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ORNL-3391
CHEMISTRY DIVISION
M. A. Bredig
4
i
u
a-
iii
CONTENTS
i
Page
Abstract..........................................................
Introduction......................................................
......................... 4
Phase Diagrams. .........................................
4
Physical Properties..................................... 13
Alkaline-Earth-Metal-Halide Systems.. ........................ 23
Phase Diagrams. ......................................... 23
Electrical Conductance..................................
29
Rare-Earth-Metal-Trihalide Systems. .......................... 30
Phase Diagrams.... ...................................... 32
Electrical Conductivity.. ............................... 37
Alkali-Metal-Alkali-Halide Systems..
'
41
Transition Metals............................................
43
Posttransition Metals........................................
44
S~aly.
References...................................................
52
..................................................... 51
M. A. Bredig
i! - -+
!
!
1
! l i
1
INTRODUCTION
F'
sol-
seems t o be inclined,
S a l t s contain-
ing anions such as n i t r a t e s , sulfates, o r phosphates are l i k e l y t o decompose i n reactions with the m e t a l .
L i t t l e of a precise nature i s as
Facts w i l l be
with
recent statements,8 no evidence whatsoever seems t o e x i s t f o r t h e occurrence of t h e colloidal state of metals i n fused salts (with t h e exception
mobile electrons.
similar solvents, but are distinguished from these largely by the ionic
nature of the solvent (the salt), which, it i s t o be especially noted,
usually contains one of the constituents of t h e metal which it dissolves,
namely the cation.
, those
having positive
2.
(b)
The d i s t i n c t i o n i s between
i
1
There are l i k e l y
t o be intermediate cases not c l e a r l y defined, and t h e attachment of electrons (or "subhalide" formation) may o r may not be a matter of degree
only, rather than a matter of a s t a t i s t i c a l equilibrium between two
d i s t i n c t l y different s t a t e s of t h e electron, attached and unattached.
Also, t h i s may vary with temperature and composition.
The variety i n t h e
6)
4
"mmC'' METAL SOLUTIONS
1I
review has been published by Ukshe and Bukuneg Many of t h e earlier re-
i n any detail with these older data, many of which were r e l a t i v e l y inaccurate, or were given erroneous interpretations.
We s h a l l confine our-
Alkali-Metal-Alkali- H a l i de Systems
Phase Diagrams
A study of alkaline-earth-metaldkaline-earth-halide systems under-
seem t o have
Indeed, t h e
L,
le
UNCLASSIFIED
ORNL-LR-WG. 2 t 8 9 4 A
4 200
t MOLE FRACTION MX
UNCLASSIFIED
ORNL-LA-DWG. 38872
'
t MOLE FRACTION MX
.9 .8 .7 .6 .5 .4 . 3 .2
.4
1200
' 0
900
TWO LIQUIDS
900
900
800
800
050
600
4400
10
20
30
40
50 60
mole % K
70
80
Ml
700
90
-006
MOLE %SODIUM M E T A L
64, 64 (1960)l.
\
ONE L I Q U I D
(026'
.I .2 .3 .4 .5 .6 .7 .8 .9
MOLE FRACTION OF METAL+
700
600
ONE L i a u i ~
4400
656'
N
.I .h .:.k .k ;.
METAL
SOLI~SALT+LIOUID
;.
.b .A
6oo
65 (1960) (reprinted
Ln
UNCLASSIFIED
ORNL-LR-DW. 34067A
UNCLASSIFIED
ORNL-lLR-OWG.370
UNCLASSIFIED
ORNL-LR-DWG. 32909A
800
MOLE % M E T A L
MOLE
METAL
Fig. 5.
Cesium Metal-Cesium
Halide Systems [adapted from M. A.
Bredig, H. R. Bronstein, and W. T.
Smith, Jr., J. Am. Chem. SOC. 77,
1454 ( 1955)l.
Table 1
satMetal
system
MX-M
(m)
LiF
LiCl
LiBr
LiI
NaF
NaCl
NaBr
NaI
KF
KC1
KBr
KI
RbF
RbCl
RbBr
RbI
CsF
CSCl
CsBr
CSI
Salt
(?):
Tap
(OK)
Salt-Rich
Solid
1121
883
823
742
1268
1073
1020
933
ll31
1043
1007
954
1068
995
965
920
976
918
909
899
Consolute
n20
882b
Liquid
lb
0.5b
MetalRich
Liquid
Temp
(OK)
Comp
(mole $ M)
Eutectic
Compa
(mole m)
1603
40
83
97.7
96.6
98.6
1453
l353
1299
l306
28
50
52
59
10-9
1122
1024
981
931
51.7
75 .o
69.2
82.5
40b
57
20
39
44
50
3 x 10-4
10-9
10-9
10-9
73
1177
1063
1001
990
1063
979
globre
907
1046
969
21b
37
ub,e
51
lb
3b
0.15
0.15
0.04C
0 .03c
2.1
2.9
1.6
4.9
10.5
19.o
13.5
9b
888
18
d
22
d
d
d
d
d
d
d
d
d
d
d
d
d,a
d,a
d,a
d,a
d,a
d,a
%stimate by extrapolation.
bEstimated.
