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OXIDE: ELECTRODE POTENTIAL from 20" to 30"; SOLUBILITY in NEUTRAL and ALKALINE SOLUTIONS at 25"G

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OXIDE: ELECTRODE POTENTIAL from 20 SOME THERMODYNmiG PROPERTIES OF SILVER(II)OXIDE: ELECTRODE POTENTIAL FROM 20" to 30"; SOLUBILITY IN NEUTRAL AND ALKALINE SOLUTIONS AT 25"G DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By JAMES FREDERICK BONK, B.S. The Ohio State University 1958 Approved by: Depart Chemistry AGKNOWLEDGM0JT The author wishes to express his sincere appreciation to Professor A. B. Garrett for his supervision and counsel during the course of this investigation. I wish to thank him for his interest in my welfare while I was a student at The Ohio State University and especially for his guidance and encouragement in my teaching career. I also wish to thank the DuPont Chemical Company for granting me the DuPont Teaching Fellowship for the 1956-1957 academic year. I wish to thank The Ohio State University for the Assistantship, Assistant Instructorship, and Instructorship granted me during the course of this investigation. TABLE OF CONTENTS Page I. INTRODUCTION 1 II. HISTORICAL a. Methods of Preparation of t/ Silver(II)oxide 2 b. Properties of Silver(II)oxide 7 c. Uses of Silver(II)oxide 13 III. THE SOLUBILITY OF SILVER(II)OXIDE IN NEUTRAL AND ALKALINE SOLUTIONS AT 25“G 1? a. Experimental 17 1. Preparation of Reagents 17 2. Preparation of Samples 19 3. Equilibration 23 4. Sedimentation 23 5. Filtration 23 6. Potentiometric Analysis 23 7. Analysis of Solid Phase 26 b. Solubility Data for Silver(II)oxide 27 c . Discussion 34 111 CONTENTS (continued) Page IV. A STUDY OF THE SILVER (I) OXIDE- SILVER (II) OXIDE ELECTRODE 39 a. Introduction 39 b. Historical 39 c. Experimental 43 1. Preparation of Reagents 45 2. Preparation of Cell 49 3. Calibration of Apparatus 50 d. E.M.F. Data on Silver(II)oxide 52 e. ThermodynamicConsiderations 66 f. Discussion 71 V. CONCLUSION AND SUMMARY 79 AUTOBIOGRAPHY 85 IV LIST OF TABLES Table 1. Solubility of Silver(Il)oxide in Solutions of Sodium Hydroxide at 25°C. 2Ô 2. Solubility of Silver(II)oxide in Pure Water. 29 3. Solubility of Silver(I)oxide in Solutions of Sodium Hydroxide at 25®C. 30 4. Solubility of Silver(I)oxide in Pure Water. 31 5. Solubility of Silver(l)oxide in Pure Water at 25®C as a Function of Settling Rate of Silver(I)oxide Particles. 32 6 . SummsLry of E.M.F. Data at 25®C for the Silver(l)oxide-Silver(II)oxide Electrode. l+k 7. E.M.F. Data at 25®G of the Cell: Ag,Ag20/Na0 H(M)/Ag0 ,Ag20,Ag. 46 8 . E.M.F. Data at 25®C for the Cell: Ag,Ag20/Na0H(M)/Ag0,Ag20,Pt. 53 9. E.M.F. Data at 25®C for the Cell: Ag,Ag2Q/NaOH(M)/AgO,Ag20,Pt. 54 10. E.M.F. Data at 25®C for the Cell: Ag,Ag20/Na0H(M)/Ag0,Ag20,Pt. 59 11. E.M.F. Data at 25®C for the Cell: Ag,Ag20/NaOH(M)/AgO,Ag20,Pt. 6l Table Page 12« E.M.F. Data for the Cell: Ag,Ag20/Na0H(M)/AgO,AggO,Pt at Various Temperatures. 62 13. E.M.F. Data for the Cell: Ag,Ag20/NaûH(M)/AgO,Ag20,Pt at Various Temperatures. 63 14. E.M.F. Data for the Cell: Ag,Ag20/NaOH(M)/Ag0,Ag20,Pt at Various Temperatures. 64 vx LIST OF ILLUSTRATIONS Figure Page 1. Preparation Train Assembly. 20 2. Solubility of the Oxides of Silver in Sodium Hydroxide Solutions at 2$*G. 33 3. E.M.F. Data for the Cell; kg,Ag20/Na0H(M)/Ag0,AgaO,Pt as a Function of Time. 55 4» E.M.F. Data for the Cell* Ag,Ag20/Na0H(M)/Ag0,Agg0,Pt at Various Temperatures. 56 5. E.M.F. Data for the Cell; Ag, Ag20/Na0H(M)/Ag0, AggO^Pt at Various Temperatures. 57 6, E.M.F. Data for the Cell; Ag,AggO/NaOHCM)/AgO,Ag^O,Pt at Various Temperatures. 58 VLl INTRODUCTION The purpose of this investigation was to obtain data on the equilibria of silver(II)oxide in water and in dilute solutions of sodium hydroxidej and to obtain data on the characteristics of the silver(I)oxide-silver(II)oxide electrode. The solubility data make possible (1) the determination of the character of the ions in dilute solution, (2) the evaluation of the free energy of these ions, and (3) the evaluation of the solubility product of silver(II)oxide. The data on the silver(I)oxide-silver(II)oxide electrode make possible the determination of the standard electrode potential of the silver(I)oxide-silver(II)oxide electrode in basic solution, and the evaluation of the free energy of formation, enthalpy of forma­ tion, and entropy of formation of silver(II)oxide. Although silver(II)oxide has become a relatively important compound in recent years, investigations of a number of its properties have either not been reported, or