ORNL-1592.txt

 
 
  
   

 

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

<l

8
g
2

m/1000 LiTeR
 

-

FIGURE |4

.
53 UNCLASSIFIED DWG. 20373

 
 

 

 

 

 

—

(b mommqn_\.d(._.us 30 SN SY) oy N 1 39 ALiavion

3.4 3.0 38

3.2
10°

X

30 |
Tebs)

.8

20

 
OLUBDILIT

15

10

JorupiLiTy OF ALkarl MeTaLs Aap JALTs IN
JELECTED JOLVENTYS

 

09
&
o
5
3 50
)
0]
b
J
o
LEGEND
ITEM JOLUTE JOWENT
| Li CL POA
2 L1 Co EDA
3 L1 Be EDA
4 Ls Hg
5 K Hg
6 MNaq Hg
7 Mg Hg
8 LiCL H20
9 L1 OH H20

2
o

UNITJ
MoLe/L At Tewmp.
MorLe/L AT TeEmp
MoLe/ L AT Temp
MoLe/ 1355049
More/ 13550g
MoLe /135509
MoLe/ 135509
MoLe/ |000g
More/ 1000g

°C

20

30

40

60

70
80

90
100
110
120

130
140

—32
4.0

rlllf
® -J e v
o O O o

= ©
o
oo

WV N -
o ©O ©

N — — G e wem s Sew
o &
g & 886§

~
~N
o

2

IfllllllIIlTT I Tt | "1 lIlIIIlllllllllllllllllllll]fl”llllllllll'IIIIIHITIHW[TTI

 

|m|mlluuluuluulullllllll||ll||l|llunlunIlulllmlulllulllnull|||| 1111 Itllll llulu uluuluu, 1l IJ il l|

g

280

Gs

COL0z *oMd
S

330914

9|
56

Lithium - Potassium

 

See phase diagram Figure 17

Lithium - Sodium

 

See phase diagram : Figure 18

Lithium-— Potassium - Mercury

 

Solubility Curve  See Figure 19 (38)

Lithium - Sodium - Mercury

 

Solubiiity Curve See Figure 20 (38)

Lithium - Mercury - Water

 

Reversible Electrode Li(Hg) | Li* (aq)
o _
E2980K = 2.079 volts (107)
Chemical Reaction Li(Hg) + Xs H,0—&
(LiOH)aq + Hg + 1/2 H,

AH = -33.5 k cal/g mole

O
298 K
AF, 3g% = -28.75 k cal/g

mole (107)

1/2 1/2
2(00/ - cf/ )

st

Rate of Reaction k = for weak

 

(29,30,
acids and water solution 108)

Appears to have following
dependence i?/LiOH figlution:
2

1 ks (Co'% - ct/'f(c

)
k* = = = 70 = ~f '{lgyy
2 T
ST UNCLASSIFIED DWG. 20304

 
% Hg (100%)

AR
JAVAVAVAVAVAVAVA “
JAVAVAVAVAVAVAVAVA _N_Q_E_
Li- K- He QIR M ls A
éfie:g%v#g:'x%v%z%x%‘ OLARITY |3 APPROXIMATELY
y
AVAVAYAVAVAVAYAVAYAVAVAVATA -
Jorusitity Curve RIS = ¥ x MoLe o/ AT <5 Mowar JoLUTIONS
° VAVAVAY, V‘VVé""'
Temperature 25% LR RRT L IRLTTN
: SRR
i
K MPERATURE 48°C 1.0 0008 AR 1.0
SN N S S N SN S PP AT T
Rer 28 R LR BTN
N /N
:‘ F' A'A'A'A'A'fi‘v eAvA'A "yA¢AvA‘ YY) l‘" ““ |4 I‘“"%"A
R S S AN DT
TR TN\ %v;wvn“nv‘vAvAv 7N/ vAvAvAv v‘

AN A'AVAVAV‘\VAVA QVA AOCEBSONN NN
AVAVAVAVAYAVAYAV.. .Y, 67 AT L A AN
A'.""AVAVAV“'AVAVAVA e' AVAYAYA' aYAVAVAVAVAYAVAVAVAVA