C
By extrapolation from ref 13.
%o miscibility gap.
e
Unstable.
(E)
452
452
452
452
822b
741b
1263
1068
103.3
930
Metal
10-3
10-8
10-7
10-7
370
370
370
370
337
337
337
337
312
312
312
312
302
302
302
302
8
special i n t e r e s t i s t h a t near the melting points of t h e salts and above.
The melting points of the a l k a l i metals are very much lower than those
of t h e i r salts and are not f a r above room temperature.
The s o l u b i l i t y
loo7,
as estimated by extrapol&
between two l i q u i d s and one s o l i d of a composition not intermediate between those of t h e two liquids.
I n t h e alkali-metal sys-
m e t a l s t h e potassium systems (Fig. 1) exhibit t h e highest degree of miscib i l i t y of the salt with t h e m e t a l i n t h e l i q u i d state.
i n t h e l i q u i d phase.
T h i s consolute tem-
1180C i n the sodium systems, and ranges from 717 t o 904C i n t h e potassium systems (Table 1). The temperature range i n which two l i q u i d s
coexist i s about 530C i n t h e l i t h i u m fluoride system, about 200 t o
sys-
the
The l i q u i -
dus curve, depicting t h e temperatures f o r t h e s o l i d i f i c a t i o n of t h e cesium halide from t h e l i q u i d mixture, descends without discontinuity
(except t h a t t h e r e ought t o be a slight kink a t t h e transformation temperature of CsC1) from the melting point of the pure salt t o t h e eutectic
point, which i s almost i d e n t i c a l i n melting temperature (30C)and compos i t i o n with t h e pure metal.*
j :
It i s i n t e r e s t i n g
1026C f o r Na(F, C1, B r ) ; 904, 790, and 728C f o r K(F, Cl, B r ) ; and 790,
706, and < 655C f o r Rb(F, C1, B r ) respectively] is, i n t h e iodide systems
*Delimarskii and Markov ( r e f 18), i n Table 29, page 211, "Solubility
of Metals i n Fused Salts," misstate t h e case of t h e cesium systems, by
erroneously taking t h e metal concentration of t h e solution i n equilibrium
with s o l i d salt f o r a metal concentration of a s a l t - r i c h phase i n equilibrium with l i q u i d cesium metal. Many other metal s o l u b i l i t i e s i n t h i s
t a b l e a r e much outdated and quite i n error.
10
UNCLASSIFIED
ORNL-LR-WIG. 6707
'200
'
'
'
'
L,OC
900
800
700
600
Rb
8
R
'
42
'
- (cm3 mole-')
46
'
UNCLASSIFIED
ORNL- LR-DWG. 701
5000
d
4000
c
0
3000
s
c
k 2000
4000
t
0.1
4;
Fig. 8. Excess Free Energy of Mixing as Function
of Volume Fraction of Metal.
11
and Rb(I):634'],
o r consider-
interest.
tions (28, 47, and 65 mole $ cesium metal f o r CsF, CsC1, and C s I solution
with cesium respectively).
where
and
metal
The temperature dependence of t h e s o l u b i l i t y of the s o l i d salts i n
t h e l i q u i d m e t a l s i s another feature of i n t e r e s t .
No explanation of these phenomena which i s f r e e of a r b i t r a r y assumpt i o n s has been proposed, although r a t h e r i n t e r e s t i n g speculations1'* 2o
lead t o a crude but i n s t r u c t i v e picture of the solution behavior of these
systems.
Pitzer21 suggests t h a t the excess f r e e energy of mixing i s associated
with the conversion of t h e metallic s t a t e of binding of the metal elec-
He obtains
+*
M(gas)
-+
M(gas)
in
d i l u t e solution)
The i n f l u -
In p given i n Table 2, where p i s the p a r t i a l pressure of the metal monomer i n t h e vapor i n atmospheres.
process, the influence of the vaporization s t e p would tend toward an increasing r e l a t i v e s o l u b i l i t y of metal i n salts i n the order of increasing
vapor pressure, L i
%,
Table 2.
