CRNIL = - M TC-"R e h"-'h'\j ' PoEs nal B T RO B e @ E 2 s i Vv m*:g Py & e,!‘,ig’}.fiwlflr ! LQ é;li.,,r t:r*-r' b Uieibs § ORNL 1592 1;{—1{)} Special ot A ™ - o 51 4 (L ' CHEMICAL METHODS FOR THE SEPARATION D OF LITHIUM ISOTOPES - 192 54A KS V. D. Allred lvan B. Cutler L . 1 - s - i Hm - 83 savagnwven 1.*a et *Eared Bracusgsi o Suhann T 4 He ot ELASSIFICATION “g’f,“&‘ 2oy AK RIDGE NATIONAL LABORATORY € JATEUL 12 1m<@r\i-er OPERATED BY ; < CARBIDE AND CARBON CHEMICALS COMPANY : A DIVISION OF UNION CARBIDE AND CARBON CORPORATION # ) L [ e ’ te—AT A — POST OFFICE BOX P BECLASSIICATION SFTIVER , | CAK RIDGE. TENNESSEE BAK RIDGE NATiONAL LABJSLTORY ' AVTHORITY DELEGATED BY ERDA B-15-77 ORNL- 1542 Special ACCESS LIMITED TO This document consists v AUTHORIZED PERSONNEL of 176 pages. Copy of 77 copies. Series A. ALLOY DEVELOPMENT PROJECT CHEMICAL METHODS FOR THE SEPARATION OF LITHIUM ISOTOPES V. Dean Allred and Ivan B. Cutler (of the Catalytic Construction Company asslsting the Oak Ridge National Laboratory under the terms of AEC Contract AT (L40-1) 1520) MATERIALS CHEMISTRY DIVISION - G. H. Clewett, Director July 10, 1953 Date Issued AUG 1 & 1953 OAK RIDGE NATIONAL LABORATORY Operated by CARBIDE AND CARBON CHEMICALS COMPANY A DIVISION OF UNION CARBIDE AND CARBON CORPORATION Oak Ridge, Tennessee Contract No. W-7405-eng-26 ii Internal Distribution l. V. D. Allred 32. B. B. Klima 2. T. A. Arehart 33. W. B. Lanham 3. M. D. Barringer 34. L. Landau 4, G. M. Begun 35. C. E. Larson 5. R. E. Blanco 36. D. A. Lee 6. E. G. Bohlmann 37. W. J. Lilley 7. W. H. Brand 38. R. B. Lindauer 8. F. R. Bruce 39. A. C. Martinsen 9. W. L. Carter 40. H. M. McLeod 10. C. E. Center 41. R. P. Milford 11. G. H. Clewett 42. D. J. Oriolo 12 F. L. Culler 43, A. A. Palko 13. W. Delany 44. F., S. Patton 14. M. L. Drabkin 45. R. H. Powell 15 J. S. Drury 46. G. A. Ropp 16 G. A. Eaton 47. A. D. Ryon 17. W. K. Eister 48. A. C. Rutenberg 18. L. B. Emlet 49. J. Shacter 19. D. E. Ferguson 50. G. A. Strasser 20. H. H. Garretson 51. J. W. Strohecker 21. H. E. Goeller 52. E. H. Taylor 22. R. M. Healy 53. L. P. Twichell 23. W. B. Humes 54. W. E. Unger 24. E. D. Innes 55. A. M. Weinberg 25. H. K. Jackson 56. H. 0. Weeren 26. A, C. Jealous 57. J. J. Williams 27. W. N. Johnson 58. C. E. Winters 28. K. O. Johnsson 59, L B. Yeatts 29. C. P. Johnston 60-63. -12 Central Files 30, M. T. Kelley 64-67. X 10 Central Files 31. H. T. Kite 68. ORNL-RC External Distribution 69-70. R. W. Cook, c/o A. J. Vander Weyden, AEC, Washington 71. Brigadier General K. E. Fields, D.M.A., AEC, Washington 72. Jane Hall, L.A.S.L., Los Alamos 73. T. H. Johnson, AEC, Washington 74~75. K. Kasschau, AEC, Oak Ridge 76. J. H. Rushton, 1111no1s Institute of Technology, Chicago 77. W. W. Welnrlch Catalyti _ Phi ladelphla Pa. S e ’ ) s ¢ t 8 dem g . ed - f:ansm*ttal .fi w 0 o ANy manner L0 orized pnws N h Y pd. % iii PREFACE This report has been prepared by personnel of the Catalytic Construction Company (Philadelphia, Pa.) under technical supervision of the QOak Ridge National Labora- tory for ADP development under the terms of AEC Contract AT-(40-1)-1520, Many members of the ORNL staff and Catalytic Construction Company personnel in Oak Ridge have made contributions and aided in making corrections to the preliminary draft. Special acknowledgement should be given to G. M. Begun, R. E. Blanco, G. H. Clewett, J. S. Drury, H. H. Garretson, K. 0. Johnsson, and D. J. Oriolo for their assistance. This documyent ed dat defi imthe At ata as defined 46, Itg-transmittal ny -mapner to - - II. III. II. This document c iv CONTENTS PREFACE. . . . . © vt v v v e e e e e e e e e o iii INTRODUCTION . . . . . v v v e v e e e e e e, 1 PART ONE. PROCESS CHEMISTRY CHEMICAL EQUILIBRIUM METHODS A. Introduction. . 6 B. Exchange Equilibria e e e e e e e e 7 C. Exchange Kinetiecs . . . . . . . . . . . . . . 14 REFLUX PROCESSES A. Introduction. . . . . . . . . . « . . . < . . 15 B. The Dual Temperature Process. . . . . . . . . 16 C. Chemical Reflux Processes 1. Waste End Reflux a. Electrolytic Reflux . . . . . . ., . 17 b. Magnesium Amalgam Reflux. . . . . . 21 c. Potassium and Sodium Amalgam Reflux. . . . . . . . . . 25 2. Product End Reflux . a. Decomposition Reflux. . . . . . . . 30 b. Hydrogen Chloride Reflux. . . . . . 30 c. Sodium and Potassium Chloride Refluxes . . . . . . . . 31 SOLVENT AND FEED PURIFICATION A. Solvent Purification. . . . . . . . . . . . . 33 B. Feed Purification . . . . . . . . . . . . . . 34 PART TWO. CHEMICAL AND PHYSICAL DATA » INTRODUCTION . A. Arrangement of Data . . . . . . .+ . . « « . . 37 B. Contents . . . . . . . . . . < . . ... 39 LITHIUM AND LITHIUM COMPOUNDS A. Lithium . . . . . . ., . . . . . . . . . . .. 44 $ TIPONES ted data as defined in the A‘omle rgy Act of tg trapsmittal CURITY INFORMATION or the d‘s~'osure of iis contents in ner to an unau-::g;ized person is prohibited. L i AR e B S A 8 L4 e e s AR AR, BT N I A o P DS TS S L e T - SE T SECURI I MATION v v B. Lithium Chloride. . . . .« ¢ o o &« o « o & o o 72 C. Lithium Hydroxide . . . . . .« +« « ¢ « ¢« o &+ 94 III. MAGNESIUM AND MAGNESIUM COMPOUNDS A. Magnesium . . . e e o e e e e e e e e s 99 B. Magnesium Chlorlde o . s a2 & s w e & 8 s o o 108 IV. POTASSIUM AND POTASSIUM COMPOUNDS A. Potassium . . . e e e s e e e e o e a2 e 112 B. Potassium Chlorlde e e e e e e e e e e e e s 117 V. SODIUM AND SODIUM COMPOUNDS A. Sodium . . . . . o 4 o v e e e e s e e e e 120 B. Sodium Chloride . . . . ¢ « « &+ « « ¢« « « & & 123 C. Sodium Hydroxide. . . . . « + « « « « « « + o 126 D. Sodium Phosphate. . . . . . .+ . « « « « + + 127 VI. LIQUID SOLVENTS A. B. C. D. E. F. G. H. I. J. K. L. Ammonia . . . . c s o & 5 o s o & & & & o & o 127 Benzene . . . . ¢ « + o + o o a2 4 & 4 4 e o a 133 Decane . . . ¢ « o o o o o o o o o o & o o 137 Dodecane. . e « o « o o o a s @ o o e & o 142 Ethylenediamlne e e e e e 4 e e s e e e e e 142 Ethylene Glycol « . . . . . o & « ¢ o « o o 148 2-Ethyl Hexanol . . . . . . « « « « o + + o« o 150 Isopropanol . . . . . . .+« « o .+ « ¢« « & 4 . 151 Methanol. . . . . « o &+ « & « « « o + o o &+ 153 Mercury . . e s o & o s e e s = 2 s s & s 155 Propylenedlamlne c o o s o o o & o e o = o 158 Tetrahydrofuran . . . . . .« « « « « o & o o o 161 REFERENCES ., . . . . . . . . 165 This document contal in the Atomic Energ - or the disclosure . T % * SECU INMEORMATION SECUR I TION vi & FIGURES 1. Simplified Chemical Reflux System Z. Amalgam-Amine Dual Temperature System 3. Energies of Lithium Isotopes . . . . . . . 4. The Effect of Temperature on the Separation Factor o e e Closed Reflux Systems o Effect of Temperature on Decomp051t10n of Lithium Amalgam in Water e s e e e e 7. Vapor Pressure of Metals. . . o e+ e e s 8. Viscosity of Liquid Alkali Metals 9. Density of Lithium Amalgam. 10. Density of Lithium and Magne51um Amalgams 11. Viscosity of Lithium Amalgams 12. Conductivity of Amalgams o e e e e 13. Surface Tension of Amalgams . . . . . . . . . 14. Lithium-Mercury Phase Diagram . . . . . . . . 15. Solubility of Metals in Mercury . 16. Solubility of Alkali Metals and Salts in Selected Solvents . . . . e o+ &« s+ s & e 17. Lithium-Potassium Phase Dlagram e e e e 18. Lithium-Sodium Phase Diagram. . 19. Lithium-Potassium-Mercury Solub111ty Curve 20. Lithium~Sodium-Mercury Solubility Curve oo 21. Effect of Temperature on the Separation Factor. 22. Separation Factor as a Function of Temperature. 23. Effect of Temperature on the Separation Factor. 24. Effect of Temperature on the Separation Factor. 25. Effect of Temperature on the Separation Factor. 26. The Kinetics of Sodium Chloride Inversion 27. Viscosity of Anhydrous Ethylenediamine. 28. Solubility of Lithium Chloride in Propylenediamine and Ethylenediamine. 29. Solubility Curves for Salts in Anhydrous Ethylenediamine . . s o e s e 30. Phase Diagram for L1th1um Chlorlde- Ethylenediamine System. . . . 31. Density of Lithium Chloride Propylenedlamlne Solutions . . . e e 32. Density Nomograph L1th1um Chloride- Propylenediamine Solutions. . . . . 33. Vis%ositx of Lithium Chloride- Propylenediamine Solutionss This document in the Atomic ergy Act of 19486" ET data as defined transmittal SECU or-the disclosure of its contents in a nner to &b unautherized person is prohibited, 10 18 22 45 48 49 50 51 52 53 54 55 57 57 58 59 66 67 68 71 74 76 77 80 ATION CRE SECURIT ION vii ¥ 34. Viscosity of Lithium Chloride- Propylenediamine Solutions . . . . 82 35. Integral Heat of Solution of L1th1um Chloride in Propylenediamine at Room Temperature. . . . . 83 36. Vapor Pressure of Propylenediamine and Lithium Chloride Propylenediamine Solutiomns. . . . . . . 84 37. Lithium Chloride - Water Phase Diagram . . . . . . 85 38. Phase Diagram: Lithium Chloride - Magnesium Chloride - Propylenediamine. . . . .« « . 87 39. Solubility of Magnesium Chloride in Lithium Chloride - Propylenediamine Solutions. . . . . . 88 40. Solubility of Sodium Chloride in Lithium Chloride - Propylenediamine Solutions . . . . . 90 41, Lithium Chloride - Propylenediamine - Water “ ‘ Phase Diagram . . . & .« « +« & o + o e« o+« 91 42. Effect of Temperature on the Magne51um Reflux ' Reaction Rate. . . . . . R K 43, Percent Conversion of Potassium to Lithium Amalgam. . . o o + s & + 5 0 s s s e+« + « « 95 44, Effect of Temperature on Conversion of ; Potassium Amalgam to Lithium Amalgam . . . . . . 96 45, Equilibrium Concentration of Lithium Amalgam for Close Cycle Reflux at 100° . . . .. ... 97 46, Percent Conversion of Sodium Amalgam to Lithium Amalgam . . . e o e o+ . .98 47. Phase Diagram for Lithium Hydroxide - Water. . . . 100 48, Solubility of Lithium Hydroxide in Water . . . . . 101 49. Densities of Water Solutions of Lithium Hydroxide. . . . . . e o o o e« + e s + e « 102 50. Densities of Water Solutions of Lithium Hydroxide. . . . . . e o s + o & 2 e + « . . 103 51. Density of Magnesium Amalgams e s+ s s + « + s+ « . 105 52. Viscosity of Magnesium Amalgams. . . . . . . . . . 106 53. Magnesium - Mercury Phase Diagram. . . e o .o« 107 54. Vapor Pressure in Atmospheres of Magne51um Chloride - Ammonia Compounds . . e+ o« . . . 110 55. Solubility of Magnesium Chloride - Tri- Propylenediamine in Methanol . . . . . e o« . 113 56. Solubility of Magnesium Chloride Hexammonia in Methanol . . - . o8 114 57. Effect of Propylenedlamine 1n Solution on Propylenediamine in Magnesium Chloride Hexammonia Precipitate . . . e e « « +« o « « o 115 58. Potassium —4Mercury Phase Diagram e o o + + « « . 118 59. Potassium - Sodium Phase Diagram . . . . . . . . . 119 6. Sodium - Mercury Phase Diagram . . . 122 61. Solubility of Sodium Chloride in Ethylenediamine . 124 transmitt SECU ATION or the disqgffsure ef its contents in nner 1o 80 unauthdrizeq person is prohibited, viii 62. Solubility of Sodium Chloride in Propylenediamine . . e s 4 e 4 e 63. Sodium Hydroxide Phase Dlagram . 64. Miscibility of the System Ethylenedlamlne - Sodium Hydroxide - Water o . 65. Miscibility of the System Propylenedlamlne - Sodium Hydroxide - Water . . . . c o 66. Solubility of Tri Sodium Phosphate in Water 67. Solubility of Ammonia in Methanol. . . 68. Densities of Ammonia Solutions in Methanol . 69. Vapor Pressure of Benzehe. 70. DPhase Diagram: Benzene - Ethylenedlamlne 71. Vapor-Liquid Composition Diagram Ethylene- diamine -~ Benzene. . . . . s o o s s e 4 s 72. Propylenediamine - Benzene Phase Diagram . . . . 73. Vapor-Liquid Equilibrium Composition Diagram Propylenediamine - Benzene . . . e e e e e 74. Decane - Propylenediamine Vapor—L1qu1d Composition Diagram . . o o 75. Vapor Pressure of Anhydrous Ethylenedlamlne . v 76. Density Curves . . . o . e 4 e e s 77. Surface Tension for Anhydrous Ethylenedlamlne 78. Boiling Point Composition Curve for System Ethylenediamine - Water. . . . o 4 o e 79. 2-Ethylhexanol - Propylenedlamlne Vapor— Liquid Composition Diagram . . . 80. Phase Diagram: Isopropanol - Water System 8l1. Phase Diagram: Methanol - Propylenediamine. 82. Methanol - Water Phase Diagram . . 83. Methanol - Propylenediamine Comp081t10n Dlagram 84. Viscosity of Mercury . . - o « o o« « « + « + o o 85. Density of Propylenediamine. . . o o e e e 86. Propylenediamine - Water Phase Dlagram e« e o 87. Vapor-Liquid Composition Diagrams for Water - Propylenediamine . . . . . . . « .« « +« .+ .+ . . This do icted data as defined {n thes . Itg transmittal or the disclosure of its conten any mannet (0 RITY INFOR 125 128 129 130 131 134 135 136 138 139 140 141 143 145 146 147 149 152 154 156 156 157 159 160 162 163 ON e i AL R e e A T B S 2 1 et S B R e S s SECURI ON INTRODUCTION By the first part of 1953, the program for the sepa- ration of lithium isotopes by chemical methods had expanded and matured to such a point that it was believed an interim report condensing the chemistry under one cover would be advantageous. Consequently, under the direction of the pro- ject director, G. H. Clewett, the task of compiling this re- port was undertaken with the following original objectives: (1) Organize all chemical and physical data under one cover. (2) Make data readily available with logical presentation, visual representation, and cross indexing. (3) Evaluate data to give clear understanding and stimulate research activity. Although these objectives were not attained in their entirety, they guided the assembly of this material. This report is divided into two parts. The first part is an evaluation of the data pointed toward an understand- ing of some of the current problems. It is expected that this section will rapidly become out of date as a better understanding of underlying principles is obtained. The second part contains physical and chemical data that should be of more lasting value to those who continue development of separation processes for lithium isotopes. The data pre- sented are largely those available from classified infor- mation available as weekly, biweekly, monthly, quarterly, etc., reports from the divisions of the Oak Ridge National Laboratory. In addition, several excellent topical reports and handbooks issued by this laboratory have been drawn upon heavily. The ideas and methods utilized in the correlation and evaluation of the data are not original with the authors. The ideas of many of the chemists and engineers associated with the project have been used freely. Special acknowledge- ment should be given to the chemists in the Materials Chemistry and Chemical Technology Divisions. To the uninitiated, it may be well to illustrate briefly the main features of a chemical system for the separation of isotopes employing chemical reflux. It may be seen in Figure 1 that the heart of the process is an isotopic exchange and enrichment section which in most instances is a column in which lithium amalgam flows countercurrent to a lithium salt dissolved in a suitable solvent. Next in importance are two reflux sections which remove the lithium from the phase flowing from the column and insert it into the phase flowing to the column. A certain number of auxiliary processes, of course, are necessary for continuous operation. The product in the separation of lithium isotopes is enriched in lithium six (Li¢) and the waste is enriched in lithium seven (Li7), Experimental data from all of the systems investi- gated for the chemical separation of lithium isotope have shown the separation factor to be a marked function of temperature. For this reason it is possible to consider a unique method of achieving reflux known as the dual temperature process. A simplified sketch of a dual tempera- ture system for the separation of lithium isotopes is pre- sented in Figure 2. This process has maximum utility when it is possible to operate an exchange system between two widely separated temperatures. The theory of the dual temperature process is not given in this report but may be found in the work of Spivack (114), Eidinoff (115), and Demarcus (116). 