... ". , .. . NASA CR-72407 R-6754-6 PROPERTIES OF NONAQUEOUS ELECTROLYTES SIXTH SUMMARY REPORT (20 September 1967 to 19 March 1968) BY Rudolf Keller, James N. Foster, Douglas C. Hanson, John F. Hon, Otto F. Kalman, James S. Muirhead, and Jack M. Sullivan Prepared For National Aeronautics and Space Administration I GPO PRICE $ CFSTI PRICE(S1 $ Hard copy (HC) Microfiche (MF) ff 653 July65 I Contract NAS3-8521 I Rocketdyne A Division of North American Rockwell Corporation Canoga Park, California https://ntrs.nasa.gov/search.jsp?R=19680014004 2020-07-10T02:24:38+00:00Z
Transcript
... ". , .. .
NASA CR-72407 R-6754-6
PROPERTIES OF NONAQUEOUS ELECTROLYTES
SIXTH SUMMARY REPORT
(20 September 1967 to 19 March 1968)
BY
Rudolf Keller, James N. Foster, Douglas C. Hanson, John F. Hon, Otto F. Kalman, James S. Muirhead, and Jack M. Sullivan
Prepared For
National Aeronautics and Space Administration I
GPO PRICE $
CFSTI PRICE(S1 $
Hard copy (HC)
Microfiche (MF) ff 653 Ju ly65 I
Contract NAS3-8521
I Rocketdyne A Division of North American Rockwell Corporation
This report was prepared as an account of sponsored work. Neither the United State National Aeronautics and Space Adminiatra nor any person acting on behalf of NASA:
A . ) Makes any warranty or representation, expressed or implied, with respect to the accuracy, completeness, or usefulneee of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or
Assumes any liabilities with respect to the use of, or for damages resulting fromthe use of any information, apparatua,*methdd or process disclosed in this report.
B.)
As used above, "person acting on behalf of USA'' includes any employee or contractor of NASA, or employee of such contractor, to the extent that euch employee or contractor of NASA, or employee of such contractor prepares, disseminates, or' provides aocew to, any information pursuant to his employment or contract with NASA, or his employment with such contractor.
i , *
. .
Requests for copies of this report should be referred to
National Aeronautics and Space Administration Office of Scientific and Technical Information Attention: AFSS-A Washington, D . C . 20546
t
NASA CR-72407 R-6754-6
3 PROPERTIES OF NONAQUEOUS ELEXTROLYTES
SIXTH S ’ U W Y iizF9ItT
(20 September 1967 t o 19 March 1966)
BY
Rudol f K e l l e r , James N. F o s t e r , Douglas C. Hanson, John F. Hon, O t t o F. Kalman, James S. Muirhead, and J a c k M. S u l l i v a n
P repa red For
N a t i o n a l A e r o n a u t i c s and Space A d m i n i s t r a t i o n
19 A p r i l 1968
Con t rac t NAS3-852 1
Techn ica l Management NASA Lewis R e s e a r c h C e n t e r
Cleve land , Ohio Space Power Systems D i v i s i o n
M r . Robe r t B. King
Ro cke tdyne
Canoga Pa rk , C a l i f o r n i a A D i v i s i o n of Nor th American Rockwel l C o r p o r a t i o n
BECEDlNG PAGE BLANK NOT FLL~~L-
FOREWORD
T h i s r e p o r t was p r e p a r e d under G.O. 08892 i n compliance
w i t h A r t i c l e V I and Pa rag raph B of C o n t r a c t NAS3-8521
f o r t h e N a t i o n a l Aeronau t i c s and Space A d m i l l i s t r a t i u n ,
L e w i s R e s e a r c h C e n t e r , C leve land , Ohio. The work was
conducted i n t h e Chemical and M a t e r i a l S c i e n c e s Depar t -
ment of R o c k e t d y n e ' s Resea rch D i v i s i o n , d u r i n g t h e
p e r i o d 20 September 1967 th rough 19 March 1968.
ABSTRACT
S t u d i e s of a p r o t i c e l e c t r o l y t e s based on three s o l v e n t s :
p r o p y l e n e c a r b o n a t e , d ime thy l formamide, and a c e t o n i t r i l e ,
w e r e con t inued ~ C h a r a c t e r i z e d components were used t o
p r e p a r e t h e e l e c t r o l y t e s o l u t i o n s .