RT ~n
p monomer)
(kcal mole)
( a t looo'~)
-13.8
Li
Metal bp
Range of Values of Tc
(OK)
(OK)
1604
1603
Na
-3.6
ll63
1303-1453
4.8
1039
981-ll77
Rb
43.3
974
907-1063
cs
43.6
958
(<850 t o 4 5 0 "submerged")
&,
This is, of
course, only suggestive, and much more data and a more complete quantitat i v e analysis are necessary f o r any d e f i n i t e conclusions.
Physical Properties
Optical Observations.
findings
M 0 l l w 0 ~measured
~
t h e v i s i b l e and near-infrared absorp-
14
alkali-metal vapor.
three sodium salts studied (NaCl, NaBr, and N a I ) and a t 980 m + ~f o r the
energy, of a r i g i d crystal. l a t t i c e .
I n a very f e w r a t h e r crude experiments,
ELectrical Properties.
M 0 l l w 0 ~found
~
no directional transport of the colored cloud from a
nondissociated) m e t a l atoms.26
firmed by l a t e r observations.
measured t h e conductance of a l k a l i - m e t a l -
mixtures.
28
system.
I n t h e sodium sys-
ohm-
15
a t 42 mole
76
equivalent conductance
UNCLASSIFIE0
ORNL-LR-DWG. 23048A
6P
'845'
2l
Na-NaBr
20
NO NoCl
2I
4l
~6
l 8~
0l
,2 l
4,
l 6,
8l
, 4l
0
,
Fig. 9.
Specific Conductivity of Alkali Metal
Solutions in Alkali Halides [H. R. Bronstein and M.
A. Bredig, 1. Am. Chem. SOC. 80, 2080 (1958) (reprinted by permission of the copyright owner, the
American Chemical Society)].
16
UNCLASSIFIED
ORNL-LR- DWG.54649
J
Specific Conductivity of Solutions of
Fig. 10.
Sodium Metal in Sodium iodide [H. R. Bronsteiii and
M. A. Bredig, J . P h y s . Chem. 65, 1221 (1961) (reprinted by permission of the copyright owner, the
American Chemical Society)].
I
2
I
I
I
I
I
4
6
S i 0 4 2
MOLE PER CENT SODIUM METAL
UNCLASSIFIED
ORNL-LR-DWG. 54650
48 -
46
42-
a
2
I
4
I
8
I
0
Ir'
where Asoh
and
The term
% repre-
sents t h e change of t h e conductance caused by t h e addition of one equival e n t of m e t a l t o an mount of salt contained i n t h e solution of t h e given
composition which i s between two electrode plates 1 cm apart.
Figures 1 2 and 13 show, i n a more s t r i k i n g form than Figs. 9, 10, and
%,
of t h e observed conductivity.
How-
K2
iw
i
18
UNCLASSIFIED
ORNL-LR-OWG
23047A
40-
c)
1
0
T
CT
No in NH3
at -335'
6
0
40
METAL (mole %)
42
44
4(i.e.,
n, extrapo-
vs m e t a l con-
centration.
Two d e f i n i t e trends may be seen i n these data: F i r s t , the contribut i o n t o the conductivity by t h e metal solute increases greatly i n going
from t h e fluoride t o the iodide systems, t h a t is, with atomic number, or
size, of t h e halide ion. Second, it decreases i n going from sodium t o
potassium (i.e.,
t o the increase
f e c t i n aqueous solution shows a very high power dependence on the polariz a b i l i t y of T (the bimolecular rate constant f o r electron exchange between [Cr(NH3)5Xl2+ and C r 2 + changes from 2.7 x lr4t o 5.1 x 1r2t o 0.32
t o 5.5 f o r X = F, C1, Br, and I respectively), i n t h e metal-salt m e l t s
I
on p o l a r i z a b i l i t y of X i s of a lower power.
This i s remi-
small
W
_i_
not nearly accurate enough for t h i s purpose, except t o show t h a t the temperature dependence a t i n f i n i t e dilution i s very s m a l l .
A t higher metal
20
Crystal Radius
of cation (A)
e1
Na
0.95
6000
1.33
Br
2800
6,000
8,100
(820O C )
(870OC)
800
Molar r e f r a c t i o n
of gaseous
anion
(cm3 moleo1)
2.5
Cube of c r y s t a l
radius (A3)
2.52
5 094
....
1 207
7.43
%stimated.
4
5
6
REDUCED TEMPERATURE,
r/e
(1934)l.
19
9 095
21
concentrations t h e temperature coefficient (positive) of the m e t a l solute
conductivity appears t o depend both on metal concentration and temperature
(cf. Fig. 13). T h i s might be attributed27*2 8 t o the equilibrium between
associated species such as Na2 and
K2
and electrons, 2 e
2e'
F=
K2.
