Document pLBOY543gBXxk4NRGzX6ajYw

AuAg,g..2222,, 11995500 ne. AJ.HH. SSMIMOONNSS oe comm2e,51199,998833 rieddo5r5,.1030 ELECTROCHEHICAL PR0~ESS 0F ItChING FLUORINE-CONTAINZNG CARBON~C01iPOUNDS F~A.ed Nov. 29, 1946 EL 2 iw wdik octconser (Flvorocarbeentsc,) efi Fras I Tl [T- HH qr "imal fragen i y Hydrogen Fluoride Gigoidarair 77Lo sflllgoyra-- [Fr fiCee Colin Fersg rite ZSNA EZzf]| Lkectrolyss cel! oSpelerinon cornttaiinngicnogmprond &3 Eras tSod= GaNgemsater Coola CE, Fz aur(i rr ctfosr pr~dvcfs fri Lnverdtor Dts poditod rrnigns EExxhhiibbiitt 11001100 State of Minnesota v. 3M Co., Court File No. 27-CV-10-28862 11001100..00000011 STATE orsadsat STATE_07524631 PPaatteenntteedd AAuugg.. 2222,, 11995500 22,,551199,,998833 UNITED STATES PATENT OFFICE asa 2,519,988 ELECTROCHEMICAL PROCESS OF MAKING ELECTROCHEMICAL PROCESS OF M~I~N'G ORECOVAKIING CARBON. GON. FLUORiNE-CONTAINING CARBON (~OMTORS POUNDS JoshI.Simon. tate Cole, Pa. sgn Joseph H. Simons, State College, Pa., assignor to iesSin Memes Compass, Minnesota Mining & Manufacturing Company, frat ar St. Paul, Minn., a corporation of DeLaware AvplcatinNovember2,148, Serial No. 62450 Application November 29, 1948, Serial No. 62,496 . 20 Clima. (1.2001) 2 20 Claims. ! Ths applcation i Continuation input of ditvopeermsofcect ud hdrcgen This application is a continuation-in-part of oe Be Wo, BOT heh Boo von neat Adm wih Tone my copending application Ser. No. 677,407 (filed ok aio aotenAbeneipoanrudof hhaeaTeonwaes 8h8 lAckInsa,obwehiceha0n nsoak rbiovnicsomspeosunadtss, ustnh" June 17, 1946), since abandoned. The latter was filed as a continuation-in-part of the following Fr i rg pe ee prior applications which thereafter were abanEee. ho Si leq March i, os. Some, The dectrbte doned in its favor: Set. Nos. 384,729 (filed March SET SS ledDemi 1000 and Ifr oh water mace haa 8smal ro 22, 1941), 569.265 (filed December 21, 1944), and 1 re Naver. 1 Dorion Do me wk be ane 8 Sc 626,434 (filed November 2,1945). "His imvtin rites to my discovery of 8 fone. This inve~ntlon relates to my discovery of a baits Tox oc. 1 Baki Sunroaroos 10 Excelent rce ubechl ainedwit sale basically new process of making fluorocarbons he earscotaiing cation compu, single SPADE ceive so Tange: and other fluorine-containing carbon compounds. ne In rao do wo I. hes. Ro aphra peeded etnies ole The process is simple in operation, does not inin eo tai fe Burn 437 ods, Paring ca becompl1i.e50d0 volve the use or formation of free fluorine at any Se ea re venti i nabing the 50 40 dire obi fly Toriatad prod stage, and has great versatility in enabling the ea ofa ob e rota Som 16 SaBOuns which are Fen Moe and direct production of many. types of product comSa i ar aking Snnds hich "CHS She ih thc ats 7 ee fo the pounds using organic startlng compounds which Be Tati eibeobe, Solon, of ihe tal a `hh hy etn be are readily available and relatively inexpensive. Hn deshoshamtel proces Sod he ably dined, depending. upon ines olive Fonte It is an electrochemical process and its utility oe Cente by centre plot pant To prices mae fo conti8n6 Fe 33 has been demonstrated by extensive pilot plant erbion copie a 200-ampescl at well 0 batch operation. The cll can be spersied at operations employing a 2000-ampere cell, as well any ors Spent, Supa prere Tanocnecaanodles as by many laboratory experiments. EweB Dubeyduas ed tn theoral Gam OFmae of ie or i,480 he 504sof This process was publicly disclosed in the oral Dreesoh Sep 10 OU a4 BOBO Bike, Sed Sh ols Rane Ben. sttuctoy presentation on September 15, 1948, at the PortTent rekon, dn offhe hh heingof 5 Speried at 18 608, D.C 1 producing wile land, Oregon, session of the 114th meeting of t~c Is Cher Sait. of he pups we 1Tactof pachCOU, American Chemical Society, of five papers Bet Bnd atin "tr Th SE ms vo ty mde thored by me and my assistants. Abstracts of nispapers aa btn reiousy Pl standbt he'cearoproycesrsapiparnentg these papers had been previously published in Ae oF Papers volume sand Santor ihe rgune Sng Sompounds ot of the advance "Abstracts of Papers" volume issued Soy oe i to 0. News ms sala toandand oa beeras41 by the society (pp. 42-0 to 45-0). News items Ping ho oi nydein teprocs 30 Salepees Hydrronotgtheecanth relating thereto and briefly describing the process are Se pusiihed 1 ok soos magsise ode, Sn. deve from te adios Susie] have been published in the society's magazine ica 5 Einering News vo 20.5, 2618 aad wil an vanneth cl Geman rom. Chemical and Engineering News, col. 26, p. 2428 Chom Tot ed. STs gh FIT, Se Roo SePan mp SR (Aug. 16, 1948) and pp. 2878-9 (Sept. 97, 1948). The persver sect DUS nh aybe rect Pre ok crave: ad he These papers were subsequently publlahed in the Touma oo Bolom Sales, vo 35, 35 eA chan dos ot OveUn forma: Journal of the Electrochemical SocietY. col. 95, Ro ppbat FD oof cr Cie smstay Buonao 48 No. 2, pp. 47-67 (Feb. 1949). ich aed, tise and eet cece. termediateagent. Briefly stated, this new and useful electrocommen roc re oho ing 3 Tv Bradt compsrae lulziabse Goh xc chemical process involves electrolyzing a liquid Soiree aie ky scion oming 8 808 cycle ch WAVEShe sun. abe oF hydrogen fluoride (HF) solution containing a rete guns aig CESouL 8 4h 0 SBh SSBI As Chon Se) SERS fluorinatable organic starting compound, at an rong pont wha is HauBdent 1 5 So the Haring Compoundu,t wh Fai electrolyzing potential which is insufficient to Genta i Morne unde the ching cond. of al one Seem elacebent of hers generate free fluorine under the existing condiEo Sh Suen cho fo pre. in Ko Sh wis hal Bonind tions, but which is sufficient to cause the prooo otBoecopa come compound ih ation Akio of th molec. Faeroe duction of fluorine-containing carbon compound Dred sn ra THEA Wid VARY of 45 Slimoir fhe a of eatiried and products at a useful rate. A wide variety of Dron cpoune ar ll: unbydros* Sos 7p ofHAASESompRIRAS Bo Podhna organic compounds are soluble in anhydrous SE apn Baoice 428 ove adele Duk rei predut Compounds NohSree liquid hydrogen fluoride and provide adequate Sore mbunits, Di Can ho bo Bade comport. naan to ye compoumas electrolytic conductivity. Use can also be made inesmi and rE SOOM ade Doin me umber of arb ems ar Ob of eoluble organic and inorganic conductivity ad- (CI. 204---62) dlt~ves to permit of electrolyzing liquid hydrogen fluoride solutions thereof admixed with relatively insoluble organic starting compounds, such as alkanes, which do not provide adequate con~ ductivity. Pure anhydrous liquid hydrogen fluoride, per se, is non-conductive. The electrolyte is free trom water in more than a small proportion but need not be anhydrous in a strict sense, 10 Excellent results can be obtained with simple single compartment electrolytio cell arrangements. No diaphragm is needed between electrodes. Fluorination can be completed in one step to directly obtain fully fluorinated product 1~ compounds which are relatively insoluble and either evolve with the cell gases or settle to the bottom of the cell from which they can be drained, depending upon their boiling lmints. The process ~ suitable for continuous as well as 20 batch operation. The .cell can be operated at atmospheric pressure. The cell and the cathodes can be made of iron or steel, and the anodes of nickel, and such cells have been satisfactorily operated at 5 to 8volts, D. C., in producing a wide ~ variety of product compounds. The reaction mechanism ls not fully understood but the electrolyzing process apparently transforms the organic starting compounds at or adjacent to the anode and may be regarded as an 30 anodic process. Hydrogen is evolved at the cathode, being derived from the hydrogen fluoride; and will also evolve in the cell by derivation from other hydrogen-containing compounds which may be present, l~uorinc is not evolved, and the a5 reaction mechanism doe~ not involve the formation of molecular (free elemental) fluorine as an intermediate agent. Product compounds are obtainable (both cyclic and non-cyclic) which have the same number of 40 carbon atoms and same carbon skeletal structure as do the starting compounds, but with partial or total fluorine atom replacement of hydrogen atoms and other atom_s and radicals bonded to the carbon skeleton of the molecule. Fluorine 45 addltlon occurs In the case of unsaturated and aromatic types of starting compounds to produce fully saturated product compounds. Non-cyclic compounds (in addition to cyclic compounds) having the same number of carbon atoms are oh- 11001100..00000022 STATE 075246%2 STATE_07524632 2 fe omeormorecan im saane punt so10008 . tFatrluaeaieisoaniu,abllbttisoleeoffffurrbBoooom monnfddccpcryolceclleilepiacacevvsaaastrgtgoaaeeertUanianncnngdgdecfclofuolmou~aproPnioroinduntemneBddaoasdsudad-duiscitytiietooilnlnes.. shuchpcraadmpororGeursooubAefccanaeAiossftbheboeu bptraaeisrneenndtpfaperre.eooncmte CfCAscalM tlrkaarotibril,oUeenntigh~ys.ieisehccluodossmsmesoaopfofopfuprptnrmoooodelddsyIuucggcacpeoertnbnclceoeoorrnomomaapcl,lpelyyoncTuAiulrvienneceddmsassutinnollbtdmsavrivniintdonnansg-~fpcfgpeiyespwrwcraeleeeir.c-r DProonosle:ndButarhraitfnIogrtapmrraoekvoiifndmgenoso&rremaallaSplalybeolAninqudsiidesmRcusm1sormoictaehsae-l SSC.(o-~ at~olomam~marpOptfothutam hhateoten~mc(h~arhhar~oibevnvo(is.immtnnahs~graektkeLmieeSla~oeieglt'oeaeonc~ontutmeaaolerpinr,dodnnduuufuSlnuem muodbotbeoserieirnortaroseraoaefagfdSdmCddbaeiosltnihnoatoa,nnn-. bmyTethsheeeffsoormramtaitoinoonfofuBeorroocclasharysdcsrboimbdopeasons4i5nsedd S~f himm aao tt1hhaentr hethmmeiisvd ttoalfrotcnho.~uTplcoionemgopKofiuncndasdrs4bo2anrderraeodlbiatctaaiilvnsePfroorpmoretdioinnstohfe aporloudfuloc~tcoTmhpeoukmlnddsscb~laina~bellaetiivne '19 BaDlaselieaelhulyiydeBrsuocTgreihnnreatpeedhrypdorlocpaarbobndoctnershp,ueetdcnudmaisuteopoolofnsnentohtshee ECParonno~mporisinrsveeidnnscaceaniasdossetwiwhtieill1lopdpodeesepripeabentnldidenugu1ppooocbnontoiadtihhineiessensxastca.errlteiJBn~yst 15dcDinaayvneedriiadeeshm.iagrTh.ehdeeofgSorboearrsdoccfavrtibahorenrTmmaoalmloenybaedcbrtiuldseyest4ih5ne4dy LFp~ sieepripopeaparrrreaaorotifnesofddedalfdieSrecbrytsoylioeTmreerfadrlaaoicpptcwkrxt-ioio~syodndinupalucaoldtclsstbss,idy,b-iwlwspelhthriaitloiolcctdahhiutocicoobcatnntanacnibonfrbrmeooeeprm mxorecueaenteda~daaidesccln~h.hyt| GehhiaaimhyiceaatlAeydsseoreoeofn sStaooremosaaorrebsnornpodoentre-iovcfeasot.tracekTsh[,uodsf pTroIanothdc_esocrc~maimenormdncefiorracofllmaolmpoluepolrewlamit-pyitlioioeennlpsds,r,boeuydso-uepccrcotaadnn1bub5ceetbmmaaalddieenoogffutthhpes g_p chhlsoerinatuecdroacnardbMornoAmpiinuriiaddetrcoaTnilbde tthheercmoarlel.y FpM mioroozrioc~~sdkemlmusliociiommftflae,im~m tceadadaonsnBfyneyumuwsmmrrubueelbeetiiefrplurnolloeocfucfosposm~ rummopradpoitouuneucnrgntdsidscsaiconfofmrm ropbopum ofmo~uoundraantdmtndsm eo~s.d.uu|uccIpnhh*i4lapecoiAnomeneegrdiIScnan&upChaepomeirrpcaacblhleSliootrchciiededet1sa.avanoirdlheb88riJ,oopmuoiar.dnea4,lsaofa tetInculmo~b4mu0etdcateguesasri~odltnyoucsleurmbetreenrWltaihlkeistsfhlooercmtOrpeoedirrtiaen 35 8B5atCuriaeied164S8) uofowhircho1ncwdasafi4crrSoboca-rohbeonnrdse- fofluanmiin~nnteeaiTisnnoipnpomrruoiosppnopoyfrrcitoioaodns~ussc4utphsoitocoo6an6l0t0ad%~irBnhieaanlrvgieecabbe)oeeTenanmdooebab- sbirovlulamiinvtghegaaKsrimeupOlpebsi0tahcioamibplogeu1nh3d,-C2Fb0c,4ooTWmhipbiocculshniTdinasnnDoiaivgvn:d tained. In man~ cases .no. solid residual mato- Fal arefoundevenafisextendedWe of tbe rl~ aee found even ~fter extended use of the Besec`tIrgoedneernal her ileor corrosion Of cell. In i~eneral, there is little or no corroaton Of 3 l4"n3TgdhahgahvftinograTooloriencrap4sh0ooodtn seacaltabotomaevsdec1zo1m00hpbeouCT.neodlscnebs- o"foBfTtothhceberbeprrtoroccIeendssdeseirIciiarnntaeeic enainavtabsblC,a liiminnseggnotrttllhhoeenh 1p(prbrOeomddruac Uecdrctstieiaoot(n nnilcoloyfrf tcpaauirrnobacobenlsesh.ybydT,rihtdheeissea,pcSriorcauieessds heSavuoecsUcriLchIaeeLrYasr,rfsobharSdeua.naotsrnDro,.: UkifllviluueeosrrstoraGacettaiiroobgnnon4naa0tnd4ededprn5iovo7attLsliivuimepisieit,raam ttiooefnnno))tirofomnfatitshshweemh{feaOodrltleoeowiw(InifDnoBg~tr35> dBeugorroecoarfbtohneArmmioness,ia(boirteyxaAdBBSIh,ePmivAaBTBBeeSth: BoFtron e~errbpprierneesosnscnden-netca sstsysitgcoaslnmiatacatit):uerrdaRacn itoobOenenYdsRdsi~gfSs"tletnuin_uo(ne~c ~gsr.soisccasaoeirrflnboelaorlobm ynle orucerofealffaddcareiicaocaawrrmalrblhbse) boeotr(nnhceoeyiCarnacsnlnnl)iIdd~,et lhosoawe,croetmfhrpeaaycrtdeidovehwioin,hBduoirrnet,ioaaanrdy odtrhigeeaycnhtiarveceocumonnpksaealnnyi,a fRIBEBtluR'RRRohI'r"ViNNnR1(eIE"~Ga'NbNto((iomab((sitooaG:bbbinIateatat'ibOnbfnarlaIetobtflm"ileferpr(ooroffmmaibrromtosamamsieincce aytotbeencAlrroedtmto iaiiafarr~ rnraoyyeymAsiA,mebmmtRilhennOeeeersOss))F).,, TthceanersbiooInndsadataodcmvoissmcpoohsauivtneid.ess,sc(oscuopenltexadinpiwntigtolhiohnwiaevonrrtTGtoelearncyese ~ (obtainable from prlmar~ an~lnes), Cobtiodblefrommosceocaorno"osyiesca, (obtainable from monocarboxylic acids), R~"~)~' 48 ptofooixnn' t"ss)iToasnseFpaanreiosrosthie(rdcegBproenedemixnigrp.ngonusctpaieontnrbns,espdoivln,ieeirntgd i((ootbbittaaeiinnsaa4bblleedffRrroAommPee(stoteberris)a),i,a~ BblONfro((omobbmtae~triancaaabbpllteeafrnreooymm. DTinniveaamt4psiea5lalddeibdnriieil,ainde,tneetl.se,Tthehset,tpheyxccrhravnaoglecofSmduechihiduat,npirucsormc.se CFinFboiioilntnunrrteoieaoldreicoc~ncach)iahisnroalbgbornoorsidinntnn~ aeercctsoocaimamnnp(pgoobob`buutese~nno5oddo,mbs~sbpt_toabaWwiulihennnhiefeidccrddsohhmffCrcroomoonmnmei(tcoraac.hciahnoeplrhcotiiacroonniontme~moe.).--. 5018ha8ecstshneoifTsoovubeorewcrhaedomi4cacIcaanllctroSumeboproroiudmnnedses.d(IRninOapPtha)terabetrrsoen- rioslcnn~nog~egntotoltacncnteane~ coninoeird~rbm)meo.eortaoreHeHrvteoeiaotnxtlree~vinrrgeooeeecccdnyonycbom oollfyiprosoniT~ccirtm ooerommo~glpgpeoeoan(nuuen.cnaaddtigsoeso.m,mmccaosoocIefnhnininltnaoattitrihntohnhee.