首页 【放射化学系列】钠的放射化学

【放射化学系列】钠的放射化学

举报
开通vip

【放射化学系列】钠的放射化学 N95?U c-g !NationalAcademy vofSciences . National Research Council NUCLEAR SCIENCE SERIES I The Radiochemistry I of Sodium COMMITTEEON NUCLEAR SCIENCE L. F. CURTISS, Chairman ROBLEY D. EVANS, ViceChairman National Bureau of standards Massachusetts Ins...

【放射化学系列】钠的放射化学
N95?U c-g !NationalAcademy vofSciences . National Research Council NUCLEAR SCIENCE SERIES I The Radiochemistry I of Sodium COMMITTEEON NUCLEAR SCIENCE L. F. CURTISS, Chairman ROBLEY D. EVANS, ViceChairman National Bureau of standards Massachusetts Instituteof Technology J. A. DeJUREN, Secretary Westinghouse Electric Corporation C. J. BORKOWSKI J. W. fRVINE, JR. Oak Ridge National Laboratory Massachusetts Institutenf Technology ROBERT G. COCHRAN Texas Agricultural and Mechanical College SAMUEL EPSTEIN California Instituteof Technology U. FANO National Bureau of Standards HERBERT GOLDSTEIN Nuclear DevelopmentCorporation of America E. D. KLEMA Northwestern University W. WAYNE MEDiKE University of Michigan J. J. NICKSON Memorial Hospital, New York ROBERT L. PLATZMAN Laborstnire de Chimie Phyeique D. M. VAN PATTER Bartol Research Foundation LIAISON MEMBERS PAUL C. AEBERSOLD CHARLES K. REED Atomic Energy Commission U. S. Air Force J. HOWARD McMILLEN WILLIAM E. WRIGHT National Science Foundation Office of Naval Research SUBCOMMITTEE ON RALNOCHEMISTRY W. WAYNE MEINKE, Chairman EARL HYDE University of Michigan University of California (Berkeley) NATHAN BALLOU JULIAN NIELSEN Naval Radiological Defense Laboratory Hanford Laboratories GREGORY R. CHOPPIN G. DAVID O’KELLEY Florida State Universi@ Oak Ridge National Laboratory GEORGE A. COWAN ELLIS P. STEINBERG Los AlamOs Scientific Laboratory Argonne National Laboratory . ARTHUR W. FAIRHALL PETER C. STEVENSON University of Washington University of California (LivermOre) JEROME HuDIS DUANE N. sUNDERMAN BrookhavenNational Laboratory Battelle Memorial Institute CCWSULTANTS HERBERT M. CLARK JOHN W. WINCHESTER Rensselaer Polytechnic Institute Massachusetts fnstituteof Technology The Radiochemistry of sodium w. T. MjLLINS AND G. W. LEDDICOTTE t2ah Ridge .Natt”ond Lahorator> Oak Ridge. Tennessee Imueme Date: Much 1962 MS ALAams SCIENTIFIC M.WFUTORY Subcommittee on Radkhemi*ry National Academy of Sciences —National Research Council Prmti in WA. PriceS0.60. A=eikhlefromrhe Officed Tedmlmi Services, DepunnentofComuiema W.WMWDJU W D. c. FOREWORD The Subcommittee on Radiochemistry Is one of a number of mbcommltteea working under the Committee on Nuclear Science within the National Academy of Sciences - National Research council . Its member6 represent government, induatrlal, and university laboratories In the areas of nuclear chemistry and analytical chemistry- The Subcommittee has concerned Itself w%th those areas of nuclear science which tivolve the ohemlst, Buch as the collec- &ion and distribution of radiochemlcal procedures, the e~tab- llshment of speclflcatlons for radlochemically pure reagentB, avallabilit$ of cyclotron time for service Irradiations, the plaoe of radiochemlstry i.n the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radlochemical information end pro- cedure.B. The Subcommittee has endeavored to Present a aeriea which will be of maxim~ uae to the working scientist and which contains