At
a t i n f i n i t e dilution,
4,
I n t h e c r y s t a l s t h e rela-
t h e character-
Here,
the l a r g e differences i n t h e electron mobility f o r different halide cryst a l s of the same a l k a l i metal are wiped out by the use of a reduced tem-
ample, t h e melting point of the s a l t obviously (cf. Fig. 13) does not
exist for
&,
and t h e electron mobility a r e as high as they are i n the m e l t , t h e remaining individual differences i n
4 may be
T h i s does
,1 - w
'
t r a t i o n range f o r several potassimpotassium-halide systems and demons t r a t e s the l a r g e deviation from additive behavior.
Bronstein, Dworkin,
22
!
,7,
UNCLASSIFIED
pRNL;LR-DyG.5726:
KI the r e s i s t i v i t y of potassium
23
f r a c t i o n of potassium of 0.95,
990,000 = 370,000/49,500
t h a t is, (990,000
or 7.5 times f a s t e r .
- 620,000)/0.05
It i s not unexpected t h a t
Alkaline-Earth-Metal-Halide
Systems
Phase Diagrams
The older l i t e r a t u r e 1 t 3 contains a r a t h e r bewildering variety of
claims f o r t h e existence of extensive s o l u b i l i t y of alkaline-earth metals
i n t h e i r molten halides and the existence of subhalides of t h e formula
MX o r M2X2 (similar t o Hg2X2).
Considerable s o l u b i l i t y of t h e metals i n t h e i r
salts and some s o l u b i l i t y of the salts i n the l i q u i d metal were found, but
no indication of s o l i d reaction products, subhalides (MX).
A more recent
suggestion37*38 of a layer-type crystal. structure f o r a preparation pres u e d t o be "CaC1" turned out soon thereafter39 t o be erroneous; the crys-
24
1
I
I
I
I:
700 -
"
0 0
+ L,'
a+#
Y,
(I
40
20
30
40
50
60
70
80
90
f00
BaClp
Fig. 16.
Hinkebein,
Ea
(J. A.
Ph.D. Thesis,
The difference
i s due t o faults of t h e e a r l i e r technique i n determining t h e temperatureconcentration area of the coexistence of two l i q u i d s by analysis of
quenched m e l t s .
To avoid
these errors it i s necessary t o r e s o r t t o e n t i r e l y different techniques
such as thermal o r d i f f e r e n t i a l thermal analysis, t h a t is, t h e taking of
cooling curves, as SchEfer and Niklas did, o r t o a process of separating
on diff'usion of t h e metal i n t o t h e salt contained i n a separate compartment of a capsule,44 i s subject t o some doubt, as t h e wetting characteri s t i c s of the salt and m e t a l and t h e creeping of l i q u i d m e t a l along t h e
25
a t 80O'C.
5.5; Ba-BaC12,
Mg-MgCl2,
< 0.5;
Ca-CaCl2,
2.7;
Sr-SrCl2,
20 mole $.
i n t h e other three calcium-halide systems a r e very similar, y e t t h e temperature range of only p a r t i a l m i s c i b i l i t y i n these systems covers 500'.
This, of course, i s caused by t h e r e l a t i v e l y much lower melting points
of C a C l 2 , C a r 2 , and Ca12 (772, 742, and 78OoC respectively), as compared
F
From
Cao o r Ca
Ca2+
Caz2+, both
where N2 i s the
Raoul-GVan't Hoff formula &I2 = (Tm T) = (RT2/%)*m2,
mole f r a c t i o n of calcium metal. I n both cases, s o l i d solution was assumed not t o occur, and it was concluded t h a t t h e reaction Ca
2Ca+ did not take place.
%in
+ Ca2+ +
the formula
saltMetal
System
Salt
mp
MX2-M
(OK)
(m21
Temp
Salt-Rich
(OK)
Solid
Liquid
987
-987
0.2
C@2
1691
1563
25.5
CaC12
1045
1093
Ca33r2
1015
CaI2
MgCl2
Eutectic
(OK)
-923
Comp
(mole 46 M)
Consolute
Temp
(OK)
Metal
Comp
(mole M)
-100
923
67
1094
98.6
1595 k 5
45
U O
2.70
99.5
1033
2 .o
1610 k 5
62
lll0
1100
2 .3b
99.6
1000
3.0 ?
1610 k 5
64
U O
1053
1104
3 .8b
99.7
1033
2.0 ?
1650 k 5
74
lll0
SrC12
U.45
lll2
5 05
1044
BaC12
1235
1163
15.O
95
50
1002
985
-99
1290
a
Considerable metal s o l u b i l i t y i n ( f l u o r i t e type o f ) s o l i d i s l i k e l y .
bSee r e f 46.