--e TiAisdTseAoSt:hSeumeabiceirvooefsdtrearrriaviodantigicvcaceloamcanpoeom.upnrohdausvnibdnfsogcrmaonLaikEainiNnnEg: h~ c"SRoryoTdmdmrrrpopuopo~ ogeeueunnDnn,ndsssabutiecooffmmoosccbsoo-btrrbarrryieynusfeppo(fduoolcunonadordbcririiyibnnnnggoeasrnesaspatSiretrluoaourcm cmcetbsausmrIr.eee~no.nnc.tSosantnormtfta~stidhn~e es PrreosAplcearoigregwsainotinhcfMacuotamrspiocnueoncudatsnpboeteenmtpalloyyecdapiaoblberoo-f ICniddniotg~rTroeemrc~nuotllpelnyyyloyflcuoo,caobbairrtAoarabnbiicononadneernbdadaolasnnnffosrddrobo(mcmyfAalourrtbohhiloryynienddnecrr.erfooloccuaayaaotierrroobibimdmooneennsss))scacssocltaaanatrnnitrt~foiblunnb~esge- adcuhleosmsicbTayltulhyeoApcrriveiemsnpirbeosciea-scnscac.er.boFoNnoictuoraaaelaymnruitcihiePmnomRaoaigesds:-k scosOumfof~bmevvsn"paaionrtrttiiuimooameuudb]slssi, riyhhaiyyndeddoldsdrfroosc~ ccoaaaorfrrfbbbooofSblnnnyuuoadderooeileercarciriamtvvrrasaoobttloiiyacvvn~eestnsas_,ha,h~rveattoviossb.ionanlogroO~ubtbtntiitobtaanhsniiegnesn tbtFoiilrnaLiieceonmdptlMeuteuolyrsri(sCedrPteaOon.ctBactoenaBrnoeartrcnhteebbbyocayteeprnatoscansir.n. `maSoaom mmopeocorannrudbmrso.brelhrPoiaocovrfeieccncigadtrsxbchaoaennatbaaratemloekmem mabmnepsps~lb,aoytlheedhotnfoesocltaasrrisat,biennod~dn 5scaaArbbbloen4&bnrodanpcdrcoildauelcatmvbaaegtietebrCIdFnCfreosprecat dalton,the to thecom slf0clnotudedmcTba~om o.on~ar~a1erehb2caoacavndarsidrnbbihgoot~nnivfo,iensnaw~i,toeoMtm rmhsusecaasoarrarebmeroepnporrnoosucddmuuoahccbameeervddri..obtnfhgFIoaeNlfn~ouenroovbriroesehon.e-r mcleoernsctsiaoainlneiunhdgyldozrrapotagiaeoinncoctfotomhebpmornodpceedws1oh,0it&cucehahrcnybodnortndoagaiensna.t MHaDhaser~tekatrtaeberirotolnnt~bgsccyoehconmoamvmprpionpoouo~uonundnfndesd"wchwce-oaarehannertscmroaeceaamrilbsnpsoooc,a.bnea4beearearabb1rtprpooerarnmnootiMddbshuuaoectctnomheeoem~ddatdnsfefarrntosm oorhm mfee7|0AIDlbuhoeoMeorldeicfornmeaarke-ionfCcgarmBobaoiunnnIccnotrtmeoarpeacsittanaTrhnibedsoWoenhbinccega,hrn 9hers 10dSuscercooocunadsrabbroyeanisnn.gdrFteelruatcsireaorcdyaztabomofinnosersBmA;cToItRrhG.a75cOcoafnrttbhaoeinsneaaOttrogmeaInaisncHtbahreetmBioonlgveicSnuoelmeps.OiTUoLhmLeSboosfoutbDe-adcr(il0eans4:s 11001100..00000033 STATE07524633 STATE_07524633 Jarvalue for makingSu5 orocaarnbdSouonra,os-100f8o8r . the generationof Treeflorins(%) 8ap BClrcaohaarermerrbtoVaothhnnaneelaudhdeeherRyri~yiydvoivarrraototm icdigvvaeaeernksbsrsiono,onfgfaso(ncfcwlh(hcuwihcioeehltrffiohccaccechhaoccormcobormonommmnltpletasbeoar,icuirninanao!odldoadsfnilnoln~wytyteeuhrrc0cieseaarscs0rrtth--,:. DVvfpporoolrarorltctxoaaitigghimxeeeessiaohtgmehfieltigaynghhehte83ereavperrvotrtilotoohhllyntac.as.nbeotTsfthTwhhifhiirasseebcerocraeaeuafnnaltsubscooobenarneiiunwiuwsehsnehegy(dydfIt~riont)neoteataaiaclslctcutucuooaea.lllll biaSoreeincooaaxnnyvdgeethnoyc-ccboloernnoitngnageiinn)hin,noggaarnooodrgrenuntlh-iztcerooonpcgioeeamnni--npcisoonoungnnt.~distanEitwnnxhgieincIimnhgn DpaClldraadgcriayytnoiiocfntahtcoeebsaetineAglrcaobrhyoedlrt,ohgeeentch-yecerosln,itaaeltnneldrnsgh,,enk-ecEiyxoenelemls-e, sTfpttinhihrnnoaeeeecdftttsiofooacotrtenaramm llodafecatsettialihlooltenhnvo1opolidsrlsiotsaccgbbgeeeoesccsoaa((uwummssneieeetahasa&soguuurSrstueeeubcddbsastucaauatscacntirntrniioitoglsaisazslfolerepedepxxauentatrneerftrldrtusnneoooaaforlfl ihe existing conditionitovercoming the eis of the latter are the cyclic and non-cyclic anode and Cathode connections) is utilized under organic acids, alcoholsi ethers, esters, ketches, the existing conditions in overcoming the resist- idhyde, micas, amines, amides oe. Thess ances of theseeds, iheresistanceof th sec- aldehydes, nitriles, amines, amides, etc. These ances of the electrodes, the resistance of the elec- aoxngiiens-tcaornitnagnicnogmpaonudndnsiiarroegesnn-kcuonneiailninAgnhoyr.-|1g rreosilsetabneckewoefenltehceroedleectprooldaersi,zastidontfhiensb.acking oxygen-containing and nitrogen-containing or= l0 trolyte between the electrodas, and the blocking QGgdqBiraruonoonaouuitcecsesdcoslTiotqaunnuTrdtaihuiddnecghthuihyyvyddcicdtroryroomt,oggnncpeeiooaonnsuocvoBnfdoalduunUniscodsErrutaiAdc(drVtsweeyihvIaaisi,toncnyhlddsuabappidrlrrdeovooivtvireiinivdedeeeBvabeneaaeihddilnynoeg)og.- wrwoaeIlassIuhsintsffatiooaaonuunnnnnceededoxxsftptphheSoeraaefritstiremilealceleeoeacnntcctttrtrirouudoodsslleyiienenspsggissolaalooaaffccrdiaaazrrahbibtydnoiaodrnntrno--ohaagegfnneieolofnmnddosesrff.lmuuccaroeetlrlliilddoi1eent niasneloseajcocdoolileunnbdbdTd.iulnuecet)ctTtirihccvvoaiaeintntnyyh.byb"eaeadTddrhsdeodiemmcitsptaipielrvvlboeoe,ogy,sneeuadsdabss-w(wwceehlhxxhepapinlceslahasUuiisansnaeeeermded.ib1srreiim amnlncaaateddsisveoeoteommhlofyeeef 1155 4sopoasoffslsfTualbutuiiocbocurrn~ooo0m moc0:ef.e55uivtahhvcockaoaetelnnltlt.iee.lcIe&((aICnncChIiayHd~andP-nForr)o)etosthghu8 aoeeeltrtnr&eaecAdexcuxmepeirpnlenierrdvtoiioholemmetleteaanifnggtodtteeriium8aos3nsainsntglligoooowwn&fa rdknKFeaaeeganntadaeedii,slltl,yyhleaaa`alltcavecwovarnoahinlhlooaiyolnbbsd,.l,lreeieedttTaahehhnneeerdarssfs,e,orrrecca~lmaaaaur)trtbbii.b-vovoeexxl4llyayyy0sllisdeceiInsnaaaeeccemxxiimippddneessbnenrss((sai,iiBcnvveeecebilouutathtddlleoh-- 5; nickel-anode cell, a hydrogen fluoride solution of acetone (CHOC was lecroyaed for ive acetonltrlle (CI-I~CN) was electrolyzed for five udealyeIanctludceedlGvRo.lCtaNg,eCFofSH1,1FvoelCs AanVd tahnedpGriotd. days at a cell voltage of 1.~ volts and the prod- eiceCon~fmtrg'cptlmcilhcotpheyaaerelnndddeTaiyonnnnrhooettiynnhhdn--deece<rypip-ydcrceeleolirpcnc,afiorwewaarhnhtmiiiipoecnsnhh)g,caoocfCafaaannfrnSrladuubaooolalrlrnaboobmccteeaaiOenrrembiebclp~osoaO,nenoUnlaseRabtnaEonntntStldydhy. *20TuTlalhoocthwewteeseeslrrieyncttcchl3elhualllYadnevvsdottlh)hliCteeaa~ggr'mm~seeCiqirvunnNiaiiu,rmlmuCteuudeFsmsmf~.woHwes,ceseaCreelleFlnt~evvV,erooyCrunlytaia~ggosSH euuenbbs(oa(siaftanaappdmnRppoLtrrCliaooa~elxxlFclili~y.y:-. ohoofrlCrggCsooaaontnnwhniiiecjcieoriissnItTttltaauowrrouuttsirsilnieennggceIcoanccacnooniommmnbpptbpoaroeolomunuvninmainddngdassgdece4atoannhrdodfeb1fooinnptvwecorsSoooaomtmOmoirpeernomgum cconaeuodsrMeers:sees. 35uuilm uthalhaeiartsrfeeetlflyloeueorxxo3fpiprveinensorrseeliistmcmse)evivenrenrntnletssqynuuiccdninoordengenecdcrlipluuIiosadostiieervvtnaegetllcleiyycoanonleddsndreiedamtm wittioihiooonoinnsnncstssho.tr.fraaamtxtHHeeeeoenlntteichchcneeee- tccholieiesninccwyys..ilolFFfrooerrs&useeloxxtlaaiimmntpoplnileme,o,pfrttohhBveeeineexgll~cctlhieeetennhcceoyyrpoceofarfatntthihbnee~eesileemec:.- susuuultli~cleilctlyieeennnotttftiteoooleccggtaeerunonesleyrerzaatittnehegeffrpreepoeertoedSfnlutuocioatrrliisionnnewohaafinocddhfuJyaooerrtetinaaerr-ee prptoSrorrroog"gvlTvaayehnensedidiisccbpbryossyofaitpanriaornctrtcliiStnlunOiudgogldiUnintnccigaOogofmnmspptprOrhoooofeupuphnlnoledoordxu.ng.iyiacclnaieacctchidsdetraaSrcstainna8gs~semeecucootnned.d *3*0 oscinuno~ln"ITI1tnaac6ail8arine1nenriivte(nnviCggiteheocuewwarrcrppbiabaaoueopsnpneeeRcrecotwwvomhrimpeieprtowotpusuer,nninbodddYbyssuoyt.mc..tmoieeo.anannonoddnfgpp~uulpbbullroiirissihhoneeterdod- oCocrviavmealTeplrrhosrrea.neelwlepaawintrtiidoitdvvpeeeeaorrrratwaatoionmotggnathheejeeaooafnNrnhytdyhdcdreI1ro~ooopcmgcreaaegpnnnnabnobSfeilceunuooooesetrfrtiihitatnddhreheetetercirncalg&aanunmtm miivviBoanaantooerr.Fy-ry titt0mhnoheeaen1aidn9ndla3ddiil1sSccsdou(ouavmCvmtemhemarreayaymrooriifoicfzfzaPetlerdthdahRpedeprpevreprnievreheviewaslossogeeu,uennssntvtllopyyalppr.nrpuood8ubcc)beei,lCsssisal,sh,odheneeIIgddnerrpbexeerfcfxipepeoheerrrrrrs0iete1-dod cLiinoinvAAmeoSv)splvaopreBrneueevovttnhirhitoeioeuonuseruullasyayaeetmmmeoaoaenfrnjntoytiggirooBeecionnnoaneeegm drdre,aa,:ptttotiihohnoIiintnessn1pptoorfrfofoofuccfftenerehsedseseseadmsdoe(o(onmelemutssoeatBilnloleolonc.ly-t. 3 vvmttshahoaereelrniivtooessauduoelssluiudnbibnnalonitolraiirtcigeiaoeasnsfny-iiFanecnnroeddaadnneeelddqnqauhuiuooaivvrdrgageaelaalhneennynniidatcternccodccogooonenCmmnddappuudfoocceuutuininenvvbdrdiiatsdsieeeshsdsdii(occs5.nf-f SrudFoeella~aalfccree)ietrreeeeddfnnnltutwwoofiIrirrrttiomohnhmmieoopsarrrpegtgoradaocanncweniieciyccstlsesCceh~sosoa,mmWgwpqephuo.hoeiueudrrnInhetdediysnnisdsfrfwwfroruhehgenieiecdcnh~ha0m uafaooerorrreenrilntiodadedelliesli1y=,s gp solved in anhydrous liquid hydrogen fluoride (p. 123 e 860). TheWeI-KJsnboroaiawryTpr.o: ~-23, et seq.). The well-known laboratory proceamdpilsoeysfor4 mseaesluricnagllcoprnidduecdivweihof pslaotinnusm cedure for measuring conductivities of solutions as2aacnosctltdivbiboeoyCdnnhzaIiinzncnootetnrnoiroeeonrd..dmuusccFitFxiioonneocgrgdrkawEtganahanissetyyeheroogetlugimi1qsivvueefS&ildnnuocmohicerryenidldliilermaoaugiomrnmekartnaoonongfogltteuhehomeemYreiOeTdnRonei..,t40frseteeeoemlaenctscpitutlrroboo((ysAddsiA.eeasCsnCat).aa)ionsnamddolfflaUul11elbt,il0l0lic0i0azme00eeilslsnccayytpa&ccelrloeerFssavsAopieDdoirtidermildlym yoodrowrrsreeeietvvphpeepeorrersspcriiinlsnszaggeetaicstnccooiuuunnormrddn.- aSCaeg6lnle0eodrmeraacen7ethni,aaataarbnnrgrdduyyinfSuaglbu5rhsoo0itvero0neicrnekeeww)s)hthuhiiiilscecthhrffaeoonmmrritmosmoeleealeeeddcccmufutrlriloaosnam rimrmsSfthrulhuuem eeoohQirhciynuynededeierlroov((fgcgofreielretnn:ee- 4458otarteforffoofodeidsccueecttsbsippsrtraaraoononnddddd.tusuicac1tptlot0olsslyaccrtiaeaoioutlslysm rreeeeFlvvnmmeaearobrottmteemerwwneettilinehtahthcraatirrneieloflaayydoccehhffeoposiarromctlmltaaeeeeprrrddeinazaatefettillriieeooooccnnnm:- fluoride, but the resultant effects are quite dtf= Lert omthose AIREinthe PTC proccss ferent from those obtained in the present proceas Sa cianTibceeeaisoythriecorgtDiicaaedl. vaWlue hrthheiecguhlelrVntihte: and can be easily recognized. When the cell volt= | tommm thhfeeeeennentltletesslceoettcftrhhtocrveedoaeidlCceiuuposarro8rgradleeeasnnfretifVtrtreIyseirssesrpapppotarrhssooeseSddeurduudr,cot:f[httesfosan.orntrIfItenenowaaccSse,huhusccmchhmaQepuaeexeisaxpnusfpeursreorreremit.5-- Uhfaougonnneresmmmetiiaitssstotoiriafafokifinafsaerebnevddleyyuetfoulbbtucyytoorhrii8taisnnheecm mefrafoiarortrriarkkmcm peaaeidldtaditvioAccaonhhlnnuaamdennmggapoeaeorlnwhiliIefninergeshhpbteiserrrooi,ddtedstuueehlcclet.ft 80. 50 vsAvam ecnenreerddyuynrtoohsafhftooltosferernn!atvlo8attoilimetfmfaeeeegwIfwenisrntsevteeceercsrordvovsnenuadsdslsis(r(ocseaouFdrrffretelaewewnceamt)smmi),,filplmnofoeuoweftr,resosoadttua8hhtcerteaiurmrnmnwwagrnioissosesateett CCrfcooorrogrmimmaoappnnaooitecossiaoifttcncioooonnnhmmdpeupsaoeonnuusddtnnoddf(ssirtrahaaigegnmmeartteanhhonpiecectaiacdttecuiilerotaallsnnln:;;dretees~xcpoeetiomceocewnettnssesigrdvvfaOoeeusBnlececodttoouhhersree--s85bfabfeoceorcPoouboobtrttatahhartieeiennrrveerrdadeeelauaddsseuuooseendnssfts.tooio.rhdehaeeCdauaetdinsneitrgneotidohfafntcetthhmghaeseptseeaelrtegacecttdturrroofeelsyntctteaeahnnanennolddtr rosion of the electrodes occurs; come gaseous arin scapes 4nd can be deected 1 ie cx fluorine escapes and can be detected in the exit n8d4 t"imirnoer vaendn Wehveenn p`marjor eIenxptsrlawcieeoansmnouctcu;r. gas mixture even when p~esent in trace amounts; p2vp6e4aa-sFp5ps6e-ree8c0rlr0d))((sm2Zn.at.hhhdpapaahehgttyyelsnttokhihfakeealayy.nl.deeCmmCChopphlalele-dooampcyy,nle.e,dabdAAtabaaciibhn.t.ccuAoAosm.tnn.a,ddatvuveulocodcoltli.i.vni11nil4t4Wyy6,th,hiScpbeceepipllhr.l hatSahSvhnoaaeividtinissmnagfomgaslciteantcooosurrrulyyebiasclyntaiddenlbatdseisavlenbnoonsDeffuunom mmbbfBiblaieiuoaejorooirronrrioitefonafdecaa.xtcatpeearddlribobosoinccnooonaamamsttpopooom omuculssncn1uddir0sns. 80 whsswveaeeearsrssvsvese&adetl opaupamlatspsateiioodrnnnneudsemoolecwfelcaencapcisptlIrrinlologltdadaooerre,lyy,1dt,ha-atupnnublddbaveeteheitenhexleuxet.omteeotnntdhhdTaieeihlnnrlreoggytae,ctlhlheelrcrwclootirhruuwooiggadcdhhshee Cctc"hoooenrITvteehimarreyi.yonpliperthnhrceageuasstletoeernnllsc.tiuaqpinnpurlnriaoodoocctceehhobssyysmesddprroiooosbgubgtenabeandina.snsseeeffdddcluu.auoonuprrbpidodooeennemBtsmoocylllyuuedttniidtooiilnsn=yss 4ta(m(haeespasammspsuarptaorlolexllppmipomeornennearteto.edlaaoxynnw1ddT.1inc.h33ocamiCnncotouttnabobtatlaithiectiehnniiyeeeennddceclv2hhme~e0epsy.s0ssl7.)e~olcy.wwcceho.hdT.eeohnnaofmelfmtaaecnsakreolknilluliaunnittwgoiionnana8gs `EMefcillooucecnrocietltirrarliooninnllv.eyiyo-cnzulcogeelondadntogttateraootgipaanWpirnhinnroiiocggcddhucucccocaaImeerrnbMbpofoaolunnnuuyonGccrdoogorsmmicvpcpoaeoaornubcnunoncdabnadsesssAr,e,aennhbebIddseyyocObiUouieensstnMlhiitnoesnelwgyrgr 85 csm csbucyeurerirriatrpepsehntiunietoorttIennm isswmooemefanf tad.oaadefnnecT4lc`uhelnnetaacaectorlobnetnbvhpyvyeehetnoyntthnhtieeeieoomanTnaapseabllcelsoeenylppnecvrrcderooeoccaeeoIflnddfteuuaabrrrnnneeayyaldtaaidaonnnen:dgd- tagEnheeoencncdeerlm merlaaittivtnniyiooioipmlnntme,a.uusgmome fwvVFFoohoolllirtrtcalahgescgxeehifanaorrmeremapqcWpnuluehy,ii,riceegwwddihvheeffeSononnprrecnurffassrrasiieeneinee~ngigfSsnlnouivibrcocoekkrilieioennltwla.e-70 bittitnhnhyeggeetntttthhothoeemaetiaob]rblrutriuntiiiddsimgmegeeeeed.oo.offtNfNooacctouTuthrterohrirlrieeennpnenggthtwowffhanlooaasewswnrssffeaaooaciirdrdefiasv1teonewyyrssuumgviggniisevgeteebnsnesattlsisattohlnhl3cuaaub-t-t CaaairtgneeohaastdaissesinenbbteetttyehheopeeeennsfareffaonoonnutfVgdnasec.sdoetotfl1ftlhhs0a5as-{ftto10otr0t8hh81Aweea3rvlr~vebeoloeciGqlhftauuaoggiotrteepeaemeeMsmroaviautsitdiifsstnetafbgacnbcteevtoJooriorlnsOty.~=,f,- | ptm mmumieoraosnpdstteo,a,aasm afSeetoAvvideeunnnnnintdeeterrwwvdevwhaahaeslsteso.nn.dmlBssEceeoaavavrcceerehrhdrasatelhsldoaolm mnwuehteialaeaossnnufuhuerhraweteadhm mtdeemsenmseniiteenrtsrasuvvstoeeeuwwdd~reefneriirat.eest cfr"rreeTeeahsfeBelumduooirtrinoinnieeamtggueelmneneafersaratatrtiei1oot0nnigteoocnccsc1uu2crressbl..elfvoorletaegveidTeonqcueirosfd 78 Sm pTuguegrtnpestotwswieooornarkknUdihhsaawdtdabdsbeeeledeenincsctcacoabormldmpeelpdralieewctedehd.e.AnTThTothuehserelreemsoewwfaeasssfu7rrnee0o-e The minimum theoretical cell voltage required suggestion that detectable trace amounts of free 11001100..00000044 STATE 07524634 STATE_07524634 , astnoes mmoolleeccuullaarr hh~yddrroo~geenn oorr oot~hheerr ealkeecttrroollyyssisi pprroodd-- Ser es reduced Toa mae ro ed Dakskh Bot eoAbant cu 1ut0oebtbseeewexxeprpeeecctptered~dsusicinneccdee.pprerTecchiisasitiooninloccnooonndwduecurtecivftiotiyrmmvmeeiedattlsIlyS-- SETTERS, es ree nh urement procedures are deliberately deldined to mn pes Se | SA| iroLaid pteSo &void the lrzever~lble production of free e]eciros hashe, Sh oi isBo oo Se trolysis l~roduets, ~s indicated above, which would rr Vie Sov 4 Pat ee mai Ti eollsume ener~3 and thus render the voltale-curESI i hin sel ih a eat So rent relation inaccurate is meislire of the e]ec- which - fluorocarbon oxygenor nitrogenatoms ptporosoisltiytitioeonnroeosfifsttathhneecseo,sloaulsutitwioonenllbebaiesinn~g~ltteteresisntteledd.t".heTTchhoeemsseeaauut~hlioorrss ssppeeccuullaatteedd aass ttoo tthhee m maannnlieerr 'o`off tloonnlice sddoiilssssvooecdciiiaatntiiotonhneoofaf ntthhhyeedoorrorgguaasnniliiccqcucioodmmhppyooduurnnoddgssenwwhfhleeunnoridddiiess,-aasnonlddvoeodnntinthhetehpeopsoassnishibbylldeefrofoourrsmmaliatqtiuiooidnnohofyfdrrreeoaagcctetinioofnnlupporrrooiddde--. uuccttss rreessuullttiinn~g tthheerreeffrroomm,, Iinn ccoommmmenetnitinngi uppeonn `ntnthihiteteuuddvveeaassrroiioooffuutssthhecceoolnnladatduttutceectrrtiiwvvwoiittuoyyulldvdvadaldleuuepeepsese,,nndssdiiunnupccpoeeonntt.hhewe hhaatt iit mnie at She iesl wputaesdri.who"TsTIohlilcssonhhdsa~udlctrriveeffiteeyrreewnnscc~ee aoocnntlllyytllyttoobessuulnbbissttmaanneccaeelss- foformrmeedd aa~8 tthhee rreessuulltt ooff ddiissssoollvviinngi tthhee oorrilzgtinn~all o`orrggaanniicc ccoommppoouunnddss iinn tthhee aannhhyyddrroouuss llkiiquulidd hy- ERE CLA LE drdrooggeennfflluuoorriiddee aannddnnoottttootthheeffoorrmmatitiioonn of fBrle,e oySe a a Pn `priorto adding te ary compoume A, consu> format or rare oxygen fi Ta ne i- a ai ove bs i. hydrogen.0fh)ta it otdo oh Batis ri Sonisisine a NL mete Sipe E- SnSe ies prelim. loarywter-remorraelat & ot eleActmmroeelryreesissscclipeeranottdiiffuiiccctscc.oonndducutcitviivtity determination Is Sereno scppicyed, exiess irvine, wh PTE ttySemin so To ed So Shan iL) marine Sand dala Sion Suara coatin1ga vile . nuuccotttssa ffurrsooemfmulaaprssoooclleuusttsiiofononr ooIfnfskaainss~tt~aerrltetiicnntgrlolcyosims pproo~dd- = whose conductivity is being measured, and the ok walesgut ci 5 wm. Brreinth ts M1 ln Soe ie thot 0 objectives are intlthettcal. It will be understood ne hedSe LS a WE mmtheearrtee nccooonndadutuctectm tiivvpiitttyyIsmmebeaeissiunurgreemmmeeanndttess..herein to el=ira me Cnty when vee omemeaebxropreaorriymSeansotcnsltshaprreaseentinpeectrot. laes the Fepyotion ocavweeer dhe When laboratory size ceils are used in perform- Ing batch experiments on the present process, the es TE Doofthoors gdenes rmis continue for periods of hours (geneiilly for aiy ter WL ULL cb kt ea a day or more). I~ikewlse the commercial oper- ation of the process eco, ea erring Caese i arro ation of the pro~es~ usin~ !