ORNL-TM-2180

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2

.. '

OAK RIDGE NATIONAL LABORATORY operated by

UNION CARBIDE CORPORATION NUCLEAR DIVISION

for the U.S. ATOMIC ENERGY COMMISSION

ORNL- TM-2180

D A T E - M a r c h 2 6 , 1968

ELECTRICAL CONDUCTIVITY OF MOLTEN FLUORIDES.

A REVIEW.

G. D. Robbins

ZI . "b, c NOTICE This document contains information of a preliminary nature

and was prepared primarily for internol use at the Oak Ridge National Loborotory. It is subject to revision or correction and therefore does not represent o final report.

LEGAL NOTICE _ _ _ ~

This report was prepared os an occount of Government sponsored work.

nor the Commission, nor any person acting on behalf of the Commission:

A. Maker any worronty or representation, expressed or implied, wi th respect to the accuracy,

completeness, or usefulness of the information contoined i n th is report, or that the use of

any information, apparatus, msthod, or process disclosed in this report may not infringe

privately owned rights; or

Assumes any l iabi l i t ies wi th respect to the use of, or for damages resulting from the use of

any information, opporatus, method, or process disclosed in th is report.

Neither the United States,

B.

As used in the obove, “person acting on behalf of the Commission” includes ony employee or

controctor of the Commission, or employee of such controctor, t o the extent that such employee

or contractor of the Commission, or employee of such controctor prepares, disseminates, or

provides access to, any informotion pursuont t o his employment or contract with the Commission,

or h is employment wi th such controctor.

r

A

iii


A REVIEW

G. D. Robbins

Reactor C h e m i s t r y D i v i s i o n Oak R idge N a t i o n a l L a b o r a t o r y

Oak R i d g e , Tennessee

ABSTRACT/SUMMARY

A r e v i e w o f e lec t r ica l c o n d u c t i v i t y measurements

i n m o l t e n f l u o r i d e s y s t e m s c o v e r i n g t h e p e r i o d 1927 t o 1967 h a s been made, w i t h p a r t i c u l a r emphas i s on e x p e r i -

m e n t a l a p p r o a c h . I t is p o i n t e d o u t t h a t t h e common

p r a c t i c e of m e a s u r i n g r e s i s t a n c e w i t h a Wheats tone

b r i d g e h a v i n g a p a r a l l e l r e s i s t a n c e and c a p a c i t a n c e ,

R and C i n t h e b a l a n c i n g arm c a n r e s u l t i n c o n s i d e r -

able error i f t h e r e l a t i o n R P = Rs[ 1 + Rp2CpZ (2IIf)’] is n o t employed i n d e t e r m i n g t h e s o l u t i o n r e s i s t a n c e , Rs. The f r e q u e n c y dependence o f t h e measured r e s i s t a n c e a n d t h e p r a c t i c e o f e x t r a p o l a t i n g measured r e s i s t a n c e s t o

i n f i n i t e f r e q u e n c y v e r s u s 1/df is examined i n terms of e l e c t r o d e p r o c e s s c o n c e p t s . A summary o f e x p e r i m e n t a l

a p p r o a c h e s a n d r e s u l t s f o r 56 m o l t e n f l u o r i d e s y s t e m s

P P’

is p r e s e n t e d .

.~

r------lEGAL

I

1


A REVIEW*

I n t r o d u c t i o n

I n v e s i t g a t i o n of t h e e lec t r ica l c o n d u c t i v i t y o f m o l t e n

s a l t s y s t e m s h a s been a n area o f l i v e l y r e s e a r c h i n r e c e n t

y e a r s , a n d a number o f r e v i e w s have a p p e a r e d which deal w i t h

t h i s a s p e c t of t r a n s p o r t phenomena. (1-3)

i n t e n t o f t h i s r e v i e w to l i m i t i t s e l f t o t h e s u b j e c t o f

c o n d u c t a n c e measurements i n m o l t e n f l u o r i d e s . The c o n t a i n m e n t

I t w i l l be t h e

p rob lems e n c o u n t e r e d w i t h t h e s e materials set them a p a r t from

t h e o t h e r m o l t e n h a l i d e s w i t h respect t o e x p e r i m e n t a l d i f f i -

c u l t i e s and t h e c o n s e q u e n t p r e c i s i o n o f measurement which c a n

be e x p e c t e d . By l i m i t i n g t h i s r e v i e w t o f u s e d f l u o r i d e s , it

is hoped t h a t s u f f i c i e n t d e t a i l s may be p r e s e n t e d t o p e r m i t

w o r k e r s i n t h e f i e l d t o o b t a i n a comprehens ive s u r v e y c o v e r i n g

t h e p e r i o d 1927 t o 1967 . To o u r knowledge, no s u c h r e v i e w

e x i s t s which a d d r e s s e s i t s e l f t o t h e q u e s t i o n s which w e pose

be l o w .

Many i n v e s t i g a t i o n s i n t h e p a s t have been c o n c e r n e d w i t h

c r y o l i t e - c o n t a i n i n g melts b e c a u s e o f t h e i r r e l e v a n c e t o t h e

aluminum i n d u s t r y , and a r e v i e w o f t h e s e s y s t e m s h a s been g i v e n

by G r j o t h e i m and Mat i a sovsky .

p o r t p r o p e r t i e s of f u s e d f l u o r i d e s i n g e n e r a l h a s r e s u l t e d from

t h e i r u s e as f u e l , b l a n k e t , and c o o l a n t materials i n mol t en

s a l t reactors.

Renewed i n t e r e s t i n t h e t r a n s - (4)

( 5 )

* R e s e a r c h s p o n s o r e d by t h e U.S. A t o m i c Energy Commission

unde r c o n t r a c t w i t h t h e Union Carbide C o r p o r a t i o n .

V

2

Because o f t h e h i g h s p e c i f i c c o n d u c t a n c e of

e x p e r i m e n t a l a p p r o a c h e s s a l t s (1-6 Q - 1 cm-' 1, (6

most mol t e n

have t e n d e d

t o f a l l i n t o t w o groups''):

c e l l s , which r e s u l t s i n a c e l l c o n s t a n t o f s e v e r a l hundred

c m - ' , t h e c a p i l l a r i e s b e i n g c o n s t r u c t e d from e l e c t r i c a l l y

i n s u l a t i n g ma te r i a l s ; or ( 2 ) u s e of metall ic ce l l s i n which

t h e c o n t a i n e r is u s u a l l y one e lectrode, w i t h a s e c o n d e l e c t r o d e

p o s i t i o n e d i n t h e m e l t . The l a t t e r t y p e o f c e l l s have c e l l

c o n s t a n t s o f t h e o r d e r of a f e w t e n t h s c m - ' , r e q u i r i n g v e r y

a c c u r a t e m e a s u r i n g b r i d g e s and d e t e r m i n a t i o n of lead resist-

a n c e s . S i n c e t h e v a l u e of measured r e s i s t a n c e i n s u c h ce l l s

is less t h a n la, errors due t o t e m p e r a t u r e g r a d i e n t s , c h a n g e s

i n c e l l c o n s t a n t w i t h t e m p e r a t u r e , and p o l a r i z a t i o n become a

s i g n i f i c a n t problem. Hence, c e l l s of t y p e (1) are c l e a r l y

desirable for u s e i n m o l t e n s a l t s . However, e l e c t r i c a l l y

i n s u l a t i n g mater ia l s for c a p i l l a r y c o n s t r u c t i o n which are

r e s i s t a n t t o a t t a c k by mol t en f l u o r i d e s are scarce.