the. latest available information. Each mono- graph collects in one volume the perttient information required for radiochemlcal work with an Individual element or a group of olosely related ,elementa. An expert in the radloohemistry of the particular element has written the monograph, following a standard format developed by the Subcommittee. The Atomic ’Ehergy Connnission has sponsored the printtig of the series. The Subcommittee is confident these publications will be useful not only to the radiochemist but also to the reeearch worker h other fields such as physics, biochemistry or medicine who wiehes to use radlochemical techniques to solve a specific problem. W. Wayne Meinke, Chairman Subcommittee on Radlochemistry . . . 111 INTRODUCTION iv I. II. III. Iv. v. VI. VII. v. ——-.——. -—— Geneti Reference8 on the Inorganic and Analytical Chemistry ofscriium. m.... . . . . . . . . . . . . . Radioactive Nuclides of Sodium . . . . . . . . . . . . . The Chemistry of SodiuIUand Its Application in AnalyEls M?thods for Stable Sodium or Its Radionuclides. A. The Geneti Chemistry of Sodium. . . . . . . . . . . 1. Metalllcsmthun.. . . . . . . . . . . . . . . . 2. The Chemical Gxq0und60fS&um . . . .. . . . a. Sodium Hy&ide, NaR. .,. . . . . . . . . . b. !l!hetiid es ofsodiu m.... . . . . . . . . Ek=Mum Hydroxide, NaOH, . . . . . . . . . . :: !CheNitrogen Conrpounda, . . . . . . . . . . e. The Sulfide. Sulfate. and SuMite Camound.e. f. The Halogen”Compouu&. . , The Phosphorus Cknnpounde. :: The Carbonate Compmnda. . i. Sodium cyanide . . . . . . J. Other Sodium compounds . . B. The Analytical Chemistry of .%dium 1. Sepsxationsby Rreclpitatlon . 2. Sepamtione by Electrolysis. . Solvent Exkaction S~thru3 z: ChrcauLtoPphy Separations . . a. Witi Organic Adaorbents. . b. With Ion Exchange Resine . c. By Papr Chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dissolution of Samples Containing Sodium . . . . . . . . S#ety-ctices . . . . . . . . . . . . . . . . . . . . tiunting Tecbnlques for t~ Re.dioactiveSC-Mum Isotopes. RsiMochemLcal R’oceduns for the Sodium Radlonuclides. . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,.. . ,.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 2 2 3 3 3 : 4 4 ; 8 8 0 9 10 12 12 12 12 12 13 lb 15’ 16 16 39 v The Radiochemistry of Sodium W. T. MULLINS AND G. W. LEDDICOTTE Oak Ridge National Laboratory * : Oak Ridge, Tennessee I. GENERAL REFERENCES ON THE INORGANIC AND ANALYTICAL CH@@IWY OF SODIUM Remy, H,, Treatise on Inorganlc chemistq, Vol~ I, Eleevier, AmeterdeJn(1955). Kleinberg, J., Argerelnger,W. J., Jr., and Griswold, E., Ihorganic chemistry, Heath, I!aston(1~0) . Hillebrand,“W.F., Lundel.1,G. E. F., Bright, H. A., and Hoffmm, J. L., Applied InorganIc AnalysiB, John Wiley and Sorm, New York, 1958. Wilson, C. L., and Wilson, D. W., ComprehensiveAnalytical Chemistry, Elsevier, Amsterdam, 1959. Sienko, M. J., and Plane, R. A., Chemistv, McGraw-HilJ, New York, 1957. Chariot, G., and Bezier, D., Quantitative horganic fqalysi~> John Wiley and Some, Ww!iork, 1957. Sidgwlck, N. V., The CinemicalElements and Their Corapounda, Ihiveraity Press, Oxford, 1951. Hutchinaon, E., Chemistry - The Elements and Theti Reactions, Saunders, Philadelphia, 1959. Sneed, M. C, and Maynard, J. C., General College 44. Chemlatry, Van Nostrand, New