(NN NP VNN \VAV AVAZAVAVAYAY \VAVAVA”. YA VAVAVAVAY A
AVAVAVAVAVAVA‘A"'A"AVA FAVAVAVAVAVAVAVAYAV A VAVA A v ANAVAVAVAVAN,
OSSN SO VAVA"AVA'AVAVA\'\VAVAVA'AVAVAVAV VA
AVAVAVAVAVAVAVAVAVAVAVAV . . VAVAVAVAY, VA' VNN eVAVAVA' N/ VA‘I"
INOSINNINA NN RN PO w IS INIINISIN RN AN TSN
JAVAVAYAVAVAVAVAVAVAVAVAVAVAVAV AN | . VAV AVAY] vAvAv‘v \.«vx_v‘v N
OSSN YNVY #VAVQVAVAVAVAVA'AVAVQVA S AAATRBA N PN
AVAVAVA' AN N NN N NN ORI N P/ I AN ety v.VAVAV NN
/N A'AVA'A'AVAVAVAVAVAVAVAVLVAA WA, AVAVAVAVAVAVAVA VAVAVAY, VAA
2 D AVAVAVA'A'AVAVAVAVAVAVAVLVAVA'AVAVA AVAVAYAVA% \VAVAVAVAVA'AVAVAVAVA'AVAVNAV‘ IZ 0
- AVAVAVAVAVAVAVAVAVAY Y’ N NN ST IS N AR e‘AVA'.. AVAVAVAVAYA
AVA'A'AVQVAV AVAV VLVAVA AVA‘A'A'A'AVAV SNV VAVAVA \WAVAVAVAVAVAVAVAVAVAVA
AVAVAVAYAY AVAVAVAVAY e#v FAVAYAY VA'AVA NS \VAVAVAVAVAVAVAVAVAVAVAVAV /5NN
NN 'A'AV NN AAVA'A'AV FAVAVAVAYAVAVAVAY, ~AVAVAVAVAVAVAVAVAVAVAVAVAV,)
AYAVAVAVAVAVAVAVAVAVAVAY AVAVA'AVA AVAVAVAVAVAVAVAV A 'AVA"AVA‘ N SNINANAINTANANIN
AVATAVATATAVAVAVAVAVAVAVAVAVAVAVAVAVAVAY AVAVAI AVAVAVAVAVAVAVAVA ‘A o#YAYAVAVAVAVAVAVAVAVAVAY,
AVAVAVAVAVAVAVAYAN 9' VA'AVAVAVAV VAVAVAVAVAVAYAVAYAY AVAYAMVAVA'A\ ' AVAVAVAVAVAY AVAVAVAVAVAVA
NN 'A'A'A'AVA'AVA \VAVAVAVAVAVAVAVAVAYAVAVAVAVAY, NSO AR NANTNTININAINTIN NN
AVAVAVAVAY AVAVAVAVAVAYAVAVAVAYAVAVAVAVAY VA VAVAYA A'A'AVAVAVAVAVAVA' “AVAVAVAVAVAVAVAVAVAVAVAV,
OO AN SN NSNS SRS SAAAAAA LA
AVAVAVAVAY AVAVAVAVAYA' "Y VAVQVA'A'A"AVAV \VAVAVAVAY 4 "AYAVATAVAVAVAVAVAVAVAVAY, VAVAVAVAVAVAV AWAVAPAVAY 2
AVAVAVAVAVAVAVAVAVAY, fA TAYAVAY AVA'A'AVAVAVAVAVAVAVflevé e' 'AVAVAVAVAV‘VAVAVAV M AN nv‘uv‘m.uv
AVAVAVAYA \WAVAVAVAY AVAVAVAVAY A QVAVAVAVAVAVA'AVA'AV NN NINANTNTN G N GOSN BTSN AN,
AVAVAYAVAVAVAVAVAVAVAVAVAVAVAVAVAN NN 'AVAVAV NN NN ‘VA‘Afla FAVAVAVAVAVAVAVA
AVAVAVAVAVAVAVAVAVAT AVAVAVAVAVAVAVAY AVA'AVAVAVAVAVAVAVWA TAVAVAVAVAVAV AN AVAVAVAVAVAVAV . %) S AVAVAVAVAV AVAVAVAV
AVAVAVATAVAVAVAVAVAV AVAVAYATAYA 'A'AVAVA'A'AVAVAVAV N m" ' WV ‘QVAVAVAVAVAVAVAVAVAVAVAVA (SN NI NINININT TSN