(1) u s e of c a p i l l a r y - c o n t a i n i n g

Measurement o f e l e c t r i c a l c o n d u c t i v i t y i n m o l t e n s a l t s

d i f f e r s from s imi l a r s t u d i e s i n aqueous s o l u t i o n s i n s e v e r a l

s i g n i f i c a n t a s p e c t s . I t is o f t e n t h e p r a c t i c e t o employ some

form of a Wheats tone b r i d g e '7) ( F i g u r e 1) i n which t h e t w o

u p p e r arms a re ma tched , s t a n d a r d r e s i s t a n c e s , and t h e imped-

a n c e of t h e c e l l i n one l o w e r a r m is b a l a n c e d by a v a r i a b l e

impedance, 2 , i n t h e f o u r t h a r m . The b a l a n c i n g impedance is

u s u a l l y a v a r i a b l e r e s i s t a n c e ,

c o n n e c t e d i n p a r a l l e l . The s o l u t i o n r e s i s t a n c e , R s , and

s o l u t i o n - e l e c t r o d e i n t e r f a c i a l c a p a c i t a n c e s , Cs , i n t h e c e l l

are c o n s i d e r e d t o be i n s e r i e s ( 8 ) ( F i g u r e 2 ) .

cP , and c a p a c i t a n c e , RP

By r e q u i r i n g

3

v a

one e l e c t r o d e t o have a much g r e a t e r area t h a n t h e o t h e r , t h e

impedance associated w i t h s u c h a n e l e c t r o d e becomes n e g l i g i b l e ,

and t h e e q u i v a l e n t c i r c u i t r e d u c e s t o t h a t shown i n F i g u r e 3 .

( A l t e r n a t i v e l y , one c a n employ e l e c t r o d e s o f s i m i l a r area and

t r e a t t h e c a p a c i t a n c e r e s u l t i n g from t h e i r series c o m b i n a t i o n

.) The c a p a c i - 1 - 1 -r+r as a s i n g l e t o t a l c a p a c i t a n c e , S I 3.2

t a n c e r e s u l t i n g from t h e electrode leads is i n p a r a l l e l across

t h e e n t i r e c e l l shown i n F i g u r e 2 . However, a t f r e q u e n c i e s

o r d i n a r i l y employed, and w i t h some care i n p o s i t i o n i n g , t h i s

c a p a c i t a n c e can be n e g l e c t e d .

When a s i n u s o i d a l a l t e r n a t i n g p o t e n t i a l is impressed a c r o s s

t h e c e l l , a s i n u s o i d a l a l t e r n a t i n g c u r r e n t r e s u l t s . If t h e

p o t e n t i a l is i n s u f f i c i e n t t o c a u s e e l e c t r o c h e m i c a l r e a c t i o n s

t o o c c u r a t t h e electrodes, t h e e q u i v a l e n t c i r c u i t o f F i g u r e 3

is v a l i d , a n d t h e i n t e r f a c i a l c a p a c i t a n c e is c h a r g e d and d i s -

c h a r g e d d u r i n g e a c h h a l f - c y c l e t h r o u g h t h e s o l u t i o n r e s i s t a n c e .

By employ ing a n o s c i l l o s c o p e as t h e n u l l d e t e c t o r , one c a n

b a l a n c e t h e c e l l impedance w i t h t h e p a r a l l e l c o m b i n a t i o n of R

and Cp shown i n F i g u r e 1.

s tandard r e s i s t a n c e s are matched) are

P The two b a l a n c e e q u a t i o n s (when t h e

C RS + P = 1 Rp cS

and

RsRpCsCp(211f)Z = 1

These may be combined i n t o

RP = R s [ l -F CpZRp2(211f)2] ( 3 1

I t is o f t e n t h e p r a c t i c e t o e q u a t e R ( t h e v a l u e o f t h e bridge

d i a l s ) t o Rs ( t h e t r u e s o l u t i o n r e s i s t a n c e ) . (9y10) ( I n t h e case

o f unmatched s t a n d a r d r e s i s t o r s , t h e i r r a t i o is u s e d . ) T h i s

P

4

is u s u a l l y v a l i d i n aqueous s o l u t i o n s where Rs and Cs are s u c h

as t o r e s u l t i n R 2 C 2(211f)2 b e i n g n e g l i g i b l y smaller t h a n

u n i t y . However, i n mol t en s a l t s e x p e r i m e n t a l c o n d i t i o n s fo r

t h e measurement o f e l ec t r i ca l conduc tance can r e s u l t i n

P P

c o n s i d e r a b l e e r r o r i f t h e s e e q u a t i o n s are n o t c o n s i d e r e d when

u s i n g p a r a l l e l components i n t h e b a l a n c i n g arm of a Wheats tone

bridge. For example , on r e w r i t i n g e q u a t i o n s ( 2 ) and ( 3 ) i n

t h e form

R p = R s [ l 1 1

4- Cs2Rs2 (211f)2 (4)

i t is e v i d e n t t h a t i n mol t en s a l t s , where RsZ may be smaller by

a f a c t o r o f 1 O 1 O t h a t i n aqueous s o l u t i o n s (Cs h a v i n g a p p r o x i -

m a t e l y similar v a l u e s ( 1 3 ) ) , a n awareness o f t h e s e r e l a t i o n s is

*

n e c e s s a r y .

U s e o f e q u a t i o n ( 3 ) t o c a l c u l a t e Rs is l i m i t e d by t h e

a c c u r a c y w i t h which t h e v a l u e s of t h e v a r i a b l e capacitance,

C p , and t h e f r e q u e n c y are known.

can be a v o i d e d by employing a b r i d g e i n which t h e b a l a n c i n g

components are i n s e r i e s . ( 1 4 )

chemica l r e a c t i o n , t h e v a l u e of Rs is w e l l r e p r e s e n t e d by t h e

r e a d i n g on t h e b a l a n c e d b r i d g e ; however, t h i s method does

r e q u i r e t h e u s e of l a r g e c a p a c i t o r s .

U s e o f p r e c i s i o n c a p a c i t o r s

Then i n t h e case of no electro-

When a s u f f i c i e n t l y l a r g e a . c . p o t e n t i a l is impressed on

the c e l l t h a t c h a r g e is t r a n s f e r r e d a c r o s s t h e s o l u t i o n -

e l e c t r o l y t e i n t e r f a c e s d u r i n g p a r t o f e a c h h a l f - c y c l e , corres-

ponding t o a n e l e c t r o c h e m i c a l r e a c t i o n , t h e s i t u a t i o n becomes

c o n s i d e r a b l y more complex. However, i t is under t h e s e c o n d i t i o n s

W

~ ----- by J o n e s and B o l l i n g e r (I1) w a s a p p r o x i m a t e l y 5 0 , 0 0 0 0.

and Waddington ( 1 2 ) r e p o r t a measured r e s i s t a n c e o f a p p r o x i m a t e l y 0 . 5 $2 i n mol t en c r y o l i t e .

The measured r e s i s t a n c e of 0 . 0 0 0 5 - m K C 1 i n c e l l s employed

C u t h b e r t s o n

5

W . t h a t c o n d u c t i v i t y measurements are u s u a l l y pe r fo rmed . Based

on t h e work o f J o n e s and C h r i s t i a n , ( 1 5 ) r e s i s t a n c e i n aqueous

s y s t e m s is g e n e r a l l y measured a t a ser ies o f f r e q u e n c i e s and

e x t r a p o l a t e d t o i n f i n i t e f r e q u e n c y employ ing t h e f u n c t i o n a l

form f-’. U s e of t h i s p a r t i c u l a r f u n c t i o n a l form is a t t r i - 1 -

b u t e d (15) t o Warburg ( 16’ 17) and Neumann (18) who, on t h e basis

o f F i c k ’ s l a w s o f d i f f u s i o n , p r e d i c t e d t h a t t h e p o l a r i z a t i o n

r e s i s t a n c e ( t h a t p a r t o f t h e measured r e s i s t a n c e due t o elec-

t r o d e p o l a r i z a t i o n ) was i n v e r s l y p r o p o r t i o n a l t o d f .

