. among chemically equivalent dimensions. After unsuccessful initial attempts using conventional direct methods, the structure was solved using the Oak The molecular structures found for the two component Ridge programs. Four phase sets for the 132 unique molecules are shown in Fig. 10.3. reflections with \E\ > l.S were produced; an £ map based on the set with the highest overall self-consist ency contained 24 of the 26 nonhydrogen atom 1. An expanded description of this work has been accepted positions among the 29 largest peaks. The remaining for publication in Acta OystaUogr. two atoms (the carbons of the ethoxy group) were 2. Oak Ridge Associated Universities research participant from EarUum College. Richmond. Ind. located by Founer techniques. Full matrix least-squares 3. C. K Johnson. H L. Reed II. and R. F. Hall. Chem. DH. refinement of these atom positions with anisotropic Amu. Prog. Rep May 20. 1974. ORNl-4976. p. 155: W. E- temperature factors, as well as the hydrogen atom fhiessen and R. M. Metzger. ibid., p. 149. positions (found in a difference Fourier synthesis) with isotropic thermal parameters, led to a final R{F) of 0.05. In addition to the two chloride ions and one water of 10.1« The Stractave of Sax'rtoxin: A Test hydration, the asymmetric unit contains the structural of Improved Methods for Sohrng the Phase FroMem entity 11 (R = C3H5). The inference from this work is W. E. Thies«en Jon Bordner1 that the corresponding entity in saxitoxjn dihydrochlor- ide is II (R = H). a result consistent with the available 1 In a previous report. Busing and Thiessen presented chemical and spectral properties of saxitoxin. some improved computational methods for solving the crystallographic pha problem. We describe here the results of the solunoi. of a complicated structure which I. Department of Chemistry. North Carolina State Uni- was obtained by these methods after a widely used computer program3 had failed. 2. W. R. Busing and W. E. Tfnessm. Chem. Div. Anm. Frog. Saxitoxin is a neurotoxin which is among the most Reft May 20.1974. ORNL-4976. p. 150. poisonous substances known. A decade of chemical 3. P. Mam, M. M. Woolfson. and G. Germain. MVLTAN. a Computer Program for the Automatic Solution of Crystal work by H. Rapoport and his colleagues at the Structures. University of York. York. England. 1971. 4 University of California, Berkeley, led to the proposal 4. i. L. Wong. R. OesterHn, and H. Rapooort, J. Am. Chem. of structure I. Subsequently this group succeeded in Soc 9i, 7344 (1971). 102 10.1.9 Sloa* New OIIM* Conductors: TV However, there may also be some I" and I. species present since the calculated occupancies for die lj" ion alone are 0.67 and 0.33 for sites A and B respectively. C. K Johnson C. R. Watson. Jr. A more elaborate model or a different space group may R. J. Warmack1 be needed to describe the disorder properly. The 71 The fact that certain organic crystals such as the present let/ ) value is 10% for the IS6I unique x-ray adduct of tetrathiofufvalene (TTF) and 7.7.8.8-tetra- datx cysnoquinodirnethane (TCNQ) are good electrical con Crystals of 2 cannot be characterized adequately with ductors has prompted the search for other "organic conventional crystaltographic terminology. The dif metals." Mas' of the current research in the field has fracted intensities do not fall on the points of a single focused on the complexes and salts of TCNQ. and reciprocal lattice, but they do occur on a pattern several are described in last year's annual report.2 We arising from the mathematical convolution of two are now studying die products3 formed when TTF in reciprocal lattices. For convenience, an approximate acetonitrile reacts with iodine or bromine. The principal supercell can be chosen with measurable intensities products we have found and characterized are (TTF)- specified by the selection rule 5k* 15**/= 7m+30*. where A. k, I. m. and n are integers. This unusual pattern (TTF*V>, <1UTTF)10.,0» (2)- *»<> ** isostructural bromine analog of 2. The room-temperature single- of intensities arises fron two interpenetrating distorted crystal conductivities for these three compounds are direct-space component lattices. The first component 0.001 ft"' cm"' .300 12"' cm''.and SOOn"' cm"', lattice arises from the mean packing arrangement for respectively, with the latter value equivalent to that the TTF molecules and is C -centered monoclink. The observed for TTF-TCNQ at room temperature- second component lattice is A-centered monodinic and X-ray structural studies of I and 2 show that both arises from the mean configuration of I ~ ions. The two have unusual crystallographic properties. Crystals of I component lattice systems have parallel c axes, b axes, are orthorhombic with a = 8.184 A. b = 21.2S7 A. r = and a* axes, but the r-axis length for the second component is specimen-dependent and varies linearly 7.046 A. Z = 4 (C«S4rL.I2). p„ = 2.49. and pc = 2.48. 4 s An average structure for 1 can be described using space with the l/TTF ratio over a limited range - near 0.71. group Immm with TTF molecules on two independent The approximate supercell containing l_ [(TTF)7lsj structural columns is monoclinic and has space group ntnm sites at 0.0.0 and 0.0. V2 forming a stack along the c axis. The disordered iodine atoms fractionally occupy symmetry Pa with a = 48.008( 16) A. ft = 16.043(6) A. r two independent m sites A and B, with occupancies of = 24.877(7) A and p* = 91.33(3)°. This approximation is 0.79 and 0.21. respectively, to form chains along c. The rather poor because the iodine component sublattice requires a \% longer c axis: thus a supercell with 12 predominant iodine species in the chain is the l3~ ion with I-l distances of nearly 3 A as shown in Fig. 10.4. |(TTF), 7l|i) would provide a more precise descrip tion for the particular specimen used in the data collection. The mean structuie of 2 for the C-centered TTF subcell is shown in Fig. 10.S. A reasonable refinement for the iodine atoms in the supercell has also been obtained with individual iodine atoms displaced from their mean sublattice positions by about 0.2S A in a complicated modulation pattern The superstructure modulation of the TTF molecules must also be re solved. The stacked TTF molecules are displaced from their ideal sublattice complex positions by displacement waves with rigid-body translations! and rotational com ponents. One- and three-dimensional Fourier analyses of the displacements show that TTF molecules are displaced predominantly by transnational displacements along b and torsional rotations about c and that (he Fig. 10.4. Packing drawing of (TTF) (TTF'l.Oj viewed periodicities are related to the iodine sublatlke com along 0 with c vertical. The major iodine site A is shaded, and plex. A similar analysis for the iodine substructure (he minor complex: thus the ' SJQaHB i rHated to the deal saMarace •on M F«. 10... *f "y X C K. MM H l_ KcaJ •. aaf *. F Hal. \ i Amm. Anr. ffrsi Jfc? J* /»?*. OKNL-WK. Bu 155; W. E. v * ' * Thamca MUN. Meaner, ataf.. ^ 149. 3. )Jawn fecfaietcfcnr aamnaja* aar aeaaks ai she mm afUK AarnaaC A! Va-ia ^B JThj_ Nan* 1975. *e loao! ikatdot Y mtf If MoMaato CheMical ae ate •X-T ^£#* *«». §•* a*w*arw haa, ^* ^^ r »aem.iianiiaa»n>t»iuiu.tta' sDvctaac Cat 2. 4. The IMI mcardk pnmm neaora MM the « for the braajiae aaakf of 2 BJTTF Or*. „ _„». 5. The tern -jafiaafctj aiaawc stractaac' hai arupuMi for mac lam of das tynr. See I. S. AaaVno*. J. Chem. Sot. MM 1107(1973). It I 10 F* I0L5. Omhag of C-oMta* »M - rTTF*..*. C. K JohwoB VFhw (aaamanaely (TTFMsl »ir»«d ata* r TV tabceft k» C- Lnensfcy* C. R. Watson. Jr. panaloieuzfoajl syaMartiy. Tke I' nn form dams aViac c wh j«a*«aB:j|«Ma#of5.023.A.TlarTTFiwilecaloli«ea» Two neutron diffraction studies were carried out in tmttfc perindKHy Joac r nt 3.554 A collaboration with the organic chemistry group. The OKNL Owa. 7H3744 Ftj> IW. IwajBKnpka^awiajofiTTFnVTtt 104 tost study was a **»2|3) A. fi * <»2 <*H1)\ a, = 12* * = 12*. r = 4. waknoan reactioa prodact KtF*. 3336 arutroa data)* 0LO7I CWjy OTmWg SyUlWCM « In contrast to the straightforward structure analysis ductors. The second study ate structure of dneuterated 4-bo- designed to dariry die tasytate (see Fig. 108) has presented rhe sakarysrs reacttoas of < : difficulty. The tiuublfjomt portioa of aV Neutroa diffraction is a any powerful tool i awiecule is the aearfy jphtriul kmtoadamaafaae cage. meat studies uwohaaj diaatiaan tracers because rhe which leads to disorder ia the crystal. There are two fraction of deuterium at each hydrogen site ofiea can major modes of this disorder. First, the eaaabomers of be deteraaaed with high pteciuoa. the racemic mixture can each fit onto exactly the same The reactioa of IS-dtaheaytojaiaoae and raaloayl site, and second, there is a second isomer (2-homo- nitrite ia erJuaol produced a previously uakaown adaaaataae tosylaie) formed by rhe sorvotysis reac ciystaliae coapouad. Siace large crystals were aval- tions, which can randomly cocrystaln/e with the first. able, rhe structure was determined by neutron diffrac The remarkable crystafographk compatNity of this tion crystallography rather than by more traditional system b probably the reason that all chromatographic chemical techniques. The product turned out to be and recrystalization procedures attempted have failed 2 • amain - 3 - cyano -4.7-dJpheayt-S-hydroxybeazofuran to resolve the mature. The neutron structure analysis eftaaorate (see Fig. 10.7). The structure was solved by shows that the tosyl portion is not disordered, but the direct methods, and rhe whole project from the growth complicated density pattern at the cage position has not of the crystal to the correct trial structure took about been explained satisfactorily- An elaborate rigid-body three weeks. Refinement progressed somewhat dowry constraint routine was added to the least-squares because of the extremely high thermal motion of the refinement program and used successfully to refine rhe emaaol molecule. An interesting resonance system major component shewn in Fig. 10.8; however, there occurs in the malonyl nitrite portion of the molecule appears to be more than one additional component and produces some rather unexpected bond lengths, but present. The disorder precludes any precise analysis of the geometry of the rest of rhe molecule is completely the deuterium distribution in the crystal studied. normal. The crystallographic details are as follows: Further work is planned after the cheroical separation space groupP2,ln.a= I5.S*C> A.*= l4.l7(l)A.r = problems have been solved. 0»K».-0«6 T»«lT5 Pi$. 10.7. Motrcw* of 2-smwo-3-cyMO-4.7-dipliciiyl-5-hydn>xybeiKofBran cdunol jolrate. 105 ORNL Do*. 74 13331 But. snee the rase curve hes be*"-* ike neutralfor afl dtesnees m nesr cases, dws mecatamim is difficult to trmai stales), aad me piohfcm has : theoretical and practical aspects. Expcr- charm-exebanged accelerated beams at ORNL aad win aozde-acccfcraicd beams at Argnwnr National Laboratory (ANL) have shown large ioa yields. It has been our am 10 awrstsgafe bo* the ion-pair reaction and o*e exdunjr reaction m craned molecular beams starting with the thermal energy icgion and to extend measurements up to me nozzle beam energy region, approximately 2 to 3 eV. We previously reported' negative results from a study of the angular distribution of ion-pair icactioa products using crossed thermal molecular beams of potassium and cesium. Subsequent experiments were done win a sodium beam, and. as was the case for potiijium and cesium, the total cross section at dtermal energies of me I. dm Ukm CtMcpa AaocBinn Kmrdi Pulkqaii gas-phase km-pair reaction, if it occurs at afl, must be from F-afffum Cnacgr. RKJMXMML Ind. smaller than 10'" an3. The possibmty of contamina 2- C K. Jotawn. Chrm. On. Amm. fng. R MX2 Samnttfcajcliaaianj spectromeler. In nV case ••» a tantalum surface it has been shown by uVauckamp tf afctoran Institute of Technology, private cuuuuuuacaiion) biat the tuns arc P F. Dittaer £ DM/ K F Krawse exekrnuery bF»~. The re run's of una exprruuruis show IKAMB dm with dinaam at temperatures abuv* iOOOlL la dK coarse of expnunents on gas-phase reactions of about JO* yields of negative Ms JK obtamed mde- LT. wi* aftab MMBL sajnais doe to was formed at pendent of umpnatuw up to lTO'tv. Mow IOO0*K various surfaces were anted. These reactions bear upon UK efficiency drops sharply — i B dependent upon certain aspects of dK wurk of dK AXL group amsri- bene; miensMy and taae of exposure, foe example, : gauag ion-paw production widi noz/ir beams and also at •toO'K widi a beam An of 3X |0* mdrcusrscm- 1 upon stuutiu aad selective defectum schemes for LT* sec" . an exponential rise occurs to a steady state, and odurr lunh-etetfrou-affmity Aaondes Surface H» when dK beam b turned off. an cxpunenttd decay «vith zatkm of atomic species is a wW uuuiiuood phenome a tune constant of about 15 sec is observed. This non. The Fermi sea of electrons m a conductor can act uwuipundj to a heat of adsorption -if about TO 2 as cither aa electron acceptor or aa electron doaor. la cat mole. At sKghdy higher Aaxes. 4X I0* audecules : dK first erne, atoms with Vow magatioa potential / caa en sec"'. dK untul rue m current is Mowed by a •we up aa electron to dK metal widi a net energy dfchnt corresponding to multilayer coverage and a change / - •- autre • is die djuaauait work function decreased efficiency: when dK beam is turned off. dK of dK metaL la dK second cax. atoms nwh ekxtraa cunjcnt rises, Liiiicipimrhwft, to desorption from a affinity EA caa accept aa electron widi a aei energy surface of inn iimg efficiency, before agun attaining charge • EA For molecules sack as abb haadrs. dK characteristic exponential arsojptnm- MX adsorptioa followed by dtssucatioa caa yield bodi M* aad X ~ was according to dK separate energetics for ••.13 Hyper andPbnurnii i ili|,of dW formation of positive or negative ions. However. dK CharnrStafe-Sdecved 27.54*«V mechaniwn for rfce fbrmaonn of negative molecular was OxyncnluasuiSavcr is obscure. S DM/ C D Moak' B- R Apc4et •ntck) as a Innctiim of mput C* or *• I and (ui i 7* or •binrlfd ions depended wpoa the entering MM charge x* I chare* *taie For both planar and bvpetvliawiinu. state (6* or H+y For entering charge state 6*. rhe rano dtr charge-stale effcvt <« aoppnu pinter * seen for the of oV cha—elrd ytthi to the rand— yield was 2 0. and nwami <•* rgy l«u poeinm bu( mcrease* rapvdK with *•* 9* entrance charge H was »0 Saw the ejections •KUnrcnc uawmc energy. wdtcaOM- a rapid me m are emitted from exiting t JWS. the dependence of yield charge vhmgmi. pmbabr!ii\ with MCKUMI snptituaV •m input dntge snnpK reflects the dipt •dean ef exit Alrhmteh ih. effect tit sun charge on restoring farce charge on mpnt charge and the lack of charge equaSb- 5 cuntd »n be detencme-X two new aspects «»f channel- rtam for channeled wns The exn charge distributions MC were disclosed These arc 11) equftntaum charge were measured and found to be 0 2 <6*).0-5 (?•). and dtsinbartoa* as a function »f amplitude and 12) the 0.2" <«•! iot random emergen. . and abo dosdy the same for .hanndrd wets wnh inttaJ change state 6*. observation «j" a peafc M the exit energy dranbat*>« at a greater rhan randVwn energy loss «iien the crystal was (Note this does mn mean eqwhbrmm is adncved.)For idled win a planar-btockmg dnecuun. mitial charge stale S«. the exit charge fractions were An additumal observation was Ifce appearance of two 0.12 (6*1. 0.35 stripped &+ ions do n-w contribute to this peak and that the electrons in I nh«3DnBM das p^ak do not. in dns case, arise from capture to 1 S«M S'-rtr Dana* continuum states. Instead, m agreement with Burch.* 3. S Dart t « Mama, C D Mxofc. • R Antrum. jntf who measured electrons lost in single collisions of LI niMfecl.JUanr tff 12.1*3.1*7:, k 4. S Otat/. • R Afwfc-roa. J. A RwfenuiT. M D IMML oxygen ions at these energies, we propose t at they :ie H. I Kw*. C D Miofc. ariTS N-nvftr. p *J a Atomic electrons rcnumd from the moving km in the lasi Cimmmt m SnhJi. Pit—m ftrw. 1975 «Bi C D M«sk. S. ionizing cotttaon The fact that the random yield is DM/. J. .V Bwrrtlali. H. F Knar, an) T S ?*n*k-- An higher by a factor of 2 than for the 6* channeled km * N anernoi experimental methods have been employed J : Hfcjwn IM • H, - Hgr*U ll3 : , >» • « to study neutral-neutral reactions involvmg excited J The bp' Dy state of mercury has a configuration atoms, bat there are few reports of sineJe ~! 