Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations
1950 Part I Chemical kinetics of the oxidation of manganese to permanganate by periodate Part II Solubility, activity coefficients and activity product of manganese (II) iodate Anson Mack Hayes Iowa State College
Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons, and the Physical Chemistry Commons
Recommended Citation Hayes, Anson Mack, "Part I Chemical kinetics of the oxidation of manganese to permanganate by periodate Part II Solubility, activity coefficients and activity product of manganese (II) iodate " (1950). Retrospective Theses and Dissertations. 13713. https://lib.dr.iastate.edu/rtd/13713
This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS
This reproduction is the best copy available. UMI
Signature was redacted for privacy. for redacted was Signature
j»fi^ ^ fs#i
Signature was redacted for privacy. for redacted was Signature Signature was redacted for privacy. for redacted was Signature
tpiiy©iii#r
i^%#p»10 tW|«^ i%a«fq*S »piii
iSiBiiltii JB-
J©' •sg^eii »it%
©f wn%mmn ac»i%»f4#siff ?
i|#ii^,. 'w&twf
iwm Mi ft'ltr njai> -IMW n Uii •« niw •iiiiiii»n sfiiitsa IS srsf^nmsi m t^fiifi m mtmmm m m mtimM toims i um UMI Number: DP12747 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform DP12747 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 % 8»««Ii©«9f 'A, $i Jif«f 'AI tf wmm m iBitasiif *111 ^ g«^«»idf *g 99 8H©|%mf©f J© •§ Sf Sf ffisaijiMra *11 a?®! (ii) m immm umm «f gMaii<»o miaiw *mmmm$ 11 Cf . afwfflg 'Ai Of f®%i#tRS 'i gS *'§ ^ Illl .g €t «ii« «f mtmsmsL *m 2^ .g g 't ^ ^ ifttWliat 'II t mTt^amXMT *% Sf®IiII ii SfifSMlli SI wmm&m m mmmm « m soimm TOiiaii i ttSHOO M WIW3> ' " '"^ 'Z 9 H I05CL1S) f&rl I KPKIiS 0 fIE MW&ft&S Cf to mmmamAm if plilliJii •^® &i -Ite# mm» ®0M« ia«3yil®ai pr®e«diif»i im ii^ridiia- %%m «£ hf it fewmm0m%» Im ae^ imbse* i«t©iwtaini tt % is* tttf»^trl0 sa'&eAs* fhn agSBts awllslil# t0p this iKlAsSl^ft geSitoi bis* mttiftt®, petasiiwB ftriiodat# a«iit wia^' <»mwiiaE fes^nlfa^ with flilwr as a i3»tal|«t# ®h»«i@itl kSiMi%i@» «€• ^ p«Fi®aati «:Mftti« aai »&m all4«4 pteiii«»Bsa im tli« ««ib|«0t -of ^ie mmhi^ la i<»i# tmm i^is x*«a«tiM wA 1»« gi^raa. an 0.) 2 I 10^ • f l^i v_ 2 ite®£ • I lij • ^ aaiGipiaas# |Xt)^ i» exliis^i t# ptiraanptiMta' Ir iiitaf«ric»(lat«» Tlia pariodatA' «iiati<» @f ni»^&##o as aii a^al^tioal. satlisi i&t 0.'el®et»tri@ #»tliiati®tt «f wtsfaaasa im« fii?»t prcf«iwl ^ ffcia ©oaftoiicai ia the mmtt ef i«is* @««fpaiiaiaf t® tli® mwims «ij|«tlon states of fflattfan®## ©aa' fe® atdii## by hs# of tha Steek «yst«a 0f mfflBeaelatar®. fr«p®atl.y tli# iwiioMaaat Itmio li »qmm» aol^tlcm ^ tti® iat#i*iiiate' itatas ar® a©t kaoia «t tto as®ii«ptiM if a «»• .i»»®3Piftlw •»«» aot b« J«»tifi®i. fb« ata tiia t©y« p»«siiapinitt@ -iasttai -af »ai&aat« (fll) h&& beta wtaiaed baaaas# lc«g established asafi* IRia w« af tbi» ijnteai i® itt aaeapA with the Report of the CamsAttaa fsr Sef®r» •ef lawfinie i««a®latw«. ®f the latarnational faifim ei Ch(Wtt*igr., 1941?, fhia Im baaa iniieated by ¥. ?, Janissea, I» Baa set, A* ©ataieiMi, F, fiahter mtd I. aesy in Jjg. Gh»a. |sj£., M» ^ (im). lillftiri 'i»i &mmn^ «<9iiei»itiiiSg $M tlwls* si^SSelss Is *tlm- i# iwim itm «11. th® faidtg .of «b« mstm )»i.4fe««s f««wi.ts «t m. hi0 i(ip«® of II, ' CtZ) salts wliisAd If" p^riodatu Hmm tfe« »«» tut.®* a# •%»#«» siilittie««t «f far# psiimsstwi mil Ml iniii^i iiili iiiiift •» iiH fii ilt ft I. w i«pimt«ly mA M €eait#al»tl.Ms wt^t* m Img m stfiTitioitt m^M ma pmmmt %<& pf*f»at py#®%4t«tl« ^ tii» iixipui«ft»k 4# fte «ily mtim% -rf rnvfim^ psyieiate. &mmn%m^m ir»t tfe# ^rmt# at.wlteli -Hi# i6«l4«tl« pretai^St Ctely a aaietsa @1* paipfMat# va® M#€9ii tw Ih# sdUhttl®a ctf *sBpunir#»* I. *A mmw^Wk% featwr® «f tiai s«lmtl«8 i» ill# i««t stability wfeaa a sli^t WEOtss i® prmmtt* Swsli a solatlaa tm tfeiNi# ia a ftcppiftd flatk aiieaai m dhaag# utot- mmtt nfeea «w|a«i with a alailar oarMisai, ffeli- wia It fwaibla to- l««iw *ii@ is th® It iml3r"««®Mii©Ba3.ly testaai pyafaftei a frath ea@b ti:^ a® is mmmmff wimm la iwiai. i, fha t®Mtiw fflital® iii H0% ImUtiem ta ^4t wetboi -faE^pt la s® far a» %h»f a t« tfe® a«a«t%t®s# %. 