A Thermodynamic Study of Germanium Sulfides
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Scholars' Mine Masters Theses Student Theses and Dissertations 1960 A thermodynamic study of germanium sulfides Sham Lal Malhotra Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses Part of the Metallurgy Commons Department: Recommended Citation Malhotra, Sham Lal, "A thermodynamic study of germanium sulfides" (1960). Masters Theses. 2798. https://scholarsmine.mst.edu/masters_theses/2798 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]. A THERMODYNAMIC STUDY OF GERMANIUM SULFIDES BY SHAM LAL .MALHOTRA A THESIS Submitted to the faculty of the SCHOOL· OF MINES AND METALLURGY ·OF THE UNIVERSITY OF MISSOURI in partial fulfillment of the work required for the Degree o~ MASTER OF SCIENCE IN METALLURGICAL ENGINEERING ABSTRACT The vapour pressure of germanium monosulfide (liquid) was determined by a boiling point method. An expression forthe vapour pressure as a function of ·temperature was obtain~d. and the heat of vapourization calculated.. Using the heat of sub limation data obtained by other investigators, the heat of fusion was calculated. The thermodynan1ic properties, change of standard-free 0 0 energy(fi FQ) heat content·(~ H ) and entropy (~ s ); of ger manium disulfide were determined by using an indirect method. The equilibr_ium H2S/}k0 ratios are determined for the reaction: GeS2(s) + 2H20(g) = Ge02(s) + 2~2S(g), in the temperature . range of 410-560°C by using a fiow method and extrapolating the values of H2S/~o ratios to zero flow rate. An - expression for the standard free energy of the reaction as a function of temperature was obtained. Using the known values of standard free energy of foi'Illation of Ge02 (s), H2S(g) and H2.0(g) an expression for the dissociation of ger manium disulfide was calculated • . A detailed. description is given for ·the methods and the apparatus used. for both the vapour pressure and equilibrium studies. ii The methods used for the preparation of the compounds GeS2 ana GeS and their properties are described. X-ray diffraction patterns are given for GeS2 , GeS and Ge02 phases. ACKNOWLEDGEMENTS The author wishes to express his appreciation and gratitude to·Dr. A. W. Schlechten,. Chairman of the Department of Metallurgical Engineering and Dr. A.H. Larson, Assistant Professor.of Metallurgical Engineering for their counsel and assistance throughout the course of this investigation. The author is also indebted. to Mr. J.P. Hager, former graduate student, for his help in the construction of the experimental apparatus. The author expresses his gratitude to the International Cooperation Administration, Washington, D. c., for their financial assistance for him to study in this country. TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION. 1 Statement of the problem • 0 • . 1 Organization of the problem . l Importance of the study . 1 II. THE EXPERIMENTAL METHODS •• . 3 A survey of the experimental methods. 3 Vapour pressure measurements o 3 Static methods •• 3 Dynamic methods . 5 Method.s based on rate of sublimation • . and evaporation . 7 Indirect methods of determination of. sulfur pressures. 8 Selection of methods •• . 10 III. PREPARATION AND PROPERTIES OF GERMANIUM SULFIDES 14 Preparation of germanium sulfides 14 Preparation of ge~anium rnonosulfides • • • 15 . Review of the literature • • • • • . • . 15 Methods used i~ this investigation .•• 16 Preparation of germanium disulfide . 18 Review of the literature •••• . 18 CHAPTER P.A.GE Method used in this investigation 20 Properties of germanium sul:fiides\.·. ., • ·22 Properties o# germanium disulfide 22 Properties of germanium monosul·fide 22 X-ray diffraction . 25 Review of the literature ••• 25 Experimental work 26 IV. VAPOUR PRESSURE STUDY THE APPARATUS AND. EXPERI_:·. MENTAL PROCEDURE . 30 The apparatus . 30 Reaction apparatus. 30 Furnace . 30 Reaction tube .... 36 Temperature record~r.• . 36 Gas Supply and pressu~e regulating system 36 Gas supply. .. 37 Pressure regulating system . 37 Pressure indicating unit. 0 • • • • 38 Procedure • • • • 0 • • • • • 0 . 38 V. THE EQUILIBRIUM STUDIES THE APPARATUS AND · EXPERIMENTAL PROCEDURE . 0 • • 42 The apparatus ••• . 42 vi CHAPTER PAGE Gas purification system • • 42 The saturating apparatus 49 The equilibrium -apparatus 53 Experimental procedure ••• 58 Standardizing of iodine solution •• 60 VI. EXPERIMENTAL RESULTS • • 62 Vapour pressure data. 62 Equilibrium H2S/H2 0 data 64 X-ray diffraction data •• 65 VII. THERMODYNAMIC CALCULATIONS 84 Vapour pressure study of germanium monosulfide 84 C~lculations from ~esults of previous investigat~ons •• 86 Equilibrium studies of germanium disulfide 88 Calcalations from previous investigations 92 VIII. DISCUSSION OF THE RESULTS. • • • • • • • • • • 98 Vapour pressure study of germanium monosulfide 98 Equilibrium studies of germanium disulfide 100 IX. SU~RY AND CONCLUSIONS . 