C
Considerable metal s o l u b i l i t y i n high-temperature c r y s t a l form of BaCl2 ( f l u o r i t e type ?) is
likely
iu
UNCLASSIFIED
ORNL-LR-DWG. 70746
I
I
k!
Fig.
(P. S.
son, p
((00
DIFFERENTIAL
SOLUBILITY
50
COMPOSITION ( mole % Ca 1
4 00
- N2 (Solid)]
would leave t h e p o s s i b i l i t y open f o r a cryoscopic n l a r g e r than 1,
possibly 2, a t low m e t a l concentration.
T h i s cryoscopic n = 2 would be
c r y s t a l s t r u c t u r e being quite different, with s i x f o l d r a t h e r than eightf o l d coordination of anions around cations. I n both cases the reaction
would then seem t o be Ca
I
U
?i
Ca2+
2e-,
28
plausible, additional. dissolution mechanism, Ca + Ca2+ -+ 2Ca+, not excluded at this stage, and with increasing formation of (Ca2)2+ at higher
metal concentration.
essen-
tially confirmed the low value, which actually gives fair agreement in the
rather low entropies of fusion of CaF2 and SrCl2 (4.2 and 3.4 e.u.) of
similar, fluorite-type crystal structure. Mollwo found the solubility of
strontium in solid SrC12 to be high, similar to that of calcium in CaF2.49
Tm
-T -m
43
= ll00"C
- N2(C) i l l 2 0.04
N
N
N2(J)
Lsm m
n=x-RT
LJI2
4xlloo
2 1.8 N" 2
2 X 1233
(observed e~perimentally~l)
Again, a solution mechanism corresponding either to Ba + Ba2+ + 2eand/or (less likely) Ba + Ba2+ + 2Ba+ seems indicated by these experiOn the basis of activity measurements carried out by equilibration of MgC12 with MgAl alloys of known activity, Rogers, Todinson,
and Richardson45 suggest for Mg-MgC12 the solution mechanism Mg + Mg2+ +
men-bal data.
( M ~ z ) ~ + . The precision attained does not exclude the alternate mechanisms Me; + Mg2+ +,'e2
or Mg + Mg2+
2Mg+, and the data appear to fit
or 2Mg+ e
(Mg2)2f,
2Mg2+
29
E l e c t r i c a l Conductance
Dworkin, Bronstein, and Bredig50,5253 found it impossible t o apply
the method used f o r measuring conductivity i n t h e alkali-metal systems t o
t h e alkaline-earth systems.
With pure
How-
ever, the addition of even small amounts of metal, acting as a depolarizer, removed t h e frequency dependence.
Only results f o r solutions of calcium and strontium i n t h e i r dihal i d e s , excepting t h e fluoride, have been reported thus far.46*50 It was
concluded, as far as the limited data permit, t h a t calcium behaves somew h a t l i k e sodium i n t h a t the rate of increase i n s p e c i f i c conductivity
,
:
The
decreasing equivalent conductance of the calcium-metal solute was a t t r i buted t o t h e formation, not of diatomic molecules, C a 2 , as with sodium,
but of hypothetical molecule ions, (Ca2)2+, i n which t h e t r a p f o r electrons i s t h e single two-electron bond similar t o that i n Na2, or i n Cd2*+
and Hg22+.
30
UNCLASSIFIED
ORNL- LR- DWG.70122
Fig. 18. Specific Conductivity of Alkaline-Earth Metal Solutions in AlkalineEarth Halides (partially unpublished data).
4 .O
I
I
2
MOLE PER CENT METAL
I
3
Table 5.
1131
1061
1052
11.5
(ll.8)(e)
470
2.4
9.0
1099
None
None
None
None
1 2.o
1273
1193
375
(2.4)
14.5
1001
None
None
None
None
15.5
ll73
ll93
(12.0)
490
(2.8)
8.2
1007
10231
None
None
1103c
33
ll.73
1193
1090
11.7
4.80
2.6
9.0
1050
None
None
None
None
1173
1068
1005
(U.8)
12.o
345
12 .o
960
None
None
None
None
14
1173
1068
460
(2.0)
2.7
8.8
988
1004i
None
.None
10811
32
1173
1068
1059
ll.4
565
3 .O
17.0
919
None
9321
None
None
1208
(12.0)
545
3.4
16 .O
852
8741
None
None
None
19
18
1073
966
1023
1208
loll
12.6
500
3.1
11.9
939
946c
None
None
10311
29
1073
1208
1032
ll.6
590
3.3
14.0
9W
None
9533.
