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ORNL-2749
Reactors-Power

TID-4500 (14th ed.)

 

SOLUBILITY RELATIONS AMONG RARE-EARTH FLUORIDES

IN SELECTED MOLTEN FLUORIDE SOLVENTS

DOCUME‘NT COLLECTION g
,, I.IBRARY LOAN COPY
DO NOT TRANSFER TO ANOTHER PERSON

If you wish someone else ATy thns A
LT TY TS R LR s L3
" _cm_d__ Ty hbr_c_ry IR Tede Lol

 

 

 

    

OAK RIDGE NATIONAL LABORATORY
operated by
UNION CARBIDE CORPORATION
for the
U.S. ATOMIC ENERGY COMMISSION

 

 

 
 

 

 

 

 

 

 

 

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Off[cg of Techmcol Servu:es .
Deporfmenf of. Commerce_, S

Woshlngfon 25 ‘D.C.

   

 

.

 

 

 

_LE(;AL 'N'oflcs =

This report was prepared asan occount of Government sponsored ‘work. Neliher fhe Umfed Sfofes, ‘

nor the Commission, nor: any person. uchng on behul! of the Cammlss:on. . -

  

A. Makes any warranty. or represenfohon expressed or lmplled wflh respeci to 1|'le accurucy, .

completeness, or usefulness of the.. |nformahon contained. m fl'ns report, B thuf the use ‘of

   

any information, apparafus,, mafhod Jor process dlsclosed |n thls report moy not. lnfrlnge'

privately owned rights; or

 

B. Assumes any liabilities with respecf to the use of or for dumages resu[h'ng from 1'|'|e use of

any |nformahon, apparatus, methed, of process dusclosed in this report.

As used in the above, "person octing on behalf of the Commission"’ |no|ud_fes .un;y em.p'lo)'ree or

contractor of the Commission, or employee of such contractor, to the extent that such employee’

or contractor of 1|1e Commission, or employee of such contractor . prepares, diseeminotes, or

- provides access to, any information’ pursuanf to his employment or. contract with the Commcssmn,

or his employment with such contractor.

 

 

 

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Troe AN T

 

T it Ty B Bt ewisfins Db WS tTP BTG

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ORNL-2749
Reactors-Power

TID-4500 (14th ed.)

Contract No. W-7405-eng-26

REACTOR CHEMISTRY DIVISION
SOLUBILITY RELATIONS AMONG RARE-EARTH FLUORIDES

IN SELECTED MOLTEN FLUORIDE SOLYENTS

-DATE ISSUED

 

0CT 131959

OAK RiDGE NATIONAL LABORATORY
Ook Ridge, Tennessee
operated by :
UNION CARBIDE CORPORATION s
for the [
U.S. ATOMIC ENERGY COMMISSION ' MARTIN MAR

(R

 

 

 
 

       

 

 

 

 

 

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CONTENTS

.....................................................................................................................................................

..............................................................................................................................................

Results

----------------------------------------------------------------------------------------------------------------------------------------------------

Solubilify of Single Rare-Earth Fluorides

------------------------------------------------------------------------------------

Solubility of Rare-Earth Fluorides as Functions of Composition .......c.uienenmnenincninnns

Solubilities of Mixed Rare-Earth Fluorides in Lil:-Ber-UI:4 (62.8-36.4-0.8
Mole %)

..........................................................................................................................................

Additional Data Pertinent to a Solid-Solvent Extraction of Rare-Earth Poisons.....cccceuuunnne.

Appendix —~ Solubility Data for Cel:3 in Yarious Solvents

--------------------------------------------------------------
SOLUBILITY RELATIONS AMONG RARE-EARTH FLUORIDES IN SELECTED
MOLTEN FLUORIDE SOLVENTS

W. T. Ward R. A. Strehlow

W. R. Grimes G. M. Watson

ABSTRACT

Solubility measurements of rare-earth and yttrium fluorides have been made in various solvents

containing zirconium or beryllium fluoride with certain alkali-metal fluorides, and in some cases

uranium fluoride, present.

Tests have been performed which pertain to the development af a

method of removal of rare earth fluoride nuclear poisons from certain mixtures of interest to the

Molten Salt Power Reactor Program. The method is shown to be effective in several concentration

ranges.