3 o’ JimMpLIFIED CHEMIcAL REFLUX JYSTEM Fog LiITHIUM lsoToPric QOPERATIONJ WasTe —— WasTte Enp ReFLux LiTiium AMALGAM * P Litviom JaLT lsoTopie [T LEER ExcHAaNGE Anp EnricHMENT JecTIoN MeRrcury SJoLveNT LiTniom AMALGAM -—_—— mnafipess LiThiom Jary Propucr Eab RerFLux PropucT e FIGURE" 2 JIMPLIFIED DuaL TemperaTURE Ppoceus Fop LiTHIUM looTorE JEPARATION - B _birhium JaLr Proouct - - EAT o FXCHANGE LiTHium AMALGAM 3 CoLD Hort ExcHANGE ExcHAAGE CoLUMA CoLUMAN —_——— Feep — < — — — JTRIPPING LiTHIUM® From JaLr - — — —JTR1PPING LiTHIUM® FRoM AMALGAN Enrictineg LiTHium®In AMALGAM o Euviching Livurom @ In Jaur_ . _ _ > Pe LiTHiuM AMALGAM . Y ' N Heay ~ L\THIU WASTE - > M JALT ExXCHANGER F—0- PART ONE PROCESS CHEMISTRY I: CHEMICAL EQUILIBRIUM METHODS A. INTRODUCTION Theoretically, the energy requirements for the sepa- ration of isotopes of the same element need not be any larger than that needed to overcome the entropy of mixing of the isotopes provided a thermodynamically reversible system is employed. In addition to being slow at times, thermody- namically reversible processes are difficult to obtain; how- ever, it is desirable from an economic point of view to approach these ideal conditions within engineering limits. Processes carried out at chemical equilibrium offer this opportunity. The separation of isotopes by chemical equilibrium methods is possible with two phase systems such as a gas and a liquid, two immiscible liquids, a liquid and a solid, or a gas and a solid. Since compounds of lithium which re- main gaseous at room temperature are unknown, the sepa- ration of lithium isotopes by chemical methods has been limited to liquid-liquid and liquid-solid systems. At present, all of the systems which have plant production feasibility are liquid-liquid systems in which one of the liquids is lithium amalgam. If lithium isotopic sepa- ration could be extended to a gaseous-liquid system by dis- covery of a volatile lithium compound, perhaps some improve- ments over present systems could be realized. Separation of lithium isotopes in a system of lithium amalgam in contact with lithium chloride dissolved in ethyl alcohol was described by Lewis and MacDonald (110) in 1936. This important contribution indicated that isotopic ex- change took place with astonishing rapidity, that the sepa- ration factor (o) per stage was at least 1.025, and that the heavier isotope was found preferentially in the alcohol phase indicating that chemical bonding of lithium in the solvent was stronger than it was in the amalgam. The separation factor, o, may be defined by the equation (Li® /Li7) - amalgam = TT I T . @ (Li® /LLi") - light phase where the ratios shown are atomic ratios. Systems involving lithium amalgam in contact with lithium hydroxide in aqueous solution have been reported in the literature (111) but confusion as to whether the separation factors were due to equilibrium or to kinetic effects developed because potentials were applied to these systems to prevent lithium depletion through de- composition of the amalgams. The isotopic separation systems for lithium under current investigation may be classified according to the stability of lithium amalgam in contact with an organic or aqueous solution. Reactive solvents such as water and various alcohols decompose lithium amalgam to form lithium hydroxide or lithium al- coholate and hydrogen gas. These solvents depend on a slow rate of amalgam decomposition for their usefulness. Much more research and development has been applied to aqueous solution of lithium hydroxide in contact with lithium amalgam than any other reactive system. Stable solvent systems employ lithium chloride dissolved in amines or unreactive ethers in contact with lithium amal- gam. In this latter class of solvents, propylenediamine (1,2, diamine propane) has received the most attention. B. EXCHANGE EQUILIBRIA The reasons for expecting separation factors for systems at chemical equilibrium aredue to the difference in chemical properties of isotopes of the same element. These differences are accentuated with isotopes of ele- ments of low atomic weight; consequently, chemical methods of separation have proved to be the most efficient methods available for separating isotopes of hydrogen, nitrogen, carbon, boron, etc. One method of representing the chemical separation of lithium isotopes is illustrated in Figure 3. The heavier isotope is found preferentially in the organic or water phase indicating that the chemical stability of the lithium in this phase is higher than the stability of the lithium in the amalgam phase. Since chemical stability is associ- ated with low free energy content, lithium in the propylene- diamine phase, for example, is at a lower free energy level than lithium in the amalgam phase. For the energy changes indicated in Figure 3, we have Li” (amalgam) —s— (Li’) (PDA) + e,Z&FO = -A (1) Li® (amalgam) —> (Li®)" (PDA) + e, AF® = -B (2) where (Al is larger than |B| , but -A is smaller than -B. Subtracting equation (2) from (1), Li’ (amalgam) + (Li6)+ (PDA)—£>Li6(ama1gam) + (Li7)+ (PDA) (3) AF® = -A + B = —C (4) Since our illustration is greatly exaggerated, ~-C does not represent a very large free energy change ( AF <« - 31 cal. at 25°C for the system in question). The separation factor (o) and equilibrium constant for equation (3) are identical since o is defined as the Li6 /Li7 ratio in the amalgam phase divided by the Li®/Li’ ratio is the amine phase. The dependence of o on temperature may be given by the equations - —AF° AH® | as° log, o = RT = “jr * = (5) and _ AH® as® a - 1=-RT + "R (6) where AH® and AS® are assumed to be independent of tempera- ture over small temperature changes. The binomial approxi- mation that o - 1 is equal to log, o contains an error of lesg than 3% up to « = 1.06. The assumption that A H° and AS~ are independent of temperature over the range of temperature in which isotopic separation factors have been measured (0 - 100°C) appears to be as accurate as the ana- lytical methods available for the determination of isotopic abundance. Other ideas concerning the dependence of sepa- ration factors on temperature have been given by Begun, Drury and Palko (111). The temperature dependence of the separation factor for three systems having approximately the same degree of chemi- cal stability is shown in Figure 4. The agreement with theory is within the accuracy of the data. Furthermore, it EArROY FIGURE 3> EneReies O LiITHIUM lSoTOPES A CL VED ProepviLene Diamineg F-————- L7 (1) (2) _________ Y }As Litnum Amaieam - _ _ _ - _——_—C }Ag LitHium MeTAL "y, ‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ FIGURE 4 b 07 06 05 04 0> 02 Ol 11 should be noted that one of the systems investigated was an aqueous solution of lithium hydroxide in contact with amalgam in which a variable holding current was necessary, yet the agreement with the other systems indicates the rate of electrolysis and decomposition has little or no effect on the separation factor. Not all solvents for lithium salts in contact with lithium amalgams yield similar results to those shown in Figure 4. Table 1 illustrates the results obtained with solvent of markedly different properties. Evidently, both the salt and the solvent determine the separation factor obtained in contact with lithium amalgam. This is explain- able on the basis that different solvents have varying affinities for lithium ions and that different salts dis- sociate in varying degrees to produce lithium ions. Table 1 Separation Factors* for Solvent Systems in Contact with Lithium Amalgam¥* Salt ' Solvent Dimethyl- Tetra- Propylene cellosolve hydrofuran diamine Lithium chloride 1.023 £ 0.013 1.036 £ 0.006 1.057 = 0.021 Lithium benzophenone 1.056 t 0.008 1.045 £ 0.008 1.055 t 0.016 Lithium benzophenone anil 1.037 £ 0.008 1.046 £ 0.012 1.047 t 0.012 * Precision given for 95% confidence interval. ** Data by G. M. Begun, ref. 40, 12 In a liquid-liquid method for chemical separation of lithium isotopes, one of the difficulties encountered in the development of economical systems is the limited number of solvents for lithium salts and lithium metal that are available. Three factors limit the selection of an organic solvent; limited solubility of lithium salts, rapid re- activity of some solvents toward lithium amalgam, and emulsi- fying characteristics of some organic solvents toward lith- ium amalgam. The emulsification of amalgams has received very little attention. Probably very few of the amalgam "emulsions" described as such are true emulsions, but appear to be insoluble reaction products containing chemically bonded or physically adsorbed mercury. Solvents for ionic salts as a rule have large dielectric constants which are a measure of their ion separating and isolating power. Other effects, however, appear to be more important in the case of lithium chloride solubility. Ethylenediamine which has a rather low dielectric constant of 12.9 compared to 81.7 for water shows low solubility for sodium and potassium chlorides, but high solubility for lithium chloride. 1t is expected that propylenediamine would have an even lower dielectric constant for it shows only one-tenth the solubility for sodium and potassium chlo- ride, yet lithium chloride is four times as soluble in pro- pylenediamine than in ethylenediamine. The logical conclusion to these results is that a specific interaction exists between lithium and some solvents. At least part, if not all, of this specific interaction effect is the result of the coordination demanded by lithium ion. With a coordination number of four, two ethylenediamine or two propylenediamine molecules could be tightly bound to a lithium ion. Because of steric effects due to the methyl group, propylenediamine probably has a greater chance of accomplishing the desired coordination. The cyclic ether series gives even stronger indication of this coordinating effect. Six membered rings are apparently too large and any additional groups on a five membered ring (tetrahydrofuran) also presents a molecule too large for four- coordination. Tetrahydrofuran itself is the borderline size for four-coordination as indicated by the inverse solubility of lithium chloride with temperature. Table 2 illustrates these conclusions. 13 Table 2 Specific Interaction Effects of Selected Solvents I Solvent Dielectric Constant Solubility in moles/liter at 250C T o 1iC1l NaCl KCL Ethylenediamine 12.9 (25¢) (17) ~0.27 (&S} 0.04%5 (11) 0.00I7 (11) Propylenediamine 12.9 1.0 (47) 0.0048 (60) 0.0001 (43) Q Water 81.7 (18°c) (17) 1k.0 (56) 5.43 (%) k.13 (4) Specific Interaction Effects of Selected Sclvents TI (105) Solubility of LiCl Solvent Structure (moles/liter at 25°_C) Propylene oxide CH3-——CH<—>CH2 \ 0.22 0 Trimethylene oxide ,CHa_ 6.0 CHz ,CHp N Tetrehydrofuran CHy — c|:H2 0.78 | CHz, ,CHo 0 2-Methyltetrahydrofuran CH, — CHp | 0.07 I 033—0}12\ , CHz 0 Tetrahydropyran CHo 0.08 N\ (|:H2 CHx | CH» CHo \O/ 14 Mercury as a solvent for lithium metal has many ad- vantages and disadvantages for a liquid-liquid system. Unfortunately, there are no alternate solvents for lithium metal that remain liquid down to room temperature that have been brought to the attention of the research groups. C. EXCHANGE KINETICS One property of alkali metal amalgams which deserves particular attention is their high surface activity since it may account, at least in part, for the rapid exchange of isotopes. The application of Gibbs adsorption thermo- dynamics to data obtained by Convers (26) and by Johnston and Ubbelohde (112) indicates adsorption (surface excess) of alkali metals at amalgam surfaces. Qualitatively, amal- gams have been observed to disperse much more readily in propylenediamine than mercury indicating the amalgam inter- face has lower interfacial tension than the mercury inter- face. The lowering of surface or interfacial tension upon the addition of another component to a system is the result of adsorption of the added component at the interface. The limitations of analytical techniques for isotopes and the extremely rapid exchange reaction (even at room temperature) have made the direct observation of reaction kinetics very difficult. It is quite possible that with a rapid continuous method of isotopic analysis, such as the neutron adsorption technique, a system could be devised which would prove satis- factory for such an investigation. Theoretical stage heights obtained from operation of isotopic exchange columns reflect the kinetics of the ex- change reaction. If the reaction is diffusion controlled, the following factors appear to be important to the amalgam phase or solvent phase which ever is rate controlling: (1) agitation, (2) concentration, (3) viscosity, and (4) temperature. Of these factors, agitation is the most im- portant since better agitatiaon would produce larger inter- facial areas as well as thinner diffusion films. If the adsorption of lithium of the amalgam interface produces a rigid film, the rate of formation of fresh surfaces may be 15 a rate controlling step. Temperature has only a slight effect on diffusion controlled reactions. If diffusion is not the rate controlling step in the isotopic exchange reaction, the following factors appear to be important: {1l) interfacial area and (2) temperature. An increase in interfacial area or temperature should in- crease the rate of the reaction and decrease the stage height; however, these two factors are difficult to vary independent of each other in the system employing propylene- diamine because interfacial tension increases with increased temperatures resulting in poorer dispersions and lower inter- facial areas. If the rate of the exchange reaction shows first order dependence on the lithium concentration in the amalgam (similar to the waste end reaction), then the stage height should be independent of lithium concentration in the amalgam. II: REFLUX PROCESSES A. INTRODUCTION A major consideration in large scale isotopic sepa- ration by equilibrium exchange is the reflux process. Re- fluxes may be achieved by either physical or chemical pro- cesses and many alternate schemes are possible. No attempt will be made in this report to differentiate between reflux methods with regard to economics and with the exception of the dual temperature system discussion will be limited to chemical reflux processes. Further, only those schemes which appeared to have engineering adaptation to existing systems have been considered. The degree and rate at which the inversion (refluxes) are attained are prime considerations in evaluating the re- flux processes since the systems involved require recycling of solvents. The degree of inversion or removal of enriched lithium from the amalgam phase (product reflux) is important in that this material not only represents a valuable product but also either its loss or its cycling to the waste end would greatly 16 affect the cascade equilibrium. On the waste end the last traces of lithium must be removed prior to cycling the sol- vent stream to the product end for even small amounts of material are capable of reducing the enrichment to a point where the desired product could not be attained. The rate at which the reflux processes proceed is equally important. It must be very rapid not only to yield the desired degree of inversion, but also to prevent a large holdup of material which would greatly influence the length of time required to reach isotopic steady state con- ditions. B. THE DUAL TEMPERATURE PROCESS The dual temperature process is applicable to any of chemical isotopic exchange system employing nonreactive sub- stances and in which the separation factor is a function of temperature. It may be seen from Figure 4 that the sepa- ration factor in several lithium systems is a function of temperature. The operability of the dual temperature process has been demonstrated by the Materials Chemistry Division (See - ORNL reports 1238, 1306, 1401, YB 35-12, and ORNL CF 53-4-299). The extremely rapid isotopic exchange noted in the laboratory was confirmed by pilot plant data. Both ethylenediamine and propylenediamine were utilized as solvents for lithium chlo- ride in contact with lithium amalgam. Propylenediamine appears to have the widest useful temperature range of from room temperature to 100°C; however, the stability of pro- pylenediamine above 100°C in the presence of an alkali amalgam has not been well established. A schematic representation of the dual temperature pro- cess 1s shown in Figure 2. Since the effective separation factor for a dual temperature system is dependent upon the difference between the factors in the hot and cold columns and is generally less than either one, many more stages are required for this method than for a chemical reflux system (to effect the same overall separation). 17 C. CHEMICAL REFLUX PROCESSES Although chemical reflux schemes are classified in this report according to which end of the isotopic exchange system they are applicable, this is not entirely satis- factory since many of the waste end refluxes can be tied together into desirable overall processes. Two such pro- cesses are illustrated in Figure 5 to indicate how reflux at one end may supplement reflux at the other end. 1. Waste End Reflux a. Electrolvtic Reflux Four reactions have been considered for the elec- trolysis of lithium salts to form lithium amalgam: aqueous electrolysis of lithium hydroxide with a mercury cathode, aqueous electrolysis of lithium chloride with a mercury cathode, electrolysis of an organic solution of lithium chloride, and electrolysis of fused salts with a liquid lith- ium product from the cathode. These may be illustrated in the following equations: ZLiOHaq +{potential}) —> 2 Li(Hg) + 1/2 Ozgas + H,0 (7) LiClaq +(potential) — Li(Hg) + 1/2 C1zgaS (8) LiClOrg + Na(Hg)+(potential) > Li(Hg)+ NaCl (insoluble)(g) LiCl(fused salt with KCl)+(potentialj>Li(metal)+ 1/2 Cl, (10) Industrial equipment and methods are available for the processes utilizing reactions (7}, (8), and (10). Current efficiencies of 90% or higher have been reported for such installations. Reaction (9) which has a mercury cathode and a sodium amalgam anode would require an extensive cell de- velopment program for successful application as a plant re- flux method. Under completely thermodynamically reversible conditions reactions (7} and (8) would be impossible as only hydrogen would be produced at the cathode. Under actual operating conditions hydrogen ion develops an over-potential which pre- vents the electrolysis of water. Certain impurities in the electrolysis systems catalyze the formation of hydrogen by lowering the over-voltage. Possibilities of minimizing this 18 CLosen RerFLux JYSTEMS KCu e e — — FILTER EILTER [ I ~ [PoA-LICL I KCuL | PDA PDA 2 I O E y I 2 9 l $ PDA L | < LitL EVAPORATOR 3 o | ' I \._-\ b PDA-LICL l ! I | = | b) 3 | 2 | q 3 ] 2 < 8 I a U pon] | O 2 | < T | 2 ¥ | I I 8 PDA-LiCL | : KCL/“"" | o 55 | o i l I } PDA- KCL JLURRY ¢ DotassiuM CLOSED E::ELUX J!,J rEM A ( L} AMALGAM MERCURY (Ll AMALGAM FiGURL 5 T DWGRP0293 CLq LiCLtHa0 | IEVAPORATORI LI CL 2 % < DRYER 1 LiCLt He0 ¥y JOLVENT § e ] — JOLVEAIT+Li1 GL ’ CRYSTAL LIZATION [EVAPQOATOR ) < 2 2 9 11CL O S 4 O 2 < X 3 HCL ¥ HCL hgwfum. c._ |DEGASJIE y &= 1SOLVENT L1 HGL . FORMER v H 1 & - Q x . l JOLVENT+HCL ELecTRowyTIc CLoseD RerLux Jys [EM 19 important side reaction are: (1) purification of cell feed, {(2) addition of inhibiting agents that complex the catalyzing impurities, and (3} removal of oxygen and other depolarizing agents. Reactions {8) and {10} if applied to organic systems require the desoclvation of the lithium chloride. This is no problem with tetrahydrofuran or isopropanol according to preliminary scanning experiments (see Part II - Lithium Chloride-Isopropanol and Lithium Chloride - Tetrahydrofuranj ; however, with ethylenediamine and propylenediamine the problem becomes significant. At the time of the writing of this report, a research program was well under way for the determination of vapor pressures of lithium chloride sol- vates with propylenediamine. Preliminary scanning experi- ments have demonstrated the engineering applicability of several methods of thermal decomposition to this material with success. Reaction rates for systems involving electrolysis are not generally defined in the same sense as those of the usual chemical reaction. The kinetics are usually studied from the single electrode standpoint*. They are complicated for the usual type of rate study in that there are an increased number of variables not strictly chemical in nature which may be rate controlling or else have an effect on the rate con- trolling step. Further, electrolytic reactions often have complicating side or decomposition reactions which proceed spontaneously. From a viewpoint that the applied potential only over- comes the driving force (free energy) tending to keep the reactants in their present low energy state it is possible, at least qualitatively, to look at electrolytic reactions as though they were only simple chemical reactions with an additional energy term involved. One such method of looking at the rate process for an electrolytic reaction is as follows. The equation: 1 k (E} + 2LiOH + (Hg) —— >- 2Li(Hg) + H;0 + 1/2 O, represents a process that produces liquid lithium amalgam Li(Hg). The rate of formation of amalgam may be represented by: Li(Hg)] d _[__a,%_._il..