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Page 1 32 the THERMODYNAMICS of CONCENTRATED AQUEOUS gTiE THEB{OÐSIA3üCS OF CCi}üCmTAAl@ AQTIÐOUS SOÎ,UTTONS OF ITDNOGEN BNCMTÐE Fei¡rg a TtresiE Subrnitted to the Faculty of Gradr¡ate Studles a¡rd Research of, the tftrivereítY of lf¡nltoba fn Partlal FulftLLnørt of the Requiremenùs for the Ðegree of Maeter of Science by Roy Solchl Ya¡nasald. ÞIey L95t+ TI{E TI{Ð]ìMODIINA¡IICS Otr' CoNCtrNTPuitTEÐ AQÜ80ÜS SOLUTTONS OF H]TÐROBROI{IC AGTD A Ëhests submitted by Roy S. Yarnasal<i, and- d-one urrd.er the d'j-rection o.f .åssociate Frofessor t¡'¡.end-el.l J* Bierrirarur" The accugaey and. complotoness of the thernrody:ranLe che'raeter- 1za1íon of hydnochlori,c aeicl by å,i<erlof and. Teas'e lqith tbe silver- sllvor chlorid.e electrod.e suggested that an analogoìrs lnvostigation of hyd.robronric acld. by an exËen.elon of the u'ork of ÏIamed- s K-eston and, Donelson wlth the silverr-s1lver-brornid.e eleetnode v¡ou1d be practical. Electnomotirre forces of the cell- Iþi IIBr(m)i AgBtr;l¡g Were measìfred- ov61' a range of concentratlon and. tempe:ratu::e' The slor,crytegs of estaþlishment of equlllbrirxte ascnibed- to the sofubillty of AgBn in HBr¡ liniited tkre work to the region below 5"0 mola.l, In the region below 1u0 molaL agreement was exoelJent wlth the earlior vrork of ÏIe-med., Kêston anCL Donolsion' I{amod-p Keston and. Donolson obtained- tkre staJrd.a-rd- potenti-al's by use of a conventionâl Hitchcock extrapolatj-ono Re*extrapolatiort of thoir data using tho trÐobye-tsii.ckel function"gi.,/es a substa¡tially d.ífferont sot of resuJ-tsr and- slnce the extrapo1ation 1s nuch nrore nearly a. stnaight llnee may be consid-ered- mone reliable* Using the lnproved values of the stancLa-rd. potentlals the actir¡1t)¡ Goefficionts aeld' and. relative partial molal free energles of aquoous hydrobromlc solutions were calculated- up to õoO molal' 3 ACKNOIüT,ÐGB{ENTS the author wlshes to e:çress his apprecíation to Dr, Tü" J" Biermann for the helpful adrrÍce and sympathetic r.¡nderstanding during the course of this research, and to give thanks to Mr. T, t[, Sutherland for the translation of some of the papers enployed The author also rrishes to aclsrowledge his i¡debtedness to the National Besearch CounciL of Canada for a Bursary and its strnmer supplement wh:ieh rendered thj-s i¡rvestigation possible -ii* çe¡[18{TS CHAPTffi PAGE I" INÍBODUCTIO$o o ô o o o o ø ô o ø ø ø 6 cê ø ø . o o ø a o o ø ø ø ø ø ø ø o ê øo ô o o o o o ø o o oo I Ir" THEOREIIOAÍ, ASTD EXPMIMH\ITAÍ, CO]ÙSTÐERATICÑÏS"ôô6ó OOOOOOOOOOO h A" Ttrermod¡rrranic Calcr¡latlongo. o o o c o o o e e c. ô o o o o o o. o o o o o o€€oo h f,., Observed Activ:ity CoeffieÍent Of (¡rdrogen Bræ1de trr hlatef o o o o o o o . û . o . o ô ê c r o o o ó o o o o o c ó o r o c . o c o o o o g I o ø 5 2u Calcul¿ted Activ:ity Coeffici.ent Of l{yitrogen Br@Íde I¡r I¡fater" o o c o o. o e o e e ø ø ø. o e e. e c. ð o c. o e o o o o o o o o o. oooco 5 3" Rel¿tive Partial Mol¿L Free Êrerry Of tlyrdrogen Brcelde nr Ï{atef . c. o o o o ! o o o oo o o o oo o o o o o o o o e o e o o e o c o o o o o ogo os 5 Bo SLLver; Silver Erontde Et ecürodgs o e " o o o o s o o c e o o o o o e o s o o o @ 6 f," titgratur€.. r