have led to conflicting results. One of the major conflicts concerning this conç)Ound is whether it is actually silver(II)oxide, AgQ| or if it is silver(I)peroxide, AggOg. For reasons which will be presented in the Historical Section of this thesis and discussed in the summary and conclusion of this thesis, the author considers the compound to be silver(II)- oxide and refeisto it as such throughout the thesis. HISTORICAL SECTION A. Methods of Preparation of Silver(II)Oxide Anodic Oxidation of Silver Nitrate Solutions Of the many methods of preparation of silver(II)oxide, the earliest literature reference 1 is the anodic oxidation of silver 1. Ritter; Neus allgem. Journ. d, Chemie, ^ 561(1804) • nitrate solutions. However, the material which Ritter considered to be silver(l)peroxide, AggOg, was later shown by numerous in- vestigators2"9 to be silver peroxynitrate, AgyNOn* 2. Mahla, Ann., 3 ^ 289(1852). 3. Sulc, Zeit. anorg. Chem., 3 ^ 89(1896). 4. Sulc, ibid. 2k> 305(1900). 5. Mulder and Heringa, Rec. trav. Chim., 2âj 1(1896). 6. Tanatar, Zeit. anorg. Chem., 2 ^ 33l(l90l). 7. Watson, J. Chem. Soc., 82» 578(1906). 8. Brown, J. Phys. Chem., 20, 680(1916). 9. Weber, Trans. Electrochem. Soc., 391(1917). An excellent summary of all the early papers dealing with silver Ô peroxynitrate is given by Brown. Silver(II)oxide may be prepared from silver peroxynitrate by 3 heating to 100"G or by treating silver peroxynitrate with boiling water for one to two hours. 10. Noyes, J. Am. Chem. Soc., ^ 1339(1937). Jolibios^^ describes a method of preparing silver(II)oxide in- 11. Jolibios, Gompt. Rend., 200. 1469(1935). volving the plunging of high voltage electrodes (about 350 volts) into silver nitrate solutions. Anodic Oxidation of Silver in Sulfuric Acid The anodic oxidation of silver in sulfuric acid solutions was first used by Fischer^ and later by Wohler.A study of the 12. Fischer, J. f. pr. Ghem., 240(1844). 13. Wohler, Ann. d. Gh. u. Ph., 146. 263(1868). process by Jones and Thirsk^ concluded that the following reactions occur at the anode; Ag -- ^ kgzSOj^. -- ^ AgO + Og 14. Jones and Thirsk, Trans. Faraday Soc., 50. 732(1954). 4 Anodic Oxidation of Silver in Alkali The anodic oxidation of silver in alkali was described by- Luther and Pokorny^5 as occurring quantitatively and reversibly as follows; Ag ^ AggO -- ^ AgO 15. Luther and Pokorny, Zeit. f. anorg. Chem., ^ 309(1908). Hickling and Taylor^^ suggest on the basis of their study that 16. Hickling and Taylor, Disc. Faraday Soc., 1^ 277(1947). an oxide higher than silver(II)oxide is primarily formed and that silver(II)oxide results secondarily from the decomposition of this higher oxide. A more recent study^^ proposes that the aiodic oxidation of 17. Jones, Thirsk, Wynne-Jones, Trans. Faraday Soc., 52. 1003 (1956). silver occurs in steps each involving the introduction of an oxygen into the face-centered-cubic lattice of silver metal as follows^ Ag — ^ AgO^ — ^ AggO — ^ AgO — ^ AggOa — ^ AgOg AgO^ is a suboxide where x is less than one-half. (The compound AgOg has been prepared and studied by Talaty.^^) 18. Talaty, J. Indian Chem. Soc., 2 ^ 413(1951). 5 Oxidation of Silver by Potassium Persulfate The oxidation of silver salts by potassium persulfate in one of the best methods of preparation of silver(II)oxide ard has been widely used,^^ 19. Marschall, J. Chem. Soc., 1891. 771. 20. Moeller, Zeit. f. Phys. Chem., 555(1893). 21. Austin, J. Chem. Soc. Trans., ^ 262(1911). 22. Yost, J. Am. Chem. Soc., 48. 152(1926). 23. Barbieri, Ber., 2427(1927). 24. Kleinberg, Inorganic Synthesis. ^ 12(1953). The reaction as given by Kleinberg^ is 4AgN03 + 2K2S2O0 + 8NaOH — > 4AgO + K2SO4 + 3Na2S04 + 2NaN03 + 2KNO3 + 4H2O. Other Methods of Preparation Other methods of preparation involve oxidation of silver(I)- oxide^^ or silver metal^^*^^ by ozone, oxidation of silver(l) salts 25. Schiel, Ann. Ch. u. Ph., 2 ^ 322(1864). 26. Schonbein, J. f. pr. Ch., 2Jo 322(1858). 27. Jirsa, Zeit. anorg. allgem. Chem., 158. 33(1926). 6 by fluorine,^® oxidation of silver(l)oxide by sodium hypochlorite, 28. Fichter and Goldach, Helv. Chim, Acta, 1^, 99(1930). 29. Dutta, J. Indian Ghem. Soc., ^ 95(1955). as a by-product in the reaction of moist silver(I)oxide with carbon monoxide,^ and by the photoxidation of silver on the surface of 30. Szabo, Soos, and Deak, Zeit. anorg. Ghem., 252 . 201(1944). rutile. 31. Forland, Proc. Intern. Symp. on Reactivity of Solids, Gothenburg, 1952. 291 (G.f. G.A., M , 8059^(1954)). Of the methods described above.
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