1, WilMH mw0. Ji» mm* &»••# Mt 23^ a 3^ # 0 «i» Q. i O 1^ i sy I* ts sr M § ± f . m & •» a f It m «*• e*" ® •» § — f. • • ^ • • S3 M » 1% m E M d Isr I*. m m m i s €1 % Icr w w s ^ I* • I* I pit m .@k m « &• m i i m f # 15 E % & »9 «. ® « 4^3 P ''^ ft » ST' « $ ^ It ® m «*• # t*- 0" •m "V ff *fS » «#• I 3 n I f#• S ft a ft A » 1% » u* s » « #• f f s % t* I tM # «*• |>4». a i i 9 a. » ^m Im Im «*• » m tk m 9 m 0>§• **• 2 •a0 f w va ¥•* e*' •SI »* s. li' m m #It Pi'2 U.m» ^ ^l» ft«»ti<«» flk®i« •kHfiia'i r«^©r% Wt» «% »mt iM tkmy mte mm fp®f»ii3.s #«• mmmskimm A* mdhMtiLSB @£ #># wasMflB &% %&«• fteMiter., app#«i»«i/'l0 tet f»fr mtiBimt'mf* , a tdloftJwi'lfA# »»lli®i wm t© i&U.m llai fetiiiM^ •ffett ^ IIMII avMiiti mf mi^mm (X?) ^ii* Mi i^it •%ir«iif%lt« fb i0 iMi'mm%im eMetmiif %k» imi pi'mm% IB stlntliMi &i pi»p#fl'^i« ««ii wiMi' tipailiiM#- «l»ai Am« »«» pii>li»h*i.. fliSj hit# 'hmm •«®i s«N %•# l'« H. ¥» »»«k# i-# §• l«iftl» |{.# f» ii«l0S.| I# an« i3i*» (1949). I# Jk* i# iiflr#® ®« s« fcrtla.,. A«@#pt®i fm im* Chftg* ^1^. I 1 m I •k a I • -fk- g <«-% • I Im- % s I «« ^ m • J M t Tm- I 11 I I »•w % * 41 1 J i I s *# I £ 2-1 # i m ^ « i p tli«. • i«B, 1©^.,. Is ia tfc»i Al^®^ i«lr' &m ar%i@l# wm» foi^ with tlie oi %km miM%im ^ (H) to mtl&m anthewi'^* 10,11 iia nil iMgiS iNip^Hfeei «»• %fe» •fWittlsR (II) «ii^ fliA mm%' eaiqp»»i»»«iw And' bcw't wmk »pp»mm t# hm tbat «f f III, h» »hoii#i' il»% %tm «mt#iiktia3rsl«. JEiM | 1* p*j^Q««i fbftt iHffipWM ClZI) i& prdNet^}^ ttES' i&itiftl praiwt, ®ii JbiAtSal pr@im@tla« ^ mufifii'SO (SII) "has %©•» If tM of iwiif. mm§um9* •toy h&'m (III aw pp«fHiat| ill® ^©©atrJLMtl* @i iht® ri««tiiai «»% fe# flt.ij» re&ntim hm %•#'hmmu tte wmMmm %« ias8«t :«»€ I. §m^«mm„ 4* -HaB* iit«t (lWl>h f« &im®r tti^ 4« 1* fos%t i* ®sa» ilSI«* M# Ci934)« 1,. A. i«ii« aM I* mnrnii., m Mm, i» U9f J, f#lisiar, i. ill 4® C1936). %. i» «• mrmA& mA S. filigilK^afftiflffi*. Ji.* Cl%s). %. t. F®ii®w«p, i- to* ia».t JS» tm7 (im§). • %. 0, fsaklw, p^m. fmemAm. 131 iimS). 0 1 i II I m I s 1 i I 0 I S I ^ s I 1 43 I s 1 ©f 4I»© % « I i« I % 1 11 I M t I i»' Si « « 0 llMlls j I 11 s 1 • #- I - 3 I I II M ' 1 I f s s. sIP« iigtllliiig irm alfcaitu# pioiasfiia wittr irm th« nattr- smpplf • 'lli# ©eiriiiiatifie© «f this w&i»r WB» ImB %hita 10*^ ahm e**^#' B* in tp»e%r0p&®l«»»«a»t.© »a»«r®»ats »•» mim mMg m §mej- ©0», fmMem, ©tlifwala. tt® ^syst#® ti «f «a* & afeliag •«to apa»t» to m&tk l». sf«0t»l r®fi« 2050 A «ai TIC© t witli liglht whiefe ©©aM "b# ®»8«iitiiill3r »«©- ®Jif@ni%ie« 'fha teaii ii. «plii hf iptiml lialf fftssinf tit# bla^ ««l.i aM tii# tAmr ^hoM the wto^l® -©all aftea*' nitiei^ tb® li^t falls Sie alaetrieal aigmls irm tbia |fei'«f6imlle a» aa^lifi^ «i«atr»i3allj iii a iiff»3r®ntlal aapltfitrj,, aiai "fee iiffa*«»tial sip^l is iia^ip®ss®4 mvm& a le^ifl'lteleal^ wmmA »aii%©r ito«» aipal ia msaswsi % a Mvmrn yaefiafiiisg fetaatl^tai-. Ifcit mM» pm»lhl9 th» pm" faatatiMi af tlia li#tt«atss®rfei»g eli«raft»i»i8ti®s ^ ^ a^l® «i*««tly i» ^i««l iaisffliii' wits.* *The ^ti«al iaasitf «# a ««lmti«i it iaflMMl as ©.i, 5 logi© «feere 0*D, tfea ^tieal itaslty,-1^ a«^ I tha i»taH8i% of lit H#t p[,#»i»g tlopwtgh tha bia^ aisi wii^la ©all jrespaetiiwly# fhia ii ©eeiwsiaiBt siia#® smh a is pr*^i»*i«©al t® wiMiii tfet a^Efeiaii Wmr*Wmgm Im is f0H J s I & * I a I I • I » IL 1 s f «• 1 a i i! I * f ^ 8 I e •- m - ix€«ss 'fdtkSsiiaK hmj dliti t© ih® utMifiei e«tiiiai®g %im fee ittito® m$ tliyatti wl® a-faH^Ay^, •teMna«l.yati> ttsSag f W tm Stea5fti€ 'ssiiiii ttetosilfsi® vai pi'sporwl ito.t&s sansBz 4»8«isife«i, If *aai 'lli® «iiow»t «# IMosiafat® KM HMmlmA to »«^3p t# glw ^ itiPPfeaEiwstt awwility itsijNii# Pd'tetolsW' aotf vmm t# skm^m Itoe %i*« im %fa« t© «titbllij«# Iftw feeiaf stisrei im « m^k th% «©lwfcl» ww staaAaipiiiii wilii sittffi ft6ii i@aik%« tb» primf tteeiafi militf sum sfttlioi m»& i&t tlm ef fli# t04«t® 4#i«»idLi«ti«iai mm mi.® br niilsg «sieii«s puffc&ssiwi ioiti# t© «fee' atM.4fl«i eMtaSMaf %hm 8«j^3L«, Hi# 31l»fa,t®i iodto® ««»• irltfe Itt %hm mmsl wmmitp ?«ri0dte Held •«»» tm- he^ ptrltiat® ittirt %& ^ • m%h&i ^ 'IMtltr «aii fii® «©lTiii« !• tttlaM «ii I. Mtitl.,. ^atttatiin.Arolysi#*, Sew t&tk, »# I#, i* tsB ^«»p«af Ine» tlM$) W 3*^. I, &M ». !