 

INTRODUCTION

Rare-earth fission products formed in a reactor
fueled with a circulating molten fluoride solution
may be expected to account for significant neutron
loss.  Appreciation of this fact has motivated
studies of solubilities which would be pertinent
to the design and operation of such a reactor.
The feasibility of several processes in which
rare earths could be extracted from molten fluoride
solutions depends substantially on the solubility
relations among the rare-earth fluorides. This same
information also is of interest with regard to the
maintenance of homogeneity of the fuel, since
precipitation of a rare-earth fluoride in the fuel
circuit of the reactor might interfere with its satis-
factory operation.

This report presents some of the data obtained
on the solubilities of LaF,, CeF,;, SmF,, and
YF, in solvents containing sodium fluoride and
zirconium fluoride and in others containing beryl-
lium fluoride with lithium or sodium fluoride.

Two.. specific uranium-containing compositions
which -are potentially useful in a molten-fluoride-
fueled reactor have been selected. In addition,
a sufficient variety of non-uranium-containing
solvents have been chosen to assure that the
solubility relations among this selection of rare-
earth fluorides would be adequately known. This
is a continuation of work reported earlier! con-
cerning a solvent of composition NaF-ZrF ,-UF,

 

"W. T. Ward e al., Solubility Relations Among Some
Fission Product Fluorides in NaF-ZrF4-UF4 (50-46-4
mole %), ORNL-2421 (Jan. 15, 1958).

(50-46-4 mole %). The same radiotracer technique
was used for the present work.

RESULTS
Solubility of Single Rare-Earth Fluorides

The solubilities of CeF,, LaF,, and SmF; meas-
ured in the solvent, LiF-BeF,-UF, (62.8-36.4-0.8
mole %), are shown in Fig. 1 along with the cor-
responding results from the earlier work. Although
the solubility levels of these solutes in the LiF-
BeF,-UF , solvent mixture are considerably lower
than in the NaF-ZrF ,-UF, composition, they are
still adequate to assure that precipitation of the
rare-earth fluorides would not be inimical to re-
actor operation at probable burnup rates for about
four or five years.? A second feature of the data
is the closer approximation of the data for the
beryllium-containing solvents to a straight line
on the plot of log solubility vs T~!, which may
be interpreted as implying a lower degree of in-
teraction in the solution between solute and
solvent cations. This approach to ideality of the
solute in the beryllium system would not be ex-
pected to affect the feasibility of a solid solvent
extraction process, since both the substituting ion
[presumably Ce(lll)] and the extracted ions [e.g.,
Sm(I11)] would behave similarly.

For comparison, the solubility of YF,, along
with that of CeF, is shown in Fig. 2 for a single
NaF-BeF, composition (61-39 mole %). From these
results it may be inferred that the same qualitative

 

2Molten Salt Reactor P}ogram Status Report, ORNL-
2634, p 234 (Nov. 12, 1958).
UNCLASSIFIED
ORNL-LR-DWG 31423R

| IN NaF-2rR,-UF,
(50-46~4 mole %)
l I
PROBABLY UNSATURATED

SmF. ‘
3
YFy
Sm F3
CeF3
La F3

SOLUBILITY {mole %)

IN LiF-BeFp-UF,

 

(62.B-36.4-
0.8 mole %}
9 0+ N 12 13 14 15 16
10,000/ 7 (°K)
Fig. 1. Solub‘llity of Some Fission-Product Tri-

fluorides In Molten Fluoride Fuels.

order of solubilities exists for the rare-earth fluo-
rides in these solvents as was observed in the
NaF-ZrF ,-UF, (50-46-4 mole %) and LiF-BeF,-
UF, (62.8-36.4-0.8 mole %) solvents. This de-
crease in solubility with increase in the size of
the trivalent solute cation is probably related to
an as yet unmeasured trend of the heats of fusion
of the trifluorides. "

Solubility of Rare-Earth Fluorides as
Functions of Composition

Figure 3 shows that the presence of UF, in
small amounts does not affect the rare-earth solu-
bility greatly. The proportion of alkali-metal fluo-
ride to BeF, or ZrF ,, however, has a considerable
effect. : o

Several experiments were performed to determine
the solubility of a typical rare-earth fluoride,
CeF, in various solvents in each of the systems

UNCLASSIFIED
ORNL-LR-DWG 39655

0.8
c6

0.4

0.2

<
RARE-EARTH FLUCRIDE IN FILTRATE (mole %)

 

04
0.08
0.086
0.04
9 10 1 12 13 14 15
10,000/ 7 (°K}) '

Filg. 2. Solubllity (mole %) of YF3 and of CeF, in
NaF-Ber (61-39 mole %).

