. - 5. i '"\ 2

- OAK RIDGE NATIONAL LABORATORY operated by

UNION CARBIDE CORPORATION NUCLEAR DIVISION for t h e

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b' c

T; L.2 L

ORNL - TM- 3763

.

ESTIMATED BEHAVIOR OF TITANIUM IN MSBR CHEMICAL PROCESSING SYSTEMS

L. M. Ferris

NaTlCL This document contains information of a preliminory noture and was prepared primarily for internal use a t the Oak Ridge National Laboratory. I t is subject to revision or correction and therefore does not represent a finot report.

UTMN W THIS DOCUMENT is UULIMITUI

. I .

..- . , - *.’ I 6

This report was prepared as an account of work sponsored by the United States Government. Neither the United States nor the United States Atomic Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness or usefulness of any information, apparatus, product or process disclosed, or represents that i t s use would not infringe privately owned rights.

ORTJL- TM-3 763

C o n t r a c t No. W-7405-eng-26

CHEMICAL TECHNOLOGY D I V I S - I O N

C h e m i c a l D e v e l o p m e n t Sec t ion B

ESTIMATED BEHAVIOR OF TITANIUM I N MSBR

CHEMICAL PROCESSING SYSTEMS

Lo M, F e r r i s

A P R I L 1972

N O T I C E This report was prepared as an account of work sponsored by the United States Government. Neither the United States nor the United States Atomic Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, corn- pleteness or usefulness of any information, apparatus, product or process disclosed, or represents that its use would not infringe privately owned rights.

OAK RIDGE NATIONAL LABORATORY O a k Ridge, T e n n e s s e e 37830

operated by UNION CARBIDE CORPORATION

for the U.S, ATOMIC ENERGY COMMISSION

iii

CONTEN'IS Page

1.

2.

30

4,

5. 6. 7. a, 9.

Introduction p p . . . 0 . U D . F i . 0 . . . o . 0 . 0 0 . m . Thermodynamic Treatment c 0 0 . . U . . . ., . E . 0 . o . . e D Leaching of Titanium from Titanium-Modified Hastelloy into MSBR FuelSalt ., + I v a e I' LI o q i G G 5 ,. .* .* v e .* c = Estimated Behavior of Titanium During Fluorination of MSBR

FuelSalt n d ( L 0 o 0 r o c D ..E s =, . ..* o . . e D (I Behavior of Titanium in Reductive Extraction Processing . 5 = e Estimated Behavior of Titanium During Hydrofluorination . .- + . Behavior of Titanium in Oxide Precipitation Processes 0 o s o ,

Acknowledgments , Q E o e o 1 c v . 0 . e n e a i( D . . e . c . References p C.O cI *..* ,.+ y Y.,.l 7..0 u *.a 0

4

5 6

9 13 13 14

1

ESTIMATED BEHAVIOR OF TITANIUM IN MSBR CHEMICAL PROCESSING SYSTEMS

Li, M, Ferris

ABSTRACT

Available thermodynamic information was used to estimate the behavior of titanium in a fluorination--reductive extrac- tion flowsheet for processing MSBR fuel salt. It was first shown that titanium is likely to be leached from a titanium- modified Hastelloy N containment vessel into a LiF-BeF2- TnF4-UF4 fuel salt at 600"~. The primary reaction would

The estimates showed that, during f uorina ion, TiF3 wou d be oxidized to TiF4. expected to volatilize during fluorination, Any titanium not volatilized by fluorination would be present in the salt that enters the reductive extraction step. Experimental data confirmed the prediction that titanium would be prac- tically quantitatively extracted from the salt in this step. It was also shown that titanium can be transferred from a bismuth phase to a salt phase by oxidation with gaseous HF, and that HF is not a sufficiently strong oxidant to convert TiF3 to TiF4.

probably be 3 m4(d) + Ti(&,stelloyl = TiFz(d) + 3 uF3(d]a

A large fraction of the TiF4 would be

KEY WORDS: "MSBR, *Processing, "Modified Hastelloy N, *Titanium, fused salts, fluorination, reductive extraction process,