• Wmmm iB»»tit»Mir» Aanl^is". 3wA m.., «m t»k, W, f. i. f«a Sditewia &«• CW) P i. llll&ifi 'ma *• !• fwwmi, iWd, i<r aM §• |8E»#»JSf^'S2 (ifSI). * 11. tontalfliag %h9 ima witti At thin «eMity p«Pi«iial^' iws t® Iffllat® with ifflili#* , f•silairtiSfeg ttili a, t#^l l©ai.t# «si ptfloiBt® m* Wii# i© & A%&k m§ t® tif i®i«t« «o«|i btt itaiiittd fefsai^mte mm bi* Aii» •©Ivlaf litt :3!m0At ffmd« §€LM i» mt®f l^r A iittttreA. glafs tisk. iiiiim wm «« « friaati^ ittMaM tm Itolf «# 4» th# hf fmlm aJwt mtm mS.» hf mmml iiitrntmt m^ks&9m «4i«tl®a «P ttoi la aotrnti^ t© ftifwospmi# «@id omA .e^^pftriag #^«rl»slrf.®aHy with « pf»pBP«i SSarfsmi hw WSllSl'S tilEIWtihUfiSen* was MtiiM m® iAi»«©t to irhiiih mm^gmm (tt) 1# titratfti with S'tMiSsrt psfiWiagBBalHi stiBtSflB was als# nt'ti€* lii ®i&ejp ft#### sdss ««r« saM p»«vli(«li*t@iAl^ hy ipiittoi ih® iff aalt t® «» ia f IJlai€ a^ i* fmlms' msi 1» i» Wsti0% £* 'li««agA j|s£, .g'MMagia WIISai^ ftBd Ifn <£• jy§*< »•* 2J(66 CimfK %. 1. arf u i. it. ImDi S, 125 cimi), 1, tilJafi i». •Wtafei.,, »^*aai(»i Qaaatt'tetliii® imf t«rl:, i# t, 1* fan I««^pai^ I«e* Ci|!43j f* li4# * 11 I 1I •r H I M - 13 - 6 - 4 - >• 7 - o 6 - S 4- 2- 0.0 - 2000 2400 2800 3200 3600 4000 4400 4800 8200 6600 6000 WAVE LENGTH (ANGSTROMS) Figure 1 - Absorption characteristics of an aqueous solution of potassium pertnanganate on the Gary Spectrophotometer, % IS • e *0 ^ I 'SI ^* m « J ffi % ^ .1^ II' «*»' @ I 1 l^l •r4jS ^ Pt 1 t A ^ 1 IB Bo fr @ sii S» I4» *f P a# I t '& w fe '« J M d 4^ « ntt 1« % 4»® s Is# # •m % m ii 5 1^- i £ m • -?*• » 4^ fi « w •l-it m m '4^ © € •• i I # •^ If ^4* «t ^ ^© pS 0 • «' <0 9 (ft t .£ 9 I % 3500 4000 4500 SOOO 5860 5S00 6000 WAVELENGTH (ANGSTROMS) Figure 2 - Example of rata data obtained by periodic scanning# a i ^ s f t III I i I I! I i!^ ^ I -1 11^ !i )I ^ « i1 Z }I ® ? s1 I I II 1I I s ! M i I ^ ! i i !- I I M 1 115 I I! s I IU « HI i II 1 fU w H-iiinjii 8 I I I I f I - ^ - 4»-o lllllllt if till i f • It • fh« itseiflfeei aetfeods ««r© tfe® mrlsus rmetlLem dttcrltei ia I wtr® ftai ,mm t# ®i3K Irn^mim w®.?® Mi@ with p»i"Al»i.© »#ii tha ehi«f mriiibl## wmm f2.@lti»d sM glvm m tigmmw 3 aM 4* flie mmetlem w»to«rei iinrttt la«l.i»i'W»'lui'f® III® p«rioi«t« eoaetBteatiaii at tli#. waia' wrtabie# fte «ai:e#ai p«rto4ft'lN> was nlmgw »«r@ titoa am tiiiM tii« 3t0i#M@Mitrie &mmA» 'Ski» ia^ WA® flefe^ a.»i tats l»®a gtwa. ia fifw®s f aM fli© rm&timm lusi mmmm% ei mmgmnm (II) «» th» ehief "wrii&l®, aat •&» f3.®ts -Ito#© r«&eti©ftS mn iafilmaed as fipre 7. ffa«. pi«As 0f ,r#aeti«»» M-th iodAt® as Uie wrialil# iHiirt fe®«a iaelM«A a® figw® i# fi« aeeamey ®f tto iaiA ia fig&m is 8«ffi«i®«t i© that ft© iatA is la^iied ia fifel# I. We mmM.mm »««b®r©i «i#t««a Iwaaty tm» iaelsiaiw kmm th® iaiti»l i«0«at of p0tA:8#itt* f®CT»igaii«t# i» ill® pf«a«a@® of i©i«t® tlwi ^aily mflmbl®,, aM t&»»i r#salta at® ia fifia»' f, 'Tbm waetiimi awtotjpei ^mtf ft-m thrm^ tir^atf s«w w#» t® i«-t«r«ii»i tk« M«a» ^ fm®ti« ^ *«ipffl®«® Cllll i©AAt® eoi^iK, -aai^tlMWie hAw fe«®a flf®a m tigma !©• I®ii«ti«8 'At tf® aM 4@® »i^# with m»gpi«@s« |II1) ASi p«ri©aAt® t# i«t«ir«itt» aa Ae-tiimti tmrn X « %ei04= 0,47(1 0,250 • 3-« « 10-* i#t»f stro «tes®iTptl«i to 0i®|0 iiftteal ttaits tti® ©•© 1.0 3»0 5.0 7.0 f^© 10.0 11.0 13.0 ®.i. ®.O30 0.051 ©*10a 0.19i 0.368 O.ffT 0,720 0,148 1.016 tiwi 15.0 It.o ao,© 23.0 ©•»•• l.aift 1.314 1.31^ 1.34© «Iil©4 » o.m %|I% « 0.25® %RC«l©4)a • M9m 'HfeiftPptisB t® 0*03© ©ftteal «miti til® 0»i 3*0 6.0 f.o M.O 13 •# 15.0 17.0 19.0 ©.». 0.030 i.OlS 0.153 O.ja 0.522 ©.f3i 0.956 1.M7 1.2m %im 21.0 24.0 27.0 2f.0 0J>. 1,3®6 1.46© 1.4^ 1.4^ %i0^ m t.ffo %|i% « o.af© ^coi%la • l®%«i ter& %e §*@30 mi-Ni tiB» ©.© 3.# 6.© 9.0 11.© 13.0 1S.0 lf.0 ©3. ©.03© ©.©47 ©.na 0.^7 ©44t o»m ©.904 1.11© • J. time i©.0 23.© 2i.© 29.0 32.0 ©3. 1.3tO l.42f 1.4« 1.497 l.:» » 1M3 %|I% * %a.C«l%)a • i#tei s#rd a^scirptiM. e«r»sp@i«it i© ©.©3© @pti@&l ieasii^ mtiti tin® ©.© S.O 1©.© 13.t 15.© 17.0 19.0 21.0 ©.». ©.©I© 0.^s ®.2a ©.413 O.lfz 0.1«9 0.9i5 1.11® ti» 23.0 .al.O 29.0 3a.0 35.0 ®.i. 1.277 1.391 1.46© 1.4iS 1.497 - if • tmm I » 2.% %5iG^ * $am «3.S4 * i#t«i §•## ©iitreipeeit' %9 '<0*010 -opticMl t«iMiit|r 'imita %is« §•© 5*0 10,0 II4i ii*o ao.o 2a«@ ©,@30 om$ O.XOS ©*344 a«i4i i« IM 'tim U.