NaF-ZrF ,, LiF-BeF,, NaF-BeF,, and LiF-NaF-
BeF,. Figures 4 to 6 show the graphically inter-
polated solubilities in the selected compositions
in the four systems for several temperatures. Data
from which these curves were obtained are listed
in the Appendix. Figure 7 displays the 600°C
isotherm for the solubility of CeF, in the three
solvent systems containing beryllium. These curves
indicate the magnitude of the solvent interaction,
which is apparently less in the LiF-BeF, system
than in those containing NaF. The solubilities
exhibit minima in each case at compositions near
37 mole % BeF,. These minima appear to occur
at slightly higher BeF, concentrations at higher
temperatures (Figs. 5 and 6). '

Solubilities of Mixed Rare-Earth Fluo_rides in
LiF-Ber-UF4 (62.8-36.4-0.8 Mole %)

Rare-earth fluorides form solid solutions with
each other. However, they apparently do not form
solid solutions with the fuel solvent components.
These facts, coupled with the strong temperature
dependence of their solubilities, suggest that a
solid-solvent extraction might be a feasible method
UNCLASSIFIED
ORNL- LR-DWG 39656

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

4
.
2
v ' X
o
£ o\
E o8 X
{0
& 06 @,
5 R
T
z ‘%
m
5 04 ‘%
\Y
0.2
SOLVENT COMPOSITION {mole o}
© 61.6 LiF, 38.4 BeF,, O UF,
® 60.45 LiF, 38.3 BeF,, .25 UF,
- A 61.5LiF, 36.6 BeF,, 1.9 UF,
0.4 | | |
8 9 10 1" 12 13 14

10,000/7 (°K})

Fig. 3. Effect of UF, on Solubllity of CeF; in LIF-
Ber (62-38 mole %). Solvent composition calculated

from filtrate analyses (average values).

for substituting a low-cross-section rare earth
(e.g., Ce) for the high-cross-section ones (e.g.,
Sm). For a thermal reactor the differences in
poisoning between Ce and, say, Sm are large.
The advantages from the standpoint of neutron
economy of such a scheme are, consequently,
great. The advantage of this type of extraction for
an intermediate- or fast-neutron reactor is con-
siderably less. In the consideration of any of
the extraction schemes which are based on the
substitution of an innocuous rare-earth fluoride for
a high-cross-section one, the required data include
the solubility behavior of mixed rare-earth fluo-
rides. Such information will allow the single-stage
equilibrium distribution to be calculated.

The solubilities of selected pairs of rare-earth
fluorides in LiF-BeF ,-UF , (62.8-36.4-0.8 mole %)
have been determined, with substantially the same
techniques as those reported earlier.! In the
earlier work it was shown that the pairs LoFs-

UNCLASSIFIED
ORNL-LR-DWG 39657

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

i
10 |
9
!
8 !
7
5 \
E s 1
E \\ 800°C
. \
= \ 675°C
T
\
| /
\
\ .
A \\‘ ] 4550
\ / /.
\\ /
| \\; /‘ / /
/8
2
o

 

0 10 20 30 40 . 50 60
Zrf, IN SOLVENT (mole 7o) '

Flg.‘ 4. Solubllity of CeFa_ in NuF-ZrF4 Solvents.

CeF, and CeF,-SmF, form solid solutions and
behave in fairly predictable ways.

The equation representing a single equilibrium
stage for the extraction of a poison (e.g., SmF,)
from the solvent by a solid (e.g., CeF,) is

CeF3(ss) + SmFa(d‘) = Ce.FB(d) + SmF3(.'ss') ,

where (d) indicates that the rare-earth fluoride
is dissolved in the solvent, and (ss) that it is
in solid solution. With suitable restrictive con-
ditions the equilibrium constant for this reaction
can be shown to be approximately equal to .a
UNCLASSIFIED

ORNL-LR-DWG 39658

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

" BeF, IN SOLVENT (mole %)
.