App ly ing t h e c o n c e p t s r e s u l t i n g from electrode p r o c e s s

one may e n v i s i o n t h e e q u i v a l e n t c i r c u i t shown s t u d i e s , i n F i g u r e 4 f o r an e l e c t r o d e - s o l u t i o n i n t e r f a c e across which

(19-21)

c h a r g e is b e i n g t r a n s f e r r e d . Z r e p r e s e n t s t h e impedance

associated w i t h t h e r e a c t i o n , which is i n p a r a l l e l w i t h t h e

s o l u t i o n - e l e c t r o d e i n t e r f a c i a l c a p a c i t a n c e . Under t h e e x a c t -

r

i n g a s s u m p t i o n s o f f a r a d a i c impedance s t u d i e s , z may be re-

p r e s e n t e d by a f r e q u e n c y - i n d e p e n d e n t r e s i s t a n c e , 0, i n series

w i t h a f r equency-dependen t impedance, -W-, t h e Warburg imped-

r

a n c e . The l a t t e r is c o n v e n i e n t l y r e p r e s e n t e d as a r e s i s t a n c e

a n d c a p a c i t a n c e i n series, Rr and C r , a t c o n s t a n t f r e q u e n c y

( F i g u r e 5 ) . A t a g i v e n f r e q u e n c y t h e impedances r e s u l t i n g from

Rr and Cr are e q u a l . 1

However, b o t h v a r y as f-”.

The a s s u m p t i o n s upon which t h e m a t h e m a t i c a l a n a l y s i s

which r e s u l t s i n f-” dependance o f Rr a n d 2nfcr rests i n c l u d e

1 ) s e m i - i n f i n i t e l i n e a r d i f f u s i o n o f r e a c t a n t s and p r o d u c t s

and 2 ) a small a m p l i t u d e a .c . p o t e n t i a l supe r imposed on a n e t

1 1

d.c . p o l a r i z i n g p o t e n t i a l . These are n o t t h e c o n d i t i o n s of

c o n d u c t i v i t y measurements. However, d u r i n g t h a t p a r t of e a c h

6

h a l f - c y c l e d u r i n g which r e a c t i o n is o c c u r r i n g a t t h e electrodes,

t h e e q u i v a l e n t c i r c u i t o f F i g u r e 4 is a u s e f u l c o n c e p t , even

though 2 may n o t be treated r i g o r o u s l y a c c o r d i n g t o F i g u r e 5.

T h a t t h e above c o n s i d e r a t i o n s lead t o t h e same f r e q u e n c y

dependence as t h a t e x p e r i m e n t a l l y d e t e r m i n e d f o r many conduc-

t i v i t y measurements (15? r e n d e r s t h i s c o n c e p t u a l a n a l y s i s

wor th cons i d e r i n g .

r

I n b r i e f , t h e n , one may c o n s i d e r t h e e q u i v a l e n t c i r c u i t

o f F i g u r e 4 as a rough a n a l o g o f t h e s o l u t i o n r e s i s t a n c e ,

e l e c t r o d e - s o l u t i o n i n t e r f a c i a l c a p a c i t a n c e , and r eac t ion

impedance ( b e a r i n g i n mind t h a t Zr c a n n o t be r e p r e s e n t e d

e x a c t l y by any f i n i t e c o m b i n a t i o n o f r e s i s t a n c e , c a p a c i t a n c e ,

and i n d u c t a n c e which w i l l r e n d e r i t f r e q u e n c y i n d e p e n d e n t ) .

D u r i n g t h a t p a r t o f e a c h h a l f - c y c l e i n which t h e p o t e n t i a l is

below t h a t which r e s u l t s i n an e l e c t r o d e r e a c t i o n , t h e e q u i -

v a l e n t c i r c u i t o f F i g u r e 4 r e d u c e s t o t h a t o f F i g u r e 3 , i . e . ,

Z becomes i n f i n i t e . I t is a l s o u s e f u l t o c o n s i d e r t h e e q u i -

v a l e n t c i r c u i t o f F i g u r e 4 i n view o f t h e p r a c t i c e o f e x t r a -

p o l a t i n g measured r e s i s t a n c e t o i n f i n i t e f r e q u e n c y . I t c a n

be s e e n t h a t a t i n f i n i t e f r e q u e n c y t h e impedance o f Cs is

i n f i n i t e l y less t h a n t h a t of Z r , and F i g u r e 4 a g a i n r e d u c e s

t o F i g u r e 3 .

r

I t s h o u l d be emphas ized t h a t w h i l e one measu res res i s t -

a n c e a t a series o f f r e q u e n c i e s and e x t r a p o l a t e s t o i n f i n i t e

f r e q u e n c y , one does n o t make measurements a t f r e q u e n c i e s

which a p p r o a c h i n f i n i t y . I n f a c t , v e r y h i g h f r e q u e n c y measure-

ments ( i n t h e megahe r t z r a n g e ) are t o be a v o i d e d b e c a u s e of t h e

i n c r e a s e d a d m i t t a n c e of t h e leads and t h e f a c t t h a t a t v e r y h i g h

f r e q u e n c i e s one ceases t o measure a p r o p e r t y a s s o i c a t e d w i t h i o n i c

7

m o b i l i t y and o b s e r v e s p r o p e r t i e s a s s o c i a t e d w i t h d i p o l e moments

and p o l a r i z a b i l i t i e s . Hence t h e q u e s t i o n o f c o n c e r n r e m a i n s

v i z , wha t f u n c t i o n a l form of t h e f r e q u e n c y d o e s one employ t o

e x t r a p o l a t e t h e measured r e s i s t a n c e t o i n f i n i t e f r e q u e n c y ?

-

Robinson and S t o k e s (22) c o n s i d e r t h i s q u e s t i o n i n terms

o f electrode p r o c e s s c o n c e p t s as a p p l i e d t o aqueous media and

g i v e b a l a n c e e q u a t i o n s f o r a b r i d g e w i t h a p a r a l l e l - c o m p o n e n t

b a l a n c i n g a r m , a s suming v a r i o u s r e l a t i v e magn i tudes of Rs, 0,

and Rr . f-' dependence is p r e d i c t e d .

Under t h e c o n d i t i o n s employed by J o n e s and C h r i s t i a n , (15 ) 1

Robinson and S t o k e s c o n c l u d e t h a t

one s h o u l d measure r e s i s t a n c e as a f u n c t i o n o f f r e q u e n c y and

e x t r a p o l a t e t o i n f i n i t e f r e q u e n c y i n a c c o r d a n c e w i t h t h e o b s e r v e d

b e h a v i o r . T h i s is a l s o t h e c o n c l u s i o n of N i c h o l and FUOSS,

who o b s e r v e d a f - I f r e q u e n c y dependence of r e s i s t a n c e i n me thano l

( 2 3 )

s o l u t i o n s .