§ 2«»© 3is m.o 3?«@ %glll^ S #aS® X esrftffifSiiiii %& 6*6|0 mUa ©.0 !•# i,o t.o 1®.© n*® M.® 13.0 i.6s© ©.i4 i.i27 ©.fit 0,Sfi 15.© !?•© If,© ' ti.,,i t4.i 26,§ @*i« 1 UMl t t 1JL«4TT 'SlW «.•#«t X,. i.iia ^ • IM§ %|I% # Q*m %taCm©4)g • I.S4 * Vot*t 20^® rnhnmp^^m &mm»pmAit %@ 0*i|§ 'i«iuiii^' mits %im 0.0 i.0 2,0 3,0 i.0 5,0 ^,0 f.© t.O 0'JI. 0,03© 0.01^ O.©f0 0.110 0.2|i O.ISS 0*5?3 O.fli 0,f0t tins f,0 10.0 11.0 12.0 13.0 U.0 11.0 16.0 17.0 h i*m i.im x.afs 1.313 i.i4f i.*8 i.frf- 1.3^ i. I104«l.iif %|I%«'0.312 %aCei04>2 •-'3«S4 X ir^ iotfii s»f>9 e^WMifi^'S t# 0.010 'ipti^l wit« tlwi 0.0 1.0 1.0 3.0 5.0 6.0 f.0 f.© 0.1. o.o» 0.052 ©•( 0.iaf 0.190 o.4ia o.iss 0.t?3 tlSMk ia.0 '14.0 16.0 ii.0 ai.0 0.B* l.oii 1.^ I.36S 1.4ii X'.4S0 1.460 - 2§ - ^ %|I% « e.2®0 %aC#l%)2 - 3*54 x 10*^ »0t«i ttr© stea^ttos MmmBpmAs t© §.©30 immitf mliB Urn §»0 3.© 5.® 8.0 ll.i U.O 3JS,§ 1$.0 m» 0MG QMO %m ©.m ©.isa Q,m qm9 I#Q43 Urn ii.i a4#® •a?.§ 3i..© m® i,an , i.,4©5 i.m isu i,m$ %|i%sta^ %aCeai4)2*'3:.i4s3LO'^ i#tii §•*-© »teiaeftl®i %# ®,i|§ mi.^ %im ' ©.© S*§ IS.© IS.©' 2©.® 33.0 2f,.0 2i.O ©•t. @.Ofi §<©4© 0.0f? §,m 0.24S ®.Sf3 O.sa? 0.t5« tim M B#i 3i-#i 4|.i 13.© S8..® ©a. »tfff3 i^.:i33 i.sm -i.aa i.s64 i.m ^ %mj^' IMS *^5!% 5 Qjm s 3.S4 x lo"^ i«iMit t«f® •fei-®rptl« %# wit# §•© 5.0• 1®.© If.©' as.§ ^.0 33.© t.i. §•©»! §.03S ®.€!4f Q.OfS 0.13© ©•» 0.3i3 ©.SH %im 14.© 3f.i 43.® 4i#® 51.0 ^.0 il.O ©.©. §.m &.m isfr i*m i.m ijm i.iie^ um %$,m H.O ®.i. %^m ^ %Sli4 » Q*m %|I% = 0.136 %«#io4)2: s 3.i5 * wr^. I0%»t itiFii a¥fi ^ %ei% » s ©.If# %iCi®j)2 s 1.94 X ir^ • 3 »mx ir-^ !©%•! *»r® ®'eri?(isf«B^s %& ®»02O 9p%im.l i«mi%f wai^ tl*# §.© J.O 5.0 f.® f.© n.© 14.0 li.o ©.i. §.®© ©.eif 0.01^ O.Mi ©aff ©.4i® 0.ifS i.ffi tils 1S.0 tl.O 24.6 ©•». 0.« s 0,424 %|3[% - §M *«iCl0|)2 * *^(6104)2 S 7.8f * %im ©.0 3.0 f.0 6*0 ?*0 S.© f.O 10.0 11.0 OJI. 0.020 0.06© 0.1i4 0.311 Q.m QM6 O.S?§ 1.0§6 l.lf? Urn 3S.0 14.0 M.O lS.t ©.i. 1.100 1.40f 1.4fl 14^ - 0,424 « l.m s 10-^ %5l06 ® *^(0104)2 s li«® 0.0 2.i 4.® i.0 «.§ 10.0 12.0 14.0 16.0 §.». 0.0 0.01 0.022 0.i4S 0.097 0.166 0.24f 0.433 tiae li.0 ao.o 2^.0 I4.O 16.0 2i.0 ©.i. O.in 0.573 0.62t 0.654 0.6% ©.6i© « 5IM X wr^ \t% « QM "ialoio^lg S 3.fa X 10-4 S 1.02 3C10-5 il*» 0.0 0.P 1.0 2.0 1.0 4.0 f.O 7.0 f.0 0.». 0.063 0.067 §.O«0 0.113 ©.Iff O.tOf 0.2§3 0.37t ©.4S3 Mm 11.0 13.0 IS.O 17.0 lf.O 21.0 $S» ©.#7 0.6te 0.61® 0.700 ©.mi 0.72t • 12 • fmm 1 X lO"-^ » 0.1.€4 • 4 w»4 9 M X IQ'^ tins ®.0 t.l® 1.© iti !•© f.0 ©.i, ®.ltf 0.i4O ®.15i 0^10 §#267 0.3ff ©.5li %im US US US IfS t9S ©a. $.m §,m Q^m &M$ e.m m % C 0M «i.m * %5it| %ftC61%)2 •- l.fl * tim ©.0 0.33 0,66 IS- 2,0 4.0 $S ^S OS, §,2^f ©.im oam $M ©•381 QMl 0.#f27 O.fil 8.0 f.n 10*0 11.0 ms us 11.0 •#*f f 0.695 O.m 0.763 0.787 0.W2 ©.«« %C1@^ 5 §.ia4 S l.fsi * 10-3 » ©.161 « $m X ir4 11^® IS a.o 3.0 4*0 fs ©.». §^m i.6f7' ©.m • ©*fso §.«fa o.fii 1.034 i.ff i.is© %!»» 7.0 S.O f.© 11.0 13.0' #J6. 1.117 1.216 1,.232 l.i§0 l.MO %1% s ©.414 "KHdO^]!^ s l.m X 1©'^ %I% 2 .^nCClO^)^ S |.f2 x l©*^. %aO^ S 6.05 X 1®-^ Itm ©•© 0.33 ©*66 1.© a.© 4.0 f.O 6.0 0.1. 1.34s 1.372 1405 1.44i 1.SS7 1.647 1.7©2 1.746 1.71^ tis* 7.© d.© 9.© H.© 0.1. 1.1®6 l.»0 1.808 l.m3 h S QJM * }2 5 l*n X 10"^' %|I% s ,%§f S X "ofeii s fM M tiae §•© ©.ll ®«66 !•© 1.5© a.i 3.i 4*® S.0 t.i|0 2,05f 2.1i4 2.141 2 2.|4f a.Jtt 2.41? tliMI i.O t.© •.§ 1®.© 0,i, 2.41? 2U4f 2.4S§ 2*454 = i 4 .y@%0i »ex>0 ucd'to ti«t 0.® 0.25 0.1 ©.?f l.S 2,0 2.1 1.0 0.035 ®.050 ®*tr© 0.103 0.13? i.lM ©.l«f 0. tiiw S.f 4.® 4.1 s.e §*it o.aji ©.a4i ©.tf2 o.a,5f -3'r=^ m S I "1% - 1 fotei s@3*9 ft'bsia*ptic» te#i>M3fwis 0.045 apMenl ttnii^ Sisi 0,0 §M 0.25 0.5 0,?5 1.25 IM urn 0.045 0.0?4 0.0% 0.121 ©.142 0.18? 0,215 0.22f 4>4v3LfBm fMJk 2.1? 2.i? 0*19. 0.243 0.24i #2? 0, 3*.* Qt "mWj s 1 '3^X ^ w ai^ ^ 80t«i 2®r0' ateSQi^iioR e«rr*sf«3ni» t& 0.04$ @ptiml deXMiitf' tiiw 0.0 0.25 §.3? ©.f 0.?5 "1.© 1.25' l.f© 0.». 0.045 0.13? 0.1?1 ©.Iff 0,210 0.2# 0,33# ©.3?0 ti»® • l.?5 2.© 2*5 J.O 3.5 0.». 0.3f2 0.410 Q*m 0.43i 0«441 • 24 • ftfUi X #i- mim *^i©^ «t a# i»fo ««KfWi#|»©»iii to 0.053 e^tml 4«iaitsr Wfti^ i,0 ,2f .f .f| l.i l.s t.§ 2.5 3.