1. INTRODUCTION

Hastelloy N (68% Ni--l@ Mo--fi Cr--5% Fe) was used' for the con- tainment vessel and other metallic components in the Molten-Salt Reactor Experiment (MSRE). However, use of a modified Hastelloy containing up

to 2 w t % titanlum is being considered' for molten-salt breeder reactors

(MSBRS) since an alloy of this type is expected to be more resistant to

radiation embrittlement than Hastelloy N, In the event that a suttable

alloy is developed, it is of interest to know what extent titanium will

be leached from the alloy into the molten salt and, if the extent of

2

leaching i s s ign i f i can t , how t i tan ium w i l l behave i n an MSBR chemical

processing system. The present re ference flowsheet2* f o r chemically

processing an MSBR involves, f i r s t , f l u o r i n a t i n g the sa l t t o remove

uranium as uF6 and, then, contac t ing t h e r e s u l t a n t salt wi'ch l i q u i d

bismuth containing about 0 002 mole f r a c t i o n each of l i t h ium and thorium

t o remove protact inium by reduct ive ex t rac t ion . The rare e a r t h s remain

i n t h e salt during these process s t eps and are removed i n a subsequent

metal t r a n s f e r process Protactinium and o the r elements ex t r ac t ed i n t o

bismuth w i l l subsequently be t r a n s f e r r e d t o a salt phase by hydro-

f l u o r i n a t i o n of t h e bismuth i n the presence of t h e salt . The purpose

of t h i s r epor t i s t o estimate the behavior of t i t an ium both i n t h e

r e a c t o r system and i n t h e var ious chemical processing s teps . The es-

timates, which were made using t h e general thermodynamic t reatment

developed by B a e ~ , ~ could be compared, i n some cases, d i r e c t l y with

experimental r e s u l t s .

2 . THERdODYNAMIC TREATMENT

&es4 has summarized a l a r g e amount of equi l ibr ium da ta involving

molten LiF-BeF2 so lu t ions i n terms of s tandard h a l f - c e l l p o t e n t i a l s

( E " ) referred t o the r eac t ion HF

E" i s def ined as zero a t a l l temperatures; ( g ) and (d) denote gaseous

and dissolved species , respec t ive ly . The s tandard s t a t e f o r most s o l u t e s

i s t h e hypothe t ica l unit mole f r a c t i o n i d e a l so lu t ion i n LiF-BeF2 (66.7- 33.3 mole $ ) + a c t i v i t y of each o f these spec ies i s def ined as u n i t y i n t h e re ference

sa l t composition.

s t a t e , t h e a c t i v i t y c o e f f i c i e n t s f o r so lu t e s a r e uni ty , whereas

f o r which m' + e- = F-(d) + l / 2 H ( g >

+ The exceptions a r e LiF, BeF2, Be2+, L i , and F-; t he

With LiF-BeF2 (66.7-33.3 mole %) as t h e s tandard

Y L ~ F = '*5 and yBeF2 = 3: The p o t e n t i a l f o r a complete r e a c t i o n i s obtained by a l g e b r a i c a l l y

adding t h e necessary h a l f - c e l l r e a c t i o n p o t e n t i a l s . For example, a t

600°C t h e equi l ibr ium of pure c r y s t a l l i n e chromium metal with U4+ dis -

solved i n LiF-BeF 2 sum of t h e two h a l f - c e l l r eac t ions :

(66.7-33.3 mole %) can be expressed as t h e a lgeb ra i c

3

The standard free energy change for reaction (3) is:

A G O = -ZFE" = (-2.3~~) log K ,

in which z is the number of' faradays, F is the Faraday constant, R is the gas constant, T is the absolute temperature, and K is the equilibrium constant. For our purposes, we will assume that E" values (and K's derived from them) are the same in LiF-BeF2-ThF4 (72-16-12 mole %), the composition

of the MSBR carrier salt, as they are in LiF-BeF2 (66,7-33.3 mole %) estimates included in this report were made at 600"~.

All

The electrochemical behavior of titanium species in molten fluoride salts has been studied voltammetrically by Manning.'

Manning' estimates the following at 600"~: From this work,

Ti3' + 3/2 Ni = Ti + 3/2 Ni2+ , * E" = -1.8 ? 0.1 V (5) (e)

Ti4+ + 1/2 = Ti3+ + 1/2 Ni 2+ ; E" = 0.2 10.05 V (6)

Combining Eq, (5) with

; E" = 0,368 V (e>

3 /2 Ni2+ + 3 e- = 3/2 Ni

yields

; E" = -1.43 -t 0.1 V . (8) (4 Ti3+ + 3 e- = Ti

4

Similarly, from Eqs. (6) and (7) we obtain:

- + e ; E" = -0,568 f O,O5 V . (9) Ti3+ = Ti 4+

Use of Eqs. (8) and (9) , along with values of E" for other appropriate half-cell reactions, allows estimation of the behavior of titanium in 8

molten-salt reactor system and in the associated chemical processing plant.