2.4 H
LiF - BeF, SOLVENT | NaF -BeF, SOLVENT
2.2
2.0
700°C
1.8
700°C
1.6
\ /
° °
52 44 — o — 7 o
® o
o
g /
O o9 /
5 1.2
a
5
z /
.2 ®
"
8 1.0 //
/o
0.8 e
. \soo°c ‘\ o
A o' /
0.6 / \ /
: \«/L 600°C /
0.4
' A/{A /c/
X D,fi O/ »
02 w0~ 500°C p}x{ ‘
o7 500°C
0 .
20 30 40 50 20 30 40 50

BeF, IN SOLVENT (mole %)

Fig. 5. Comparison of CeF3 Solubllity (mole %) In LIF-BeF2 and In NaF-Ber.'

60
UNCLASSIFIED
ORNL-LR-DWG 39659

GREATER THAN 4%
mole %o AT 650°C

0.5

0.2

CeF3 IN FILTRATE (mole %)

0.05

0.02

‘NaF ~LiF

 

0.01
0 10 20 30 40 50 60

8eF, IN SOLVENT (mole To)

Fig. 6. Solubility (mole %) of CeF, In NaF-LIF-BeF,

Solvents.

simple solubility ratio:!
NeoF  (d) VsmF Seor
ceF ,(d) "SmF4(ss) " CeFg4
K: = ;
NSmF3(d) NCeFa(.ss) ng

 

F3

where N is the mole fraction of the given species
in the specified phase and $° is the mole fraction
of the given species_ in a saturated solution in
the absence of the other rare-earth fluoride, all
at the same temperature.

The results of equilibrating CeF3-LaF3-so|ven'r
of several different compositions are
shown in Fig. 8. For the three relative com-
positions of CeF3-LaF used as solutes, the total
rare-earth solubility in virtually every case fell
between the solubilities of the pure rare-earth
fluorides. Figure 9 shows the corresponding re-
sults with one mixed composition in the CeF -

mixtures

UNCLASSIFIED
ORNL-LR-DWG 39660

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

® LiF-BeF, -
O Lif — NaF -BeF,
A NoF-BeF,
2 N\ea p
3 o8 N - /
£ r
l}"_J \ \‘ ./ /A
3 \ 4 pai
H os e, e
T \\\ .
= \ e A
< \ Ne~” o,
s A //
S oa \ '/
\,_+
A
0.2 . :
20 30 40 50 60
BeF, IN SOLVENT {male %)
Fig. 7. Comparison of CeF, Solubility {mole %) in
'LiF-BeF,, In LIF-NaF-BeF,, and in NaF-BeF, at
600°C. ‘

SmF ;-solvent system.  These results are con-

“sistent with those observed for the NaF-Zer-UFd

(50-46-4 mole %) solvent.! Table 1 shows the
calculated extraction coefficients along with those
based on the experimental results for the CeF .-
LaF, system. Although the estimated values are
somewhat poorer than in the earlier work, the
present data appear' to be entirely adequate for
practical purposes.

A possibility existed that AIF, might offer some
advantage as the solid extractant in view of its
lower cost and neutron cross section. Solubility
measurements of AIF, in the same LiF-BeF ,-UF,
solvent indicated that the solubility increases with
the amount of AIF, added. The data presented in
Fig. 10 show also that the addition of CeF, de-
creases the AIF_ solubility somewhat. The pre-
cipitating phase is probably 3LiF-AlF, (ref 3).
Figure 11 shows that the solubility of CeF, is
somewhat higher in the presence of AlF, than in

 

3P, P. Fedotieff and K. Timofeeff, Z. anorg. w allgem.
Chem. 206, 266 (1932).
UNCL ASSIFIED ' UNCLASSIFIED
4 ORNL—-LR- DWG 39664 ORNL—~LR—-DWG 39662
I I { 4 -

CALCULATED TOTAL COMPOSITION {mole %)
© 1.80 CeFy, NO LaFy
1.82 CeFy, 0.78 LaFy
A 185 Cefy, 2.27 LaFy , \
183 CeFy, 330 LaFz \
® NO Cefy, 2.20 LoFz ~ > \

 

 

 

 

»

 

 

 

 

 

”

 

 

 

o
™
rd
v
o
™
L~
L~

 

 

 

 

 

 

 

 

&

7
-
vd
/ .