9751
11141
31
1173
1297
955
(12.0)
1060
9.2
740
3.2
26.5
764
None
None
None
835C
37
1073
1297
1204
(12 ?)
555
(2.8 ?)
14.0
1098
None
None
None
11041
14
ll73
1585
1270
(10 ? )
390
(1.5 ? ? )
12.0
1221
None
None
None
None
15
1423
1782
1034
1297
March 1963.
('In
i3
= (dT,/dNM)o
(d)see r e f
(Sm/RTm).
U.
etal.
ll87
ll73
1064
1180
32
and posttransition elements, where metal-salt m i s c i b i l i t y i n general becomes more limited, where e l e c t r i c a l conductivity of t h e solutions gives
no indication of metallic character, and where s o l i d "subhalides" do
occur.
Phase Diagram
An e a r l y phase diagram by C u b i ~ c i o t t iof
~ ~t h e system Ce-CeCl3 in-
dicating a s o l u b i l i t y i n
cec13 as
l a t e r 5 6 found t o be i n error:
high as 33 mole
A s o l u b i l i t y value of 9 mole
46
cerium,
w a s obtained by Mellors
and S e n d e r ~ f f ,and
~ ~ confirmed by measurements of Bronstein, Dworkin, and
B ~ - e d i ga~t ~855'.
No intermediate s o l i d
~ e ~ -,
1 3~ C ~ Co rI 2 ~ +
e Me~13
according t o 2Ce
= I
3 ~ e ( ~ e ~ l unless
4),
no o r few ( ~ e ~ 1 4 ) -
ions a l s o w o u l d
4d
L
II -
33
I
UNCLASSIFIED
O R N L - LR-DWG. 70745
400
- 90
0
W
K
3
I-
3 801
0
O
701
THERMAL ANALYSIS
SALT- PHASE SAMPLED
QUENCHED
IO
20
30
s
I
40
50
60
MOLE PER CENT L a
70
80
90
(00
Ce
2Ce3+
ce3+
3e-.
phase diagrams
such as NdC12.3
7
, NdC12,2 7 , P r I 2 . 5 ,
(Figs. 20-23)
Some of
Significantly,
t h e s o l i d diiodides of lanthanum, cerium, and praseodymium a r e charact e r i z e d by melting points higher than those of t h e t r i i o d i d e s (Figs. 22
and 23) and, above all, by high metal-like e l e c t r i c a l conductivity
(>1
x
lo3 ohm-
cm-),
34
UNCLASSI FIE0
ORNL-LA-DWG. 56015
g
w
*
UNCLASSIFIED
ORNL- LR-DWG. 56816
MOLE%Nd IN NdIs
G.
-..
I
UNCLASSIFIED
ORNL-LR-DW$. 70759
IQ
880 + T H E R M A L ANALYSIS
860 -
0
X
::Tr
EQUILIBRATION
LITERATURE
840 -
l!
*+-+-'
820-
+-
w 800(r
760-
I =
740 720 -
7000
d,
tk
4;
La13
Lb
L aI
2.00
L0I2.q2
214
'28
22' 26
"'916
(00
La
UNCLASSIFIED
ORNL- L R - DWG. 70758
820
+
0
780
I /
T H E R M A L ANALYSIS
EQUILIBRATION
LITERATURE
++
36
40
'4
640
I
4
0
PrI,
Fig.
System
u
2
I
8
I
42
I
16
I
20
I
24
I
28
I
32
"
700
Pr
23.
Praseodymium Metal -Praseodymium Triiodide
D. Corbett et al., Discussions Faraday Soc. 32, 81
EJ.
36
s a l t l i k e , nonconducting, and m e l t s 225' below N d I 3 (Fig. 21).
The prop-
This inter-
emu/mole, in-
t h a t is,
20 i n PrC13,61*64
and 9 i n CeC13.53*56
per mole
MX3, corre-
sponding, with an estimated heat of fusion of 10 kcal/mole, t o a cryoscopic n, t h a t is, number of p a r t i c l e s per t r i i o d i d e molecule dissolved,
of only 0.2.
per
--$
M3+
The increase i n t h e s t a b i l i t y of the M2+ rare-earth ion with increasing atomic number leads t o a sharp maximum with Eu2+, which contains
seven 4f electrons, t h a t is, half of t h e full 4f shell, and i s more
s t a b l e than Eu3+ even i n aqueous systems.