___, k' / [(E), LiOH, Li(Hg), 0,, T] (11) ¥ For a detailed and quantitative approach the reader is re- ferred to the work of H. H. Garretson (109) and W. E. Clark (107) . 20 where the items inside the brackets are variables which are probably involved in the rate. The effects of these variables have not been elucidated at this time. However, for a given cell operating under steady state conditions the reaction can be represented by the equation: [Li(Hg)] d —4gt = k' (E) (12) where k' is not a true rate constant but is dependent upon operation at steady state condition with fixed current density, temperature, concentrations, etc. For the case under consideration the most important side reaction is decomposition which proceeds as follows: Kk Li(Hg) + H,0 —5-[LiOH] aq + 1/2 He (o + Hg as) The rate of disappearance of amalgam is given by the equation: _d —[%i;i—H—g)] - k, 7[’{[L.i(ng)] , LiOH, s, T] (13) where 'S' is the interfacial surface area between phases, '"T' the temperature: [Li(Hg)] the amalgam concentration, and LiOH the hydroxide concentration. These variables are known to effect the rate 29,30, 1p addition, this re- action rate may be greatly affected by the catalytic action of certain impurities which have low hydrogen over-voltages. For example, the presence of oxygen is considered to greatly accelerate the decomposition rate. Other variables not well defined, such as, rate of agitation are incorporated into the rate constant 'k,' by operating under fixed condition. The function,f‘[Li(Hg{], has been shown to depend upon the one-half power of the amalgam concentration 29,30,108. For constant conditions of lithium hydroxide concentration, interfacial area, and temperature, equation 13 becomes: (Li(Hg)] 1/2 -d - dt = k' [Li(Hg)] (14) or 1/2 1/2 Li(H - Jri(m . L g)]o [Li( g)]f (15) t 21 The effect of hydroxide concentration has not been clearly established, but available data tends to show that the rate constant decreases in direct proportion to the in- crease in hydroxide concentration 29, The pronounced effect of temperature is shown by Figure 6. The effect of the interfacial area per unit of amalgam volume upon the rate apparently is directly proportional (1lst order), but methods of completely elucidating the actual area of the surface involved have not been devised at this time. By combining the electrolytic rate (equation 12) and the decomposition rate (equation 14), one obtains an ex- pression for the net rate of amalgam formation for steady state conditions as follows: Li(H 1/2 d —[—%%—g—)—]= k' L (E) - ki [Li(Hg)] / (16) Equation 16 qualitatively defines the kinetics of the "Elex" process. For example, if kj f?(E) is greater than k; [Li(Hg)]1/2, the reaction rate is positive and lithium is transferred from the aqueous to the amalgam phase. This corresponds to the waste end reflux. When the two terms are equal the rate is zero, and no net lithium transfer takes place; however, the exchange reaction between isotopes proceeds uninhibited. This corresponds to conditions main- tained in the exchange section. Finally, when ki f"(E) is less than kj [Li(Hg)] 1/2 the rate is negative and net de- composition of the amalgam occurs to provide a product end reflux. Similar treatment could be extended to the reactions represented by equations 8-10; however, little is to be gained by such a generalized development. It is important, however, to recognize that these electrolytic refluxes are complex and that the presence of traces of impurity can greatly alter the rates especially by influencing the de- composition reactions. b. Magnesium Amalgam Reflux Magnesium amalgam as a reflux agent is of importance in systems using the amine solutions of 1lithium chloride. The details of the reaction, Mg amalgam + 2 LiCl(PDA sol'n)-> Li amalgam + MgCl, -3PDA (17) . f(C 22 UNCLASSIFIED DWG. 20294 T 0P 23 have been worked out for propylenediamine solutions, but they should apply equally as well to ethylenediamine so- lutions. Reaction (17) proceeds very near completion be- cause of the high stability and insolubility of the mag- nesium chloride solvate with propylenediamine. However, the equilibrium ratio of lithium to magnesium in the amal- gam as a function of temperature or amine concentration has not been fully investigated (57). ' Laboratory batch data (90, 91, 92 and 100) indicate that the conversion of magnesium amalgam to lithium amal- gam follows a first order rate with respect to magnesium in the amalgam and to be independent of lithium chloride concentration in the amine phase as long as it was in stoichiometric excess. The rate may be defined as follows: Mg (Hg)] - d —at - kMe(He]] (18) o Mg (He)], - kt (19) Mg (He ] where (Mg(Hg)J, and [Mg(Hg)] ¢ are the initial and final con- centration of %he magnesium in the amalgam. In addition to the effect of magnesium concentration in the amalgam, the reaction rate is greatly influenced by the degree of dispersion (interfacial contact area) of the two phases. The optimum rate of agitation has not been estab- lished but will probably vary considerably from one type of equipment to another. Increasing the temperature also increases the reaction rate. However, the optimum rate is likely to be determined by the maximum temperature for which the organic solvent will remain stable in the presence of the amalgam phase rather than by decreasing the holdup time to a point where a further increase of rate would not be economical from an equipment standpoint. An important side reaction of the magnesium amalgam re- flux is the chemical combination of trace amounts of water with magnesium amalgam to form magnesium hydroxide and hy- drogen as follows: Mg amalgam + 2 H,0 —> Mg(OH), + H; (20) Although propylenediamine is a very hydroscopic solvent, reaction (20) is likely to contribute heavily to preventing any buildup of water in the solvent. 24 The favorable equilibrium conditions resulting from reaction (17) making it an excellent reflux reaction for the waste end of the exchange system are largely due to the stability of the complex salt, MgCl,-3PDA. The chemical stability, however, has prevented the utilization of simple thermal methods for complete desolvation of the magnesium chloride and recovery of the propylenediamine. (See Part II, Magnesium Chloride - Propylenediamine System for Vapor Pressure Data). Chemical methods for recovery of propylenediamine by cleavage of the MgCl, -3PDA structure fall into two classes: (1) replacement of the propylenediamine with a cheaper chemical having the ability of forming a more stable solvate and (2) chemical reaction to form new salts that do not have stable solvates with propylenediamine. Successful methods have utilized ammonia in the first classification and sodium hydroxide in the second. Reaction of the solvate, MgCl,° 3PDA with ammonia may be illustrated as follows: MgCl, 3PDA + 6NH, —3= MgCl,'6NH, + 3PDA (21) This reaction may be carried out either at room temperature under pressure or below the boiling point of liquid ammonia at atmospheric pressure. Research is currently under way to disclose the details of this reaction. The same reaction has been studied using methanol as a solvent for the solvate, MgCl, °3PDA. (See Part II, Magnesium Chloride - Ammonia - Methanol - Propylenediamine Systems). In this instance, the amount of excess propylenediamine accompany- ing the solvate, MgCl, °3PDA, limits the solubility of the solvate. Apparently, lithium chloride dissolved in the ac- companying propylenediamine also limits the solvate, MgC1, * 3PDA solubility (see Figure 55). The degree of completion of the precipitation of MgCl,-6NH, from a methanol solution, MgCl, -3PDA is highly dependent upon the concentration of ammonia. Some propylenediamine has been found in the precip~ itate, MgCl,-6NH;, as may be seen in Figure 57. From the data available, it is impossible to predict whether this propylene- diamine content is the result of mechanical occlusion or chemical interaction. y 25 The reaction with sodium hydroxide may be carried out in aqueous or nonaqueous media. The reaction is essentially the same and may be illustrated as follows: 2 NaOH + MgCl, 3PDA —>— Mg(OH), + 2 NaCl + 3PDA (22) The released propylenediamine must be separated from the sol- vent (water or alcohol) before it can be considered as com- pletely recovered. Although the propylenediamine can be chemically released by reaction (22), because of the nature of the magnesium hydroxide precipitate, physical recovery of propylenediamine is difficult. Evaporation from the slurry has been effective where water and 2-ethyl hexanol have been used as solvents. Advantage may be taken of the two phase immiscibility with excess aqueous caustic. With methanol as solvent for sodium hydroxide, the magnesium hydroxide was found to be filterable. These propylenediamine recovery problems have been largely engineering in nature. Regardless of the solvent used for reaction (22) the rate of reaction and equilibrium are very favorable for the release of propylenediamine. The reaction under agitation proceeds more rapidly than measurements can be taken. The propylenediamine remaining with the magnesium hydroxide is held there by physical entrainment as the chemical reaction apparently goes quantitatively to the right within the limits of analytical measurements. Some decomposition of the pro- Pylenediamine has been noted at high temperatures and high caustic concentrations and constitutes a disadvantage of this desolvation method. 1In alcohol solutions some dehydration of the magnesium hydroxide may take place due to the great af- finity propylenediamine shows towards water. If this dehy- dration is appreciable, wet propylenediamine will result and the advantages of using an alcohol solvent will be lessened. c. Potassium and Sodium Amalgam Ref luxes Both potassium and sodium amalgam reactions have been shown to have application to the waste end reflux uti- lizing propylenediamine as solvent. The reactions do not proceed to virtual completion as they do in the case of mag- nesium amalgam, and a mixed amalgam is the result in both cases. The reactions are as follows: K(amalgam) + LiCl1(PDA sol'n)==LiK(amalgam) + KCl(ppt.) (23) 26 Na(amalgam) + LiCl(PDA sol'n)== LiNa(amalgam) + NaCl(ppt.) (24) The conditions under which the mixed amalgam is produced is that of high temperatures and high lithium chloride concen- tration in the amine phase. These conditions are also ideal for the reactivity of any trace amounts of water in the amine phase with the mixed amalgam to produce insoluble lithium hy- droxide and hydrogen gas. Reaction rates for these types of inversion (similar to isotopic exchange) are extremely rapid (93, 101). For this reason the reaction mechanism has not been elucidated to this date. It may be inferred, however, that the rate determining step will be similar to that of the magnesium inversion re- action and probably shows first order dependence upon the amal- gam concentration. An indication of why potassium or sodium amalgams reflux at the waste end at high temperature, and yet at low tempera- ture form very stable amalgams can be shown qualitatively from thermochemical considerations. Table 3 gives a series of idealized reflux reactions in- volving alkali amalgams and alkali halide salts. The heats and free energies are computed from data presented in Table 4. These equations represent reactions in which no interaction (solvation) of the halide salts would be involved, however, the effect of solvation will be discussed in a following paragraph. From Table 3 it is observed that for these reactions under ideal conditions at room temperature the formation of lithium amalgam is slightly favored over sodium or potassium amalgam. The tendency being much more pronounced with in- creasing atomic weight of either the anion or the cation in the salt. Experimental data (See Part II: Lithium - Mercury - PDA - NaCl - KCl) show that at room temperature lithium amal- gam in contact with amine solution of sodium or potassium chloride is unstable and an inversion to sodium or potassium amalgam proceeds rapidly and to virtual completion (this is discussed under product end refluxes). These data indicate that the behavior of the halide salts in amine solution de- viate widely. This behavior can be best understood by examin- ing the solvation energies involved since a difference in 27 Table 3 Thermochemistry of Idealized Reflux Reactions 0 O 1. LiCl(S) + Na(Hg) 9 ~= NaCl(S) + Li(Hg) 140 -0.3 — =0.05 LiBr(S) + Na(Hg)looziz;NaBr(S) + Li(Hg) 4, =2.6 -1.9 Lil oy + Na(Hg)lOO::::NaI(S) + Li(Hg) ;459 =3-9 -3.3 2. LiCl(s) + K(Hg)looz:;: KCl(S) + Li(Hg)100 -0.2 -1.5 LiBr gy + K(Hg);099 —~— KBr( gy + Li(Hg)jpq -3.8 -4.8 Lil(g) + K(Hg)j90== KI(g) + Li(Hg)y1pq -7.3 -8.1 solvation energy between lithium and potassium or sodium halide as small as 6 k cal could account for the observed re- actions. It is well known that neither sodium or potassium chlo- rides solvate to any great extent with PDA or EDA. It is equally well established that lithium chloride solvates readily with these amines. Solvation is accompanied by the evolution of an appreciable quantity of heat as follows: (53) (47) LiCl g, + (345) PDA ;, —>— LiCl-(345) PDA 1, AH % -19.41 k cal/g mole (25) LiCl gy + (10) PDA ;) —s= LiC1-(10) PDA 1, AH ¥ -13.5 k cal/g mole (26) —~— LiCl-(10) PDA LiCl-2PDA + (8) PDA (1) (1) AH = -7 k cal/g mole (27) (s) 28 Table 4 Selected Thermodynamic Properties T = 288.16°K Kcal/g mole Component State .AHE AE% Reference LiCl c -97.7 -92.2 6 LBr c -87.4 -82.3 6 Lil c -72.5 -67.5 6 NaCl c -98.3 -91.9 6 NaBr c -90.3 -83.9 6 Nal c -76.7 -70.5 6 KC1 c -104.4 -97.8 6 KBr c -97.7 -91.2 6 KI c -86.3 -79.7 6 ZnC1, c -99.6 -88.4 7 ZnBr, C -78.2 - 7 Znl, c ~50.0 - 7 ZnC1l, - EDA c -138 ‘ - 7 ZnCl, - 3EDA c -179.4 - 7 ZnBr, - EDA c -112.5 - 7 ZnBr, - 3EDA c -157.1 - 7 Znl, - EDA c 86.9 -~ 7 Znl, - 3EDA c 133.7 - 7 EDA 1 -8.8 - 11 Na(Hg)100 1 -19.9 (-19.95)% 7,13 K(Hg)100 1 -26.08 (-24.4)* 7,13 * Free energy data from single electrode potentials (13). 29 In the absence of any free energy data it is assumed that they will be in the order of magnitude of the heats of re- action. In this event the reactions shown in Table 3 will have lower free energy in the direction which yields stable sodium or potassium amalgam. In order to appreciate the magnitude of the energy in- volved in solvation more fully the system zinc halide versus ethylenediamine is presented. Thermochemical data are avail- able and are presented in Table 4. The solvation reactions are presented in Table 5. In addition to the magnitude of the heats of formation of these solvates another fact becomes quite evident from Table 5, i. e., apparently the anion contributes little to the heat of formation. If this observation holds true for systems involving lithium halides solvated with EDA or PDA then it is expected that solvation energy would have a less pronounced effect upon the inversion reaction in going from sodium to potassium and especially from sodium chloride to potassium iodide systems. Table 5 Solvation of Zinc Halides with Ethylenediamine o Reaction 4H293 ZnCl, + EDA —>— ZnCl, °EDA -29.8 ZnBr, + EDA ——> ZnBr, -EDA -25.0 Znl, + EDA —> Znl,-EDA -28.1 ZnCl, + 3EDA —» ZnCl, - 3EDA -53.6 ZnBr, + 3EDA -—»= ZnBr, -3EDA -52.0 Znl, + 3EDA —»— Znl,-3EDA -56.9 Lithium chloride may be desolvated from EDA or PDA by heating to a moderately high temperature {113). From this it can be concluded that the degree (energy) of solvation is greatly affected by temperature. Such being the case at high temperature the effect of solvation energy upon the reaction given by equations 23 and 24 would be largely overcome and the more idealized reactions (Table 3) proceed to yield 30 lithium or mixed amalgams. These conclusions are borne out by examination of figures 43, 44 and 46 (Part II) where the effect of temperature and lithium chloride con- centration upon the inversion of potassium and sodium amal- gams to lithium amalgam is shown. 