S t r u c t u r a l s t u d i e s of e l e c t r o l F t e s c o n t a i n i n g l i t h i u m
c h l o r i d e , aluminum c h l o r i d e , and c u p r i c c h l o r i d e were
performed u t i l i z i n g n u c l e a r magne t i c r e s o n a n c e .
The p h y s i c a l p r o p e r t i e s s t u d i e d i n c l u d e s o l u b i l i i i e s ,
v a p o r p r e s s u r e s , d i f f u s i o n c o e f f i c i e n t s , and d i e l e c t r i c
c o n s t a n t s .
i i i / i v
CONTENTS
Foreword . . . . . . . . . . . . . . . . . . . iii Ab s tr a c t . . . . . . . . . . . . . . . . . . . iii Summary . . . . . . . . . . . . . . . . . . . . 1
I n f r a r e d Spectrum of Phosphorous P e n t a f l u o r i d e (PF #1) . . 10
I n f r a r e d Absorbance of Phosphorous T r i f l u o r i d e and
Phosphorous Oxychlor ide a s a Func t ion of P r e s s u r e . . . . 11
High R e s o l u t i o n P r o t o n (H ) Resonance i n 1 M A l C l /AN . . . 15 A12? N u c l e a r Magnet ic Resonance i n 1 M A l C l /PC C o n t a i n i n g
v a r i o u s C o n c e n t r a t i o n v of L iC l . . . . . . . . . . 17 Approximate R e l a t i v e P o p u l a t i o n s of C o o r d i n a t i n g A1 S p e c i e s
i n 1 M A l C l /PC a s a F u n c t i o n of Added L iCl . . . . . . 18
A127 N u c l e a r Magnet ic Resonance i n 0 .1 M A l C l /PC . . . . 19 S p l i t t i n g of Large P r o t o n Peaks a s a F u n c t i o n of T ime
f o r L iC l + CuC12/DMF . . . . . . . . . . . . . . 22
P o s i t i o n of S m a l l Far-Downfield Resonance a s a F u n c t i o n
of T i m e f o r L iC l + CuC12/DMF . . . . . . . . . . . 23 Examina t ion of P r e c i p i t a t e Obtained i n D i s s o l v i n g CuF
i n 1 M LiCl/DMF . . . . . . . . . . . . . . . 2 7
A p p a r a t u s f o r Measuring Vapor P r e s s u r e s by Gas
S a t u r a t i o n Method . . . . . . . . . . . . . . . 29 Chronopotent iogram of 0.01 M CuC12 i n 1 M LiCl/DMF; t h e
C u r r e n t D e n s i t y i s 1.6 ma/cm . . . . . . . . . . . 33 Microwave S e t u p a t 8.5 GHZ, TE Mode . . . . . . . . 35
5
1 3
3 --
3 3
2
2
0 9 1
v i i/v ii i
TABLES
1 . 2 .
3 .
4 . 5 . 6 .
7 .
Characterization of Distilled Solvent Batches . . . . . . 4 Impurity Concentrations in CuF2 #3 Determined by Spark Source Mass Spectrometry and Emission Spectroscopy . . . . 5 Impurity Concentrations (ppm by weight) in TMA-F Determined by Emission Spectrography . . . . . . . . . 7 Solubility De termina tioris . . . . . . . . . . . . 26 Vapor Pressures . . . . . . . . . . . . . . . . 30
Electrolytes at 25 C . . . . . . . . . . . . . . 32 Dielectric Constant Test Results at 8 . 5 GHz (24 C) . . . . 38
Diffusion Coefficients. D. of Dimethyl Formamide
i x / x
SUMMARY
P h y s i c a l p r o p e r t i e s and s t r u c t u r a l s t u d i e s were conducted i n the s o l v e n t s
p ropy lene c a r b o n a t e (PC), d i m e t h y l formamide (DMF), and a c e t o n i t r i l e (AN);
t h e w a t e r c o n t e n t of the s o l v e n t s was no rma l ly i n the r a n g e of 40 220 ppm.