~rge ceils requires ShonrkZs aenoJm lhcaim 3be eethdeve as et iBm electrolyzin~ the cell charle for a period of many yhyiioeelulddrsrraiatntiioooorodffeprprrtoooddouubcctttacicnoommappcooouumnndmdssefrfcrriooam mllytmhdeee.ssirtaabrtle- ES mmi E rR eImT e nen l vilE ed ue se 11~ Dlatcrlal, and a cell will normally be contlnu- Simi a |, BE he ae 2 propor olisly operated for days before being shut down, cena pi dees the hydrogen fluoride and startini material ~ SEERA OT EERE replenished during operation. Alternating currents can be useflllly elnployed . tn practicing the present process when polariz- edt CC Td a Eis Seas B5 reanne aabtilveeelylecloltorwwodferesqf(rueeeq.unge.cnocyyn(ci(ce.k. egl..,,e6l6e00cctcryoycldceleess)s)) and aarree. a relused. hhSENS Sri So Ha Bo rons lioPaane In this case each electrode alternately flinctions as an anode and as a cathode, but the operating SEE a fA rit Ly pcorondddulutctcisotsn~aatt.petrl~meilteetlchetcertroroeddleeesas..se Tofhefreuuesseeeleoofcftrddoiilrryeesccitst 50 Bu Sc. The Sadi ** rp ris, compound ay shan caAlulttreerrrennnaatttsiinnigsg ccguurerrraretlenyntstpiIssrsemmfeuurcrcehhdii.nnffTeerrhiioeorreaafnnfiddcieirnecayteoorrf ral ela hecane of cmi eal nd ima cao heating ofthe electrolyte Is produced. In the case of normal direct current operation each He t ood EeTd e tonceGRl (ach 55 E BrentR on we hcSi hesksen n ve ine t`ciaottnhsoiadasosessnuaunccsdhhaaatnt oaaduuennieiffloeorcrtm mrovvdooellttcaaoggneeti((nwwuhhoiiuceshhlymfyauynebce- * varied during the run for optimal operation), and Soiondntao SeERoIEfSnd p Tbir io i atthe ss ee ede ra the cathodes and anodes can be made of different illaterials adapted to produce the mo~t etllclent SF ars in nedI EAL THRmIEet A oEl aSnTILSR results. Pulsating unidirectional currents, un- fo it Hu ama Oride Seyi delved water in the mote thaa. 755 wich ary to rirosen Bama ere Tora pore of weir filtered rectified A. C., and superlmporsed JL C. 4aosnttDyypp.eeCss.o,ofcfdadinriraeelccstot ccbuuerrrrueesnnetdts..and are to be rel~arded AAsspprreevviioouussllyy m menetion nedt ,pl~uui rreeaaonzhihyndyrdoe rou~sdlliiqq, uuiidd prsSrey os we 4 rt in ai hysrore:Bunce to vh[ayrdrireotygoeonaf folurmgoaarinidiec IS non-conductive but a Zstuarrtiinsi ccoommppoouunnddss aarree wide ssoolluy-- pe ee ble therein and provide adequate electrolytic lecelocentcdrtrouolclytyizzviiinntgygcctuourrrrpeeennrttmss..itTTthhheeeslst~taa_rr~t_|nig~ne.g~cocofommepfpofoeucuntnidvdses re Re Be iHe ttohhfeechooixxeyyfggecenon-m-ccmoonnettraacilinnailtnni~gnteaarnneddstnniiinttrroto~hgeiesnn--rcceoosnnptteaacltntniinanri~eg oorrggaanniicc ccoommppoouunnddss wwhhiicchh hhaavvee aatt l]eeaasstt oonnee `hhyyddrrooggeennaattoom m aattttaacchheeddttoo a ccaarrbboonn aattoommiInntthhee re ni BehreeaHe aiorisned|1", BALle oid Todrn osen Buide ci ontinie onnal molecule, of which various examples hive lrea~ty 1nexcess. esabo Rates ot Some ora meus ma soctic acd, equilibrium mixture containing wat i `amount - capable formed 108 a or mensionadwest ay a necomconiy operating emctency, stnos itIsnot aye "added J 1010.0005 STATEo7szseas STATE_07524635 asteoms 9 9 proportion of sched we, asdsced bors, poses not ctrl ofdv Briain proportion o! dissolved water, as described above, 1100 proces~ is not an equivalent of direct fluorination in corey teresin oter eects rom Sreeks seyCHa Koof ho is also entirely different in other respects from ~roces~es but is an entirely different kind of proc- hd autos Shuions of Fyirore Sudo when Ss which dots ok Iv he ao evo the aqueous solutions of hydrogen fluoride which ess which does not involve the use or evolution re Snoe43d rs commonlyered10 Offe (BoO reRnd ThS ich poAde are sold in bottles and are commonly referred to of free (molecular) fluorine and which produces EE Spdroors acl. These. conestiaan produc minds hak Cannot onobi as hydrofluoric acid. These contain less than ~ produc~ compounds that cannot be obtained in Si elon of nose Bind ag normaly Samitcant. paperions by dest. Sucrimton 50% by weight of hydrogen fluoride as normally significant proportions by direct fluorination Sos. Bouh otboa Kep Hn a Or w0iBuhne: sold. Such solutions cannot be kept in glass or with free fluorine. ort Comair and If codices nto ceo. "Thesuahmecha fthh trolipnrgc. metal containers and if introduced into elecSa Such 1 ae a it resent roc. sn Tomei Toston. Tok vio sng bet trolysis cells such as are used in the present proc- The exact mechanism of the electrolyzing prOCo ess remains a mystery. The gases and heat i oxime, sl Gl ving AE 10 rsved heoohvent aiefo ol co ess (for example, a steel cell having nickel l0 evolved in the cell vigorously agitate the cell con- Sods nad vn cathodes) wou chs Tapd fete 9 that & miki of HtIsobeeerie anodes and iron cathodes) would cause rapid tents s~ tha~ a mlxture of the Insoluble organic Coroof tnhe metal saniacted nen In the saring compound hd the iui dioees Tae corrosion of the metals contacted even in the starting compound and the llquid hydrogen flu- eof cum fo, Weiss to bling OrrSecORAS sosPent ot Io de absence of current flow. Whereas the boiling oride electrolyte solution is present at the anode, Donte of hydroborc acd sloion contining | 4nd 118fst that oe xing conlions co points of hydrofluoric acid solutions containing and it is a fact that the existing conditions cause 30 gh of Regen Suara ox es se 15 hefrmaion of ors contac ato come 50% by weight of hydrogen fluoride or leas are 15 the formation of fluorine-containing carbon com- ne anaokf 00" heCr heSJ e n Poamat PosStoetooe in the range of 100 to 114' C., the boiling point pounds, including fluorocarbons, at the anode. 51 pr anhpieou lla hydofes oid 1s The sanducivy atime fal otspiral of pure anhydrous liquid hydrogen fluoride is The conductivity additives fall into two general S687E, tna' peeks of 104, byvatof| grove, oar nd rm ss. 19.5 C. and the presence of 10% by weight of groups, organic and inorganic. te see in Blin pon of oh SO. _ "Fhe ange Cony Adis are come water results tn a boiling point of about 32 C. The organic conductivity additives are com- The pacanye0 saute sales,1s: 2 pounds WBICh San EEO ot SRA The specific gravity of aqueous solutions in- 20 pounds which can themselves be employed as nse wih hes of ndnogn Tice OF, Baring GImpOuDAl, sha. RaDCos TMD creases with Increase of hydrogen fluoride from starting compounds, and numerous examples 0 s imum vas Of Root 130 shot haveabepenn ddistyTonmck Imp 1.0 to a maximum value of about 1.26 at about have already been indicated The most impor- Tos hyo Biol snd hen Teply de. unt are ihe omyBen-contlog ana momen: 75% hydrogen fluoride and then rapidly de- tant are the oxygen-containing and nitrogen- es oFLD1a 0 SRSu Su 13.__Coming pone smSohiht cor eah creases to a value of 1.0 for anhydrous liquid hy- containing organic ~ompounds which contain at Grog Suoride meae0eG3: Toecon. 25 oktcae pious si atacahcaerbdon drogen fluoride (measured at 0 C.). The con- 25 lea,st one hydrogen atom attached to a carbon ucivy deca8rtheehydarogsen fuorde per. Simof th motel, Thuasne ecules sre: ductivity decreases as the hydrogen fluoride per- atom of the molecule. Illustrative examples are Cag reas shone T5%. and EY So 8 Moe i, sete Al. POD a. a centage increases above 75%, and rapidly so as acetic anhydride, acetic acid, propionic acid, ca- hopercentageIncrease above $05 These dita bol acd, meh akong Gi thet, the percentage increases above 90%. These data proic acid, methyl alcohol, diethyl ether, 7 5 ners ux Showing Sad ld myogen | Sng `mie, Poon, and 3-bucropridine, are of interest as showing that liquid hydrogen ethyl amine, pyridine, and 2-fluoropyrldine, ride, so whch SATS S53 Rha i 50 which aveAL Bh Cove In DERE fluoride, both when anhydrous and when con- 3o which have all been employed in experiments {ain a mal rosoonofdiedvale as| Wheel hodiocaroon abi compoundsmers taining a small ]~ro~ortion of dissolved water, as ~herein hydrocarbon starting compounds were ose ie pent procs Sas TAAL Sovered te Boban and PR employed in the present process, differs radically converted into fluorocarbons and fluorocarbon aeG in physical as well as chemical properties from hydrides. The proportion of the conductivity ad- drome sla sionswhe oni res,GHWEinthePegen Bioca t TRACED hydrofluoric acid solutions which contain a large ditive to the hydrogen fluoride ~an be relatively Dioopf oatetr ainaowicnh cambaeoemt 3 Sm, 5 % 10 5%, bu mksNghe Foor. proportion of water and which cannot be em- 3~ small, e. g., ~ to 5%, but much higher ~ropor- Piped ntherentproces. oncinanea BS Br em ployed in the present process. tlons can be used. These additives are them- Foe Prcen eocs ht Hedtothe eof bes sorot piatieoftnhsg o The present process is not limited to the use of selves converted during operation of the process, ran arin oman Wh ae chil 3 An Bench GOAN chron Son organic starting compounds which are soluble in and hence the fluorine-containing carbon com- Soho ia nydiotenfords and prov Sond eset,pagar a7 Sve pr rom anhydrous liquid hydrogen fluoride and provide pound reaction products are derlved in part from Sichunte clelroyis sonaucinty pert of 40 Foo ali conduc Shivsnd Ir fom adequate electrolytic conductivity to permit of 40 the soluble conductivity additive and in part from ieCine cco. have made ME SUPE: th Houle ore. SARE Soo Th effective electrolysis. I have made the surpris- the insoluble organic starting compound. Thus, In coer thtthe acer Stross So. 1 Ft, Eea on sofSHA HARE ing discovery that the necessary electrolytic con- in effect, there are two types of organic starting icky ce be proiaea by id Sompomen compounds lec by Lh roca, oo bing ductivity can be provided by a third component compounds utilized In this procedure, one being ke which can oe sr Sut x mGPEAN, | Sin an Sn Gh 4 Sonus ~lute which can be either organic or inorganic, soluble and serving also as a conductivity addi- soit orgiesarin comWhpichaatn 43 Lvand heorping Intl. Fo hams so that organic starting compounds which are in- 4~ tire and the other being insoluble. For example, ie nthe Tala dont ToccarnbiesF when eran empoTod ih admire wih soluble in the liquid hydrogen fluoride can be ef- when he~rane is employed in admixture with Tey mpioed n admits wi ATS. lous Bodeogen Sura wh comin a fectively employed in admixture with liquid hy- liquid hydrogen fluoride which contain~ CroonmiTknridseasdeo.insTciohnaarne aofAtEeS1T6: SSoot demo merter d OtoUi rooedeg evanMsacssodonpiaonne drogen fluoride solutions containing a dlssolved solved pyrldine, both the hexane and the pyrldine cnmoeernrlidceucpptrrioovccieteyssssaggdrrdeeiataittvllyey. eexxTtteehnnisddssfeHitasstuvvreeerrssaoatftiilltiihttyey aagnnedd- %50 ccaaarerrbboocnnonppvrreoorddtuueccdtt cctooommpppooruuonndddussc,,e iifnnlccullouurddiiinnnegg-cffolunuotoraroionccaianrrg-- ines Thus f makes pois 1h 10 of Cone" Knghet coun of i seunle Sods usefulness. Thus it makes possible the use of bons. Another example of an organic conduc- Ty hsp rani compound, ich 20 Bo 10. ky wa8dmeee Sani ehh sr be very cheap organic compounds, such as the hy- tlvity additive is mercuric cyanide, which also rsrhons, 3 Sern Aare oe DOING Toa oralBorin omovistata eh drocarbons, as starting materials Ior producing lustrates organic starting compounds that do not verbens und Meoroasbon hy: Soni ese, fluorocarbons and fluorocarbon hydrides. contain hydrogen. pic of hydrocasion Sarin capo 8 i resortun ctiity addinsare fore Examples of hydrocarbon starting compounds 5~ The inorganic conductivity additives are frier= ich ch ot Cv CH WHE ORNS pscos a which can be effectively utilized when a conduc- ganlc compounds which are soluble in liquid hy- ivi sins caplord,aethe kanes bon Shores BaAoderosi Chev chsh tivity additive is employed, are the alkanes (both drogen lluorlde and provide effective electrolytic lend han) he smack: conbuaunky. Th sible Sacer. och ae so. cyclic and non-.cyclic). The aromatlc com- conductivity. The soluble fluorides, such as so- LFrouvnide.nseu,chaMononaeee Lahnd porboecneCpane3i0, SShuum SBuurekdleesundd puublensar Boorid,,ocanbbeetwoedd ,bpe~uenmdps,losyuecdh. aMs obreenozveenr,e thanisdptroolcueednuer,ecpanermalistos 60 danidumhfalvueortihdee aanddvapnottaagsesioufmnofltuodreicdeo,mpcoasnibne~uasnedd nof5a0m0d? uttmsboefrrof cutonsioCnosmpoutnhdestrTiAnTgE Dkkacnlagdcccoosstmeeds. Ammmoonina coaobetdBtolre compound. Thus hexane can be used for make Gun SCTE TE le of good yields of fluorocarbon compounds having not being consumed. Ammonia can be used but is the same ntunber of carbon atoms as the starting gradually consumed, yielding nitrogen trifluoride compoUnd. Thus hexane can be used for mak- (NF~) which is a low-boiling relatively insoluble a Boercatson hu oe prendre wh dis ero er as be sed id Bintg SC~uF1s4 S(teotruatdemciafulunoriotheaxsande.). a normalAly76655 ggaassaannddiiss eevvoollvveedd.. WWaat~eerrccaannbbeeuusseeddIinnlliimmiitteedd liquid fluorocarbon As in the procedures uti- ine hi mp sain dompouns fhe mount. "Theproorin ofwer inthe li lizing soluble organic starting compounds, the amount. The proportion of water in the liquid Ceising potcatas oor Haden a Rydrost Buoride oluln haul ot exceed 8 electrolyzing potential employed is insufficient to hydrogen fluoride solution should not exceed a PC i Wete smal prpboesre ithoerns threwilbe generate free fluorine. In contrast, if it were small proportion because otherwise there will be cis ha oan edinine Doo Cincy Ah i yd of deed Sm attempted to fluorinate hexane (as an admixture poor efficiency and a poor yield of desired c0m- Chiphocs te acd mrdroren Boarae wires T0 pounds. Elec risus an be ianed tone dispersed in liquid hydrogen fluoride) with,free 70 pounds. Effective results can be obtained using Sine the racio wou ba vot ont nd aa hi an 110 2% ofdddvata,The mer fluorine, the reaction