Zinc Sulfide-Sulfate Reaction Pressures" (1963)
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Scholars' Mine Masters Theses Student Theses and Dissertations 1963 Zinc sulfide-sulfate eactionr pressures William L. Hallerberg Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses Part of the Metallurgy Commons Department: Recommended Citation Hallerberg, William L., "Zinc sulfide-sulfate reaction pressures" (1963). Masters Theses. 2810. https://scholarsmine.mst.edu/masters_theses/2810 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. ZINC SULFIDE - SULFATE REACTION PRESSURES by William L. Hallerberg A Thesis Submitted to the Faculty of the University of Missouri School of Mines and Metallurgy in partial fulfillment of the requirements for the Degree of Master of Science in Metallurgical Engineering Rolla, Missouri 1963 Approved by: Advisor ABSTRACT A static manometric method was used to find the equilibrium reaction pressure as a function of temperature for the reaction: 11 ZnS04 + ZnS --> 4 (Zn0*2ZnS04 ) + 4 S02 From the reaction pressures, the standard free energy of the reaction was found to be: AF° = + 51,320 - 36.68 T Using thermodynamic data for ZnS04, ZnS and S02 the standard free energy of formation of the basic salt Zn0*2ZnS04 was found to be: AF° = - 377,000 - 6 5 . 9 T cal/mole in the temperature range 350 to 420° C. Above 420° C. the reaction, 2 ZnS + 3 (ZnO.2ZnSO4 ) --> 11 ZnO + 8 S02 proceeds. ACKNOWLEDGEMENTS The author wishes to express his sincere appreciation to Dr. A. H. Larson, Associate Professor of Metallurgical Engineering and to Dr. A. W. Schlechten, former Chairman of the Department of Metallurgical Engineering for their assistance and counsel during the course of this investi gation. The author also wishes to thank Dr. W. J. Kroll for the granting of a fellowship without which this graduate study would not have been possible. TABLE OF CONTENTS CHAPTER PAGE I. Introduction.............................. 1 Statement of the Problem................ 1 Organization of the Problem ............ 1 Importance of the S t u d y ................ 1 II. Literature Survey ........................ 3 III. Theoretical Considerations................ 9 Reaction Mechanism...................... 9 Thermodynamics............................ 11 IV. The Apparatus...............................14 The Reaction System ...................... 14 The Drying System ........................ 20 V . Procedure.................................. 24 VI. Results and Calculations.....................27 X-ray Diffraction Studies .............. 27 Reaction Pressures........................ 27 VII. Discussion of Experimental E r r o r s ........... 32 VIII. Discussion and Conclusions...................34 Bibliography................................ 41 Vita........................................ 43 LIST OF FIGURES FIGURE PAGE 1. Schematic Diagram of Reaction System..........15 2. Photograph of Reaction System................16 3 . Schematic Diagram of Kern-Springham Manometer 19 4. Schematic Diagram of Drying System............22 5 . Photograph of Drying System ................ 23 6. log p vs. 1/T Relationship for the Reaction 11 ZnS04 + ZnS --> 4 ZnO.2ZnSO4 + 4 S02 . 31 7 . Effect of Temperature and Gas Composition on the Stability of Basic Zinc Sulfate at 1 Atmosphere Total Pressure .................. 38 8. Effect of Temperature and Gas Composition on the Stability of Basic Zinc Sulfate at 0.5 Atmospheres Total Pressure....................39 9 . Effect of Temperature and Gas Composition on the Stability of Basic Zinc Sulfate at 0.2 Atmospheres Total Pressure....................40 CHAPTER I INTRODUCTION Statement of the Problem. The purpose of this investigation was to determine the reaction pressure as a function of temperature for the reaction: 11 ZnS04 + ZnS 4 (Zn0*2ZnS04 ) + 4 S02 where Zn0*2ZnS04 is a stable intermediate phase in the sulfide-sulfate reaction mixture. From these data the standard free energy of formation of the intermediate basic sulfate phase can be calculated. Organization of the Problem. The problem was attacked experimentally by obtaining the pressure versus temperature relationship for the sulfide- sulfate reaction by a static manometric technique, incor porating the use of an all glass closed system with a glass spiral manometer. X-ray diffraction patterns were made to identify the solid reaction products. Importance of the Study. During the roasting of zinc sulfide ores the primary objective is the conversion of the ore to ZnO. However, 2 deep in the bed of the roaster (hearth type), there may be a deficiency of oxygen and an excess of zinc sulfide. The question as to whether or not these conditions favor sulfate decomposition is of practical interest. CHAPTER II LITERATURE SURVEY A substantial amount of information has been published concerning the decomposition of zinc sulfate both in the presence of zinc sulfide and in its absence. However, a few of the