2. Product End Reflux a. Decomposition Reflux Product end reflux with lithium amalgam in the water system appears to be comparatively simple upon first inspection. During isotopic exchange the decomposition of lithium amalgam takes place all the time that the amalgam and the aqueous solution are in contact. An applied po- tential in the exchange system does not prevent decomposition but replaces the amount decomposed. Thus reflux may be ob- tained by discontinuation of an applied potential and/or an increase in temperature of the system to increase the rate of the reaction. The kinetics of this reflux have been pre- viously discussed as a complicating or side reaction to the Electrolytic Waste End Reflux Section, Page 17. Decomposition is illustrated as: Li(amalgam) + H,0 — LiOH + 1/2 Hz(gas) + Hg (28) The similar type decomposition has application to systems utilizing the simple alcohols as a solvent to replace water. Li(amalgam) + ROH —— LiOR + 1/2 Hz(gas + Hg (29) ) The rate of reaction is expected to decrease with the series of solvents - water, methanol, ethanol, propanol, etc., with water having the highest rate of reaction; however, solu- bility of the decomposition product decreases as the series increases in molecular weight. b. Hydrogen Chloride Reflux Product end reflux with hydrogen chloride has promise in exchange systems containing lithium chloride dis- solved in a solvent in contact with lithium amalgam. At the product end where lithium amalgam is to be decomposed and the lithium sent back to the isotopic exchange system as lithium chloride, the reaction with hydrogen chloride is perhaps the fastest and most complete of all product end refluxes. 31 Li amalgam + HCl —=— LiCl + 1/2 H, + Hg . (30) One of the problems encountered in utilizing this re- action is decreasing the rate of the reaction rather than in increasing it as with other reflux reactions. The re- action appears to go entirely to completion and at a rate far too rapid for measurement under conditions applied to date. Two methods are available for application of this re- action: (1) solution of the hydrogen chloride gas in the solvent and subsequent contact with the amalgam phase and (2) contact of the hydrogen chloride gas with the amalgam with subsequent contact with the organic solvent. Only the first method has been investigated to date. This has proved to be successful with propylenediamine and iso- propanol as solvents. With tetrahydrofuran, some reaction of the solvent with hydrogen chloride was noted. c. Sodium and Potassium Chloride Refluxes Product end reflux with sodium and potassium chlo- rides has been extensively studied in amine solutions, especially propylenediamine solution. The reactions in- volved are the reverse of reactions (23) and (24). As pre- viously discussed, it is evident that solvated conditions of lithium chloride contributes greatly to the reversal of these reactions at low temperature. Several so-called equilibrium constants have been given for the reflux reactions. This method of reporting data may have many advantages but the fact that the equi- librium constants are greatly different for the forward re- action compared to the reverse reaction points to the con- clusion that the given constants are not applicable beyond the range of concentrations and temperatures in which they were measured. It is quite evident that activities of the constituents are markedly different from their concentrations and have unusual temperature coefficients. The rate determining steps in these reactions are markedly different from those of the forward reaction given by equation 23 and 24. Laboratory data (89 - 94) indicate that the rate determining step is independent of (zero order with respect to) the amalgam concentration and may be interpreted to follow a rate: 32 [Li(Hg)] S 4T - k)f[s, I,] (31) (I4) is the interfacial area between phases. The quantity (S) involves the surface area of the salt particles in the slurry and is not well-defined. However, when a large ex- cess of finely divided salt is used (S) is constant and under conditions of fixed agitation (Ih) is approximately constant. For these conditions, equation 31 becomes: - il (32) . _ [Li(Hg)] | - [Li(Hg]], 1:1 'tz and k (33) These data indicate that the rate determining (slow) step is the rate of solution of the salt particles. This is further substantiated by the observation that the relative magnitude of the rate constant is consistent with the rel- ative solubility of sodium and potassium chlorides in pro- pylenediamine. (See Pages 69, 70 for evaluation of rate constants). Furthermore, the rate constant does not increase as an exponential function of temperature which would be ex- pected if a chemical reaction were the slow step. Figure 26, (Part II) shows the results of laboratory in- vestigation on the rate for sodium chloride inversion as a function of the temperature, size and amount of sodium chlo- ride particles in the amine phase. These data indicate that size of the particles is more important than the temperature in the rate determining step. The effect of agitation on the rate constant has not been fully investigated. As pointed out in the section on waste end refluxes for the potassium or sodium amalgam Systems, temperature and lith- ium chloride concentration have marked effects upon the final degree of inversion. If the general behavior predicted by the equations given in Table 3 holds then from equilibrium considerations a sodium chloride system should yield a better reflux than bromide or iodide in that a lower concentration of lithium remaining the amalgam per given stage would result. However, the rate at which equilibrium is achieved will probably change in the opposite order due to increased solu- - bility of bromide and iodide. 33 III: SOLVENT AND FEED PURIFICATION A, SOLVENT PURIFICATION As chemical technology advances. chemical specifi- cations become more difficult to meet and engineering complications increase. Certainly isotope separation is no exception to this trend. For successful separation of lithium isotopes by present chemical methods, exceptionally low impurity levels are required that have and will con- tinue to demand chemical research and engineering develop- ment. Impurities in the aqueous-amalgam system for lithium isotope separation are: (1) those that cannot be toler- ated because of the catalytic effect they have on the rate of decomposition of lithium amalgam and (2} those that pre- ferentially build up in some part of the system or dilute the product. Quantitative knowledge of tolerances for im- purities in the first class is unknown indicating the necessity of further research. Having determined the cata- lyzing impurities and their concentration effects, at least two different avenues of approach should be 1nvest1gated i, e., solvent purification by such means as filtration and ion exchange, and the use of additives to poison or complex the catalyzing impurities. The second class of impurities may be controlled through feed purification. Impurities in the organic-amalgam system for lithium isotope separation are little understood except for the system employing propylenediamine as the organic solvent. Even with propylenediamine, the impurity problem is only partially understood because pilot plant data for extended operation are not available as yet. The tolerance for water in propylenediamine is believed to be at least as low as methods of analysis {less than 0.01% by weight) for propy- lenediamine systems utilizing a waste end reflux with mag- nesium, potassium, or sodium amalgam. No quantitative data is available on the thermal stability of propylenediamine or of the nature and effects of the decomposition products. Methods of drying propylenediamine consist of dis- tillation and chemical reaction methods. Benzene azeotropic distillation (See Part II: Benzene-Propylenediamine and 34 Propylenediamine-Water Systems) has received engineering attention. Some data on an alternate system are avail- able (See Part II: Ethylene Glycol-Propylenediamine- Water System). Chemical reaction of water in the propy- lenediamine with calcium carbide which produces calcium oxide and acetylene gas constitutes a successful chemical method of drying propylenediamine. Mercury, like propylenediamine may be purified by distillation or chemical reaction. In this case, however, the serious impurities are contaminating metals and not water. Chemical reaction with an aqueous solution of di- lute nitric acid under oxidizing conditions has long been used as a satisfactory method of removing base metals from mercury and need not be discussed here. B. FEED PURIFICATION Purification of lithium amalgam feed in the aqueous- amalgam system has been investigated and it is understood that partial decomposition of the amalgam has been success- fully used to control sodium and potassium impurities; how- ever, published data are not available as yet to sub- stantiate the extent of the purification. Among the systems using propylenediamine as a solvent, lithium feed purification is most important to the closed reflux system employing potassium chloride and potassium amalgam as reflux reagents. Impurities introduced with the feed are likely to build up in one of the reflux ends if the solubilities of the impurities are exceeded. Since it is possible to feed either lithium amalgam or lithium chlo- ride solution to the exchange columns, a feed purification section could be designed for either situatioén. Data on the solubilities of the major impurities as metals in the amalgam phase and as chlorides in the amine phase are needed as a function of temperature. Assuming withdrawal of pro- duct and waste and introduction of feed are made in the same phase, predictions could be made with solubility data as to the extent of impurity build-up. 1In the absence of ex- perimental data it appears that amalgam feed and amine feed are equivalent provided either feed stream is equilibrated against the opposite phase in a clean-up section prior to introduction into the exchange columns. 35 Generally the drying of salts and metals utilized as reflux reagents and isotopic exchange feeds can be ac- complished by using a dry air except for lithium chloride which forms a hydrate which is stable at room temperatures. (See Part II: Lithium Chloride - Water System). In order to obtain anhydrous lithium chloride drying at temperatures above 100°C is required. Fortunately, little if any de- composition to form hydrogen chloride takes place in the drying operation (55). Dry, inert atmospheres are required in all organic- amalgam systems. Nitrogen and helium when properly puri- fied have shown no reactivity toward amalgams (13,28,67). 36 PART TWO CHEMICAL AND PHYSICAL DATA 37 1. INTRODUCTION A. ARRANGEMENT OF DATA Systemization of information often leads to complexities in presentation. The attempted arrangement of chemical and physical properties presented here is organized in a some- what complex but ordered manner. All information falls under the general headings: Lithium and Lithium Compounds Magnesium and Magnesium Compounds Potassium and Potassium Compounds Sodium and Sodium Compounds Liquid Solvents Under each of the above-mentioned headings, technical information is classified according to the initial chemical components of the reactions or equilibrium systems under con- sideration. While this method of presentation requires a knowledge of the initial components of the chemical reactions involved, it has an advantage of being self-indexing to those who are aware of the method of arrangement. For example, in the product end reflux with sodium chloride, lithium and mercury are reacted with a slurry of sodium chloride in pro- pylenediamine to produce a solution of lithium chloride in propylenediamine and sodium amalgam. Lithium, mercury, sodium chloride and propylenediamine are the initial components, and the physical and chemical data for this reaction can be found with the system "Lithium - Mercury - Sodium Chloride - Pro- pylenediamine". This system is listed with other four com- ponent systems under "Lithium" which is found under "Lithium and Lithium Compounds' since this is the first general head- ing that contains any of the four initial components. In some systems the initial components are identical with the chemical species present at equilibrium. Such is the case with magnesium and mercury. The information con- cerning solubility, density, viscosity, etc., is to be found among the two component systems under "Magnesium" which is under the general heading '"Magnesium and Magnesium Compounds". The compilation of all chemical and physical data on the Orex process (as of April 1953) was one of the objectives 38 that guided the writing of this report. Much of the data has been plotted or replotted in an attempt to obtain a correlation and, consequently, allow for extrapolation beyond the area of experimental results. Justification of this procedure may be questionable in several cases where limited precision or small number of data are available; however, in the majority of cases, theoretical considerations were utilized as a basis for this "best guess', All data appearing in this report have been referenced for easy access to the original publication and to give credit to those who have derived the data. Some confusion was encountered in the ORNL literature over the use of the term "molarity'". 1In many instances, molarity appeared to be the number of moles per liter of solution regardless of the temperature of the solution. In other reports, molarity referred to the number of moles per unit weight of solution corresponding to a liter at room temperature. When these differences were recognized, they were tabulated in this re- port accordingly. The convention utilized in previous reports to indicate liquid amalgam has been followed here; for example, liquid lithium amalgam is designated as Li(Hg). Missing from Part Two, Section VI, of this report are the chemical and physical properties of water. These data are tabulated in the usual handbooks of chemistry, and con- Sequently, they have been omitted in this report. I. II. 39 B. CONTENTS INTRODUCTION. . . . « . ¢« o « « « o = LITHIUM AND LITHIUM COMPOUNDS A. Lithiumn o o o o a o 0. ° ® o o o - o e . Lithium - Mercury . . . .« o .+ o Lithium - Potassium . . . . . . Lithium - Sodium . . . . . . . . « . . Lithium - Potassium - Mercury. Lithium - Sodium - Mercury Lithium - Mercury - Water. Lithium - Mercury - Ammonium Chloride - Tetrahydrofuran. . . . e . Lithium - Mercury - L1th1um Anthracene - Dimethylcellosolve . Lithium - Mercury - Lithium Benzophene - Dimethylcellosolve Lithium - Mercury - Lithium Benzophenone anil - Dimethylcellosolve. . . . . . Lithium - Mercury - Lithium Chloride - Dimethylcellosolve . . . . . & Lithium - Mercury - Lithium Benzophenone Propylenediamine . . o e e Lithium - Mercury - L1th1um Benzophenone anil - Propylenediamine. . . . . . Lithium - Mercury - Lithium Benzophenone Tetrahydrofuran. . . o « o e Lithium - Mercury -~ L1th1um Benzophenone anil - Tetrahydrofuran . . o e e Lithium - Mercury - Lithium Chlorlde - Ethylenediamine. . . . Lithium — Mercury - L1th1um Chlorlde - Isopropanol. . . . e« ¢ o o Lithium - Mercury - L1th1um Chlorlde - Propylenediamine . . o . Lithium - Mercury - L1th1um Chlorlde - Tetrahydrofuran. Lithium - Mercury - L1th1um Hydrox1de - Water. . Lithium - Mercury - Pota581um Chlorlde - Propylenediamine 37 44 47 56 56 56 56 56 60 60 60 61 61 61 61 62 62 62 65 65 65 65 69 40 Lithium - Mercury - Propylenediamine - Propylenediamine - Hydrochloride . . . Lithium - Mercury - Sodium Chloride - - Propylenediamine . . . . . . . . . . . Lithium -~ Potassium - Mercury - Lithium Chloride - Propylenediamine. . . . ., . Lithium ~ Sodium - Mercury - Lithium Chloride - Propylenediamine. Lithium Chloride o Lithium Chloride - Ethylenediamine . . Lithium Chloride - 2 Ethylhexanol . . Lithium Chloride - Propylenediamine. . Lithium Chloride - Tetrahydrofuran . Lithium Chloride - Water . Lithium Chloride - Ethylenediamine - Propylenediamine Lithium Chloride - Ethylenediamine - Sodium Chloride. . . . . . . . . ., . . Lithium Chloride - Magnesium Chloride - Propylenediamine . . . ., . . . . . . . Lithium Chloride - Potassium Chloride - Propylenediamine . . . . . . . < e Lithium Chloride - Sodium Chloride - Propylenediamine . . . , ., . . . . . . Lithium Chloride - Propylenediamine - Tetrahydrofuran. s« s e o e o o o Lithium Chloride - Mercury - Water . . . Lithium Chloride - Propylenediamine - Water. . . . . . . . . . . ... .. . Lithium Chloride - Propylenediamine - Magnesium - Mercury. ., . . o e e Lithium Chloride - PrOpylenedlamine - Potassium - Mercury. ., . . . Lithium Chloride - PrOpylenediamlne - Sodium - Mercury . . ., . . . . . . . . Lithium Hydroxide. . . . . . . . . . . . Lithium Hydroxide - Water. . . . . . . , Lithium Hydroxide - Sodium Phosphate - Water. . . . . . . . . . < e e e e o - - - - 69 70 72 72 72 73 73 73 78 78 86 86 86 86 89 89 89 89 89 94 94 94 99 99 III. IV. V. Magnesium Magnesium - Mercury Magnesium Chloride Magnesium Chloride Magnesium Chloride Magnesium Chloride Magnesium Chloride Propylenediamine Magnesium Chloride Propylenediamine Magnesium Chloride Propylenediamine - Magnesium Chloride Propylenediamine Magnesium Chloride Propylenediamine Magnesium Chloride Propylenediamine Magnesium Chloride Water Magnesium Chloride Propylenediamine. Potassium . Potassium - Mercury " Potassium -~ Sodium Potassium Chloride Decane - Ethylene Glycol - 41 MAGNESIUM AND MAGNESIUM COMPOUNDS Ammonia o e 2 Ethylhexanol Propylenediamine Ammonia - Dodecane - 2 Ethylhexanol - Methanol - Propylenediamine - Ammonia ~ Methanol - POTASSIUM AND POTASSIUM COMPOUNDS Potassium Chloride - Ethylenediamine. Potassium Chloride - Propylenediamine . Sodium Sodium - Mercury SODIUM AND SODIUM COMPOUNDS 99 104 108 108 109 109 111 111 111 111 111 112 112 112 112 116 117 117 117 120 120 121 VI. A. 42 Sodium Chloride Sodium Chloride -~ Ethylenediamine Sodium Chloride - Propylenediamine . . Sodium Chloride - Tetrahydrofuran Sodium Chloride - Propylenediamine - Water Sodium Hydroxide Sodium Hydroxidé - 2 Ethylhexanol ., . Sodium Hydroxide Propylenediamine . . . Sodium Hydroxide Water Sodium Hydroxide - Ethylenediamine - Water. o e e s & o« s e = o s s Sodium Hydroxide Propylenediamine - Water. . ... . . o o o« o o o e o s s s Sodium Phosphate . . . . . . . . . . . . . Sodium Phoéphate Water . . . . . . . . . LIQUID SOLVENTS Ammonia . . . . . . . . . Ammonia - Methanol . . . . . . . . . . . Benzene Benzene - Ethylenediamine. Benzene - Propylenediamine Decane . Decane - Propylenediamine. . . . . . . . . Dodecane . . . . . . . . . . . o . . . . . Dodecane - Pfdpylefiediamine. o e e s Ethylenediamine . . . . . . . . . . . Ethylenediamine - Water. . . . . . . 