3. LMCHING OF TITANIUM FROM TITANIUM-MODIFIED HASTZLLOY INTO MSBR FUEL SALT

The question of whether titanium will be leached from a modified

Hastelloy into an MSBR fuel salt at a significant rate is a difficult one

to answer since the overall rate of leaching would depend both on the rate a t which titanium diffuses to the surface of the a l l o y and on the

oxidizing power of the saltr Of the species present in the salt, U is

the most likely oxidant for titanium.

4+

The reaction would probably be:

E" = 0.286 10.1 V ,

4+ for which log K = 4-94 1 1.7, since the reaction producing Ti , given below, is thermodynamically much less favorable:

Ti + 4 U4+ = 4 U 3+ + Ti 4+ ; E" = -0.282 1 0.15 V e (11) (4

The value of log K for reaction (11) is -6,5 f 3. for reaction (10) with that of reaction (3) confirms earlier predictions" that titanium would be much more reactive than chromium to oxidants in

the fuel salt. Despite the fact that the thermodynamic driving force

for the leaching of titanium from a modified Hastelloy N is much greater than that for the leaching of chromium, it is nearly impossible to es-

timate the thermodynamic activity of titanium at the surface of the alloy.

Not only will the concentration of titanium in the bulk alloy be less than

one-third of that of chromium (about 2% vs 7%) but also the diffusion coefficient for titanium in Hastelloy N is about a factor of 10 lower

Comparison of the E"

7 than t h a t f o r chromium,, Thus, the t i t an ium a c t i v i t y a t t h e Hastel loy

surface a t a given t i m e should be considerably lower than t h e chromium

a c t i v f t y .

low enough t o o f f s e t t he l a r g e d r iv ing f o r c e represented by the 3' f o r

r e a c t i o n (10).

Only d i r e c t experimentation can show whether t h e a c t i v i t y i s

An experimental study conducted seve ra l years ago by DeVan and

Evans' provided evidence t h a t t i t an ium might be leached from Hastel loy N

a t a h igher r a t e than chromium,

Mo containing up t o 8 w t % of an add i t ive were made i n t o tubing from

which thermal convection loops were f ab r i ca t ed - These loops were exposed

t o NaF-LiF-KF-UF4 (11,2-45.3-41.0-2.5 mole %) f o r 500 and 1000 hr .

hot-zone temperature of each loop w a s 815"c, and t h e cold-zone temperature

was 6 5 0 " ~ . add i t ive . The corrosion s u s c e p t i b i l i t i e s ( io e, the amount leached) of

t h e a d d i t i v e s increased i n t h e following order : i r o n < niobium < vanadium < chromium < tungsten < t i t an ium < aluminum. With t h e excep-

t i o n of tungsten and niobium, t h e s u s c e p t i b i l i t i e s increased i n t h e same

order as d id t h e thermodynamic s t a b i l i t i e s of the f l u o r i d e compounds of

t h e r e spec t ive elements, It i s s i g n i f i c a n t t o note t h a t t h e ra te of

leaching w a s much h igher during t h e 500-hr per iod than during t h e 1000-hr

period. This r e s u l t suggests t h a t nea r ly s teady-s ta te condi t ions were

e s t ab l i shed wi th in t h e f irst 500 h r ,

I n t h e i r s tud ies , c a s t a l l o y s of N i - - l %

The

After each tes t , t h e sal t w a s chemically analyzed f o r t h e

4, ESTIMATED BEHAVIOR OF TITANIUM DURING FLUORINATION OF MSBR FUEL SALT

I n t h i s and the ensuing sec t ions , it will be assumed t h a t t i t an ium

i s present i n measurable concentrat ions i n MSBR f u e l sa l t t h a t e n t e r s

t h e chemical processing p l a n t , A s noted i n Sect , 1, t h e f irst chemical

processing s t e p i s f l u o r i n a t i o n of t h e salt t o remove uranium as UF6. F luor ina t ion should r e s u l t i n t h e q u a n t i t a t i v e oxida t ion of Ti3+ t o T i 4+ :

9 Eo = 2-30 zk 0.1 V

6

for which log K = 13 .t 1. Reaction (12) can also be written as:

Since the boiling point of TiF4 is only about 284"C,' it is probable that a significant fraction of the titanium would be removed from the salt as

TiF during fluorination and would accompany evolved UF6 to the fuel reconstitution step. An example of the inherent tendency of TiF4 to volatilize from fluoride melts is provided by the experience of Manning