AVAVA'A'A' NN SN SINNYS VQ'AVA A'AVQ'AVAVAVA' N A A'A"AVAVAVA'AVA'%VAVA'A\ AVAVAVAYAVAVAVAVAVAVA
A'EAVAVAVAVA'AVAVQVA'L #VAVAVQ e VAVAVA'AngVAVAVAVflAVAVAVAVAVAVAVAVAVA RSN NI NN NNV
AVAVAVAVAVA“VAVA NSNSV NIV NNV AAVA‘A'AVA VAVG ANSEASATAAAR vguv. %‘ NI
5 O AVAVAVAVAV AV AVAVAVAVAVAYAVAVAVAVAYAVAVA  AVAVAVAVAV AVAVAVA FAVAVAYA AAVAVAV‘,.‘VAYNAV A
AVAVAVAVAVAVAY VA'AVA' NN S SIS PRI SINTSTUINR7RT TN VA YN 'A'A'A'A".‘VAV \WAVAVAVAVAY VA A""'AVA'L'A'A'A'A'
NNV VAVAVAVA' VAYAYAVAVAVAYAYAVAVAY, QVAVAVA VAVA NN SR VAVAVAVA &AVA ‘# "’e WAVAVGV NN
AVAVAVA‘AVAVAVA e' VA A"L 3 A'A'A'AV VAVQ NN 'AVAVAV VAV A -‘I"A'AVAV%V FAVAVAVAVAVAVAY AVaVa \ \VAVAVAVAVZ.. 'AVAVAVA
AVAVAVAVAVAVAVAVA' A AA‘A’ AVA S AVA"AV AV VAV AVAVAVAVA FAVAVAVAVA V 7y AVAV NN
#X#X‘I‘I%'% A TN vAuvAv‘v‘v‘v v 7 'm W #fi'w NP7 vv¢'¢ ¢ HoOO0L #““ ‘ 7 #fi #‘% v, """"""“'%A
/N A /N
ARV %w egynm.vyawn PaTaTe uv Av.uuvfigefifi 5 i’ %Vé ST
NN V‘VAVAVAVAVAVA'A N e‘ ATATAVAYA AV¢ AVAVAVAV
NSNS AVAVA' VA"AVA AVA'A'A'A PAVAYAVAYAY VA AV VAA AV A' A'AVAVAVAVA' "
exevvv‘;;#"‘x%xgfie . 'zgvg '%v S %'A"AVAV OIS V\"A'AVA A\'\VAVAVA"‘A"VA A A AVA AVA # Axe g¢V¢'AVAVAVAVA Aveve:%';‘
AVAVAVAYAVAN JAVA
AVAVAVAVAVAVAVAVA 9’&#‘ VN VA'A'AA'AV 'AVAVA'AQA"AV'QAV QAVAA A'A"# % %%? V FAYAVAVAVAVAVAYAVA
AVAVAVAVAVAVAN QYAVAVAV NN A g VAV A% % AV \ VAVAV AVAVAVAVA
AVA GVAVAVQ AVAV#' A VeAA TAVAVAVAVAYAVAVAV
A AVAVAVA'AVA A A

NN NN
AVAVAYA'AVAVAVA AVAVAVAVAYAVAVAVAVIA'AVAYA AVA'AVAV AVAVAVAVA A’
3“"""" T, 7N s N #%““‘v %Zv %3'# v v v Y 7NN v v 7 vv
QR uv ‘:gfiwfiafin“ '9 PPN ‘ #'#"' y’&fififinp&v“ ‘z“ v, i;v%mw %’ FHERITLIN
AVAVAVAVAVAve NN a#VAVA 'AVAVAVA" 'A'AVAV ¢'¢ AVAVA VAVAV AVAVAVAVAVAVAYA'A
AVAVAVAVAY AVAN A'A"e AVA AYAV \/ ' 'AVAVAV 'AV¢VAVA AW V AVA A"A VA NN AVAVA INOINOININININININN
4 O AVAVAVAVAVAVAVAVAY VA’ A‘ AVAA A
- AVAVAVAVAVAY AVAVAVA'AVAV uu V’ 7% v v‘v‘v
Q" VAVA' AVA "e

85

NN NN SN

:
E
{ >
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! xޣ 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.