123 123 123 123 126 126 126 126 127 127 127 127 127 127 133 133 137 137 137 142 142 142 142 148 43 Ethylene Glycol Ethylene Glycol -~ Propylenediamine - Water. . . . . . . . . . . . o e 2 Ethylhexanol . . . . . . . . . . 2 Ethylhexanol - Propylenediamine. 2 Ethylhexanol -~ Water a4 . Isopropanol Isopropanol - Water . . . . . . . Methanol Methanol - Propylenediamine. . . . ., Methanol - Water . . . . . . . Mercury. . . . . . . . + . . . . Propylenediamine . . . . . Propylenediamine - Water Tetrahydrofuran . . . 148 150 150 151 151 151 153 153 155 155 155 158 161 161 44 | II. LITHIUM AND LITHIUM COMPOUNDS Atomic Weight Normal Isotopic Abundance Melting Point Boiling Point Latent Heat of Fusion Latent Heat of Vaporization Vapor Pressure Density Heat Capacity Thermal Conductivity Viscosity Electrical Resistivity A. LITHIUM 6.94 7.5% Li°, 92.5% Li7 179°c, 354°F 1317°C, 2403°F (1640°C from vapor pressure data) 158 cal/g, 284 Btu/lb, 1100 cal/g mole, 1970 Btu/lb mole 4680 cal/g, 8430 Btu/1lb, 32500 cal/g mole, 58500 Btu/1b mole -8143 Logj P (mm) = TTUET + 8.00 Accuracy - 10% (1100-1400°K) 30% ( 700-1100°K) See Figure 7 0.534 g/ml at 20°C, 0.507 g/ml C, 0.441 g/ml at 1000°C at 200 34.4 1bs/ft® at 68°F 1.0 cal/g ¢ (200°C to 1000°C) 1.0 Btu/1b °F 0.09 cal/sec - cm - oC (218 = 233°C ) 23 Bfi“ See Figure 8 45.25 uohms at 230°C (2) (1) (1) (1) (1) ‘ (20) (2) (1) (1) (1) (1) 10® 102 10~ 10-% 10-4 ,0-! b5 UNCLASSIFIED DWG. 20295 FIGURE 7 L6 UNCLASSIFIED DWG. 20296 M—a— T (%K) Volume Change on Fusion (% of solid volume) Lithium - Mercury Density Heat Capacity Viscosity Electrical Conductivity Surface Tension Phase Diagram Solubility of Lithium in Mercury Chemical Reactions With O, With N, With H,O Heat of Solution Activity Coefficient 47 1.5% (1) See Figures 9, 10 (21) o 0.0340 cal/g at 25 C and 0.0336 cal/g at 75°C (106) See Figure 11 (21) See Figure 12 (13,29) See Figure 13 (13,26) See Figure 14 (22) See Figures 15, 16 (13,23 24,25) Rate of reaction is appreciable at room temperature (28) Apparently stable against drg N, at tempesatures from 20°C beyond 165°C and at- mospheric pressures (28) See Lithium - Mercury - Water System (Li)g + 99 (Hg),—>Li(Hg)gg (5) o AHZQSOK = -19.6 k cal/g mole O O Log16Y = 0.1428M(15 C to 55 C)(54) Where V= activity coefficient and M = g-%toms Li per 13,534 g Hg at 25 °C HD HL% 2 13.40 3 «<£ W ™~ a — I.b & 1530 I 110.5 A o 13.20 2 80 re IempepaTURES C ciilenpre DWG. 20298 260 220 200 180 140 TemPegaTURe °F 120 100 hmlunlnnI|||||unhmhmhmlmllnn||n||m|||u|hm|nnlunlludunh1||lnn|mlluul |]|lllIII!IIlllIIHIIHHIllll|l||l|]”||ll|l|HHIIIH[IHI'H”]HHIIHT]IHIlITfl[fl]lFllll”llIIIHIIllllllllllllll_lfllillllIIIHIIIH'HH'TTUI 8 8 r o o 100 W o o o -~ o 8 50 20 10 ' o FIGURE 10 49 DeASITY oF LI AND M6 AMALGAMJ Data by EL Compere Per 65,67 CM.Bovp Rer 2I No MAL!TY* M L Amaceam TemMPeERaTURE®C ¥ A 0 3,540 (Moemarivy Ar 20°C) Lb;/GAL. o ) Ib.5-—- o 15 105 110 vl ool oyt bt oot oot b ot llll]llll‘IIIIIIIllllllilllll']llllllil IllllIIIIllllililll‘IIIillll]lllTllllliIlllllIIITlllllllilll o & o 13.50 12.40 DenJiTY 6/ML — 12,20 13.20 — 13.10 ViscoJdiTy OF LiTHIUM AMALGAM.S 0§ 66202 oM MNP I Nafoiyg 3.0 1.06 1.04 1.02 1.00 0.98 0.90 0.4 6 8 Gram Atoms/13550g H UNCLASSIFIED DWG. 20300 0 12 g (Mores [LiTer Hg) TS 8 2l JANoIi4 UNCLASSTFIED DWG. 20301 0.@ P W A 0 aNBO- N w » uo~oold N w W > W 0 NODOO b U o oo - N 420 410 2s ~aMNSOid fi ] 1 g» S ) M LAY S0 SO A A'AéVAV L NG VAVAVA'AVAVAVAVA 4.0 e‘e ‘V V ‘ e' VQVAV‘VAV‘W‘VQV /NN VO LN é FAV A A'!A' veene'e "'e Ae #'%A'A' NN/ SN o/ IIOAO0 'fimfi % e’"‘fi %"‘ V""# EAAHK AVN mu; mn I¢ "" "#1 OO S fifi&fi.fl‘rfifi.fim@fi‘ O XOOK mu & XA AVAVAVAVAVAVAVA % S VAVAVAY, 7 <. §LRDLRNAR L N 'e'e'e% e'e”e.fi .é;fl“ j‘i‘!" SRR ;.e' KA o e‘AVAVAVAVAVAVA AV efi e t edAéA Y ?'&VA #VAVAV% ‘AA %VAV% VA'A'A'#'A 1~ DRSS e:ewe:e.e;é S ‘e%:‘ %{“ e.ee' ""e {“ ,v,e, @ X em, R0 TXIONG £ A A A 5 RN EEREER LR %t 5’ e :? : ee¢ LR eé;e“. RRT, SRR :e'e'e'e'e'e!e’fi"' e'm'"‘ “e,e, eee e, e’& XX .ae'e’ :e:e}xe:e:e:eie;%;‘:e. 0 AVAY:?eAVA K VAvfiA A%Aee /\ O fli VQVA A‘A'A‘A'AVA'AQAV’ ‘% ‘V'A AVAVAAVAV 'QAVAVAVA AVAAVAVAVAVAVNAVAVAVAVAVAVAVAVAV‘V¢V¢VAVA' AVAYA' A AVAVAVAVAY AVAVAVAVAVAVAVAY/ B —SAJNO (A G| Hqg (100 %) #I%A%A M O T A . - - AT . Li - Na - Hg LRI E NN AVAVAVAV) VAVAVAVAVA JoLumlLiTy Cunve LSOOG MoLaRITY |5 APPROXIMATELY 5,0 ORI o/, , A : o TeMreERrATURE 22°C JAVAVAVAVAVAVAVAVAVAVAVAVAVA ProvorTionAL 1o MoLE AT RO {5 M A A Q = -3 ARCY TN - _O.L._AE.J Qlall) ON.J _._.....E.'—...F._._._....g_ (] lV,‘vA'AVAVAVAV YAYAYAVAVAYATAYAVAYA' - T"I - _l’\'l RIS . O AT ATAVAVAVAVAVAVAVAVAVAVAVAVAVANRE I § N N X SO SISINISIN TS SN AVAVAVAVAVAV,VAVAVAVAVAVAVAVAVAVAVAVAVAVAVA S S S R S SN SN S S5y S S AT P N NSNS S SIS SN v‘vAv‘v‘vAvAv‘vAvAvAvn‘%vAvev‘v FAVAVAYAVAVAVAYAYA' AN ANL ORI IR TAYAYA PRI AVAVAVA’AVAVAVAVA FAYAVAVAVAVAVAY, VAVAVAY AV, VAVAVA'AVAVAVA IR IR IARIAN KK AYAY, IIPIPOOIFIIN AVAVA"AVAVAVAVA'A'A'AVAVAVAeVA’A‘AVA\'\VA‘A'AVA'A AVAYAVAVAYA NN S SIS N S SN S NN S ORI SOOI AN YOG IS A'A'AVA'A'A'AVAVAVAV LR AVAVAVAVAVAVAVAVAVAYAVAVAVAVAV AVAVAVAVAVAVAVA VAVAY AVAVAVAVAV AVAVAVA mmuv‘unv.muuuuv‘nuvmnuuuv i T AVAYAVAYATATAVATATA FAVAVAVAVAVAVAVAVAVAVAVAVAVAVAY AVAVA AVAVAVAVAVAVAY . VAVAVAVAVAVAVAVAVAYA AVAVAVAVAY AVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAV 2 '/, YAVAVAVAVAVAVAVAVAVA' AN S A A AR A JAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVA "AVAVAVAVAVAVAVAVAVA! 2 .0 OSSOSO O OOORNEOOE5 AVAXAI 7.0 N/ VAVA”A'AVAVA'A'AVAVAVAVA"AVAVAVA AYAYAVAVAVAVAVAVAVAYAVAVAVAVAYAN VAVAVAVA‘AVAVAVAVAVAVAVAVAV TAVAVAVAVA:"A\VAVAVAVAVAVAVAVA AVAVAVAVAVAVAVAVAVAVAVAVAVAVAV AVAVAVAVAVAVAVAVAVAV AVAVAVAVAVAVAVAVAVAVA \WAVAVAVAVAVAVAVA' AYAYAYAVAY AVAYAVAVAY AVAVAVAVAYAVAVAVAVAY AVAVA AVAVAVAVAVAVAV AVAVAYAVAVAVAY, WAVAVAVAVAVAVAY . \WAYAVAYAYAVAVAVAVAYAVAVAVAVAVAVAVAVAVAVAVAVAVAYAY, e'AVAVAVAVAVAVAVAVAVA FAVAS . VAYAVAVAVAVATAVA! VAVA'Q'AVAVAVAVAV YAYATA 'AVAVAVAVAVAVA AVAVAVAYAY, A'AVAVAVAVAVAVAVAVAVAVAVA'A'AVAVAVAVAVAVAVA TAVAVAVAVAY ANAVAVAVAY AVAVAVAVAY AVAVAVAVAV AVAVAVA' 'AVAV SINNTSINAINNTSIN TN ININININNNININT #'AVA B AVAVAVAVAVAVAVAVAVAVAAVAYAVA'AYAV VAVAVAVAVAVAVA'AVAVAVAVAVAVAVAVAVAVAVAV SAINIANANI AN o YAVAYAVAYAVAVAVAVAVAVAVAVAAY N ) NI/ vuvvuuv /N NTNTNAN AVA‘A'A‘A'AVA'A"AAVAVA'AVA % é' VAVAVAVAVAVA"A QVA'Q Q'AVAVAVAVAVAVAVA AV NN RY VAVA'AVA'AVA AVAVAVAVAVAVAVA INISTSININININISINA ININININ NN AR AVHAVAVA JAVA /5 (NN A A AVAVAVAVA AVAVAVAVAVAVAVAVAVAVAVAVAVAY AV ' NAVAVAVAVAVAVA' AVAYAVAYAVAVAVAVAY) ‘-\"A'AVAVA'AVAVAVAVA'AVAA N O Y SIOOMNAININININONAN AN VAVAVAVAVAVAVA AVAVAVAVAYA YAVAVAVAY A VAN 'A'A'AVA'A'A'AVA'A'AVAVAVAVA'AV % NN VAVAVAVAVAVAYAVAVAV TAVAY, VAVAVAN AVAVAYAVAYAYAVAVAVAVAN VAVAVA'Q'A'AVAVA' VAvAVAVA'AVAVAVA NSNS SO NININ NN NNV eVAVAYA'A AA'A A /N AYAVAVAVAVAVAVAVAVAY AVAVAVAVA“ LVAVAVAY, AVAVAVAVAV NN AVAVAVAVAVAVAVAVAVAVA AV A FAVAVAY . VAVAVAYAYAVAVA' TAVAVAVATAVAVAVAVAVAYAVAVAVAVAYAN VAVA' AVAVAVAVAYAVAVAY, VAV VAVAVAVAVAVAVAV ‘ G GV OIS ININININNTN 3 O AVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVA AVAVAVAVAVAVAVAVAV)) VAVA'A'AVAVA AYAVAVA AVA FAVAVAVAVAVAVAN VAVAVAVA 5 0 ' AVAVAVAVAY AVAVAVAYAY AVAVAVAVAVAVAVAVAVAY LVAVAVAVAVAVAVAVAVAV AVAVAVA'AVAVA'A' NN/ % \WAVAVAVAVA "AVAVAVAVAVAYA' AVAVA"AVA‘A'AVAVA'A'AVA'AVAVAVAVA'A'AVAVAVAVAVAV VAYA'AVA'A VAVAVAVAV VAYAVAVA SN NS AV QVAVA' VAVAVA\VAVAVA TAVAYA YV S DN SN SNBSS NN uvm& e Afl'e ‘eVAVAVA\\VAVAVAV N 65 > OMd AVAVAVAYAYAVAVAY, VA"A‘AVA‘A‘A‘A‘A‘A‘A‘A‘ VAVAVA'AVAVAV A'A‘AVAVAVAVAVAVAVAVA'A' VA FAVAY AVAVQVA'AVAVAZ’VAVAVAVA FAVAVAY AYAVAVA g e NG SN AYAVAVAVAYAVAVAN IVAYAVAVAYAYAYAVAVAY AVAVAVAVAY AVAVAVAVA™ AV, AN SIS VAVA AVAVAVAVAYAVANAN VAVAVAVAVAVA' \VAVAVAVAYAVAVAVAVAYAVAVAVAVAY i VAV CAVAY . AVAVAV AV A VLVAVAVAY, AVAVAYAVAV \VAVAVAVAVAVAY. WAVAVAVAVAVA' AVAV N e N0 AVAVAVA‘A‘AVA'AVAWAVAWAVA NSNS SN NN RN NN 'AVAVAVAVA" AVAVAY A'A'A'AVAVA?VA'AVAVAYAQ @w NSO AVA'A NN INAS NN NIRIN N NN AVAVAVAVAVAVAVAVAVAV AVAVAVAVAY, ee AVA'AVAVAVAVAVAVAVAVAV JAVAVAYAY, SN YN NN N NIRRT AVAVA AVAVA'AVAVA"%VA AVAVAVAYAVG %'A V’AVA SANINANIN NN N Y AN VAV VA‘ VAVAVAVAVAVA i AVAVAVAVAVAVAVAVAVAVAVAVAV \WAVAVATAVAVA' £oc 90 R T M ISR L, KL N AVAVAVATAVA NN NN 2 PANTINININNTY An uv.v‘v‘v \VAVAVAVAVAVAVAVAVAVAVAVAVAYAY, Av T uuv‘uv.v%v‘v A ‘vfi'é'%‘é.w. ‘eve .v;vev‘vgv;'.uv SINTNTY AVAVAVAVAVAVAVAVAN ININT NN AVAVAVAVA'A'AVA% @A‘ VA‘A Y AVAVAVAV VAV 'AYAYA % SOOI SN NN A'A'AVAVAVAVAVAVAVA'AVA‘A"A N SINNININININ ¢ e e A'AVA‘A AVA AVAYAVAYAVAVAY, 3 6‘ Ve VAVA'AVA\. NSO AVAVAVAVAYAVAVAVAVAVAVAVAVAVA AVAVAVAVAVAVAVAVAV‘oAVA'AVAVA"fi' O AWAYAVAVAVAVAVAVAVAVAY Vg. AVA' AVA 2 A'AVA AVAVAVAVAVA\'\VAVAVAVAVA AVAVAVAYAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAY AVAVAVAVAY . AVAVAYAYAVAYAY; é""'é' N/ VAVAV V VAVAVAV NN N X AN AVAVAWAVAVA'AYAVAVAVA AVA‘A'AVA‘L'AVAVAVA" VAVA %VA'AVAVL'AVAVA'A NS A'A A‘VA NN AVAVAV VAVAVAV v 'AV VVAVAVA'AVAVA"A \AVAYAYAV \VAVAVAVAY; AVAVAVAVAVAVAVAY EAVAVA 'AVAVe e NN RSN YNNI NN AVAVAVAVA G # e A VAVAVAYY AVAVAYAVAVAVAV¢\.\'A'A'AVAVA AVAVA"A'AVAVA A'A'Am AVAVA AVAVAVAVA O\ AVAVAVAVA'AVA'AV VA'A'AVA AVA AVAVAVAVAVAVAVeVAVA‘A' G ev A AVAVAVAVAVAVAV¢VAVAVAVA XN NSNS 4 AVAVAV‘? NSNS NN A'A‘A'A‘A' T AVAVAVAVAVAVAVAVAVAYAVAVAVAVAVAVAVAVAVAI ¥ AVAVAY, NS 'AVA"AVAVI.\ 4 0 ] AVAVAYAY, VAVNAVAYAVAVA AVAVA' VAVA SN NN VAVe‘A'AVAVA'AV VA"'A'AVA NN NN e ‘*' ¢ A AY AVAVAVAVAVAVAVQVAVA‘A'A\VAVAVA' P AV"""“A‘A" TN A‘AVA'A'A'A‘AV AAm \ VAVAVA AVAV AVAVAVAV NN AV# 7y AVA"A A A VA NN A" SN SO SR -fi AvAVAVAVAVAVAVAVAVAVAVAVA AVA AVAV NATNNAY 'fle""‘ e"e AV 'A%VAVQ ININN A'A e AVAVAVA'A'AVAYAVAV AVAV VAV \VAYAYA ) ), \'A'A')VAVA AVAVAYAVAYAVAVAVAVAVAVAVAVAVAY, FAVAVAY; VA #AAVA‘A'A AVAve AVA 'A'A AVAVA #A ‘9 FAVAY AVAVAY¢ NN 'AVAVA'AVAVAVAVAVAVAV FAVAVAVAVAY \VAYA' AVAVA\Sg AVAVAVAVAVAVAVAVAVAVAVAVAVAVA - A AVA'A INTAININ VAVAVAVAVAVA'A .uv NN AVN AVA"A FAVAY AVAVAVAVAVAVAVAVAVAY AVAVAVAVAVAVAVA\ -VAVNAVAVA AVAYAVAVAVAVAVAVAVAVAVAVAVAVAW'{#VA'QVAVA NNV A‘AVAVAVQ NN AEVAV 'A SN/ AVAVAVGVA VA AVAVA'AVAV NN AVAVAV fié"""r’ uYAYAYAYA(#) AVAVAVAVAV AVAVAVAVAV AWAVAVAVAVAVAVAVAVAY sWAVAVAYAVAVAVAVAVAV AN AVAVA AVAVAVAVAVAVAVAVAVAY NN AVAVAVH 6 # NNINANINNNTONTN FAVAVAN W’AVA'AVAVA < 3 R T T S BB AVAVAVAVAVAVAVAVAVAVAVAN £\ £\ /Y £\ N P N AVAVA&VX&V}AVAVAVA%AVAKVAVA% V ° QQA A’ AVAVAVAIAVAV%V#'%YA'A'A'Ay A'A'AVA‘ZVNM% _'v‘ éh. X v v v / NN/ 4 "/ v q}' ¢v¢vvv¢'v‘vv 3' vvv f"%'#'#'#"'%'#" #“v‘v‘ 0 I N TN TN TN WA AA A#fi.‘v‘&‘#“ O 9 & # O #A‘ O ‘A¢A A#AVA%AVAVA‘I %AVA' ‘A¢A¢A¢A eA% * #g %AVAVIA’ AVAVAV 'A"' V N e AVQQ NN/ VAVAVAVAVAVAV AV VA 257N Q AV VA‘AVAVA 3 5 %A VAVAVAVAV A’ AN V#‘AV ee NV AVAYAVAVA 6 ¢ %Y ININNINEN/ 'A'A‘AVAVAVA'AvA JAVA! Yfie VA"A"AVAVA VA VAVA flAVeVAV j NN NTSINTN v AVAVAVAVAVAVAVAVAVAV AVAVAVAVAV AVAVAVAVAY ANAVAVAVAVAVAVAVAVAVAVAVAVAVAY 6 A VAVA A' SO NN VAVAVAV aY .6 A 'A VAV VAVA AVAVAVAVAVAVAVAYAVAVAVY! L AN VAYAVAVA AANANIAANNI AN NINT NI NINI TN A AVAYAYA) AVAVAVAVA AVAVAVA V AVAVAVAY AVAVA‘A V NN AN TSENTNTNININ /NN AVAVA.VA‘#VAVAV#‘#V%"AVAVAVA‘A‘A‘AVA"""“’A‘AVAV%V%VAV‘VAV#V#A“' VAV%IVIA 6‘% VAV AVA'AVAVAVAVAVAVAVA A'AVAV VAVAVA AYAY #AAAQ uv"‘v‘efl‘v‘ IvI"%I‘I%.vlvxfivl"v‘lfi‘v‘fli 7 0 %‘ 6 efi SINANTSININ e AVAVAVAY. AV# VAYAVA'A AVAVA AVAVAVAVAVAVV NI AN AN AINTNIN N NN S TN N L V AV 'A‘A'A'AVA A AVAVAVAV AN AVA'A'A'%VAVAV¢'¢VAVAVA'AVAVAVAVA'A'A'AVA'AVAVAVAVA'AVAVAVA'V#V#" ¢V¢V¢ /5NN B 02 3zanoid 60 ’ Where k is the specific rate - constant, s the interfacial » area, Co and Csf the initial and final concentration of Lithium in the amalgam, t is the time corresponding to Cf, and (Coyg) is the LiOH con- centration Activation Energy E % 7.75 k cal/g-mole (See Figure 6). Lithium - Mercury - Ammonium Chloride - Tetrahydrofuran Chemical Reaction Li(Hg) + NH4Cl(solid) + THF —- LiCl 4igssolved)t THF + Hg + 1/2H, + NH, Rate of Reaction Apparently limited by solu- ' bility of NH,C1l in THF (31) Lithium - Mercury - Lithium Anthracene - Dimethylcellosolve Isotopic Exchange System Li{Hg) vs Li Anthracene dis- solved in Dimethylcellosolve (33) Separation Factor o = 1.042 £ 0.012(95% CI) at 27°C (32) Lithium - Mercury - Lithium Benzophenone - Dimethylcellosolve Isotopic Exchange System Li(Hg) vs Li-Benzophenone dis-~ solved in Dimethylcellosolve (33) Separation Factor First Run - @ = 1.057 t 0.012(95% CI) at 27°C (32) Second Run - a =~ 1.056 £ 0.008(95% CI) at 27°¢ (40) 61 Lithium - Mercury - Lithium Benzophenone anil - Dimethylcellosolve Isotopic Exchange System Separation Factor Li(Hg) vs Li-Benzophenone anil dissolved in Dimethyl- cellosolve (33) First Run - a = 1,038 £ 0.011(95% CI) (32, at 27°C 34) Second Run - a = 1.087 - 0.008(95% CI) at 26.,5°C Lithium - Mercury - Lithium Chloride - Dimethylcellosolve Isotopic Exchange Separation Factor Lithium - Mercury System Li(Hg) vs LiCl dissolved in Dimethylcellosolve a = 1.023 £ 0.013(95% CI) at 26°C (34) Low solubility of LiCl in Dimethylcellosolve made this run difficult. - Lithium Benzophenone - Propylenediamine Isotopic Exchange Separation Factor Li(Hg) vs Li-Benzophenone dis- solved in Propylenediamine o = 1,055 £ 0.016(95% CI) at 27°C Lithium - Mercury - Lithium Benzophenone anil - Propylenediamine Isotopic Exchange Separation Factor System Li(Hg) vs Li-Benzophenone anil dissolved in Propylenediamine 7 £ 0.012(95% CI) C (40) 62 Lithium - Mercury - Lithium Benzophenone - Tetrahydrofuran Isotopic Exchange System Separation Factor Li(Hg) vs Li-Benzophenone dissolved in THF a = 1.045 = 0.008(95% CI) at 27°C (40) Lithium - Mercury - Lithium Benzophenone anil - Tetrahydrofuran Isotopic Exchange System Separation Factor Li(Hg) vs Li-Benzophenone anil dissolved in TFH a = 1.046 = 0.012(95% CI) at 27°C (40) Lithium - Mercury - Lithium Chloride - Ethylenediamine Isotopic Exchange System Separation Factor Isotopic Exchange Rate Mass Transfer Stability of System Interfacial (Surface) Tension Li(Hg) vs LiCl dissolved in EDA See Figures 21, 22 (36) £ 30 seconds required to reach isotopic equilibrium according to shakeout tests. (35) Af ter Before Equilibration Amalgam phase 3.7g Li/1 3.4g Li/1 Amine phase 1.8 g Li/1 1.9g Li/1 (35) Temperature and metallic contact increase decomposition of EDA as indicated by color change. (36) Dispersion in pulse column in- versely proportional to tempera- ture. This indicates interfacial tension increases with temperature. (37) TeEMPeERrATURE °C ®0 26 . DWG. 20 0.06 0.05 A =| Lc)c-.-e ok © o o 0.02 0.0l 0 7.6°10°% 2.%-10-% 3.0-10-% { 3.2-10" 3.4+10° 5.0'10"3 T(°K) - DWG. 20308 L4 T 08— 07—+ —— ToR 106+ JEPARATION Fac Ao ™~ I 105~ 64 ~JEPARATION FACTOR FOR LITHIUM |JSOTOPE AJ A FUNCTION TEMPERATURE Rer (34) (36)(40)(42) LEGEAND & |y(Hg) vs Li CL-PDA © Li(Hg) vs LiCL-EDA @ L1 (Hg) vs LiOH-H.0 % Li(Hg) vs LiCL-THF Lithium - Mercury 65 - Lithium Chloride - Isopropanol Isotopic Exchange Separation Factor Lithium - Mercury System Lithium amalgam vs LiCl dissolved in Isopropanol a = 1.055 £ 0.009(95% CI) at 26.5°C (40) ~ Lithium Chloride - Propylenediamine Isotopic Exchange Separation Factor Lithium - Mercury System Li(Hg) vs LiCl dissolved in PDA See Figures 22, 23 (34,40) — Lithium Chloride - Tetrahydrofuran Isotopic Exchange Separation Factor Rate of Reaction Lithium - Mercury System Li(Hg) vs LiCl dissolved in THF See Figures 22, 24 (34) Isotopic exchange was re- ported complete in less than 5 minutes in laboratory shakeout tests. (41) - Lithium Hydroxide - Water Isotopic Exchange Separation Factor System Stability of System (Reaction Rate) Li(Hg) vs LiOH dissolved in H,0O (Chemical reaction Li(Hg) + H,0 —> LiOH + 1/2H," + Hg minimized by applied potential and/or low temperature.) See Figures 22, 25 (42) See Li-Hg-H,0 system TeMmpEpaTune °C ~RRERET. DWG. 20372 100 20 80 10 @0 50 40 30 24 720 i i0 ' 0.05 99 0.04 0.0% Loce A 0.02 0.0l 2.8-10-% 3.0-10-% 2. -3 v -5 . - | 2.2+10 2410 3%6°10"® DWG. 20309 0.06 67 v 907 0.02 FIGURE 24 od © Q 0.06 0.05 0.04 0.03 0.02 89 S¢ JANoi4 69 Lithium - Mercury - Potassium Chloride - Propylenediamine . , : —_— Chemical Reaction Li{(Hg) + KCl(solid) f PDA = Reaction Kinetics Laboratory data indicate that the rate determining step is independent of the amalgam concentration, but is a function of available surface area of KCl when both phases are well dis- pensed by rapid agitation. (93,94) LLi(Hg)) | —a ~2LHEN L p(xkCY) kK 2 0.06 M ~at min temperature of ZSOC and . 