would be a violent one and as little as 1 to 2% el added water. The water is armen vot Sh 50 vers hae wh Srahally comme, icing oxen Buonde 1ragmentation ~ ould be so severe that there gradually consumed, yielding oxygen fluoride Vote x no nial i of psc 5. (OF: cron loads (COR: ce andhe ho: would be no substantial yield of polycarbon flU- (OF~), carbon dioxide (CO~), oxygen and hydro- cians aod Si If ry Cie Soul cb | Gon ad mt he. rplenehed ing extended toarionceadr.bonTshiasndLlulistttrleateifs aangayinCs1t%ha4tctohueldpbreeseonbt- 7755 rrguuennnss,.. anSSdoommmeeusootrrggbaaenniirccepcclooennnddiuuscchtteiidvviittdyyuraaiddnddgiitteiivxveatssenaadllessdoo tained. This illustrates again that the vresent 11001100..00000066 STATE 075248% STATE_07524636 Droride water 5that h1enlvasackunly so1008 nvcives Suspended from the co1ve2r, s0as 0be cated otptpbireroetoothhvdaaouiccdorciierdegdglawaaionnscaiietGccdetorieanhchnsydyoAdddinrtinryhnaaoitoatrerertggdidatabdhnnbeeyiiyiccrhdahaurndiysddderdtwitoaraivpecoaeteru~s.n,a. lSfTll"uynulho~oidurhnruimviasddoak~eelsvcoettee:oo:s- iwbiihtkehicilene4ct5thre4oo4deu4PlaalcwlkehrcaaoanttshiooetgissnigeroeisfsJaosef13Irpneatetorfimoennao,nde8de 2aBhpw0oortal~oeatsderurmm,ncaeaPdlyyu~p~ruccchrceotthhoonicertrganaiinhnltlhus&raystaaFtdircrsmriaiimicatddvilanve,ellelTaeAxanhxumdamemompwDulpu~nelsetotsoestraorf,arftureaGiednvus~sdnesufsiooluafolvruivtcrerieoi.dsdoc 55 Cbpc~eA4aliIaatn0nhRtgeo4dOsdccaeaaatntppthhldleaoioteddaersenesp.e.plaaAallAa4ttnten0eredneT~xaxanaittrerirrneeetesgmi~mhheeb~ oooolwwuuent.tw,wttaao2h~ rrfeddhkiol~nentmthhoecoeerrdmdreeewpDepiciatalnhategtet~e.des HaatpBarcloniitdyilieceandwnagdoidddidncinpi.oitvhimvvoeepeesxxospesppuaheenrnoiraiddrimmm m isceewene"~dtedncsatris.adbeb.owoCwrvhoTehenehevhrhereaeaerivivtlnsleeeuBdasayhitllrdnyllatrdbtboeoriveoecSeecnaunaricerneabrormooernn:-- _10TW4bTehhppehIimeiecncwhgeddanttnhoooreededtahelaeatebtiipDeroaelnonataftebrebstysayhaneadarrlceesncrciorucoet~eousvsnAnibnserbieacbacrwilrteeeecdikdconoiamnadtnmhnn:cdeaedtcbdtodhhorraereswldd$iin1it4lg8no. PSsncEoitiaiufafrrlrcnbctbaodaionnnsnnsttgHaayicann~ovdeddm]isdpfRnsloutucuoohorffnerofdsofcscuaaulaslywmrbybeeMoorfunnelouhhurocoyimrdodnbi-nrainevidiadereteersoedst.fd,pedrpnIenrcocieohdnlhdiuvtodudocicltnntfa_glc~tcuooosorrmmions..-= |I0 1l$8Cw~.u.hrroliTyycTnhhtthhehtedheececococotTaan4norttsthbndhesoeococdd1otfe8ecratrsnhpp~iedlaasaprttrcl~aaeeaatsearts~retehmuaerpeJeoecip~nwondlneeeeedldddefebbntfdyyrro;oocradmomn1md0nanaadnncooidd|doeree epama 2 nsoeau.dtnehadefrsfrsrsheotoaaxmamrvaroitimoclnncpnttglggeacentnc.oeheo,e,mampasponadodumunenCCdd~nP.P.ati4mTATbahhbenuurddssCoCCfH~CIaucPl~a~.trf.fbhrhooaoanamsabtttbeoaoelemeu.nsn- 1156coCrccTneoOopcsvnTpeeedenc,ruc,tibctrivbetvioeeiecriylnnnyr.gg.oaIdintTnTshs!iuh|uelenlsa~asgteet1eeTmdrdaooctddhtaehssetrehrirbIoeae~adlffm ser,roaotcmntmorhdnrao~doenuuuuxdcgttehossrtreetnahhr)loeleesddcoaab!bld.Yy to"rinVveVilai.atryeryfiiaosoOdaruuddsedisdxittaiccivmovepdmelobsaeic.nnicamdaantnaibibnobenesveihoemoomffrppntpellthwoowcyaoyolseoeedoadr.trdmTmdoiTothrhrieuueoecscaocaonnnannnddousuborcr.ce--: s2nceeoT4Ttcncht.hcioeeoennncTitcerriesisolclTlnmbiincboacsoadduedteylyhatcto0oicandattgennhhenDbembmameeltce{fecrrrsoioooamnmlamv, eathdhenneeidenpnnpeoitoxilwcwytkeemeeerrnrlnas~naeadtrlcdnteceuoeoordyneo~fe-f (TgJdoaouiI~nnnlnptcyltasyoeaoemmdmdmpeiplctlocasioaysvpyseeeeeodssdan.t.nththdheeesasvenoilbinulnbdloeaercngcadcnonaidmcnuocautddlndvitcittiwyiveaeaddvdclsdawttinihtyvWbieee 20 |20 phspdUltlueecaacetatstle.oersraTarrIlororeetodssnsculchiipcataualaubabttlbhtlebeeoe,es,dAsmraemenanradddpvdoeleehtahodteoeebftscdyictrhhratooeennhs~dsabeabammnnarirseecTskmahmealnneeetdda~psi]anc~oiooned1na.ess- Dfofo(eittudhnhneeacecprprtiwepwioirniosnedsnecie:in4aasgsibnnlsuysa4opolslommiunaobublttltieeiuhlaaeoollkrriigsgsanooatlndlnvihveiaceennntsssdtttlasaa3erormttioiaarnnusaggnytttmmotoaauttccsseeaaeorruudmiiss)aaetellowAiantflnnoo,l 5 the electrode plates ser~od by them. The plates calsbocloselyspaced.& spacingGstncs epwoes ca~ be closely spaced~ a spacing distance between odf J5ace1ntanoocdhebaenindgcuhleets ectori ofthees oriner s~Jacent anode and cathode surfaces of the order aTrTbthhhheeeiieaGSpoohpppcaireecterraticaainoittoeaininGobdonlnnodoyoeofeossfstotlFthnuhoeboewltkeppriraAioopDnccptpeteeeshssaahe.,rressttstloiohecntcbecebteelreaoaurhlsnsnyeeeeotfschedfuebelssiosisilrraruetrnetsyy~iuntoolgtnteof,so o(D~peo(ml~-yocttooelrtrr~ayofdileinuncogthrormbeaettaihneyrSglieqainlueoi)fte1orr1~s~oaIt&alea~vnvateectrrntyonyrsagysaa.itt4sie"0satfdecanfctsletooeorrnr)y:y" n1on-tchoercroondidnugctmoartreoridaslffroormintshuelactoinvgeraannddfoe "atirThseehssoetabatrpraitriinnnigegcdscoonemmoptopwofeiuwtnnihdsn..tgand8icnogndtuhcetilvuisotlyubafdldlittyivoef 30 DArovindoifntgghaecgelalsk.et betweenthecorerandbody ins the conductor ro~ from the cover and provid!ng a gasket between the cover and body cSceraiavcenTeninnhlaeywoslhshoposernbhinbtnueectnihpeeeelmceorsprclrogr,ofaetynhusefdasdctifaIsnttogtoanIrauitnniicecnodrrgneeecdcahunoossceeemmttppiwathvoohiaeuuetrenneyeddfwftallfiidosidebocgsiinoutueficunnltvlcyt.e-y 301{|6lfhTel4eatTcnhDphagiipleepebleob.ofo1!Tttl21hthoheoihmcasaeocvolfilafn.vttgnhhe&bieacecvnevweaallelllg~videespdpr1!3r$oi,o,vuvni~ siddegeedoddfwpwofioertirtrhdhdaaeartnsn~iiuto_ontuo~-ntgr- sSrustiuocaccnrauhhttelieynrx~xapsceolicdloduimibepihlnoeot.u.dnsnrT~dohTsggtiloehon~asffctflMlisioiisomtmriihhcitteeomeelluddpplsfspdeounoldllbuduoeb1bilinwlultriehsttyheihydec1eiihsnwdceuiaanaotssnyheeniodono:uyof=ft _3_8 ddttorohTru~meohitnfcioeief~ntclKltgh.lheellciTccquehoaluililirdsdl.rcp1parrsonopddrbuuoeccvttussisdowwedbhdiidwccuihhtrshisneegtaltlvoeepte6rortatetthhiaoebnboloe.t-t ppdrrr"oooAvvuniisoddteelhiaenqurnideee~cxhciypldeeerndnotitgeeccnonontsndfdultcuutoairtcv/ih/dteaiynya.gnedtwhheicopherdaotniontg p&pirippToeeghee1[n|cfeC(uwlulchilcicdochveheccrcooiannsdnpneerncosctvsetiredtoosetdthhwehebibtohoottttoatoobrmvmeeodrtoeftisfctctahlrhlieebinoyhhdlyye).-t tfCfteaaeomvvAmmoonppprreoeoaartbburahllnateeedurtreSsee`ooowxllohupruribebeipdlplhrliri1teetesynysstsirpurrieeroselleoaoartttoroliirbyoocnnbo..hSotatnhTTgotehhouuctusseuoh~rieusabsreoeep~slea&ahlarsartamirtatovileirernnnleegggy 44004tgdac0honoroenudcgnale8aeenlccl.thcefslhtauhartioehrshrgeieiIidrrnnueecggtlLcooiAonnnhittlodeyoktednpprBpeseoiierprgerm meei~nitIht1S|o,,ooorftfhrhiyaiaiivvdnntiioettnrn,robggtodedhAauudecceVYiiosannacrglgrgviabefi1nennid8itoc)o EibbciRenneosDsmmompoalauodlidbunleeencerdmmnienuuawscclhiihhinqlmcgumiiohddohrerhiRetseyysddPoserroloooolumgusrbbleellypnneeffstetloohhulereorurrirbeeidlwladieehnenitoaalbbrtteyyu00rtss"euhurClCbeba.sstsemlitmovaaaaei,nnyly-..y Hseata2nhtstare.ra8itccinonTeclnghogldinctcusdohocfumetmacpilltpoviilqovui.uutintniydyPdd,ia,aphdadaeyendndddxdiirtatvoiavengeneney)y)dnowostwfhtlhdhiuheeocoirchwrShisndtuee1b5~,itnsattttohaononebctbceeoheep(reg(rpuscareuecnasc~ilhh:c- ebtBc"rilrlasTellYaahtlsyyeoeadiodfnfbcbynnrycoeoruarnssmimicianannlgglglyyotTlhoogpwewaaeemtssrdreetermoteoppueamsempirreccnaearootrammusbtltrpuns~ueoror,oueeusnwsnydh.d.diissslieegcaratnanhnmebbmeseafogtilninu.c-- 4485 1w8wea3enSel8stluu.nlffbobf'ecTireclilmiIooena~wwntltttidhhdnOieeilspsemtetstaarrunnapfrctcfiaeipeacoecns5e,oeooxtfttfthhhfeaetanhthrtdeee(bsiytslsidlquoolumolwwiwadenksersiorionnleeltugunnoitddio+otwnhlwnieiltidluullcuirebbrd:le-el scsciehalrcTerotrrehiyniteoinna"naaglTglchoocceuuleloetedmvvrttpaahhtaatieeniwooDypninrrionooonfgccfgeehwassdnanssrasaIianlwbenldidesunsiaeatglalnrsassdiotosiiissvaeemeerrdiaavvlppeehapsPsgeaaaravrda~seariabatninuSmfsatolttofhwoiwoe:-crr$0 4SiaTne0enagbdhdL.1ein3sopIIscratpem1aclisslcaedcelldodooorcttephachreteeererrad1eastftaiIirornolnomFfm,orr..opothrnnetotrvoeofi~bdytehhdemewaieeklteikhncgter8ovadderetlTipiqacaucacilkkd PsfsiJlhnmaaoettcceveakktrriee.eettassssgttcaaToononhnffddevcecccondolvatrvaeseriarirtowitiynlnynsnggigssbbo,,yycehcoaooousummprpileibltiptietrnnieieggnnnsssgge,,sneikthhtmaceep.tael,itiao-afanlninsentdaadsusboiilyycnaentoetimmmghn.-e~ 50 ttoCGhhuoueelTptclldheeecelheetnllsl.pnc,eeiwiwrPlhleehi1ci8cocI1~hvh,l,ecocroffconooiannsrrenedaecrg.lctaasatsssosbesotooptvoouuretosstvhhLppieehdrreheoohdyddyCududlwcrclrtot.iosstggheTeeennavvhooSifvllalvveuoeerocoddtriiicnddiIaneenl mpmao5epolprn7nopiIylamelireyrnanrgtutiusscsseeoddnaaavnsiisennansss.sthhccicooohawhwnennanmelaiiumstszsieesscoduaccirht1bheaeeipbmmrlaileerccsfsfaaeooellnrrrtddalrafrtaabaoibwwooroiinrmrnnsasggtbaissos~.eerycyeeTToemxhhmxa..-e,, 86 CDGcdcoeooeoronnlAeldsabaeneinrtnrBthesha.leaisrTqsduuhi!ai$ddeeJplfAfaooiocccrrprkmakemetetaad1i1Iine8|ttax~ntbototonetvippn~eaede_rrs~timmdhaiaoenidttwoedcinosefefsilniclir.crneegrirddoceTullatoIloh~watwetiitcLnceo~noemnogma- bDupTpelsoleoeeord.,rytceemsddAellnfnfatlooerasrrrgdpgeapeoiincldcnooootmmmcmpomalelernaarrnecccatckiiloasaooomllrsp~pismlImlaeaatlllnxllat-lrwwwsgioceoanaruuellll,edfeadocaanroeemmmcccmmehebseeemesrmraacirecricirlaaalaly=syl|| bpfG{doogeet0rrrntmma%eotermuororfs~esh.&ohosaforpTtrtsithphoreioefrafapfcllitfoPhh~oneeeodrb!re~bobnbtoetesetxotteottmteremsnrt,d,va~heheanseednraeadodltwmm r1tnaras~aiysnmycttboo~ebneeretsrh,.e1ieancciTTtotehhhhndeeee-. babbehsanesgieiidccinedpesrepreirirgisisnnnnwcecwediililppnlollueneunsndomdeofoefrrrtssethtthaeacennoddtmi,,ipnlvvbbeeuautnxtttwiwilooioonunnuellss,addsssaeisiimiblbclsoohutdsedtyanyrdtattctehhaedeeld bottom of the condenser vessel is connected, 8{roughvalve 8, withthetoresidverses ini through valve 2|, with the aforesaid vertical inlet GDiimpmi1e of tdhaecel.uTkhinsoptrecutr.h mliidcsa pipe I~[ of the Cell. This ~ermits the liquid con- TppaiaadrnRrRoadaeedttfdtuueeewsssrricrtiriiIhisnnbtggetahdht1ce.eoocnttelhlhlecieeccntdtrgrrraooavJlowiayisscnniksgsgec,,ectetlhlhlleehhaIhIe,,veaiwawnhrrhgitt/aeocohfnhfttithishsiepepartrpoo-:8o5, d2~do1ewTtntnhosoa1ettnt0chthkoe9etopoortorefdehfaraUecatcvhntitneioeosrarcbclvavoc,eenksoswdsieshenulitsnoc$1e3~hr,t1,IhtidssethhcAceceooletneinentlun.udebebcwcenettieeeetddxbxstbtye3eyntndt3ueduid5blne%~eg 2va3a/n5nndda0deoaa)qlucqtuuuwwtleeihleoiettucthsh4s4aoisffloscoluxorutoptifliuoloiomonnwnwpgoooefoJffdfeatceatahktchehcrotyoeoolouln2elagnaenhenhtagttgvlllhiqeiyenqcolguolilJddaaoocn((rksmemimutneecoalhhtetnathhds= Y3testdooos0oedsw10eiiunlsmmiIiinnnh,htyfioyeturdrtrrohaionxexibicccvdooeeeeunssessn~oxeeeoitclc,lueiutiewentiddodohbinnibn.cy.yghtTTdtuihusohbbewefeenifltliao21ep5ipdootw oaotfihttttthhehhheeeeaYrareederuaraieescelo:rr 2Ftara4aense7rco1etylr.0oc)ml"meawAadhnniitntiohcthparhareoiorianuascgtahihpnuddgaeemtsspr riieererfeedrddicmtge coehelrpr~aootuopeogpgerefrh(rra(n5attnt0thoie aihe%tnnsgegtsJthhaete? colouemkwgmewpnhptr)ev:e,raoreanras:-d.o1T?00Tp0TvpoeolhtstiasasetsslvYshieeZuesw4m se,eF)tlhhahiyesysfddftrloiuroloblexexemiddiidedwwxexeittitpetuphhnerede&lalliaendtitigssr,,lind~ofnoogggrwrrmnmeraeeriemmndeutoiioousnhvmt,rihn,oegsuwuvcgwacehhhsla;tateaaehslsr. Tgh cthhup~orereoera.dcatoteoio iAffloo0nn0nhaoia.Cspt.esIrsuiasausbtbrcscisteontamnagnovonttetveiinaaaminbllpellleneyyrtvcaaaaoattntvmnuemdcderopeersppenpeihrhrneemmwtririhhikiteistcscenohpopeffrricsengesasihlssnabmusptoPbrelrlee,e-e,| 3hhf1raaT,oTvvm htiihhnneeteggthtTtoevueoapbgprloeaveosfefeetox$3thu~t,h.senem td0oditirtnxthilgeteiuedrer1poepisrswr~ oonccddoaouunnhcnnecteercccscotttoohneendfedddbreeehnbyntysheseertktorruuvoubbvgereeehs1nes.Zhe|:l,l, Bolted 0anoutwardtop angeof The cell has a removable cover S bolted to an outward top flan~e of i #1 mate. which can be tl~.~ ~L' ~. 76Ths (ube Ga be Spiraled so 80 0JmprorsBes 2~, the tube extena~,~S down short of the bottom. ~5 Wh.e ~u.b~ ~t~ b~ ~piralled so as to improve he~t 11001100..00000077 STATE 07524837 STATE_07524637 trnatr, Thisvse 1i3roviedwith a pemoavs.100t0h8esodium hydroxide1b4ubbles for amoral of transfer. This vessel is provided with a remov- 14 the sodium hydroxide bubbler for removal of Te aie lr cooling uke 3. ormainaining dun Rydrope Audids fom, th Ene ask: able liquid-air cooling Jacket ~8. for maintaining residual hydrogen fluoride from the gas stream. he Conder very low ampesurcieent Oxogen Muoride (OE, foraea whe sit 1s in the condenser a very low temperature sumclent Oxygen fluoride (OF~), formed when water is or Condening ow Such Ion Tolling product Drscnt n he tery seven ofthewl cs for condensing even such low-boiling product present in the electrolyte solution ~f the cell, can Co 3 cam ro teap iuerides (CFO. and bsremoved rom he $23 Siva by Dubbing compounds as carbon ~e~rafluorlde (CFO and ~i be removed from the gas s~ream by bubbling raion (CRD out IAS to condense thou an Tues pots SME le so fluoroform (CFaH), but insumcient to condense through an a~lUeOUS potassium-sulflte-iodide so- heaccompaying hydogen: ion contained I & reactor vessel owed 1 the accompanying hydrogen. "Ine op af ths concenser s provided wih an th tren ahofethwerde, Whennitrogen-con. The top of this condenser is provided with an lution contained in a reactor vessel included in the train aaxead of the drier. When nitrogen-con- cuteSb 3, ha&vgive J, frconducting {aiing Sewn. siacing. ompouns ses en outlet tube 29, having a valve 30, for conducting taining organic starting compounds are being hehydrogen5s oth as rier 31, th lair 10 processed, the gh trai wih nia some ro: the hydrogen gas to the gas meter $~, the latter lO processed, the gas stream will contain some nltro. Being ted for TeseuTng Ios hydrogen rode. Gensnfuorde (NE. Tiasbl ow.boling being used for measuring the hydrogen produc- gen trifluoride (NI~). This is a stable low-boiling ln The ute tab Is provided with a pranch 8 4nd anbe Sgarafrto ehde PROBE CO tion. The outlet tube is provided with a branch gas and can be selmrated from the product com- Sb 31, havivanlvge 33. which conoentshe poundsby ractonation tube $2, having a valve $3, which connects on the pounds by fractlonatlon. Sosasde of ave 6. During vormal pert. Afuriher sheroative i o remove trhesidual upstream side of valve SQ. During normal opera- A further alternative is to remove the residual om valve 16 and 8 are. open Sn YAS 33 13 18 raafcmyderogse Buorie (rom the 3 sires tion valve 26 and 30 are open and valve ~ ls 15 traces of hydrogen fluoride from the gas stream sed. However, vais 25 and 30 can be closed avin the ren Rurids condenses by poss closed. However, valves 25 and $0 can be closed Sr vain 33 opcfowhitehdrdaw the condemsete in threosue Pgackhedwihsium fords and valve $3 opened to withdraw the Condensate leaving the hydrogen fluoride condenser by passing through a vessel packed with sodium fluoride Compounds, he ar bing Tporied op warm. peli It 1 hak neceery 10 remove COs, OFs compounds, the latter being vaporized by warm- pellets. ~[t is not necessary to remove CO~, OF2 ng the aban ofthe Hava ies on uring an NE rom thesu