The d i s t i l l e d s o l v e n t b a t c h e s were analyzed by vapor-phase chromatography
on a r o u t i n e b a s i s . were
ana lyzed . S e n s i t i v i t y t e s t s of c o n c e n t r a t e d l i t h i u m p e r c h l o r a t e s o l u t i o n s
were n e g a t i v e .
Some s o l u t e m a t e r i a l s such a s CiiF2, 9F3, and PF 5
H i g h - r e s o l u t i o n p r o t o n
f o r b o t h 1 M A l C l /AN and 1 M A l C l /PC specimens c o n t a i n i n g v a r i o u s concen-
t r a t i o n s of LiC1. This a n a l y s i s i n d i c a t e s t h a t t h e major s p e c i e s formed
when A l C l i s d i s s o l v e d i n b o t h AN and PC a r e , r e s p e c t i v e l y , A l C l and a
s i x f o l d c o o r d i n a t i o n complex, A1(AN)6
d a t a i n d i c a t e a l s o t h e p r e s e n c e o f s m a l l c o n c e n t r a t i o n s of C1- i n a l l of
t h e AN specimens.
and b r o a d l i n e A127 NM& d a t a have been ana lyzed
3 3
- +++ o r A1(PC)6++f. B r o a d l i n e C 1 35 3
H i g h - r e s o l u t i o n p r o t o n NMEi s p e c t r a were t a k e n o v e r a 6-month p e r i o d of 1 M CUCI /E.W specimens c o n t a i n i n g v a r i o u s c o n c e n t r a t i o n s of LiC1.
changes i n t h e s e s p e c t r a have been noted and have been f o l l o w e d .
t h e d a t a have n o t been e x p l a i n e d c o n c l u s i v e l y ; however, t h e y have shown .
t h e need f o r a r e v i s i o n i n t h e i n t e r p r e t a t i o n of t h e e a r l y d a t a .
Long-term 2 Thus f a r ,
S o l u b i l i t i e s of CuF2 i n p ropy lene ca rbona te and d i m e t h y l formamide were
found t o be low i n t h e pu re s o l v e n t s , b u t enhanced i n t h e p r e s e n c e of l i th -
ium s a l t s , e v i d e n t l y because of the f o r m a t i o n of i n s o l u b l e l i t h i u m f l u o r i d e .
Vapor p r e s s u r e s f o r v a r i o u s s o l u t i o n s were measured a t 2 5 and 60 C by the
s a t u r a t i o n method. D i f f u s i o n c o e f f i c i e n t s of some d i m e t h y l formamide so lu -
t i o n s were de t e rmined a t 25 C by a porous d i s k method. The d e t e r m i n a t i Q n
o f d i f f u s i o n c o e f f i c i e n t s of coppe r s p e c i e s b y c h r o n o p o t e n t i o m e t r y w a s
s t u d i e d .
d i e l e c t r i c c o n s t a n t s was e s s e n t i a l l y completed.
P r e p a r a t o r y work f o r the measurement of h e a t s of s o l u t i o n a n d
DESCRIPTION OF PROGRESS
PREPARATION OF ELECTROLYTES
P u r i f i c a t i o n of S o l v e n t s
S o l v e n t s were p u r i f i e d by d i s t i l l a t i o n and ana lyzed a s d e s c r i b e d p r e v i o u s l y
(Ref . 1 t h r o u g h 5) . t i o n c o n d i t i o n s were summarized i n R e f . 3 . The p u r i f i c a t i o n p rocedure f o r
DMF was somewhat modi f ied . Most b a t c h e s were d i s t i l l e d k i t h a 1 - f o o t
V ig reux column a t a tmosphe r i c p r e s s u r e .
b u t i t s u s e h a s been d i scon t inued because of t h e p o s s i b i l i t y of a s i d e
r e a c t i o n producing w a t e r . The procedure used m o s t r e c e n t l y i n v o l v e s a
p r e d r y i n g w i t h mo lecu la r s i e v e s and a d i s t i l l a t i o n of the c e n t r i f u g e d
p r e d r i e d DMF.