3 molar (325 mesh) KC1l slurry in a laboratory sized mixing unit. o [KC1J [Li (Hg)] eq [LiCl] [K(Hg)) . =5 K £ 1.6 x 10 at room eq o temperature (- 25 C) Equilibrium Data (39) (These data are valid when start- ing with 0.4M K-amalgam and 0.7M LiCl - PDA solution). Lithium - Mercury - Propylenediamine -~ Propylenediamine- Hydrochloride Chemical Reaction 2 Li(Hg) + PDA°2HC1 (solution in PDA) + 2LiCl + Hg + PDA + H; Rate of Reaction Rapid: decomposition of a lithium amalgam was complete within 10 minutes with in- efficient laboratory agitation. (39) 70 Lithium - Mercury - Sodium Chloride - Propylenediamine Chemical Reaction Reaction Kinetics Equilibrium Data mrp———— Li(Hg) + NaCI(solid + PDA =— LiCl (solution in PDA) + Na(Hg) Laboratory tests show rate determining step is a function of the particle size of solid NaCl when both phases are well dispersed by rapid mixing. (89-92) -d [Li(H - [Lt( g) - k f(NaCl) where f is some function &NaCl) of the total surface area of salt particles. Data shown in Figure 26 indicate that . moles , . : k(max)= 1.2 —I:HE/mln. where the NaCl (PDA-slurry) is 3 molar (~325 mesh) and rate of mixing is 578 rpm in a laboratory sized mixing unit. Temperature (25 - 100°C) appears to have a negligible effect upon the rate of reaction. k- Na(Hg)[Licy (97) eq "[LiZHgEHNaCIJ K< 2.8 x 10* at 25°C K< 1.6 x 10° at 58°C (These data are valid when starting with 0.7M. Li- amalgam and excess NaCl in PDA) . K (Moies/LiTee- Hg/Mw.) N w i o~ DD w A b'alUnioe- P R B b hgage KINE i T AR TIC % & B OEYHOE it B @ B o THEE % & TR J QF JODIUM CHLORIDE INVERJION Na CL._CoucenTtRation N Jrurey (Mores Na G/ Liten-PDA) TL TIEOS "OM 922 _3IN9i4 72 o - Lithium - Potassium - Mercury - Lithium Chloride - Propylenediamine ” Isotopic Exchange System Li(Hg) + K(Hg) vs LiCl dissolved in PDA Separation Factor o = 1.045 £ 0.008(95% CI) at 23°C (38) (K/Li in amalgam varied from 2 to 1) Lithium - Sodium - Mercury - Lithium Chloride - Propylenediamine Isotopic Exchange System Li(Hg) + Na(Hg) vs LiCl dissolved in PDA Separation Factor a=1.051 % 0.05 (95% CI) at 23°C (38) (Na/Li in amalgam = 1) B. LITHIUM CHLORIDE Formula Weight 42.40 (3) Melting Point 614°c, 1137°F (6) Boiling Point 1382°C, 2520°F (6) 1360°C, 2480°F (3) Latent Heat of Fusion 3200 cal/g mole, 75.5 cal/g, 5760 Btu/1b mole, 136 Btu/1lb (6) Latent Heat of Vapor 36,000 cal/g mole, 850 cal/g, 65,000 Btu/1b mole, 153 Btu/lb (6) Vapor Pressure 10™* atm at 663°C, 10-3 atm at 769°C, 107% atm at 911°C (6) Density 2.068 g/ml at 25°¢ (3) Cnamdy’ Heat Capacity 0.288 cal/°C g(Btu/°F 1b) at 25°C, 12.2 cal/°C g mole (Btu/°F 1b mole)at 25°C Refractive Index 1.662 (3) Structure Cubic - NaCl type (3) Purity of Reagent £0.01% Basic constituents in Grade Baker and Adamson reagent grade LiCl - (43) Solubility in Anhydrous See "Experimental Solubilities Solvents of Salts in Anhydrous Solvents" by G. M. Begun (44) Lithium Chloride - Ethylenediamine Thermal Conductivity 5.78 x 10~* cal/sec °C cm, 0.140 Btu/hr £t OF for 0.2M LiCl solution (45) Viscosity See Figure 27 (11) Conductivity 1.73 x 10™* mho for 0.227M LiCl at 25.2°C (46) Solubility See Figures 16, 28, 29 (47) Phase Diagram See Figure 30 (48,49) Lithium Chloride - 2 Ethylhexanol Solubility {approx.) Temp. °C LiCl mole/liter (50) Rm 1.1 165 0.23 184 0.09 Lithium Chloride - Propylenediamine Boiling Point Rise 3.5°C/mole LiCl in PDA Constant solution (51) Latent Heat of 129.5 cal/gm (79-119°C) (51) Vaporization Th SRRGRNEIY /G, 20312 FIGURE 27 4 2.0 2.8 3 Y 3.4 o 3.8 0 Yrass x 1o =ElIGURE" 28 T5 PREE DWG. 20313 76 S puc. 2031h FiGURE" 29 0 2 40 0 80 100 Ho 120 TempPeeATURE (°C) om™®uc. 20315 (& 20 78 - Density See Figures 31, 32 (47,52) Thermal Conductivity 5.5 x 10~* cal/sec °C cm, , 0.133 Btu/hr °F ft for 0.8M LiCl/1liter (45) Viscosity See Figures 33, 34 (47) Heat of Solution See Figure 35 (53) Solubility See Figures 16, 28 Chemical Reactions LiCl + 2 PDA —» LiCl-2 PDA at room tempera- ture to ? (49) LiCl + PDA—LiC1-PDA at 120°C Vapor Pressure of PDA solution containing See Figure 36 (51) LiCl Lithium Chloride - Tetrahydrofuran Solubility 1.67 moles/liter at 1°¢ 0.8 moles/liter at 27OC (31,32) 0.2 moles/liter at 60°C Solvation No stable solvate at 100°C (31) Lithifim Chloride - Water Phase Diagrams See Figure 37 (56) Chemical Reactions 2 LiCl + H,O-»2 HC1 + Li,O (55) This reaction does not pro- ceed to any marked degree at temperature up to 150°C. Formula Weight 60.41 LiC1+H,0 Stability LiC1l-H,0 - LiCl + H,0 ~96°C (56} Formula Weight 78.43 | LiC1-2H, 0 FIGURE~ 3] 79 Swwemag D¥C. 20316 | S S 70 3 & 3 ' l | is,, 8 Loyl 1 FTrTTT 5 IJIII‘ 8 lllllilll llll llll’lll L1y 1 ‘1111 il 11 |llllll|| I t T 141 |ll|||ll|1r|| I FTTT L1 1 llll’ ll'llll|| ll,[ "flll lllll,[l L IIFII T o MoLariTy In M/LiTER JOLA. rTT Sl o 200 160 —140 1 8 100 2 0 - 80 S— ©0317 EIGURE 22 [ T MPERQAT NOIGATED Lt GITI|TITT o o DengiTy NoMoebAPH LiCL- PDA JoLuTIONS 40 Data By R M LeRovy Rer 47 W E Hite Rer ZZ'SQ,QQ oo o ~ \» IlllllllllllllllilIl!Jlll_IilllllJI .IIIIIII|I§TIIII|IIIUII'rIIIIII lllllllll S E Lbs/gal. a/mlL - O lllllll11:Iil|“{|11[114 AEEERARELERNLREAN YNNI RERE g E 2 DensiTY "“ 81 O™ ;. 20318 FIGURE 33 it o O o n o o o © Viogcosity IN CENTIPOIJ & ® 3 e o [THIIIIlI|IHIHll||”[”Hfl'lllfl[lli'lllllllll||||||HI| IR |lii|lll III]IIIIIIIIIIIIIIIHII [ IIIIIIIII > Loverenoc]boodboemnbomead e oo b reron oo ooud il FIGURE 2 @, 0310 82 VIJCOJITY orF Li®&i-PBA JOLNJ — 120 DATA BbY R H.LERoY REE 47 — 110 ]llll lIlIIIIH o o 200— o o 180 v o MoLariTy In MoLes/LiTER (AT TemprRrATURE IN QuesTion) o o 140 TEMPERATURE ° ¢ TemMmPERATURE °F N o \n o !ill|llIII]TITITIITITIIIIIlil'lllllllllIIIIIIIIII|IIII‘TIT||HH -t O l | g o o W o o~ o Iillllilllll]lllll IIIIJII:||illll_LJll]Illllllli,IHJLLIIIIHIIIIII [ [IT]I'IIII[III]IIIII(IIIIIIIII o 83 sl Dvc. 20320 FIGURE 23 MoramiTy Or L CL w Prevssure (MM Hg) 2000 1500 1000 400 ™~ o 100 »- - (r» 20 10 & 8L FIGURE 36 VAPOR PREJIJURE oF PDA aap LiCL-PDA JOUMNJS IATM +°C 150 — 140 — 130 120 — 100 — Rer. 51, 86 SIS DWG. 20321 DWG, 20322 85 UNCLASSIFIFD FIGURE 3 86 Stability LiCl:2H,0 -~ LiCl'H,0 + H,0 ~ 20°C (56) Lithium Chloride - Ethylenediamine -~ Propylenediamine Solubility of LiC1l in % EDA* Solubility of LiCl mixed solvents mole/liter at room (40) temperature 0 1.2 10 1.63 20 1.55 30 1.37 40 0.72 50 0.72 60 0.44 70 0.3 80 0.3 100 0.3 * 4% EDA was reported as % of original EDA - PDA mixture prior to addition of excess LiCl. Lithium Chloride - Sodium Chloride - Ethylenediamine Solubilities in Solution Solubility moles/liter (45) Saturated with NaCl and LiCl Temp.°C NaCl LiCl 26 0.078 0.31 60 0.074 0.69 80 0.049 2.85 101 0.026 4.6 Lithium Chloride - Magnesium Chloride - Propylenediamine Phase Diagram See Figure 38 (57,58) Solubilities. See Figure 39 (57,58) Lithium Chloride - Potassium Chloride - Propylenediamine Solubility of KC1l in ~0,005 moles KCl/liter of LiC1-PDA solutions LiCl solution between 24° (59) and 115°C and between 1 and 3.4 molar LiCl s PDA (100%) PHASE DIAGRAM LiCLMyClo, PDA Room TemPreaTURE —— 100°G MG. 20323 Baseo Ou wt. % OF ComponenTs Rer 57, 58 & Data Dy ' 6.M. Deeun A C. RutenpERs L. B YeaTts Lt CL 2 PDA. }. B CuTLeg o Mg GL2-5 PDA e —WNIIH 0.10 0.09 0.08 0.07 0.06 Q.05 0.04 0.0> 0.02 00! 4 a8 omm® DG, 20324 .6 B 1.0 MoLariTy L:CL FIGURE DO ® @7 Lithium Chloride - Sodium Chloride - Propylenediamine Solubilities in Solution Solubility moles/liter saturated with NaCl and LiCl1 Temp.°C NaCl LiCl (45) 30 0.008 0.943 72 0.0047 3.31 92 0.006 3.73 100 0.018(?) 3.97 130 0.013(?) 4.28 Solubilities in Solution See Figure 40 (60) saturated with NaCl Lithium Chloride - Propylenediamine - Tetrahydrofuran Solubility of LiCl in % PDA ‘Room Temperature (34) mixed solvents of PDA Solubility (moles/liter) and THF 1.4 0.31 40.9 0.054 87.4 0.77 Lithium Chloride -~ Mercury - Water Chemical Reaction LiCl (in H,0 solution) + Hg + e —»— (electrolysis of LiCl) Li(Hg) + 1/2 C1, + H,0 Effect of PDA impurity PDA/LiC12Z 0.001 lowers cell (62) efficiencyZ 10%. This may be due to two indistinguishable side reactions H,O0 + e »1/2H, + H,0 and Li(Hg) + H,0 —+» LiOH + 1/2H, Lithium Chloride - Propylenediamine - Water Phase Diagram See Figure 41 (61) Lithium Chloride - Propylenediamine - Magnesium - Mercury Chemical Reaction Mg(Hg) + LiCl (in PDA solution)—» Li(Hg) + MgCl, *3PDA (insoluble) + PDA 20 90 ememal' DWG. 20325 10 2.0 MowariTy OF Li CL (MoLes/LiTER) FIGURE 40 20 ¢ 100 ‘1’°L.| CL. - CoMDITIONS 2% + I°C. ATMOUPHERIC PRESSURE. ALL MEASUREMENT AsS WeileHT PeRceNT L1C-PDA-H:0 PHAJE DIAGRAM 1o 1 455 g/I00g. Jax Jou. p T Jeioeil ReE 4 20 80 1-46 g/100g. JaT JoL. |uTERPOLATED FROM Orex ReporT YH-30-107 Rer 6l 30 70 1.1 GL-He0 50 280 T6 TueJouo Line RepreveaTs Tue Jorusiuity O LiICL M Various MixTures Op €0 PDA Awp H20. 70 30 LicL-2PDA 80 20 |4 7 24an 1009%PDA. , Reaction Kinetics Equilibrium data 92 (1) Reaction Rate appears to (100, be first order with respect 90, to concentration of Mg in 91, the amalgam and independent 92) of the LiCl in the amine phase when LiCl is in stoichiometric excess. -a' %8 - k(ug) ® or: (Mg}, 1D(M§)—f— = kt where k is specific rate constant, Mgo and Mgf are the initial and final Mg amalgam concentrations, and 't' is the time required to reach a concentration of Mgf° (2) Effect of temperature: See Figure 42. ln k € -2000 + 5.92 T where T is the absolute tempera- ture (Kelvin) k ¥ 1.8 (min.” ') when the phaseg are vigorously contacted at 100 C in a laboratory (Rushton type) contactor. ) 2 ~ [Li(Hg)) " [MgC1,] eq = p—me (57) [Licl * [Mg(Hg)] o K = 78 at 25 C K ¢ 10.6 at 60°C (These data are valid when starting with about 0.4 molar Magnesium - Amalgam and excess LiCl - PDA solution). FIGURE 472 I DG, 20327 93 goaon~ O B ¢ ~eaQopM~ O B < o0~ O W < -0~ © N 94 - .. Lithium Chloride - Propylenediamine - Potassium - Mercury Chemical Reaction K(Hg) + LiCl (in PDA solution) === Li(Hg) + PDA + KC1l (insoluble) Reaction Kinetics Reaction rate is very rapid when phases are well dispqrsed. Equi- librium was reached in less than 2 minutes in a laboratory mixer column contactor at 100°C. The effect of temperature on the re- action rate has not been investi- gated. (101) Equilibrium Data See Figures 43, 44, 45 (93,102) Lithium Chloride - Propylenediamine - Sodium -~ Mercury (See also Li-Hg-NaCI-PDA) Chemical Reaction Na(Hg) + LiCl (in PDA solution) == Li(Hg) + PDA + NaCl (insoluble) Reaction Kinetics See page 70 for kinetics of re- verse reaction. Rate of forward reaction has not been investi- gated. Equilibrium Data See Figure 46. (93) C. LITHIUM HYDROXIDE Formula Weight 23.95 Melting Point 46200 (5) 450°C (2) 445°C (3) Boiling Point Decomposes 900°C (63) Density 1.43 g/ml at 20°¢ (3f 2.54 g/ml at 20°C (2) o A vic. 038 FIGURE 42 100 }0 30 9 80 8 70 7 60 G 50 5 40 4 30 9 20 2 } 2 3 4. 5 MoLe U CI./ Liter Op JoUAL 100 Q oo! xfi£ 3%838 1 8 Vaodad T T A AT 4 o A 53 i R A T e e W e, 31 by ey o FIGURE 44 - ot ) < 0 9 0 N e ! ™~ —_._P—____—_“_.___h_—____—____—___,_____—________m—__m_________h____r_\____*_____—____—___H—___——r.__—— film_... - u INYOIVRY N NOILVELIVIIN0) WNIHLI| TvYNIJ / CATON FIGURE 45 ; / - Q > O ] o A " A 0 o =1 A Q o of A 2 S o IS8 ¢ .[ « u} F \ ¢ & 2| x \ 2 — w ¥ / El o 4 5 / 3 © / 3 / 2 o 5 / 3 2 —.—.'—Q mIIN\ \ 1 i A (Trow) 540._4_24\2_ NOTIVIINGONO™ WATSEVIog TViLiv] —l—______q_—____—“____—.___—____—\flfl_fl___“_—__d_—____—_“_____—__—“___—____—_—4__—_____—_“__«___—_______dfi— 3 < o = o 3 0 ~ 9 ) ' 1 * 40 30 20 98 WA DVG. 20331 4 MoLes LiCL/LiTeR OF JoLuTion FIGURE 406 Lithium Hydroxide - Water Formula Weight (LiOH*H,0) Phase Diagram Solubility of LiOH in H, O Density of LiOH Solutions Lithium Hydroxide - Sodium 99 410 96 See Figure 47 See Figures 16, 48 See Figures 49, 50 Phosphate - Water Chemical Reaction Conditions for Filterable Precipitate LiOH aq. + Na,PO aq —& Li, PO, (insoluble) + NaOH aq. Determined by A. A. Palko III. MAGNESIUM AND MAGNESIUM COMPOUNDS Atomic Weight Melting Point Boiling Point Latent Heat of Fusion Latent Heat of Vaporization Vapor Pressure A. MAGNESIUM 24.36 651°c, 1204°F 1103°C, 2017°F 82.2 cal/g, 148 Btu/1b, 1990 cal/g mole, 3590 Btu/1b mole 1337 cal/g, 2405 Btu/1lb, 3250 cal/g mole,” 5850 Btu/1b mole 1 p - 22T | g 088 °€10°mm = T(Of r e Accuracy a 10% 1000 - 1400 K 20% 600 — 1450°K See Figure 7 (64) (64) (9) (53) (1) (1) (1) (1) (1) (1) FIGURE" 47 100 UNCLASSIFIED DWG. 20332 101 UNCLASSIFIED DWG. 20333 FIGURE 48 8 60 70 TEMPERATURE® C 50 20 10 5. 0 DENJITY g/em® — g 101 102 UNCLASSIFIED DWG. 20334 .0 2 Movres LI OH/LiTER FIGURE" 49 JouN(AT IuDICATED TEMR) 103 DengiTies 0 Water Jorutions O Li O HGLRE 20 DaTa Fpo E, Accuracy Y 0.00] 6/mL Fop TEwue, <20°C ¥ 0002 o/mL For MorariTy 3.5To 4.5 ¥ 0.0} /ML For MorLaRiTY £3.5 TeMr 2 20°C 4 o o ] [T T T T S 8 lllllllTll'llll'I]llll]lllllll TempepATURE °C 30 | Illllllllllllll[llll'llll]llll 20 * AT INDICATED TEMPERATURE UNCLASSIFIED DWG, 20335 ® \» DensiTy Lag/6GaL. THT T Ty I o w S - o ~ amluulnnlnulnulnnlmr' lll”l[lIIIIIH]IIIIIIIIIIIHI Lt S T o o I m — o = llll[ll”lllll[l“ 5 NJITY [N M/ ML 1hmlunlunlunl| [ 5 N lll”lllifl s b g8 & &% & §& 8 W w i oo luulunlnulimImlh IIIIHHIHII'HHIIHI[IIIIIIIIlllllllll 3 s Density Heat Capacity Surface Tension Volume Change on Fusion {% of sol. volume; Magnesium - Mercury Density Viscosity Surface Tension Phase Diagram Solubility Chemical Reactions with Impurities Thermodynamics 104 1.74 g/ml at 20°C, 1.536 g/ml (3) at 700°C, 108.5 1lbs/ft*® at 68°F 0.317 cal/g9C at 651°C, 0.34¢ cal/g®C at 1120°C (1) 5¢3 dynes/cm at 681205 502 dynes/cm at 894 C (1) 4.2% (1) D - 13.55744 - 0.0022656t (°C) (13, for 0.8N amalgam o 65, D - 13.4388 ~ 0.002125t ( C} 66, for 3.0N amalgam 67) See Figures 10, 51 logoh = - 0.2489 + 132.3/T O, (ég, for 0.8N amalgam 66’ logygn ++ = 0.2799 + l48°4/T(°K) 67) for 3.0N amalgam See Figure 52 See Figure 13 (13,26) See Figure 53 (14,15) See Figures 15, 16 (13,25) No reaction with O0,, H,;0 free N, has been observed at room temperature. Both O, and H;O0 impurities in N, or He blanketing gases form scums on magnesium amalgams. (13,67) AH mixing + - 17.3 K cal/mole for Mg + 40.5 Hg -+ Mg(Hg), in Hg (13) AT U MR i A T FIGURE S| 105 UNCLASSIFIED DWG. 20336 13,600 15,500 18,40 18,500 19,200 13100 5 20 40 &0 0 100 20 40 2.00 .80 .80 10 160 .50 .40 1.30 .20 .10 1.00 106 UNCLASSIFIED DWG. 20337 T FilGURE" B2 UNCLASSIFIED DWG, 20338 M > OLARITY WEIGHT PrRCENT 1 107 FIGURE 5% B. Formula Weight Melting Point Boiling Point Heat of Fusion Heat of Vaporization Vapor Pressure Density Refractive Indicies Preparation of Anhydrous Magnesium Chioride 108 MAGNESIUM CHLORIDE 95.23 714°¢c, 1317°F (5,6) 1418%C, 2584°F 10,300 cal/g mole, 108 cal/g, 18,500 Btu/1lb mole, 194 | Btu/1b (5,6) 32.700 cal/g mole, 344 cal/g, 58,800 Btu/1lb mole, 618 Btu/lb (5,6) 10”° atm at 763°cC, 10~° afm at 907°C (6) 2.32 g/ml, 145 lbs/ft? (2) 1.675, 1.59 (2) Best method of preparation was found to be that of thermal decomposition of NH,C1l-MgCl, -6H,0 discussed by Richards, Proc. Amer. Acad. 32 53, (1896). Magnesium Chloride - Ammonia Formula Weights of Compounds: MgCl. . 6NH. MgC1, - 4NH, MgC1l., * 2NH, MgCl, °NH. 197.41 163,35 129.29 112.26 109 Decomposition Temperatures and Heats: (9) Reaction Temp®C MgCl, - 6NH; —— MgCl,-4NH, + 2NH, ? AH = ? MgCl, - 4NH, —e=— MgC1l, - 2NH, + 2ZNH, ? AH = ? MgCl, - 2NH, —%~ MgC1,-NH, + NH, 272°% AH = 17,900 cal/mole MgCl, :NH, —® MgCl, + NH, 365°C AH = 20,800 cal/mole Vapor Pressure See Figure 54 (9) Magnesium Chloride - 2 Ethylhexanol Solubility of Magnesium (0.07 moles MgCl,/liter) Chloride in 2 Ethylhexanol| (solution at room temp. ) (69) Magnesium Chloride - Propylenediamine Chemical Reaction MgCl, + 3PDA - MgC1, - 3PDA (crystalline) Solubility of MgC1l, -3PDA Temp. Solubility mole/liter (43, in PDA o . 55) 27 C 8.5 x 10~ 60°C 2.1 x 10-° Vapor Pressure of PDA Species Vapor Pressure Temp. (70, over MgCl, in PDA 71) MgC1, - 3PDA 30 mm 160°C MgCl, 2PDA A 0.04 mm 162°C MgC1l, - 2PDA 2.1 mm ZOOOC MgCl,.1PDA < 2 mm 400°c 110 FIGURE 54 °c ¥ - - UNCLASSIFIED DWG. 20339 ¢°°' T oK A o D AR e M S e S0 e L 8 1 B o e v e i e e e i L 2 111 Magnesium Chloride - Ammonia - Propylenediamine Chemical Reaction MgCl, -3PDA + 6NH, -+ MgC1l, - 6NH, + 3PDA Mole ratio PDA/MgC1, Pressure Temp. Starting Mat. Product (104) in washed MgCl, ° 6NH, PDA/MgC1, PDA/MgC1, precipitate o 1 atm -33°C ~ o3 0.031 o 1l atm -33 C ~N g .050 | o 1l atm -33 C ~ G .053 Magnesium Chloride - Decane - Propylenediamine Apparent equilibrium 0.46, 0.75 PDA/MgCl, (68) PDA/MgCl, ratio after refluxing and dis- (decane returning to the system tilling at decane boil- upon refluxing carried room ing point temperature saturation of PDA) Magnesium Chloride - Dodecane - Propylenediamine Apparent equilibrium 1.1, 1.2 PDA/MgCl, (72) PDA/MgC1l, ratio after refluxing and dis- (dodecane returning to the tilling at dodecane system upon refluxing carried boiling point room temperature saturation of PDA) Magnesium Chloride - Ethylene glycol - Propylenediamine Apparent equilibrium 0.2 PDA/MgC1l, (73) PDA/MgC1l, ratio after refluxing and distilling (Ethylene glycol replaces PDA at Ethylene glycol boil- to some extent in the solvated ing point salt structure) Magnesium Chloride - 2 Ethyhexanol - Propylenediamine Apparent equilibrium 1.3 PDA/MgCl, (73) PDA/MgCl, ratio after refluxing and distilling at 2 ethylhexanol boil- ing point 112 Magnesium Chloride - Methanol - Propylenediamine Solybility of MgCl,°3PDA See Figure 55 (103) in Methanol-PDA mixtures : Magnesium Chloride - Propylenediamine - Water Chemical Reaction MgCl, + xs H,0 + xs PDA —v»— Mg(OH), + 2PDA*HC1 + H,0 + PDA Solubility of Mgt in Solubility Mg'? Temp (60) H,0 - PDA mixtures in moles/liter % PPA °C 0.007 90 25 0.033 60 25 0.012 30 25 0.010 60 60 0.003 30 60 Magnesium Chloride - Ammonia - Methanol - Propylenediamine Chemical Reaction MgCl, - 3PDA (in MeOH sol'n) + NH, > MgCl, - 6NH + 3PDA (in MeOH sol'n) Solubility of MgCl, - 6NH, See Figure 56 (103) in MeOH in presence of NH, and PDA PDA content of MgCl, -6NH; See Figure 57 (103) precipitate IV. POTASSIUM AND POTASSIUM COMPOUNDS A. DPOTASSIUM Atomic Weight 39.096 Melting Point 63.7°C, 147 F (1) Boiling Point 760°C, 1400°F (1) Latent Heat of Fusion 14.6 cal/g, 571 cal/g mole, 26.3 Btu/lb, 1027 Btu/lb mole (1) JOL 0 . N T FicURE 55 ATA BY L.B. TTS ek |03 WG DWG. 20340 113 FIGURE 5¢ 114 UNCLASSIFIED DWG. 20341 FIGURE 57 115 UNCLASSIFIED DWG. 20342 Y Latent Heat of Yaporization Vapor Pressure Density Heat Capacity Viscosity Thermal