 

 

\\ \

 

TOTAL RARE-EARTH FLUORIDE IN FILTRATE {mole %)
o
N
A
TOTAL RARE-EARTH FLUORIDE IN FILTRATE {(mole %)
o
N

©
Ny
.

 

 

 

 

 

 

7
Z

SmFy ONLY (NO CeF3 PRESENT) N
CeFy ONLY (NO SmFy PRESENT)
SUM OF SOLUBILITIES WHEN BOTH ARE PRESENT
(TOTAL COMPOSITION: 2.83 mole % Cefy,
01 . . - 2.22 mole %o SmFz)

9 10 1 12 13 . 14 0.1 : : . L

10.000 / 7 (°K) 9 10 11 12 13 14
’ 10,000/7 (°K)

-
[ 2 = v]

 

 

 

 

 

 

 

 

 

 

Fig. 8. Solubllity of CeFé and of Lc:F3 (Separatel* Fig. 9. Solubility of CoF 5 and of SmF 4 (Separately
and Mixed) in LIF-Ber-UF4 (62.8-36.4-0.8 mole %). ond Mixed) in LiF-BeF,-UF , (62.8-36.4-0.8 mole %).

Table 1. Extraction Coefficients for the Process CeF3(ss) + LuF3(d) = CeF3(d) + LaF3(ss)
in LiF-BeF ,-UF , (62.8-36.4-0.8 Mole %) - i

 

 

 

: 0 0 K*
SCeF.”SLaF
Temperature (°C) 3 3 - 1.82 Mole % CeF3, ~ 1.85 Mole % CeF3, 1.83 Mole % CeF3,.
' 0.78 Mole % LaF ,**  2.27 Msle % LaF ;**  3.30 Mole % LaF ,**
70 w4 0.97 . 1.55 BRI
600 1.15 1.18 1.82 - 1.38
500 1.09 1.52 2.28 - .68

 

NCer(d) NLaF3(s's)
Koo T
' NL_.an(d) NCeF3(s§)

**Total composition in container.

 
UNCLASSIFIED
ORNL-LR-DWG 39663

 

 

 

 

 

 

 

 

 

 

 

 

 

20
10 4 0 \; \“
™ .
B AN >
. Po \\ ~.

3 |

6
& N
3 ]
£ . o* * N
z 4 .
s N\
_g_ \\.
> N
2 3

® FIRST EXPERIMENT: CALCULATED TOTAL Al CONTENT
5 | INSYSTEM=4.1wt% - i

4 SECOND EXPERIMENT: CALCULATED TOTAL Al CONTENT
IN SYSTEM =104 wt %

O SECOND EXPERIMENT: AFTER ADDING 11.8 wi % CeFy
TO SYSTEM

 

 

 

 

 

 

9 10 1 12 13 14
10,000/7 (°K}

Fig. 10. Solubility of AIF3 in LIF-BeF,-UF, (62.8-
36.4-0.8 mole %). ' :

its absence, probably due to a change in solvent
similar to that seen above upon addition of BeF,.
As a consequence of this behavior, it is clear that
AlIF, cannot be used as a solid extractant for rare
earths.

Additional .Dcn‘a Pertinent to a Solid-Solvent
Extraction of Rare-Earth Poisons

In addition to determining the single-stage equi-
librium extraction coefficients, it is necessary
to know something of the rate of reaction of dis-
solved rare earth with solid extractant and to know
whether trace amounts of rare earth would be ex-
tracted as predicted. A simple isothermal experi-
ment was performed at 500°C which used unlabeled
LaF; as solid extractant for 0.15 wt % CeF
(tracer labeled) dissolved in LiF-BeF, (63-37
mole %). An amount of LaF, equal to about four
times the amount necessary to saturate the solu-
tion was added. One minute after the addition, the
CeF ; content in the liquid phase had dropped to
0.04 wt % and 5 min later (when the second filtrate