-- et a1.I' or LiF-BeF2-ZrF4 solutions at 55OoC, TiF4 volatilized from the melt and condensed on cooler parts of the system,

4

They found that, after K2TiF6 was added to molten LiF-NaF-KF

5. BEHAVIOR OF TITANIUM IN REDUCTIVE EXTRACTION PROCESSING

Any titanium not removed during fluorination will be present in the

salt that enters the reductive extraction step2'

In this step, the salt is contacted with a liquid bismuth stream containing

about 0,002 mole fraction each of lithium and thorium, residual uranium from the fluorination step, zirconium, and some of the noble-metal fission products are transferred to the bismuth phase in this

step.

for protactinium isolation.

Protactinium,

The extraction into liquid bismuth of a solute MF,, present in l o w

concentration in molten LiF-containing salts, can be expressed as the

general reaction:

(a) ' = M + n LiF n(d) + Li (Bi) (Bi) MF

in which (d) and (Bi) denote the salt and bismuth phases, respectively,

This reaction is the sum of the half-reactions

- ne ne = M

+ n L i = n L i + n e -

7

'v The s tandard p o t e n t i a l f o r r eac t ion (14), i .e. t h e a lgeb ra i c sum of the

p o t e n t i a l s f o r r eac t ions (15) and (16), i s r e l a t e d t o t h e equi l ibr ium

constant as fol lows :

n M "LiF (nFE" /RT) = e K = n ,

a

all MFn L i a

i n which a i s a c t i v i t y and t h e o the r symbols a r e as def ined previously.

By l e t t i n g a = Ny (where N i s mole f r a c t i o n and y i s an a c t i v i t y co-

e f f i c i e n t ) and by def in ing t h e d i s t r i b u t i o n c o e f f i c i e n t f o r a given

element as DM = NM/Nm , it was shown by Ferr is" t h a t n

With LiF-BeF2 (66.7-33.3 mole %) as t h e salt phase, kes4 defined yLiF =

1.5 and ym = 1. Thus, n

l o g = (nFE0/2.3RT) + n log yLi - n log(1.5) - l o g yM ; (19)

or, at O'OO"C,

l og 4 = n(5.773)Eo - 0.176n + n l o g yLi - l og yM ( 2 0 )

I n order to c a l c u l a t e l og KM f o r a given element, we obviously need

values of t h e a c t i v i t y c o e f f i c i e n t s yLi and 7, t h a t are r e f e r r e d to t he

pure metals as t h e s tandard s t a t e , i n add i t ion t o the appropr ia te E"

values . Values of E" f o r a l a r g e number of s o l u t e s are ava i l ab le from

B a e ~ ; ~ those f o r titanium spec ies were est imated by Manning.'

yLi and yM f o r s e v e r a l s o l u t e s were taken from the l i t e ra ture and were

summarized by F e r r i s -- e t a1.l' These va lues of y ~ i and yM a r e f o r very

d i l u t e so lu t ions of M i n l i q u i d bismuth. No information on t h e a c t i v i t y

Values of

coefficient of titanium in liquid bismuth could be found in the literature. I

Thus we will assume that yTi is equal to yZr. Laboratory obtained13 yZr = 0.012 at 700°C.

chemical potential pZr = (2.3RT) log yzr does not change throughout the

temperature range 60O-70O0C, we can calculate log yzr = log Y T ~ = -2.1 * 1 at 600" c.

Workers at Brookhaven National

If we assume that the excess E

From the above sources, we obtain E" = 1.224 f 0.1 V at 600"c for the react ion

1

and, using Eq. (20), estimate log K~i3+ = 10.4 f 2 with LiF-BeF2 (66.7- 33.3 mole %) as the salt phase. for other selected solutes with values obtained experimentally using LiF-

Table 1 compares this value and the values

BeF2-ThF4 (72-16-12 mole %) as the salt phase. log Ku are those measured earlier by Ferris et a1.,14 whereas the value of log K T ~ was determined in the course of the present work. Note that

the values of log Ki obtained for LiF-BeF2-ThF4 (72-16-12 mole %) are somewhat higher than those calculated for LiF-BeF2 (66.7-33.3 mole %) .