York, 19 Sneed, M. C., and Brasted, R. C., Comprehensive Inorganic Chel?dstry, Volwne 6, Whe Mkall Metals,” Van Nostrand, NewYork, 1957. LatNner, W. M., and Hildebrand, J. H., Reference Bcok of Inorganic chemistry,MacMillan”New York; 1940. *Operated for U. S. Atomic Energy Comisslon by Union Carbide Corpmation 1 II. TEE RADIOACTIVE NUCLIDES OF SODIUM The radionuclidesof sodium that are of imberest in the ra.dlochemdstry of sodium are given b Table I. This Table hae been completed from irfor- (1) m3tion appearing In reports by Strominger, et al, and by Hughes and Eku’veyw Half- Llfe 0.3s5 s 23 6 2.6 Y. 15 h as TABLE I TIIERADIOACTIVE NUCLIDES OF SODIUM Mode of Energy of - Rdiatlon, Mew P+ P+ 3.5 P+ p+ 2.5 P- p- @+ 0.542 @- 1.39, 4.14 Y 1.38, 2.76 P- 3.7, ‘.7 Produced By Ne-p-m, W-y- 3U 20 -p-y, N -p-n, Ne-d~n tg-p-a, & -p-a F-~m, He-d-n, Ne2~-p-y Na-n-2n, *-d-a Na-d-p, Na-n-y, Mg-d-a Mg-n-p, Mg-y-p, Al-n-a Al-d-pa, Al-y-@p, Al-p-2-n 3i-7-2p Ms-7-P, ~-n-p m-y-2p III. THE ~ OF SODllM AND ITS APPLICNCION IN AK41.YSISMETHODS FQR 91!4BLESOD~ OR ITS RADIONUCLIEE9 Redioch&ulcal analysis =thode usually follow the Ideas and techniques established in conventionalmethcde, such ae precipitation, solvent ex’crac- tion, chrcmmtogIaphy,and electrolyels. Since these methods are dependent upon chemical reactions to bring them to completion, the general bfonnatlon presented below on the formation of acdlum compunds attempts to relate these more conventionalmethods to the radlochemisiaymethods used in ana~~ a ~~ctive matefid for the sciliumradionuctides. A. The Geneml Chemistry of ‘odium Sadlum composes about 2.83$ of the earth’s cruet and occurs”pfincisly in the form of scdium chloride. Other natural compounds of Eodium include the titrate, the sulfate, the csxbonate, the bicarbonate, and the tetraborate compouude. sodium also occurs as the silicate In ingeous rocks. Most of the ~-~ c~ ~ found in soils, nters, and in the bodies of plsmta 2 sad aDlnlsls. Sodiummetal Is chiefly flrBt preparing the chloride and then BOdiUI!J carbonate. produced fram these compounds by electrolytlcalJyfusing it nlth 1. MetalXc Sodium Sodium metal is a soft, silver-white met-alhaving a demi~ of O.~ and a melting @nt of 97.5°. It ~shes quickly in air and must be kept under a Ilquid such as kerosene. It will burn h air with a bright yellow flame, and it reacta violently with water. It will unite directly with the halogens, sulfur, selenium,,and tellurlum. Sodium forms an amalgam with mercu# to become a very active reduc~ agent. Sodium also alloys with lead, tin, and anthony, but it will not alloy with iron. 2. The Chemical Compunde of sodium The only oxidation state of sodium is +1. Its reactions with carbon dioxide, hydrogen, Wgen, nitrogen, sdfur, W the halogens are similar to those for the other alkali metals, 1.e., llthium, potassium, rubidium, and cesiwn. Its violent reactions with water and aqueous solutions can be moderated by using an ~, i.e., a solution of sodium in mercury. Sodium also forms etrong salts with au of the common acids. Table II shows the relative solubil.ityof may of the sdlum compmnda in %mter and other reagents. The folloulng information gene- describes the reactions of sodium with other el-nta. a. The Hydrogen COlnpOund. S9dlUm hydxide, NaH, cau be fozmed by heating sodium