UNCLASSIFIED
ORNL-LR—DWG 395664

 

 

 

 

 

 

 

 

 

 

% 1 AN \
g o8 \ \\
o \ \
< N\ N\
0.6
z LN
N\

 

 

0.2

1

®  SOLVENT: LiF - Bef,—~UF,— AIF; (52.5-30.4- 0.7
— {6.4mole %) {CALCULATED TOTAL COMPOSITION

EXCLUDING CeFy)
. .| © SOLVENT: Lif -BeF,~UF, (62.8— 36.4- 0.8 mole 7).
O" 1 1 1 1 -
9 10 i1 t2 13 14
10.000/7 (°K) )

 

 

 

 

 

 

 

Fig. 11. Effect of AIF, on Selubility of CeF,. .

was taken) it had dropped to the equilibrium value
of 0.03 wt %. ' _

To determine whether trace amounts of rare-earth
fluorides would behave as predicted, a polythermal
experiment was carried out in which solid CeF3
(unlabeled) was added in two increments to LiF-
Ber-UF4 (62.8-36.4-0.8 mole %) in which was
dissolved 0.0795 wt % SmF3_(fracer labeled). The
results of this experiment are shown in Table 2.
The really excellent agreement with the calculated
amounts of SmF, indicates that trace amounts of
rare-earth poisons act in an essentially predictable
manner. o .

An initial attempt at performing a solid-solvent
extraction was made in which LaF, was packed
in a horizontal column as the solid extractant for
dissolved CeF in LiF-BeF2 (63-37 mole %). The

solution was saturated with L_aF3 and then forced
Table 2. Removal of Traces of SmF 5 by Addition of CeF; to LiF-BeF,-UF , (62.8-36.4-0.8 Mole %)

 

Total Rare-Earth

 

Rare-Earth Fluoride (wt %)

 

 

 

Filtrate in Filtrates
Fluoride {wt %) in T '
System (calc.) smpsTaTure a SmF3
ys . .
) C) CeF3 ;
CeF3 SmF3 Observed Predicted
Before CeF, addition 0 0.0795 749 0.0795
First CeF 5 addition 2.12 0.0778 695 2.1° 0.0750
2.12 0.0780 580 2.1¢ 0.0757
2.12 0.0781 487 0.90 0.0542 0.0471
Second CeF3 addition 10.1 0.0731 736 8.34 0.0662 0.0662
10.2 0.0735 587 2.57 0.0397 0.0300
10.7 0.0757 492 0.96 0.0262

0.0131

 

%Determined in a separate experiment; disregards effect of small amount of SmF 4 in system,

b . .
Calculated from relationship NSmF

“Unsaturated.

by gas pressure through the column. The CeF,
concentrations of four successive effluent liquid

samples are shown below:

Starting material

Effluent sample
No. 1
. No. 2
No. 3
No. 4

Concentration (ppm)

1000

80
50
30
30

3ld) ~

0
S
SmFa

0
CeF

NSmFa(ss)

NCeF3(ss)

N .

The drop in CeF,

content of successive samples
is probably related to a change in flow rate as the

column filled with liquid. The thirtyfold reduction
in CeF 5 concentration obtained for this experiment
indicates that quite large decontamination factors
may be ultimately achieved. |
Appendix
SOLUBILITY DATA FOR C0F3 IN YARIOUS SOLYENTS

Table A. 1. Solubilities of CeF 4 in NaF-ZrF, Solvents of Yarious Compositions at Three Temperatures

 

Average Analyzed
|

 

 

 

 

5°"’e'(‘r:j:"‘;)‘f‘“i°" » Molecular Weight (g/mole) | Solubility (mole %) of CeF ,**

— o of Solvent Mixture | ArsseC At 675°C At 800°C
42 58 114.6 3.0 8.2 10.3

50 50 1045 212 3.0 44
53 47 100.9 1.64 2.37 3.9
59 41 93.3 0.56 0.62 1.61
63 37 _ 88.4 ‘ 0.26 0.44 .07
80.5 - 19.5 66.4 \ | | ’ 47
*10.5,

**Graphically interpolated.

Table A. 2, Solubillfy of CeF3 in LiF-Ber Solvents

 

 