® i3. ®.i5l 0.120 ®.141 0.1% 0.231 ©.2f4 0.3lf tiwB 3.1 4.® 4.5 f.t 5.5 ®3. 0.3P 0.3^ 0.401 0.41f #2f fttae%i« 4^ 8510^ a* 4# mit& rnhmmptlm %& ©.©43 optical i«asitr «sii» time 0.0 .25 .5 -.75 1.0 1.25 1,5 1.75 2.0 0,D, 0.043 tail 0.158 0.202 0..;^ 0.277 0.30f 0.336 0.351 %$m 2.25 2.75 3.50 4.® 4.5 ®a. 0.373 ®.|f4 OUlO ©.412 0.42# #30 MmnUm ^ to{Sl©^)g «ith •1^1% nt 2^' Xe^s a«r® ato»«ipii®a %m 0«®3i iftisil wsaits tim 0.0 2.0 4,§ 5.® 7.® f.® ll.O 13.0 03. 0.O3t O.oa QM9 ®.ii7 0431 0.204 0.2m nm 15.0 17.0 lf.0 21.® 23.0 25.© 27.0 m, 0.3m ©.4^ &M1 0.6% 0.6^ ©.m #31 ^ fcCeiO^)^ at 40* S®t«i s#r© *bsflrpti« mmrmmpm&s te 0.^®:® a|»tl«l wtlt» Ma® 0.0 2.0 4.0 6.© 7.© t.O t.§ 10.0 11,0 0.0. §,m» o.oa 0.^ 0.172 ©.t3f 0.311 0.3m 0.410 0.545 tin# 12,© l|.t U.0 16.0 is.i lO.t #.i. 0.607 ©.6ff 0.700 0.747 O.Tlf 0.773 - 25 - 1.2- 1.0-- 0.4- 24 28 96 40 44 48 time (minutes) Figure 3 - Rate curves at 5260 A No. %G10^ %5l06 %n(010^)2 1 .478 .250 3.54 X 10-f 2 .974 .250 3.54 X 10-f 3 .990 .250 3.54 X 10-^ 4 1.923 .250 3.54 X 10--^ 5 2.94 .250 3.54 X 10-4 - 26 - (.8-1 1.5- .3-' I.S-, r 0.7- o.s- 0.4- 0. a^- 01- TIME (MINUTE S) Figure 4 •• Rate curves at 5260 A %C10^ %5lO^ %n(C10^)2 5 2.94 250 3.54 X lO--^ 6 3.78 ,250 3.54 X lO"-^ - 27 - 1.6- I.S 1.4- 1.3- 1,0- 03- j 0.8- o 0.7 0^- 0.5- 0.4- 0.1- O.O^ TIME (MINUTES) O Figure 5 - Rate curves at 5260 A %C10^ %n(C10^)2 7 1.885 .500 3.54- X 10--^ 8 1.885 .312 3.5A X 10-4 •• 28 « 1.80. Ill 100- 't' 2-^ 32 40 43 TIME (MINUTE) Figure 6 - Rate curve at 5260 A No. %G10, H^IO, to (ClO^), 5 6 9 1.885 .250 3.5A X 10 10 1.885 .1871 3.54 X 10"rU -4. 11 1.885 .1248 3.54 X 10 - 29 - 1.4- s i.0-- 0.4- 0.2 - 0.0 20 28 32 36 40 4s time (minutes) - O Figure 7 - Rate curves at 5260 A No. %C10^ ^51% ^KH (103)2 %n(C10^)2 12 0.424 .136 1.94 X 10"^ 3.65 X 10"^ 13 0.424 .166 1.94 X 10"^ 3.92 X 10"'^ 14 0.424 .150 1.94 X 10'^ 7.85 X 10'^ - 30 0.9 08 >. 0.7 "m 0.6 z o 05 < 0^4 u pa3 a. ® 02 00 TIME (MINUTES) Figure 8 - Reaction rate curves No. %n (010^)2 %C10, 4 '"HIO^ "^5106 1 3.92 x 10""^ 0.424 1.13 x 10"2 0.232 2 3.92 x 10"^ 0,424 0.379 x 10-2 0.241 3 3.92 x 10"^ 0.424 0.15 X 10-2 0,243 A 3.92 x lO"'^ 0.424 0 0.245 - 31 - 2.50- 8.00 — C I.S0 1.00— 0.30 0-®® ! M TI I I I I I I I M I I I I I I 1 I I I 1 I 1 I I I I I I I I I 0 2 4 6 a 10 12 14 16 18 20 28 24 26 28 30 38 34 36 hme (minutes) O Figure 9 - Rate curves at 5260 A No. %ciO '^KH(IG2)2 ^^5^% ^Mn(ClO^) '^'kMNO 18 .4-24 1.94 X lorl .167 3.92 x lO"/" 0 19 .424 1.94- X lOo .166 3.92 X 107 3.02 x 10"^ 20 .424. 1.94 X 10 o .166 3.92 X 10 7 9.06 x 10"^ 21 .424 1.94 X 10"^ .165 3.92 X 10"7 1.21 X 10-4 22 .424 1.94 X 10":; .163 3.92 X 10"7 3.02 X 10-^ 23 .424 1.94 X 10"^ .160 3.92 X 10-7 6.05 X lO"; 24 .424 1.94 X 10'^ .157 3.92 X 10~^ 9.06 X 10"^ - 32 - g 0,^"- , "T—i—' 1 I 1—I—!—^—1—T I' 1 ' I——r , , 0 0.80 1.00 i.so 2.00 2.50 3.00 3,50 4.00 4.50 5.00 5.50 6.00 time (minutes) O Figure 10 - Rate curves at 5260 A Ko. H^IO^ HOIO IO3 U 25 1 i 1 1 26 1 1 1 1 27 2 1 1 1 - 33 - 40. 0.3C 29: 2.WV 2.So 3.50 S.5V TIME (MINUTES) Figure 11 - Reaction curves at 29° and 4-0° III Mn - 34 - w O.SO— 4o; O 0 40 29; 30 — O.OC- time (minutes) O o Figure 12 - Reaction curves at 29 and 1^0 Mn^^—^ MnO' - 35 - teaetieai »#re Mte Im wlii«& ipeistfal wiiflB ff®b 3$^ t ta |0©6 |. was smm»& m mpMly as pe»#ifel#, ftt eriftaal emmo" tmtim ©f ttaiw mmtimm «r® giwa ta fafei# II* 1 plot «ff ttea # ® <2|>ti@al itii»lt|' at 1 aat at t&e p«i*»gg«wt« ptak at 5®60 A wai mle' &»i bat 1M»@& as figaiNi 3.1. s* ifisny^yyi, ©wlag aicpltamt^ aa^ mpmeimw^@ it mm notle#^ ^t whll® aiilag a s©lttti« #f p-ftasii®® fe»iiigarait« t» a »c»l«fei@a ^ wiaganpe (II) p®r ^4, Biff, S*|e IMIM (tm)* m ^ m film JI laltliEl fa? S'saafilag 'Iteaeti^s %5l(% %ei04 •w^ «I1©, %h %f2 m •263 .424 0 @ M. 3,m X1©*^ .a63 .424 © 3a X 10*3 n 3.f2 3C iO-^' .263 ,4S>4 0 §.2 X 10-^ 44 * 1©*^ .^3 .424 3 X 10^ 3.1 X 10-3 5A 3.»ia X .m #424 3 X 1©"^ iai. 6A 3.ft X ir^ .131 •424 6 X 1©*^ 3dl ?1 3.f2 X 1©*^ .a63 , ^•424 © ® iA 3.