I n m o l t e n s a l t s f r e q u e n c y dependence of t h e r e s i s t a n c e h a s

been r e p o r t e d a t p o l a r i z i n g p o t e n t i a l s much lower t h a n r e q u i r e d

for f a r a d a i c p r o c e s s e s . ( 2 4 * 2 5 ) Buckel and T s a u s s o g l o u (2 6 , have

found t h a t measured r e s i s t a n c e v s . f r e q u e n c y p l o t s show a p l a t e a u

in t h e range 10-100 k H z i n aqueous potassium c h l o r i d e a n d m o l t e n

p o t a s s i u m bromide. They s u g g e s t t h a t e x t r a p o l a t i o n of r e s i s t a n c e

v s . f-" would lead t o e r r o n e o u s c o n d u c t a n c e s and t h a t one s h o u l d

s t u d y f r e q u e n c y d i s p e r s i o n i n a p a r t i c u l a r a p p a r a t u s and se lec t

a f r e q u e n c y - i n d e p e n d e n t r e g i o n f o r p e r f o r m i n g c o n d u c t i v i t y

-

1

-

e x p e r i m e n t s . D e N ~ o i j e r ' ~ ~ ) r e p o r t e d t h a t i n m o l t e n n i t r a t e 1 -

m e l t s p l o t s o f measured r e s i s t a n c e E. f - 2 were n o t l i n e a r , b u t

approached l i n e a r i t y as t h e f r e q u e n c y approached i n f i n i t y . H i s

8

v a l u e s o f measured r e s i s t a n c e a t 2 0 kHz o n l y d i f f e r e d from v a l u e s W

e x t r a p o l a t e d t o i n f i n i t e f r e q u e n c y by a b o u t 0 . 1 %. W i n t e r h a g e r

and Werner ( 2 8 ' 2 9 ) have c o n s i d e r e d f r e q u e n c y d i s p e r s i o n i n m o l t e n

n i t r a t e , c h l o r i d e , and f l u o r i d e m e l t s and have a p p l i e d "electr ical

l o c u s c u r v e t h e o r y " (30) t o t h e i r r e s u l t s o b t a i n e d employ ing a

Thomson-type b r i d g e . They c o n c l u d e t h a t a t s u f f i c i e n t l y h i g h

f r e q u e n c i e s measured r e s i s t a n c e becomes i n d e p e n d e n t o f f r e q u e n c y ,

and t h e y employ a m e a s u r i n g f r e q u e n c y of 50 kHz. T h e r e f o r e , i n

t h i s r e v i e w p a r t i c u l a r a t t e n t i o n w i l l be g i v e n t o t h e o b s e r v e d

b e h a v i o r of r e s i s t a n c e w i t h f r e q u e n c y and t o t h e c o n d i t i o n o f

t h e electrode s u r f a c e s , s i n c e i n aqueous mdeia i t is observed

t h a t f r e q u e n c y d i s p e r s i o n is less i n cases o f heavy p l a t i n i z a -

t i o n ( i n c r e a s e d C,). (11)

I n l i g h t o f t h e f o r e g o i n g d i s c u s s i o n t h e f o l l o w i n g in fo rma-

t i o n w a s s o u g h t from e a c h s t u d y which was c o n s u l t e d :

A . C e l l m a t e r i a l , i ts g e n e r a l d e s i g n , and t h e r e s u l t i n g c e l l

c o n s t a n t , ( ! , / a ) , or g e n e r a l r a n g e o f measured r e s i s t a n c e ,

B. E l e c t r o d e m a t e r i a l , s h a p e , s i z e , and s u r f a c e c h a r a c t e r .

C . Type of b r i d g e employed. *

D . F requency r a n g e employed.

E . Dependence o f measured r e s i s t a n c e on f r e q u e n c y .

F. V o l t a g e a p p l i e d t o t h e b r i d g e .

G. R e s u l t s . R e s u l t s a re r e p o r t e d e i t h e r i n terms of t h e

* The g e n e r a l t y p e s of b r i d g e c i r c u i t s employed a re shown

i n Appendix I a s an a i d i n d e s c r i p t i o n . The c i r c u i t s a c t u a l l y employed were u s u a l l y m o d i f i e d v e r s i o n s of t h o s e shown. For d e t a i l s of c i r c u i t y , t h e r e a d e r is r e f e r r e d t o t h e c i t e d work.

9

Y s p e c i f i c c o n d u c t a n c e , K , t h e e q u i v a l e n t c o n d u c t a n c e , Aeq,

or t h e molar c o n d u c t a n c e , Am.

as

These q u a n t i t i e s a re d e f i n e d

e q u i v a l e n t w e i g h t d e n s i t y Aeq = K .

Am = .mo lecu la r w e i g h t d e n s i t y

( 6 )

( 7 )

These q u a n t i t i e s are r e p o r t e d a s f u n c t i o n s o f t e m p e r a t u r e f o r

t h e minimum, maximum, and one i n t e r m e d i a t e v a l u e f o r p u r e s a l t s .

For b i n a r y m i x t u r e s a 3 x 3 g r i d a l s o s t a t i n g t h e extremes and

one i n t e r m e d i a t e v a l u e o f c o m p o s i t i o n is employed where conven-

i e n t . C o n d u c t i v i t i e s o f m i x t u r e s o f more t h a n two components

a re p r e s e n t e d i n a manner d e s i g n e d t o convey maximum i n f o r m a t i o n .

The t a b u l a t i o n is o r d e r e d a c c o r d i n g t o t h e s y s t e m unde r

c o n s i d e r a t i o n ; and w i t h i n e a c h s y s t e m , by d a t e o f p u b l i c a t i o n ,

t h e e a r l i e s t a p p e a r i n g f i r s t . Where one i n v e s t i g a t i o n h a s

c o v e r e d s e v e r a l s y s t e m s , a c r o s s r e f e r e n c e is g i v e n . A d d i t i o n a l

v a l u e s of K and A may be found i n J a n z ' s Molten S a l t s Handbook

f o r many o f t h e s y s t e m s r e p o r t e d h e r e . A s p r e v i o u s l y s t a t e d ,

t h e p r i m a r y c o n c e r n o f t h i s r e v i e w is t o p i c s A-F. The r e s u l t s

p r e s e n t e d h e r e i n are g i v e n fo r compar i son and c o m p l e t e n e s s and

w e r e , i n a l l cases, t a k e n from t h e o r i g i n a l p u b l i c a t i o n s

( e x c e p t i o n : Appendix 11).

(31 )

I t w i l l be o b s e r v e d below t h a t a number of p u b l i c a t i o n s

have n o t a d d r e s s e d t h e m s e l v e s t o some of t h e q u e s t i o n s r a i sed

above . If t h i s r e v i e w s e r v e s o n l y t o remedy t h i s p r a c t i c e , i t

is c o n s i d e r e d j u s t i f i e d .

TABULATION

r,- . . .. -~

;+- _I

- . . . . . ~

e l e c t r o d e s .

l ; r aph t tp c r u c i b l e ( i d 3.5", 5" ~ ( m t a i n i n g L BN c y l i n d e r s ( i d - enoase,d I " vraDhitP and e n l a r g e d a t toI)

- ~ - _ _ ___

.. . t o sccamodate r ~ l r r t t ' o d e a . ( f / a j 100cn'

Pt c ruc ib l e ( 4 0 0 ml), ( ? / a ) 0.0815cm' Hemisphe r i ca l P t e l e c t r o d e f i . - ~ _ _ _ _ _ ~

p l a t i n i z e d o r i g i n a l l y .

_. P t c r u c l b l e (0.2 mm wall) IR) - 0.02 R Crucible and a P t c y l i n d e r (area - 2 cm') , bo th p l a t l n i z e d

$ 3 i i 3

li

iil

I ii 2 # 2

f I'ridge Range VPP

( D e t e c t o r ) (kHz) R VII. f (v ) - -.