BeF, CeF, BeF, ~ CeF,
in Solvent Temperature in Filtrate in Solvent Temperature in Filtrate
(mole %)* ' cc) {mole %) (mole %)* cc) I (mole %)

24.4 766 >1.8%* 37.3 720 1.50

' 722 >1.8%* 643 0.73
681 >1.8%* 556 0.31
623 1.35 ' 467 . . 0.108
600 1.10 40.7 704 . 1.29
28.5 : 733 2.04 627 0.68
648 1.44 - 544 © - 0.286
573 0.67 476 0.128
510 0.207 43.3 723 1.64
32.5 740 1.57 - 612 0.62
666 1.15 508 0.219
586 0.55 . 425 0.082
513 0.232 46.2 717 1.76
34.5 734 2.13 ~ 655 1.00
729 1.79 632 0.79
662 1.00 ' 511 0.27
656 0.92 412 0.094
566 0.34 48.4 726 1.80
556 0.32 615 0.83
476 0.127 ' 501 0.284
474 0.123 407 0.105

 

 

 

*From chemical anclyses of filtrates.
**Not saturated.
Table A.3. Solubility of CeF3 in NaF-'Ber Solvents

 

 

 

 

B.eF CeF BeF ‘ CeF
in Solvent Temperature in Filtrate in Solvent Temperature in Filtrate
(mele %)* C) (mole %) (mole %)* C) ‘ (mole %)

23.9 794 >3.3% 38.6 676 0.55

768 >3.3* 596 0.256
744 >3.3* 516 0.155
714 >3.3* 425 0.060
29.7 742 2,71 41.1 749 1.14
684 1.99 668 0.56
613 0.98 , 584 0.258
32.2 748 1.96 503 0.133
| s34 103 423 O 0.062
617 0.51 46.0 738 1.39
35.5 763 1.41 668 0.72
616 0.312 513 0.232
537 0.134 429 0.134
| 463 0.065 52.5 733 1.73
37.5 752 1.24 . - 678 1.21
673 0.62 589 0.64
527 0.116 405 0.175
440 0.054 |

 

*From chemical analyses of filtrates. k
**Not saturated.

[V L T

e
Table A. 4. Solubility of CeF3 in LiF-Nch-BeF2 Solvents (LiF-NaF Eutectic, 60-40 Mole %, + BeF, Shown)

 

 

BeF2 CeFa BeF2 CeF3
in Solvent Temperature in Filtrate in Solvent Temperature in Filtrate
(mole %)* °C) (mole %) . (mole %)* C) {mole %)

Nonhe 778 >4,5%* 31.5 743 2.41

732 >4.5%* 648 1.04
712 >4,5% 544 " 0.380
671 >4.5%* 449 0.085
4.0 806 >4.5%* 366 0.029
750 >4,5%* 34.9 738 1.47
707 >4,5%* 653 0.65
654 >4.5%* 546 0.207
10.4 790 >4.5%* 453 0.075
748 >4.5%* 357 0.027
692 > 4.5%* 41.4 751 150
669 >4,5%* 640 0.52
12.2 803 > 4.5+ 37 0.192
2 754 5 4.5%4 453 0.085
202 S 4,54 364 0.035
664 >4,5%* 45.2 716 1.29
642 >4.5%* 623 0.57
21.2 796 >4.5%* 522 0.241
762 >4.5%* 440 0.112
716 >4.5% 359 0,054
687 >4.5%* 51.2 736 1.99
652 3.86 641 0.91
613 2.30 542 0.398
22.9 728 > 2.40%* 446 0.176
692 > 2.40%* 358 0.085
666 >2.40** 56.2 727 2.45
658 >2,40** 638 1.26
634 2.04 529 0.50
614 1.73 443 0.249
599 1.28 363 0.142
580 0.88

 

 

 

*From chemical analyses of filtrates.

**Not saturated.

11
VPN AW

Poobe bbb P B WW W W W W WWWOOWORNRMNMMODNNONNNNN 2 o et — o e o ad ey =
CURUN SO 0SNG ROD ZOOPINTOROIN O 0BICORONEES

EC-ME-PRO0OEQCYOE-TNEZAC-MZOEPOLSMP>PAMNO>AMOINTND > A0 O

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