1- a.oook- 0-J noti«*r »'-o — r»i r*-o-«) •i ' 0-0 f _>=£ t=i c tsso a » the feci dot ! « 1 ' I ' 1 i » in.iT! t fat both of i i~ BOI^rr'• O -* JT*1 r*-4| fordWT =0.1.2.3 m M*C~ *«v, - - • h - -"^'^. X „ of nc resctMo prooscts hB bcca § IO prcokt Wbtatiooal pop •twioau m CTcinaV •- ' " • i* Ik theory appM w IkjHM^,^) % • — , afoHMO laWtioaal caercr ofetri- -. i to •. • HfHbf'II,,,) is 0.79 cV or ^ • r «^. • The with the esti- LA-«r * * • ^ MOO ! . ! . I.I, 1. D- H. Statu »iD.r Scwr. GMoM ». pan 4. p. 193. hicn. Krw Y«*. 1*71. 2. H. F. Uwt. S. G. MMM. S. Ban. a»l F. K- SJwiiOlftMiilL.Oiw. I*n trw 31.577 <197S»- 3. C B. Nrnt. iMMr tep Lttb. «at X f*. 1*2-95. NSSCpcafci 4*7. US- Ciiirwii •>•*•» Qtfcc »»*•> M.DJC. 195* TV fHM «*T dan AWW Inm of Mr Ondt. Mavrt LA-43M ItJ.I ' & e. A A It UvaajMoa D. Doktrty* HZiUct Ptj, Mill. CftaaBMM MM4 MtapiMWaMn i«r ISA In iftt hn OMMHI report* a otw «•%> «wtacribt4 aaatiarttai offcyaVopaa thjuop attack of OH. Tht vjmk • a cooporativa aavtava with tko Hoiopjy Dtriakm. ajooof B^^aBj*oa^B3w p aa^P Wv oa^^vO^^FwOa^Mi v aw IPv ajJHJBajoja^pB) WWavvM^Pa aJoog fjMh aoowt 1% byaroan poroxM*. Upon photol- Th* dMaaflaoaiMOJOMH fpoctioot aitotiffear M Pip, yaji tM pnonw pwai OH. 10.11 iooieiiH thai Haratioaal lewm aw popataiil ay hy4ropM froai dw poptala to ^vt tfc* < IOv'>5«Ml »'• 3 for Utt/l'll),] MMl/I'll,,jtlaWS Tfct proem it of dprillcMK* in rifclina Moiogy. A rwpottfcaiy (vibrational qaaMvot ft (US «V). MOM «•*> of 110 ; (ejycmc. i-J i . aaOatacmcl has been completed.1 TV wsufcs on five of aVsc pepodes were eirea last yeaf.: The JMHM4 ones wett c ,o )ca j^ianyi-t alanmt and d^taaytd-dinmi In a6.• ases OV *v^ rj s . *'Vo*ioSc!wc?»0"*!OSja!ii' MM of OH attack is hajhly systtmatn.; hvwrugcn B abstracted from the carbon between the per'Jde nitro gen and the carboxytate group. In cases where ,1-ataame is dK second residue. rJacre arc two swell carbon, and a of radicals is objured which reswlts front o 0 0 . Al of these peptides ate • £ la every case, hyperfme ~M^IO^CM£NMO^C*MCHC^~ O'T SM ••• >JO ir-w 1g values were measured, and spaa density • •ZMM< for the front which abstraction took place ' The study has been extended to dipepiides cant t-pwiyhjryuwt and tf-alawyl-L-pruiinehar e been identi fied, and in both cases the point of hydrogen abstrac tion foftows me systematic behavior described above. In known whether this simplicity wil be exhibited by rhe former case the hues of the spectram are quit; longer peptides. If the trend continues, the formation lesumabty dne to the presence of cif and mna of the radical is not only significant in pinpointing the which have shghtty different (unresolved) region of OH attack but in labeling a peptide with an for the hyperftne coupling cunstants. in the unpaired electron which, in principle, is sensitive to latter case the spectrum shows additional complexity conformational effects. n thought to arise from a "flip-flop" of die ring. The nature of the chemical attack on 1. Mntnyy Dhrcnua. £abaytsarcosme is quite different. Hydrogen is ab 2. R. Li*MfMn«. D. Duherly. Mm H. Zrfdcv Chrm Dn stracted from the methyl group of the sarcosine residue, Amm tfot Hep Mtv 20. 1974. OKNL4976. p. P7. and a mixture of two radicals, en and mm isomers, is 3. R. Lmnpton. D. DuhcTly. and H. Zddo. J Am. Chrm. Soc *7.3I9S(I975>. obtained. Also in 0-alar.yl-L-valine and eJycyl-L-valine the attack of OH is not at the peptide link. In these cases hydrogen is abstracted from the isopropyl group 10.3.2 Electron Spm Resonance Studies of of the valine residue. A mixture of two radicals is A^-Heterocydic Compounds in Liquids obtamed which results from abstracting one or the During Photolysis: 2*-r>ridw)tdkarboxylic Acid* other kmd of hydrogen present in the isopropyl group. H. Zddes R. Livingston Results have also been obtained for four tripeptides: 0-alanyfajrycyl-L-alanine. p^aianylgh/cylejycine. 0-alanyl- Transient ir-ekctron JV-hetcrocyclic radicals which are L-prolylglycine. and 0-alanylgh/cyl-L -proline. It was felt present during the photolysis of solutions near room that a difficult-to-anaryze mixture of radicals would be temperature have been investipted by electron spin obtamed through hydrogen abstraction from carbon at resonance with the principal aims of identifying the both peptide links. This n why 0-abnine was used fo: radicals, measuring g values and hyperfine couplings, the first residue, since work on the dipeptides showed and determining the mechanisms of their formation and that more easily analyzed spectra were obtained in such disappearance. In a few cases, equilibrium and rate cases. Much to our surprise, essentially only one radical constants can be deduced. The radicals studied have is formed in each case. The hydrogen abstraction takes resulted from the reduction of the parent conjugated pbec almost exclusively from the peptide link at the compounds by two methods. In one the parent is carboxylate end of the tripeptide. Results for two of excited in the presence of isopropyl alcohol, causing it these peptides along with results from corresponding to abstract a hydrogen atom from the alcohol io form a dipeptides are given in Figure 10.12. The coupling radical. The abstracted hydrogen usually attaches to a constants and g values are very little changed in going ring nitrogen, and where there are two ring nitrogens from the dipeptide to the tripeptide. It is not yet the second is very readily protonated. In the other Ill omw. -owt M-mrm f2. Spectra haw been =aaiyzcd for rwin.all formed by the 3L225 11^2-23 2J63C^JI54 ft: of a hydmgm atom lo me nitrogen atom of CO,' CO£ 13.04 by carboxytate groups m me 2:3:2 ami 3:2 and •*- 2 mi 5: mi I M 3 and 4. The radii dt were pre pared aang bom of me F» IHJ. O method* described m rte preceding section. Oatr the aarogea and the NH-hydrogen coaaaags were mignrd cxpeniaeataSy. The latter went assigned by anarysng me spectra in solutions coataaaag D,0. NH-hydrogcns were paroaly replaced by deal method. acetone as weB as rsopropyt alcohol is incor- This and previous work give g vines and a! of me poraled m the sutaUoa. An exerted acetone molecule ennpingi for afl l-hydrocnnmwc radicals sabstttuicd by- abstracts a hydruarn alum from isapropyl alcohol to one or two carboxylaie groans. The itiigamfau of form the hydroxy isopropy 1 radical, which donates an couplings are known completely fur the radicals derived electron to the heterocyclic compound lo form a from 2.6- and 3.3-py ijawedmrboxytatc anions. For the radical which is CO. and O3 • HCOOH + 02. The last system was alio complex. The following reactions become important at used to study the reaction of oxygen ('/» atoms with high bromide ion concentrations: HCOOH. This was shown to be a very fast reaction which occurs with collision frequency, while the re action with ground-state oxygen atoms. (*P). was Br + Br"*Br2". CD shown to be very slow. Br2 • Br" * Br3". (2) In the H2O + CH« system, the CH4 reacts rapidly Br + HiOj-Br' + H' + HOj. (3) with OH to form CH3 (observed in the bands at 2160 A). Reaction of CH, with H is very slow. The CH3 H02 • Br2 - H* + Br2" + 02. (4) radicals decay by reaction with CH3 and with H atoms. Added CO competes for OH, and from the reduction in Br," + Br2" - Br3" + Br", (5) yield of CHj. the relative rate constants for reaction of CHi and CO with OH were evaluated. Studies of Br2" + H02-"Br2+H02", (6) reactions of peroxy radicals continued; additional HOJ+HOJ-^0,+0,. (7) measurements were made to improve the accuracy of the rate constants for reaction of CH3 with 02, tor combination of methylperoxy radicals, and for ccinbi- The formation of Br2" inhibits the reaction of bromine nation of methyl radicals. The study is being extended with H202 according to reaction (3) (predominant in dilute bromide ion solutions) and induces bromine to include reactions of CH302 with NO and other molecules. formation through reactions (S) and (6). We attempted to compute the dependence of bromine concentration on irradiation time by numerical integra I. J. P. Keene. Y. Raef. and A. J. SwaOow./Wir Radidyih. tion of the appropriate differential equations for the p. 99. Academic Presi. New York. 1965. production of H02. Br2~. H202. and Br3\ using the reaction mechanism and absolute rate constants from 10.3.5 Bromine Formation m the Radioiysis the pulse radioiysis studies; no agreement could be of Aqueous Bromide Ion Solutions obtained between theory and experiment. However excellent agreement between theory and experiment F. T. Jones' T. J. Sworski can be obtained if the reaction mechanism is modified Definitive evidence that the yields of earliest detect by postulating that H02 car react with Br2~ in two able intermediates in the radioiysis of water vary with ways: oxidation of Br2~ by HOj according to reaction 113 (6) and reduction of Br;" by HOi according to reaction 3. A-IUTiwIH. C. SvttoN. TVno Amdey Soc. 61. S77 (IMS). (8): 4. F. T. tames and T. J. Swanto. Ckrm Dh Ammm. hot- Bri' + HOj-rT + lBf' + O,. (8) top May 20.1973.0RNL4t»!. p. St. 5. 1_ I. Grosswonrr and M. S. Maihesoa. / Mjn. Obrm. 61. with reaction probabilities of approximately 0.SS and 10B9(1«ST). 0.45. respectively, for 0.01 M bromide ion solutions in 6. B. Cera*. M. Ebert. I. P. Kent, and A. J.SwsSov./abr JUfiolySB. p. S3. cdL M. Efcert el at, AcadeMk Pre*. New 0.4 M sulfuric acid solutions. This is analogous to th; York. 1965. report from Brookhaven National Laboratory* Uu.t 7. H.C. Satloa, G. E.Adanu. J. W. Boat and £. D. Mklwd. H02 can react with OH in two ways: combination to Md..p.61. yield H203 and oxidation of HOj by OH. with reaction S. G. Czapdu aad B. H. J. KeMa. / tkjn. Oem. 47. 2110 probabilities of 0.7 and 0 J respectively. (19o3). 1. Stems Institute of Tcchiwiagjr. Hobafcen. NJ. 2- T. l.Swanki./ Am Chrm. Soc. 7»,4M7 (1954). 11. Electrochemistry III ELECTROCHEMICAL BEHAVIOR reduction of TilIV) ions to T4III) at the active surface. OF COUPLED ACTIVE-PASSIVE The latter oxidation and reduction reactions are first- METAL-ELECTROLYTE SYSTEMS order in the concentrations of Til III) and Til IV) H2SO4). By use of a dual potcntiostat. one of the dipjdt and \dia/dt\ approach the same value. k)k4(J. titanium electrodes was maintair d at a constant Using independently determined values of ky, k4, ij. potential in the acti.t state and the other at a and if. one obtains a calculated value of k^k4Q equal to constant potential in he passive state. In the 6.47 X I0"10 A'min. a value in excellent agreement active state, titanium is oxidized to TKIII) ions in with the results shown in Fig. I I.I. The decline in ia solution. In the passive sta'.e. the metal is covered with lime is a consequence of the buildup of TKIV) in with a passive film (TrOj). and the substrate metal solution. The ability of coupled active-passive titanium is oxidized to form TrtIV) ions in solution. In the systems to generate an ever-incrrasing concentration of coupled system, coupling of the active and passive TiflV) is especially significant, because, as shown in reaction systems occurs as a consequence of tw« previous studies.1 an active titanium surface is passi- additional electrochemical reactions the oxidation of vated by TiflV) ions when G > 8.6 mM (in I /V Ti(lll) inns in Ti(IV) at the passive surface and the H1SO4). Thus these considerations provide a rational 114 115 kinetic mechanism for the phenomenon of scif4ie«Uij: observed in pitting and crevice corrosion. For small values of t. the exponential term in Eq. (2) that is. for small values of t. ip is a linear function of t. may be expanded to yirld a new expression for ip. Moreover, if C? = C? = 0. or if SMar • -*4>.g i »n i • ij is proportional to the slope. Aip)t^dt. a change in tj pr.Mkiced by a change in the potential of the active-state electrode leads to an immediate change in the slope. This phenomenon is shown in Fig. 11.2. Initially the active-state electrode was at a potential of 530 mV vs S.C.E.. and iA -530) was 1.36 X JO"* A. The potential was then changed to - 730 mV vs S.C.E., and. from the resultant change in the slope, the value o\ iA 730) was calculated to be 5.53 X 10"' A, a value corresponding to a weight loss of only 33 pg/hr. In addition to confirming the theoretical expectations, the results shown in Fig. 11.2 offer a novel and very sensitive method for measuring corrosion rates. at acovc a* ekctiolyle- I. F J. Kelly. Chrm. Dir Annu. Pmg. Rrp. May 20. 1974. ORM.-4976. p. 102. OmL-OWO. 75-M03 1.0 "! ' 1 '— Ii.2 ELECTROANALYSIS WITH THE PACKED-BED SILVER ELECTRODE S {-730) • 2.26 • 10"° onaytae . R. E. Meyer As part of our continuing investigation of the properties of porous electrodes for electroanalysis and treatment of solutions, we have studied further uses of the silver packed-bed electrode for electroanalysis.1 Emphasis has been placed on analyses of substances like cyanide and sulfide ions because of recent interest in the monitoring of effluent streams for toxic substances. With the aqueous cyanide system, accurate analyses (E '-530 mvr* SCO were demonstrated for solution concentrations down to S(-S30> '5.56 < 10"' 10"* M. In addition, the complete current-potential behavior of the cyanide ion was investigated by polarization studies with the packed-bed silver electrode in essentially oxygen-free solutions. The range of . (-730).i Sl-730) d d SI-530) interference of dissolved oxygen was also investigated, • 5.53 «10s amp and it was shown that, by setting the electrode Wt. Loss • 33 pq/hr potential within a certain potential range, analysis for O.t AC • 3.44 i fO"*mo* Mrr VM the cyanide ion can be accomplished without the need for the time-consuming removal of dissolved oxygen from the sample. Furthermore, by making use of the _L I _L I 2 3 current-potential behavior of cyanide and of chloride TIME (minutes) i I0"3 ions, a simple and accurate method of simultaneous analysis of CI' and CN" ions in solutions containing Fig. II .2. Determination of dissolution rate of active lila- at tarious potentials. mixtures of both ions was devised. Some advantages of 116 the use of the packed-bed electrode include simplicity In experimenta! work, a large number of pufari/ation (the analyst has only to dip the end of a piece of tubing cuives were obtained under a variety of conditions on into the sample and turn on a pump), direct readout of electrodes fabricated from natural Jingle crystals of the concentration (not die activity), and high speed of FeS; (iron pyrite). These curves show that FeS- analysis. The results of this investigation were included undergoes considerable oxidation in acid solutions at in a paper in press in the Jmrtml of Ekcavmttlytictl electrode potentials more positive dun about •0.6 V vs Chematry mid Imerfmhti Ekarochtmamr. S.C.E. In alkaline solutions, oxidation begins at much Other uses of the silver packed-bed electrode were lower potentials. There b also die possibility of investigated, and it vas shown that small volumes of cathodic dissolution of FeSj in acid sohituws through solutions containing reactive species may be analyzed die reduction of the sulfur in FeS; to form H»S. by a current-pube integration method. Analysis of die Cathodic polarization curves are also being measured: sulfide ion wim the silver packed-bed electrode was also drse are being analyzed. investigated, but this type of analysis proved to be only approximate (5 to 10%) due to the unavoidable presence of side reactions. 