trem,andthe i of ing in the absence of the liquid air; and during and NF~ from the gas stream, and the use of ns pero the gaseous BroGuct from the. cal 20 aRueDispuriving sunscanbeomiied. The this period the gaseous l~roducts from the cell ZO aqueous purifying solutions can be omitted. The canFe divested fo an alemate recover Systm Eas sires fromthesod oriceves] can can be diverted to an alternate recovery system gas stream from the sodium fluoride vessel can ou Shim i continous cell operation. Is 0direc1ttlnyproduct conece in a case (not shown) if continuous cell operation is in go directly to the product condenser in this case prose The wAnGraUn produc can be od 4 50 31 heeded The CO an 433 OF progress. The withdrawn products can be led as no drying is needed. The CO~ (and any OF~ EF mctcns tition yes (ot showy and NE presen can be separsied from he to a fractional distillation system (not shown) and NI~ present) can be separated from the {or sepuesting he Yalous radict compounds 25 productsbydilation, This proce1dsuesrpee. for separating the varlous product compounds Z$ products by distillation. This l~rocedure is espe- Thc pn formes BT ef when esc ubrocarbon dora. which have been formed. cially useful when reactive fluorocarbon deriva- "Tnegaan misiore crise from the cll wil tvs (sich as Auceocuroon 204 Aucrdes made The gaseous mixture evolved from the cell will tives (such as fluorocarbon acid fluorides made Doral ConA som, Sdroten Maori (Gvap. frm CrSGADIG Air are comin 1 Lhe #0 normally contain some hydrogen fluoride (evap- from carboxylic acids) are contained in the gas Gratedih th cuinactto hydirogoenanndfo heen orated in the cell) in addition to hydrogen and to stream. Soule Brine-tonaining chron roduc com 30 The rinlpal zon vlatile prodofuncetrs volatile fluorine-containing carbon product com- 80 The principal non-volatile products of interest Bounds I ah xyien-conAmIng rEanle Sart.are GublIe the hydropen fuoride detroit pounds. If an oxygen-containing organic start- are insoluble" in the hydrogen fluoride electrolyte opcompound s rmpioyedthis willAp estin tution And ede0fe Drm afth cll roma ing compound is employed this will also result in solution and settle to the bottom of the ceil from ht formationof somoCOs.TheIydrogenTuo. which {hey can be Grained The imei the formation of some CO2. The hydrogen fluo- which they can be drained. The immiscible Fd Comdence 1814rantained a treats Maud dred from th: col may chu ner. ride condenser ~8 is maintained at a temperature liquid drained from the cell may include nor- OF out etn 40C. andserves 4condensuet 35 mally sod. coupons disor Were This of about minus 40 C. and serves to condense out ~5 really solid compounds dissolved therein. This i of the hadron orice, which Ie Thien Haul cn be wed wih peu nydroride most of the hydrogen fluoride, which is returned liquid can be washed with potassium hydroxide The call. "The other consisuents of the ga Solon lo remove traces of hydrogen Macrds to the cell. The other constituents of the ga~ solution to remove traces of hydrogen fluoride mixtie are subsuntaly soluble 0 the Ha and hen fractionally dled. Sotae product mixture are substantially insoluble in the liquid and then fractionally distilled. ~oluble product Eyirogen force coninate 4nd re cared materia which remain in he decronis ohn hydrogen fluoride condensate and are carried materials which remain in the electrolyte solu- alo fn vaporphase 1 Gs hydrosen ka src. 40 fom can be Tesovered. by dition. oon along in vapor phase in the hydrogen gas ~tream. ~0 tion can be recovered by distillation following apie fom ty Heber boing Torine-contain the run. Some ret comps (of Intere: Vapors from any higher-boiling fluorine-contain- the run. Some product compounds (of interme- 1a carbon product compounds formed in tho cell dite veabty wil bo reaver fn part rom ing carbon product compounds formed in the cell diate volatility) will be recovered in part from 1 Ts conde and sel {5 the ce; Such the Easeous misture cvoved fom he ei and will also condense and return to the cell; such oman i he min kingto th boom of _ In part from, the mmbee had wn + compounds in the main settling to the bottom of the gaseous mixture evolved from the cell and in part from the immiscible liquid which is fore 45dato toe the hoor of theGal the cell. 45 drained from the bottom of the cell. "The sodium hydroxice rescor 22 serves to o- The bod of the lacrosse can be used The sodium hydroxide reactor 22 serves to re- The body of the electrolysis cell can be used move from he go ca ry rtdunl FF and 0 a atmos, hing Gomme 0 the cathodes move from the gas stream any residual H:P and as a cathode, being .connected to the cathodes "any Cor Uhich 5 rest The drt 3 in the sal. o, ke penal prelrus, cun also any CO~ which is present. The rifler ~ Servs to remove wae vapor which tas been | Simply "float: ht bing electrically Connesied serves to remove water vapor which has been ck thereac. Ths Buorocasbons nd 0or grounded picked up in the reactor. The fluorocarbons and in the cell, or, as is generally preferable, it can simply "float," not being electrically connected 50 or grounded. Otherfoorine containing carbon product come Thecathode ments do not need to bo made other fluorine-containing carbon product comPoti are sepia rom ihehydtopeh by bong of tronar cel. Any mall Condusing Tate: pounds are separated from the hydrogen by being The cathode elements do not need tube made of iron or steel. Any metallic conducting mate- Troan out Tn the product candeer 2, Tom ial whieh reise the corse acin of he frozen out in the product condenser ~, from rlal which resists the corrosive actlon c~ the Which thay canbe WEbrawn in the panier al. hodrosen Borie soion ca bo wid, clu: which they can be withdrawn in the manner al- hydrogen fluoride solution can be used, includ- Tey indicted 55 ig copper, mages, aur, Mok), hel ready indicated. 55 lug copper, magnesium, aluminum, nickel, nickel Other means can be usd for separating the lov. ei. Anode cements cai be made of Other means can be used for separating the alloys: etc. Anode elements can be made of Dyrore from the IIe gaseous produc come lek alors a nel 2 of mike,o of Monel hydrogen from the purified gaseou~ product corn~ nickel alloys as well as of nickel, or of Monel Donde A concer Cooled by % mixers of eta, icon Garde, carban, 6 pounds. A condenser cooled by a mixture of F06-GO Su sceons sun bo incited ahead of "Tei ro cathods nd eke ads, operat solid-CO~ and acetone 9an be included ahead of {he uid condanse 1premioartycondense 901g call Toles In he nie oi 5 to 8 Yoke ave the liquid-air condenser to preliminarily condense metal, silicon carbide, carbon, etc. Using iron cathodes and nickel anodes, operat- 60 lng cell voltages in the range of 5 to 8 volts have out the iehorbling product sompound. Tne bec found Sener tans fo most Scent out the higher-boiling product compounds. In- been found generally suitable for most efficient Sind of ig HOGA condones he gaseous Tess, wh 3 1 8 ols uly ben: (heahi ~tead of using a liquid-air condenser, the gaseous results, with 5 to 6 volts usually being the opti- mixturecanbecombrtied andTOBAfo mum. Curentdenseos RED 8 20amperes mixture can be compressed and refrigerated so mum. Current densities as high as 20 amperes 5 conden out th prods compounds. This, or iEher pe ure foo of anode rarface ase as to condense out the product compounds. This or higher per square foot of anode surface are San ho fn Sova) Sage 50 a tn st con: 65 avainab. S0-smpere cl avin abot 350 can be done in several stages so as to first con- 65 obtainable. A 50-ampere cell, having about 350 ee" out th lk of he hgher-Sling om. 50. In. of anode race hae rove ae sin dense out the bulk of the higher-boiling compoanudthenn, tdalsowes iemperaaorre igh. fatty fo genera borat esearch We and pounds and then, at a lower temperature or high- sq. in. of anode surface, has proved quite satisfactory for general laboratory research use and 2 Dresre (or bah). condense out the remain. permis of Tika subsania) aunties of er Pressure (or both), condense out the remainfr rods compounds. The hydroseh cam also| product compounds for shdy of properties and ing product compounds. The hydrogen can also Be separatec by chica meat, 43 by pasang 0 for preliwinary tne crauston. The compact: be separated by chemical means, as by passing he re rou beni copper oxide. peso th ceeper i of paver1sanadvan the gas stream through heated copper oxide. permits of making substantial quantifies of product compounds for study of properties and 70 for preliminary use evaluation. The compact- ness of the cells per unit of power is an advan- "The sloesid During and recovery Siem taeous eae of th proces. Operating te The aforesaid purifying and recovery system Bain wid spaton bk an be madly eds Darare i the ante. f about min 20 to has a wide application but can be readily modi- tageous feature of the process. Operating tem- peratures in the range of about minu~ 20 C. to CohldordideeibunbeblePoarnebexHaermaepndAlq1useeoiu,secbaelfeourme 70Dolss T0E0CC,. havepepraturresioofgyAvbeofufeec0tidvCe.tW2i0iC. fied as desired. ~or example, an aqueous calcium 75 pthluiss 80 ~. range, hteamvepeprraotvuerdeshiogfhalyboeuffte0ctivCe., toW20ithiCn. chloride bubbler can be inserted in series before 11001100..00000088 STATE 07524838 STATE_07524638 seaypermit 5 con1ve5nes operationa4 aboeut108oductsat weful rt1e6, nd recovering oa r~tdlly permit of convenient operation at about products at a useful rate, and recovering one or ince peescure Gi bing, book Of bY. aor Burin Soialing Arboncompoundpo atmospheric pres~e (the boiling point of hyL roger corde beng 105 C.and be Ted i of oe proves: drogen fluoride being 19.5 {3. and being DMsed more fluorine-containing carbon compound products of the proeees. 7 ficied comapndiapetcs)c,oo. Inorder t furor rate theinvention by by dissolved compounds), and the necessary cool- In order to further illustrate the invention by canberealyeeced: & speci examinthe Lollowing abebs resated ing c~n be readily effected. specific exa~nples, the following table is presented to undusioo, however, that the ta. 12s convenient summaries of the rere 1 It is to be understood, however, that the in- as a convenient summartzat|on of the results of reninfs resid 1 tht Ta Condl: large umofbsupeernra, Thisaiels2k vention is not restricted to the operating condi- a ledge number of experiments. This table is not on mold above. Desappropriate Codiions Intended ses aro compote ha havebees tions noted above. Under appropriate conditions intended to ~et forth all compounds ti~t h~ve been Col valnge a Tow 8 abotJo lt ca beld had rc be ad, ond asrvn fo tention cell voltages as low as about ~ volt can be used. nmde oe-can be nmde, and ~rves ~or illustration ile DiesSelvoltagesthan thoe mentioned 10 rather thanNation It Jae & coGAb W3Atle higher cell voltages th~n those mentioned |it rather than ~tmltation. It lists a considerable En Sh in oie hrumance without pumber of ert Biine-consinmg. carbon c~n be used under some circumstances without number of different fluorine-containing carbon amine Tre urine seseradon, AranGuments produc omponds hich bave ben made 0 ns c~using free fluorine generation, arrangements product compounds which have been made by this ling cohvoltgte hob exceeding TOS are procs ro subi ova sins compounds utilizing cell voltages not exceeding 8 volts are proc~s from ~oluble organic ~rting ~ompo~nd~ uch ected io th uoof 8hahet Toads dorvedin sanydroun ui drogen Succ much preferred since the use of a higher voltage dissolved ~n ~nhydrotls liquid hydrogen fluoride. Teas atmuch eperes isbina JsIn. Over 15 Bolingbk values for ehof thecompounds means that much energy is being lost in over- 1~ Boiling point values for mo~t of the compounds Coming cument Bocking conditions 5 the cl ar ave th band column. Thee ae 5 coming current blcoking conditions in the cell. are given in the left-hand column. These are to Vide ante of operating lemperatures and be fearded 1a approsimate vanes. Many of A wide r~nge of operating temperatures ~nd be regarded ~ approxin~tte value~. ~ny of prembeisploered This emperaties toes aloe ert Gearing a about 40 procures can be employed. ~-T~us temperatures these values were dete~rmtned at about ~40 ram. 500 lous 8 C. and higher than its 51 presur and hav nok ben coveted fo Sand: as low as minus 80 C. and higher than plus 75 pressure ~na_ have not been corrected to stand- Raveactualytne iedin experimen. The so ard condition (10mm taA.e henc, e we C. t~tve actually been used in experiments. The ~0 srd condition (~60 ram.) values, and hence axe eine onof ure Rogenfuride a minon *0 Romeo over (1103) hen the ner Tis freezinz point o! l~re hydrogen fluoride is minus somewhat lower (1 to 3~) than the latter. These E57 a werfeinpl volts when compan wee separaidsdcel denied 83 C. and a still lower freezing point results when compounds were separated and clearly identified icontin dolemater Thisthe BAU by pope) nd chepienproper. Th 5Be it contains dissol,~ed material. ~'hus the liquid by physical ~nd chemical properties. In all nec- sae of Tila hydrogen Aoride soutions can aetycass te content of Huang hud of other state of liquid hydrogen fluoride solutions can essary cases the content o~ fluorine and of other be mania at yer low bmperutres "Ten 25 Don: asbon cements prea vas ried be maintained at very low temperatures. Tem- ~.~ non-carbon elements present was determined by Deratures ianer han about 30C, generalTloy ** Snail. 