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The Reactions of Lithium with Nitrogen and Water Vapour By The Reactions Of Lithium With Nitrogen And Water Vapour by Wayne Ronald Irvine A Thesis Submitted In Partial Fulfillment ' Of The Requirements For The Degree Of Master Of Science in the Department of Mining and Metallurgy We accept'this thesis as conforming to the standard required from candidates for the degree of Master Of Science Members of the Department of Mining and Metallurgy The University Of British Columbia April, 1961 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of Mining and Metallurgy, The University of British Columbia, Vancouver $, Canada. Date May 3rd, 196l ABSTRACT The reactions of lithium disks with dry and moist nitrogen and with water-vapour were investigated at temperatures from 22 to 70 degrees Centigrade with the use of a thermal balance. The reaction in nitrogen commenced with nucleation of lithium nitride at corners and edges of the sample and the reaction proceeded by lateral growth of these nuclei through the specimen. In moist gas, this reaction was accompanied by the simultaneous formation of lithium hydroxide at the plane surface of the specimen. Based on visual observations of the samples during the reaction, a model describing the geometry of nucleus formation was constructed and was used to calculate growth velocities from the reaction curves obtained with the thermal balance.The dependence of growth velocity on temperature, nitrogen partial pressure, and the moisture content of the reaction gas was investigated. The reaction with water-vapour was observed to proceed in three distinct stages.The results have been explained in terms of a model involving recrystallization and hydration of an initially coherent lithium hydroxide film.. ii' ACKNOWLEDGEMENTS The author is grateful for financial aid in the form of a Fellowship provided by the Foote Mineral Company„. The supervision of Dr. J.A.»Lund and the technical assistance of Mr, R.. Go Butters, who constructed the recording balance, are gratefully acknowledged. The author is indebted to Mrs1. Margaret Armstrong for her many helpful discussions.. Ill» TABLE OF CONTENTS . Page I a U\[ X RO D U O i. ION ooo«o«»oooooe«oeooe«oo"ooeooooooaoaoooo- 1 A* General Considerations * . o. , . .. .. .« . <>. .. I Bw Previous Work with Lithium ....,..„.........„, 3 Co. Scope of the Investigation. „„„.„..„ . .. „ .0 » . 4 II. EXPERIMENTAL' PROCEDURE A.. Design of Thermal « Balanco © 6 • o eoo oan odo oAuxiliar o o o o o a oy o oo o o -o a a o .i^ p jp cl I" d t U. S OOOCOOOOOOO OOOOOO'OOOOOOOOOOO o o » 0 o 0> © 3'' .Bo. Specimen Preparation ........................ 7 C„. Procedure OOOOOOOOOO oo O © OO OO O OO O O O O .« O OOOO o o O 0 III, RESULTS FOR REACTIONS WITH DRY AND MOIST NITROGEN.. 10i A'«. Reaction with Dry Nitrogen ...... ............ '10- 1 o« R© SVllt/S oooooooo ooooooooo-oooooo© ooo oooooo o -1-0 20 . Discussion of Results for the Reaction in Dry Nitrogen ............ ............. 13 B. Reactions with Moist Nitrogen . ............... 14 1.,-Effect of Reaction Temperature .......... • 1U • 2. The Effect of the Moisture Content of the Reaction 3o Effect of Partial Pressure', of Nitrogen .0 0 1-5 C Analysis of the Results Obtained Using ^iO.l St N 11 r O 1*1 000000 »ooooooooooeooooooo«OOoo 1^ 1... Analysis' of Results for Run in which Surface Nucleation was Abs,ent ............ 22 2. Analysis of Results for Ruin in which. Surface Nucleation was Present .". ........ 24 D 9 DXSCUSSlOn 0.f R© SU.1 *t> S • ooooooo-oooooooooooooooo*' 0 I... Factors Influencing Nucleation Rate ...... 30 . 2„ Factors Influencing Growth' Rate <, ........ 31 E Q SOUFC6 S OT ErrOT* ooooot.ooooooooooocoooooo.oooo 3 5 F 9 G OT^C 1U. S 10 IT S ooooooeoooocooooooooooooooooooooo 3 7 IV. REACTION! WITH WATER VAPOUR . ... .................. 33 A. Reaction with-Dry and Moist Oxygen .......... 3'$ B„. Reaction with Water Vapour . .................. 3$ •I.-General Characteristics of the Reaction....' 3$ 2. Comparison of Oxygen, Argon, and Helium as ' Carrier Gases; .............. .... 43 3:« Effect of Temperature .................... 43 4. Effect of Partial Pressure of Welt©!*- VcH-pOU.!** ooooooo'oo 0000 oooo©ooooot> ©©000 A* C „ Discussion of Results. ....................... 46 1, General Considerations ....... ........... 46 2. The Effect of Partial Pressure of Water , in the Reaction Gas ............. .......... 4$ 3 , Suggested Mechanism ....... ................ 48" Do S o u. r c © s o JT Error ooooooo.o©oo©oooooooo©ooooo©o 5 1.' Errors due to Variations in Surface COridltlOn 000'©0000ft»00©00©0©»©0©0©»»0 0©0©0 iv. TABLE OF CONTENTS ( continued ). page 2. Error in Temperature Measurement Due to Liberated Reaction Heat................... $2. 3. Zero 4. Errors due to Transport of Water Molecules to the Lithium-Hydroxide: Gas Interfere ... 