Wheatstone ( t e l e p h o n e )

S p e c i a l l y d e v e l N.S. oped by E. F a i r s t e i n . (34) f range-.2-6 kH R range-.oi-ion T ( " sc i l l 0 sc"pe )

Wheats tone, no capac i t u r s ( o s c i l l o s c o p e )

(osrilloncope)

Jones ( n u l l d e t e c t o r )

Ke lv in

I

N.S. - Not N.S S t a t e d

T a p p r e c i a b l y between 1 and

a t lower f , i ndependen t a t

1-20 kHZ

e x t r a p o l a t e d t o f - m

~

91

42 #2

Results

9 0 5 20.3 9 5 0 23.4 9 9 5 27.2

1040 5.74 I O R O 5.95 (*several %)

997 w = 5.2,-

1020 Y - 5.15 (* 1%)

0-1.05 .Xeq ~ 1 1 3

1003 4.960

1138 5 . 3 3 5 ion6 5 . 1 7 9

K = 5.29 + 5.64x10-'(T-1I13O0C)

e-1.2 Aeq - 156.6 ( t 1 9

860 4.14 9 0 0 1.28 1000 4.77 (is t o in%) 869 Y - - 3 . 4 9 3 + 1.480x10-zT(oC) 1040

-6.60R~lO'~T~ ( o - . o o ~ ~ - ~ c ~ - ~ )

14 KF 2 R ' 4 # 4 2 9

#4 iy4

2 2

z i

2 4

2 5

2 6

CuF, 2 8 #4 #4 #4 #4

ZnF, 2 8 i , 4 #4 #4 #4

PbF, 28 l ~ 4 #4 #4 8 4

KBF, 2 8 1'4 #4 #4 #4

29

2 9

2 9

L 9

Na,TaF, 2 8 114 #4 #4 #4 2 9

2 7 K,TiF, 2 8 "4 #4 #4 #4 2 9

VPP ( V )

#3

Y4

_. _.

__

- N.S.

Y 2

#15

__

-

__ #4 - N . S .

__ N . S . _.

#4

f C e l l B r i d g e Range

S y s t e m Rcf [R) or ( j / a ) E l e c t r o d e s ( D e t e c t o r ) (kHz) R vs . f

#3

$4 8 5 9 3 . 5 7 3 9 3 8 3 . 7 9 3 1 0 1 2 4 . 0 2 1

9 0 5 3 . 7 7

725- u = - 4 . 5 1 1 + 1 . 6 4 2 ~ 1 0 - ' T ( ~ C ) 9 2 1 - 7 . 6 3 Z X ~ O - ~ T ~ ((I-. 009R-' cm-' )

737 2 . 5 1 784 2 . 7 3 8 5 2 3.03

(+2%) v a r i e d <0 .3% - #2

J o n e s . 5 -1 ( :: 4 3 cOntalner VgO, s i n g l e c r y s t a l , d i p c e l l ; P t C o n t a i n e r and P t e l e c t r o d e

3 3 :i2 # 2 # 2 *2

I #15 #15

#4 5 9 0 4 .0* 6 7 0 6.0*

f i n d e p e n d e n l 2-10 kHz

Pt -Rh (20%) c r u c i b l e ( i d = 2", h t . = 2+*) C r u c i b l e and Pt-Rh (20%) bob " W h e a t s t o n e 2-10 ( ? / a ) = .ll or .28cm-I R-C b r i d g e "

( s c o p e or VTVM) 7 0 0 0 . 7 1 x 8 0 0 1 5 . 3 x lo-' 9 5 0 236 x

1 4 1 8 Y = 3 . 5 6

( t l O % )

2 0 I CaF, 146 I C a r b o n c r u c i b l e ] Y o e l e c t r o d e s I N.S. 1 N . S . N . S .

#4 9 4 0 4 . 7 5 * 9 9 0 5 . W -2

#4 #4

# 4

#4

-

-

t-J 9 7 0 2.2*

1 1 1 0 2.5* P 900 3.2,* 9 6 0 3.7 '

# 4

#4 8 2 0 5 .1* 1 0 0 0 5.8.

5 4 5 1 . 0 5 2 569 1 .1Zb 652 1 . 2 4 5

#4 #4

5 4

#4 __

702 1 . 1 6 5 733 1 . 3 9 6 8 1 4 1 . 5 9 5

#4

#4 8 4 3 1 . 3 4 6 888 1 . 4 3 5 9 7 6 1 . 6 0 4 .. 747 0 . 7 2 8 5 8 0 0 0 . 9 1 9 3 8 8 7 1 . 0 3 6 6

6 4 d14

.. . . .- . I ,z ,AIF6

- .. . N ~ , A I F ;

Nn 3 A l F,,

N.7, A 1 F,

Nn,AlF6

Nil, AIFa

Nn,AIF,

K,AIF,

.~ ~~..

I . i F + ThF,

LxFtUF,

-~ NaF + CaF, ( 6 7 W'l,)

: f , Y6 i I 1000 2.80 1040 2.90 Aeq 2 . 7 4 4 - && 1080 3.00 ( s e v e r a l 9

Y7 #7

#3

3. . 1013 M - 2.82* A-

1000 2.80* 284 a t 10100 lo60 2.958 296 a t 1040'

I'3

Y4 1 ' 1 H4

Thomaon p l u s p h a s e I n d i c a t n

h n t a i n e r a n d P t r o d ( d - 3 mm)

Y3

1 0 0 0 2.84 in4n 2.92 loan 3.00

H J 1 h 1000 2.22' 1060 2.42. -

15 LIF ThF &(myq)

78-22(.4.) - 2.50 + 7.58x10-'(T-64OoC)

I - 7.14 + 10.97x10-'(T-H8O0C) Aeq - 117.2. for fl - 1 . 2

.zeq - 2 9 . 9 . for 0 - 1 . 2

,z=q - 3 1 . 0 , for e - 1 . 2 ,*,n 50.2-49.H(rn%) I - 2.13 + 4.19x10-'(T-820°C)

3 7

3 H

.~ > ',

8 5 I - 7.55 + 5.86x10-'(T-900°C)

A" - 9 9 . 3 , for e - 1.2 ~~q - 2 3 . 8 . for e - 1.2 heq - 33.5. for e ~ 1.2

60-4O(n%) x - 2 . l i + 5.68x10-'(T-70O0C)

40-60(m%) x - 2.89 + 3.29x10-'(T-9OO0C)

(114.)

900 4.837 1000 5.373 1 1 0 0 5.879 ( * .5%)

C a r e y - F o s t e r C u r c i b l c and P t rod, b o t h p l a t l n i z e d or l g i n a l l y

.

- . Cell Results

p(oc) u(n-' em-' or .4(cmln-'eq-' (mol-' ) )

?OO 4.441 1000 4.961 1100 5.642

300 4.027 1000 4.602 1100 5.319

( * . 5%)

( * . 5%) * 565' 730' 885'

50-50(m%) 0.52 0.92 1.73

m) E%g3&)m.r(Ts;m

(*lo%)

I = 3.49 + 3.74x10-'(T-90O0C) Aeq - 71.3, for 0 1.2

67-33(&) I - 1.76 + 3.88x10-'(T-80OoC)

50-50(.%) I( = 1.48 + 5.23~10-~(T-800~C) Aeq - 28.1, for e ~ 1.2

Aeq - 28.6, for e * 1.2

K ~ 2.81 + 3.56~lO-~(T-850~C) Aeq = 57.7, for e = 1.2

Aeq - 26.6, for 8 - 1.2 Aeq = 36.9, for e = 1.2

(*lqa)

3%) 65-35(m%) K - 1.37 + 4.65~10-~(T-700~C)

25-75(n%) K = 2.18 + 3.56~lO-~(T-90O~C) (Llqo)

Bridge Ra6ge (Detector) (kHz) Electrodes ___ ~.

1\39

Svs tcm Ket - - #39

- #39

- N.S

- # 5

- #5

- N . S

- #6

- 44 5

- N.:

-

439

1139 1139 I #39 1139 #39

Hot-pressed Be0 tube in a cylindrical Pt crucible <!/s) 24 cm-'

Pt crucible across bottom of the tube and Pt rod at top

N.S. and fl in parallel 0.ci110sc0

115 # 5 k5

#5 #5 #5 I #5

I Described in R e f . 51, not readily available

Pt electrodes N.S. 450' so 800' ?Ti02

w;s;3 ~

40-60(w%) 0,905 6.350 14.105 10-90(w%) 2.408 8.801 14.978

P W

Wheatstone, 5 with balancing d ( o s c i l l o s c o ~ ~

NaBF,

Na,AlF6 #6 #b 1 #6 #6 46 1000D ;040° 1080' A ~ ~ O O o

3.19 3.30 3.41 99 35.7-64.3(a%) 5 0-5 0 (m%) 3.12 3.23 3.33 100

#4 5 I 645 #45 #45 450' 650' 800' - -KT61 40-60(w%) - 2.255 11.495 lO-sO(w%) 0.281 3.601 12.703

#45

7data taxen from grapns) Pt cell N . S . N . S .

