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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.
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any information, opporatus, method, or process disclosed in th is report.
Neither the United States,
B.
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or contractor of the Commission, or employee of such controctor prepares, disseminates, or
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or h is employment wi th such controctor.
r
A
iii
ELECTRICAL CONDUCTIVITY OF MOLTEN FLUORIDES.
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
ELECTRICAL CONDUCTIVITY OF MOLTEN FLUORIDES.
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
Sons , N e w York, 1967.
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 -
l y t e s " i n Fused S a l t s , B. R . Sundheim, Ed. , M c G r a w - H i l l ,
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
Mol ten S a l t Chemis t ry , M . B l a n d e r , Ed . , John Wiley and
Sons , N e w York, 1964.
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) .
G r i m e s , W. R . , "Materials Problems i n Mol ten S a l t Reactors ," i n Materials and F u e l s for High Tempera ture Nuclear Energy
A p p l i c a t i o n s by M . T. Simnad and L . R . Zumwalt, t h e M.I.T.
Press, Mass., 1964.
Yaffe , I . S. and E. R . Van A r t s d a l e n , J. Phys . Chem., - 60,
1125 (1956) .
J o n e s , G . and R . C . J o s e p h s , J . Am. Chem. SOC., - 5 0 , 1049
(1928) .
Grahame, D . C . , J . Am. Chem. SOC., - 63, 1207 (1941) .
D a n i e l s , F . , e t a l . , E x p e r i m e n t a l P h y s i c a l C h e m i s t r y , 5 t h
e d . , M c G r a w - H i l l , New York, 1956 , p. 396.
G l a s s t o n e , S. and D. Lewis , E lemen t s of P h y s i c a l Chemis t ry ,
Van N o s t r a n d , P r i n c e t o n , N e w J e r s e y , 1960, p. 430.
J o n e s , G . and G. M . B o l l i n g e r , J . A m . Chem. SOC., - 53, 411
(1931) .
C u t h b e r t s o n , J. W . and J. Waddington, T r a n s Fa raday SOC. ,
3 2 . 745 (1936) .
13 .
1 4 .
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
S a l t C h e m i s t r y , M . B l a n d e r , E d . , 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, 1964, p . 715.
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
D i v i s i o n Annual Progress Repor t for Period End ing
December 31 , 1 9 6 7 , ORNL-4229, p. 5 7 .
J o n e s , G . a n d S . M . C h r i s t i a n , J. A m . Chem. SOC., - 5 7 , 272
(1935) .
Warburg, E . , Wied. Ann. P h y s i k , - 6 7 , 493 (1899) .
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 .
(K of c r y o l i t e v s . T)
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 .
(K of c r y o l i t e v s . T)
-
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