11.4 PART-TBt-MUJON ELHmtOANALYSIS WITH PACKED-IB) ELECTRODES I. R. E. Meyer aad F. A. Posey. Chem. Da Amm. hog. Rep. H. R. Bronsiein F. A. Posey *fcr 20.1974. ORNL-4976. p. 105 In previous work1 an apparatus was designed, con structed, and tested for investigation of the applica 113 ElfCTKOCWMICALKMETICSOF bility of packed-bed electrodes to quantitative decfro- SULFIDE REACTIONS analysis of trace amounts of oxidizaMe or reducible R. E. Meyer F- A- Posey solutes in small sample volumes (down to SO ul or leu) by linear-sweep vniummetry and/or coutometry. The Consukrabte interest has arisen in recent years rela new electrode system was based upon use of a packed tive to the investigation of metal sulfides. Among die bed of glassy carbon spheres (about lOOu in diameter). more important reasons for this interest is die effort to Microgram quantities of lead, cadmium, and copper develop technology which could lead to suppression of ions and dieir mixtures could be determined by dirs SOj from the combustion of coal, which contains a technique with an accuracy of better than I?. The considerable quantity of pyrites (FeS;). Another re results confirmed the theoretical computations, which lated reason for this interest in sulfides is the role of suggested dial the method should be at least the equal heavy-metal sulfides (MoS?, FeSj. CoS) as catalysts in of conventional polarography in sensitivity, and showed processes for die desulfurization of coal. Certain aspects dial very small sample volumes could be analyzed of die electrochemistry of metallic sulfides have been precisely with relatively simple experimental equipment examined in die past, but usually from the standpoint and manipulations. Such electrochemical techniques of hydrometallurgical ore processing. There has evi have an important mission in energy and energy-related dently been litde effort directed toward the systematic pollution investigations and problem solving. They may development of information that could be applied to be used as sensitive laboratory methods or perhaps the sulfur-abatement problem. adapted to fk'd use as continuous, automated moni Accordingly, we have initiated a program with die toring mediods and thus are applicable to both current objective of establishing a useful data base for die and future problems in energy-related water pollution electrochemical behavior of metallic sulfides. Much of In recent work we have demonstrated that submkro- the first portion of the year was spent conducting an molar concentrations of reducible ions in a stream extensive literature survey of the electrochemistry of flowing through die packed-bed electrode assembly, metallic sulfides. Two significant conclusions could be which is maintained at a controlled electrode potential, drawn from this survey: (I) the studies report *hus may be removed quantitatively. For example, in one 7 far have been made mostly from die standpoint of experiment using 1.65 X 10~ *f CdCI2 (about 19 pph) recovery of the metal from sulfide ores, and (2) studies • I M NaCI. flow of 2S0 mi of solution through the that included consideration of die kinetics of interfacial cathode bed resulted in deposition of 4.1 X 10'* mole reactions have been limited in number, but die data of cadmium, corresponding to approximately 8 mC. indicate that die dissolution of metal sulfides probably Subsequent analysis with anodic linear-sweep coulom- follows an electrochemical mechanism. etry of the packed-bed electrode confirmed die prior 117 deposition of die proper amount of y«dnm"w «*••» •IM' process ssd is sBswiag speraUucj far much iimjri tunes ekclrude jurfaces. Tke aarueod competes fjaorabry m una for an ekctrode material such as porous carbon sensitivity with wcM knew methods of anodic scanning before repenetauou would be rwjuued due lo blockage voHauuuetry. which make me of tohd thxtrodes M oi etccwatyvc passages uy csfciroacajosujeu scan. How cMwiaowl cefc. and often an important advantage ever, the penalty to be exacted for these advantage* « •Mi •ofwvi lo freedom frueii mterfcreuce by convec * dated removal efficiency at any given hour rate tion. Ii should have direct auphcalaai tomnniiunugof oanpand with a -tighter" electrode structure, such as low levels of dissolved icducmte aaetab MI waste waters porous carbon. The lead shot cathode did not perform aad natural and process u seam*. Fdhmnug uunplriinu to our satisfaction, and later studies were made usmg of studies oa several alternative modes of operation of tauch more efficient porous carbon cathode structures. d* ceM aisembty. we expect to swbmM die results of However, me extensive series of ssnamnuuvzuts obtained Aesr hwe [ligations for pwhhcatiou at ate Anaamf of with lead-shot cathodes clearly estabhabed use unhseuce Becmmmytkm Cktmbtnt md hmrf*.wt Ekrtm- of a ntsnvbn of experiaaental variables (Sow rate. electrode potential, bed dhuemnuj. etc.) on removal efficiency, and the results were found to be consistent with a theoretical treatment of the couphng of mass- I H It IMUW JOB t- A- Pmcy. Chrm. Dm 4mm hag *rp Mux y>. 1074. OKNt<«976. p. 10* transport aad efcetrodeposition processes m porous electrodes. The Mrvestujabons. m addition to greatly m.rearing our undintaading of the fundamental principles of 115 EI^CTKOCHCMCALtfCOVEKYOr operation of electrolytic metal-recovery eels of uus REOUCMLE MORCANIT POLLUTANTS type, have led to development of an improved cefl FROM AQUEOUS STREAMS' design which b to be used m a new test or demon A A Pafto FAPoiey stration unit. The new cell is capable of treating 1000 to IOJOOO gpd of effluents of various types, depending Tfco work seeks to develop cffkieni aad ecomamcal upon solution conductivity and metals content. The methods for removal aad recovery of reducible metal modular cefl design wnl make use of a newly developed, torn from various effluents aad process streams by highly oxidation-resistant perfworasulfonic acid mem porous aad packed-bed electrolytic cells. Previous brane to separate anoryte and cathoryte compartments. work1 "* was concerned with recovery of mercury from The porous carbon cathodes and the rncmbranes may chlor-amab plant brine by porous carbon electrodes and be replaced without dismantling or draining die cell. We with removal of dissolved lead from two different estimate, based on experimental measurements on die industrial effluents, one obtained from a lead lead porous carbon to be used in die ceH. that removal dioxide plating plant and nar other fran a major efficiency should exceed 99* at a flow of 10.000 manufacturer of organolead antiknock con pounds. A gpd/ft3 for certain types of effluents (conductivity comprehensive series of measurements was also carried greater dian about 0.01 mho/cm: concentration of out on the reduction behavior of lead, cepper. cad reducible metals less man about S X 10'* Ml Tot use mium, and some outer reducune metab as a tancuon of with organolead manufacturing plant effluent, it should the medium. In addition, theoretical relations were be fuxMt to operate die cell for several weeks before derived that could be used for estimating the per regeneration of cathodes is required. formance of practical-sized metal-recovery ecus. Upon completion of die new. rugu-efficiency test Later work* on recovery of dissolved inorganic and unit, we expect to conduct a series of tests to establish organic lead from organolead manufacturinf plant experimentally die operating characteristics of die large effluent was carried out using cathodes of lead shot, unit over extended periods of ome on organolead plant and a number of alternative metal-recovery cell configu effluent, on spent photographic processing solutions, rations were tested on bom simulated and real plant and on other appropriate effluents. These tests wil effluents. It was (ell Mitiarty that use of a lead-shot provide data for evaluation of economic and technical cadkWe coutd be advantageous hi droning easy recycle aspects of the electrolytic metals-recovery process in a of recovered lead to die organoiead manufacturing realistic manner. 118 1. ftcwatdi onri OM arid ifcr OKNL-NSF Ea**y aal 3. F. A- •»»*> mm A. A Pi»». ~F kMrwvfcraucil RCOWCM Ammfmt of Tuor CoatanwMm pfueraa. ^oawotcrf »>• ol" RcriaciMe laorfaaK' PnRabat* from AqiK»sK Strcimv'' NSFlRANN). «•*» UMM C«k«dc Corpooina's coMncl villi Ecology mid Amah SB of Timer Omumumxis H»g Rfp ton. - "- I' n - -|] " i ii II ii 1973 Sept. 1973. OftNL-NSF-FATC-6. p. 360 2. F. A. rwejr mm A. A. Mu>. -Ekxttuckamcrf Rcammai ol I F. A- IWy mm A. A- fjato. ~Hn.-ltm.-fccnmr.il Rctuwrt MMMC hi^fjli- MbMb from Aqacou Slanav." «>. RraaoMr lauf-jaa; Pulaljalt fr>«n Aqurow Simon." firainfv aarf 4—>JIJ»» •>/ Tnanr CMMMMMI fng. Hep tome Hevtagy mmd Audit lit of Timet Commmmmtli Fmt. Rep. t*cf. 1972 Mm. 1973. OKNL-NSF-EATC-I. p. »7 1973 Sept. l9M.ORNL-NSF-FATT-ll.p. 14* 12. Thermal Generation of Hydrogen C. fc. Bamberger D. M. Richardson The properties of hydiogen make it an attractive where M » preferably sodium or potassmm. Reaction candidate as a secondary energy source and energy- (3) requires a temperature that is loo high for present transmission fluid, and an unportaM commodity in the nuclear technology: however, both reactions (11 and (2) chain of food production and for synthesizing gaseous can be used 10 replace and liquid hydrocarbons. The experimental search for 70O°C , dosed cycles for the thermal generation of hydrogen Fe,04(c) + %Otig) i=f %Fe20,(ci. <4, from water was continued based on previously estab lished criteria.1 The experimental approach was favored which is part of several European cycles.1 thus in (Tver the calculation?! approach because it provides creasing their hydrogen production by 50%. direct information on the paths of reactions, permits the identification of reaction products, gives an esti II CHUIJ/MOH mate of the kinetics of the reactions, and. even more 700°C important, allows study of reactions of compounds for Cr20,(c> • 6MOH(t> *==? 2M,Ci04(c) which no thermochemkal data exist. The experiments consisted in reacting solids, mixed *H,G!«)+2H2(f). (5) by grinding, at temperatures up to 1000'C in suitable ~500°C 4M Cr0 (c) + 4MOrK«) , 4M,CK\ (c) crucibles (platinum, copper. Morganite) located in a 2 4 5 quart/ enclosure inside a tubular furnace. A flow of • 2H20 perometry respectively. The low-temperature «100°C) • 4M2Cr04(d) • !0M0H(d). (7) hydrolysis reactions were performed in Soxhlet ex tractors under an argon blanket. Analyses of the where M represents K. Rb. or Cs. the lightest element products consisted in v-ray diffraction2 and wet- being preferred because of its abundance. The dissolved chemical methods (Analytical Chemistry Division)and. species produced in reaction (7). M Cr0 and MOH. less frequently, electron paramagnetic resonance meas 2 4 urements (M. M. Abraham. Solid State Division). can be separated by crystallization without difficulty- The feasibility of the following cycles has been Ill. CrtlliyBKOHh established: 650°C Cr20,(c>* 4BafOH)2(«)i=^ 2Ba,CrO„(c) I. FediyMOH + 3H20(g)+H2(g>. (8) < 5nn°<- »50*C Fe,04(c)t 3M0H(f) <- , JMFeOj(c) 2BaCr04(c) + B40H)2(C) *=, Ba,(Cr04)j(c) • H,0(g>* '/,H,(g>. (I) •H^gH'/jOjfg). (9) JMFcO^o* V.H2OH) -- —; .'MOIKd) 2Ba3Cr04(c»* Ba,(Cr04 )2(c) • YtFejO.-aqfd. C> inoT • 5H20<«I^—>Cr20,aq(c)t 2BaCr04(c) -. |4nn*r •V.Fe.O.lc)- ,Fe,CMc)+ V40,(g) . (.') • SBafOHMd) (10) l» Reaction (IO|L me hydralyiK dnwruportsonatioa of howevti. a practical awl economical physical separation harm* cJHWUti (IV> and IV). was rmMwIifd hy method has not yet been esuMnhed. separately itudymg the reaction of each chroma* lii Cydes H and HI psesent several attractive features. water. The hydrolysis products were OjGb and namely. (I) mey cumutf of only mme danmcal taCiO* m a I: I aad 1:4 ranorespectively Aa alternate (eacwoas; (2) ate npper hunt of tensnefatwe. aVmt •eactioa for die evolution of oxygen, reaction (9). may •Sfjrc. should he atlamaatr umhout dfflkulty.<3)ney he used. It neon win a dnleitnt hi— lixhriwai— •a not mvotee undtjcontponeai gas separations: and (4) ratio and proceeds al a lower temaeratuar *ey appeartohavesastaWe tactics. Since espetanents were performed wins the reagents in a stationary stale, wlypg mainly on daffunim processes for die unctions to occur, it may he dannm^amnmmmni nmmmt dram" m smmmn* V^ran* faramsMw* hranm^rammmn^mn1 fc^4 %iaf(CrQ.bOH(c»*HlOl») ajstatirn would he used, the kinetics of she leartsans *%Ot(ti (III may he cum move favorable aad die itquMcd tempera tures atay he lower. The apatite-mte mmpnanJ fcMCiOUhOH warts with water aad also disproportionate* iato CrtOs aad 1. OM Ttdmat Dm Amm. An* ***. Urn. 31. 1974. •aCKV Using high dtasity solutions of dnuiuni sdts of OKNL-vUM. a. 73. organic acids, we were aUe to separate she solids 2. U. A mm* Ohm Dm. Amm. Av« ****** 2* 1974. OftM.-4*7*. •.!«•- BaCrO« and Cr O, formed in leactioa (10). Almough z J. C. IUwlj-Cw». Thermal Drtmmmtmm of Mjsrr m some reduction of BafiO* occurred, the method Chtrnkml Cftkt of Mr *WT, FmmTt. IV* 49St t llWl. demonstrated die fcasamity of separating the »Ws: mimlli in Esau* *OM*l.-a-27M. 13. Surface Chemistry 111 AMOtrrtONQNANANMEAUDAND thaw* in Fig. 13 1 Water had nhnin—Ty afurcd nV MRAOUTED LUNAft FMBSAMTU' anface ptopeiUe* of the innvast ti d ban* Rats snnple. The specwk surface area « nJ from 0.29 to 0JS H-FHoInn E. I_ Faftn. Ji. m*/g. and diere was a cap! mdensafion bysteresB PAAgMi KIGMMV1 loop which dearly mdiuli E. FJchter C. 0.OXeMey s a | nroas sample. These results are definitive evidenc e in inapnrt of oar arter- Adsurbed water at h«> relative pnrnwc* converts pretattnu. nonporiHts Iww fines particles hMo porous particles and. m the process, mcreases the specific surface area I Rntsrcfc fOMM-fcrf by NASA by a fact** of 2 to 3.1 We have pnsMlaW* dial d*ese physical changri result from die interaction uf die j adsorbed water film with latent damage tracks earned 3. M F. Ilamms. E. L Fwfcr. Jr.. and *. a 1 3m (MrSa Camf. Gear*** CMMMMR. Actm 5. wot. by CINWNC rayv It has aha been cstabhwted -* dial i. p 227S. IHrpi—w. New York. 1974. water dues n<»t induce physical changrt in lunar fines 4 M F. HohTi. F L. fata. Jr. aai R. t dnt have been healed to IO0O°C (this anneals die 4t» Umm Sri Comf. (iroemim. CammtUm Aet*. 4. vol damage tracks I Cosmic-ray damage tracks were sauu- 3. p 2413. tVnjuno*. Hem York. 1973 bied by irradiating an annealed (at lOutPCJ lunar fines sample with a beam of l30MeV Fe** ions at the Oak 13 2 hVrauCTION OF GASES Ridge Isochronous Cyclotron. Irradiation was sufTkieni WITH LUNAR MATERIALS !<• produce abmit 10" damage tracks per square REVBED RESULTS FOR APOLLO 11' centimeter. Pintirradiatwn experiments consoled in 2 oulfBssmg at IOO°C. nitrogen adsorption at 77°K. H F.Holmes R. t. Gamnaje water adsorption in saturation pressure (at 20°f I. The surface properties of an ApoHo 11 sol outgassing at MXfC. and nitrogen adsorption at 77°K. hare been reanvslipted. The present study allows dial Results from the nitrogen adsorption experiments are the preliminary results3 for this specific sample are in error, principally because of incorrectly applied antra- •***.<•* Mm mental background effects. The surface properties of o«- these Apolo 11 fines are very simiar to dtase of fines from die odter Apollo landing sites dial we have examined.4 On die baas of results reported to date, die surface properties of lunar sod samples are. to a first approximation, independent of chemical composition and location on die lunar surface. Drastic alteration of the surface characteristics of lunar fines by adsorbed water continues to be the dntmguistimg feature of their surface chemistry. Rnrarch spomored by NASA MNWT iMrncemy Afwe- 2. Health Physics Dmmi 02 04 0* 0* 10 »U»TIVC M*SSU*f, *//» i. F. L Fuarr. Jr.. H. F. Hntam. R. • C.tmmty. and K. Becker, hoe. 2d l.umr Set, Com/. Otnclnm. Cotmmkm. Fig. 13.1. Aforpnmi of nrtroara on sample 12070.403 at Ac* toppl. 2. *M 3. p 2009. NIT Frew. Cambrnfcr. Man.. - IWT. Sjmpk irradiated and itx'~A with wafer al HVC. 197). 121 122 4. H r. Huwarv F- I HuVt. Jr. «il.|. fwuiir. ft«f 13 5 tttAi of mmmsKjHOf zmroHmm Mt LamtrSti Comf.. &•***•. ComwHmm. 4 »J BITERACTION OF SORRED WATER The heat of munersion of /Howuum oxide has Willi LUNAR FINES(SAMTLE I2MH previously been measured at 25°C as a iunctum of sample uulgmmg temperature.1 In the present study t L Fuier Jr. P. A- Agron me temperature ai which the samples were immersed m The hydratiun mrdnuiim whereby the Ac weal hutud water was varrd from 25 lo I75°f Specific cumpuMiou and surface structures of lunar mineral! are surface areas of the three samples were 87.4. 2 **. and 1 altered by sorbed water is of considerable mteresl m 23.0 m g for samples A. F. and C respectively !n fomufitmg geocbermcal and cosmodieutical concepts. agreement wnh results untamed in the thorium oxide 1 The stoichunctry and structural rearrangement is very water system. me heal <»f inwwcrjiim increased suniar lo ite hydration of anhydrous lerrcsterial (became more exothermic) as the immersion tempera rnmerab (plujiirliir. pyroxene, feldspar, etc. I lo form ture mcteased. The magnitude of the heal of umnersion days I botanies, smectites, dhles. etc.). Thermal treat was a dear uubcaiioa of dienusorrlion under all ment O*00°C) of the hydraled lunar material reads to conditions. On a umt area basis, the high tpfiific- km of active surface and porosity simaar lo die surface-area samplti are more energetic- The depend dehydration and anneabng of clays. The hydration ence .of me heat of immersion on the unmet SM HI behavior of the lunar materials of mis study is virtual) temperature can be explained in terms of ordering of identical lo thai observed for lerreslerial analog*. The several layers of molecular water ai the oxide-water rate of reaction of me lunar material is enhanced interface Average net heals tif adsorpl;on will be because of the high degree of disorder inherent in the calculated from results obiained with samples twlgassed particle surfaces due lo meteoritic. ionic, and electro at200andal500°C. magnetic bombardment over the eons. 1 H I H»»an. I L tufcr I. tmi R ft. I.jimisi. / /*« Chrm. 7*. I4«7||97>» 13 4 REACTION OF SOftKD WATER WITH 2 HI tt<*i*v Chrm Mr. Amm h»m. Ktp- M*\ 20. 