and hydrogen directly. It has a melting petit of 800°. ‘l?ne -de reacts with w=ter to produce hydrogen gas. b. The Oxide Compounds. Two oxide compounds are fomed by sodium in ite reactions with ~gen: no?xml oxide, Nh20, and the peroxide, Na O2 2“ Sodium rcmcmide, Na20, is formed by heating either sodium hydroxide, or sodium nltmte with excess sdium metal. It can also be formed by heating a mixtme of sodium azide, NaN 3’ and mdlum nit=te at 280°. Na20 is a colorless compound that combties with wwter to form NaOH. Sdiuln peroxide, air or oxygen. Na202 is added to a ndxture ‘a202‘ ie formed by burning scdium in ~ excess of is a pale yellow solid that m&ts at h&lO. If it of ice and water; sodium peroxide hydrate, Na202s8E20 3 is produced. When Ha202 is heated, oxygen la given off and carbon dioxide Blowly decompose~ it to form sodium carboriateand to evolve oxygen. At 0° C, sodium peroxide reacts with elcohol to produce sodium hydrogen peroxide, iiaETl 2“ Sodium pero~de will react with water, ~th some violence, to produce sodium hydroxide, oxygen, aud hydrogen perotide. ~2°2’ either in aqueous solution, or as the fused peroxide, is a powerful oxidizing agent. c. sodium H@-o tide. !13J0general processes, i.e., the action Of calcium hydroxide on sodium carbonate and an electrolysismethod uelng sodium -Igam and brine, are used to prcduce eodlum hytkoxide, NaOE. Sodium hydroxide is a colorless andwax-liks solid. It melts at 319° and boils at about 1390°. NaOE dissolvee in water with the evolution of heat “tomeld a strong basic solution that can be used as a precipitant for sweral of the chemical elements. d. tie Nitrogen CompundO. Sodium nitfide, Na3N, a salt of hydrazoic acid, ‘3” ean be fommd by react- sodium and nitrogen in an electric discharge tube. Sdium azide, NaN3, can also be fcn%ed by pas@g nitrous oxiti, E20, over sdamide, N-, .ati~o. NaN3 decomposes when gently heated in vacuo to give mdlum rdtride and nitrogen gas. The eodium nitride cmpounde are rapidly attacked by water, forming sodium hydroxide and emmonia in the reaction. Sodium nitrate, NzN03, is obtained by the action of HIW3 on sodium metal, sodlwn hydroxide, or sodium carbonate. NaNo3 is hygrcmcopic and diseolves more rapidly in hot water than cold. It is a@drous, and it will melt at 380° and be decomposed. When heated above @o, NaN03 will lose oxygen and form sodium oltrite, Ne.l!122.sodium nitrite is prcduced as very Emu, hygroscoQic crystals. NaN32 is a st~ng electrolyte, and it will nelt upon heating to fomn a yellow liquld which decomposes at ~er tel!lpemtures.lblf02will hydrolyze to nitrous acid when boiled ulth -*r. e. The Sulfide, Sulfate, and Sulfil% . Sdiura till react ~1~-*’ ‘a2s2. with a meltingpoint to form either sodium monosulfide, Na2S, or scdlum Sodium nmnosuJfide is a tiless crywklline solld of UE!O”. Nn2S is hygmacopic, and it reacts readily 4 mid. Zmbltal hlublainmludml SOlllblo inm; vow awiltlyMdJM.0in &lcObl Tnble II is continuedm tie follmvlngpage. ~ Sdnblm SOlubln Selmla &lubl.a Wlmlm mlubl.s alublm Sdm10 Vmg Mlnbla alnbu with water to form a strongly aWaline solution. irlaolublmin m.ublninnlealml allbl.ninnldnl Sodium sulfide solutions are unstible and till break down to form polyeulfides, thiosulfates, and aulJ?ates. Sodium hydrogen sulfide, NaES, can be fo?.medby saturating a sodium hydroxide solution with !