The values of log KZr and 1

1

1

Table 1. Comparison of Values of log KM Calculated for LiF-BeF2 (66.7-33.3 mole 4) with Those Determined Experimentally at 600"c

for LiF-BeF2-ThF4 (72-16-12 mole %)

log KM Calculated for Measured with

log YM E" LiF-BeF2 LiF- BeFz-ThF4 M n 0) (66.7-33.3 mole %) (72-16-12 mole %)

Li 1 -4.13 - - Zr 4 -2.1 1.226 13.2 1

U 3 -3.87 1.143 10.7 f 1

Ti 3 -2.1 1.224 10.4 f 2

- 14.7 f 0.3 11.1 f 0.2 13.6 f 0.4

9

1

The experiment to determine the value of log KTi was conducted using

the general procedure outlined previously. l4 by simultaneously hydrofluorinating, in a molybdenum crucible, LiF-BeF2-

ThF4-CsF (71.7-15.9-12-0.4 mole 5 ) and bismuth containing dissolved titanium. This treatment resulted not only in the transfer of the titanium to the salt phase but also in the removal of oxide from the system. With the

system at 600°c, thorium was added in increments to effect the reductive

extraction of titanium from the salt into the bismuth phase.

hr was allowed for equilibration after each thorium addition before filtered samples of the respective phases were removed for analysis. metal samples were analyzed for titanium by a colorimetric method; the

lithium concentration in the metal phase was determined by flame photometry. Data from this experiment are summarized in Table 2, and a plot of log

This experiment was initiated

At least 24

The salt and

D T ~ vs log DLi is shown in Fig. 1. determination of the value of n. However, thermodynamic considerations

(Sect. 6) strongly indicate that n should be 3 (and not 4). log Kii3+ = 13.6 f 0,4 is the mean of the values calculated from each data point. however, the agreement is good, considering the uncertainties in the

thermodynamic quantities used. Furthermore, the experimentally determined value of log K$i3+ is consistent with the results of an earlier experiment by Moulton -- et a1.,15 which indicated that log K;i3+ should be greater than

log Ku3+. bismuth did not effect detectable reduction of either U3+ or Pa4+ from LiF-BeF2-ThF4 (72-16-12 mole %) at 600 to 7'00°C.

The scatter in data points precludes

The value of

This value is somewhat higher than the estimated value (Table 1);

1

In their experiment, it was found that titanium dissolved in

During the chemical processing of MSBR fuel salt, it appears certain that titanium, if present in the salt entering the reductive extraction

step, will be quantitatively extracted into the bismuth stream along with protactinium and other easily reduced species.

6* ESTIMATED BEHAVIOR OF TITANIUM DURING HYDROFLUORINATION

In the reference MSBR chemical processing method, 2 9 the bismuth

phase from the reductive extraction step used to isolate protactinium would be treated with an HF-H2 mixture in the presence of a salt phase

10

Table 2. Distribution Coefficients and Values of log K.;li3+ Obtained at 600" c from Measurements of the Equilibrium Distribution of Titanium Between Molten LiF-BeFz-ThF4-CsF (71.7-15.9-12-0.4 mole %) and Liquid Bismuth Solutions

f

log KTi3f 5 Sample lo6 NLi 10 DLi DTi

3 6 7 8 9 10 11 12

13 14

8.73 16.0 18.7 16*6

20.8

20.5 33.7 65.0 28.3

27.4

1.218 2.226

2.604 2.310 3.822 2.898 2 * 856 4.704 9.072 3.948

0.038 0.435 0 9 695 1.06 1.. 31 1.76 2- 33 3.88 5.94 150 7

13.3 13.6 13.6 13.9 13.4 13.8

13.6 12,9

14.0

14.4

11

I .(

0.

0.0 I I

O R N L D W G 72-3210

;

0

Fig. 1, Equil LiF-BeFZ-ThF4- CsF ( Solutions at 600"~.

2

.ibrium 71 7-15

3 4 5 IO' D L ~

Distribution of Titani .9-12-0.4 mole %) and

6 7 8 9 1 0

.um Between Molten Liquid Bismuth

12

to oxidize protactinium and other elements present in order to effect their dissolution in the salt phase. Since titanium could be one of the

elements initially present in the bismuth phase, its behavior during

hydrofluorination is of interest. The reaction of primary interest is:

3 m(g) + Ti(c) = 3/2 H2(g) + TiF3(d) ; E" = 1.43 f 0.1 V , (22)

for which log K = 25 2 2 at 600°C.