Conductivity Electrical Resistivity Surface Tension Volume Change on Fusion {% of Sol. Vol.) Potassium - Mercury Surface Tension Electrical Conductivity Density 116 496 cal/g, 1940 cal/g mole, (1) 892 Btu/lb, 3490 Btu/1b mole ' _ 4552 _ t9810 Pun = TR ) 0.5 log T{°K} + 8.793 o Accuracy 5% grom 600-1100 K; 20% 350-1200°K See Flgure 7 0.86 g/ml at 20°C, 53.6 lbs/ft’ at 689F. 0.82 g/ml at 100°C (1) 0.1956 cal/g°C (Btu/1b°F) at 759C (as a liquidj (1) o 0.515 centipoise at 70 C, 0.331 ¢cp at 167°¢C (1) See Figure 8 0.1073 cal/sec cm®C at 200°C (1) 13.16 ¥ ohms at 64°C (1) 86 dynes/cm (100 to 1500C) (1) 2.41% (1) See Figure 13 (13,26) See Figure 12 (13,27) 13.371 g/ml for 0.629 moles (13, K/liter sol’n (0,184 wt %) 74) 12.908*% g/ml for 3.14 moles K/liter sol’'n (0.950 wt %) both at room temperature * must contain KHggq crystalline solid Solubility of K in Hg Phase Diagram Heat of Solution Activity Coefficient Potassium - Sodium Phase Diagram B. Formula Weight Melting Point Boiling Point Heat of Fusion Heat of Vaporization Vapor Pressure Density Refractive Index 117 See Figures 15, 16 See Figure 58 K + 199 Hg —-E—--K(Hg)199 AH = 26,350 cal K + 49 Hg —v— K(Hg)49 AH = 26,120 cal log, f{ = 0.4396 M (25°C) whereY= activity coefficient and M = g atom K per 13,534 g C Hg at 25 See Figure 59 POTASSIUM CHLORIDE 74 .55 770°C 1407°C 6410 cal/g mole 38,840 cal/g mole 10~% atm at 607°C, 1073 atm at 806°C, 10-2 atm at 948°C 1.984 g/ml 1.490 Potassium Chloride - Ethylenediamine Solubility 0.0017 moles KCl/liter sol'n at room temperature (13,25) (13,22) (54) (6) (6) (6) (6) (6) (2) (2) (11) 118 UNCLASSIFIED DWG. 20343 FIGURE 58 119 UNCLASSIFIED DWG. 203k FIGURE 59 120 Potassium Chloride - Propylenediamine Solubility V. 0.0001 moles KCl/liter sol'n at 20°C 0.0002 moles KCl/liter sol'n at 60°C 0.0004 moles KCl/liter sol'n ave. from 24%to 115°C SODIUM AND SODIUM COMPOUNDS Atomic Weight Melting Point Boiling Point LLatent Heat of Fusion Latent Heat of Vaporization Vapor Pressure Density Heat Capacity A. SODIUM 22.997 97.8°%, 208°F 883°C, 1621°F 27.05 cal/g, 622 cal/mole, 48.7 Btu/1b, 1120 Btu/lb mole 1005 cal/g, 2315 cal/mole, 1810 Btu/lb, 4160 Btu/lb mole - 5567 10glopmm‘ T - 0.5 log, T - 9.235 T = 9K Accuracy 1200 - 4502K, 5%; 1250 - 370°K, 10% See Figure 7 o 0.97 g/ml at 20 C, 0.928 g/ml at 108 C (Liquid) 60.5 1b/ft3 at 68 F 0.3305 cal/g’°C at 100°C (Btu/1b °F) (as a liquid) (43,55) (1) (1) (1) (1) (1) (1) (1) Viscosity Thermal Conductivity Electrical Resistivity Surface Tension Volume Change on Fusion (% of sol. vol.) Sodium -~ Mercury Density Viscosity Surface Tension Electrical Conductivity Solubility of Na in Hg Phase Diagram Heat of Mixing Activity Coefficient 121 0.686 centipoise at 103.7°C (1) See Figure 8 0.2055 ca1/sec(§m°c at 180°c (1) 49.7 Btu/hr ft " F at 212°F 9.65 p ohms at 100°C (1) 206.4 dynes/cm at 100°C (1) 2.5% (1) 13.448 g/ml for 0.601 g atoms Na/liter sol'n (0.103 wt %) (13,74) 12.965 g/ml for 3.37 g atoms Na/liter sol'n (0.597 wt %) both at room temperature. 1.74 centipoise for 1.95 g atoms Na/liter sol'n at 25°C (13) 2.2 centipo%se for saturated sol'n at 25°C See Figure 13 (13,26) See Figure 12 (13,27) See Figure 15, 16 (13,25) See Figure 60 (13,22,14} Na + 199 Hg —> Na(Hg)199 (13) AH = -19,930 cal Na + 49 Hg > Na(Hg),q AH=-19,860 cal log. 1 = 0.2148 M at 25°C (54) 10 where” = activity coefficient and M =g atom Na per 13,534g Hg at 25°C 122 VG, poghe. FIGURE GO 123 B. SODIUM CHLORIDE Formula Weight _ 58.45 Melting Point 800°C (6) Boiling Point 1465°C (6) Latent Heat of Fusion 7220 cal/g mole (6) Latent Heat of 40,808 cal/g mole (6) Vaporization Vapor Pressure 0.01 atm. at 99600, 0.0001 atm, at 741°C (6) Density 2.165 g/ml | (2) Heat Capacity 11.88 cal/°C mole at 25°C (5) Refractive Index 1.5442 (2) Sodium Chloride - Ethylenediamine Solubility of NaCl in Sée Figures 29, 61 (11) EDA Sodium Chloride - Propylenediamine Solubility in NaCl See Figure 62 (45,60) in PDA Sodium Chloride ~ Tetrahydrofuran Solubility of NaCl ~2 x 10~* moles NaCl/liter in THF sol'n at 27°C (31) FIGURE 73 124 UNCLASSIFIED DWG. 20346 24 26 2.8 125 3.0 UNCLASSIFIED DWG. 20347 Tlok) FIGURE" G2 30 25 126 Sodium Chloride - Propylenediamine -~ Water Molarity NaCl/liter sol'n (60) Solubility of NaCl Temp.°C 1% H,0-99% PDA 2% H,0-98% PDA in wet PDA | 25 9.4 15.2 x 10~ 40,5 6.8 x 10™3 11.2 x 1073 56 5.1 x 10~ 8.6 x 103 63 5.0 x 1073 8.0 x 10°3 80 4.3 x 10~ 6.9 x 10~ C. SODIUM HYDROXIDE Formula Weight 40.01 Melting Point 320°C (5) Boiling Point 1390°C (2) Latent Heat of Fusion 1700 cal/g mole (5) Density 2.130 g/ml (2) Heat Capacity 19.2 cal/°C mole, (Btu/1b°F) (5) Refractive Index 1.3576 (2) Sodium Hydroxide - 2 Ethylhexanol Solubility 0.51 moles NaOH/liter sol'n at room temperature (79) 0. 47 moles NaOH/liter sol'm at 184°C Sodium Hydroxide - Propylenediamine . Solubility.of NaOH ~0.0008 moles NaOH/liter (313 in PDA sol'n at room temperature <0 013 mole/liter sol'm at 75°C 127 Sodium Hydroxide - Water Phase Diagram See Figure 63 Sodium Hydroxide -~ Ethylenediamine ~ Water Phase Diagram See Figure 64 Sodium Hydroxide -~ Propylenediamine - Water Phase Diagram See Figure 65 D. SODIUM PHOSPHATE Formula Weight 163.97 o Melting Point 1340 C Density 2.537 g/ml at 17.500 Sodium Phosphate - Water Solubility of Na,PO, in See Figure 66 water VI. LIQUID SOLVENTS A. AMMONIA Formula Weight 17.03 Melting Point - 17.7% Boiling Point - 33.35°C Latent Heat of Fusion 1352 cal/g mole, 79.4 cal/g 83.9 cal/g (4) (11) (75) (3) (3) (76) (16) (16) (16) (17) FIGURE 63 160 128 UNCLASSIFIED DWG. 20348 140 (20 100 80 00 40 20 UNCLASSIFIED DWG. 20349 AN NIN NS A AVAVAVAVAVAVAVAVAVAYAVAVAVAVAY AVAVA VAVATAVAVA' AVAYAVAVAYAVAVAVAVAVAVAVAVAVAYAVAVAVAVAVAVAVAVA' A TAVAYAVA' 0\ FAVAVAVAYAVAVAVATATAVA AVAYAVAAYAVAVAVAVAV AVAVAY, WAVAVA‘A’A'L'A'A‘A'A'AVA'A TAYAVAVAVAVAVAVAVAVAY, F B\ A NN SININNINTNINTNINT AYAVAVAVAVAVAVAVAVAYA .. A I\ & u\‘ ‘4 PRI U NAIRNT NN AVAVAVA'A'AVA'A'AVA'AVQVA"e"A'l’AVAVAVA'AVAVAVAVA'A'A'AVAVAVA AYAYAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAY AVAVAVAVAV AVAVAVAVAYAVA AYAVAVAVAY AVAVAVAVAVAVAVAVAVAY AVAVAVAVAY AVAYAVAYAYAVAVAVAVAVAVAVA' AYAVAVAVAY AVAVAVAVAY AVAYAVAVAVAVAVAVAVAVAVAVAVA VAV AVAVAVA VAV AVAVAVA' LSININININININNININT SN NIV N ININ BN NIN NN AT TN U AVAYAVAVAY AVAVAVAVAY AVAVAVAVAV AVAV A+~ v AVAVAVAYA™ 4> YAVAVAVA VAVAVAVAY A NN N N NN N S S NN N N NSRS NN NN ’.rAVAVAVAV SN S NN TAVAVAVAVAVAVAVAVAVAVAVAYAVAVAY - vAVAVAVAVAVA 'A'A'A‘AVA‘A'AVA\ NANINNATY NN SN SN N NN NSNS NN OSIAPEN NN NN NI NN ; = VAVAVAYAYA' AVAVAVAVAVAVAVAVAVAVAVAVAV..CAVAVAVAVAY) ™. 'AVAYAVA"AVAVAVAVAVAVAVAVAVA KA L N N NN N N NN P S SN S ST L SN N SN SN NN N SN SNV C7 AT\ N SN S N N S S AE O AOSSOASOLOALLESBNONOEA AVAVAVATAYAYAVAVAYAY - AVAVAVAY A% YAVAYAY AVAVAVAVAY AVAVAVAVAV AVAVAVAVAYAVAYAVATA AVAYA. N S NN SN NN N NN N NN S NSNS NI T NN TAVAYAYAVAVAVAYAVS”, 'A*AYAV'TA'AVAVAVAVA'AVA'HAYAVAVAVAVAVA'AVAVAVAVAVAVAVAVAVAVAVAV.'AVA N S N NN S NN PR NI NTNININT NN A'AVAVAVAVAVA'AVA'AVA'A'A'AVAYA'A'.».\'A VA'A'A'A‘AYAV).«A‘A"".'AVAVA'AVA‘AVAVA'AVA"A'A"A# \WAYAVAYAVAVAVAVAVAVAVAVAYAY AVAVAVAVAY .V, NN N ST SN S A"VA"A'AVAVAVAVAVA" \WAVAVAYAVAVAVAVAVAVAVAVAVAVAY AVAVAVAVAYAVAVAVAVAVAY, VA vAvAvAvAvAvN.vn A AVAYAVAYAYAVAVAVAVAY AV AVAVAVAY AVAVAVAVAY ANAVAVAVAY AVAVAVAVAV AWAVAVA VAVAVAVSA ™4, BN fAVA'A'AVAYAVA'AVAVAVAVAVAVAVAVAVJ'«\VAVAVA'FAVAVAVAVAVAVAVAVAVA NNNANNISEAITNKN g AVATAVAYAY)* a"AY, e'A'AVAVA'AVAVA'A'A"AVAVAVA'A"AVA‘AWAVAVAVAVAVA"A'A'AVAVAVAV MDD TAVAVAVAVAY (AVAVAVAT AVAVAYAVAY AVAVAVAVAYAVAVAVAVAY AVAVAVAVAVAVAVAVAVAV AVA VAVAVAVAVAVAY "o YAVAVAVAVAVAY, NN N NN S NN VA'A'AVAY 'AVA'AV \WAVAVAVAVAVAVAVAYAVAVAVAVAVAVAVAVAVAV AL, -'AVA'AVQVL’AVAVAVAVA AVAYAVAYAS” AVAVAVAVAY AYAVAVAVATAYAVAY AVAVAVAVAVAVAVA'AVAVAVAVAVAVAVAVAVA ‘Y‘VAVA"AVA e FAVAVAVAVAVAVA' (NININISIEN NN Q‘AVAVAVA"AVA'AVAVA'AVAVAVAV AYAVAVIVAVAY AVAYS A A NN LPON NN NN A NN AYAYAYAY ./ AVAYAVAVAY AVAVATATAY AVAVAVAVAV A VAVAVAVAVAVAY, g&VA'AVA' XA NE rA'AuVAV NANASTNININNININT VTN NN TAYAYAVAY oY AVAVAVAVAVAVAVAVAVATAVAVAVAVAYAVAVAVAVAV AVAVAVAVAY AVAVAVAVAY AV, vAVAVAVAV, VAVAVAV AW A‘AVAVA A'AVA'A'AVA NN AT ISV VAVAVA'A AVAY VAVAVAVA'AVAVAVAVAVAVAVAVAVAVA""AVAVA'AYAVAVM. NN ANTNININNTN AVAYAVS” AVAVAVAVA' 'AYAYAVAVA'A A!AVA'A'AVAVAVA'A'AVA' TSI IINI NN VA'A?G AVAVAVAY AVAVAVAVAVAVAVAV A LN NN TN TN N AT A N AN AT N T NN NN ANV NI W‘ AR N N ASANNANINATN NI (NN WA‘AVAVAVA'AVA'A Q'A'Au'A'A'A'LVA e'AWAVA'AVA""A’IVA‘A‘A’A‘A‘A‘A‘A’AVAVAVAVAVAVAVAYA'A'AVAVAVA"A'A'AVL"A'A'A AYAYAY/ JAVAVAVAVAVAYAVAVAVA A'AVA'A' VY VA‘A %"VA"""AVAVA‘ AN 4 N k'A'A'AVAVAVA NN VAVAVA'AVA'A‘A'A'A'AVA'A'A 62T YAVAVA'A'AVAVAVAVA' NN "A'A'AV S S SN Af P AVAY, “AVAVAVAVAVAVAY AVAVA VAVAVAVAVAVAVAVAVAVAVAVAVAVAY AVAVAV‘VA'NAVAVA'A'A'gA FAVAYAVAY A"A'A'A'AVA"AVA JAVA‘A"'A'AVAVG'A A‘A'A'A'AvAVAVA‘AVAVAVA‘A‘A‘A 'A'A AV 'AVAVAVA'A'AVA'A‘A N N N A A A N A N e N N A A NN A N A N AN NN AN AN NN AN AVAVJ'A"A'AVAVA'A‘A'AVA‘VA'A'A'AVAVA"A'A'A T N SN N N SN SR\ e"AVAvAVA"A'A'AVA“'AVAVAVA'A'AVHA'A'AVA'AVAVAVEA'AVA'AVA'A TAYAYS AVAYAVAVATAVA AVAVAVAVAYAVAVAVAVAY T VAYAVAVAVAVAVAVAYAVA VAY VAV A'AVAVA'AVAVAVAVA'AVAVAVAVAVA é‘"A NN NSNS NI A"A'A e'A'A'A‘AVAVA'AVA‘ ' !fl' (o7 VAVA'A" A"AVAVAYAY, " ?fil # VAVA"AVAVAVAVAVAVAVAVAVAVA \VAVAVAVAVAVAVAVAVAVAVAVAVAVA' NYXNY "A'A‘A'"A’A'AVAVAVA'A"AVA'AVA' A Y A'X‘A“A A AVAVA"A eVAvA'A'A INAN N VAVAVAVA A'A"AVAVAVAVA'A'_A NN NI S A TS NI N N PN AN N N SN N SN AVAVAYAVHs S VAVAVA AYAYAVAY AVAVAVAVAV AVAVAVAVAV AVAVAVAVAVAVAV- o p) N 'A'A'AVA'A"A'A'AVAAVA"’A'A'A'Q'A'A"AVAVA'A' VAYAYAYAVa TAYAYAYA A7) TA'AVAY-VAV VAYAVAVAVAVAVAYAVAVAVAVAY A"AVA'AVA' V_VA"'.'A'A'A" AYA, NN .'A‘AVAVAVAVAVA"AVA'A 'A'AVAVAVA 'AVA'A?AVA 'A'A'A"AVAVAVAVA ¢'A'A'A'AVA AVAVAYAY, VAVAVAV 'A'A'L'A 9" FAVAVAVAV ¥ o aVAVAVAVAVAVAYAVA AVAY JVAVAYAVAVAVATAY AV . 7AVAVAY AV AVAVA'AVA'A NN SN SN NTNT NN/ VAVA' A'A'A'A AVAV;V¢7¢ 6'5 gfl"?.n' \VAVAVAVAVAVAVATAVAVA AYAY SYAVAVAVAVAVAVS™, AVAVAVAVA'AVA"AVA"AVA! NN NN VAVA "A‘A'A'A'A'AVAVA 'A‘A'A'A‘A A VA NN % FAVAYAVAVAVAVAYAVAVAVA PN A PEATN N NTNININAN NN A'AVAVAVAVA'A'AVAVA'A'A.'AA YJA A A NN A."WAVAVA' A AAANAAN N N NN AP A NN A N NN A N AN NN RN N XY KXY ' VAVAVAY; m‘-‘—'.‘i;'fl’ YAVAVAVAVAY 4 VAVAVAVAY ' AVAVAVAVAYAVAYAVAYAVA' TA‘AVAVA fAfiVAVAVAVAV A'A'AVA'A‘VA'AVAVAVA'A'AVA'A‘A'A'A'A'Afi'&'fle QVAVA'AVAVAVAYAVA 7N/ S .fAVA'AVA' AVA VAV e AVAVAVAVAVAVAVAVA'A'A'A'A' AV:"A" AYAYAYAYAVAVAVAY, VA‘AW'%‘AVA‘A‘AVA‘I'AVLVA'A'A'A"A LN NN NI N TNINN NN e WAVAVAVAVAV,LY, A‘A AVAVAYAVAVA'AVAVA AVA'AVA A‘A NS "’e‘AVAVA'AVA NN NI SIN TN TR NFNIANTNINT SINININTRT SIN N WP ST AN NTN 'AVNAYGVA A'AVA" VA VAVAVAVAV ¢ \YAVAVAVAVAYAVAVAVA' AW aVAVAVAvAVAVAvA'AVAVAVA FAVAVAVAVAY VAVAYAVA'AV.VAVAVAVAVAVAVAVA'A IS AP STN N NT AVAVAVAVAVA‘A FAVAN W NN ANININ NI NINININININANININ AY/ (AVAYAYAVAVAVAYAY, 'AVAVA'A‘A'AVA P N o T N S T PN N N T TP T NI ¢ e Ag‘ TAVAYAVAVAVAVAVAVA FAVAVAVAVAVAVAVAVAVAYA' AR NSNS NI N AN A'AVAVAVAV \WAYAVAVAVAVAY AVAVAVAYA .7 8 VAVAVAYAYA' A!A'AVAVAV VAVAVAVAV AV%VA INNINININNINING VAV VAVAVAVAVAV V NN Y Y VY IR INTSNININN NSNS %VA"AV \/ A‘A‘AVAVA'e AVAVA'A'Avé'A'A""'A'A'A'A'A""AVA‘AVAVAVAVAVA INNATNN AVeVA"A"L'AVAVAVAV AVAV AVAVAVAVAYAVAVAVAVAVAVAVA' AP NI TN TN 'e &VA"AVAVAVA %‘AV’AVAVA“ -fll’%VAVA'AVA'AVAVA' AN flA‘AVAVAvA'flA‘A‘Ave fi" A 'AVAVA'A'AVAVAVNAVA 6 AVA‘VAVAVAV FAYAVAVAVAVAVAVA NPANANINANININ ;V‘VAVA-A FAVAY VAYA'A NI ABSFCNININ T A'A'AVAVAVAVAVL"HAYAVAVAVAVAVA'AVAVAVAVA NTSINAINAN NN NN TNINININININT NNV Y NN VAVA'AKVAVAVAve uu NN A" TN AN e‘ "e NN NIV T NSNS 'AVAVAV ININNSN 'e'a #"'é" VAVAVAVAVAVAY VAVAVAVAVAVAYAVAVAVAVAVAVAYAYA| N NINININ N NSNS A'A FAVAY 'A'A'- "AVA'A FAVAVAVAVAVAVAVAVAYAV/ 'A'A 'AV¢ AVAYAVé NIN/NTN " N/ AVAYAVAVAVAVAVAVAVAVAY, VAVAVAVA'AVAVAVA'A'AVA NN N NS AN S AN SN ANSSSODNOSOAANDDON A'A'AVAVA AVA'A'AVAVAVA ‘A A e 'A'A'A'AVAVAV N 'AVAVA aVAVAVAVAVAVAVAVAVAVAVAVA' '/AVAVAVAVAVAVNAVAVNAV PPN SNININTN NN NN SN N N *VAVAVAVAVA"AVAVAVAVA \WAVAVAVAY, VAV Vi AVAVA'AVAVAVAVAVAVAYAVAVAVA NN NISIN NN NI TN 7 AAVAVAVAY AVAN VAV, :.IAYA"_'.’.vAV‘YAVAVAVAYAYAVAVAVAVAVAVAVAVAVAVAVAVA AVAVAVAVAVAVNAVAV AVAVAYAYAVAVAVL) A'A' AN AVAVAVAVIAVA NN AININATN AN NG A'AVAVAVAVAVAVAVA uv‘_uvn‘v NS .uv;uv‘v‘v‘uvAvAvAvAvAvAv‘uv‘v‘vAuv‘vAvAuv v Auv‘v NN mv‘uuv‘vn‘uv‘vAvAvAv‘v‘uvAvAvAvAuvAvAvAvAv‘uvy‘vAv‘vAv NPT Av AT 77\ .'A PN NSNS OO VAVAYAVAVAVAVAVAVAVAVAVAY AVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAY NNV AVA AVAV RO NN PA TR A‘AVAVAVAVA AVAVAVAVAYJAVAVAV \WAVAVAYAY. VAVAVAVAVAVA'A AYAVAYAVAVAVA'AV VA'A'A'AVAVAV 'A'AVA' VAVAVAVAVAYAV 'e'A 'A'A'AVAVAVAVA' A'A"A #VA. AVA jAVAVA'A'AVA"A PN LA VAN NININA N NINI NS NN AN I NN AN INININ A ININININ N A' Y AVAVAVAVAY AVAVAVAVAVAVAVAVAVAVAVAVAY A \\/ A 6 e BTN TINNNNANINANAANTIANNINANANININAT AVAVAVAV‘VA'AVAVA NN N ANTNAANNINAN S ANN AN NN VA'AVAVAV AVAYA AVAVAVAVAVA AVAVAVAVAWAVA AVAVAVAV, | PN NN SIS NN TAINNINNININNINN VAVAVAVA‘AVAVAVAVAVAVAVA‘AVAVA"A"A'AVA'A"A'AVHeA'A'AVAVAVA'A‘AVA‘AVAVAVAVAvevA e'A'A'A'A'AVA'AVAVLVA'AVAVA'A'A'A'AVA'AVA'A' DN NAPATNT STV AN NN SN NN NN NNTNNIN NI NN NTATNT N % YAV AVAVAYAVAY AVAVAVAVAY VA VAVAVAY AVA VAVAVAY AVAVAVAVAY AWAVAVAVAY VA VAVAN e e"'A'A'A'A'A"AVAVAVA'A'A'AVAVAVAVAVAVA'AVA'A'A'A'A'A NS AN AN SN NNNNANSINI NN Av. A'AVAVAVA'AVAVAVAVAVA‘A'A'A INANSININAY VAVA'AVAVAVAVAVAVA A'AVA A A'A NN AV% ININININANIN SNININA TSNS INN IS A AN TN T A 0 10090 EDA. XX RO OO OO0OOOO0C OO OO OO OOOCOOOOOO0 A A S S A A RS N H NN AVAVAVAVAVAVAYAVAYAVAVAVAVAVAVAYAVA'AVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVA'AVAVAVAVAVAVAVAVAVAVAVAVAVAY VAVAVAVAVAVA DANNNINNANANNANNNNINSNANSNNANANNNANSINNSIN N SN B Yo 330914 A IOO °/° H,0 A O VAVAYA OO%00 AVAVACAVAYA MIJCIBILITY OF THE SYSTEM PDA Na OH-H20 AXTIIR AR @ 2 jo c + l ( w p BEOARETON UNCLASSIFIED A A - EIGNT MERCEMT AN INISI TN DWG. 20350 AIRIIRIENIRIIN Rer 75 AR LRI LN —_—— . .vAvAvAv I TR AT I vfi v‘v A AVAVAVA'AVAVA Vt’ VSIS AVA'AVAVA'AVAVAV ST NI Av;nuv‘uuuuuuuu FAVAVATAVAVAVA AN AL RN A0 AN ‘uv‘v‘v‘v‘ e‘% X 77 v A AT N I NN AV VA'A'AVAVAVA'A'A'AVAVA "AVAVAVA'AVAVAVA A TAYAY ' NN NI AVAVAVAYAVAVAY, v‘vAvAv‘v‘vAv‘v‘v‘v‘ AVAVAVAVAVAYAVA AYA'AV VAY N NNININNT SN ST ’Y VAYAVAVAVAVAVAY AVAVAVAVAVAVAVA AVAVAVAVAVAVAVAVAV "‘o VW VA M SN N S SN SN AYAVAVAVAVAVAVAY, NN AL AN AR AN N NN NN 'A'A ' Vevev VNA’AWA' FAVAVAVAVAVAV 4 VAVA™ “VAY 5 AVAVAVA A.'AVAWA" AVA NN 'A':.'.-.uuu' N\ NP \'AVA FAVAYAVAVAVAVAVAY AV, V VA -'AVA Y AVAY VAVAVAV‘J TN AVAVA"AVA‘AVAV \WAVAY; AV’ AYAVA N/ VA'A'A".'A e 4“ 'A‘AVA SOV 'AYA cA'AVA A'A‘A‘A NN TN TR AVAYAVAVAYAY V AV AVAY AVAVAY o (A AVAVAVAYAY AVAVATAN. Y A AVA'AVAVAVAVA 1 VA'A'AVAVAVA"A S NPT SIN NN NN NS AVAVA'AVAVAVA‘V V % NN NI fAVeVAVAVA'AVA NN '.v. A AVAVAVAVAY, VA‘AVAVAVA'I'A'A N NININTSINI NI TSN IR N TN A'A'AVAVA'A v» fmv AVAV NI MNNINNINT NN A GENT NN N ST v‘vr.g‘v’v‘v’ fi TN v‘gvn‘vg\‘rAVAVAVAv‘vAv‘v‘uv‘v‘v‘f AN 7 RN NN NN e AY . AVATAYAVAVAVAVAV AVAVAVAVAV AV (AVAVAY AVAVAVAVAVAN |} (SO Q‘AVA' V 'é fAVA'AVAVA"AVAViAVAVAVAVAVA NPT/ 'AVA'AVAVA'A'AVAVA‘ ? /N7 -. -WA"\'. ;"Aflfl't VAVAVA".fAVAVA FAVAVAVAVAVAVAVAV 0.\ AVA"A'A" 'AVAVA VA BN fA'AVAVAVAVAVA"AVAVAVAV)'AVA'A\\ 'AVA e VA 'AY ' M 'AV‘.rAVAVAVAVAVAVAVAVAVAVAW' WO N VY V VAW fAVA A .‘VAVAVA N N/ VAVAVAVAV SISO NINNINNINTIN T NI NT ORI\ N AVAV. AVAVA 'A'AVAA AN VAV I Ae ‘e ‘A 7 iAVAVAVAVAVA'AVAVAVA . QVAVAVAVA ONINAA —~ AYAY) A A‘AVAVAV‘ rA'L AVA.VAVA' e \WAVAYL AVAVAVA VAVAVAVAVA VAV AV AVA VAV AVAVAVAVAYAVAVAY. w b AVAV‘IA'A'A'A ¥ AVAVAYAVAYAVAYAYAVAY AVA‘AVAVAV‘.‘FJ'G’AVA AVAVAVAVAVAVAV”«AVAVAVAVAVAVA AVAVAVAVAVA‘A O TR 7 NPT N I ew vAv‘v TAYAVAVAVAVAY: f‘v‘p‘rAvAv‘v‘vAvAuv‘w‘r‘v AT N 'A'A'A'A'A' "Ve‘fl # NN N vAVA' 'AV 'A‘AVAVAVAVA'AVA 'AVA"A'A"A VQVAVAV! A'AVA S NN NN AVAVAVAW‘?A"AVAV 7 ' TAYAY... TAVAY AV, AVMVNA'A e" AW VNN NN NN SN #‘AVA'AV VAVA'e YA‘AVA‘A VA AVAVAVAV VAV NNININS D 6 7N AVAVAVA X aVAYAVAVAYAYAY, \VAVA FAVAVAVAVAV -4V AVAVAVAVAY AN Yf!‘ ‘VAVAVAVAVAVAVA A'A AN AY/ . AVAVAVAVAVAVATAYA! 'AVA'A'A"A""NQVAVA'AVAVAVAVAVH)"'AVAVAVR' A VAYAVAYA VAVAVA /‘ ‘ eVAVAVAVAVAVA (A 'AVAVA'AVA‘AVAVA'A‘AVA'A AVA'eV FAVAYAVAVA YAV AVAVAVAVAY AV, VAVAVAV AV A VAV . VAV VA AVAVAVAVAVAVA NN NN AV, SAVAVAYAY VAVAYA'AVAVAVAVAQ b\ N NT NN ev NI P VAVAVAV VA'Q'AVAVAVAVAV v.v L/ TN SN AV JAVAVAY. VVAVA'A'AYAVA'A"’A‘AVAVA'A YA A'A'.'A VAV GVA' OADNNLN, AVAVAVAVAVAVAVAVAVA AY JAVAVAVAVAVAVAVAVAVAVAY/ AVAVAVAVAYA™ A AVAVA'AVA'A"A ’AVA L AVAVA"‘VA JAVAVA AVA'AVAVAVAVAVAVAVAVA 'AVA'A'A'A'A'AVA 'A'Q &A'A'A'A'A'A'A‘LT AV}' NN NN NN NI N NN P T VAVAVAVAVAVAVAVAVAVA'A'AVA'A'A e’e:e‘e'e'e‘a 91:.‘ KOOI AA) L "“’""‘" "',%""" "1¢I¢I"#I¢' R v,‘uv‘v;v;uuuuv A L A7 AVATAVAV A flw 7 Auvm_,s B wfi vfié n'AVQAA'AVAVAV¢'AVA¢ & % “3 AR R T X0 RO LB AR LRI A’A‘Aefirfifié V‘é‘ A V v v; 9‘ Y AVAVAY, 'Q'%VA' 'gw VAV uv;uuu’é 0" P VAVA"A"AVAVA FAVAVAVAVAVAVAVAVA AVAVAVAVA«A e VA‘A"'«A'A’A'AV #A'A'A'A'A'AV VY AVAV VAYAVA" AVAVAVA'A"A'AVA' A' AVA‘A" N e .vAVAVA'A NN Q'A'A'A" 5 e 'AV VAV 'A‘AVA A‘ A' ‘% A'A'A VAVAVAVAVAVAVAVA Ao 'AVAVA‘AVAVA A"AA A'A'A on A AV2Y & A N A A AVA ININININININI PR IR SRR RS eé;:;e.e;} ,z;v"'s' 'e;,:;"e'e'*;' AT, AR vuu .«.v 9"'# OOKK v»- 95 XX "% £ A eVVA'A A 00 XA AN X OO0 OOCFAATIFFINN AR AIRTO .vffivmm;umf QA 5 ‘ 0 eifia 9 "# G XN 2 flv XOOOOOOOOOOOEETON 9id PP j:;"'mm RX ee'..e, IR AT 'e'e' .eg.w'o'e'fi.q.w:ezo'eu:e. f? 'AVA'AVA AVA A"# e ‘Yi; A'ev O AV% L 9 AV'V' 7 “""v""‘v ? XA Aea." A'A A"‘AA:‘ ‘% i&nfi \ A#I%Y'AAV 74‘ ggg‘h*‘#kA#AeA t’lxgx‘vuVAVflAVAVAVAV oK ‘:e" % ‘;‘ "‘ VQ ¥¢ e e e TN TN AN ? "‘% %99 g 'A uv ; fi? % ?euv"g;uuv# FRLIRL N fik ’%':e: ,gge, L s %m%:e‘e'ege#e ks 7 FAVAVANAY AVAVAVANAY AV /AN A A A N immuuv‘uu , l'r A \WAVAVAVAVAVAVA' UI 'AVAVAVAVAVM SN va AVAVAY AVAYAVAVAVAVAVAVAVAV 5 a”e‘#‘.’er‘;'v'e":e'e‘ o ? ,0 m*exe:- RN o /) /A AKX fiv‘vfi—%&g %fi N "éé% % é A“ 3"'% mvmm S AA X 00N IRANNNDS RSN S PO\ v v v 9‘ v v v v FAVAVAVAVAVAVAVAYA' /IIA#A‘ o ‘ GAV .&Aeé ’ 'é ev % ’ egvev;? %’e‘ 'A'AVE Afl AN/ é' .é;v NN NN 4 0‘ VA AVA VAVAV AVVAV e e A'A VA ‘ VA"Q A A VA 'AVA PN SNV VA" V VA AVA? VAVAV ’ A A"A ‘ 6 ’ ” 5 .