20m chs wherS corpoundoaf the peratures higher than about 20 C. generally re- a~alySis. Ill some ca~es where compounds of the ui opertion a supeadmershirl vapor pes. Same sie or of. un Analouous erica bad Bre: quire operation at superstmo~pherio vapor pres- same series or. of an ~r,~logous series h~d pre- Sir 2 rer io leat the ming Don of the viualybee Suaiedavd anid, was nok sures in order to elevate the boiling point of the vionsly been obtained and identified, it was not Suton." Howener, the Pecesary prestire can Soneidered necessary 5 chemically saul the solution. However, the necessary pressure can considered necessary to chemically analyze the 2 inne4nd ven afmosrpehaiereiacb 3a product compounds or SuamblguOts 1c be minimized and even atmospheric pressure ca~ 30 product compounds for unambiguous identifica- De lied py Smolin ls Which mAkdly Co ihe pha 4 Chemie properties. to be utilized by eraployil~g solutes whle_~ markedly tion; the physt~l and chemical properties, to- Tower th hydrogen, ride vapor Puce 85 ester with Knowledg of iheraring compound lower the hydrogen fluoride vapor pressure, as gether with knowledge of the starting compound Bo Gavin poiorasasiniBiuordemIn Spore. bein gai suBiettochinedenne by dissolving potassium or sodium fluoride in employed, being quite sttl~cient to enable deRulte Hativy Tare proportion nthe Tororen __ {denihesion, In some ches Gervais were ~elatively large proportion in the hydrogen identification. In some cases derivatives were Turkle, Superaimomheri el reine Are 35 made and isnt, furiner coroborsine the fluoride. Sul~r~tmospheric cell pressures 3~ made and identified, further cor~oborating the iedIn SomecacestoTain the Staring Menicaofttiheoconl proce Torared ab needed in some cases to lnaintain the starting identification of the cell product. Infrared ab~ Copan lla pha or to brevent Tap sop peesdieminheavte ieeonmnadse cenrpound in liquid phase or to prevent rapid sorptlon ~pectra deterxninations have been made reevep nthouge h lowr opera , lene om arons erie of hee combounas tSUTDY evaporation, even though a low operatinz temo on various series of these compounds to supply periseimplaoyend. ThisIsspeciatlraleiyn further faenifeation coroboraion. Several perature is employed. This is especially true further identification corroboration. Several he cae of ow-boding starting Compounds WHI 40 compouwnedrs salby tvh Feass pein the c~se of low-boiling starting compounds which 4@ compounds were aDallrsed by the mass spectro- A deth n i ronTrice. gh eons are not dissolved in the liquid hydrogen fluoride. graph method. Rr thane bas 8 "Undertheing ofcachproduct compound To take an extreme illustration, ethane has Under the li~ of e~h product compound Lubin podofmos EaC 6almo. hirls tates tadI te oben a obs of re boiling point of minus 88 C. at atmospheric there is listed in the indented cel~mn one or more pressing eos toh ol mes persed 8H ue ring comp onvic at pressure and hence ~the cell must be operated at Hl~-soluble ~trting comlx~ from which it was 0tvaid preti order to matnain cians 45 em "aadtcoem an elevated pressure in order to maintain ethane 43 made. No attempt has been made at complete- 1 ania haeIntecal 8 LempeatuArbeovse pnLn er specooncata in a liquid state in the cell at temperatures above ness in the latter respect--thus carbon tetrafluo- ivale Fide (CP.anaSuorotorm (CHAD,wespes this value. ride (L"I~,) m~d fluoroform (~"I~H) were presum- It beevident framtheforeolag descrip- abyproduced in SutaamliSxspemlenyts It will be evident from the foregoing descrip- ably produced in stlbstantlally all experiments. tion That hie ventionpertainsto & basicaly a produc compaunasare hosewhichwerere. tion that this ln~entlon pertains to a basically "fhe product compounds are thee which were re- iw wri proces In hemany ansBoks er 1 Gey oes een in To er new unit proces~ in chemistry and is not a mere :~ garded as of particular significance in the ex- Dives tor proadParulcucar pofe com: Jarimnts an" the Tied `Mardis compounds process for producing a particular tYl~ of periments on the listed starting compounds. Tota trom prt typ of staring mate. Bonsselon cuspounis Ma pesdoent shia: pound from a particular type of starting mate- Some starting compounds have produced signifi- fab Practical ll reuse materials can be con las of ioar mors os of spo, rill. Practically all organic ~terials ~n be cant yields o! two or more types of compounds, lied 33staringCOmpwhoeuORr 0,00 5 or exam. te irshaves bh utilized as starting compounds, whether or not as for e~amlxle, the eth~ h~ve yielded both fluo- `5porlo1u2vibdueiedswhydrogen Buide, ainrdoc: 53 Tocris a. Mucrocasoon Side, 1h. armies soluble in liquid hydrogen fluoride, and the proc- 5"~ ~arbons and fluorocarbon oxides, ~he amines general etd by Which Gey ae slid fully eriaated igen contain: ess provides a new general method by which they have yielded fully fluor~ted nitrogen-contain- Gnbe transformed into 8 freadvaritoyf Logcarboncompu ell 13 Buprocarons, can be transformed into a great variety of tug c~rbon compound~ as well as fluorocarbons, rinconialning Carbon brodut empotsds, ing camo sds pave vist Moorea fluorine-containing carbon product compounds, the carboxyllc acids have yielded fluorocarbon rE er tig including many novel compounds not hitherto mTpaiwl nyster yom. of hessproductcompen haveben, and wl l~e by any other process. acid fluorides as well as fluorocarbor~, etc. Most 6{~ of these prodtlct compounds have been, and all present cvaesnetiotnhe1sbeamspilcgoyeende,rsapmrncc,iltwhaoeftthse O0re,eB0dl6bct,cprooducmewdiphhaovetbhuteyepn,e uodndsll In all cases the basic generic principle of the present invention is employed, namely, the useful Sirchenical preparation of Auoie-costain: Bas bon swnrond 1son. electrochendcal preparation of fluorine-containnk carbon roduccompounds {rom fosatabe _ Decien with he araving, ulin rn cathodes ing carbon product compounds from fluorinstable of them could be, produced with the type of cell arrangement which has been described in connection with the d~wing, util~dne iron cathodes Crean siariagcompobyuenctdrysan,g for 1s55 2d mike!Anodes wd cl voltages bow 8vols or~nie starting compounds, by electrolyzing for ~ and nickel anodes and cell voltages below $ volt~ ein nt 07 2 Can operaing temperin tth unreeh a period of hours a current-conducting mixture D. C., and ol~erating temperatures in the neigh- Sos ben oricesone wy a or. borhoof o- dThesolouftbheelsare of liquid hydrogen fluoride solution and the or- borhood of 0 C. The solubilities of these start- uni saring mere (other Glare of og. 156 compounds anhydrous ud hycogen fa ganic starting materi~l (either dissolved or ado ing ~ompounds in anhydrous liquid hydrogen flu- Fie which i fre from water 1mor than Ode 840 G: peti ne of lating Soutions ntixed), which is free from water in more than oride at 0 C. permitted tree of starting solutions emul operon, tatereratur an prs TO conta ular bout. 1 10raib wel a small proportion, at a temperature and pressure V0 containing at least about a 1 to I0 ratio by weight SURI 3 a stateis maintained830 a1 45 | of heFartingcompoundtothe hycregen fo at which a liquid state is maintained and at an of the starting compound to the hydrogen fluo- Sacro poenia] Whichis Iaruicient to TideandIn Tany cast SUATADLghYer electrolyzing potential which is tnsut~cient to ride and in many cases a substant~lly higher emeraiefre Bcrine underWeexiningconde ratio AsAckualy Used.ThusInsamo expert: generate free fluorine under the existing condi- ratio was actually used. Thus in some experi- Smut whic mien 0cueheproduc. __mentewok sce ck, theGiaamount hee. tions, but which is sut~eient to c~use the produe- ments truing acetic acid, the initial amount there Moa" or fuarine contain carbon compound T6of exceededtha ofth Bydroeen Suri. t~ of fluorine-cont~n_~ carbon compound 75 of exceeded that of the h~drogen fluoride. 11001100..00000099 STATE 07524839 STATE_07524639 " asinsen g,519,988 ng [rere c meos Flourine-Containing Carbon Produt Gompouud~ made from the under-li~ted organic eompeund~ 1Lieoo oo im [orgiomEy bo i 10 re 18 Flourin.e-Con.~lning. C.arb~on. Produ.ct Compound~ made ~rom me unaer-~ea orgamc - on LL CsF.OCsF. (didlnde~fluoroemayl ether) Cd~[.OC~Hn (diamyl ether) | C,l~lzOOsF. (di-trid~flu~ohcxyl ether) C~HzzOC~Hzz (dihexyl ether) |r 3~ C~F,~ C F~(nonafluorobutyl-tflfluoromethyl ether) - C~OCH~CH~OH (ethylene gly~l monobu~yl O(CffiH~OC~H~)~ (d~e~hylene gly~l dibutyl ether) |e ECE OF,OOF,CF=OOF, (de~fluom~ly~l d~ethyl ether) -| CH~OO~0H,OCH~ (1,~i~ne) --78 |CRA, a. iy ey no L E EE t . Ji --2. 5 POH Cuties | gaa Ine | Eh e e, i Ee 5| 2 L-- i aE - EEE 82 104 = | Ea ege CCE 127 12~ - "a Tn 143 ia --78 --52 wes --83 a Ee EE LL aees - = -49 ae' SJaolt2 -1.5 Je. --16. 5 , |r oa --59 TEE i 101 w . = f ir tone ~] m-~nmuuor~my~ e~ner~ " C~$OCH~CH~OCH~CH~OC~ (~lethylene gly~] dlethyl ether) .... 81 C~FnOCF~ (~d~n~or~c~ne~ ~uoromethyl owoa0|[|~owPqhougrnRpS cEonecnnso,R mmeanrL teasss --4~ C~OCH~ C~FsO (~fluorote~ameth~l~e o~de) C~H~O (~methy]e~ o~de) C~F~O (de~fluoropen~met~ylene o~) C~H~O ~ntame~hylene FCF1 (hezafluoroProPyleue oxide-l,2) OCH~CHCH~C1 (epichlorohydfln) 25 C F~C 0 F (trifluoroacety! fluoride) CH~COOH (acetic acid) C~F~COF (DentafluoropropienTl fluoride) |e Ee C~H~COOH (propionic acid) G~F~COF (heptafluorobutyryl fluoride) C~[~CO011 (butyric acid) iE C~F~COF (unde~afluorocaproyl fluoride} Wo p neB ae e - 30 CsH,,COOH (eaproie acid) C:F~COF (~entadccafluorocaprylyl flyoride) C~H.O OOH. (capryllc aci~i) C~F,,C OF (nonadecafluorocapryl fluoride) C~H~ COOPt (eapric add) C,FnCOF (undeeafluorocydohemuecarbox~Hc sdd fluoride) ee] ER tse 35 C~H~COOH (benzoic acid) 0 - | E REE E 4O " Ea 45 oG mIP|hE eaEEE Rs E an (CtHu)=N (triamylamine) 11~ CFa):NCsFn (N,N-di.trifluoromcthyl-undecafluorocy- 50 clohexylamine) " . -- (CHa)~NC~Ha (dimethylaniline) 165 (C~F|)~b~F~CeF~] (N~N-di-pent~fluorocthyltEdecafluo- zo cyc-~oh ex-ylmeth ylamine) o [oo EE nt (C~Ha)~N'CH~C~H~ (diethylbenzylamine) (C~F~)=NC~F~ (N,N-di-pentafluoroethyl-heptafluoropro- pylamine) EE (C~H0~NC~z (diethylpropylamine) n3 (C~Fs)~NOdF~ (N,N-di-pentafluoroethyl-nonafluorobu- tylamine) '. (C~HD~NOdF~ (diethylbutylamine) .... wr |cS RR seasons 111 (C,F:)~NC=Fs (N,N-di.hcptafluoropropyl-pentanuoroe~n- "= EEERE re 108 (i-CaF~)~ N C=PI (N~N.di-heptafluoroisoprol)yl-Pcn~,lluoro- ethylumine) | cm (ioCaH~)~NC~Wa (diizoprep~lethylaminc) 159 CF;(CF:)~SF (octadecafluorooctyl mercaptan) CHa(CH~)~SH (oetyl mercaptan) om E pee ee Many of the product compounds lis~ed in the Many TE ~ foregoing table have not been disclosed in prior publications or patents and are believed ~o be Bem novel: Some of them are claimed as new compositions of matter in the followin~ al~plieations SE of which I am in each case the sole or a joint ocean sos fo tie ora 70 applicant, and which describe their preparation by the present process and give further informaFA erry tion on their physical ~nd chemical properties, SE EEE R ERREI viz.: Ser. Nos. 29,955 (filed RIay 28, 1948), now abandoned, 38,751 and 33.752 (both filed July 14, Ss eduy 21. 150, S47rh ~5 19~8), 39~999 Lfl~d July 21, 1948), 48,777 (filed oro 1010.0010 STATE 07524840 STATE_07524640 aston 2,519~983 September 10,1609 O811c Bary 10, 1949) ~Ie9 154 (fied. 10, September 10, 1948) and 70,154 (filed January 10, ar Am Sot omen boar euce van 1949). 8or. Nos. 38,751 and 38,752 have since Is- tds btini oe 34hin and 3apo ormaatea ow |Poerge | Qact et) sony |PEP sued as Patent~ Nos. 2,490,098 and 2,490.099, dated cut Fstehiopialih Jatoad | Re December 6, 1949, and 8or, No. 39,999 as Patent FTIR ted Shr 1 1h . i -- No. 2,500,388, dated March 14, 1950. 8 hi ning ons a vat on sont * | wns | | [OE i The following examples are based on actual 1 ..... expen es sv te Thi pv I I 5 experiments and further serve to illustrate the ~2 ..... or mene 37) huss] B| 2 invention. Additional detailed examples have ~ ..... Er oh ois ren spies: B| ioc EEE E been set forth in my aforesaid parent applica- Ho Be Sead od tad wd | HE | Bowe) 8 tions, Ser. Nos. 384,729. 569,265, 628,434s and 10 Ens is tens mis 5 mde vols fee| HE b| B[RERCL 677,407, to which reference may be made, but ha 17 ..... aren a hy To en an 82] HER] B| B[EEm the interest of brevity have not been set forth tt en Fo] eR] S|S| in the present specification. Boiling range, --133 to --48 --48 to --42 to --41 to --39 to --~ to --16tO ~4 to -42 -41 -~8 --4 --2 = Quantity, Mol. we. Identity Fowrtm. ula pure temp. [CF~H ..... LC~F..--..-. ~0 1~ Intereu~ ............... 80 1~ ' ...do ....... ~0 185 ...do ....... 188 7O 170 C~F~H .... 170 165 Iatercu~............... I~ CtF~Ht... 1,52 150 Residue............... Samper vil dentfa thedone le hate Example I 1185 ggaasIsteeoowuuissllmmbieixxtetuvurirdeeecncootnnftrtoaaiminneetddheaa allbaaorrgvgeee tpparrboolppeoortrhttiiaootnnthooeff To this experiment use was made of & 100. fuorocarbon compounds having hres carbon In this experiment use was made of a lO0- Iluorocarbon compounds having three carl~n are Geoca ass oan sl Sneha, STEN: BRS, Icarom ampere cell. The casing was a rectangular steel atoms in the molecule, i. e. C~P~ (octafluoropro- box naving a removable steel cover slate bolted pane), GIIT (heptaduoropropanes and CoPetl box having a removable steel cover plate bolted pane), C~I~H (heptafluoropropane) and C~I~Ha ements th cab, TonSender Pn no to the flanged top of the casing. The conductor (hexafluoroprol~ane). ER Rie 4nd i to th coer 20 ERIE i ty me charge rods were insulated and sealed from the cover 20 After several runs using this same "charge aeBy ea of "Shr (pSp mbes Che (woe ssn fo a plate by means of "Saran" (polyvinylidene chlo- (without replenishment of the butyric acid) the Fas Cong wins 40 CHE I heh a a pen Ce er bra ride) tubing, which was also employed In sheet following materials were collected from the gas fmste tere a ee SY ARS esp form as a gasket between the cover and the Cas- mixture: Boiling below --38 C., 1141 grams; at Tine Bt neds pies of ike md Ito HG. te rane beeen ing flange. Eight anode plates of nickel and approximately --38 C., 1988 grams; between ee nein ie ee bt ro wre 58 Tr CS ame wares UH ea seven interleaving cathode plates of iron were ~ --~8 and --17 C., 182 grams; between --17 and arc a the diane ben Sn+ 8 Cia ni se O31 used, spaced so that the distance between a~a- --4 C., 1183 grams; above -4 C., 9~2 grams. SE tins was 0 aR. Te Cain Son he clare cent electrode surfaces was 0.29". The dimenSonor a we 0 1x he La so ke i ne sions of each plate were 18" x lllA'' x ~td'. The Sin Steen teot ano padputts es Ske ana 1 hn mend distance between the outer anode plate surfaces The residual solutk~n in the ceil. after an extended period of ek.ctrolysis, was found to contain 2.27 kg. (5 pounds) of organic material maT cal wale way 140 Ths cl Gog 20 Shs somone 5 3 ons and the cell walls was 0.40". The cell casing a0 which contained abou~ 40% by weight of com- Eas chai Semin dnd ws SR Dc ome Th nn ab re served as a cathode element and was connected. bined fluorine. Thus non-gaseous lluorine-con- oe hh ate Foe At DAES TAA A Ae coho comShen mb by to the cathode plates. The anode plates had a taining carbon compounds were also produced by ating ot 21m LA Gh), Sains A CompoundstsA total operating area of 23 sq. ft. (21,400 sq. cm.). the process and remained in the cell. ot as anid 14 foetus arnt OE eres hae Send the fr The cell was maintained at a temperature during Other experiments have demonstrated the for- nso a om Tis Cp 10 6B 55 mie ovr oS ra operation of from minus 5 C. to plus 10 ~, by .25 mation from butyric acid of a substantial yield ne hs Ea Tend vin line means of a chilled brine bath. of C~F~0 (decafluorobutane), having a boiling 7 Ch 40 he GOS Soto ob 0 ha ne This cell was charged with 4.45 kg. (50.5 tools) point close to 0~ C., as well as ether compounds. Cad are 0 pounds and i he Asrecrion sd a oa of n-butyric acid (apl~roximately 10 pounds) and including the fluorocarbon acid fluoride com- USoeEaRToLsTIhorde eI AL1 