T h i s s t a b i l i t y , which i s very
37
E l e c t r i c a l Conductivity
The f i r s t measurements of the e l e c t r i c a l conductance of solutions
of cerium i n cerium trichloride, by Mellors and S e n d e r ~ f f ,indicating
~~
a rapid r i s e i n conductivity up t o 0.65 mole
$J
In
t h e neodymium system t h i s r a t i o amounts t o only 1.7, and i n the praseoA similar relationship holds
UNCLASSIFIED
ORNL- LR -DWG. 70425
-E
E
r
>-
k
2
(0
45
20
25
MOLE PER CENT METAL
30
38
estimates of the equivalent volumes on t h e basis of t h e density measurements of Mellors and Senderoff i n t h e CeCls-Ce system.58
The results
Where
e M3+ + e' t o
be far t o t h e right.
UNCLASSIFIED
ORNL-LR-DWG.70123
I
10
I
I
I
Fig. 25.
Specific Conductivity in Rare
Earth Metal-Rare Earth Metal Iodide Systems
[R. A. Sallach et al., 1. Phys. Chern., in press
(1963) (reprinted by permission of the copyright
owner, the American Chemical Society)].
a
-.-
15
20
25
MOLE PER CENT METAL
(0
30
35
39
bs
Bredig
e t a1.67 i n t e r p r e t t h i s maximum i n terms of an electron exchange between
but,
68
Now, according t o
It equals the
ze',
and t h e reciprocal of
, $*NM
= Asoh
e r a l chloride systems.
f o r sev-
Mzs
ze-,
40
UNCLASSIFIED
ORNL-LR-DWG. 6 6 9 3 0
6
Fig. 26. Electronic Conductance in Some Metal-Metal
Chloride Systems. Left: Eq uivalent Conductance of Metal
vs Mole Fraction of Metal. Right: Electronic Contribution
to Equivalent Conductance of Solution vs Product of Electron and Cation Concentrations [M. A. Brkdig, J. Chem.
Phys. 37, 914 (1962) (reprinted by permission of the copyright owner, the American Institute of Physics)].
UNCLASSIFIED
ORNL-LR-DWG. 66931
6-
a04
0.08
0.42
0.46
V I
0.04
I
0.02
I
a03
a04
Fig. 27.
Electronic Conductance i n Ce, La, and K
Metal-Metal Iodide Systems. Left: Equivalent Conductance
of Metal vs Mole Fraction of Metal. Right: Electronic Contribution to Equivalent Conductance of Solution vs Product of
Electron and Cation Concentrations (M. A. Bredig).
L4
1
41
as i n molecules (e.g.,
Na2),
o r singly i n lower
SrC12-
for
This i s t h e
e,
Table 6 .
~
Solubility
Of
~~~~
M-MXZ
Solubility
(mole '$ M)
Temp
("C)
Solid
"Subhalides"
Refs
M-MXZ
Solubility
(mole '$ M)
Temp
("C)
Solid
"Subhalides"
Refs
N i NiCl2
9.1
977
None
70
In-InC1
Ag-AgC1
0.03
0.06
490
700
None
71
TI.-T1C1
0.09
0.09
550
650
m-mc4
0.18
1.64
500
600
None
80
Sn-SnC12
0.0032
500
71
zn-znI2
0.28
1.65
500
670
None
80
Sn-SnBrz
0.068
500
71
550
800
None
54,79
Pb-PbCl2
0.020
0 -052
71
0.123
600
700
800
0 0024
4-40
0.15
0.41
600
700
Sb-SbCl3
0.018
270
~b-sb13
1.69
3.5
5.8
200
300
c a-C a c l 2
C d- C dBr2
Cd-CdIz
Hg-HgC12
Hg-Hgl2
Ga-GapCl4
Ga-GazBrq
14.0
21.0
30 .O
1000
14.0
20 .o
28 .O
550
700
900
None
2.5
15 .O
25 .O
400
700
950
None
7.0
18.0
4.0 .O
280
4.00
500
Hg2 c12
25 .O
35 .o
230
280
Hg2 I 2
3.7
180
14.0
180
79
79
Pb-PbI2
73
Bi-BiC13
76
Bi-BiBr3
95
80
Bi-BiI3
InC1, In31nC16
"1n~12"
( I N C h
TlCl
(TlAlC14?)
a214
202
320
"BiCl"
21.0
57.0
45 .O
205
294
"BiBr"
80
80, 102
400
28.0
46 00
28 .O
100.o
10000
48.0
10000
97
107
108
4-40
>538
336
#t58
108
"MI"
43
rapidly within each group with increasing atomic weight (see Table 6 ) . It
a l s o depends on t h e halide ion, and Corbett e t al. a t t r i b u t e t h i s l a t t e r
trend t o t h e r e l a t i v e tendency toward s t a b i l i z a t i o n of t h e higher oxidat i o n s t a t e by complexing with the halide ion, normally i n t h e sequence
C1
C d and Hg.