(oscilloscope)

Cell .R:, or V / a ) System R r f

CaFI 4 5 3 G r a p h i t e c r u c i b l e K R j W 0.511 Nn,AlF, 12

Wheats tone , d Carbon anode and mol ten A 1 ca thode and e* i n

f Bridge Range

( D e t e c t o r ) (w;)i ;,;;, i f . E l e c t r o d e s

f ' *

f Bridge Range E l e c t r o d e s

1 1 # 3 4 3 ( ti3

/t6 I *6

#P t 3

C u r r e n t e l e c t r o d e s : crucible and N o b r i d g e : P t s p h e r c ; p o t e n t i a l e l e c t r o d e a : VTW and c r u c i b l e and P t c y l i n d e r ammeter s u r r o u n d i n g mphcre

P 5 5 1 5 5

I 4 3 1 1 1 # 3

#4R P48 t 4 8

&6 &6 4 6

# 3 1 3 #3

. 5 N.S. N.S.

455 #55 #55

1010 2 3 2 1040 242

AlF -Na AIF *1070'

2.5-97.5(1%) 7 .5-92 .5(~%) 2 . 6 2 . 8

* T ; h - 0

AlF,-NI AlF 1000' 1040' 10BOo '?:0Oo

11.6-88.4(m%) 2 .68 2.77 2.86 88

740 2.12' 880 2 . R 2 *

. - 82'1(&) . m rn 27 6 7Fb

565 1.18' 675 1 .528 815 1.80'

"- P .r

565' 730' 885' NIP-ZrF -VF 33.5-4046.fim%) m8 m8 n 3 50-46-4 ( d o ) 0.79 1 . 0 8 1.60

* I n t e r p o l a t e d f r a a l i n e a r p l o t of I VS. T

15

REFERENCES

1.

2 .

3 .

4 .

5 .

6 .

7 .

8 .

9 .

1 0 .

11.

1 2 .

J a n z , G . J . and R . D . Reeves , "Mol ten-Sal t E l e c t r o l y t e s - T r a n s p o r t Proper t ies , " i n Adv. i n E lec t rochem.

and E l e c . Eng. , V o l . 5 , C . W . T o b i a s , E d . , John Wiley and

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Sundheim, B. R . , " T r a n s p o r t P r o p e r t i e s of L i q u i d E l e c t r o -

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N e w York, 1964.

--

K l e m m , A . , " T r a n s p o r t P r o p e r t i e s of Molten Sa l t s , " i n

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G r j o t h e i m , K . and K . Ma t i a sovsky , T i d s s k r . -- K j e m i Bergv.

Meta l lurg i , 2 6 , 226 (1966) .

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Yaffe , I . S. and E. R . Van A r t s d a l e n , J. Phys . Chem., - 60,

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Grahame, D . C . , J . Am. Chem. SOC., - 63, 1207 (1941) .

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C u t h b e r t s o n , J. W . and J. Waddington, T r a n s Fa raday SOC. ,

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13 .

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1 5 .

1 6 .

1 7 .

1 8 .

1 9 .

20 .

2 1 .

22 .

23 .

24.

2 5 .

26 .

L i u , C . H . , K . E. Johnson , and H. A . L a i t i n e n , i n Mol t en

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Robb ins , G . D. and J. B r a u n s t e i n , Reactor C h e m i s t r y

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(1935) .

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Warburg, E . , Drude Ann. P h y s i k , - 6 , 1 2 5 (1901) .

Neumann, E . , Wied. Ann. P h y s i k , - 6 7 , 5 0 0 (1899) .

Grahame, D . C . , J . E l e c t r o c h e m . SOC. , - 9 9 , 370C (1952) .

Grahame, D . C . , Ann. Rev. Phys . Chem., - 6 , (1955) , pp. 345-6.

De lahay , P. , N e w I n s t r u m e n t a l Methods i n E l e c t r o c h e m i s t r y ,

I n t e r s c i e n c e P u b l i s h e r s , N e w York, 1 9 5 4 , pp. 146-168.

Rob inson , R . A . and R . H. Stokes, E l e c t r o l y t e S o l u t i o n s ,

B u t t e r w o r t h s , London, 2nd e d . ( r e v i s e d ) , 1 9 6 5 , pp. 88-95.

N i c h o l , J . C . and R . M . FUOSS, J . A m . Chem. SOC., - 77 , 1 9 8

(1955) .

H i l l s , G. J. a n d K . E. Johnson , J . E l e c t r o c h e m . SOC., - 1 0 8 ,

1013 (1961) .

H i l l , D. L . , G . J . H i l l s , L. Young, a n d J. O'M. B o c k r i s ,

J . E l e c t r o a n a l . Chem., - 1, 79 (1959) .

B u c k l e , E . R . a n d P. E . T s a o u s s o g l o u , J . Chem. SOC. ,

London, 667 ( 1 9 6 4 ) .

W

27 . De Nooijer , B . , "The E l e c t r i c a l C o n d u c t i v i t y of Mol t en

N i t r a t e s a n d B i n a r y N i t r a t e s , ' I t h e s i s , U n i v e r s i t y of

A m s t e r d a m , The N e t h e r l a n d s , 1965.

17

W 28.

29 .

30 .

31 .

32 .

33.

34 .

35 .

36 .

37 .

38.

39 .

40 .

W i n t e r h a g e r , H. and L . Werner, F o r s c h u n g s b e r . des W i t s c h a f t s - u .

V e r k e h r s m i n i s t e r i u m s Nord rhe in -Wes t f a l en , N o . 438 , 1957 .

I b i d . , N o . 341 , 1956.

Oberdorfer, G . , Lehrbuch - der E l e k t r o t e c h n i k , Bd.11, 1944 ,

p. 212 .

-

J a n z , G . J . , Mol ten S a l t s Handbook, Academic Press, N e w

York, 1967.

Ryschkewi t sch , E . , 2. E l e k t r o c h e m . , - 3 9 , 5 3 1 (1933) .

Yaffe, I . S . and E. R . Van A r t s d a l e n , C h e m i s t r y D i v i s i o n

Semiannua l P r o g r e s s R e p o r t f o r Period Ending J u n e 20 , 1956 ,

F a i r s t e i n , E . , I n s t r u m e n t a t i o n and C o n t r o l s Semiannual

P r o g r e s s Report f o r Period End ing J u l y 3 1 , 1955, ORNL-1997,

P. 9 .

Y i m , E. W . and M . F e i n l e i b , J . E l e c t r o c h e m . SOC. , - 1 0 4 , 622

(1957) .

I b i d . , 626 (1957) .

Brown, E. A . and B. Por te r , "U.S. Depar tmen t of I n t e r i o r ,

Bureau of Mines , " 128 .23: 6500 (1964) .

E d w a r d s , J . D . , C . S. Taylor, L. A . Cosgrove , and A . S.

R u s s e l l , J. E l e c t r o c h e m . SOC., 1 0 0 , 508 (1953) .

Edwards, J. D . , C . S. T a y l o r , A . S. R u s s e l l , and L. F.

M a r a n v i l l e , i b i d . , 9 9 , 527 (1952) .

Landon, G . J. and A . R . Ubbelohde, Proc. Roya l S O ~ . ,

A240, 160 (1957) .