1974. GROUND VOLCANIC MJNERALS OltNL-t97t. p. IIV E. L. Fuier Jr. P. A. Agron ISA MfVARFJ) SPECTRAL STUDES OF The mechanism of weatherinf (hydration I .if primary INTERACTIONS ON OXIDE SURFACES minerals (pbgiociase. feldspar, pyroxene etc) to form P. A. Agron clays is directly reiaicu »• "ur studirs of lunar materials of 9mlar composition. Volcanic sand was found lo be The activation of ceramic oxides in various catalyti- virtually immune to water attack in ib natural stale. catty promoied reactions is governed by prior thermal Percussive grinding was used lo expose fresh surfaces treatments ai a controlled partial pressure of water. Ii and to induce surface disorder as an at tempi lo simulate has been suggested that the formation of Bronsled and the meteoritic impact on the moon. This ground Lewis acid ales' play a governing role in their material reacts with water vapor in a manner very much activation The transition and aclrmdr oxides have like that of lunar fines. The initial nitrogen sorption served as catalyst supports or as catalysts per se in reveals a low specific surface area and porosity. Sorbed selected reactions. The enhancement of the surface water (»07 relative humidity) reacts with the surfaces properties may be due lo the row-lying unfilled d and is irreversibly bound at 2S°C in vacuo. Thermal orbitals of these surface cations. Thus, the hydro*vb- desorpuon (300*0 of this bound water lead* to a linn of the oxides of Croup IVA and reactions with twofold increase in surface area and reveals the exist other vapors have been studied.2'4 ence of considerable restricted porosity Internal dimen A d urn riur mfrared spectral Kf>a 2000 to 43000 tentatively attributed to O H cm V comers and ccfl edges to a smg) cation.*'* The poorly A uuuporuus preparation uf dwrann oxide was Ksohred shoaiders on eHher ank of dw fatier band may selected to ifl—it nW study of dur dtenanoratioa uf be due to water it-bonded to BV hydroxy! oxygen. water on external oxide surfaces. A gravimetric water Titrations of the bydroxylaicd oxides with -probe" adMwplMin study of das sued, sedanentcd fraction* of molecules jvnl aid in nW arterpretatioa of dw tentative tfuiriuui oxide Was been reported'' A uniform particle spectral unpiiirats. The band maxima at 35«*>cm ' sve of SRO A was cunJijiMd by an electron pboto- are attributed to a water molecule coordinated to a mkrogranhandx-ray crystanrte-soedetenMRatson.7 canon, as m crystal hydrates * The brand band at the TV ctiemisoiptinn of H,0 and DjO vapors on a lower frequency is assumed to molecular water bound setf-suppiirtmg pressed diss uf das thorium oxide to the oxide surface. sanude was Mrowed with spectral traces in die stretch Smutar exposures of the hydroxyiaied oxide to 4 ton frequency region of the O HandO D moieties. Traces DjO avowed rapid exchange, indicating a surface irf die spectra obtained m the temperature range 40 tu reaction. Repeated exposures reduced the spectra of the 40D*C aie shown in Fuj. 13 2. The bands beyond 3600 hydroxyl bands, with a resultant growth of the equiva cm"* have been prevmrsly identified'-4 asO H bands lent deuterated spectral bands. bound nt surface cations at oxynm lattice sites. A BET surface area of 1.3 m2/g was determined for a The eujudibralion of die thorium oxid.- with 4.6 ion standardized sample of TiOj supplied by the Bureau of H20 at successively lower temperatures from 400 to Standards.* Heats of manersion were also determined.* I50*C resulted in the spectral traces of F* I J.2#. o. The activity of das oxide to water and CO was followed and <-. The marked decrease of the 3726-cm"' band at with rpectral studies as a function of temperature and me tower temperatures with a monottmic increase m pressure to evaluate its surface activity. the broad absorbance band at 3550 cm ' is indicative Thermal adsorption and drsorplion cycling of the <>• the greater r<4e of the adsorbed water molecule m titanium oxide with H,0 and DjO resulted in the both of these frequency regnms. resolution of equivalent high-frequency absorption The expanded trace (Fn> I3.2r'| shows the resolved bands. The strongest hydroxyl absorption peak at 3678 strung peak at 3666 cm ' that B assigned to hydroxy Is cm'1 (Fig. I3.3*> was assigned to Off species biiund to more than a single cation on low-index coordinated on surface oxide lattice sites to more than faces." The partially revived band at 3726 cm"' is a single cation. The assignment of die partially resolved «MV( KuaK* to* ' • «o-') 40 M M M H I ' T T»0,-S oto}- 9 / , ' 400 4«T»r«jO JOO 4«r >tjO 3M -1 OT ISO 4«tatn/> 4 ISO WM* -4 f.. 40 !_ 1/ A £ u *// o» 11 /* - 0» - 010 . - -.4 .1 J 1 •—I , * 1 * . 40 M M 34 H SO M •art WW) ton'i 10 ' ) Fig. 13.2. Triwmnnaon mvttra. ausurpnrai «taurpwoi^HiOonTliOaS. 3000-4000c»~' reffcm. Lint** h. c adtorpfinn of H]0 al 4.6 tori jnd 400. 300. and I50*f resprcrntly; d outgasard oxide al ISO'C; t. outdated oxide at 4 QML-MG. *VJ7S2 (•neaaircd against the reference ceil) At die same time, i | I IAP ^P | i | 1 the incresse in the number of bands m the O H stretch frequency region (Fig. 13.36 and c) was resolved on 0:90- mowing the TrO? disk out of the infrared beam (Fig. I3.3J). These bands were identified as combination bands of COj. namely. *, + r, and 2v2 • •>».'• The use of SiO? and AI>Os as supports in catalysis studies has been widely investigated. Various physical measurements have attempted to evaluate their effec tiveness in specific catalytic reactions. Extensive in frared studies of Cj toC* molecular species adsorbed in hydrogenation reac'ions on supported metal catalysts have appealed recently"',z over the temperature range 15C to 150°C." The use of materials such as SOj. A120,. ZK)2. and TbOj provides a wider range of acidity for evaluating die effectiveness of these oxides as supports in hydro genation catalysis studies. The hydrogenation of hydro Ti(>2 + 695%irC0 carbons can be evaluated at temperatures used indus Twee rtXI »IM trially on our infrared spectrophotometer. Hence, the •' ZOO i/4 spectroscopic identification of chemrsorbed inter »,»' ZOO t-J- mediate molecular species can provide improved con 3O0 1 cepts for understanding the mechanisms involved in 4 Oat of catalytic reactions. •VWM- 40 38 36 24 22 20 WAVE NUMBER (cm'-i1 , x 10'') 1. L. H. Little. Infrared Spectra of Adsorbed Species, p. ISC. Fn> 13.3. TnMMm sfectm. expos** of hydroxyMed Academic Press. New York. 1966 TiO, to 69S ton CO. 200O-2400cm'1 Md 3300-4000en'1 2. H. F. Hotmei. Chem. tfir. Arum. Proa. Rep. May 20. 1974. reams. Lion «'. b': growth rj band of COj at 200*C and ORNl-4976. p. 113. depletion r3 band of CO in sample cril. c tunc, at 300*C: h. c: 3 P. A. Anion. Chem. Dm Arum. Pm*. Rep Mav 20. 1974. growth of CO] combination bands superposed on hydroxy! ORNL-4976. pi 72. bands al 200 and 300*C respectively; d: spectu of C02 4. P. A. Agron. 1. L. Filler. Jr.. and II. F. Holmes. IR Studies combination bands )I>I • PJ and 2»2 • «^> with sample out of of the Adsorpzinn-Deiorption of Water on MonocUnk and beam. Tetragonal y.r02 as a Function of Temperature. OR NL-5001 (September 1974): IR Studies of Water Sorplion on ZK)2 Po|ymorphis-l." / CnUndInterface Sci 52. 553 11975). bands al the higher wave number frequencies will 5. f. L. Fuler. Jr.. H F. Holmes, and R. B. Gammafe. / require further titration studies with "probe" nv'ecules Colotd Interface Sci 33.623 11970). to delineate their surface binding. 6. F. H. Swecton. Reactor Chem. Dir. Annu. Pmt. Rep Jan. The exposure of the hydroxylated surface of the /M/.ORNI.-3I27. p. 71 oxide to 94 forr CO at 300°C *or extended periods 7. H. F. Holmes. E. L. FuUcr Jr.. and C. H. Secoy. J. Pfiys. Chem. 72, 2293(196*) indicated a lack of surface reaction as denoted by the R. G. Brink and M. FaJk. Can J. Chrm. 40. 2096 (1970) absence of apparent growth in the background absorp 9. H. P. Frecr^n. NBS Technical Report No. 73 (1963) tion band of C02. However, the titanium oxide reacted 10. (;. Her/here. p. 272 m "Infrared and Raman Spectra of readily with higher pressures of CO. The spectra in Fig. Polyatomic Molecules." vol. II of Molecular Spectra and Molecular Structure. Van Nostrand RrinhoM. Cincinnati. Ohio. 13.3a'. b'. c show the increased growth of the C02 I94S. band with temperature. Likewise the negative absorp 1 11. B. A. Morrow and M. Sheppard. Pmc. R. Soc. IstnJon. tion bands of the CO al 2120 and 2180 cm" are Ser A ill. 391 (1969). indicative of the depletion of CO in the sample cell 12. J. Kfkrkm and Th J l.icfkcns./ Calal. 11. 165 (1972) Publications, Patents, Lectures, and Papers Presented at Meetings 1. MOLTEN SALT SYSTEMS A. L. Bacarclla and J. Braunstein,* Transport Properties in Hydrous Mens," Gordon Research Conference on Chemistry of Molten Salts, Brewster Academy. WoMeboro. N.H.. Aug. 25-29. 1975. C. F. Bacs. Jr.. R. P. Wichner.1 C. E. Bamberger, and B. F. Freasier/ "Removal of Iodine from LiF-BeF: Melts by HF-H; Sparging. An Application to Iodine Removal from MSBR FueL" Sitci. Set. Eng. 56. 399(1975). C. E. Bamberger. "Experimental Techniques in Molten Fluoride Chemiswy." Chap. 4 in Advances in Molten Salt Chemistry. Vol. 3, ed. J. Braunstein. G. Mamantov. and G. P. Smith. Plenum Press. New York. !975. C. E. Bamberger. J. P. Young.' and R. G. Ross.1 The Chemistry of Tellurium in Molten Li>BeF«." /. Inorg. AW/ Chem. 36. 1158 (1974). J. Braunstein. "Application of Molten Salts in the Development of Energy." Plenary Lecture at the South African Chemical Institute Convention. Durban, South Africa. Jury 17. 1975; seminar at the Atomic Energy Board. Peiindaba, South Africa. Aug. 4, 1975. J. Braunstein. "Electrical Transport and Thermodynamic Properties in Molten Salts ot Reactor Interest." Battelle-Geneva, Geneva, Switzerland, Sept. 20.1974. J. Braunstein. "Electrochemical Studies in Molten Salts and Concentrated Aqueous Electrolytes." Electrochemistry Laboratory. University of Paris VI. Paris. France, Oct. 3. 1974. J. Braunstein. "Electrochemistry of Molten Fluorides." Chemistry and Chemical Engineering Division. Atgonne National Laboratory. May 1975. J. Braunstein. "Hydrous Metes: Bridging the Gap between Molten Sates and Aqueous Electrolytes." Laboratory for Thermodynamics and Molten Salts. University of Provence. Marseille, France. Sept. 25. 1974. J. Braunstein. "Ionic Solution Chemistry in Concentrated Electrolytes." Battelle-Geneva. Geneva. Switzerland. Sept. 20. 1974. J. Braunstein. "Migrational and Diffusionai Mobilities in Structured Melts." EUCHEM Conference on Molten Salts. Freising, Germany. Sept. 8-13. 1974 (invited). J. Braunstein. "Solution Chemistry in Hydrous Melt Solvents." Analytical Chemistry Department. University of Genoa. Genoa. Italy, Sept. 30. 1974. J. Braunstein. Transport and Thermodynamics in Molten Salts and Concentrated Aqueous Electrolytes." Chemistry Department. University of Natal. Durban. South Africa. Aug. I. I97S. 'Denote* speaker. 1. Chemical Technology Division. 2. Louisiana Techccal University. Ruston. 1.3 3. Analytical Chemistry Division. 125 126 J. Braunstein and H. Braunstein.4 "EMF Measurements in Molten Salts." tlxperintemal ThtrnuHlinumus. Vol. II. I.U.P.A.C.. cvi. B. LcNcindrc and B. Vodar. Buitcrworihs. London. iv75. p. wl. J. Braunstein. G. Mamantov/ and G. P. Smith, eds.. Advances in Molten Salt Chemistry. Vol. 3. Plenum. New York. 1975. S. Cantor. "Reph to Comment Tr« Affinity of Oxygen for T«*o Electrons.'"/ Chem. Phys. 62,4584 (1975). S. Cantor, ed_. "Controlled Thermonuclear Reactors. Panel Report and Discussion" Report of the Conference on Thermodynamics and Satkmal Energy Problems. National Academy of Sciences. Washington. DC. June 1974. p. 203. S. Cantor and W. R. Grimes.1 "Fused-Salt Corrosion and Its Control in Fusion Reactors." .VIM7. Techno!. 22,120(1974). R. DeWitt.* L. J. Wittenberg." and S. Cntor. -Viscosity of Molten NaCI. NaBF* and KBF*," Phys. Chem. ^.4,113(1974). B. Gilbert/ K. W. Fung.5 G. Mamantov/ and G. M. Begun. "Raman Spectra of Molten Mixtures of an Alkali Halidc with a Group IB (Copper. Silver. Gold) Halide." J. Inorg. S'ucl. Chem. 37, 921 (1975). B. Gilbert/ G. Mamantov/ and G. M. Begun. "Raman Spectra of Aluminum Fluoride Containing Melts and the Ionic Equilibrium in Molten Cryolite Type Mixtures." J. Chem. Phys. 62, 950 (1975). B. Gilbert/ G. Mamantov/ and G. M. Begun. "Raman Spectrum of the AIF4 Ion in Molten Fluorides." Inorg. Sucl. Chem. Lett. 10, 1123 (1974). B. Gilbert/ G. Mamantov/ and G. Begun, "A Simple Raman Cell and Furnace Usable at Temperatures Higher than I000°C for Corrosive Melts," Appl. Spectrosc. 29, 276 (1975). E. J. Kelly and H. R. Bronstein.* "A Potentiostatic Method for Determination of Specific Conductance: Application to Molten Salt Electrolytes." Gordon Research Conference on Chemistry of Molten Salts. Brewster Academy. Wolfeboro, N.H.. Aug. 25-29.1975. A. P. Malinauskas' and D. M. Richardson, The Solubilities of Hydrogen, Deuterium and Helium in Molten Li;BeF«," tnd. Eng. Chem., Fundam. 13, 242 (1974). L. E. McNeese. L. M. Ferris, and F. J. Smith. "Method for Removing Rare Earths from Spent Molten Metallic Fluoride Salt Mixtures." US Pat. 3353,979 (Dec. 10, 1974). G. P. Smith. "Chemistry of the Lower Oxidation States of Bismuth." in international Review of Science. Inorganic Chemistry Series Two. Vol. 2, ed. H. J. Emekfus and D. B. Sowerby, Butterworth, London. 1975, p. 269. G. P. Smith. The Science and Witchcraft of Molten Salt Catalysts." Gordon Research Conference on Chemistry of Molten Salts, Brewster Academy, Wolfeboro, N.H., Aug. 25-29, 1975. C. E. Vallet," "Concentration and Temperature Dependence of Interdiffusion Coefficient in BeF-LiF MelU." EUCHEM Conference on Molten Salts, Freising, Germany, Sept. 8-13, 1974 (invited). C. F. Vallet' and J. Braunstein, "Concentration and Temperature Dependence of Diffusion and Conductance in Molten BeFj-LiF Mixtures,"/. Am. Ceram. Soc. 5*. 209 (1975). C. E. Vallei*' and J. Braunstein, "Concentration Dependence of Diffusion Coefficients in Molten BeF;-LiF from the Eutectic Composition to Pure BeFj," Gordon Research Conference on Chemistry of Molten Salts. Brewster Academy, Wolfeboro. N.H., Aug. 25-29, 1975 (invited). 4. InformalMi Division. 5. University if Tenntwce. 6. Mound Laloratory. Miamitourg. Ohio. 7. Director. Molten-Sab Breeder Reactor Program. I. University of Provence. Marseille. France. 127 C. E. Vallet** and J. Braunstein. "Conductance ei Diffusion dans ies Melanges de Fluorure de Beryllium et de Fluorure de Lithium Fondus." Journeesd'Etudcs Sur Les Sebet Silicates Fondus, Moss, Belgium, Apr. •6-18, 1975 (invited). C. E. Vallet,1 H. R. Bronstein. and J. Braunstein, "Efcctromigrational Depletion (ED) Chrooopotentiometry. Temperature Dependence of Diffusion in Molten BeF,-LiF," J. Eleciwchtm. Soc. 121, 1429 (1974). J. P. Young,' C E. Bamberger, and R. G. Ross,' "Spectral Studies of/-<* and //Transitions of Pa(IV> in Molten LiF-BcF:-TnF«.~ J. burg. Sucl. Chem. 36, 2630 (1974). 2. AQUEOUS SYSTEMS AND GEOTHERMAL ENERGY C. F. Baes. Jr.. 'The Chemistry and Thermodynamics of Molten Sak Reactor Fuels." J. Sucl. Mater. Sl( I). 