authors differ in their opinions as to whether a basic zinc sulfate is formed or not. Furthermore, those who advocate the presence of a basic sulfate in the decomposition reaction of zinc sulfate differ widely in their proposed stoichiometric formulae. M. Trautz and S. Pakschwer^- (1 9 2 9 )., studying the general reaction, MeS + 3 MeS04 4 MeO + 4 S02 did some research on the Zn system. Their conclusion was that the existence of basic sulfates was doubtful, even though earlier literature suggested it. This earlier literature may have been W. R. Ingalls^ (1906) who said: "When the temperature is raised only to cherry red, neutral zinc sulfate, ZnS04, is split up into basic zinc sulfates and sulphuric and sulphurous anhydrides and oxygen. There is no record in chemical or metallurgical literature, so far as I have been able to discover, as to which of the several basic sulfates of zinc are produced during that process, except a remark in Plattner's ROSTPROZESSE that it is the tetrabasic sulfate (ZnS04*3Zn0) which is formed." 4 About this same time H. 0. Hofman3 (1905) also men tioned Plattner's idea of the formation of ZnS0 4 *3 Zn0 . Hofman admited that a basic sulfate was formed but he did not commit himself as to the formula. Later in a textbook, Hofman4 (1922) stated that ZnS04 will decompose into S03 and 5Zn0*2S03. His formula can also be represented as Zn0 *2 ZnS0 4 . I. P. Bardin^ in his edited survey of metallurgy in the USSR mentioned sulfide-sulfate reaction rates but no mention whatsoever was made of any basic sulfate or inter mediate phase. Bardin suggested the reaction mechanism for Cu, Pb, Cd, Fe and Zn as follows: MeS04 + MeS 2 Me + 2 S04 MeS04 -*• MeO + S02 + i 02 Most of the more recent investigations mention the presence of the basic intermediate sulfate, although there is disagreement as to its composition. Bui-Nam^ (1959) proposed the existence of the basic sulfate 5Zn0 *2S03, (Zn0«2ZnS04), but he stated that to his knowledge it had never been found. The work done in the USSR lead the investigators to different conclusions. V. V. Pechkovskii? (1957) says: 5 "The thermochemical decomposition process of zinc sulfate, in the absence of admixtures, can.be described by the following basic equations: ZnS04 ZnO + S03 under these conditions we did not detect the presence of basic zinc sulfate among the solid calcination products." Later on in his article, Pechkovskii stated that the major solid calcination products of zinc sulfate are zinc oxide, with oxygen, sulfur trioxide and sulfur di oxide present as the gaseous products. J. S. Warner® (1 9 6 1 ) suggested that any sulfate may or may not go through the intermediate basic sulfate phase. In their investigations of the lead-sulfur-oxygen system, H. H. Kellogg and S. K. Basu^ (i9 6 0 ) found cause to suggest the existence of the intermediate salts, PbS04* PbO, PbS04 -2Pb0 and PbS04 -4Pb0. Using the static manometric method of analysis, incorporation a mercury manometer, Motoo and Toshiaki^ (1947) studied the reaction pressure of ZnS04 and ZnS in combination. They contended that a basic sulfate was formed and that its formula is jZn0*ZnS04. Their reaction mechanism is as follows: 3 ZnS + 13 ZnS04 -*• 4 (3Zn0*ZnS04) + 12 S02 6 ZnS + 3 (3Zn0-ZnS04) 13 ZnO + 4 S02 In their investigation of the decomposition temperature of zinc sulfate, Ostroff and Sandersonll observed the for mation of an intermediate phase, which, they said, was 3ZnO•2S03. (Zn0*2ZnS04) R. Schuhmann, Jr. reports in the chapter on the chemistry and physics of zinc technology which he wrote for Mathewson^ (1959)> "Some observers have considered the possible formation of basic zinc sulfates, such as 3Zn0*2S03 (Zn0-2ZnS04) but evidence is not clear..." Twidwell^-5 (1 9 5 2 ) investigated the influence of selected sulfides on the thermal decomposition rate of zinc sulfate. He found that the decomposition of ZnS04 in the presence of ZnS, CdS or Cu2S yielded Zn0*2ZnS04. His reaction mechanism for ZnS04 and ZnS is as follows: 3 ZnS04 + ZnS -*• 4 ZnO + 4 S02 4 ZnO + 8 ZnS04 — *» 4 (Zn0*2ZnS04) The overall initial reaction being: 11 ZnS04 + ZnS — ** 4 (ZnO-2ZnS04) + 4 S02 The final stage being: 4 (Zn0*2ZnS04 ) + 8/3 ZnS 44/3 ZnO + 32/3 S02 7 Adding the last two reactions, the overall reaction is found to be: 3 ZnS04 + ZnS — 4 ZnO + 4 S02 Twidwell identified the basic salt by X-ray diffraction analysis of various stoichiometric mixtures of ZnO and ZnS04 . T. R. Ingraham and H. H. Kellogg^ (1 9 6 2 ) presented a paper to the AIME in which they studied the zinc-sulfur- oxygen system. By thermogravimetric and X-ray analysis they identified an intermediate phase of Zn0-2ZnS04 upon the decomposition of pure ZnS04. Their reaction mechanism is : Initial, 3 ZnS04 — (ZnO*2ZnS04) + S03 Final, (Zn0*2ZnS04 ) — ^-3 ZnO + 2 S03 Overall, 3 ZnS04 — 3 ZnO + 3 S03 Ingraham and Kellogg also calculated that for the reaction, ZnO + 2 ZnS04 (Zn0-2ZnS04) AH 298 = -1650 cal. AS 298 = +1.13 eu.