-

- -

41. B r o n s t e i n , H. R . and M . A . B r e d i g , C h e m i s t r y D i v i s i o n

Annual Progress Report f o r Period End ing J u n e 2 0 , 1959,

ORNL-2782, p . 59.

18

42. I b i d . , J. Am. Chem. SOC., 80, 2077 (1958) .

43. B r o n s t e i n , H . R . , A . S. Dworkin, and M . A . B r e d i g , C h e m i s t r y

D i v i s i o n Annual P r o g r e s s R e p o r t for P e r i o d End ing J u n e 2 0 ,

1960, ORNL-2983, p . 65.

45 . I b i d . , Rev. S c i . I n s t r . , 2 7 , 297 (1956) . - 46. Bagk, T . , Acta Chem. Scand . , - 8 , 1727 (1954) .

47 . B a j c s y , J . , M . Mal inovsky, and K. Ma t i a sovsky , E l e c t r o c h i m .

Acta, 7 , - - 543 (1962) .

48 . Thompson, M . deK. and A . L. Kaye, T r a n s . E lec t rochem. SOC. ,

67 , 169 (1935) . - 49. Greene , N . D . , ORNL-CF-54-8-64 (1954) .

5 0 . S e l i v a n o v , V. G. a n d V . V . S t e n d e r , R u s s i a n J. I n o r g . Chem.,

- 4 , 934 (1959) .

51. Meerson, G . A . and M . P . Smirnov, Khimiva Redkikh Elementov ,

Akad. Nauk SSSR, 2 , 133 (1955) . -

52. B a t s l a v i k , E . and A . I . Be lyayev , R u s s i a n J . I n o r g . Chem.

- 3 , N o . 4 , 324 (1958) .

53. P e a r s o n , T . G . and J. Waddington, D i s c . Fa raday SOC., - 1,

307 (1947) .

54. Malmstadt , H . V . and C . G. Enke, E l e c t r o n i c s for S c i e n t i s t s ,

W . A . Benjamin, N e w York, 1962, p . 273.

55. D ike , P . H. ,Rev. S c i . I n s t r . , - 2 , 379 (1931) .

19

DRNL-DWG 68-2215

F i g u r e 1: Wheatstone b r i d g e : pa ra l l e l - componen t b a l a n c i n g

arm. ORNL-DWG 68 - 2216

F i g u r e 2 : E q u i v a l e n t c i r c u i t of c e l l i n absence of r e a c t i o n .

ORNL-DWG 68-2217

R S GS

F i g u r e 3 : E q u i v a l e n t c i r c u i t of s o l u t i o n r e s i s t a n c e and

e l e c t r o d e - s o l u t i o n i n t e r f a c i a l c a p a c i t a n c e i n

Y absence of r e a c t i o n .

20

ORNL-DWG 68-2248

F i g u r e 4: E q u i v a l e n t c i r c u i t i n c l u d i n g r e a c t i o n .

ORNL-DWG 68-2219

CONSTANT FREQUENCY

F i g u r e 5: E q u i v a l e n t c i r c u i t f o r f a r a d a i c impedance s t u d i e s .

21

ORNL-DWG 68-2220

APPENDIX I IMPEDANCE BRIDGES

WHEATSTONE BRIDGE, NO

A. @ DETECTOR

1 ,+qT C. KELVIN BRIDGE(38)

E. - TYPE " BRIDGE ( 28129) (EMPLOYED BY WINTER- HAGER AND WERNER)

Z= IMPEDANCE OF .CONNECTIONS

F.

D. THDMSON BRI!d4')

DETECTOR

DETECTOR

~

CAREY-FOSTER BRI DGE(48) (CELL AND S ARE INTER- CHANGEABLE)

1 I Z = IMPEDANCE OF CONNECTIOYS

22

For t h e s a k e

APPENDIX I1

of c o m p l e t e n e s s , r e f e r e n c e s t o t h o s e

c r y o l i t e s y s t e m s w,,ich c o u l d n o t be c o n s u l t e d

are l i s t e d i n t h i s append ix . An i n d i c a t i o n o f

t o g e t h e r w i t h t h e s e c o n d a r y s o u r c e , is g i v e n .

n t h e o r - g i n a l

t h e i r c o n t e n t ,

Ba ta shev , K . and A . Z h u r i n , M e t a l l u r g , - 1 0 , 67 (1935) ; G., - 3 0 , 70189 (1936) .

(K of KF-AlF, s y s t e m v s . T)

Ba ta shev , K . P . , Legk ie M e t a l l y , - 1 0 , 48 (1936) ; r e f . 4 .

(K of c r y o l i t e v s . T)

B a t a s h e v , c i t ed by Mashovets i n The E l e c t r o m e t a l l u r g y o f

Aluminum ( R u s s i a n ) , 1938; r e f . 53.

(Am of c r y o l i t e + NaF and c r y o l i t e + AlF6)

Vayna, A . , A l l u m i n i o , - 1 9 , 215 (1950) ; C . A . , 44, 10 ,54?d

(1950) and r e f . 4 .

(K of c r y o l i t e v s . T; K of c r y o l i t e w i t h a d d i t i o n s of

NaF, CaF,, or AlF, n e a r 1000°C)

Abramov, G . A . , M . M . Vetyukov, I . P. Gupalo , A . A . Kos tyukov,

and L . N . Lozhk in , " T e o r e t i c h e s k i e osnovy e l e c t r o m e t a l -

l u r g i i a l y m i n i a , " M e t a l l u r i z d a t , Moscow (1953) ; r e f . 4 .


Ponomarev, V. G . , F. M . K o l o m i l s k i i , Yu. M . P u t i l i n , I z v e s t .

Vysshikh . Ucheb. , Z a v e d e n i i , T s v e t n a y a M e t . , 1958 , N o . 6 ,

78; C . A . , 5 3 , 1 4 , 6 7 0 i (1959) . - - (K Of K2TiF6 V S . T)

Be lyaev , A . I . , Tsve tnye M e t a l l y , - 3 1 , No. 1 0 , 61 (1958) ; - C . A . ,

- 53 , 6832 i (1959) .

( K of c r y o l i t e w i t h a d d i t i o n s of L i F , NaF, BeF,, MgF,,

CaF,, BaF,, o r AlF,) Y

23

A n t i p i n , L. N . , S. F . Vazhenin , and V . K . Shcherbakov, Nauch.

Doklady Vysshe! Shko ly , Met. 1958, 11; C . A . , 5 5 , 1241f

(1961) .

- - --

(K o f NaF/AlF, r a t i o s o f 1 . 6 t o 3 . 9 )

A n t i p i n , L . N . and S. F. Vazhenin , Tsve tnye M e t a l l y , 3 1 , No. - 1 2 , 56 (1958) ; C . A . , 53, 7824e (1959) .

( K of c r y o l i t e w i t h a d d i t i o n s of CaF, or MgF,)

Chu, Y . A . and A . I . Be lyaev , I z v e s t . Vysshikh . Ucheb. ,

Z a v e d e n i f , Tsve tnaya Met., 2 , No. 2 , 69 (1959) ; C . A . , > ,

2 4 , 0 2 5 i (1960) .

( K of c r y o l i t e and c r y o l i t e w i t h a d d i t i o n s o f L i F or BeF,)

- -- -

Belyaev , A . I . and E . A . Zhemchuzhina, Tsve tnye M e t a l l y , 3 3 , - No. 4 , 45 (1960) ; C . A . , 55, 1242a (1961) .

(K of NaF/AlF, r a t i o of 2 . 2 t o 2 . 7 8 w i t h a d d i t i o n s of MgF2)

-

Kuvakin, M . A . and P. S. Kusak in , Trudy I n s t . M e t . , Akad. Nauk.