149(1974). M. H. LietzKc and T. J. Lemmoods,' "The Standard Potential of the Ag, AgBr Electrode in DBr Solutions." J inorg. Sucl. Chem. 36,2299 (1974). M. H. Lietzke and R. W. Stoughton, "The Possibility of Applying Meson Spectroscopy to the Study of Solution Chemistry," in Proc. Practical Applications of Accelerators, LA-5535-C (March 1974). M. H. Lietzke and R. W. Stoughton, The Prediction of Osmotic and Activity Coefficients for Electrolyte Mixtures at Elevated Temperatures. ORNL-4999 (September 1974) M. H. Lietzke and R. W. Stoughton, "Problems Encountered in Deriving Activity Coefficient Values from Data on Mixed Electrolyte Systems." J. Term. Acad. Sri. 49, 130 (1974). M. K. Lietzke and R. W. Stoughton, "A Simple Method for Predicting the Osmotic Coefficient of Aqueous Solutions Containing More Than One Electrolyte," J. Inorg. Sucl. Chem. 36,13 IS (1974). W. L. Marshall, "Water and Its Solutions at High Temperatures and Pressures," Chemistry 48(2), 6 (1975). W. L. Marshall* and J. S. Gill, "Effect of Pressure on Liquid-Liquid Immiscibility of High Temperature Aqueous Solution Mixtures of Uranyl Sulfate and Sulfuric Acid, 280-450°C, 75-1800 Bars." 167th National Meeting, American Chemical Society, Los Angeles, Calif.. Apr. l-S, 1974 (abstract PHYS-49). W. L. Marshall and J. S. Gill. "Effect of Pressure on Liquid-Liquid Immiscibility of High Temperature Aqueous Solution Mixtures of Uranyl Sulfate and Sulfuric Acid. 280-450° C, 75-1800 Bars," J. Inorg. Sucl. Chem. 36, 2303 (1974). W. L. Marshall* and E. V. Jones,2 "Liquid-Vapor Critical Temperatures of Aqueous Electrolyte Solutions," 168th National Meeting, American Chemical Society, Atlantic City, NJ., Sept. 9-13, 1974 (abstract PHYS-52). W. L. Marshall and E. V. Jones,3 "Liquid-Vapor Critical Temperatures of Aqueous Electrolyte Solutions," J. Inorg. Sucl. Chem. 36,2313 (1974). W. L. Marshall* and E. V. Jones2 "Liquid-Vapor Critical Temperatures of Several Aqueou.-Organic and Organic-Organic Solutions Systems," 168th National Meeting, American Chemical Society, Atlantic City, NJ., Sept. 9-13, 1974 (abstract PHYS-53). W. L. Marshall and E. V. Jones,2 "Liquid-Vapor Critical Temperatures of Several Aqueous-Organic and Organic-Organic Solution Systems," J. Inorg. Sucl. Chem. 36,2319 (1974). * Denotes speaker. 1. University of Tennessee. 2. Deceased. 128 R. E. Meaner. "Review of Studies on Pretcrytic Equilibria at High Temperatures at ORNL." U.S. Geological Survey. Rr-*on, Va.. May 30. 1974; Menlo Park. June 3.1974. R. E. Meaner and C. F. Baes. Jr.. The Hydrolysis of Cations: A Critical Review of Hydroh/tic Species and Their Stability Constants in Aqueous Solution." ORNL-NSF-EATC-3. Par* II (December 1974). Part II (November 1975), Pan IV (December 75). R. E. Mesmer and C. F. Baes. Jr.. "Phosphoric Acid Dissociation Equilibria in Aqueous Solutions to 300*C." J Sokttkm Chtm. 3. 307 (1974) R. E. Mcsmer. W. L. Marshall, and others. "A Recommended Research Pv^cram » Geothennal Chcmistiy." AEC ad hoc committee report. (R. N. Lyon and G. A. Kobtad. Co-Chainnen). USAEC report WASH-1344 (October 1974). Y. Talmi' and R. E. Mesmer. "Studies on Vaporization and Halogen Decomposition of Methyl Mercury Compounds Using GC with a Microwave Detector." Wmter Res. 9. S47 (I97S). L. B. Yeans.' P. M. Lantz.' and W. L Marshall. "Cakium Snltaie SorabiMty in Brackish Water Concentrates and Applications to Reverse Osmosis Processes; Polyphosphate Additives." Desmtimikm 15, 177 (1974). 3. Aaal.-ocaJ Cfceaouy Dnirii 4. Hcakii Physio Dmsioa. 3. CHEMISTRY IN SUPPORT OF FUSION REACTOR TECHNOLOGY G. M. Begun,* G. Mamantov.' K. W. Fung,' and B. Gilbert,1 "Raman Spectra of Molten Mixtures of Group IB Halides and Alkali Halides," Fourth International Conference en Raman Spectroscopy. Bowdoin College, Brunswick, Maine. Aug- 25-29,1974. J. T. BelL* R. A. Strehlow. J. D. Redman, and F. J. Smith, "Trtium Permeation through Steam Generator Materials," International Conference on Radiation Effects and Tritium Technology for Fusion Reactors, Gatlinburg, Tenn., Oct. 1-3. 1975. F. J. Smith* and J. F. Land, The Hydrogen Isotope-Lithium Systems," ANS National Meeting. New Orleans, La., June 8-13. 1975. F. J. Smith and J. F. Land, The Hydrogen Isotope-Lithium Systems." Tram. ANS 21,167 (1975). F. J. Smith,* J. F. Land, J. B. Talbot,2 and J. T. Bell, "Chemical Equilibrium Studies of Tritium-Lithium and Tritium-Lithium Alloy Systems," International Conference on Radiation Effects and Tritium Technology for Fusion Reactors, Gatlinburg, Tenn., Oct. 1-3, 1975. F. J. Smith,* J. D. Redman, and J. T. Bell, Tritium Studies in Support of CTR," Chemical Technology Division Annual Information Meeting, Nov. 5-6, 1974. F. .1. Smith,* R. A. Strehlow, and J. D. Redman, "Current Tritium Chemistry Studies at Oak Ridge National Laboratory," Symposium on Tritium Technology Related to Fusion Reactor Systems, Mound Laboratory, Miamisburg, Ohio, Oct. 1-2,1974. F. J. Smith, R. A. Strchiow, J. D. Redman, a.td J. T. Bell, "Current Tritium Chemical Studies at ORNL," Proc. Symp. Tritium Techno!. Related to Fusion Reactor Systems. ERDA-50 (June 1975). *DcnoKs speaker. 1. University of Tennessee. 2. Chemical Technology Division. 129 4. CHEMISTRY OF TR ANSI RAMI M ELEMENTS L. B. Asprcy* and R. G. Hare. 'The Synthesis and Properties of Californium Metal and Compounds.'* Symposium on Berkelium and Californium. Berkeley. Calif.. January 1975 (invited). L. B. Asprey1 and R. G. Haire. "The Synthesis and Properties of Californium Metal and Compounds/* Proc. Symp. Berketium Californium. Berkeley. Calif.. January 1975. R. D. Baybarz.' J. A. Fahey.' and R. G. Haire. The Preparation, Crystal Structures and Some Properties of Californium Oxysulfate and Oxysuttlde." J. hwg. Nucl. Chem. 36, 2023 (1974). J. H. Burns. W. H Baldwin, and F. H. Fink.4 "Crystal Structure of Scodymkun Tnslmethykyxiopentadienide).'' tnorg. Chfm. 13.1916(1974). J. H. Burns. J. R. Peterson.' and J. N. Stevenson.* "CrystaBographic Studies of Some Transuranic Triha!nfes: "PuCI.. "CinBn. :**BkBr. and "CfBu~ /. Inorg Sucl. Chem. 37,743 (1975). G. R. Choppin and R. I.. Fellow*.' -Hypersensitivity n Complexes of %*'!!!} and Hoflll) witb Monobasic Ligands." J. Coord. Chen. 3, 209 (1973). R. L. Fellows' and G. R. Choppin.' -Hypersensitivity of Complexes of Nd(lll) and He* HI) with Dibasic and Pohbasic Lagands " J. Coord. Chem. 4. 79 (1974). R L. Fellows.* J. R. Peterson.' M. No*." J. P. Young,'1 and R. G. Haire. "X Ray Diffraction and Spectroscopic Studies of Crystalline Emstemium(III) Bromide. '"EsBr,.** hwg. Nun. Chem. Lea. 11, 737(1975). J. Fuger.': J. R. Peterson/ J. N. Stevenson.* M. No*." and R. G. Haire, "Determination of the Heat of Solution of Berkelwm Metal" J. hnrg. Nucl. Chem. 37, 1725 (1975). D. K. Fujita." T. C. Parsons.'' N. Edebtcin.*" M. No*.'8 and J. R Peterson.' The Magnetic SwccptibUrty of "Cm Metal and "**Cf Metal." 4th International Transplutonhim Elements Symposium. Baden-Baden. Germany. Sept. 13-17. 1975. R. G. Haire and R. D. Baybarz,' "Crystal Structure and Melting Point of Californium Metal," J. tnorg. Nucl. Chem. 36, 1295 (1974). 1 O. Keski-Rahkonen, ' The Sulphur KLL Auger Spectra in H&, SO:. and SF.," Annual Meeting of the Finnish Physical Society. Oulu. Finland. Feb. 14-15, 1975. * Denote! speaker. 1. Los Alamos Scientific Laboratory. 2. Deceased. 3. Chemistry Department. Bronx Community College. 4. Birmingham Southern College. Alabama. 5. Consultant. Department of Chcnvstiy. University of Tennessee, Knoxville. 6. Graduate student. University of Tennessee. Knoxville. Present address: U.S. Naval Nuclear Power School. Math Division. Bainbridgc. Md. 21905. 7. Department of Chemistry. Florida Slate University. Tallahassee. S. Department of Chemistry. Florida State University. Tallahassee; present position: Postdoctoral Research Associate. University of Tennessee. Knoxvitle. 9. Postdoctoral Research Associate. University of Tennessee, Knoxville. 10. Postdoctoral Research Associate. Department of Chemistry, University of Onneiiee. Knoxville; present address: Framatome. 77 SI Rue du Mans. M403 Courbtvoie. France. 11. Analytical Chemistry Division. 12. Institute of Radiochemislry. University of Liege. Liege. Belgium. 13. Lawrence Berkeley Laboratory. University of California. Berkeley; present address. Department of Chemistry. Santa Rosa Junior College. Santa Rosa. Calif. 95401 14. Lawrence Berkeley Laboratory. University of California. Berkeley. 15. Laboratory of Physics. Helsinki University of Technology. Otaniemi. Finland. 110 O. Keski-Rahkoaen.1* "Ultrasoft X-Ray Absorption Measurements Lung a Photociectroa Spectrometer.- J. Mrs. CI, 535 (1975). O. Kcski-Rahkoaea*" and M. O. low. "Eacrgies. Widths, and Relative Internum of Iraaium V X Rays.- UMematioaal Coafercacc oa X-Ray Processes in Mailer. Obaiemi. Fmbund. JuR 29-Aug. I. 1974. O. Kcski-Rahkoaea" aad M. O. Krause. "Energies. Widths aad Retain* Intensities of Uranium V X-Rav Law." Mrs. Fetm. 9, SI. 261 (1974). O. Kcski-Rahkoaca1* aad M. O. Krause. "Total aad Partial Atomic LevH Widths." At. Dmtm \ucl Dmtm Tmbks M.I39 (1974). M. O. Krause. "The Argon KLL Auger Spectruai: A Test of Theory." Fiiys. Rev. Ixti 34.633 (1975) M O. Krause. The Dual Role of the Photoelectroa: PAL aad PAX." lecture at University of l.abua. Lisbon. PortugaL July 22 aad 25. 1974. M. O. Krause. "Ekxtroa Shafceoff aad Shaken? ~ Gordoa Research Conference on X-Ray Photoekciroa Spectioscopy. Brewster Academy. WoUcboro. N.H.. July 15-19.1974 ,'iavrtcd). M. O. Krause. "Ekctron Spectrometry." in Atomic bwmt Shell Processes, ed. B. CrasemauK. Academic Press. New York. Vol. II. pp. 33-81. 1975. M. O. Krause. "Electron Spectrometrv ie Chemistry aad Physics." lecture at University of Lisboa. Lisbon. Portugal. July 22 aad 25. 1974. M. O. Krause. "Higfahghts and Recent Developments in Electron Spectrometry." colloquium at the Laboratoire Chmne-Physique. Unrversite* de Paris VI. Paris. France. June 9. 1975. M. O. Krause. "Neue Ergcbntsse in der Photo- und Augercfcktronen Spektrometrie." colloquium. Hahn-Meitner Institut. Berlin. Germany. Aug. 5. 1974. M. O. Krause. "Photodectron Spectrometry: Experiments with Atoms. I and II." two lectures at Summer School of NATO Advanced Study Institute on Photoionization and Other Probes of Many-Electron Interactions. Carry-Le-Rooet. France. Aug. 31-Sept. 13. 1975. M. O. Krause. "Photoelectrons: Counterparts of Roentgen Rays." International Conference on X-Ray Processes in Matter. Otaniemi. Finland. July 29-Aug. 1.1974 (invited). M. O. Krause, "Photoekctrons: Counterparts of Roentgen Rays." Phys. Fenn. 9, SI. 281 (1974). M. O. Krause, The Photoionization Process as Seen through the Photoelectron." Physics Department colloquium, Linkopiag University of Technology, Linkoping. Sweden. Aug. 9. 1974. M. O. Krause, "Principles of Electron Spectrometry," lecture at Laboratoire Curie. Unrversite* de Paris VI. Paris. France. May 28,1975. M. O. Krause, "Recent Trends in Electron Spectrometry," seminar at the Laboratoire Chimie Physique Nuclease du Centre d*Etudes Nucleaires de Grenoble (CENG). Grenoble. France. June 17, 1975. M. O. Krause and J. G. Ferreira,'* mK X Ray Emission Spectra of Mg and At," J. Phys. B 8,2007 (1975). M. O. Krause* and O. Keski-Rahkonen," "Characteristics of Prominent M X Rays of Some Actipides." International Symposium on the Electronic Structure of the Actinides, Argonne National Laboratory. Argonne, III., Oct. 9-11, 1974. M. O. Krause and F. Wuilleumier,*1' "Study of Atomic Subshell Properties by Electron Spectrometry." International Symposium on Electron and Photon Interactions with Atoms, Stirling, Great Britain. July 16-19, 1974. 16. Universidade d< l.isboa. FacuMadc de Genciav Lisbon. Ponupl. 17. I. (J RE and Lahoraloirc dc Chimie Physique de rUniversiK de Paris VI. Orsay. France. 131 M. O Krasst aad F. WWSCMHCT.1' "Stady of Atoauc SaarhtB Ptopeities by Efcctroa Spectrometry." ia Electron and Photon huermctiom wm\ Atom*. Pfcsnaa PwbL Corp.. New York. pp. o9-97 (I975)L C. Masikas" aad J. H. km. "Strecosrc aad torn** m Cnipri.ai Cnatiiaiag the NpQT aad NpOv* foas." f>or. Foan* aw. Trmupkoomw* Element Snap, andrw awaVa. Germany. Sept. /J-/7. /975. M. W* and J. R. Pctersoa.*5 -Preparation aad SaaJy of IZksaeafal Cibfniawaa 249." 4th laanaatiimal J. R. Pctevsoa.* "Receat Advaaccs ia the Caeaaatiy of the Traasanaana Elements." Soathacsana at Memphis. Mimphii. Teanu Oct. 21.1974: Western Keatacky Lawersry. Bowaag Greta. Ky.. Oct. 25. 1974; Manay Stole Uancrsity. Murray. Ky.. Nov. IS. 1974. J. R. Peterson/ "Synthesis aad Properties of Bert i ham Metal aad Coaaaoamds." Syaawjamm Cnaawrmnntiag the 25th Aaancnary of the Discovery of Fhsatats 97 aad 9t. Lawrence Berkeley Laboratory. Berkeley. Can*. Jaa 20, 1973 (awindl R. J. Sitva. W. J. McDowell."* O. L Kcler. aad J. R. Tarrant. Xuam atari* SoJatioa Chiaaiiiij. loaac Radius aad Single loa Hydration Energy of XotKaaak~a«Mf. Cfcnw. 13.2233 (1974). D. W. Slocaau*> R. L. Fcwows/1 D Beach.2* aad C. R. Ernst.3* "A L'auwe Basc-Cataryzcd Proton Eifhaajr of Satsfitaied Fcrrocenes." 161th National Mcetiag of the Asaericaa Chemical Society. Atlantic City. N J . Sept. t-13. 1974 (abstract ORGN 24) J. N. Stevenson* aad J. R. Peterson/ "Some Sew Microchesakal Tcchaiqaes Used ia the Preparatioa aad Study of Transphnoniam Ekascats aad Compowads." Mkrochem. J. 2*. 213 (197$). R. P. Turcotte*" and R- G. Hake. The Cf Oxygca System for I JO < O Cf < 1.72." 4th laaeraatioaal Traasptotoaiam Elrawats Symposium. Bade a Baden. Getaway. ScpatawVti 197$. R. P. Turcotte" aad R. G. Haire. The Cf Oxygen System for I JO O a < I.TT Pror. 4th Mr. Transpmtonaun Element Symp^ Baden-Baden. Germany. September 1975. F. WuilkumieT*1" and M. O. Krause. "Angular Distribution of Pbotoetoctrons in the Soft X-Ray Region." International Conference on Electron Spectroscopy. Namar. Belgium. Apr. 16-19. 1974. F. WuiUeumierr and M. O. Kranse. "Angular Distribution of Pbotocfcctrons in the Soft X-Ray Region." J. Electron Spectrox. 5,921 (1974). F. Wuilleumier1' and M. O. Krause. "Pbotoionization of Neon between 100 and 1000 eV: Single and Multiple Processes. Angular Distributions and Subsbell Cross Sections.'' Phys. Rev. A 10, 242 (1974). J. P. Young.*" R. G. Haire. R. L. Fellows.* M. No*." and J. R. Peterson.5 "Spectroscopic and X-Ray Diffraction Studies of the Bromides of Catifomium-249 and Emstemrom-253." 4th International Transpiutonium Elements Symposium. Baden-Baden. Germany. Sept. 13-17. 197$. J. P. Young." R. G. Haire. R. L. Fellows.* M. NocV* and J. R. Peterson.' "Spectroscopic and X-Ray Diffraction Studies of the Bromides of :"Cf and :"Es." Proc. 4th Int. Tmnspkitonium Elements Symp.. Baden-Baden, Germany. September 1975. I. Zvara,"' O. L. Keller. R. J. Sirva, and J. R. Tarrant, Thermochromatography of Bromides—a Proposed Technique for the Study of Transactinide Element Chemistry." J. Chromatogr. 103, 77 (197$). IS. C.E.A.. t-'ontenay-aux-Roics. France. 19 Chemical Technology Division 20. Department of Chemislrv. Southern Illinois I'mvervty. Carhondale. 21. Department of Chemistry. Southern Illinois University. Carhondale: present position: Postdoctoral Research Associate. University' of lennesscc. Knoxvinc. 22. Balletic Pacific Northwest laboratory. Richland. Wash. 2.1 Joint Institute for Nuclear Research. Duhna. I S S R 112 •>. SEPARATIONS CHEMtSTRY W H. Baldwin. "Production of tfagh Purity Habdes " VS. Par 3*213561 June 28. 1974). W. H- Baldwin and C E- tfeggsm. "Direct Detenninaiion of Lapnds m Sohatcd Salts " / Inurg. Anrf. Chan 34. 140711974). W. H. Baldwin and C. E- WB>S. "Down-Liquid Distribution Tributyl Phosphate between Immtscibie Solvents "/ Cham- Eng. Dum 19. 152 ( 1974). J. T- Bel. The Cheanstiy and Kinetics of Exotic Aqueous Praionmm Nitrate Solution;.*" ORAL" Traveling Lecture. Tennessee Tedaologkal University. Nov. 8.1974. J T. Bel and S. R. Buxton.1 -Phototeduction of the Uranyl Ion with Laser Light and Ethanol I. Quantum Yields and Median Effects."/ Imorg. AW Cham. 3*. IS7S < 1974). J T Bel and S. R. Buxton.' TlutoredwctMM of the Uranyl Ion with Laser Ltfht and Ethanol II. The Effect* of Temperature and Uranyl Concentration oa the Uranyi-ErJunol Reaction.- / Imoeg. AW Chan. 37. 14*9 11974). J. T. Bel. H. A. Friedman, and M. R. Swung*/ "Spectrophotometry: Stodies of DioxouiamumlV» in Aqueous Media I The PercMorate Medium." 7. Imarg. v««* Chan. 3*. 256311974). J. T. Bel. L M. Toth. and H. A- Friedman. The Photochennstry of Aqueous Plutonium Systems." VIII International Conference on PhoMchemistry.Edmonton.Canada. Aug.7 13.1975. J. H. Bums W. H. Baldwin, and F. H. Fink.3 -Crystal Structure of Scodymram TnstineihyW>c'optniadiewd€> Imorg-Cham. 13.1916(1974) L Dresner. Ion Exclusion from Neutral and Slightly Charged Pores." Dtsntmnkm IS.39 <1974)* L. Dresner. "Ionic Transport through Porous Ion-Exchange Membranes in Hyperfiltraiion and Pie/udialys:;." Dammmtkm IS. 109(1974)* L. Dresner. "Salt Transport in Composite Reverse Osmosis Membranes." Drmmmrmm 15.371 (1974).