c e o e o o o c o o c o. o c o ô co o c o â. o o r o e c e. ê o o. o eooo 6 (a). Electrol¡rbic-fhermal-Eleetro\rbic Electrod€s u ø o o o oo 6 (b) o o " ftremal-Electrol¡Éic Elecürodg" ". o o e c . o o c c c o o e o o o 6 (c) . Electrolybie-Eleetro$rtíc Electrodeo e o â o o o o o o o o e o o o 6 (d). Ttremal Electrodgoo€oooooo eóooocooôo. oo.a.ooeo ooooe 7 2n Flæ¿¡i6g¡t&1u"cocoo oo øøoo.o oo.o.oooooeoo. o o o coooo€ooco 6 (a), Silvgr ftd.dg Preparatloooo oo o o o o coo o o o e. o o o o.. c co oê I (b)" SÍ-lver Bromate Preparatloll"o. o o o c o o o o o o e o o o o ø o oo ooo I (c). Electrodg Preparatiollo o o c o o o o o o o o o o ô o o o o o o c o o e e o â o 6 6 C. Ilydrogen Electrodesoo o e e o o èo o o o e o ó o o o s e o o o o o c o o o oøo o e o o6ø ? 1" Electrodg hoper""o oo go o o o e e oo o o o o o o6 ooo cr e o o e o. o o àoeo 9 _iij_ ggAPTTE PA@ {a)r Litgratr¡r€s o s. o o o o o o ó oo o ô o o s o ó ê c o oo o o o o o eo e o eøe@@ 9 (U): Ðçenimøntâl" r. o e o o c o o o o c. o o e o o o o o o o o o o o. o oo øoooø LO 2u lfndrogen Gg,s. u o o o o o € o. o r o ô o o.. c o o o o. c o o o o ea q o o. o o o o o€ 10 (a)" llteratr¡r€.o ". o o o c o. c c c o. o o o. o o o o o o o c o. ô e. o. oo6o@ 10 (U)" fuerinenùal."ooôe.oosoôoooo.oooôoeooooocoóe øøøøø AL 3. Prgsgure.Õoo o o. c o ô o. o o o o é c o. ó o c o o q c oc. c oeo c. o.6 o o o sôo l,I Ðn ffirobronic Acidro èo o o o o o r o o o c o o o o o ô o o o e o o øcó e o. o o. o ooo 72 1o Purífieation". oo ô c c o o o o o o o o o o o o o o ø ooôo o o oeo oo o o o ao66 e U 2u Deo:qrgenatictlr"e6ro oo o o o r oo o o o o o o o € oo o ¿ ô o o êo. e o o o o q ooø 72 3" Analyeis. o. o o o. o o. o o o o o o o. c c c o c o o o o o r c. o e o c. c. o o o o o oo L3 E" Standard Electrode Potenti¿lsooooooooooôoo.oo@6oeoooo€o J3 Fa CgLL.cooo... c. o c ê o c o o o o o o. o o o oo o o. o o o oeo oo s o o o ôooo o o ooo L? Gt Thg¡mostato€ e. o â o o o o. a o o o. o o o c s o. € o o.. o e c c o o o oo o o e o o oeo 20 Ho ElgctromoüÍve Forgeoöoooôocoóoooocoûoorooooooo.co.cooo o 22 ÏIÏ. UPERIMENT¿I' RF"S[tJS Ái,¡D THEIR mEA$4Enryoo.oooooo.cooooooooø ZT An Coffecüed Potentialoeoe.cocco.eoecocco.oo.c.oocoooeocá 28 " En logarit'h Of ft¡e obeerved Á,ctiuity CoeffícÍenrtosôeoo60ø pß t. Calcul¿ted Acüívity Cogffi.clgrrt,..roooooo"u.ouooooooosoo Zû Ð' Bel¿tlve PartlaL Molal tlnee &rerry.ooooêoooococoeoooooo, zg IVa SllþlMARl"ôø ooo oo o o e o ø e o o o o o øe c oo o o o o o o o o o ø ø o o s e o o o ôoo o o s o o o oo 3t+ BIBLfætAAPFIfo ooooeoo c ooe o o oo e e o o o o oq ooeooo óe ôo o o o o ô r e. o o o. e o. o o o qêø 36 -iv- TABI,ES FTGUR&s AND HilTES TAETE PÂC.]E I" Standard Mo1al Electrode Potentials In Abs. Volü"eôc6aêesoo 30 IIo Average Potentials In Abs, VoIt Of The CeL[ Ptrl{z(l atn.)¡HFr(n);Agtsr(s);Ag,ooo€c.o ooooooooooooeooøaø go III" Corçarison Of The Obsenred And Ttre Ca.lcr¡lated Logarithns Of She Åctiuity Coefficients Of {ydrogen Bromide I¡r Vtratgr.eo. o ôôe oo o c. o.o oc. ô o. ô oo c o o o c c o o c c.. û o e o o ó oóco ôoo 3L fVu Constants of Fqratíons (5) And (6)6cooeôeooôooooøoooooôooeo 3L Y, Comparison Of The ActÍuity Coefficients 0f i[ydrogen Bronide In trÍater"e oo, e e o o o e c o.
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