This dissertation has been microfilmed exactly as received Mic 61-929 MERRYMAN, Earl Lewis. THE ISOTOPIC EXCHANGE REACTION BETWEEN Mn AND MnO” . 4 The Ohio State University, Ph.D, 1960 Chemistry, physical University Microfilms, Inc., Ann Arbor, Michigan THE ISOTOPIC EXCHANGE REACTION BETTAIEEN Mn** AND ItaO ^ DISSERTATION Presented in P&rtial Fulfillment of the Requirements for the Degree Doctor of Philosophy In the Graduate School of The Ohio S tate U niversity By Earl Lewis Ferryman, B.Sc* The Ohio State University I960 Approved by Department oy Chenletry 1C mnriEDGiBiT The author wlshea to e:qpr«as his approoiation to Profoaaor Alfred B. Garrett for hie superrieion and enocur- agement during the oouree of this research* and for his sincere interest in mj eelfare both as an undergraduate and graduate student at Ohio State University. I also wish to thank the Ohio State University Cheidstry Depsurtnent for the Assistant ships granted me during the 1 9 5 6* 7 "^ aeademlo years. The author also gratefully acknowledges the Fellowships granted me by the American Cyansuald Company during the 1959*60 academic year and by the National Science Foundation during the Summer Q u a rte r of I960* i i TABI£ OP CONTEHTS PAOE INTRODUCTION ............................................................................................................... 1 Àpplloationa of Radloaotirlty in Chomiatry 1 The Problem and Its H latory ....................................................... .. 1 The Problem Reeulting from Early Work 5 Statement of the Problem ........................... 7 Stability of Varioue Oxidation States of Mengeneee •••..• 9 MançaneeeCl) ......................................................... 9 Wanganeae(ll) * .................................. 10 Manga ne ee (III) ........... 10 Manganese(IV) ............ »............. 11 Manganese(V)« (Vl) and (VIl) ................................................. 12 EXPERIICNTAL HiOCEDURES ........................................................................................ 15 Preparation and Purification of Reagents ........... 15 Potassium Permanganate Solution ............. 15 Manganous Sulfate Solution 15 Procedure Used for Recovery of Manganous Ions .................... 17 Procedure for Determining Permanganate Using Iodide Ion . 18 Preparation of Radioactive Manganese, Ifn^^ .................... 18 Iron Target Bombarded with Deuterons, (12 Mb t.) ............. 18 Experimental Prooedure for Studying the Isotopic Exchange Reaction Between Mn*^ and iVsO]^ ............................ 23 Experimental Prooedure to Determine the Time of Formation of Manganese Dioxide for Studying the K in e tic s of th e Mi -MnO^ S y s te m 24 Experimental Prooedure to Determine whether Manganous Ions Form Complexes ........... 25 i l l T1B1£ OF OONTEBTS (oontijaued) PiOE PrapATfttlon of Anion Exehango Column# ................................ .. 26 THEORY ............................................................................................................................ 28 EXFERIlffiHTAL DATA AND RESULTS ON RECOVERY OF lUNGANESE.............. 31 Molarity of Solutions Used in the Experiments ........... 31 R eooeery D ata on Perm anganate S o lu tio n s ........................ 31 Conclusions from the Recovery Data in Tables 1 ,2 and 3* 36 Recovery Data from Solutions and Mn*^*-MaOT Solutions .......... 38 DATA AND RESULTS FROM THE ISOTOPIC EXCHANOE EXPERIMENTS 46 Discussion of the Results Obtained from the Mn'^^-MnO]^ Isotopic Exchange Reaction ........................... 50 DETERMINAT 101 OF THE COMPILING ABILITY OF MANGANOUS IONS WITH RO3 , CIO^, SO*, HgPO^, F - IONS AND THE DI*SODIUM SALT OF ETHYLSNEDIAMINETETRAACETIC ACID .......................................... 68 Discussion of the Results Obtained fr«m the Study of the Complexing Ability of the Manganous Ion , 6 9 Separation of Manganese Conqilezes Using Domex 1-X8 R esin 80 Discussion of Results Obtained from the Resin Runs 80 SraCTR0PH0T05ŒTRIC STUDIES OF THE SYSTEM M n'*^-lfaOj ........................ 93 Discussion of Results Obtained from the Speotrophotometric Studies * .................... 94 8U1C4&RY .......................................................................................................................... 117 Conclusions ........... 123 AUTOBIOGRAPHY....................................................................................................................125 iT LIST OF TABLES TAB1Æ PAGE 1. Reoorvry of KKnO^ in H^PO^ and HCl Solutions •••••••••• 32 2. RoooTory of KMoO^ in HCIO^ S olutions ................. 33 3* RsooTory of EMnO^ in HgSO^ Solutions ............................. 35 4» RoooTsry of lisngsnous Ions ........... 39 5. Rsoovsry Data on the System )bi^-UnO^ •.