^ 3i'l©-i .131 ,49J^ © © - 37 - j?c- 1,60 i.50' 1.40 1.30: Mn' !.I0— MnQ 0.90— o 0.80 0.60— 0.50 0.40- o.io- 0.00- time (minutes) Figure 13 - Rate curves at 5260 2 and 36OO Aj Mn^ O.D. obtained by difference. . IS . . mwgH if»k left «1»@« siivii*! atteiifta Isy %lm Mi ia %ht Mfesamtorj dii aofe rtpp©tiMMi MM fht awit witiwsi fytpi»ti« ei pwrfl# ®»y »at®jri»l foraA ii&s t© th« »st®ri*l with iodie aiiM ftm n^mtima i»f mw^mm |IIX) 0.m#rS)ie 4 S'@^p3.«i prc^tinir# S pe« sC p'«l«s8te w^r# tisfolii^d to fO «f wftttr, tti® r«stiltl»g ®atoti« was aMiwi i® M sdlmtlw it fM« ^ (XX) ietftt- kyiirat© ia tli® pr*8»tt««- ««©«•# hfircflaafie utM, '&• ietal wlwi was 200 *1. A 8®ltttiai e«t»toAia^ |3 p», 1©®!® atii In $3$ eite«^ VftS' aidsd. - Ute# was amh Wmt Ili8 fljoaX •tltonol e«ii®»at»ti<« was •l&tm'l §#• fr®«ipitat« was apm ft 8iat«r®i |^@@ iisk m mpMiy m an# witahti with wftt®r-»that»0l. wixMmm* l&« timl vmh was wilit ff| «tlMiii®l 1ft spitf t@ wmmm as Kotli w«t«F m poi'SiWe# a« filt«r©€ wa« th®tt fSji-eei ia, a A«8®ieatse m& mllmei. to Ary f«• kmm »til. m ©i» ^ sleito©! e . ?fet thewretlQal hsm bi®a »kmm fe®3.«« rnmmmm^ f .411 .§5f 94.111 mim ms t 2$ 9ji^€ffli^i3nL0 — ii M II A * A ClKi4ai4 in&apu3*ie'vmwie i#tli pe'ie>i.@iat@ escMfttion t® f*swMika|iiiiat# liy ®®lwtis§ii?4e &mi^viMm with a aiidtel^ fr«ptr«i stiwaiat^i aai toy iptitleia im nir «f tfe® wai^d i3^ iMllt ^1%'* gsm M»iti®«l feselti witMii tlwi lOftrlffleatol m»m% IMti® «•» lai# fey «®UL««t- iBf fi»# ioiia® la ftlliwrlsf th®ifi»l q£ « .aM tltirttlJBf wtife- tiiiosiilfitt® ttlMtlaa.. *l«if th® ©heaital p?©- fertl»s ®f %lk® i«l% *«r« taken a« •vMaae® fm tM# aaa- mms» Cllll t0iat«, ItagaiMMi .Cm) teilat# prepaid m iM m parpl® p«iy Mlvrittl iihi@!3 i«@dipd8ea spim btnatlaf t# ft'^ ieiiM aM ^3%* fh« &xf salt Is mmTMhlf fta%l# i» aJbr far a i«»fatt®8® (III) ®alt» awB't© tib® tl»i af%«f at IW® fm ae-wwil m® 11 1 w i 1.00— 0.90-— a 0.80— 0.50-^— 0.40— ' M M I I I M M ' I M I M 1 M M 4000 4200 4400 4600 4800 SQOO 5200 5400 S600 9800 6000 6200 6200 WAVE LEN6TH (ANGSTROMS) Figure 14- - Absorption eharacter of mnganese (III) iodate ccffiplex Mn(I02)^*'^. • 42 - mm- III I-8«^ fmA%t si «ii»« I« tadintleii t 0.0390 * 0.0435 $* 0.0475 f* 0.0560 »• 0.0594 # i#074i Wt 0.0825 !• 0.0854 »• 0.09X1 f 0.0972 i.H# » easaa 1* 0.131i S- 0.l6f9 §.1962 1 0.2U1 !• 0.2232 !• 0.1312 1 0.2^3 f- 0.^55 f 0.2969 0.3053 1 0.3162 t 0.34S© W 0.37^ 1 0.ISS3 I g E f* I t0 m %4 fi m S •#*43 m » i ^ Ift ^ 4I«W*• & ft W 4® •rt « $1 '«*« s § e •llSk s 1**^• *1t •5 *8 f t~^»HI ^ 1SS, ts «0 H, •g i 0 r4 « ft 4» m 4S<1 f M <4#J i.0_, 0.9_ Q3-. aT_ 0.6_ 25 • •09- 2 .08- .07- 26 .06- .06- 27 .02- .01 time Figure 15 - Semilogarithmic plots of log 3«"X versus time for the oxidation of Mn(lOo) • X % I! I n { \m y nI c*—c % s H f I I ^ f If t . I r Irf i? a m •f » s*- "t l-« _ i t • I -\ a US I € I** j S I I I <" f f 3 f M 1 i A I g & 'C s I I • « "S % 1 # •I I ^7 la © t m •M t I ® >W13 • f % f • • » I I I I I I 1 ® I 11 ^ I m <3 § } 19 #- I I 11 S % I ft 1 I I II ^ i s *' I •& I # I I I »-f II I I I I I % ^ 1 I 5 I f I i I s S 5 5 1 ^ I s 1 I i I I I 4a® 4»M I I % III k i S I 1 I I t $ g S h * .K i s s ^ I ^ i I :11 I I % f I $ II I g I ^ I S $ s 1 i I t I t I I I 1111 I - AS - 0.20-, 0^ I fc_ t' C.I4- 4 o.oe- 0.06- 004- 0.20 0.30 040 0i50 PERIOOATE CONCENTRATION (moles / liter) Figure 16 - Linear plot of the mximum oxidation rate of manganese (II) at various periodate concentrations• - 4-9 - JiX'— awcu m 0J50— h- 3z M O2 OT O> 0120- oiio. a»a —P_ ~ ^-r~ "T^ t.O a.o 3x> 4.0 ft.0 agio concentration (molcs/dter) Figure 17 - Variation of rate at various perchloric acid concentrations. <•* ^ * fiml •3e%ineti»* «x®m@«8 of ioi«ts »M»ii t© slew tke i»t«, et wte with ioadl® m "W itseieWlai^ ami Spi#«i^' tes l»®8 lji®toa^«4 ai tig&m IS. fli® f«»g«4af »(isait» mmmwul fuet® wfeieli «ay pp&pm»^ »s#t «xflai»« fk«»e' em siMMrisei %eleir. I* fhB iSml 0xila@tiM @i pmmn§m&^ m» «@l m ii^i« ilAsar tmetlm &f to® mm§mm* fTmm%,^ ft® w«r® i3»«all|r vith tlift pwater finftl a®e»i0nM' % ««r« m to tMs nal®, ' i« fte« s«pfti«t» <&i oi f«»tti,^aate tiwi to til# liifle@ti«i fdtat ^ ttie »t® ©wrw. 1li« of %oth 40iat« aad f«i»msiiRi»t« t© tii« «i# ttls tiws mtf of wm§Kms@ Clf' miM sb^rtmitf tht ti®i mmawmrf tm mtiskm^ tih« i?t«etiea Miigp^s« (IM) «M® wi^ frttrtMat® was mgllgihl», 4. i l«f 4niiieti« wm ©fe««n«i f» tMi •«nM8tl«i. in «l3i®ai» «f th« tbfft ftee#|«f«tiw> i]^ltti»et», f* a# p«rli3aate <»Atir fm th® i»t« Has 1.0, 'flte ptWKii^MMtt# «pi®ip was mhmt i»S» ft Tkm mwm^@m 'Cll) mAm wm 1»0» t. ' A «l.»l«iii rate with mtjim *®M eww^ntr&tie® tail ^®rw^ at abwt l.,5 M f®i»«M.irle a«sii# 9» I»«r®asiiif tli« sti^nfth Jtoe-iraaswi the fraction ir»lsNSi%'. 