* F. J. Hurst and D. J. Crouse.' "Oxidative Stripping Process for the Recovery of Uranium from Wet-Process Phosphoric Acid." VS. Pat. 3J83S.2I4 (Sept. 10.1974). F. J. Hurst and D. J. Crowe." "Recovery of Uranium from Wet-Process Phosphoric Acid by Extraction with Octylphenytphosphoric Acid."Ind Emg. Chem.. Process flex Dew. 13.286 (1974). J. S. Johnson. Jr.. "Filtration. Hyperfitration. and Dynamic Membranes." short course on "Advances in Membrane Technology." sponsored by State University of New York. Kerhonkson. NY.. Sept. 29 Oct. 3.1975 (invited). J. S. Johnson. Jr.. "New Options for Effluent Treatment with Dynamic Membranes." Scientific Meeting of the Corn Refiners Association. National Conference Center. East Windsor. NJ.. Mar. 25 26.1975 (invited). J. S. Johnson. Jr.. "Pulp and Paper Industry Demonstration Pilot Plants." seminar on "Industrial Applications of Membrane Separation." Gemson University. Aug. 19,1975 (invited). K A. Kraus. "Activated Carbon." Max Planck Institut fur Biophysik. Mar. 7.1975. K. A. Kraus. "Cross-Flow Filtration and Axial Filtration." Max Planck Institut fur Biophysik. Mar. 7.1975. K. A. Kraus. "Cross-Flow Filtration and Axial Filtration." Ptoc. 29th Ind. Waste Conf.. Purdue University, 1975. K. A. Kraus* and F. Nelson, "Activated Carbon II. Adsorption of Acids from Concentrated Electrolyte Solutions." I ?th Biennial Conference on Carbon, Pittsburgh. Pa.. July 28 Aug. 1.1975. •Denote* speaker. I. Chemical Technology Division. 2- Summer employee. i- Visiting scientist from Birmingham Southern College. 4. Jointly from ORNL and Weizmann Institute of Technology. 133 K A Kraus Md F. Ndson. "Activated Carbon il. Adsorption of Acids from Concentrated Electrolyte Solutions.'' 12th Biennial Conference on Carbon. Extended Abstracts and Program, Pittsburgh. Pa.. 1975. Fifteen authors including K A. Kraus. "Chemical Speciation in Sea water." in "The Nature of Seawater." Dahlem WorkshopRcport. ed.. E. D. Goldberg. Physical and Chemical Sciences Research Report 1. Dahlem Konferenzen Berlin (197S). R. E. Mm turn. Advanced Techniques for Aqueous Processus and Pollution Abatement, final report toNSF/RANN, October 1972 March 1974. ORNL-NSF-EP-72 (August 1974). R. E. Minturn. J. S. Johnson. Jr.. W. M. Schofield.* and D. K. Todd.s "Hyperfiltration of Laundry Wastes." Water Res. 8.92111974). F Nebor. H. 0. Phillips, and K. A. Kraus. "Adsorption of Inorganic Materials on Activated Carbon." Hoc. 29th Ind. Waste Conf.. Purdue University, 1975. D. M. Richardson md C. E. Bamberger. "Solid Sorbent for Trapping Iodine," US. Pat. 3,880.619 (Apr. 29,1975). 5. Water Muufcmtm Services, lac.. Atlanta. Oa. 7. NUCLEAR CHEMISTRY G. F. Auchinpaugh.' J. Halperin. R. L. Macfclin.1 and W. M Howard.1 "Kilovolt ,JS(«.o,) and "Sdr.-f) Cross Sections Importance in the Nucleosynthesis of the Rare Nucleus 3*S." Phys. Rev. C12.1126 (I97S). C. E. Bemis. Jr.. "Alchemy Updated: Or, the Genesis of an Element." Oak Ridge Natl Lab. Rev. 8(3), 2 (Summer 19751- C. E. Bemis. Jr.. "Element 104." in 1975 McGraw-Hill Yearbook of Science and Tecrnoktey. McGraw-Hill PuWishingCo.. New York. N.Y.. 1975. p. 178. C. E. Bemis. Jr.. "The Great New Elements Race." Physics Division colloquium. Purdue University. West Lafayette. Ind.. Apr. 17.1975. C. E. Bemis, Jr.. "Transnobelium Nuclei." International Conference on Reactions between Complex Nuclei. Nashville. Tenn. June 10 14.1974 (invited). C. E- Bemis. 'Transnobelium Nuclei." hoc Int. Conf. React. Complex Nud., ed. R. L. Robinson. F K. McGowan. J. B. Ball, and J. H. Hamilton. Vol 2.p. 52". North-Holland. Amsterdam. 1974. C. E. Bemis. Jr.. F. Plasil.4 R. L. Fergus ^i. E. E. Gross.4 and A.Zucker* "Attempted Coulomb-Excitation of the Spontaneous Fission Isomeric StaK of 7i*Pu." Phys. Rev. CIO, 1594(1974). R. Bimbot.' D. Gardes,* R. L. liahn. Y. De Moras.' and M. F. Rivet.' "Recoil Study of Ar-fnduced Multinuckon Transfer Reactions. Capture of 1 to 9 Charges by Rare-Earth Targets." NucL Phys. A 248.377 (1975). R. Bimbo!,' D. Gardes' R. L. Hahn. Y. DeMoras.' ana M. F. Rivet.' "Recoil Study of MultinucleonTransfer Reactions: Capture of Six Charges by Nd Targets in Ar Induced Reactions." Nud. Phys. A 228,85 (1974) R. Bimbot.' D. Gardes* R. L. Hahn. and M. F. Rivet.' "Incomplete Fusion of Ar and Rare-Earth Nuclei," Proc. XII Int. Meet. NucL Phys.. Villon. 1974. A. R. Brosi and B. H. Kelelle. "' "Nd Decay and the ' 3*Pr Ground Spin," Sue!. Phys. A 245,243 (1975). 'Denotes speaker. 1. Physics Division, Los Alamos Scientific Laboratory, Los Alamos, N.M. 2. Neutron Physics Division. 3. Astronomy Department. University of Illinois. Urba.o III. 4. Physics Division. 5. Director's Division. 6. Insltlut de Physique Nucleaire, Orsay, France. 134 L L CothW L L RuilMffi.7 C. D. OlCeaey. C. R. Baoham.7 J V Wood.* R V Fa*.* E. F Zomar • A G Schmidt.'• E. H. Spejewski.'* H. K. Carter.'* R. L MWuida,.'* and J H Hjnjdi.m.'' "Decay <* '"ft: meetmg of rhr Ammna Pfcya.il Society. ILnourafc. Teaa.. Jaae 16 IS. 1975:ML _4«t fnrs. £*- 2*. »30 I 1975). J. W. T. Dabbs.*4 V W. Hal.'2 C E. Beans. Jr.. aad S. Ranua.4 "fission Cro» Section Measurements on Soon-Lived Alpha Emitters." Conference on Nuclear Crow Secboas aad Technology. Washington. DC Mac 3 7.1975. I.i.T. Dabbs.4 S. W. Mi.1» C. E. IMB. Jr.. awl S. Ramaa.4 -fwmm Cross Stem* UtmiMMH on Short Used Alphi Emitter" But ,4m. l*rx Sac.. JO. 137« 19751. E. EKMCT. review of IfMsmv. by Jeremy Bemsiem I Vaang rVess. New York. 1973). flat Aafer Smtl Lab. Ret 74 3i. 8 (Fall 1974). E. Eb-Mer. "lifetimes of Hugh-Spat Rotational Stales." Gordon Research Conference on Nuclear Cheaastry. N*» Loadoa.N.H..Jaael975. E. Eidaer. "Nuclear Rotational States: Rejuvenation of aa Old Field.- seminar. Department of Chemistry. Waduagtoa L'niversiry (St Lowsi.Nov 14. 1974. E. Eichler, G. D. OlteBey. J. S. Eldridar." and J. B. Bai.4 -Search for die Decay of **ix.~Hm. Rer.Cf. \>"l (1974). J. S. EMridar* "tD OHeUey. aad K. J. Noribuuti'J "Itoaordial Radioekiiienis aad Cosmogrmc Radaiaackdes m Rocks aad Sods from Descartes aad Taurus-Liitrow." Sixth Laaa. Science Conference. Houston. Tex.. Mar 17 21.1974. J. S. FJdridge.'3 G. D. Olteffcv. aad K. J. Northcuii.'J -Primordial Radweiemeats aad Cosmogemc Radionuclides in Rocks aad Sods from Descartes and Taaros-liiiroar." LaaarScirarr 17. p. 242. The Lunar Science Institute. Houston. Tex. 1975. J. S. EMridge.' * G. D. OlteRey. and K. J. Nortbcull.1* -Primordial Radtoelemenb in Rocks and Sods from Taonis-Littrow." Genckim. Casmoriam. Acta. Sappl. 5. Vol. 2. p. 1025. Fergamon. New York. 1974. H. Gauvm* Y. LeBeyec * M. Lefort* and R. L Hahn. "Observed Differences between Argon and Krypton Induced Reactions Leaf ig to the Same Compound Nuclei.' * *Er and '" Er.~ Urn. Re* C10.722119741 R. E. Goans.*14 W. M. Good.1 * and C. E. Benus. Jr.. "Current Developments m External Counting of the Acimides at Hofafield National Laboratory." 20th Anniversary Meeting oi' Heal* Ptiyvcs Society. Buffalo. N.V. Jury 14 18.1975. M. W. Gtridry." "Recoil-Distance Lifetime Measurements and Multiple Coulomb Excitation Studies of "H\" Ph.D. dissertation. University of Tennessee. KnoxviBe. August 1974. Richard C. Hageruuer." G. Davis OTCelley. and E. Eichkr. "A Search for "Mo."/ Imwg. Sucl Chem 37.1111 (1975). R. L Hahn. **Kr and Ar interactinns of Very Heavy Ions at Orsay and ORNL." presented at Gordon Research Conference on Nuclear Chemistry. New London. N.H.. June 1974. 7. University of Tennessee. KnoxvaV. S. Ccorpa Institute of Technology. 9. Louisiana Slate Unrversiiy. 10. UNISOR. a consortium of 14 institution*. 11. Vanderbttt Univcnity, Nashviar.Ttnn. 12. Instrumentation and Controls Division. 13. Analytical Chemistry Division. 14. Health Physic* Division. 15. Oak Ridge Graduate Fellow from the Department of Chemistry. University of Ttnnessee. Knoxrille. under appointment with Oak Ridge Associated Universities. 16. Present address: Knerry Research and Development Administration. New Brunswick. Laboratory. Nrw Brunswick. N.i. 13S It ! Hsfc=. -TJit Qmi KM Se* tlem-ats." ORAL' Travdaw; Lcciarcs Raadoa«t-bbco" Woam's Cdkp. Lyacbbare, Vi. Jamsary 1975.DaraJsor ConVpr.Dwrahoa.XC.Madi I97>:UrnCoaeflt.aarbuanrdk.Ky.. Apni 1975. Haauafaua Coaepr. MofttpMaery. At*.. Aprd l975:Taskcfte lasmaie. Tasfceaee. Ala, Apii 197$. R. L tfaha. P. F. Ditiarr. K. S. To** aadO. I Kdkr.-^Transfer adCoaa»>aad-NacJeas ReacnoasThai Lead lo *c Nawfci I4*Cf a»d ,4*Cf lMc»LfMH of • JC aid* 5,*P« aad "••J." /fcjj. Jtew. C ». ISS911974). J Halaetau G. DeSaawue.1 R I. Pere/.s mi R L. MacUa.2 lluwiUKWt oa *e 22 eV Doaairt n :,STMJ».7»--** v«» /*»* S>r- 2». 1*5f 1*751- J H Haaahua.'1 K bin." L. Varaol." A. V Raaayya." P. E. Utile." **• N R Joaasoa. ~£0/£2 TraasHwaSireaeriHaadlaicTrrefatiuasof 0*. 2*SeattsM ,T*Hf.~Aj^ AVr. CM.25*011974). J A. Hane>.: J lUprn*. S W H*.,J R. L Mackha.2 S Un< aad E. T. Jarary. Total aad CaptweCrass Secta*^**SiforeVaadl*V^iraas.~ia*.4aLJ^5br: 2». II95II975|. P. R Jaarae/.1" -Cknctttinnom of a Low4*trasm Beta Traasibon M the Decay of **Tc."~ MS. *esn. UwKmn of Teaaasce. KaosmBe. DeceaaVr 1974. C H. Joaatua.1 J. lUatna. R. L Macktak.2 mi R. R. Weum." -Seatraa Total aad Captarc Crow SecTaoa for "S." Ja* Am. #*rx Sac. ». 11951 |975|. N R. Juaatoa. "LifeaaKs at Mab-Saai Rotatinaal Sun by the Doepler-Saifi Recai-Bistaace Twaaiipr." amed paper prcseaied at ibr lateraataanJ Coafeteace oa CUM Ray Traasnxoa PiiibaWiiiii. Deaa. haaa. Nov. II 15.1974. N R. Jofcaua. "fjfetaaes of Hajb-Spai Rotat»>aaJ Sows by rite Doapier-Saiff Recoi-Dsiaacr ler\mimt." Tab lasmaie of Faadaamtal Research, liaahar. ladta. Xo». 19.1974 A F. KJai," N R Johasua. mi J H. Haaalian.' * -Leads n ' **Ci Popabied at the Decay of 46-aaa '5,Ea." /ftrs Re*. C 10. 254011974>. A F Khsfc z* S R. Johnson, jad J. H Hamdioa.'" -Properta* of' **Gd Le««ls IViowaied m OK Decay of 1$ 24 ' ** En." /»OL *«T. C It. 1451119?4}. R L Macfchn.: J tttarnn. and R R. Winien.'* -Gold NcBican-Captsre Cross Secnon fron 3 to 550fceV." thys. KfT.Cll. 1270 79119751. J. tt*ry.:' R. J SOn. 0. L. Keler. R. W. Si<*&'xm. mi i. Hdpcxm. "Delayed Frssioa m Lead Indoced by Electro* frraauimn." propress report, \mutiui it PhysioBe Nodejwe. UnwerHte de Paris-Sad. Orsay. December 4.1974. J. Maiy.:' R. W. Si«ufbt«xi. and J lUpem. "Spnatmeoiis Fisnoa of Taonwn Undtigswaa." report IPSO RC-7-* JO. Insiiiut de Phy»aue Nocleasre. Uarrersite de Pans-Sad.Orsay f 1974). F K. Merman* C E Bemit. Jr.. W. T Maner.4 I L. C. Ford. Jr..4 R L. Robawon.* and P. H. Stetson* "Coulomb KxcifjlNHi <>f Vibrjiunul Laie Stales m the E*«v4 A«:linioe Nuclei." Pkys. Ker. C10.1146 (1974). H. W. MeMncr.32 o A. Oann." I. n. Nix/' and R W Si.wehion. "Hoa to Detect the Heanest Man-Made Isotopes." LASL repiwi LA-UR-75-704|Apr. 1.1975>. i. D. OTCdley. J. S. Eldndar.'' and K J. NortrKuii.1 * T.isin»cmK Radtonuclides in Apoflo 17 Samples Effects of the SnUr Flare of Aupisf. 1972 (k->Kham Cmimtchim. Acta. Suppl 5. Vol. 2. p. 2139. Perpmon. New VcKk. 1974 17. Vawdertilt Unrvcrtity, Mahrik. ».im. Rcwarch C. D. OYdky* and G. E. Gordon." "Saney* oa Traaa^ aad Manpower - Xsdear aad Radax^ennury ~ 170di Satmmdmxum^Amrnrmilm.mm.iSoctct\.Cm^pK».iim^. 25 28.19751 anised)- F nasi.* R L Ferfasoa. mi F Pteasontoa.4 ~Meua-ladaced Feaaoa of Saver." hue. IAEA TmrJSrmp An Cham. MM ftUxkaitr. S. Y. At 13 17.197jf. IAEA. V*wo. 1974. V«L U. p. 319 L L RitdMarr.* G J SMI.* P. H SKfcua.4 E Eidaer. G B. Haenaaae." D C. Headey.* N R Jdatsoa. R. L 4 4 Bnhauna and R O. Saver- "Ooaaaaaceafmti,Mf2 Newtroa m YbBadAeada*.-Urn. Hew. Lett. 33.1346 119741. L L R*daacr.T P. H. Stetson4 E EidaW. O C. Hcasfcy.4 V R. Mama. R L tidwnjua.4 R. O.Sayer.4 G J Sea*.4 and G. B. Haatauaa.:f -Drcoapied Rotanonnl Baa* • »*» ••*Yb.~ presented at aW hHeraatwaal Coafcseaor on Reactions between Cnaialni Nadtt NashvaV. Tcaa. Jaar 10 14.1974 T 4 4 4 L L Rnfarr. P. H Stetson. E Ekaki. S R. Johnson. D. C. Hernia* R L Robiason. R O Saver G J Sean*.4 miC B. Unpawn." -Daaapfcd Rotational Bands ai ••* '"Yb.'aiitaKtMjMwraConanfcx Jwadri. ed. by R L Rohanon. F. R. McGoaaa. J. B. BaB. and J H. Ilaaina. NortUtoBaad HI I'm Co.. AaMenJan. Vol I. p. 115.1974. R. J. Siva. ""Recent Retails wall a Gas-Jct Recoi-Aioai Traasponaitoa System." iasmm de Parriant Hadsaae. Orsay. Fnace. Jaae :974. P. H Stefaoa.4 L L- Biir pi : E. EKMCI. D C Htasfcy 4 N R. lohaina. R. L Robaooa.4 R 0. Sayer.4 aad G J. Santa.4 -GroaadSwe Rotational Rands ai ' rmW mi ,J* t. ORGANIC CJSMBTRY.CATALYSB.AND COAL RESEARCH C J. Castas. ToadMaional Cbeaastry.- coBiiqiaaan at Insulate for Organ*: Cneaastry. Uamrsity of St rassbowiK. Strassboarg. France. Oct. 28. 1974. coloqaaaa at hnatate far Organ*: Cbeaastry. Uaneran of Saarland. SaamradDea. Genaaar. Oct. 31. 1974. coBoaaaaa M lasiiratr for Organ*: CfceaMsfiy. Vmutnuy of MaaKb. Genaaiy. Not 8. 1974. lasotaie fot Orsauc Cheaasiry. TeJ—LJ! Uaneiaty. Itiawch. Geranay. No* 14. 1974. bnmaie for Orcaac CbeaaMty. Eidpewooacbe TecbaHdle Hodadade. Zundi. Swtuerlaad. No. IX. 1974. C. I. Codau. "Do S«2 Rcactwai Go Thraagk km Pan? Tbe Isotope Effect Cnttnon.' InsiitMc Un Organc Cbnarstr>. Tedaacal Uancnin. Mwach. Nov. 7. |974 C J Cotms. "An OrfEauc Cheaust VKWS die hntope Effect." Uiavenit> .»f Mamcfc-Gerancy. Nov. 13.1974 (two kxruics.8 00and 1000AM). C J. CoBats. review of The Kmehc Iwfnpe Methnd md In Apptkmrirm. by II. B Nernian and D. Gal (F.tsevm PnbkshantCo. New York. 1972)./ Am. Chtm. Snc. 9*. 7604(1974). V. F. Raara. TracTi Meibodv" p 257 in Ttthmjun nf Cmrnom: ed E S Lewis John Wdey 4 Sou. New Y.M*. 1974. V. F Raaen. T Jublke.' F J. Brown.1 and C J Collins. "Do ^2 Reactinns Go through lor. Pairs? The Isotope Effect Criterion." / Am. Chtm. Soc 9*. 5928 (1974). G. P. Smith. "Chemistry of Coal as an Energy Source." ORNL Energy ieries. Oak Ridge. Aug 19.1974. G P. Smith. "Cod Technology." January Plan Program. ORAU. Oak Ridge. Jan. 21. 1975. G. P. Smith. "Coal VtiUatioa II." Summer Institute. ORAU. Oak Ridge. Aug. 15. 1974. I. firikipon: HI the Orol Ljkci Cotcfn AuncialKMi Fill ScmMer Propam. 1972. 117 4. r Smth. "Elemental Chemical Considerations m Coal." ORAL' Summer Insiinite on Energy Sources for die Future. Oak Raier. Jcfy 23. I**75 G P Sara. liaslkatiuu «>l Coal." J<>«( Meeting of American Society for Metals. American Welding Socarty. and Society of Certified Technicians. Oak Ridge. Jan 21. 1975 G P Sun*. "ItC>al an Oi**m*~ ORNL Summer Semmar Series. Oak Ridge. Jut? 8. »975. G P S»«m. ~ls Coal m Otofiun'*' Great Lakes Couegcs Assutntuu. Oak Rtdnt Semester. Oak Ridge. Sept 25. 1975 G P South. "Molten Sab Catalysts for rlydrocraL-fcint Coal." Insntaie for Mmmg and Mmrral Research. Umwrrsm of Kentucky. Lexmgion.Mar 18. 1474. G P Smith. -Tfcemn Un Making Clean Fuels from Coal.- Nuclear Paver and Energy Crisis Vorfcmop. ORAL". Oat Ruler Apr. 10.1*75 9 MOPWYSICAL UttJnttlRY R. P. Hemeager. "The Opncai Prupcrurs of Intensely Scaiiermg Medn." Tlurd Annual Meeung uf rhe American Snorts far Pmnobtninf>. Luumme. Ky.. June 22 2*. 1475 laanied). R M Peathtem. "Sofar Energy ~ ORNL Summer SLU—I ar Series. JnS I. 1975. R M IVarhaem I with H ftertuu and L Dresner I. "Solar Energy Research at me Laboratory.- ORNL Snunar. Mar 11. 1975 R M Pearhrem. K Lanjenbrrg.1 and R P Hraaee$er "A L'mfied Approach fc» Exerted Stale Houjotransfcr m •fcdupcal Systems." • F*w EJrrnW Saves AW JftWL ed. J R. Ruts. Wary. London. 1975 R M Pearfsiem* and F Van N«siraad.: "Singlet Excrtafiou Transfer m P«iy r A at 77 K.~ 1975 March Meetmg. American P*\ steal Society. Denver. Colo..Mat >l Apr >. 1975.mat Am fkn 5nr. 2t.3l5(I9~5i 1 ( • idc.it Pflrw*: JMIO> IWHIIH ••< Tf— "•» Hofcrjl (.'•••. Itrmftm. IB CHEMICAL PHYSICS R R Apptrton.1 J A Bajcerstaff.' T S S-vgk.' S Dai/. C D ¥«ak.: M D Inm/ H F Kraose. R H Riicfcir.' and V N Vtiaratbi.' "RadoUce Electron Capfurr *.-. fhjamhd Oxygen bmi' AttmmcCatutnmm S>mrs. I'. Plenum Pr<-it. Nen York, p 4*W B R Apple!.*." J A Bu*er*taff.: T S NoaJe.' R H Ritchie.* S Datr. C D M«ak" and H Verheek* "Radnfrve Urcrr-w Capture in Hirfii. Stnpped l«*i* m Smjtle Crystal Chaaneh ~ VI IntemarMtai Conference •m Airniic CHhwrni* m SoudY Amsterdam. Netherlands. Sept 22 26. 1975 J H Barren.' B R Appief<«.' 1 S NooV.' C D M»ak.' J A tnjrmfafr.: S Dii/ and R BeJtmch.' "Hvpnctianiriint" Aunme 0>K»ms m SmV/i. V. Plenum Prrsv. New York. p. M7 J B Bales' and I M T»#». "Vrhralwual Spectra of H,0:* Inn it Crystalline YH«O:(Cj0« VH,0.~ J Otem Mir •1.129(1974) L. Bhim.' "Invjnanl ExpansHms." (i»rd«»n Conference on the Physics and Chemistry of Wa»er and Aqueous SofcifionvPlymouth.NIL.Auy. 5 9. |974(mviuJ) *Driinic« L Hum.' "Sofcioua of 3 Mode! lot the SoKent-tkc'rwiy te jntetictrom m the Mean Spherical Appc.-Mtnjii.Hi J Chan. Htn. •!. 2129\I9^4» J. Bordner.' *'. t Trues*™. H A. Bates/ and H Rapoport.