&. Sodium sulfates can occur in nature. However, Bodium hydrogen 13UM?ate, NaISOk, iS produced by heating NaCl with an exceae of H2S0h at tempe=tures lower than 150°. If NBHSOL is heated to about ho, it ia converted to normal sodium sulfate, Na2S04, which is readily soluble in wster. sodium tblo.mlfate is prepared by boiling sodium sulfite, Na SO~ ~, in the presence of Eulfur. Sodium thiosulfate, as Na2S203”V20, is used principally in photographic film processing. Here, tileexcess silver bromide, which remains 6 in photographic film after developing; dimaolvee very readily in the thio- suli’ate to form a soluble complex. Soditi thiostiate 16 also used as a tltmt for the determinationof iodine. E031uluhydrogen sulfite, or mdiwn blsdflte, NzHS03, is formed by satumting a solution of mdlum carbonate or mdlwn hydrcrdde with sulfur dioxide. Normal scdium suJflte, Na2S03, is formed by treating the eolu- tion with an additional amount of soditi carbonate~ The sulfite solutions are.alkaltie and are god reducing agents. BoththeHso-andso--iona 3 3 are retily OXidlZed tO S04-- ions by atmmphetic oxygen or oxygen-con- tairdng Cmlpounde. f. The Halogen Ccmpunda. The sodium halide c ~, i.e., stim —. chloride, HaCl; ~ Hal?;~ NaHr; and sodium iodide, NaI, may be prepared either by a direct union of the elemnts or by the reaction of a halogen acid u~n sodium hydroxide or sodium carbonate. AU of the sdium halides are strong salts and are completely ionized. They are readily soluble in water at ma tempszatum. Sodium salts of the oxygen acids of the halogens include sodium chlorate, Eodlum hypoCblofite, sodium percblorat-e,SOdiUM bromte, and saiium iodate. Sodium chlorate, liaC103,is prepared by pasBing chlorine -O into hot concen- tmted sodium hydmxlde. more solub~e in hot water will decoiqose on heating ding bromate, NaBrQ3, and NzC103 is a colorless crystalline c~und that ie than in cold. It is a etrong otidizing agent and to form free chlorine and oxygen. The correspm- the iodate, lk.10~, are PmPared in a simllm manner and ham Bid+ properties 8.9HaCIO 3“ Sdlum percilomte, NaCIOk, is formed by the tic’ oxidation of NaC103. It is a colorless compound and a etrong oxidiz~ agent. Sodium hypocblorite, NaCIO, is produced by ~sing chlorine Into a cold, dilute solution of sodium hydroxide. It is eaflilyreduced to chloride Ions and oxygen. s. The Phosphorus Compounds. Three classes of sodium phosphate c~cumis can be ~re~red by adding theroetical amouuts of phoe~hofic acid, H POk, 3 to sodium hydroxide: monosodium dibydrogen phosphate, ~ ~, disodium monohydrogNaH PO en phosphate, Na2~4, and trisodium phosphate, ~a3m4 “ NaH#h IS acidic in aqueous solutions. Na2~k IS only sll@ly 7 alkallne wkile Na3FOb Is stronglyalkaline h aqueom solutions. When sodiur W@rogen phosphate, NaH2POk, is heated, a series of EOWJJJJmetaphofiphatecompounds are formed. They appear to be all @.y- meric and are representedby the eqpirical formula (IkP03)n. Calcium and magnesium ions can chelate ulth these palyphosphates. If BCdiWIImono- -Gn phospha~, ~~~k, 16 dehydratedby heating, sodium pyruph~sphate, 17a4?207,is formed. O can be hydrolyzed in an aqueous 6olution to ‘4P2 ~ fom ~k= ions. If N.aH2POkand Na2HF0h -aremixed and heated to @O”, a more complex phosphate, sodium