SSSR, Unal . F i l i a l , 5 , 145 (1960) ; C . A . , 55, 2 2 5 5 i (1961) .

(K of c r y o l i t e )

- - --

B e l y a e v , A . I . , " E l e k t r o l i t a lyumin ievykh vann , " M e t a l l u r g i z d a t ,

MOSCOW, 1961; r e f . 4 .

( K of cryolite with EkF, additions up to 17 wt. 70 at 1000°C)

Mat ia sovsky , K . , S. Ordzovensky, and M . Mal inovsky, Chem. z v e s t i ,

1 7 , 839 (1963) ; r e f . 4 .


-

Vakhobov, A . V. and A . I . Be lyaev , " V i i a m i e r a z l i c h n y k h s o l e v y k h

komponentov (dobavok) na e l e k t r o p r o v o d n o s t e l k t r o l i t a

a lyumin ievykh vann , " i n " F i z i c h e s k a y a khima ra sp lav lemykh

s o l e i , " ed. by The I n s t i t u t e o f G e n e r a l and I n o r g a n i c

Chemis t ry of t h e S o v i e t Academy of S c i e n c e . , Metal lurgizdat ,

24

Moscow, 1965, pp. 99-104; ref. 4.

(K of cryolite with additions of LiF, MgF,, CaF,, BaF,,

orAlF, up to 20 wt. 70 at 1000°C)

Y

1. 2 . 3 . 4 . 5 . 6 . 7 . 8 . 9 .

1 0 . 11. 1 2 . 1 3 . 1 4 . 1 5 . 1 6 . ' 1 7 . 1 8 . 1 9 . 2 0 . 2 1 . 2 2 . 2 3 . 2 4 . 2 5 . 2 6 . 2 7 . 2 8 . 2 9 . 3 0 . 31. 3 2 . 3 3 . 3 4 . 3 5 . 36. 3 7 . 3 8 . 3 9 . 4 0 . 4 1 . 4 2 . 4 3 . 4 4 . 4 5 . 4 6 . 4 7 *

R . G . R . L. A . C . S . C . C. H. S. U. C . E . P. F. R'. E . C. C . J . M . R . H . G . J. S . W . G . E . W . L . J . F. J . D. S. B. L . A . J . E . D. L . H . J . E .

25

ORNL-TM-2180

INTERNAL DISTRIBUTION

K . A d a m s U. Adamson G . A f f e l G . A l e x a n d e r L . B a c a r e l l a F. B a e s J . B a l l E . B a m b e r g e r J. B a r t o n F . Bauman E . B e a l l Ber tocci E . B e t t i s S . B e t t i s B. B i e n F. B l a n k e n s h i p E . B l a n c o G . Bohlmann J. B o r k o w s k i E . Boyd B r a u n s t e i n A . B r e d i g B. B r i g g s R . B r o n s t e i n D . B r u n t o n B r y n e s t ad Can t o r L . Car te r I . C a t h e r s L . Compere H . Cook T. C o r b i n L . C r o w l e y L . C u l l e r , Jr. M . Dale G. D a v i s J. D i t t o c . D u g g i n s A . Dunn S . D w o r k i n R . E n g l e P. E p l e r E . F e r g u s o n M . Fe r r i s A . F r i e d m a n H . F r y e , Jr. L . F u l l e r

4 8 . C. 4 9 . R . 5 0 . L . 5 1 . W . 5 2 . A . 5 3 . R . 5 4 . B. 5 5 . c . 5 6 . P. 5 7 . D. 5 8 . J. 5 9 . M . 6 0 . B. 61. H. 6 2 . H . 6 3 . R . 6 4 . T . 6 5 . R . 6 6 . H . 6 7 . H . 6 8 . G . 6 9 . W . 70 . P. 71 . M . 7 2 . C . 7 3 . H . 7 4 . s. 75 . H . 7 6 . J . 7 7 . c . 78 . J . 7 9 . R . 8 0 . A . 8 1 . M . 8 2 . R . 83. H. 8 4 . R . 8 5 . G . 8 6 . D. 8 7 . w . 8 8 . C . 8 9 . H . 9 0 . H . 9 1 . C. 9 2 . C . 9 3 . L. 9 4 . R .

H. Gabbard B. Gammage 0. G i l p a tr i c k R . G r i m e s G . G r i n d e l l H . Guymon A . H a n n a f o r d S. H a r r i l l N . H a u b e n r e i c h N . H e s s R . H i g h t o w e r R . H i l l F. H i t c h W . Hoffman F. H o l m e s W . H o r t o n L . Hudson F. H y l a n d I n o u y e W . J e n k i n s H. J e n k s H . J o r d a n R . K a s t e n T. K e l l e y R . Kennedy T. Kerr S. K i r s l i s W . Kohn W . Krewson E . Lamb A . L a n e B. L i n d a u e r P . L i t m a n I . L u n d i n N . Lyon G . M a c P h e r s o n E . M a c P h e r s o n Maman t o v L. Mann ing L . M a r s h a l l D . M a r t i n E . McCoy F. M c D u f f i e K . M c G l o t h l a n J . McHargue E . McNeese E . M e s m e r

26

9 5 . 9 6 . 9 7 . 9 8 . 99 .

1 0 0 . 1 0 1 . 1 0 2 . 1 0 3 . 1 0 4 .

105-119. 1 2 0 . 1 2 1 . 1 2 2 .

123-124. 1 2 5 . 1 2 6 . 1 2 7 . 1 2 8 . 1 2 9 .

A . S . Meyer R . L . Moore D. M . Moulton T . R . Muel le r J. P. N i c h o l s E . L. N i c h o l s o n L . C . Oakes F . A . P o s e y J. L. R e d f o r d J. D . Redman G . D. R o b b i n s R . C . R o b e r t s o n W . C . R o b i n s o n K . A . Romberger M . W . Rosen t h a l R . G . Ross H. C . Savage D u n l a p S c o t t J . H . S h a f f e r M . J . S k i n n e r

153-154. 1 5 5 . 1 5 6 .

1 5 9 .

1 6 2 . 1 6 3 .

157-158.

160-161.

164-178. 179-180.

1 8 1 .

1 3 0 . 1 3 1 . 1 3 2 . 1 3 3 . 1 3 4 . 1 3 5 . 1 3 6 . 1 3 7 . 1 3 8 . 1 3 9 . 1 4 0 . 1 4 1 . 1 4 2 . 1 4 3 . 1 4 4 .

1 4 7 .

1 5 1 . 1 5 2 .

1 4 5 - 1 4 6. .

148-150.

EXTERNAL DISTRIBUTION

G. P. S m i t h R . W . S t e l z n e r H . H. S t o n e R . A . S t r e h l o w J. R . T a l l a c k s o n R . E . Thoma L . M . T o t h J. S . Watson C . F. Weaver A . M . W e i n b e r g J . R . Weir M . E . W h a t l e y J . C . White F . L. W h i t i n g J . P. Young C e n t r a l R e s e a r c h L i b r a r y Document Reference S e c t i o n L a b o r a t o r y Records D e p t . L a b o r a t o r y Records, ORNL ORNL P a t e n t O f f i c e

D. F. Cope, A E C , OR0 A . Giambusso, A E C , W a s h i n g t o n , D. C . W . J . L a r k i n , A E C , OR0 T. W . M c I n t o s h , A E C , W a s h i n g t o n , D . C . H . M . R o t h , A E C , OR0 M . Shaw, A E C , W a s h i n g t o n , D. C . W . L. S m a l l e y , A E C , OR0 R . F . Sweek, A E C , W a s h i n g t o n , D . C . D i v i s i o n of T e c h n i c a l I n f o r m a t i o n E x t e n s i o n Reactor D i v i s i o n , O R 0 R e s e a r c h and Development D i v i s i o n , OR0

W

ORNL-TM-2180

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