~ "The Structure ot 1 ("rvstiUinc bcirvatnre ui Sautoxm. The Structure of Sxxitoxm."/ Am. Chan. Svc. 97.ttOO«I ?9?51. C- H Brawn. "Dodecatungstophusphonc Acid Hexahy dratc." University »l f shntion. Seattle. Feb 17. I9?> C M. Brown. "Neutron Diffraction." Lnrcrarv of*asnn*ion. Seattle. Oct. 22. 1974 G M Brown. "Quanty Assessment of Protein Dtfiracuoe Datx" Cnrvcrsity of Wasunct»n. Seattle. May 5. 19T5 V. R. BMM$. "Recent Work at Oat Rider on Neutron Diffract** and Potential kneiey Models." h:uut» di thmuca dele Maaomukc<4e. Mian. Iiaiy. Juh 31. I9?5 V. R Basing* and J. R Bales.1 Tompantoa «»i Observed and Calculated Mean-Spure Aiiwtuc Displacement'- lot CrvsUuW HexacWorobeniene." International URM ofCrvstawojpapfiy Intercoiigress Sy moosiuni on Intra and Intermotecutar Forces. Pcnasyhania Stale Lnnrersiiy. University Park. Aue 14 ii>_ I*»74 C- i- CoBws. C- K- Johnson, and V. F Riaen. "Molecular Rearrangements XXX Applications of an AlertHaic Graphical Model for Anatv/ntf Rearranprraenb of BKYCH<;2-2.1 |hepty I Caf»*ts.~ J Air Chcm. S-< **.2524M9?4i S- S- CnHy * and B. K Aims. ' HT. M«cr«»prrthe lnv rt. North C'jromj Stjrr Vtinrruty 7. linneruty of CaWorou M. D-wloomeni Dimmn, Y'-II Pbnt 139 S Daly. B R Apprr.tt.' J A BnqBrr«aff.: M D Br.^n.1 II F Kraus*. C D Moafc : and T S Nogle ' -Char-? Sim: lXpcrrifK.c for Oxygen htk\ I hattneied in Siker." At"nic C"tta*ms in Solids. V. Plenum Press. New Yott. p 6>. S Daiy. B R. Appkt.w.' J A Btgxrsuff.: H. f Krause C D Moak.1 IS Sortie.1 and R H Ritchie/ 'Radutnx Capture b> !7 40 MeV Oxygen l«*»s from Outer fckc irons or" A.e." Ph*r 9ih Int. Can/, thy*, [term m At C< •Mourn. t'nrrersm of wastnacton Ptesv p. »25. S Daly.' B R Apptrton.1 J A- Bnspcrsuii.1 T S Noqrfe.1 and H. Verbeek.* "tkcl.-on Lmrssion from Fast Oxvten and Copper Ions VstK.pat from Thm Gold Crystals, n Channeled and Random Directions." VI International (••nfcrerweon At>*nic Collisions mSolids. Anuierdam. Netherlands.Sept. 22 2f>. 1975 S Dat/. B R Appteton.' J R Mowat.* R S Thoe.* and I A. St*>.' "Characten/atr»r> ol Charge States of Fn^nxtK lor»s m Solids faun Associated A \fd\ Production .~^h i Rer lett. 33. 734 (l«»74»_ S Daly.* M D Brown.'* P M- Griffin.- R- S Peters.*.* R S Thoe.' and I A- SeBn .* "CI arje State Dependence of X-Ra*. Productum for Contains of Ni I —I MeV nuci with S1H4." American Ptnsical S<»oct\ Washington. DC. Apnl l*»75 /But Am. Fhn. S-c M.«..W||1?5| S bat/.* C D _M.«at.: B R Applet.*!.' J A BcREerstaff.: and T. S Nojgie.' "Hyper and Planar Chanftrimc of Our** State- SHrcted 275 SfcV Oxyprn Ions in Ajt." V| Infernal! xtai Conference on Atom* Collisions in SoUs. Amsterdam. Netherlands. Sept 22 2o. I«m L T J Det^jerc." * I B Hntcheon." M V G- James.'* and % t Thiesstn "Studies on the Structures o! the Bacterial Seme Proteases SGPA and SGPB from Smrp&imrta fmnn" .4rt» OrsunVanr. .fcrr ,4 31. 5.'I «I *»~5» D L Dreyer." K P MundttMi." and * t. Thtes»r»i.-F\iracti»-es of Onto Species *. Perariwcni •»? Pfcvwrt. rwwrriitv »f Tf-iwrmt in. Deportment »f R*xhrmnlrv. I nrwrrwfv i C. K. Johnson. "An Operational Model for an Experimentally Based Applied Science Such as Structural Crystallography." Stanford University. Calif.. Sept. 24. 1975. C. K. Johnson and C J. Collins. "An Algebraic Model for the Rearrangements of 2-Bicyclo|2-2-1 Jheptyl Cations *"/ Am. Chem. Soc. f*. 2514 (1974). C. K. Johnson and H. A. Levy. "Thermal-Motion Analysis Using Bran Diffraction Data." in International Tables fur XRayCrysiaUogyaphy. Vol. 4. Kynoch Press. Birmingham. England. 1974. C. K. Johnson.* C R. Watson. Jr. and R. J. Warmack.13 "Strange New Organic Conductors: The Tetrathiofulvaiene Halogen Complexes." Twenty-Fifth Anniversary Meeting of the American Crystallography Association. University of Virginia. Charlottesville. Mar. 9-13. I97S. 4 i S. G. Johnson.' 'Reactions of Metastable Mercury. Hg 6~/»2 and Hg 6' Di with Chlorine and Chlorinated Alkanes." Ph.D. thesis. Department of Chemistry. University of Tennessee. 1974. F. T. Jones' * and T J. Sworski.* "Bromine Formation in the Radiolysis of Aqueous Bromide Ion Solutions." Edwin J. Hart International Conference on Radiation Chemistry. Argonne National Laboratory. Jury 7 9, 1975. 4 14 N. Kashihira.' F. Schmidt-Bkek. and S. Datz. "Ionizing Collisions of Fast Alkali Atoms with CI,. Br2. and 02." / Chem. toys. 61, 160(1974). H. F. Krause. S. G. Johnson.14 and S. Datz. "Crossed Molecular Beam Study of an Excited Atom Reaction of Hglop' 3£>]) with Hydrogen." Proc. 9th Int. Conf. toys. Electron. At. Collisions. University of Washington Press, p. 349. ft F. Krause. S. G. Johnson.14 S. Datz. and F. Schmidt-Bkek.'4 "Crossed Molecular Beam Study of Atomic- Reactions: Hg63Pi°) with Clj and Chlorinated Methane Molecules." Chem. toys Lett. 31. 577 (1975). H. A. Levy* and J. R. Long.1* "Platinum(1.3.5.7-tctramethyl-2.4.6 8tetrathiaadamantane)diiodide: Crystal and Molecular Structure." Twenty-Fifth Anniversary Meeting of the American Crystallography Association. University of Virginia. Charlottesville. Mar. 9-13, 1975. H. A. Levy and C. W. Mathews.17 "Discussion: Theoretical Methods." p. 603 in Critical Evaluation of Chemical anil Physical Structure Information, ed. D. R. Lide, Jr.. and M. A. Paul. National Academy of Sciences. Washington. DC. 1974. R. Livingston, "ESR Studies of Free Radicals in Phonlyzed Liquids." Chemistry Department seminar. University of Tennessee. Knoxville, Tenn.. Nov. 26. 1974. R. Livingston, "ESR Studies of Short Lived Free Radicals in Photolyzed Liquids." Chemistry Department seminar. University of Tennessee at Martin. Martin. Tenn., Oct. 23, 1974. R. Livingston. D. G. Doherty.' * and H. Zeldes. "Electron Spin Resonance Study of Liquids during Photolysis. XIX. AUnhatic Dipeptides," / Am. Chem. Soc. 97,3198 (1975). R. W. Matthews'* and T. J. Sworski,* "Photooxidation and Fluorescence ofCenumUII) in Aqueous Sulfuric Acid Solutions," Eleventh Informal Conference on Photochemistry. Vanderbilt University. Nashville. Tenn.. June 16 20. 1974. R. W. Matthews19 and T. J. Sworski. "Photooxidation and Fluorescence of Ceriumflll) in Aqueous Sulfuric Acid Solutions."/ toys. Chem. 79.681 (1975). 13. Gradual* Modern. University of Tennessee. 14. Department of Ctwmntry. University of Tennessee. 15. Stevens Institute of Technology. Hoboken, N. J. 16. Student participant in the Great Lakes CoaJcgcs Association Science Semester, fall 1974. from Ohio Weskyan University. Delaware. Ohio. 17. Department of Chemistry, Ohio Slate University. IS. BMofy Division. 19. Iioiopes Division, AAFJC Research Establishment. New South Wales, Australia. 141 C D. Moak.*2 B R Appfeton.' J. A. B^cfjliff.5 M. D. Brown.2 S Datz. T. S. Noggk.1 and H. Verbeek.4 "The Velocity Dependence of the Stopping Power of Channeled Iodine Ions from 0-6 to 60 MeV," VI International Conference on Atomic Collisions in Solids. Amsterdam, Netherlands. Sept. 22-26, 1975. C. D. Moak.1 B- R- Appleton,' J. A. Biggcrsuff.2 S. Datz, and T. S. Noggle.1 "Velocity Dependence of the Stepping Power of Charuvled Iodine lony" Atomic Cotisioia ut SoOdx V. Plenum Press. New York, p. 57. C. l>. Moak,2 S. Datz. B. R Appleton1 J. A- Biggerstaff,2 M. D- Brown.1 H F. Krause, and T.S. Noggle.1 "Influence of Ionic Charge State on the Stopping Power or" 27.8 and 40 MeV Oxygen Ions in the (011J Channel of Silver." fft.vs Re*. B 10.2681 (1974). C. D. Moak.2 S. Datz, F. Garcia Sanubanez." and T. A. Carlson.2 "A Positron Sensitive Detector for Electrons "/ Electron Spectrosc S, ISI (1975). J R. Mowat.' B. R. Appleton,1 J. A. BiggerstatT,1 S. Datz. C. D. Moak,2 and I. A- SeKn,* "Charge State Dependence of Si K X-Ray Production in Solid and Gaseous Targets by 40 MeV Oxygen Ion Impact" Atomic CoUaiohsinSoMs. V, Plenum Press, New York, p. 461. A. H. Narten. "Diffraction by Molecular Liquids.'' Tram. Am. CnstaUogr Assoc. 10.19 (1974). A. H. Nartrn. "Neutron Diffraction from Water and Aqueous Solutions " Gordon Conference on the Physics and Chemistry of Water and Aqueous Solutions. Plymouth. Nil., Aug. 5-9,1974 (invited). A. H. Narten. "X-Ray and Neutron Diffraction from Water and Aqueous Solutions." p. 345 in Structure of Water end Aqueous Soiutiom. ed. W. P. A. Luck, Verlag Chemie/Physik. Weinheim. Germany, 1974. A. H. Narten. L. Blum.1 and R. H. Fowler.2' "Mean Spherical Model for die Structure of Lermard-Jones Fluids " / Chem. toys. 60.3378(1974). MR. Noe-Sprrlel.22 G M. Brown. W. R. Busing.* and H. A. Levy. "Neutron Diffraction Studies of Three Hydrates of Phosphotungstk Acid," Tenth International Congress of Crystallography. Amsterdam, Netherlands. Aug. 7-15, 1975. MR. Noe-Spirlct.*22 G. M. Brown, H. A. 'jevy. and W. R. Busing. "SoCalled Dodecatungstophosphoric Acid Pentahydrate Is the Hexahydrate (HjOj'hfPW^O^1*)." American Crystallographic Association Summer Meeting. Pennsylvania State University. University Park. Aug. 18 23.1974. G. H. Ostrum,'4 "Low Energy Electron Induced Sputtering of Alkali Halides." Ph.D. thesis. Department of Chemistry. University of Tennessee (1974). G. L Ostrum,14 F. Schmidt-Sleek,'4 R. N. Compton.1 and S. Datz.* "Low Energy Electron Induced Sputtering of Alkali Habdes." VI International Conference on Atomic Collisions in Solids, Amsterdam, Netherlands Sept. 22-26. 197S. I. A. Sefiin.*» S. Datz, B R. Apoteton.' R. Mowat* R. Laubert." R. S. Peterson,' and R. S. Thoe.» ~K X-Ray Production by A Ions in Solid and Gaseous Si," American Physical Society. Chicago, December 1974;Butt. Am. PtiyxSoc 19. 11.84(1974). W. E. Thiessen and W. R. Businc. "Identification of Systematically Aberrant Phase Relationships Arising from Structural Regularity." Ada CrystaBogr.. Sect. A 30,814 (1974). W. E. Thiessen* and W. R. Busing. "Utilizing Molecular Structure Information in Direct Medtods of Crystal Structure Determination via a Modified Tangent Formula." American Crystallographic Association Summer Meeting. P:nnsylvar.ia State University. University Park, Aug. 18-23, 1974. 1 L. M. Toth and J. B. Bates, "Vibrational Spectra of Crystalline Li? ZrF» miC%iZfft," Spectrochim. Acta, flart A 30, 1095(1974). 20. Department of Physics. University of Mexico. Mexico City. V 21. Computer Sciences Division. 22. Graduate student from the University of Liege. BeajRun. 23. Department of Physics. New York University. I" 142 R. Trioto*24 and A. H. Narten. "Diffraction Pattern and Structure of Aqueous Hydrogen Chloride Solutions." EUCHEM Conference on Anions and Cations in Acid and Superacid Media. Montpeiicf. Fr*n«.c. May 1974 (invited )- C. G. Venkatesh," S- A. Rice.2* and A- H. Nartcn. "Amorphous Solid Water: An X Ray Diffraction Study." SamcrlM, 927(1974). H. Zeldes* and R. Livingston. "Base Catalyzed Exchange and Dissociation of the NH-Hydrogen of il*.- l-Hydro-2.S-pyridinedkarboxylate Anion Radical." Seventh Southeastern Magnetic Resonance Conference. TaUiassee, Fla., Oct. 2-3,1975- H. Zeldes and R. Livingston, "Electron Spin Resonance Study of Liquids during Photolysis. XVII. 3.5-Py ridinedicar- boxylk Add," Rmdmt Res. 58. 338 (1974). H. Zeldes and R. Livingston. "Electron Spin Resonance Study of Liquids during Photolysis. XVIII. 2.6-Pyridinedi- carboxylic Acid." Rmbtt Res. 62, 28 (1975). H. Zeldes* and R. Livingston. "Radicals Made by the Photolytk Reduction of Pyridinecarboxylk Acids in Liquids " Sixdi Sourheastera Magnetic Resonance Conference. Ckmson. S.C.. Oct. 3-4. 1974. 24. Vbrtiaf scientist Croat University of Paknno. Italy. 25. Graduate stnden: from University of Chkafo. 26. DrnwtMeiK of Chcnustty, University of Chicago. II. ELECTROCHEMISTRY A. L. BacareUa and A. L Sutton.' "The Effect of Solvent on the Electrochemistry of Iron." J. Ekctrochem. Soc. 122,11(1975). E. J. Kelly, "Anodic Dissolution of Titanium in Acidic Sulfate Solutions." Prvc. 5th Int. Cong. Met. Cams.. Tokm. Japan, 1972. National Association of Corrosion Engineers. Houstor.. 1975. E. J. Kefly, "Effects of Ti(lll) and Ti(IV) on the Electrochemical Behavior of Titanium." 1975 Corrosion Research Conference, National Association of Corrosion Engineers. Toronto. Canada, Apr. 14-18. 1975 (invited). R. E. Meyer and P. M. Lantz.' "Reactions of the Cyanide Ion with the Packed-Bed Silver Electrode - Analyses for the Cyanide Ion." ElectwgnoL Chem. InterfacidEkctrochem. 61.155 (1975). 1. Chemical Technology Division. 2. Health Physics Division. 12. THERMAL GENERATION OF HYDROGEN C. E. Bamberger. "Thermochemical Production of Hydrogen from Water." Chemical Technology Division seminar. ORNL, Mar. 26, 1975. C. E. Bamberger and J. Braunstein. "Hidrogeno. un elemento vcrsalil. Parte I." Energ. NucL (Madrid) 19(94). 99 (March-April 1975). C. E. Bamberger and J. Braunstetn. "Hidrogeno. un elemento versitil Parte II." Energ. NucL (Madrid) 19(96). 239 (Jury-August 1975). C E. Bamberger and J. Braur.stero. "Hydrogen: A Versatile Element." Amer. Set 63(4), 438 (1975). C. E. Bamberger. D. M Richardson. M. A- Bredig* and X. Cheng.1 "Thermochemical Production of Hydrogen from Water by Means of Cr- and Ba-Compounds." Science 189(4204). 715 (1975). 1. Consatlant to Ike Chemistry Division. 2. Summer particrpMl. 1974; prt«mlly at Brandeis University. Mafudniscits. 143 J. Brainstem. "Hydrogen - Key to Syndietic Fuels," public lecture at University of Natal, Durban. South Africa. Jury IS, 1975. seminar at the University of Port Elizabeth. South Africa. Jury 28. I97S: lecture at Branch Meeting of the South African Chemical Institute at the National Chemical Laboratory, Pretoria. South Africa, Aug. S, 1975. 13. SURFACE CHEMISTRY P. A. Agron. E. L FuBer. Jr.. and H- F Holmes, **IR Studies of Water Sorption on ZrO, Polymorphs."/- Colloid Interjmx Sci 52,553 (1975). E. L Fuler. Jr.,' and P. A. Agron, "Sorption by Low Area Materials." 12th Conference on Vacuum Microbalance Techniques. Lyon, France. September 1974. R. B. Gammage.' H. F. Holmes, and E. L Fuler, Jr., "Pore Structures Induced in Lunar Fines by Adsorbed Water." Proc Int. Synux Pore Struct Prop. Mater.. Acadenua Prague. Final Report. Part 1. B-75.1974. R_ B. Gammage.' H. F. Holmes. E. L. Fulkr. Jr.. and D. R. Glasson.' "Pore Structures Induced by water Vapor Adsorbed on Nonporous Lunar Fines and Ground Cakite."/ Colloid. ImerfmctSci 47.350 (1974). H. F. Holmes, E. L- FuBer. Jr.. and R. A. Ben,1 "Adsorption of Argon, Nitrogen, and Water Vapor on Zirconium Oxide," /. CbKoid. Interface Set 47.365 (1974). H. F. Hobnes. E. L. FuBer, Jr.. and R. B. Gammage' "Some Surface Properties of ApoBo 17 SOHV froc. 5th Lunar Sci Conf., Gtochim. Coanoehm. Acta. SuppL 5. Vol. 3. p. 2275, Pergamon, 1974. H. F- Holmes and R. B. Gammage.1 "Blocking of the Alteration Reaction between Water and Lunar Fines " Lunar Science VI, p. 3S4, The Lunar Science Institute, Houston. Tex., 1975. H. F- Holmes* and R. B- Gammage.1 "Surface Properties of a North Ray Crater Soil (Apollo 16)," Sixth Lunar Science Conference. Houston, Tex., Mar. 17-21, 1975. H. F. Holmes and R. B. Ganvnagc,' "Surface Properties of a North Ray Crater Soil (ApoBo 16)," Lunmr Science VI, p. 387, The Lunar Science Institute. Houston, Tex., 1975. 'Denotes speaker. 1. Health Physics Drosion. 2. John Graymore Chemistry Laboratories. Plymouth Polytechnic. Plymouth, Ffbwd 3- ORAU summer student trainee from St. Ambrose CoHcge, Davenport. Iowa. Supplementary Activities PROFESSIONAL AND EDUCATIONAL ACTIVITIES CFbo Member of dtscassioa group on nuclear materials cloved bjr R. J. Thorn iChenustry Division. AND at Conference on Thctmodyitimirs and National Energy Problems. Airac Howe. Warrenton. Va.. Jnnc 10 12. 1974. Member of Ad Hoc Advisory Panel on ""Evaluated Physical Properties Dau in Aid of Aaweons Eniiiuaamital Prohkaa," sponsored by the National Research Conned. Washington. D.C.. Aag. 14 and 15.197S. C. E. Bamberger Participant. "Hydrogen Energy Fundamentals.- a symposiam coarse. Miami. Fla.. March 1975 (working gronp drsrussnms on hydrogen production). J. BcMmteia Editor. Adiamca at Matte* Salt Chtmmur*. 1970-present. Member. Ph-D. examination committees. University of Natal. Dnrban. Natal: University of Provence. MarseiRe. France. Cochahman. Organizing Committee for the 1976 'ntemational Symposram on Molten Salts sponsored by the Electrochemical Society. Lcctnrer. University of Tennessee-Oak ».r*"e Gndnasc School of Biomedical Sciences. 1971 -present. Vice-chairnun elect. 1977 Gordon Conference on Molten Salts. Cnesi kctnrer. Sooth African Chemical Institute Convention. Jniy 11 -Ant,. 