1§« Kiap.M»e fill) i@i«t«i wm to fesfMacanate Isi. - 51 - Figure 18 - Variation of rate with ionic strength. ! « t s I I 13 i i I s 1 1-4 I (H m I I i w\ I I I t 1 « J i « S - 54 • aofc. Hie frap^ifi feil®fsi |8) m&l *> If I * la^' I f«ipli •fttilitoyitta (W) •* I I^ ^ ^ J Cn) mu^)^ • 2 -^ia®^ • fx # a)iQ| i k^. t * % {3.2| In^^ • ^ ' 2 ia^ I hj j ?«%© S. 1^ »»• •«qtt£lil!yl* wey® to' tet «iio<^' thftt «f«il.tisriw ttonfiiti®!® ©adiM l» as-swei# fbm @flh«r mmtimm m§m dhoaea m 1^- wmm rf sfeiiftiit lh« f®il%i«o m) ii 5 (IllCtll CM) Bg = ijj Cm)Cisj)2 fUs 0«s®'rsisti« of ««n«t»es# «®sa»ll^ 1C?I5 5 § i?©tialy»8 (15) 1(11) • Hul) • sfif) « -®CV1I| s % • ig fit twi^rfsile® elt.@l»«8 is 'ttt# lew®? aMation si»tt8 (U) a »CXII • 3 »CI1I) • 4 »Clt) s 6 % - 3 % •o^ 0 •1 E I1^ -<»*» M ^ n -*1^ m u w # ,•«»«» Pt 1 ***^ 1 I •en •B 1 «« aT a 11 % ^T' w I^ g •#• 15# •HH Sa s 1^ ft - fi I aw r4 . J* m n ^ • ft s< fi if* m • fi *1 I m » s^ I ^ E w 1:1 1ft n II II II »~>k S H 3 ^ jt I fe' uM •ts 1^ 1 i I o» 12 l§ m i I I i I a ^ I I III m I I I I I f i I ^ I I s % n i! s i I s i f II I 1 i! I s- I 6 I f 1. 3 ^ % i I • ^ I i S •5 *1 ft [1 i i 1 fe ® t %4 I# 41 4 s IS ^« .©I §« o3 t a i - ft - fh9> ^ ap« ih* at# Bhmm ia figire S mu Is# ««ptlata@d tl® imm&mA alailitr to f«pii tli« Cm) itiat# S'affi«4«iit iedate al«M ifat# IwieatHi# t&# ©fiHibyiwi irhi %• i» StfidklftM Sfie»r| Aaalytiea ^iM..i^ lata. S,$ 51? (mf).. * 'S® • .i«P pfiiaislwi piOTMUapynat® im mri.eas sttfia-i® aeii-««t®r fit® «f wt®r- in ®a^. %•«« 1^ 3# Shaitoaa *#1^ pwiwifsA with a emstant ® fiemetlm '©f silfsrie .aeii# fte® «4glaal lanwrluf tli® SS6o 1 p«ak for fioraai^asfttt *«s i.lr«@tl^: fn'upwftldwtl t# th© a«tlirity ifattr la seltttlQas as ®k»8 la f%«« If» A fsapw-risaiiaa AS ca?) 2M' ar 1^0^ • igO ©0tfli b« hm^trnt, iyir^tB im aettvity weiiM b® «®«®-g®ia7 i® iftteMla® if tMa 1» tkm oat®* €« SignifieitBia- fh® TOifllta rf tfcig w«»: mAm fmsihl* llstlag ©trt«ia »®e»» »»i«ti®Bs to r#fai€ t® wing ^Is «li®tl©a fer aiialytl«ml l»ir® lb«®a llstti l»l«wt J., Aflis m fHfarle l©ile iili«i« »«d«8 we ia«ia t® staMlis® .tli« Mgmme 1111) atat# «• t# 1« prefwyefl to iwiai?# ©i«pM%« Zm Miy « saadli p@fcatsiwi pcrloiat® m parioAi® a«M is imwrm • ©f rta-ttloii «M i» t© l»e (4«sir«i, SlMtewua ii»a A# E» £# Stel* lai*# Hi* 231© Clf39|» - 59 - >.7_ 1.3- is- i.4_ 1.2- ^ lO- qs_ 03_ a3_ 0 0.1 02 0.3 0.5 0.6 a7 a» 0.9 1.0 ACTIVITY OF WATER o Figure 19 - Variation of the optical density at 5260 A for permanganate solutions on sulfuric acid water mixtures versus the activity of water. m 6®- • I, f©® hi# a#li emmulmtlmm &% »M#' aitinflti' rf mteF is mrf !.«, Aseli 1» «v«4dl«i slae« •Ifct#®# Hill Ismw »#-asi'li'rtty ^isiiQa if ImmmA «tSa®ii«a i# tfe# paafwafaaat# 1<» tmrni* 4, ft# rmmmia&^Mm that wtetitB It ptrfifwii mt M..0 %9i^rtAm»B WBAi» ly Mllmei 18 wtll Mi* sia@« lai® S. .ilifljBf 0mg'S0 &e tksim '(mp0HmM$@ smmml ftb^mmmm v@m ite®#rr«d: whi# »3t|}«rii»iitg wbi^ wtlgk% to® ©f tt iwt^m fkm^ Mm h®m itswiWi tetiiwt 3.. Hii 'tjf tMai# s^ltJe «f »aBfMie#® <1II) lei %m emmmlmg km th« i®ei© In M#t 1» lilJafi anft S# £, Jp#. .JS# 23i^ cam?). m •• fe» ' •!&» ^ t&mtim&m was ral«i m% ».ime til* -wHiiaaes# {III) ii® io aot t"la¥l# i» •q'^oag ®it i»«k (s£ ani iawafe#®'^ m. tfe® ef tto® ttnwiA« @0^31®* nf nftii|^«s# ClII) «i#% Is® afplltalJle t© iiwi ietwatiatlon The 0Mistmm -af tw# 00IM fhasas was wty afiiaal. &m appaarad iiaatiaal ia apptaraaea t© Mafwwaa (II) taiat® wWlla tht otIieT was a 4afk raUdlah ktmm, flia «is.t®»ee ®e «aiipi««»e Clf) ioiattt liaabaaa si^gaatei by Bayg ai^ tli® appea»Bffie (rf iMa solM phata afp«ar«i Maatlaal wilb liy fr@lewif@i heattaf hyii*t®4 ••iigaa»»« (If) mU* wttte a«M* Bw piias® wtla wh#» SkppUM to th® afewa aol«%l«a witti tteae phaaaa ©©axlstlsf i® aqatlltoi'lia alibis s© ©as^ositioa 4ap»es «f and this reamlt B« icfeaffar »ai E« i* S^mmk»r, g* Sh#m. 2S75 (1950)*' f I I J 1 I n gig I i i i " S ? M s H t I