53 E <> Conclu.sxoris • ©©©o©»»»©o©©©©i>«o<ioo«©oo«ou©©»»» 53 V" 0* BIBL 10 GRAPH IT ooocoo°»*oooeo©o<»©«o«o90oao*o«<>*o<»««oo 55 56 V" X c* A.P PEN D I G E S 0000000© o»» ©©•••*»e©ooo»©oo©o»0o©»aoo ©• © • A,Appendix 1 ( Results for Reactions with Bo Appendix 11 ( Results for Reactions with Wcl t 6 IT" VS. POUT ) OOOOOOOGOOeOOOOOOOOOOOGOOVO'OO"* 66 V/. LIST OF FIGURES NO. Page 1. Schematic Drawing of Experimental Apparatus ........ 6 2 „ Photograph o f the Apparatus ........................... 9 3-o Reaction Curve for a Rectangular Specimen Heated in Dry Nitrogen at 110°C 11 4.. Specimen Reacted in Dry Nitrogen at 110°C ........... 12 5» Specimen for which Reaction was Initiated in Moist Gas and then Continued in Dry Gas .................. 12 6. Specimen Reacted in Moist Nitrogen at 40°C 12 7«. Reaction Curves for Samples Reacted in Moist Nitrogen at Various Temperatures ....... ....................... 16 8. Reaction Curves for Three Samples Reacted in Moist 9o Reaction Curves for Samples Reacted at 40°C in Gases of Different Compositions .... ........... ........... 1$ 10. Schematic Representation of Arrangement of Lithium Nitride During a Reaction .......................... 19 11.. Graph of" Incremental Reaction Rate vs. Reaction Time for Samples Reacted at 45°C ........................ 21 12. Graph Showing the Dependence of Interface Velocities on the Reaction Temperature ........................ 23 13. Arrhenius Plots for Interface Velocities ........... 25 14. Hypothetical Arrangement of Lithium Nitride for a .Sample Reacted in Moist Nitrogen ................... 27 15. Dependence of Reaction Velocities at 45°C on Partial Pressures of Nitrogen and Water Vapour ............. 28 16. Effect of Nitrogen Partial Pressure on Reaction 17r Reaction Curves for Samples Reacted in Moist Oxygen at Various Temperatures ..................... 39 18. Reaction Curves Obtained at 3 5°C in Moist Oxygen , Argon and Helium ................................... 40 vie ' LIST OF FIGURES ( CONTINUED ) NO'. Page 19. Changes in Surface Appearance of Specimens in Relation to a Reaction Curve ....................... 42 20.. Arrheniu:s Plots for Reaction Rate Constants ........ 44 21„ Dependence of Reaction Rate Constants on Partial Pressure of Water Vapour at 3 5°C ................... 45 Vllo LIST OE TABLES. NO.. Page APPENDIX 1 . lo Reaction Rates in. Dry Nitrogen at 110°C . „.„„..„„... 56 20 Reaction Rates in Moist Nitrogen at Various 1?G ffip 6 IT S. t Q S oooooooooo«oo»oooooooooo»eo*ooo»o»oooo*o 57 3o Analysis, of Results of Runs in Moist Nitrogen ...„.„ 59 4. Effect of Nitrogen Partial Pressure on Reaction VQ lOClty cit A*5 G OOOOOOOOOOOOOOOUOOOOOOOOOOOOOOGOOOO 6 0 5» Effect of Water Partial Pressure on . ' Reaction Velocity at 45°C 000000000000000.00.0000000 60 6. Effect of Temperature and Gas Composition on Nucleat IO IT Rclt© 00000000000000000000 0000 oc 00 e o o • o * 00 6l 7. Relative Reaction Rates of Circular and Rectangular Sp 6 C 11716 3T S oooooooooooo»oocoooooooooocooooooo 000 00000 62 80 X-ray Diffraction Data for Specimens Reacted in Moist N 11T* O ^ 61"l St 5 G 0000000 0000000 oooooooooooooeoo*o«©»o ^3 9» Reaction Rates Occuring in Dry Nitrogen after Initiating the Run in Moist Nitrogen ............... 64 10o Analysis of Results for Runs Carried out in Dry Nitrogen after Initiating the Run in Moist Nitrogen .O.o„.ooo 65 APPENDIX 11 lo Weight Increases of Lithium Disks Reacted in Moist Oxygen at Various Temperatures ..... o o o...........». 66 20 Summary of Results for Reactions in Moist Oxygen „„. 68 3. Weight Increases of Lithium Disks Reacted with Moist Helium at Various Temperatures .... 0 ............. 0. 69 4. Effect of Water Partial Pressure on Reaction Rates.. 70 5. X-ray Diffraction Data for Specimens Reacted with WcX "tf © JT* Vcl pOU.37 oooooooooooo€.ooou«ooooooo#ooooooo»ooooO THE REACTIONS OF LITHIUM; WITH NITROGEN AND WATER V/APOUR I INTRODUCTIONS A. GENERAL C:ONSIDERA.TIQNS The reaction between a metal and a gas begins at the metal-gas interface and usually the reaction product forms an intermediate layer between the metal and the gas. The reaction may be regarded as involving a series of consecutive steps including, for example: 1. Transport of gas molecules to the reaction layer-gas interface. 2. Adsorption at the interface. 3. Diffusion of one or both of the reacting species across the reaction layer. 4. Chemical reaction to cause increased thickening of the reaction layer. Depending on the individual case, other steps would have to be added to the list above. Quite generally, however, the overall rate of a reaction which proceeds by several successive steps is determined by the rate of the slowest step and the determination of the rate-controlling step is one of the primary objectives of any investigation dealing with the oxidation of metals.
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