103 Vapour pressure study of germaniwn monosulfide 103 Equilibrium study of germanium disulfide 104 BIBLIOGRAPHY. • • • • 105 APPENDICES •• 108 VITA ••• • 0 • • • • • • • • ~ • ... 112 LIST OF ILLUSTRATIONS FIGURE PAGE 1. Schematic diagram ~f vapour pressure apparatus •• 31 2. The apparatus used for vapour pressure study ••• 32 3. Reaction tube and furnace assembly for · vapour pressure study •••.•••••••• 33 4. Furnace electric power control. 35 5. The apparatus used for equilibrium study. 43 6. Schematic diagram of gas purification system. 44 7. Gas purification sy'stem . 45 8. Schematic diagram of saturating and equilibrium apparatus . , , , ~ , • • • 50 9. The saturating apparatus 51 10. The equilibrium apparatus . 54 llQ Reaction tube and furnace assembly for equilibrium apparatus •••••• 55 l~. Furnace electrical power control . 57 l}. Vapour pressure of germanium monosulfide. 77 14. variation of equilibrium H2S/H20 rati·o with. flow rate at 410 °C • • • • • • • • • • • • . 78 15. variation of equilibrium ~S/H20 ratio with flow rate at 440 '."'" 510°c • . • . • 79 16. variation of equilibrium H2S/H20 ratio with flow rate at 495 - 56ooc • . .. 80 17. variation of equilibrium H.2S/H20 .ratio with flow rate at 460°C . 81 viii FIGURE PAGE 18. Variation of equilibrium constant (H2 .S/H2 0) with temperature for the reaction GeS2 ( s) + 2H2 0 ( g) = Ge02 + 2H2 S ( g) • • • • 82 19. Comparison of vapour pressure of liquid GeS, data by this i~vestigation and Spandu and Kl anbe rg • • • • • • • • • • • • • • • • . 87 20. The standard free energy _of dissociation of GeS2 , as a function of temperature •• LIST OF TABLES TABLE PAGE l}. Vapour pressurecof germanium monosulfide between 1200 - ·1455°c •••••••• 66 II~ Equilibrium H2 S/~o obtained for germanium disulfide •••••••••••••••• 68 III. X-ray diffraction data for germanium mono- sulfide prepared by synthesis from. elements 71° IV. X-ray diffraction data for germanium mono sulfide prepared. by reduction of germanium d.isulfide by hydrogen • • • • • • • • . • • . 73 v. X-ray diffraction· data for germanium disulfide •• 75 VI. Equilibrium values of H2 S/H2 o from extrapolation to zero flow rate • • • • • • • o • • • • • 83 VII. Vapour pressure and heat of · sublimation of germanium monosulfide reported in literature 89 VIII. Standard free energy expressions used in the calculations • • • • • • • • • • • • • 94 IX. Standard free energy ~XJ?ressions from the · work of Jain • • • • • • • • o • • ... 97 CHAPTER 1 INTRODUCTION statement of the problem. The purpose of this in vestigation was (1) to determine experimentally the vapour pressure of germanium·monosulfide, (2)· to determine exper imentally some of the thermodynamic properties of germanium disulfide. Organization of the problem. Th_e problem consisted of three types of experimental work: (1) the-preparation of germanium mono and disulfide, (2) the vapour pressure study of germanium monosulfi~e, and (3) the equilibrium. study of germanium disulfide. An explanation of the apparatus and the experimental procedur~ ha'sG· been p~esented in chapters III, IV and V respectively. The experimental results are given separate!~ in chapter VI. Importance of the study •. Germanium.is ·wid.ely dis- tributed in small quantities in the e~rth's crust, but no ore mineral is known where germanium is the primary element. Based on the fact that nearly all of the ores containing· germanium are sulfid~s, the selective volatilization of metallic sulfide·s, either at atmospheric pressure or under vacuum seems to be a promising method of concentration. To predict 2 such a process, it is necessary to know the relative volatilities· of the metallic sulfides. A study of the vapour pressures of germaniwn sulfides is of:.,prime importance for evaluating ·the feas~bili ty-:.6£ such a process~ A knowledge of other thermodynamic properties such as heat capacity, heat content, entropy and free energy, and how they are influenced by temperature and pressure can enable one to design and predict the behaviour of new processes. CHAPTER II THE EXPERIMENTAL METHODS In order to detepnine the thermodynamic properties of germanium sulfides, it was necessary to consider the various methods which have been used by other investigators for sim ilar studies. Later the literature was surveyed. to find the work that has already been done on germanium sulfides, and methods were selected. for the study. I. A SURVEY OF EXPERIMENTAL METHODS Generally