n *•% f m I 11 i sie»' I i r 1^1 s I I f I f t Ml t i s i i ^ m u I I I , P— a 5 P § % a 11 I 1 I I *% 1 i 3 M S I I •3I ' 4 S i I i 11 I i f s I I 11 : I \ 1 I %* I I I I I I J 1 I I» f $ *4-I •» &4 • Pi'rt II f» SSSWIIiIffp MTIflff 0C®lfia,IIIW » mflflTI mmmf m •mmimE (ii) mAfs ^ |» IKllitCSflQi Ife# (11) ia waltf haS' fe««n r«f«r%®4 as 0.5 gA^g ®a^ « ia8©»l«»^*^' ft® imriiiti« dt i©lttbility witlk aii. •©ti-ritr praiaet w»m tt«l itsoribtd. ais Ijiwttipitiaa was isitia%«d a# tie p#sttlt ©f ktaeti# Ktirti®# i» tkiS' laberittmy .lav«lvti^ 'th# «iiatiett gf (II) ia #@lmti€« emimiMmg IMat®# a# salmMMti' dt mrngmm® (II) iodat# i® Hater at wi««s tii^imtiopis is aq»©ia »0lttti<»i8 potainia* l^ftt©,. •aoagimase (II) pmeMl&mtiSp a.®i aoiiwa elil»id« mem lOm haw h%m mmA t© «e8^ttt» th® aetivi% ftetlfitf proAoet ©ai -ttt# li«at ^ toliitioB #f wm» (II) i@a«t«* %• f, l«*wlsfe«rit ESB* $M*t Mf ^ (liA2), %. Mtt®, im* Mm* Qm*» C0# &$ wt (isfo). I I I i I 1 ^ I »» s I a i 4 g m. 1 I u •8 I I » I 1m a d' m m I II I m 46 • Ml s©lmtlai« wtw pmim^ % ijplei salts euliSag % •wit«i» t@ ttta# suits in n flwiiE# i* Asi^i^tlBi 4 wi^ & tiaip®isatte« taftteol • ,@8® im» lewei fof h&lm 4S®» iff««%iw *'fei»l^ arf agltatiaB mm pwmUunA ly ii«Mi»» rf « IfeBPrtJ. .«l«iE«,. 1. S^«fel«« &i mm§m»-m (II) 'W«m im tw#»ty imt kcfor® s.i a«i 4S®« v^Amm «# tlitwa s@lmii«ii iia.» spprtiKlw^ly ilOO isl* sSitibilswiliig swlysiji^ 2§.itl# «llQiai@%# irm t& ill# aoiitiiaiiftf 'MgiifltM (111 #oiiw* iklwUl# w»i. a»lytisi.. ^img lyiyidMlwle a«M loti€e aii tliyatipf tos iMtm# ulilk aoilwi. Bit «f •Mitt* eldl«ii« ««§ fr«p. tii® wtlg^ts •«f th« ml% «i th« mtty ^s^ini# 'fli# alt^idts fro».%i« mlm%im$ mn%a.imlMg p^nwims. mr^ eisMiaei t© p®r®Mtpusst«' m®M ia smlfwte auM ®^ » i % % m I % I m «t f I I n I SII - g ! 1^ |>p n t I I I* § I i Is i i| E I* I M m m mm I W&U f» Ctl) luiat# f»api»twi SAASlltl' JUL • ®.0O56t 0.1310 0.00 4.03 I© 0.00621 0.1637 0.01007 3® 0.00625 0.2110 0.02462 3,n 0.00751 0.2843 0.0554 3m 0.00786 0.3670 o.iioi l.is I® 0.00902 0.6610 0.4070 3M 25® 0.0G65S 0.1407 0.0 4.03 if® 0.00694 0.1760 0.01007 i»ai 0.00761 0.2179 0.02462 3.m 25® 0.00836 0.2840 0.05540 %m 25® 0.00896 0.3681 0.11080 3(»^- 25® 0.01041 0.6630 0.4070 ai« 0.00474 0.U54 0.00688 4.13 as® 0.00211 0.1688 0.02213 4.ti 25® 0.0006i46 0.2554 0.06218 4.1© 25® 0.000301 0.3335 0.1091 4.43 25® 0.00397 0.635 0.113i 1.40 25® 0.00531 0.192 0.010305 3.00 25® 0.00560 0.1Si 0.007-43 2.63 45® 0.00713 9?^ 0.00854 - 70 0.007J -D- 0.00!-. aio 0.20 030 040 050 0.60 0.70 Vll Figure 1 - Solubility of mnganese (II) iodate in aqueous solutions of sodium chloride, potassium iodate and manganese (II) perchlorate, O - Sodium Chloride ^ - Potassium Iodate • - Manganese (II) Perchlorate 71 - 2.00- -Z02_ -2i54_ -2.06- —1 -2.08- 'S o -2.10- c a -2.12_ o >- -2.14J 1— -1 S -2.16- 3 8 -Z.18_ § -2.20- -1 -2.22- -2.24_ -2.26- -2.28- -230- —T——I—I—I—I—I—I—r—I I r 2.7 2.8 2.9 ao 3.1 3.2 3.3 3-4 3.5 3.© 3.7 3.8 YI * 101^3 Figure 2 . Plot of log /solubility MndO^)^.? versus the reciprocal absolute temperature x 10^, £ i ?? S P fl •m 1 m I 1 I !{ i 'e I I i t £ I •m 11 I A I s I « « % m I a I I I 41. & >=» s 11 > I 5 I I 1# « •^Hil I III! - 73 - 1.00. Q900, 0800- o3* 0.700. s 4-1 K aeocL 0500- 0400. Figure 3 - Mean activity coefficients of manganese (ll) iodate in aqueous solutions of sodium chloride, potassium iodate, and manganese (ll) perchlorate. 0 NaCl @3° • NaCl @ 25° ^ Mn(010^)2 @ 25° • KIO, § 25° Y ® ^ i MnCl2 by EMF measurements fwm the .«srf» by mism iwill- Immm rslttimt 4 (198 V* S - U) T" 2.303 S « (|) fbt 'iMMimii wm ml&ti»9/u9l9 im t«ffipwratimi swup) ®f I® t® 25®. fcr th® r®a0ti« ((ifmttffli 5| fcCl%)g ^ • 2 I«>| (5) %&• ff«« tatrp- dto»|p lit 2S® »a« sonpttt®!' a® fsi»f th® f*l«« Sm fet«t tt® "wlm® ^itiaei f« ©utrepj' iiwt®g« «a@ • 19 4- a^«, liklmf 2i«t «»tx^ wits as tm toiai# aaft gssa*i3if ,th® i«si« mtr&pr ^ ill} i» th® ita® «® i« C- 25.f «# «.)• fiw stwiiart tati^F iolM iwapiati# (11) ieiai# Has #a3.swlatt4 to htt A%$ tatrapy miits. %. i. K« i» «»& f • ?• 3wiMt Jm* SttB. |M«) la, it8f cimo)* %• i. Mm tmk^ I. I*, Fr«a%if«*ia.|l, la®.., %9M, f. tit* fl- If« SSWSflE dt (tt) im wm^r at t0»pi«»itiQra» frm - 90® mA ta » I I