%# SVAVAVAVAYAVATAVA K A'AV‘ A A A 6 e VAVAVA'A A %fi ’ 6 A NAVAVAVA."WAVA'AVA AN $ NN VAVAV V VAVAVAVAVAVAV‘V‘V V‘VAV‘VA‘ V V v V V " v v v V" v V‘VAV‘VAVAv‘v‘v‘vAv‘v‘v‘v‘v‘v A AVAVAVAVAVAVAVAYAVAV AVAVAVAVAV sWAVAVAVAV, FAVAVAVAYAY, yv; eA’ G é" A' & g‘?’ N AVAVAVA‘}A \WAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAYAYAVA NN A'A'A'A'#'A VAVAVAVAVAVAVAVA JA'A‘A‘A'A'A‘AG ée ¢A¢3Ae AAéQAVAVAVA AN %‘ee eAVAVA'AVA'A' /AN 3VAVAVAVAVAVA'AVAVAVAVA"AVA‘ OO m%p DA A'# A A"AV VNAYA DA AVAVAVAVAVAVAVQYA AVAVAVAVAVAYAVAVAVA AVAVAVAV AVAV VGVAVA'AVA'A AVAVA'GV NN VAVA A [\ AVAVAVAVAVAVA'AVA'A'A'A'A'A'AVA"#‘%I#X%V#‘%'#‘%" 3’3:#. Eno O 131 UNCLASSIFIED DWG. 20351 FIGURE 60 Latent Heat of Vaporization Vapor Pressure Critical Pressure Critical Temperature Density Heat Capaéity Viscosity Dielectric Constant Dipole Moment Conductivity Ignition Temperature Limits of Inflammability 132 5581 cal/g mole, 327 cal/g logloP 12.465400 - mm 1648.6068 T + 2.403276 x 107°T% - 1.168708 x 10-8 73 - 0.01638646 T O (183.1 < T <343.19K) 112,.3 atm 133°C Temperatureoc Density g/ml - 30 0.6777 - 10 0.6520 0 0.6386 20 0.6103 1.1 cal/g®c at 0° 0.135 centipoise at 25°C 16.26 at 25°C 1.46 x 10-18 ¢, s5.u. 5 x 10-11 mho at - 33°C 651°C, 1204°F 215% and < 28% {vol.)NH, in dry air at 25°C (16) (16) (16) (16) (16) (17) (16) (16) (16) (17) (3) (3) Solubility of Metals Metal Solubility g/100 g NH, Temp.°C in Ammonia Li 10.7 -33.2 Li 11.3 0 Na 24.6 -33 K 49.0 | -33 (17) Solubility of Some Salts in Ammonia Ammonia - Methanol Solubility of NH; in Methanol Densities of sol'ns of NH, in Methanol Formula Weight Melting Point Boiling Point Latent Heat of Fusion Latent Heat of Vaporization Vapor Pressure Density Heat Capacity (as gas) (as liquid) Viscosity Flash Point 133 o Solubility g/100 g NH, at 0 C 0.410 cal/%g at 20°C 0.7 centipoise at 20°C - 11%, 12°F Cation Anion Cl Br 1 Li 1.43 - _——— Na 11.37 39.00 56.88 K 0.132 21.18 64.81 NH, 39.91 57.96 76.99 Mg _— 0.004 0.156 See Figure 67 (77,4) See Figure 68 (77) B. BENZENE 78.11 5.5°C, 42°F (3) 80.1°C, 176.2°F (3) 2351 cal/g mole (2) 7,353 cal/g mole, 94.14 cal/g, 169.34 Btu/lb (2) See Figure 69 (2) 0.874 g/ml, 7.29 &b/gal, 54.5 1b/ft3 at 25 C (3) o 19.52 cal/°cC g mole at 25 C, 26.74 cal/°C g mole at 127°C (7) (8) (8) (3) 1% 12 0 134 UNCLASSIFIED DWG. 20352 20 20 TeEMPERATURE 20 FIGURE &7 @0 10 0.76 135 UNCLASSIFIED IWG. 20353 077 078 0. 0712 DensiTy oF Jouwy (g/ml) FIGURE &8 a8l 2.4 .0 2.9 136 UNCLASSIFIED DWwG. 2035L 2.0 22 3.4 Feeo FIGURE 69 3.0 2.4 Ignition Temperature Limits of Inflammability Refractive Index Benzene - Ethylenediamine Phase Diagram Vapor Liquid Composition Diagram Benzene - Propylenediamine Phase Diagram Vapor Liquid Composition Diagram Formula Weight Melting Point Boiling Point Density Heat Capacity Viscosity Surface Tension Flash Point Ignition Temperature Explosive Limits 137 580°C, 1076°F (3) >1.35% and <6.75% (vol.) of C,H, in air (3) 1.05011 at 20°C (8) See Figure 70 (78,11) See Figure 71 (78) See Figure 72 (79) See Figure 73 (79,80) C. DECANE 142.28 - 29.7% (3) 172.5°C at 762 mm (81) 0.730 at 20°C (81) 58.10 cal/°C g mole for gas at 25°C (7) 0.9204 centipoise at 20°C (7) 23.7 dynes/cm at 20°C (81) 46°C (3) 250°C (3) 0.67 to 2.60% by vol. in air (3) 138 UNCLASSIFIED DWG. 20355 FIGURE 70 139 UNCLASSIFIED DWG. 20356 IGURE 7 140 UNCLASSIFIED DWG.20357 IGURE 772 0.5 0.6 0.7 0.8 0.9 1.0 0!4‘ MoLE FracTiond BedzZealE 0.5 0.2 0.1 120 10 100 30 80 70 S o k3 b it i a8 g i o SR R 2 O e e )41 UNCLASSIFIED DWe. 20358 - IGURE" 7 Refractive Index Decane - Propylenediamine Vapor Liquid Composition Diagram Limits of Solubility Room temperature Formula Weight Melting Point Boiling Point Density Heat Capacity Viscosity Surface Tension Flash Point Ignition Temperature Explosive Limits Refractive Index 142 1.41206 at 20°C See Figure 74 0.01 moles PDA soluble per liter decane phase 0.15 mole decane soluble per liter PDA phase D. DODECANE 170.33 ~9.6°C 214.5°C 0.750 g/ml at X 69.62 cal/°C g mole for gas at 259C 1.49 centipoise at 20°C 25.5 dynes/cm at 20°C 74°C 534°C 0.60 to —— % by vol. in air 1.42186 at 20°C Dodecane - Propylenediamine Limits of Solubility at room temperature Formula Weight 0.04 moles PDA per liter of dodecane phase 0.01 moles dodecane per 1liter of PDA phase ETHYLENEDIAMINE 60.08 (81) (82) (68) (3) (3) (81) (7) (7) (81) (3) (3) (3) (81) (72) FIGURE 74 143 UNCLASSIFIED DWG. 20359 Melting Point Boiling Point Latent Heat of Fusion Latent Heat of Vaporization Vapor Pressure Density Heat Capacity Thermal Conductivity Viscosity Conductance Surface Tension Flash Point Refractive Index Solubilities of Salts in EDA Solubilities of Salts in EDA at room temp. 144 10.8°C 116.2°C 77 cal/g (monohydrate) 167 cal/g (monohydrate) See Figure 75 See Figure 76 0.66 cal/g °c (12 o 0.00060 cal/sec C cm, o 0.145 Btu/hr °F ft See Figure 27 9.0 x 10~% nmho See Figure 77 110°F o 1.4565 at 20 C See Figures 16,28,29 Salt LiF LiC1l LiBr LiI KC1 KBr KI NaCl NaBr Nal EDA-2HC1 EDA ® HZ SO4 EDA ° Hz CO3 Solubility moles/liter sol'n - 26°C) 0. 0. 0. 0. b o = O 001 29 25 37 0.0017 0. 3.44 059 . 05 .09 .9 .70 .001 .0 (8) (11) (11) (11) (11) (11) (11) (11) (11) (11) (11) (8) (8) (11) (11) 145 UNCLASSIFIED DWG. 20360 FIGURE 75 2.6 2.6 | 32 4 30 YTaps v o= 0% aso 089 087 0.85 084 082 082 0.1 146 UNCLASSIFIED DWG. 20361 60 80 00 120 140 147 UNCLASSIFIED DWG. 20362 FIGURE 77 Ethylenediamine - Water Phase Diagram Formula Weight Melting Point Boiling Point Latent Heat of Fusion Latent Heat of Vaporization Vapor Pressure Density Specific Gravity Heat Capacity Thermal Conductivity Viscosity Conductivity Surface Tension 148 See Figure 78 ETHYLENE GLYCOL 62.07 - 13.0% 197.2°% 44.7 cal/g 191 cal/g, 344 Btu/lb 0. 06 mm at 20 C 10 mm at 89°C, 50 mm at 123°C loglopmm = ?.8828 - 1957/(193.8 + t°C) 1.11336 g/ml at 20°C 1.1154 20/20°C, 9.28 1b/gal at 20°C 0.561 cal/g °C (Btu/1b °F) at 20°C o 0.538 + 0.00113t C 0. 000690 cal/sec cm °C at 20°C 57.4 cp at 0 C 20, 9 cp at zo°c 9.5 cp at 400C 1.07 x 10~° mhos 48.4 dynes/cm at 20 C 50.21 - 0.089t °¢ (11) (8) (8) (18) (8) (18) (18) (8) (18) (18) 149 UNCLASSIFIED DWG. 20363 FIGURE" 78 8 %0 30 40 50 G0 76 80 20 WeienT Peocent DA 10 124 120 e ]y A 108 104 {00 5 Flash Point Ignition Temperature Refractive Index Solubility of Salts in Ethylene Glycol Salt LiC1 LiBr KC1 NaCl 150 111°, 232°F 413°%, 775°F 1.4316 at 20°C Solubility g salt moles salt 100 g solvent Titer solvent 14.3 3.76 39.4 5.05 5.18 0.77 7.15 1.36 Ethylene Glycol - Propylenediamine - Water Vapor - Liquid Composition Formula Weight Melting Point Boiling Point Latent Heat of Vaporization Vapor Pressure Specific Gravity For mole ratio PDA/Ethylene Glycol = 0.5 Mole Fraction H,O Vapor - Liquid . 694 .341 - 731 424 - 799 .524 2 ETHYLHEXANOL 130,22 -76°C 184 .4°¢C 92.8 cal/g, 167 Btu/lb .2 mm at 20°C, 10 mm at 78°C 50 mm at 109°C 0.8345 20/20°C, 6.94 1bs/gal at 20°C (3) (3) (8) Temp.OC 25 25 25 25 (83) (84) (8) (8) , (8) Heat Capacity Viscosity Flash Point Refractive Index Solubility in Water Solubility of Water in 2-EH 151 0.564 cal/g °C (Btu/lb °F) at 259C o 10.0 centipoise at 20 C, 4.0 centipoise at 40°C 185°F O 1.4313 at 20°C 0.10 wt % at 20°C 2.6 wt % at 20°C 2 Ethylhexanol - Propylenediamine Vapor Liquid Composition Diagram 2 Ethylhexanol - Water Limits of Solubility at Room Temperature Formula Weight Melting Point Boiling Point Latent Heat of Vaporization Vapor Pressure Specific Gravity See Figure 79 Solubility of H,0 in 2 Ethylhexanol = 2.6% by wt, Solubility of 2 Ethylhexanol in H,0 = 0.1% by wt. ISOPROPANOL 60.09 - 87.8°% 82.3°C 159 cal/g, 287 Btu/lb 10 mm at 2°C, 33.0 mm at 20°C, 50 mm at 27°C 0.7868 20/20°C, 6.55 1lb/gal. at 20°C (8) (8) (8) (8) (8) (8) (79) (8) (8) (8) (8) (8) (8) 152 UNCLASSIFIED DWG. 2036k FIGURE 7 Heat Capacity Viscosity Flash Point Limit of Inflammability Refractive Index Isopropanol - Water Phase Diagram Formula Weight Melting Point Boiling Point Latent Heat of Vaporization Vapor Pressure Specific Gravity Heat Capacity Viscosity Flash Point Ignition Temperature Limits of Inflammability Refractive Index 153 0.596 cal/g °C (Btu/1b °F) at 20°C 2.4 cp at 20°C 70°F 2.02% by vol. lower limit 1.3772 at 20°C See Figure 80 METHANOL 32.04 - 97.6°C 64.5°C 263 cal/g, 473 Btu/1b 10 mm at -13°C, 50 mm at 9OC, 92 mm at 20 C 0.7939 20/20°C, 6.61 1b/gal at 20°C 0.599_cal/g °C (Btu/lb °F) at 20 C 0.59 cp at 20°C 11°%, 52°F 470°, 878°F 6.72 to 36.50% by volume in air 1.3285 at 20°C (8) (8) (8) (3) (8) (19) (8) (8) (8) (8) (8) (8) (8) (3) (3) (3) (8) 15k UNCLASSIFIED DWG. 20365 FIgURE 80 155 Methanol -~ Propylenediamine Phase Diagram See Figure 81 (79) Vapor Liquid Composition See Figure 83 (85) Diagram ' Methanol - Water Phase Diagram See Figure 82 (19) J. MERCURY Atomic Weight 200.61 Melting Point - 38.9%, - 38.0°F (1) Boiling Point 357°c, 675°F - (1) Latent Heat of Fusion 2.8 cal/g, 562 cal/g atom, (1) 5.04 Btu/1b, 1010 Btu/lb atom Latent Heat of 69.7 cal/g, 1390 cal/g atom, (1) Vaporization 125.4 Btu/1b, 2500 Btu/lb atom P 1 = =3308 _ 0,81 1 Vapor Pressure oglOPmm og T (1) + 10.3735 Accuracy 2%, 400-800°K; 5%, 234-850"K See Figure 7 Density 13.546 g/ml at 20°C, 13.352 g/ml at 100°C (1) 845.68 1lbs/ft3, 113,04 lbs/gal at 68°F See Figures 9, 10, 51 Heat Capacity 0.0332 cal/g °C (Btu/lb °F) (1) at 20°C, 0.03279 cal/g ©°C at 100°C 156 UNCLASSIFIED DWG. 20366 FiIGURE 8] FIGURE 8> 157 UNCLASSIFIED DWG. 20367 158 Viscosity 1.55 centipoise at 20°C (1) See Figures 11, 52, 84 Thermal Conductivity 0.021 cal/sec cm °C at 20°C, (1) 5.08 Btu/hr ft OF at 68°F 0.026 cal/sec cm °C at 120°C, 6.3 Btu/ft O°F at 248°C Electrical Resistivity 98.4 A ohms at 50°C (1) Surface Tension 465 dynes/cm at ZOOC, (1) 454 dynes/cm at 112°C K. PROPYLENEDIAMINE Formula Weight 74,13 Melting Point -38.6°% (47) Boiling Point 120.5°C (86) Latent Heat of 130 cal/gm, 234 Btu/1b (8) Vaporization Vapor Pressure log. P = 7.6487 - 1671.2 86 10" mm T0C + 230 (%) Density See Figures 36, 85 (12) Heat Capacity 0.65 cal/g °C (Btu/1b °F) (87) O at 27°C Thermal Conductivity 0.125 Btu/hr °F ft from (45) 95-200°F Viscosity ' See Figure 33 (47) Flash Point 160°F (8) o Refractive Index 1.4492 at 20 C (8) 160 170 l-60 159 .50 UNCLASSIFIED DWG. 20368 140 1.20 1.20 FIGURE 84 @ L o b = o > - TK) 85 160 UNCLASSIFIED DWe., 20369 FIGURE" .90 0.8% .88 0.86 0.85 0.84 0.8% 0.82, 0.8} 161 Solubility of Salts Salt Solubility Temperature in PDA moles/liter sol'n °c LiCl 1.05 25 (47) LiBr 1.9 27 . (43) NaCl 0,005 25 (60) NaBr 2,4 27 (43) KC1 0.0001 27 (43) KBr 0.007 25 (59) KI 1.64 25 (59) LiOH 0.001 27 (43) Propylenediamine - Water Phase Diagrans See Figure 86 (79) Vapor-Liquid Composition See Figure 87 (78,79) Diagram L. TETRAHYDROFURAN Formula Weight 72.10 Melting Point ~108.52°C (-163.3°F) (88) Boiling Point 65-67°C (149-152.6°F) (88) Vapor Pressure mm Hg Temp. °c (88) 114 15 176 25 263 35 385 45 550 55 760 65 Density 0.888 g/ml at 20°C, 7.4 1bs/gal.(88) FIGURE && 162 UNCLASSIFIED DWG. 20371 SR AL e e e e o i A A 0ol i Sl 5 1 a5 b 5 SR ATRLHIASE 0 Bt A e e £ e b e e 163 UNCLASSIFIED DWG. 20370 FIGURE 87 . A . MoLE FrACTIiON WATER IN LIQUID Viscosity Surface Tension Flash Point Index of Refraction 164 2 0.66 0.55 0.47 0.42 o 26.4 dynes/cm at 25 C - 17%, 1°F 1.4073 at 20°cC Temp. 0 20 30 40 (88) (88) (88) (88) 10. 11. 12, 13. 14, 15, 16. 165 REFERENCES Lyon, R. N., et. al. "Liquid-Metals Handbook", U. S. Govt. Printing Office, Washington, D. C., 2nd ed., (1952). Hodgman, C. D., et. al. '"Handbook of Chemistry and Physics", Chemical Rubber Publishing Company, Cleveland, Ohio, 30th ed., (1947). Perry, John H., et. al. "Chemical Engineer's Hand- book", McGraw-Hill Book Co., Inc., New York, 3rd ed., (1950). Seidell, A. "Solubilities of Inorganic and Metal Organic Compounds'", D. Van Nostrand Co., Inc., New York, 3rd ed., (1940). Rossini, F. D., et. al. "Selected Values of Chemical Tehrmodynamic Properties:, Nat'l. Bur. Standards Circ. 500, U. S. Govt., Printing Office, Washington, D. C., (1950). Quill, L. L., et. al. "The Chemistry and Metallurgy of Miscellaneous Materials', McGraw-Hill Book Co., Inc., New York, (1950). Rossini, F. D., et. al. "Selected Values of Properties of Hydrocarbons", Nat'l. Bur. Standards Circ. 461, U. S. Govt. Printing Office, Washington, D. C., (1947). Works Laboratory Manual, "Physical Property Tables", Carbide and Carbon Chemical Corp., South Charleston, West Va., Vol. 40, (July 1, 1950). International Critical Tables, McGraw-Hill Book Co., Inc., New York, (1933). Lange, N. A. "Handbook of Chemistry'", Handbook Pub- lishers, Sandusky, Ohio, 8th ed., (1952). Palko, A. A. "Handbook on Ethylenediamine'", ORNL- 1329, Palko, A. A. '"Handbook on Propylenediamine', ORNL- 1391. Rutenberg, A. C. '"Notes on Some Selected Liquid Amalgams'", ORNL-1457. Smithells, C. T. '"Metal Reference Book", Inter-Science Pub., Inc., New York, (1949). Janecke, E. "Handbook aller Legierungen'", Heidelburg, (1949). Yost, D. M. and Russel, H., Jr. 'Systematic Inorganic Chemistry", Prentice-Hall, Inc., N. Y., (1944). 17. 18, 19. 20. 21. 22. 23. 24. 25, 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44, 45. 46 . 47 . 48. 49. 50. 51. 52. 53. 54. 166 Audrieth, L. F. and Kleinberg, J. "Non-Agqueous Solvents'", John Wiley and Somns, N. Y., (1953). Curme, G. O., et. al. "Glycols", Reinhold Pub. Corp., New York, (1952). Chu, Ju Chin, et. al. "Distillation Equilibrium Data", Reinhold Pub. Corp., New York, (1950). Ditchburn, R. W. and Gilmour, J. C. Rev. Modern Physics 13, 310, (1941). - T Boyd, C. M. ORNL CF 53-1-298. Grube, G. and Woff, W. Z. Electrochemic, 41, 675, (1935). - Eaton, G. A. ORNL-1299. Garretson, H. H. ORNL-1457, MacMullin, R. B. Chem. Eng. Prog. 46, 440, (1950). Convers, L. J. J. Chim. Physique 36, 175, (1939). Boohaviwalla, et. al. 1Ind. J. Physics 4, 147, (1929). Begun, G. M. and Rutenberg, A. C. ORNL-1401. Sklyarenko, S. I. and Sakharov, B. A. Zhur. Fiz. Khim. 21, 97, (1947). ‘—_ Ibid.” Zhur. Obshch. Khim. 17, 1385, (1947). Rutenberg, A. C. ORNL CF 53-2-174. Begun, G. M. ORNL CF 53-2-174. Dowling, E. J. and Hess, D. N. ORNL CF 53-1-328. Begun, G. M. ORNL CF 53-4-161. Drury, J. S. and Garretson, H. H. ORNL-1238. Drury, J. S. ORNL-1306. Ryon, A. D., Ramsey, J. W. and Weithaup, R. R. ORNL- 1306. Eaton, G. A. ORNL-1511. Begun, G. M. ORNL Y-B30-116. Begun, G. M. ORNL CF 53-5-164. Warren, K. S. ORNL CF 53-1-328. Palko, A. A. ORNL CF 53-5-164. Rutenberg, A. C. ORNL Y-B30-116. Begun, G. M. ORNL-1552. Lynch, L. D. ORNL CF 52-11-199. Rutenberg, A. C. ORNL-1306. LeRoy, R. H. ORNL-1388. Begun, G. M., Rutenberg, A. C. and Palko, A. A. ORNL- 1238. Johnston, C. P. ORNL Y-B30-116. Harley, P. H. ORNL Y-B35-9. Krohn, N. A. ORNL CF 52-11-199. Hill, W. E. ORNL Y-B30-124. Palko, A. A. ORNL Y-B30-124. Garretson, H. H. '"Notes on Activities and Standard Electrode Potentials', ORNL-1457. 55, 56, 57. 58. 590 61. 62 63. 64, 65. 66 . 67. 68. 69. 70. 71. 72. 73, 74, 75. 76. 77, 78. 79. 80. 81. 167 Rutenberg, A. C. ORNL Y-B30-118. Friend, Hale, Ryder, J. Chem. Soc. (Lond.)1937, 907. ' - Begun, G. M. and Rutenberg, A. C. ORNL CF 53-4-81. Yeatts, L. B. ORNL CF 53-2-174. Morrison, B. H. ORNL CF 53-2-61. McNees, R. A. ORNL CF 53-1-106. Morrison, B. H. ORNL CF 53-3-85. Friels, J. V. ORNL CF 52-11-199. Huckel, W. "Structural Chemistry of Inorganic Com- pounds'", (Trans. L. H. Long) Elserier Pub. Co., Inc., New York, (1950). Pickering. J. Chem. Soc. (Lond.) 63, 909, (1893). Compere, E. L. "ORNL Y-B30-124. Compere, E. L. ORNL CF 53-1-298. Compere, E. L. ORNL CF 53-2-174. Healy, R. M. ORNL Y-B30-124. Healy, R. M. ORNL Y-B30-118. Hill, W. E. ORNL CF 53-4-81. Hill, W. E. ORNL CF 53-4-161. Healy, R. M. ORNL CF 53-1-298. Healy, R. M. ORNL CF 53-4-81. Mellor, J. W. '"Comprehensive Treatise on Inorganic and Theoretical Chemistry", Longmans, Green and Co., New York, (1922-1937). Barringer, M. D. ORNL CF 53-2-61. Kobe and Leipper. Ind. and Eng. Chem. 32, 198, (1940). Hafem, S. Bull. Soc. Chim. France, 1949, 337, (1949). Lee, D. A. ORNL-1401. Lee, D. A. ORNL CF 53-5-164, Lee, D. A. ORNL Y-B30-124, Yogel, A. I. "Physical Properties and Chemical Con- stitution, Part IX, Aliphatic Hydrocarbons", J. Chem. Soc. 1946, 133, (1946). Lee, D. A. ORNL Y-B30-124. Lee, D. A. ORNL CF 53-4-161. Sax, N. I. "Handbook of Dangerous Chemicals', Reinhold Pub. Corp., New York, (1951). Lee, D. A. ORNL CF 53-2-174. Hill, W. E. ORNL Y-B30-116. Weeren, H. O. and Carter, W. L. ORNL CF 52-10-161. Sales Bulletin, E. I. Dupont deNemours and Co. Joseph, E. F. ORNL Y-B35-6. Joseph, E. F. ORNL Y-B35-7. Joseph, E, and Buchanan, J. R. ORNL Y-B35-9. Sachs, J. W., Decarlo, V. A. and Buchanan, ',—335-10, - Lo 93. 94. 95. 96 . 97. 98. 99. 100. 101. 102, 103. 104. 105. 106. 107. 108. 109. 110. 111. 112. 113. 114. 115. 116. Lynch, L. D ORNL-1511. Lynch, L. D. ORNL CF 53-5-123. Morrison, B. H. ORNL CF 53-5-123. Morrison, B. H. ORNL-1511. Yeatts, L. B. ORNL CF 53-4-81, Hill, W. E. ORNL CF 53-5-164. Hill, W. E. ORNL CF 53-6-208. Daley, F. L. and Sacks, J. W. ORNL Y-B35-6. Lynch, L. D. ORNL CF 53-4-210. Morrison, B. H. ORNL CF 53-4-210. Yeatts, L. B. ORNL CF 53-5-164. Johnston, C. P. ORNL CF 53-4-81. Dowling, E. J. and Warren, K. S. ORNL CF 53-4-285, Boyd, C. M. Anal. Div. ORNL CF 53-4-161. Clark, W. E. ORNL-1524. Fletcher, F. and Kilpatrick, M. J. Phys. Chem. 42, 113, (1938). Garretson, H. H. ORNL-1299. Lewis, G. N. and McDonald, R. T. '"The Separation of Lithium Isotopes", J. Am. Chem. Soc. 58, 2519-24, (1936). T T Begun, G. M. and Drury, J. S. A Review of Isotopic Separation to be Issued. Johnston, R. J. and Ubbelohde, A. R. 'Wedge Effect at Amalgam Electrolyte Surfaces', Proc. Roy. Soc. (London) A206, 275-86, (1951). T Bradley, N. C. ORNL Y-B35-6. Spevack, J. S. Columbia Univ. Report A-393. Eidenoff, M. L. '"Laboratory Studies for Separation Processes', National Nuclear Energy Series III-4D (1951). Demarcus, W, C. Y-12 Y-887.