••••••••••••••• 40 6 * Isotopie Exohange Data ............ 51 7* Increase in Solubility of MnC 2 0 , In the Presence of Various Salts ................. «............. 77 S# In c re a se in S o lu b ility o f RnCgO^ in More H ighly Concentrated Salt Solutions •«••■•••••••«•••••••••••••• 78 ■ 9» Data from Separation of Kn and MoF^ Using Domex 1-16 R e sin 85 10. D ata on L a b ility of M n^ and KnP^ ........... 87 11. Composition of Solutions for Experiments I through XL • 99 12. Optical Density of KMnO^ in Water and Various Acids ... 100 13. Optical Density of DbO, as a Function of Time in the System Mn -IfuOj-Aoid .............................................101 14. Optical Density of EMnO, as a Function of Time in the System ...7 ............ I l l 15* optical Density of KUnO]^ in Various Salt Solutions .... 112 16. Optical Density of KMoOj In Various Salt Solutions •••. 113 LIST OF FIGURES FIGURE PiGE 1. Gugn* Spectrum of Iro n S t r i p Bomb&rded w ith Douteront ...................... 22 2. Gmtmm Spectrum of Mangenese Itotopic# Sepereted from Iron Bombarded with 12 Mev* Douteront 22 3* Concentration of Manganete in the Hanganout Ion Fraction After Precipitation with Sodium Hydroxide ........................ A4 4# Deoompotition of PotatelAm Permanganate in the Pretence of Vanganout Sulfate ........... 55 5-7« Plot# of ln(l - F) Terse# Tims for Determination of t& • 56 8-10. Plot# of ln(l -F) vertes Tima for Determination of ti •• 57 11-13» Plots of ln(l- F) verses Time for Detormlnation of t^ •• 5Ô 14» Inoreate in Solubility of IfoC^Oj in the Presence of Various Salts .................... 71 15» Inoreate in Solubility of MnCgO, in the Pretence of More Highly Concentrated Salt Sdlttione .............................« 76 16* Inoreate in Concentration of IbCgO Above That in Pure Water ........... 76 17» Comparison of Stability Constants of Complexes of Metal Ions ............... 79 16. Peaks Obtained in the Separation of Different Oxidation States of Manganese Using Dowex 1*26 R esin ...................... 91 19» Peaks Obtained in the Separation of Different Oxidation States of Manganese ............... 92 20, Comparison Curves for the System Un'^'^-MDO^-Aoid 114 21. Salt Effects on the Decomposition of ObO^ *.. ». .., ... 115 22. Variation of the Order of Reaction with Concentration .. 116 INTRODUCTION Appliotlone of Radio*etIvlty In Ch#mietry The use of redioeotire et oms em treoers in the study of e wide veriety of ohemloel problems he# beoome an important research technique. For example, the tracer method is used in the study of isotopie exchange reactions, structural chemistry, self-diffusion, chemical kinetics, and analytical chemistry. The high success of the tracer smthod is due to the fact that in all but the li^test elements, the radioactive isotopes behave, within limits of the experimental error, the same as the non-radioactive isotopes in chemical and pt^sical prooesses. Also the highly efficient radiation detectors available make possible the estimation of very small amounts of radioactive material, as low as 10"^^ grams in some instances*^ Using multi-channel analysers, the various components of mixtures of radioactive isotopes often can be identified* The Problem and I ts H istory The main problem under consideration is the isotopic exchange reaction between manganous ion and permanganate ion. A literature survey revealed only three researches which dealt with the above reaction. In each the experimenter used radioactive manganous ion as the tracer. The Mn**-KnO^ exchange reaction was first studied by U. J, Polissar,^ in 1956. The results of his experiments show negligible exchange between ^ah l and Bonner, Radioactivity Applied to Chemistry, New York, John IflLley & Sons, Inc. (1961). ^Polissar, U. J*, J. Am. Cham. Soo. 68 , 1572 (1956). 1 'Un** and UnO^ in 15 minutes at room temperature. The solutions used In the experiments contained rarlous amounts of low concent ret ions of potassium permanganate (usually about 0 . 02M). perchloric sold and manganous sulfate. The reaction mas stopped by adding sodium hydroxide to the solution mhlch rapidly precipitated most or all of the manganese which was present in the intermediate oxidation states. Polissar also worked on other exchange reactions, for example, manganic oxalate com­ plex ion and UnO^ 1 on exchange and the exchange between the oxalate complex i on with Mn** ion. (Other isotopie exchange reactions were studied in addition to the above but only the Mn -MnO^ exchange will be discussed h e re .) It sit ou Id be noted here that the addition of smnganous ions to a solution containing permanganate ions produces a precipitate composed mainly of manganese dioxide* The time of appearance of this precipitate in the solution depends on the acid concentration. For a given oon-