triphosphate,Na P O , 1s formed.531.O ‘93°10 in solution IS S1OWIY hydrolyzed to H#04- and HK)4-- ions. h. The C=mbotite Ccm@ounds. Two salts, sdium carbonate, NaeC03, and .96diumhydrogen carbonate, NaHC03, are ,formedby the action of carbon dioxide upon .90dlumhydroxide. NaHCOk crystals are redily fonued by pas13ingC02 into concentratedNaOH and they may be filtered off and dried. ‘a2c03 c- be obtained by heating NaHC03 at temperatures above 200°. ‘a2w3 ‘U ‘e- comlmse at t-=mpentures above 800°. The C-n -ted fO~ Of this 8alt 18 the decahydrate,Na2C03-10~O.. Holutions of Na2C03 and &HC03 are alka- line becau8e.of the basic action of the CO ‘- 3 ioti and the slight hydrolysis of the HCO3- ions. i. sOdmJIIlcyalMde. NaCN, scdlum cyml.de, 18 produced by matting dry ammonia with a molten 8odium-charcoal mixbure. It can also be ptiuced by ‘fusing calcium cyanamide and carbon with scdium carbona~ or 8Cd1UIUchloride or ~ heating sodium carbonate, coal, and.rdtrogen with iron as a catalyst. NaCN 18 a source of --c acid. Hodium tmocyana te, NaSCN, can be produc@ by reacting.NaCNeither with 8uMur, ammnlum, @.yeuEide, or sodium thlosulfate. ~. Other Sodium Compounds. Sodium penmmgana te, Na#nOk, can be pre~ by reacting ~se diofide with 8odium hydroxide. It ts leas pure than potissium pemangan.9te, KpOk, and 18 very hYW8coPic. The heating of sodium hydroxide and chromium tide in air produces 80diUIllchromate, Na2Cr04. The chrmnate salt can be efizacted from a heated titure by a water leach. When the solution 18 heated with acid and then waporated, ~ lia2Cr207.-O, till cry8ta3Jise 8 out of the eolution. When Na2Cr207 16 heated, It first melts and then decompoaea into Na2C@Jk, Cr203, and f-e oxygen. When asolution containing scdium Ions Is heated with a potasaium salt of antimonyz a slightly soluble salt, sodium orthoantinmnate, Na Sb(OH)6 18 prcdu’cd. Sc&um fluosilicate,Na2SU?6, Is formed in the action of fluosiiicic acid, H2SU?~, upon a eolution of BOdium hydroxide. It la also Insoluble in water. The aild$tionof a lirge volume of a saturated solutlon of ua.nyl zinc acetate to a small volume containing scdlum Ions i-esultsin the fo~tion of the ttiple acetate compound, sodium zinc ~C~te, NaC H O .5(C H O ) “~ (C H O ) 06~o, results. ThiS232 2322 22322 Compound Id a Mght.ysUou.:cry’pWline solld that is sldghtly soluble in water. If a solution of borax is treated with ~020rltsOHand~02, a precipitate of Eoalllmperoxybo-te, NeW2.~0”~02. It deccsnpees very slowly In Vat%r. It Is an active oxidizing agent. Sodium tatraborate, ~@7m10~0, -be *-M frcm natural sources h the form of ptisme. If it Is heatedvlth scdlum~de, it foxms scdium~tibomte~ NaE02.~0. Borexis asaltofaweakacid. It canbe hydrolyzed and its aqueous solution glvee analkallm soluti&l. Hum ~ de, C6H50Na, 1s fonued in the reaction of sbdium hyhmxlde and cartdic acid”. Mauy otheror~c compoud
本文档为【【放射化学系列】钠的放射化学】,请使用软件OFFICE或WPS软件打开。作品中的文字与图均可以修改和编辑, 图片更改请在作品中右键图片并更换,文字修改请直接点击文字进行修改,也可以新增和删除文档中的内容。
该文档来自用户分享,如有侵权行为请发邮件ishare@vip.sina.com联系网站客服,我们会及时删除。
[版权声明] 本站所有资料为用户分享产生,若发现您的权利被侵害,请联系客服邮件isharekefu@iask.cn,我们尽快处理。
本作品所展示的图片、画像、字体、音乐的版权可能需版权方额外授权,请谨慎使用。
网站提供的党政主题相关内容(国旗、国徽、党徽..)目的在于配合国家政策宣传,仅限个人学习分享使用,禁止用于任何广告和商用目的。
下载需要: 免费 已有0 人下载
最新资料
资料动态
专题动态
is_390739
暂无简介~
格式:pdf
大小:1MB
软件:PDF阅读器
页数:50
分类:
上传时间:2010-08-07
浏览量:56