10,1975. G. M. Brown Visiting scholar. Department of BMogkal Strectare. University of Washington. Seattle. September 1974- Augnst 1975. W.R.Bnsmg Secretary-ueasam. National Committee for CrystaBography. National Academy of Sciences - National Research Council. Jan. 1.1974 Dec. 31.1976. Delegate to the Tenth mvemational Congress of Crystallography. Amsterdam. Netherlands. Aog. 7 -15. 1975. S. Cantor Panel leader. Conference on Thermodynamtcs a I National Energy Problems. National Academy of Sciences, Washington. D.C., Joae 1974. C-J.Cbams Professor of Chemistry, part time. University of Tennessee. KaoxviBc. lanaary 1964-present. Member. Editorial Board. Isotopes m Orpmc CaemmVy-. Elsevier rnkliihmg Co.. Amsterdam. Netherfaads. 1972—present. President. Committee for the Southeastern Rcpoca! Meeting. American Che natal Society. Gadmbarg. Tcna.. 1976. Senior FeBow. NATO Senior FcBovnhip m Science. Soarbracfcen. Germany. Oct. 14-Nov. 20.1974. S.DMZ AssocJatc EdMor.^MNnsr OtMaWAbdrrAm Tables. 1969-avcseai. Advisory Emtor. Case SrmaVi m Atomic fkysics. 1970-1975. Edrior. Atomic Comsmis m Soli* V. Pieman Press, New York. 1975. Member. Publications Committee. Amerxan Instiratc of Physics. Member. National Academy of SciencesCumimtW» on Atomic and Motrcabr Physics. Member. National Academy of Sciences - National Research Coaacil Commnice oa Energy Related Atomic and Mofeobr Physics. Member. International Committee. Atomic CiiBhnms m Sohds. Visiting scarntiv. Ku Planck Institute for Plasma Physics. Garchmg. West Germany. Jnae Jary 1974. L Dresner Vising scientist. Wesnnnn iivsmntt of Technology. Rcto 1973 Jnly 1974. A.S. Dworfcm Member. Site Vait and Review Commit tec for Nnfsonal Surace Foandatioa grant on "Seppof ted Molten Ehtctra(yte Catalysts," Department of Chemical Eagmerrmg. Virginia Polytechnic Instance and State University. Btukjbmg. Va.. 1975-. . ORNL Heavy ion Facnity Users liaison Grown. E. L FmVr. Jr. airman and n» nmii of the Smimg Committee. Twelfth Conference on Vacaa Texamaacs, Lyon, France. Stpumbn 1974. Cuninttjnt. Instilat sar b Catalyse. Centre Nations*; dr b Recherche Sc**ataa,ac. Sipiimbn 1974. 144 145 R. L. HJIH . ERDA TraMpmtoniam Program CommiMrc. 1975 -. Bleaker. ORNL Heavy Ion FtcSty Users Laooft CKM*. CKiohHM Member, U.S. rferionmConmatice for Oystaaofraphy. National Academy of Sonets llescaich Conned, Jan. 1.1*72-Dec. 31.1977. Member. National RcieuchCoaaciICoBM«kteeoaClH:aacalCirsttHo(nnkr.Jatr 1.1970-Jane 30. 1976. Member. American Crystantographk Association Temporary Committee oa CiystaBograpbic Projects for Nation^ Cuinpntitiurnl Rcsonrces. Mar. 10.1975. J. S. JobMM. Jl. Member. National Laboratory C< tee to Oatanr a Soar Energy Program. Lectarcr, Industrial Information "Ptoses for Feci and Ry-prodnct Recovery Daring Lionel Wane Treatment." Oak Ridge. Apr. 15-la. 1975. N. R. Johnson Member. ORNL Heavy loa Facilily Users Uatson Croap. O. L. Kdkr.Jr. ERDATi Croap. 1974-piejeal. IUPAC-IUPAP bnestigatcMscovery Claims of 104awtlOS. K. A. Krans Editorial Board. Jomrmml of Chrummmtimp/ir. l95>-prcseat. Editorial Advisory Board, lotmtoflmorgmtk mmi f/mekar Chematry. I95S- Edilornl Board.DemUmlkm. 196* present. Member. Uar>enily of Tennessee Water Resources Rcjearck Center Advisory CoavtoL Judge. Soaibern Appalachian Science and Engines* nig Fair, KnoxvnV. Tenn.. 1975. M. O. Kraast Vnitiag scientist, Instilnt da Radiam, Universale" de Paris VI. Paris. April 1975-September 1975. Gnest lecfarcr. Univerrity of Usboa. Lisbon. Portogal July 21 -26.1975. Visiting scientist. Faknltat far Pays*. Unriersitat Frcibarg. West Germany. October 1975-April 197*. Meaaber of Organizing Commit lee for Saauacr School of NATO Advanced SOtdy IMMWC on ~Paoloioaizatina and Other Probes of Maay-ElecuoB Interactions.''' Carry-k-Roact. Fraace, Aag. 31-Sept. 13.1975. M. H. Uetzke Piofcssor of Chemistry, part time. University of Tennessee, Kaoxvmt, Jaaaary 1964-arcsent. R. Livingston Professor of Cnemolry. pan time. University of Tennessee. Kaoxvafc. Jaaaary 1964-prescat. ORNL Liaison Officer for ORNL-University of Tennesiee part-time ttaihmg programs, l9M-preseal. Editorial Board. TV Jemrml of Map* tic Hetommmce. January 1971-present. Editorial Board. Muptetk Remmmmce Reriew. September 1971-preseat. WL-MarsnaK Member. National Coasted. American Chemical Society. 1969-1974; Committee on Chemkal Education. 1970-1974: Snhcommrllee oa H%h School Chemistry (Charman). 1971 -1974: Sabcommitcec on Organizational Straclare. 1972-1974: Steering Committee on Gavieftncs for Teacher Training. I975-. Member, Working Committee of International Asaxmtnn for Properties of Steam, I975-. Participant. Visiting Scientist Program. Teancsace AcJaemy of Science. 1975 -. Vice PicadcM.Oak Ridge Chapter of SjtmaXi - The Research Society of America, 1974-1975. Senaon Chaaman. latth Naoonil Meeting. American Chemical Society. Atlantic City. NJ-. Sept. 10.1974. Mrmbet.discassoa grows on nndear materials chaired by R. J. Inorn (Chemistry DrvisM, Arsl) at Confeiencc on "Thermodynamics ai»d National Energy Problems." Artie Home. Warreaion, Va., Jane 10-12.1974. Member. AEC Ad Hoc C« rnmittee Convened for Recommending a Research Program in Geothermal Cbcaw*ry, Jane-October 1974. R.E.] Member, AEC Ad Hoc Committee Convened for a Research Program in Gcolhermal Chemistry, lane -October 1974. G. D. 0*Kcncy Pwfenur of Chemistry, part time. University of Tennessee. Knoxvnfc. Jaaaary 1964 Memfrw.Nuiianuimg Committee. IJwtwon of NncJrarOicmuuy and Tcchnulugy. American Society. 1973- 1974. Aaocmte Edrtor. IrtnnnaHJ of ike Fifth Lunar Science Conference. Gtwhmmm et Cotrnmlmmim Act: 1974. MtMbcr, Nartiofttf nfaVfintfclk COVNCBI CoiwMttcc on Nttctuv iK-tYnc*; OM^NIM* SvbcofMNif ice otf faafcilpiwwuy for term 1974-1977. R. M. Pearlstcm leomtm, U-tmntty of Itmmtnet-Otk RitXfr CrMmk^S^mAMBiome4tal Somen. 19*9-proem. MnMcr, Ail Hoc CoiMifitcc on Dc^riopniciii of a ghopfcyso Flogi«itfi for ifcc DIVBRHI of ftwoiMwtocal and Environmental Research. FJtDA. 1974-1975. Mnmjcr. PaHnatnins Committee, Divinjon of ntelngical Phyists. American Physical Society. I975-, Cooidmaior of Sotar Energy Research.ORNL. I975-. 146 X. i. Sihra Mcabci. taKiibiwaj! Coauutue u« At.i'miit ttacatth. G. f. Smith Editor. .-Mrawrrs in Molten Stll Chemistry. 1970 -present. Professor of Chemistry, pan mnc. University of Tennessee. KnoxvnV. January l%4 present. Program Qsairman tot the Southeastern Regional Meeting. American Chemical Society. Galhnbitre. Teun.. 1976. Member. Natio«al Academy ol" Sciences - National Research Council Committee on tligh-Temperature Science and Technology. I97S-. Member. Site Visit and Review Committee for National Science Foundation pant on "Supported Molten- Ekctrotyre Catalysts.** Department of Chenucal tnemeerme. Virpno Polytechnic Institnte am! State University. Hacksburg. Va.. 1975 . R. W. Stoughtoa Editorial Advisory Board. Journal of Inorgmic mid .Vurfcur Chemistry. 195S - present. Consulting Editor. Imtrgmk tmdSuciem Chemistry Letters. 19*5 present. W. E. Thresscn Visiting scientist. MRC Protein Structure and Function Croup. Department of Biochemistry. University of ARtcrta. Edmonton. Canada. Sept. 1.1974 Sept. 2.197S. C0LLA1ORAT1VE RESEARCH CoRmiiraiuils) Subject Staff Membcrls) Argonne National Laboratory J. P. Unik Search for superheavy elements in R L. Ferguson K. L. Wotf accelerator targets; spontaneous fission Jllalprrm energetic studies R. ». SlourhJon Arizona State University. Center C. B. Moore Search for superheavy elements in nature J. Halprrin for Meteorite Studies G. D. OKrfky R. W. Sloughlon Australian Atomic Energy Si. Alien Neutron capture cross section of Cr I. Halpenn Commission. Lucas Heights, M. J. Kenny Australia Australian Atomic Energy Com- R. W. Matthews Pholooxidation and fluorescence of T. J. Sworski nusswn. Research Establishment. ccnumtlll) m aqueous sulfuric acid New South Wales. Australia solutions University of California. San Diego K. Lmdenberf Theory of excited state interactions in R. P. Hemcngcr tmmotccular aggregates R. M. Pearlstein K. Lindenbcrg Chemical biophysics of energy transfer in Consultant bvofagrcal systems H. W. Mddner PossiMity of superheavy elements in J. Ilalpcrm nuclear explosions R. W. Sloughlon Catholic University of America C. T. Moynihan Transport and thermodynamics in vitreous J. Braunslcin electrolytes Central College. Mi. Iowa P. J. Ogrcn Reactions of melhylperoxy radicals C. J. Hochanadel Centre d'Energie Nucleaa-c. C. Lc Rigokur Neutron capture cross section of Ni J. Ilalperin Cadarachc. France University of Chicago S. A. Rice Structure of water A. M. Narten Ckmson University C. A. Brandon llypfrftllralkm for energy conservation J. S. Johnson. Jr. Clcmson University and C. A. Brandon Mobile hyperTdtratiiin demonstratitm J.S. Johnson. Jr. South Carolina Textile J. I Porter project' Manufacturers' Association Convair Aerospace Division. Search for superheavy elements in nature J. Ilalperin O. E. Myers General Dynamics Corporation, R. W. Stourhlon San Diego Cornell University Search for superheavy elements in nature J.Ilalperin J. M. Bird R. W. Slnoghton I. Supported by EPA. 147 OOUboatatiii Srtjrn SmffhliiitLi(s> University of Drift. Netherlands B. vsn Noouen Decay properties of ,4Y N.R.Johnson University ul Delhi. India S-C. Pancholi Gamma-gamma angular correlation N. R. Johnson mentsin127! 1*1. Pearson University R. R Winferc Neutron capture cross section of Au J.rlaJpcrin Florida State University R.K.Steune Levebm lt,Tbexcited by 2. Com illanl to I.HL. Department of Chemistry. Sania Rosa Junior College. Santa Rosa. California. 3. GOT. Jiunt. Department of Chrmisiry. University of Tennessee. Knoxville. 4. Pnsi>loctoral research associate. L'niversiiy of Tennesse-.Kltoxrille:present address: Framatome. 77'81 Ruedu Mans.92403 Courbr*ir. France. 5 firi doc (oral research asvH-ulc. L'nrvcrsity of Tennessee. Knoxvrile. MS Staff Jfea*c> Los Ahan Scacatific Laboratory G.F. K*»volt "SOU*) aad >JS(a. Across I. ttUpcrin H.C Brill Heavy-«M (tana aad (nana exoeriaanus R. L. Feifiuoa R.H.Stokes at the Lawrcace Rtiktky Laboraloo' B, H. Eikkib SapcfHlLAC C. A. Coaaa Possibtliry of saprrheavy ekmeatt in J.Halperia i.R.Nix itxa R. W. Stouchtoa Ll'ltE, Ooajr. Fraace F. WMHCUIMI Pholachxtroa spccttcBBTttr H. O. Unas* University of Maiac at Praaatbat T.B. Tripp Thrnaodyaaaaq ot coaccatrated aqoeoas J. dectfotyacs Nacoya Uaiatiwty. Japaa H-Yaattta fropertits of excited 0* nam aad beta, N.R. Johnson effects ia"*Gd National Acceamtot Laboratory D. Tact tot Search for saacrheaary t-k.ww.ato in J.Halpena accelerator targets R. W. Sloaghloa Univuuty of P*ttsbarjh J. X. Saba** Aaalysriof oWonaataMaaraaartersof C. E. Be«ws, Jr. l-Y.Let cfcatft dbttibitjoa aad optical potential J.Hoatca for rare-earth i J.O'Rriea C.taktadi Rioe Uajamirjr, Hoastoa J. A. Search for aakaowa raateactmtks m R. V. Gentry aafare J.Hatpcria G. 0.Oltdary R. W. Stoarhton VmrtnKf of Rochester Hravy-ioa fissoa aad feskm cxpcriaanis at R. L. Fcreason the Lawreace Berkeley Laboratory SapcfHILAC RataErs Ibvaeiajty L. R. MOTJJ Dcttraaaatioa of the heat of soart»a of R. L. FeBows' ThaKtai J. R. Peterson* R.G.Haae Cat aaitry of itaasaraaiaai etraatats Oak Ridge Associated Universities Uaimaty of 3 M.Haasck Viayl C. J. CoMns Saajbracfcea, Genaaay (FRG) Sdeace Aaafcuiuw. tec. J.SIar/ Search forsapcrbcar y cttjaeacs ia aataic R. L. Ferrason aad ia accelerator taqpfto J. HabBCTBi R. W. Stnacfcton T. ft. Fohpn Search foff sapcthesvy ctcaatats ia aataic Irbtoeria La Mb R. W. StoocJMon D. Search fot superheavy eteoatats M J. Haiocrm D.Wab accestraf or targets R. W. Sloackton of TcdMotap. F T Joan r fonaataMt ia the radMydsof T-J.Swonfci J. R. Pefcwsoa' Chemistry of IE Coasallaai aad University of Teaa.. Knox viae rcfrcrch paat L.L. ia'^YbhiaV E.EaJder siaics ia aadei fruai coakpoaad- N. R. Johnson reactaxii F.K.ScbaaJi- S.0M2 H.F.Knaar 149 Srtjrrt Tokyo faMKateo f Technology MUpofca Properties cf excsM* 0* tales aad *i N.R. M.ScUkava •Knag effects ia '**G4 I'arrcraty of Toroato Search fat A. I. MiMrctt R.W.Stoajhtoa laio* Carbide Cora.. Starch for wyrilwi»y tfciwi ia Max J Hripcni Ink Laboratories G. J. N*KI R.W Stoaghtoa UNSORCoasortiaai Dwhiuipjuit of •ata-aquoiiioa systcai E. K. Carter N.R. G.D.O*Kttcy Decay of '**Fb G.D.O*Kdky etaL K. S. R. Snuy IWeaauaiof •jaaaii.ia^iconetttioa N. R.Johasoa etal. -"*Xe U.& Geological Sancy J. H. McCarthy Search for saacrbeavy ekajtatt ia estate R-WStoaihtoa Lamniry of Utah r.staaj Viaytcubcacs C. J. Cottars VandcrMt Uaivcnity J.H.Haaahoa rYopcRics of exerted 0* states sad^r N. R.Johasoa) r effects ials*Gd J. H. Haaattoa State of lagb-spia states ia2>2Th by N. R-Johaaoa N.C.Siagbal the Ooaakr-shift rccoMamace E. Getter J. H-Haunfcoa ct aL Stady of electric rfdectnc NUMMM ouadiaaote traasitiow stteagths i* IT*Hf C.D.I Decay of,n Aa to k«rb • * "it G D.Otdry A.V.Raatryya R.G.Afbndec Wcszaaum lmt«ate of Science G.Taaay Dyaaaaic polyelectrolyt e for J.S.Jnaaiia.Jr. Yomei Uamnity, Seoul. SHAM) Properties of exerted 0* states aad 0-? N.R.M»SOM DcMOoatic Fcopies t effects ia"*Gd RrjMbfcc ot Korea 6. SaapuiteJ by U-S^srad Kaatioaal Scrcacc Foaadatioa. VISITING SCIENTISTS OWL RoaaU After Uaiauiity of Kcatacfcy. SuaMaul chetajatr? aad C.K. Lcxaarjoa LHM Uawiriity of Paerto Rico. of A.H. RsoPiaJras R. L. FcRows Uamrajty of TcMcajec. of li UamratyofTc Knoxvak J. Faeer UajvcrafyofLaaje. Bcbjraai of NATO S. R. tferafcinm UewmiQ of Traaiam. C K Kauiidh Ccafrc d**tadcs Nadearc*. Heavy-iBd R L.rbha •». Fra *aWi4 tmwen ISO OKNL Nadear Cncaastry and Tranoajanaun NATOiadKrriM.ii Research Laboratory Government. Centre National dc Recherche Scant ifiqae niutert Centre d*Etndn NwUun. Nackar dtcnntfry CoawltiM. NATO, and Bonteaax. France French Government. Centre National dc Recherche SdcMiTique DS.Joan Uarventty of Hotth Carotoa. StracAaral dmnblry A. H. Narten Charlotte C.Mnftas linxrentcy of Jtmtatr., Chrmutry of imsaoMti ckmciH CEN.F-ntcnay- Kwxifle. and Centre anx-Rosex, France d*Elades NacUaacs. Fontcnay- aa.vRoc*. France B. Neaiknrt Fochbetekh Anortanachc Chemie Gas-pout chemical separations R.J. Sara nd Kcrnchcnae. Tcchnrjchc Hmhuhn* flMmltMll Germany (FRG) M.C.Nod Unmnity of Teaaesase. KmnvnV Chemistry of traasanmaai elements Uni»tisity of Teanewee research pant A. D. Rae Uamnitr of New Soaik Wafcs. Sfroctmal UKmalry WHBont Kcimtton, Aastnaa S. 1. Saadttr Uatwniiy of Delaware. Newark Neatroa diffraction from moicenbr A. H. Marten aajakts N.C.SMKW Vaadtrbal Unmrgty Nactcar dktantfry Vanderbih L'mversity R. J. Stana Unweraty of Marbarc. Gcrmanv Nadear ckeawvy HaxKade •FRO Foaadalion Senior Felon-skip R Trioto Uraveraty of Pakrau. Italy Neatroa diffraction from aqacoas A. H. :*arfVR wlatiua C. E. Vatn* Uniwmity of Provence. Electrochemistry of rnohra nits J. •raaastcia Jnnraedks, France Molten taks Centre National deb Rccnercfce Sorntifanje (France) F. Via Ncstrand Uarmsky of Tc Caeaajcai toDskysjcs of tntigy Consultant traanwBT ia biolaeacal fyfteani GRADUATE STUDENTS FfcMof L LCoft»u.Jr C. DOKeaey. G. D. OnUmty Narkar sptuimcopy University of Ti UnmmityofTi LLR-d-mrr' M.W. Gantry C. D.O-Kdky G. D.OXeRey Hea*y-«>o Coanxab Oak Rahjr Gndaafc C'aminty of T< E.Efckkr exoutionof actiaiae N. H. JOMMOff I. Pin/art Dtraton and L'aivemy of Tenanser. KnoxTaV. 151 rmMaf and/or I YunJao J. R. Peterson.* W. D. Bond* Kinetics of ratuctioa University of Jtnmtutt ofNplV)»Na M.-R. No^Sou-lct II BiasKur. Unrmsrty W.R. Busing Structure of heteropory University of Liege of Liege. Belgium acids D. L. RascheHa J. R. Peterson.2 J. H. Burns Solauoa of nucrocaferimetry University of Tc Unaersiry of Ti R. L. Fcaows4 of at tiaklt etrmrats and W. W. SckMidi C. J. Counts. C.J.COUMS Organic catioas aad trace University of Te University of TtnaejKf trace analysis 2. Coasatlant. Department of Chemistry. University of Tennessee, KnoxviBe. 1. Chemical Technology Division. 4. Postdoctoral fescarcb associate. University of Tennessee. KnoxviBe. UNDERGRADUATE STUDENTS ORNL J. Good nan Barnard College X-ray and neutron diffraction ORAU Summer Student Trainee Program D.J. hrenon Kafaavzoo CoDege Organic chemistry Great Lakes Coleges Association G.C. Uscnsky EarUua CoBrge X-ray and neutron diffraction Great Lakes Coaeges Association and ORAU Sunuaer Stadent Trainee Program J. R. Loaf OluoWcdeyaa X-ray diffraction ef platinum complexes Great Lakes Coaeges Association N. A. Lyster AJbsoftCoBege Fluorescence of ptutoniuin in aqueous Great Lakes Coleges Association solutions D.S-NaB Kentucky Wesleyan CoUegc Physical chemisuy ORAU Summer (1975) Student Trainee Program W.J. Roam Angelo Sute Umrersiry Physical chemistry ORA'J Summer < 1974) Student Trainee Program 153 CHEMISTRY DIVISION 311 ItHHIKI oi MaiwaiT