0 ne aet : wi~h 27.5 kg. (13q5 reels) of commercial anhy- pound C~F~COF. drous liquid hydrogen fluoride (approximately 61 40 Te re Tn mst ir pounds). The applied cell voltage was 5.3 volts, Example TR biota sv an of 190 ae which produced an average current of 100 am- Sere ene ee on Sark bh A smal Ibaratry cel was aed. Toe col peres, the average current density being about A small laboratory cell was used. The cell To soy Ti cemrens SF manof 4.4 amps./sq, ft, body was constructed of a one-foot length of Ee a a mare trom the cell wa con 45 Hon Pe (6 Gmies ROVRE sn hon Ma The exit gas mixture from the cell was con- 45 iron pipe (3" diameter) having an iron plate utes rth Ls 6 Sn he cm Ann ducted through a tube (connected to the cover brazed to one end to form the bottom. An iron RS Comat wh of HE Tod CA i as SS tn co plate) to a condenser where the bulk of the rhsad ad pe ah Boo and SXUred Spmtoay te ea he So was condenser and drained back to the ceil, then rod (~/2'" dia.) was brazed to the center of the bottom and extended upwardly to near the top. Ee Vt ite ve. Toe poe ana hie cer sok costes os through a sodium fluoride tube for further re- The pipe and this center rod constituted the oo th ash BoA Bode 0 SEI, RA ron coe Bie a SAE 0 3 moval of B1=, then through a potassium hydrox- 50 cathodes. An ~iron cover plate wa~ secured t~ a ar temas Gay Ems WA SE over not re oneh ide bubbler to remove CO~ and any residual flange at the upper end of the pipe. Through Cn Morte oi. ine camer to ives pate or ano some a potassium iodide and sodium thiosulfate bub- the Center of the cover paa~ed an anode con- men OF, os condos ote pn Te led nd A he bler to remove OF~, a liquid air trap to condense ductor suuport rod sealed and insulated there- orn Sompeynas, ahd Aly wh ire toThen vis Fema cnr of hh the fluorocarbon compounds, and lastly a wet from, to which was fastened a cylinder of sheet 5 ees for esr nSh Gheny of Ne: 10 as TE dl suroung oe rn net test meter for measuring the quantity of hydro- 55 nickel (1~'' din.) surrounding the iron center ES Tok min he part Be eh gen. rod and forming the anode. "Saran" was used Toe materials collected fn the led ar trap on ein A GRkCHRE An Soh Be The materials collected in the liquid air trap for sealing and gasketing. An outlet tube was ame To Ch ATE Toa a ofr i ow during a ~ortion of the run were transferred to connected to the upper end of the pipe for with- Ee oa veer Th woor hva, rain rae roto: To on va ced a gas homer over water. The weight of this purl- drawing gaseou~ product~. The cell was cooled BE FT eked use 10 i on Le Sot tn ata Sosa ess fled condensate was 745 grams, produced during 80 in an ice bath to maintain an operating temper- Rein Frid af 44 es wh 39 a re ye mr oC an operating period of 54.4 hours, with 232 fara- ature in the neighborhood of 0 C. roi se Ts me vis ci The cell ys chars ih 0 grams 12000) days being passed. This material was frac~lon- The cell was charged with 400 gram~ (20 tools) BE nt sb trea of pomirea Sohpciom Tab odieen Fone ated into nine Dortion~ with yields as shown in of commercial-anhydrotm liquid hydrogen fluo- ou oe Ros bhi of ha _ Sie 53 ran 1 ml ot sme and 5 er the following table, Molecular wcight~ of ~he ride, 0~ grams (1 reel) of toluene, and 5 granm {rion ice hc by ws po deny (6330 of SAO Seer ST nor fractions were obtained by using a gas density 55 (0.~ reel) of ~dded water, serving as a conductiv- ne pin i h5k gp dr ahi. To Sas was aly nc balance and applying the ideal gas law; they Tt aprotie AUNE ise fa So in he mires Furie ut bk resent approximate weighted averages in the ity additive. The toluene was substantially insoluble in the hydrogen fluoride solution but be- in So soe a Sopra Saneadie outs vn pei case of fractions boiling over an appreciable Eo Tr veh men so (aio ma Beni proses os Saad 11 am range. The weight amount of each fraction was canle adinixed therewith during operation. Eleetroylsis proceeded at 5 volts and 1.1 am- ed ron Lo Fe fF poem Th 0 pert oo pod of a3 dats, dhe en obtained from ~he pressure of the gas when the ~0 peres for a period of 12 days, during which 88 i as Sotomoveers A rece1 oe of ets oe vod Shh nds I en fraction was allowed to vaporize into a receptacle liters of gas were evolved which yielded 11 grams mn wi oro ee pe Toe, of coneaatIe: SO a rn oe cn: of known volume, ~l~l_ving the ideal gas law. of condensate In a liquid air trap. The conden- he ct wa ineof CF CR 45d etewa ning foi 53 am pv sl The first cut was a mixture of C~4, CI~zH and sate was distilled to yield a 0.5 gram portion boil- OF kar Cos comic of uO oe In bo 0-008 $a poo vie Sh C~1%. Other cuts consisted of rol~t.ivel.y pure hag below --90 ~., a 0.5 gram portio~ boiling at Sete compeani as ho Shot 7.450 Pinas Tach 14 Mngle compounds, as shown. about 0* C,, an~l a principal fraction of 10 grams 11001100..00001111 STATE 07524041 STATE_07524641 DE porerFoometembI pertatucroeo.vn3v201i5 iwaeo100e8 rong 21 boiling above room temperature. The latter was 10 smalcopper st me nhl smdwas redtstilled in a fraotionating column and the folTowing fracicnswere sparse charied wih sec aca and KPSHP in the lowing fractions were separated: A small copper cell having a nickel anode was charged with acetic acid and KI~-3H1~ in the Weight (grams) | Talo of 11a 34byweight, Current was pused " Weight (grams) ratio of 1 to 3.4 by weight. Current was passed Botingraves C3: Thrpusntneclafwho voltand amperes Boiling range (o C.): 5 through the cell at about 8 volts and 9 amperes faois STITT 16 unio fumduvs had pamed The apersion was 57-60 .......................... ~...... 1.6 until 6 faradays had passed. The operation was Gonot ITI NG Conducked at wmonphric presse and a me 60-63 ................................ L6 conducted at atmospheric pressure and a tem- Reais IIIT BE Geta averaging 15. This apersing pres 63-64 ................................ 3.2 perature averaging 75 C. This operating pres- 07, ufrre. wduee fpo eheelotw veaportphrecssrurieeodf tthenco:n Residue ............................. 0.7 10 sure was possible, despite the elevated temperature, due to the low vapor pressure of the com- g[Tnhe65S -84 C. fE raction hE ad sTR OeCA uYHAr paleof mpolteium P fuerde aR nd RirO ore fuT oiee, The 63-64 C. fraction had a molecular weight plex of potassium fluoride and hydrogen fluoride, of 383, corresponding to a 7-carbon fluorocar- which remained in a non-boiling llquld state. toTni=tonfgtuheosumre caoa trhcremaan-norcgiaeons,mtoheefnnortmsa, The Broduct iciuded Fs and CEL The products included CF~ and CF~H. s "3Sie erimen, wing cell charge of Using the same cell arrangement, the forma- fer ee'shcToa Snhadrhuadllcivet,wais vUintg mya:19sn seeses weeIP in he bi or} oy tion of fluorocarbons from n-octane, using wa- 15 sodAiusmimaiclaertaetexpaenrdimKenFt.,3HusFinign athecerilatciohaorfge1 toof win $9 pareema(n7s5iEmaeod. i33'ss weeighi, wasScoenduc wer SIA Gon ter as a conductivity additive, was demonstrated. 6.8 by weight, was conducted under similar con- of commeria anppdros auld hydrogen Tuo. The cell was charged with 550 grams (27.5 reels) ditions and wlth similar results. Fie, Teo yams (14 Tl) of pecan, and 10 samc of commercial anhydrous liquid hydrogen fluo- ride, 160 grams (1.4 reels) of n-octane, and 10 E2e,ample V Grins (06 ml of sdded water An Secs 20 tsa was made of an ron laboratory cell con- grams (0.6 moll of added water. An electrolysis 20 Use was made of an iron laboratory cell con- Broceeded during th G00hour in Dircd, tot] taining Aker anodes and rah cathodes, pera proceeded during the 600 hour run. period, a total taining nickel anodes and iron cathodes, operat- oF agitiona rusosf hosiorenMork 4nd in a Wmaspheie bres sh imperiu1m of 440 additional grams of hydrogen fluoride and ing at atmospheric pressure ~nd a temperature:of 0 rnof wsate were added from me oe 0'G The ltl 2 charg COmSst of F500 60 grams of water were added from time to time 0 C. The initial cell charge consisted of 7,500 afoinTeptehneiaconndtuhcetihviytdyr:ogen cre and to man: Gras of highly Anhydrous Had hodroeen fo: to replenish the hydrogen fluoride and to main- grams of highly anh~cdrous liquid hydrogen flue- The col oiaee Yared 26 Fae an 100 prams of iedPlane aeaionsl tain the conductivity. The cell voltage varied 25 ride and 71}0 grams of dried pyrldine. Additional from 85 fo 17vos 4nd the cel Current arid viding wat SAGE urine Ths man {ne from 6.5 to 7.7 volts and the cell current varied pyridine was added during the run to make a 1in.3ThToerruoinoagns opfu1s5.10Fr5a0chaonmaotrioen. foal of Lal of about 3000 Sram Tox Wiles em in the range of 1.5 to 3,0 amperes~ A to~l of total of about 2,00~ grams. The pyridine em- et mire Gomonsried. Of Be DTO%= popes was. ared ov Soh ek Mpdhore 47.3 faradays passed. Fractlonation of the prod- ployed was dried over solid sodium hydroxide Ditane had bon (1 Ines (AtEhaRt) hCOemVErReIEnSa1l0 |3 2D0adoutheofy fGo Hmt, Camneeowmesepas To uct mixture demonstrated that the original and then distilled. Current was passed for a Ea rads octane had been (to a large extent) converted to ~o period of four days, at an average cell voltage nuoeroicanrbowniscComip.oundSsu,bstoafntiWahlich more han of approtiiuid4y, A orl 1 aradanas fluorocarbon compounds, of which more than ylds of OP passes one-third was C~1%o. Substantial yields of of approximately 6.0. A total of 447 faradays was pansed. an"gIhCupFrweoredwuoif fcbualtraonicadro,bonns "The laud cll product mixture was drained and CsFz4 were also obtained. The liquid cell product mixture was drained us 11Gorie expenn{soimnGgeSme _3_8 Tfroomothespeoutso)m oHfY,theAnac.el,ShtseSdaSOwiRtAhILSnfo The production of fluorocarbons from n-octane from the bottom of the cell, treated with lime to di was also demonstrated in experiments using am- ~5 remove residual I-I~, and was fractionally d~s- Tron arcu crane. and Tin, 35 Sn. WiadToate Bhs iain Shek 390 seams of monia, mercuric cyanide, and pyridine, as conGtoiltay, iitoivne,of mTn:ectahereabccyeannciedeoffntwhehyB:aiplirae CrIaPAcNiEo.n (wVhiRcGhNwAaTsHJOaTeOniNnDeEdIaINrenting ductivity additives. In the absence of the n3 Bele octane, a solution of mercuric cyanide in anhy- tilled. There was obtained about 250 grams of a liquid fraction which was identified as relatively pure C~F~sNF (undecafiuoropiDeridine), a cyclic rots qua hydoren Ruoride Yieied CP and Compound Raving the 104owInS TeSsarod pro drous liquid hydrogen fluoride yielded CF~ and compound having the following measured prop- SR vs sbleced fo cal poten of About 40 eres NI~ when subjected to acell potential of about 40 erties: 75 vols, and wih he eration OF fee TRE om in (ut stout 740 mm Ce 48 7.5 volts, and ~ith the liberation of free mereur. 7 Refracine index (ag 200 C3 oT 1aat cury. Esample151 Boy mec e200 0 Example III nce of tho te disco I the preceding 1 Surienon (mse. 843C) 138 A cell of the type described in the preceding exile wa vd vin 205 Grams 3 mols Molec weight (from vapor densi) = 305 example was charged with 205 grams (5 mole) oF acetone (CHC. sna 785 grams v3 Pe cemt UU aad of acetonitrile (CH~CN) and 785 grams (39.3 ok of anhydrous Nua hydroten uorde Per cent N LLL 4a mole) of anhydrous liquid hydrogen fluoride Boiling point (at about 740 ram.) .... C__ Refractive index (at 20 C.) Density (grams/co. at 20o C.) Surface tension (dynes/,cm. at 20 C.) .... Molecular weight (from vapor density) ___ Per cent F Per cent N 46 1.281 1.744 13.6 285 73.4 4.87 Siatcerh. I"lGuarnrensownaasipnuedsa&dSfuosrtiaeinG]uycs eA4OF 20 THh yoates'for (t0h8e pPuUs ccoommppoourntd a00cceallultteed (which initially contained a substantial trace of The values for the pure compound as calculated water). Current was passed for five days at an .5~) from the formula are: molecular weight, 283; Sroka e3n7 voefoe8s5 aamnpemraeisneThecchoal wGooike Sexva:te BPiponmtT.19I1L: oErseSntNNA46, average of 5.5 amperes. The cell voltage aver- Per cent 1~, 73.1; Per cent N, 4.95. bing hi ve aay period Floorocrhon som: ,00nPrI, aged 1.7 volts and remained close to this value Other products included 2-fluoropyridine, povins were foie fring the emire un. 50 Copan ae odecsfropentane) during this five day period. Fluorocarbon com- C5F~2 and NF3; Is formed by pounds were formed during the entire run. The The C~F~2 (dodecafluoropentane) is formed by Henne products included OFs CP, OFv 55 ciavoatgthae sing bmmabon ah29Beat identified products included O~-h, CF3H, CF~, r,.~ cleavage of the ring (eliminating N) and fluorine GPE GF sad CRON. Felacemeat ond Addon to prodice the sate: C~F~H, C~F~ and CI~CN. "The Gi and CIC appeared 10 form an 120 cn chats, Subktaniahy Sl of the Cob The C~F~H and CI~CN appeared to form an aseoropl mistive and separation by ASSIA ume frre ygiine Is of the aoumel in: azeotropic mixture and separation by distillation {Yiotiongh scoped, Ts isk raclon hain pe. A highly pitied cumple (ovianed wan not accomplished. This mixture fraction replacement and addition to produce the saturated open chain. Substantially all .of the formed from pyridlne is of the normal; straightchain t.~3e. A highly purified sample (obtained in the rang f --T3 to 4 C) VAS c {ram anther experiment n When Pyrioms was (boiling in the range of --73 to --48 C.I ,was ~dt) from another experiment in which pyridine was chemical treated to enity the CRON In theTM Lie) `having moles weigh varus (ater: chemically treated to identify the CF~CN in the used) having a molecular weight value (deter- following way: The pricous mixture was PISS ined Trom vapor denis) of 8, in Asroement following way: The gaseous mixture was passed iGhr3vi0gh.SO saucous polasum bydronkio st wiih Lhe Trims NWR of 30. 4nd Sich wat through 50% aqueous potassium hydroxide at mined from vapor density) of 2118, in agreement with the formula weight of 288, and which was om, thrthe3n doytiong& uSbien,daanr,d rTecOonadceindse3d 0 _ Stinated of tIh rn ptt Tango lobs at 60-70 C., then into a standard HC1 ,acid solu- estimated from the freezing point range to be at 8 a5 Yeast 03 mo DoF Ent pe, was Found 40 pe. tion, through a drying tube, and,recondensed in 65 least 99.5 reel per cent pure, was found to have hTaitl5a2sigraemssp.oftCRiVoCNnhaodf.hheeeanciBdyIrOolLpLieed, ds folowing len properties a liquid a~r trap. Titration of the acid indicated the following physical properties: Slot hood Tabu, ollne atamo 0mm) 0 rig that 3.2 grams of CF~CN had been hydrolyzed, equivalent to 5.1 g~ of CF~COOK. The basic solu- nonews nEarea wiaHChI eanddoraapornstedwlao ro PDriesci ripnent d ool13L 0C G 168 tion was neutralized With HCI and evaporated to Boiling point (at 760 ram_)....... C__ 27.9 FTee~ing point .--C__--125.65 bes to so anabd prekodor dryness. The residue was then dried and was 70 Dlelectrie constant (at 20 C.) ........ , 1.68 which te " subjected to an analytical procedure which demonstrated ihe presence of 518. of CICOOK. Fataga gi onstrated the presence of 5.1 g. oI CF~COOK. ExampZe VI . Thegas from the Ha ai {rapwa found19 Use wasmadoofanfrn-cattiod nckel-anode The gas from the liquid air trap was found to aves molecular weigh ranceof 1130 124 604 cell of the yn Snow inthe drawing, cperang have a molecular weight range of 118 to 124 and aS mally CI (omanwh 12). 16 8% almoipheri Presume And A temperaare of was mainly C~F~H (formula wt. 120). Use was made of an iron-cathode nickel-anode cell of the type shown in the drawing, operating at atmospheric pressure and a temperature of 11001100..00001122 STATE 07524842 STATE_07524642 HoeScco T mcsotnoesi ne 2 et con 23 24 about 0 C. The initial cell charge consisted of B w BRo aniila n ms e SCRoymel blphiateee eeyy 1800 grams of anhydrous liquid hydrogen fluoride TrERty | eeries and 400 grams of di-n-butyl ether. Additional ether was added during the run to replenish that crate frec fluorine under the existing condition~ but which is sufficient to cause the production of fluorine-containing carbon compound product~ at a useful rate, and recovering at least one fluo- DE ER consumed. The cell voltage was in the range of $ rine-containing carbon compound product of r m =Tinesot msomn i5 ntnma p | STARSREETCISE Stser ro 4 to 6 volts and produced a current density of the process. about 20 amperes per square foot of anode sur- 2. A new and useful electrochemical process | mihCiS face. of making carbon compounds which have at least At the end of 60 hours. 1355 grams of immis- one fluorine atom bonded to a carbon atom in the Pe Be ME Cr et cible liquid was recovered from the bottom of the 10 molecule, which comprises electrolyzing for a BiBarel eafclhlaaSmenolnsaagnaynBL ELeiemsomnme cell, and this was washed with potassium hy- period of hours a current-conducting mixture of ee droxide solution to remove traces of I-IF, and liquid hydrogen fluoride free from water in more Sin eben ne was then fractionally distilled to yield a liquid than a small Proportion and an organic starting ed men w ESEEe ME I An HR i fraction which was identified as relatively pure compound having at least one hydrogen atom normal C~F~-O--C~F~ (di-n-nonafluorobutyl 1~ bonded to carbon atom in the molec~fle, at a Eu tm co. or MEErRe ni ether). This fraction had the following measured temperature and pressure at which a liquid state ES A a HRi eraet REA properties: is maintained and at a cell voltage which is in- eE n ws p m:e ro ot 8 e lra m oe ee Ed Molecular weight (from vapor density) 489 fh Sus seat ane fuorine atom bondedto 8 Boiling point (at 741 ram.) C 100.7 sufficient to generate free fluorine under the ex- Refractive index (at 25 (3.) 1.261 isting conditions but which is sufficient to cause Density (grams/co. at 34 C.) 1.689 20 the production of fluorine-containin~ carbon Dielectric constant (at 20 C.) 1.82 compound products at a useful rate, and recover- Molecular weight (from vapor density) __ 459 ing a carbon compound product ~f the process which has at least one fluorine atom bonded to a re pens ts in ir, i AAA SS SE ri 4 #5 3. A new and useful electrochemical process The formula weight of the pure compound is carbon atom in the molecule. 454. 2,5 ~. A new and useful electrochemical proces~ EE CEwERpEEeT nCeL ET 5IRRLh TTIeLn ae EEtaaasne einnet aay This compound has boiling point, refractive of making carbon compounds which have at least index, and density values which are slightly but a TE SerReaaln SamRieE appreciably lower than those of the narmal one fluorine atom bonded to a carbon atom in the molecule, which comprises electrolyzing a o BT EE C8F18 fluorocarbon (tool. wt. 438) which have current-conducting mixture of liquid hydrogen St In been found to be 104 C., 1.267, and 1.765, re- 30 fluoride free from water in more than a small FTrEEe:Ssiann nprsyre STn spectively, and may be compared with the values proportion and an organic starting compound | 5H8ESEyR TTeAE 4 SE es given above. having at least one hydrogen atom bonded to a Wp E a This butyl ether starting compound also pro- carbon atom in the molecule, by passing direct Em rAEe rTa | S Se Ea E te duces a substantial yield of the C4F10 fluorocar- current through the solution for a period of hours i eT pn Aha! bon, and lesser yields of lower fluorocarbon com- 35 at an electrolyzing potential which is insufficient i ei pounds. Minor yields of fluorocarbon ethers to generate free fluorine under the existing con- TH tmenEE aving fewer than eight carbon atoms are also ditions but which is sufficient to cause the pro- BEiRBTeIreEnSdn Tenn SRY Ri hSeib produced. Some material is also produced which d bGr StEo| mBetnhSn is higher boiling than the C4F~O--C~F~ prod- duction of fluorine-containing carbon compound products at a useful rate, the temperature and b ben uct. There is some evidence for the formation 4o ~ressure being such as to maintain a liquid state, C8F1~, presumably formed by the combination and recovering a carbon compound product of ofE GifradicalsiE n the solution.cco. T he process who ich has a Ieast one Bfluorrine atom of C~F~ radicals in the solution. the process which has at least one fluorine atom B B EB Tn Se e TEbD i edTS ehn oa SLlSnIhSTITUItLT ELE = m D She e anr `the productionof CF--O--CFb and. : The fluorocarbon ethers are so stable that di- bonded to a carbon atom in the molecule. rect analytical determination of the oxygen con- 4. A process according to claim 3 wherein an tent is extremely difficult. The formation of such compounds from hydrocarbon ether start- 45 oplxoyygeedn-wcohnicthainhinasg asttalretainsgt oncoemhpyodurnodgenis ateommo ing compounds has been further substantiated attached to a carbon atom in the molecule. by homologous series runs down to and including 5. A process according to claim 3 wherein'a WE the production of Ci%--0--Ci% and carboxylic acid starting compound is employed. .$0 6. A process according to claim 3 wherein a em oc derpa co er E HS TH nT nitrogen-containing starting compound is em- fBhrpeTnie eALe SeE R ldeEtR Si Et L a sa tftiirvvoeemllyy..dim TThheeetshseeylpprreootdhdueucrcttssanwwdeerrdeeiefftoohuuynnlddetttohoehhra,avvreeesbbpooeiicll--- ing points of minus 59 C. and plus 1 C., respec- apatltottayacechdheeddwhotoichan echaaarrsbbooannt aalettoaomsmt iionnnetthheheymmdorlooelgecucelunel.ea. tom 7. A process according to claim 3 wherein an SEr E RAEnE e ELaIi = i coh ns tively, and the measured molecular weights $$ amine starting compound is employed. EF EER RE ESIS a mar seaee y (vapor density method) were the same as the for- 8. A process according to claim 3 wherein a mula weights. Their identification was further hydrocarbon starting compound is employed. RE SEICSH confirmed by mass spectrograph analyses ~vhich 9. A process according to claim 3 wherein an rn admit of no doubt since the mass numbers of the alkane starting compound is employed. Bie erste mgr. pe ionic fragments were measured with ample pre- ~O 10. A new and useful electrochemical process ae se. [L BSL E A R RAR cision. of making fluorlne-containlng carbon compounds PIaving described various embodiments and ex- from fluorirmtable hydrogen-containing organic i be| Shee Te Tor amples of my novel process for purposes of illus- starting compounds which are readily soluble in wn sm vent stp EF EL GT i tration rather than limitation, what I claim is as anhydrous liquid hydrogen fluoride to form elec- malarmer ine noenct S FA e1 AE follows: ~ trolytically conducting solutions, which com- ot STr E ESTRE 1. A new and useful electrochemical process of prises electrolyzing in a nickel-anode cell a Rr making fluorine-containing carbon compounds current-conductlng solution of the organic start- from fluorinatable organic ~tarting compounds, ing material in anhydrous liquid hydrogen oe Tei eT, SE BRST Sn which comprises electrolyzin,g for a period of lluoride by passing direct current through the ELor th SdhSe Se ne hours a current-conducting mixture of the or- ?0 solution for a period of hours at an electrolyzing EEEmhomrmi enEaEseE pahSetro acmienatLoaoe ganic starting material in liquid hydrogen fluo- potential which is insufficient to generate free nn ride free from water in ~nore than a small pro- fluorine under the existing conditions but which dR | minmies i portion as herein described, at a temperature and is sufficient to cause the production of fluorine- pressure at which a liquid state is maintained containing carbon compound products at a use- and at a cell voltage which is insu~cient to gen- 75 ful rate, the temperature and pressure being such 11001100..00001133 erate oreziss STATE_07524643 25 0 maintain a qu25sat, and recoveringac10088 26 2S 160 ane Suorie-contalang carbon compounadb sol3u8,bleASpurcocreesssasescmopo ica8iona1or2nwdheeirceidn a as to malntaln a llquid slate, and recovering at 26 18. A process according to clahn 12 wherein a my least one fluorine-containing carbon compound soluble fluoride salt is employed as a conductivity Br4oder orfotvheespraocccoer:ding to claim 10 wherein, p1r0. yA ew adwot aetzcohepmrolcee product of the ,process. additive. the temperature maintained i the Tange of | for king Tuorime-contanng ss 11. A process according to claim 10 wherein , 19. A new and useful electrochemical process bout is 20 10 Blin 80 C400 i tata Pound, Vhich comprias. ecicucbaatiioosn icnom the temperature is maintained in the range of _ for making fluorine-containing carbon come pounds, which comprise~ electrolyzing in a Ce polentin dnoo exs ceed Flt Hicklinade cela Corent-condueting about minus 20 to plus 80 C., and the total solution cell potential does not exceed 8 volts. nickel-anode cell a current-conducting solution 12" new and sacl clrtrochemial process xstially Conating of Hid hodrogen firide 12. A new and useful electrochemical process essentially consisting of liquid hydrogen fluoride fofrmoamkiDlnogvfiualtaebleconlalning sarbon compounds contin 8 dso SOnGUEIY AAD wd of making fluorine-containing carbon compounds containing a dissolved conductivity additive and Which" comprises scruErAoDIlcyeSnagring &Cobmepioounddso,f |, HiusooriCaloumbilenRg.ogaennScdompiinieadinasndoanrdoiaved from fluorinatable organic starting compounds, lU also containing an admixed and undissolved rt which comprises electrolyzing Ior a period el tluorinatable hydrogen-containing organic start- CBoonusrisst4ingcoorfrintidconhdyudcrtoignegnsSiutbiroind cconoATcIDag Inrgeatmhpaoni&nsdmaallupwrhoipolsr1rtehierfoerinom var In hours a current-conducting solution essentially ing compound and which is free from waker in n dried, consisting of liquid hydrogen fluoride containing more than a small proportion as herein described, {iCnitnoogemdaSpnacdomonewduhtciutciAhvInitPydaRddsOganldeaSsoScoNn: (3 Lboye BasPeirnis doefsPtouCrusraeknatnaSroturseospnaetlgan a dissolved conductivity additive andalso con- by passing direct current through the solution re {rmwhi 1 ore (4) Veh aouc1lGeenertate t: taining an admixed undissolved organic starting IJ for a period of hours at an electrolyzing poten- 16s rine compound and which is free from water in more tial which is insu~cient to generate free fluorine hay a smal proportion 1 her descr, 11 under th cxlsting condoms but which 1 Sul than a small ,proportion as herein described, at under the existing conditions but which is su~- S=atSee"mparamionteaiannaedprpesdsestahanwhiGtehcR3OIBAoNuS iSnedntcarbcoinsce toh pmrotpproonduocotfsuafbonrewedconti a temperature and pressure at which a liquid cient to cau~se the production of fluorine-contain- il rie, state is maintained and at an electrolyzing ing carbon compound products at a useful rate, uSooteinntieadwaWdheirchtuis aisiuiinciecntoifonGsenbertiswhciesh , mtheiSnemhperaiuuiredaandtep,re4s5su8reTsboevinegriSnuh4 0es1t0 l~tential which is insufficient to generate iree 20 the temperature and pressure being such as ~o fluorine under the existing conditions but which maintain a liquid state, and recovering at least ie ebm to case tho producion of Murine. ons Auerine conan carion compo Prod is sufficient to cause the production of fluorine- one fluorine-containing carbon compound prod- Containingcarboncompound rodcis 4 % S50. ocof4h process. containing carbon compound products at a use- uct of the process. CFaakniaitinesgndcarSbeocnoVEcIoRmGpoaukndMasphroodnuectaioefinhe-e, a0.aA NprTeYusisIcodrrrdoigonegnfuoorisclam 19 wherein ful rate, and rccovering at least one fluorine- 20. A process according to claim 19 wherein Droge. rion ariig compound, are ecm,plAavc&n, ddre. containing carbon compound product of the 25 acanrhbyodnrosutsarltiqinugidchoymdprooguennd,fluaroerideem, palnodyead.hydro- process. ~ ER res acorn to cam 12wren TosEP RL SIONS, 13. A orocess according to claim 12 wherein a JOSEPH H. SIMONS. Fo REFERENCES soluble organic compound is employed as a con- CUTED ~ductivity additive. REFERENCES CITED so14b8 Seovveen Ccocnontaaoignto oarmi12 cohmepEutennd3 4", iTuusfotlliowivnsge:efrencs ae of co inthe 14. A process according to claim 12 wherein a 30 The following references are of record in the soluble oxygen-containing organic compound file of this patent: which contains at least one hydrogen atom a Sr Coty an ie moto1 en. "UNITED STATES PATENTS bonded to a carbon atom in the molecule is emPoze 1s & conductivity sade. Number Name Due ployed as a conductivity additive. 8 proces according 10 Gum 12 wherein 8 BIOS GRslr +-orrrwrec JAD. , 1900 15. h process according to claim 12 wherein a UNITED STATES PATENTS Number 2,186,917 Name Gaylor - Date Jan. 9, 1940 hE Boho Lc Capi w+ 0 0 Gree Ua Nor le soluble monocarboxylic acid is employed as a 35 2,220,713 Grosse et al......... Nov. 5, 1940 conductivity additive. siolvi Seosoaecntnoisdiinoiotso oclaasimis12 swohmpiomd3 Simons: CJheomsise RSeirei,smvoln. s8 (1930). 16. A process according to claim .12 wherein a OTHER I~EPERENCES 5p. soluble nitrogen-containing organio compound Simons: Chemical RevieWs, vol. 8 (1931). pp. TThiinchieScdoonxteabinonayk alieaos1antehe mydorloegecn ssmtom., 4 HGeElman tal; OutlinesofTheoretical Cher which contains at least one hydrogen atom 223-230. Blow as + conducting agave acy ood GOST oe 87S, bonded to a carbon atom in the molecule is em- ~9 Getman et al.: Outlines of Theoretical Chem- race ami i can 11 wherein a FOKer Chemica Sod MeugicAT Enos ployed as a conductivity additive. lstry~ 6th ed., (1837), pp. 367, 368, 473. scuble organi compound & cnplosed 65 6 156 Gulp 10439. )107, 17. A process according to claim 12 wherein a Porter: Chemical and Metallurgical Engineer- . soluble inorganic compound is employed as a ing (July 1946), p. 107. dvi sadn " conductivity additive. 45 11001100..00001144 STATE 07524844 STATE_07524644