Transition Metals
The occurrence i n this group of elements of more than one s t a b l e
I
i i
chloride
980'C.
+ Ni2+
"
interpretation.
--r
Ni2+
E l e c t r i c a l conductance meas-
Such measurements
A large rise i n
$ a t 7OOOC.
The only
w e l l known for a long time and are stable, even i n contact with water.
The phase diagram of t h e (anhydrous) HgClp-Hg system
6001
600
550
I
I
UNCLASSIFIED
ORNL-LR-DWG. 56700
1
I
I
5+L2
I
I
RUFF 8 SCHMOER
SMITH 8 MENZIES
THIS WORK
QTHERMAL LJATA
AVISUAL DAm
MOLE PERCENT Hg
CI
45
HgC12 * HgzCl2.
The
system.77s81-83
mium metal.
and by Nachtrieb.86
of 7.22 kcal/mole f o r
4.6
i
2 mole $ Cd2C12, but increasing negat i v e deviation from Raoult's l a w f o r CdC12 with increasing metal (Cd2Cl2)
Cd2C12 i n CdC12 below approximately
solute concentration.
(15 mole
deviation with decreasing metal. concentration, t h e formation of undissociated species Cd4C16 and Cd3X4 has been suggested,79 but does not appear plausible i n a highly ionized and ionizing medium such as molten
CdC12.
i
Observations by Grjotheim e t
on t h e
47
i
Br-,
states.
i s present was
a t t r i b u t e d t o the role, i n t h e former case, of t h e (highly polarizable!)
Other examples of
deep color a r e found even i n aqueous systems containing Fe, Sn, Sb,
o r Cu
I n the t h i r d B subgroup of the periodic system t h e halides of monovalent indium and thallium have long been known, and some of those of gall i u m have a l s o been prepared recently.9698
-t
Ga3+
The solu-
small,
719
go and
48
mation of s o l i d "subhalides" of t h e approximate stoichiometry BiX.
Vapor
al.1029103
Older
claimslo4 f o r t h e existence of dihalides BiX2 of bismuth were not substant i a t e d later,1o5 especially not i n more recent phase behavior and r e l a t e d
studies by Sokolova, Urazov, and Kuznetsovlo6 and p a r t i c u l a r l y by Yosim
e t al.107-10
(Figs. 2S31).
allegedly con-
t h e remarkable complex
On t h e
al.,
1. Phys.
5 DECANTATION
li~
!
49
; u
!
which they a l s o
500
400
a
3
igf
300
E!
200
o-BlBr3+ BI Br
400
300
200
100
W
! -
and t h e i r
50
densities. 7*l1 7s
The solu-
51
SUMMARY
Mixtures of metals with t h e i r molten halides a r e not c o l l o i d a l sus-
,L.
Such t r a p s a r e
Electron exchange
process and t h e state of the electron i n solutions, such as the alkalimetal solutions,in which the electrons a r e quite mobile, a r e not too well
understood as yet.
bd
'
52
REFERENCES
1. D. Cubicciotti, USAEC Document MDDC-1058 (1946).
17
.-
i
t
53
25.
26.
27.
28.
29.
S. A. Rice,
H. R. Bronstein, A.
37, 677-78 (1962).
36.
-,
43.
4.4.
45.
10(4), 87 (1935).
47. A. I. Burin, Metallurg 48. B. F. Naylor, J. Am. Chem. SOC.
150 (1945).
W
A
54
-,
67.
55
, w
73
74
75
.
.
76
77.
78.
79
rr(
.
.
.
(1954)
.
82 .
83.
85
86
-,
88
89
.
.
.
A148, 177-94
Chem. 47, 473-84
. J.
.
90
(1960).
81
87
.J. D. Corbett,
79, 3020-24 (1957).
80
84
15a,
-
llOO-llO7 (1961).
92
93.
N. Davidson e t al
94.
95
-,
96
97
98
99.
56
100.
-,
102.
103.
104.
105.
106.
1,
66,
107.
S. J. Yosim e t al
108.
S.
109.
llo.
28-31 (1962).
112.
(1908).
H. A. Levy e t al.,
36,
64,
(1959).
551-52
(1962).
113. G. Cleary and D. Cubicciotti, J. Am. Chem. SOC. 74, 557 (1952).
ll4.
62,
463-67 (1958).
115.
116.
(1959).
U.7'.
119.
120.
121.
122.
123.
124.
-,
57
ll78-81 (1962).
125. C. R. Boston and G. P. Smith, J. Phys. Chem. -66
9
59
,bi
ORNL-3391
UC-4 - Chemistry
TID-4500 (20th ed., Rev.)
i
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