coefficient for titanium in liquid bismuth is of the order of thermo- dynamic considerationsledus to expect titanium to be easily hydrofluorinated from a bismuth phase into a molten fluoride salt phase. This expectation

was confirmed (at least under one set of conditions) in the initial phase

of the experiment described in Sect. 5. In this experiment, bismuth and LiF-BeFz-ThF4-CsF (71.7-15.9-12-0.4 mole %), contained in a molybdenum

crucible, were simultaneously hydrofluorinated at 600" c to remove oxides from the system, After sparging with purified argon, sufficient titanium

metal was added to give a titanium concentration of 2500 wt ppm in the bismuth phase. Analysis of a sample of this phase confirmed that all the

titanium was dissolved in the bismuth. The two-phase system was then

sparged at 600"~ for about 20 hr with HF-H2 (50-50 mole % ) *

the respective phases showed that all of the titanium had been transferred

to the salt phase during the hydrofluorination period.

convert Ti3+ to Ti4+; consequently, hydrofluorination of a bismuth-salt

system should leave the titanium in the salt as TiF This conclusion

is based on the following estimate at 600"~;

Despite the fact that the activity

Analyses of

Gaseous HF does not appear to be a sufficiently strong oxidant to

3'

Ti 3+ + HF(g) = 1/2 H2(g) + Ti4+ + F- E O = -0.59 0.05 v

-c-

for which log K = -3.3 k 0.3. Since the activity coefficients for the

solutes are defined as unity, the expression for the equilibrium constant for reaction (23) will give:

Expressing the partial pressures in atmospheres, we find that, even with nearlypureHF as the gas phase, the equilibrium concentration of Ti is extremely low as compared with the Ti3+ concentration:

4+

1

10 100

0,0004

0 a 002

O t O 0 5

7. BEHAVIOR OF TITANIUM IN OXIDE PRECIPITATION PROCESSES

Oxide precipitation is being studied as an alternative to fluorination-- reductive extraction for isolating protactinium and subsequently removing

uranium from MSBR fuel salt.16 Pa2o5 ; 17 9 18 consequently, the salt would have to be treated with an oxidant such as HF to convert Pa4+ to Pa5+ prior to the precipitation step. shown in Sect. 6, HF is not a sufficiently strong oxidant to convert Ti3+ to Ti . No information could be found in the literature on the behavior

of Ti3' in molten fluoride salts containing dissolved oxide. work would be required to determine this behavior.

Protactinium would be precipitated as

As

4+

Experimental

Some information on the apparent solubility of T i 0 2 in fluoride melts

is available.

U02 in LiF-BeF2-ThF4 (72-16-12 mole %) at 600"c. BaesZ0 equilibrated Ti02 with LiF-BeF2-ThF4 (72-16-12 mole %) at 600" c, The equilibrium titanium concentration in the salt was about 40 w t ppm,

which is lower than the solubility of U02 in this salt.

Mailen'' had indications that Ti02 was less soluble than

Similarly, Bamberger and

8. ACKNOWLEDGMENTS

The author thanks J. F. Land for conducting the experimental portion of this work. Analyses were provided by the group of W, R. Laing, ORNL Analytical Chemistry Division,

14

9. REFERENCES

1.

2.

3-

4.

5. 6. 7. 8.

9-

10.

11.

12.

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14 e

15 0

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W. L. Carter, E, L. Nicholson, and L. E. McNeese, MSR Program Semiann. Progr. Rept. Aug. 31, 1971, ORNL-4728, p. 179. C. F. Baes, Jr., "The Chemistry and Thermodynamics of Molten Salt

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c0~~-690801 (1969), p. 617. D. L o Manning, ORNL, personal communication, Nov. 19, 1971. We R. Grimes, Nucl. Appl. Technol. - 8(2), 137 (1970). H. E. McCoy, ORNL, personal communication, Feb. 22, 1972. J. H. DeVan and R. B. Evans 111, "Corrosion Behavior of Reactor Materials in Fluoride Salt Mixtures," in Corrosion of Reactor Materials, Vol. 11, p. 557, IAEA, Vienna, 1962. C. D. Hodgman (ed.), Handbook of Chemistry and Physics, 36th ed.,

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of Uranium, Thorium, and Rare Earths from Molten LiF-BeF2 into Liquid Li-Bi Solutions, ORNL-TM-2486 (March 1969). L. M. Ferris, J. C, Mailen, and F. J, Smith, "Estimated Free Energies of Formation of Some Lanthanide and Actinide Halides at 600"-800"c Using Molten Salt-Liquid Metal Distribution Coefficient Data," J.

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20. C. E. Bamberger and C. F. Baes, Jr., MSR Program Semiann. Progr. Rept. Feb. 28, 1970, ORNL-4548, p. 140.

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