The normally a p p l i e d a n a l y t i c a l p rocedure and d i s t i l l a -
CaH was used a s the d r y i n g a g e n t , 2
The s o l v e n t b a t c h e s used d u r i n g the r e p o r t p e r i o d a r e l i s t e d i n Table 1.
Some b a t c h e s c o n t a i n i n g more water t h a n 40 220 ppm were used i n some
e x c e p t i o n a l c a s e s , e .g . , i n d i f f u s i o n c o e f f i c i e n t measurements where the
w a t e r c o n t e n t of t h e b u l k s o l v e n t d o e s n o t appear t o be c r i t i c a l .
A n a l y s i s of Cupr i c F l u o r i d e
A c u p r i c f l u o r i d e sample
had b e e n a n a l y z e d p r e v i o u s l y (Ref. 4 ) .
t a i n e d p roduc t
T a b l e 2 .
l a r g e oxygen c o n t e n t of 1.5 p e r c e n t by we igh t was r e v e a l e d by spa rk sou rce
mass s p e c t r o m e t r y , t o g e t h e r w i t h s i g n i f i c a n t amounts of carbon and some
s u l f u r . I n t h e second a n a l y s i s , which was provided by t h e s u p p l i e r of
the chemica l and was performed by the Assoc ia t ed E l e c t r i c a l I n d u s t r i e s ,
CuF 2 #2 (Ozark-Mahoning Company, s p e c i a l q u a l i t y ) , The analysis of a more r e c e n t l y ob-
CuF2 #3 (Ledoux & Company, s p e c i a l q u a l i t y ) , i s p r e s e n t e d i n
Low i m p u r i t y l e v e l s f o r m e t a l l i c i m p u r i t i e s were r e c o r d e d . A
L t d . , England , no f i g u r e s f o r 0, N, and C a r e g iven ; n i t r o g e n and oxygen
cou ld n o t be de te rmined because of i n s t r u m e n t background, and i n the c a s e
o f ca rbon , a d e t e r m i n a t i o n was imposs ib l e because t h e sample was mixed
The h i g h oxygen c o n t e n t a p p e a r s t o be due t o t h e p r e s e n c e of a copper
oxide r a t h e r t h a n an e x c e s s i v e water c o n t e n t because o n l y s m a l l amounts
of hydrogen were found . CuF2 #3 i s b e i n g used f o r measurements d e s p i t e
the r e l a t i v e l y h i g h i m p u r i t y l e v e l s ; a more s a t i s f a c t o r y p r o d u c t d o e s
n o t seem t o be a v a i l a b l e a t the p r e s e n t t ime .
Ana l y s i s of Te tr ame t hy 1 ammonium F l u o r i d e
Two tetramethylammonium f l u o r i d e p roduc t s were ana lyzed (TMA-F #2, A l d r i c h
Chemical Company, I n c . , and TMA-F # 3 , Sou thwes te rn A n a l y t i c a l Chemicals ,
I n c . ) .
P a c i f i c S p e c t r o c h e m i c a l Labora to ry , I n c . a r e p r e s e n t e d i n Table 3 . Impu-
r i t y c o n t e n t s n o t l i s t e d a r e below the d e t e c t i o n l i m i t s l i s t e d i n R e f . l . No r e s u l t s could be o b t a i n e d by spark sou rce mass s p e c t r o m e t r y because t h e
sample l o s t i t s c o n s i s t e n c y upon exposure t o vacuum and could n o t be spa rked ;
T M A o F undergoes t h e r m a l decomposi t ion t o (CH ) N, CH
of 0 . 5 t o 1 mm Hg a c c o r d i n g t o R e f . 6 , and a decomposi t ion could be expec ted
a t room t e m p e r a t u r e a t a vacuum of t o mm Hg a s i n t h e mass
s p e c t r o m e t e r .
The r e s u l t s of an emis s ion s p e c t r o g r a p h i c a n a l y s i s performed by
and CH F i n a vacuum 3 3 4' 3
I n a v i s u a l examination of the ti;o p r o d u c t s , TY!I*F j f 2 w e s folind tr, heve
the appea rance of a d r y powder, whereas TMA*F#3 was more cakey and a
r e l a t i v e l y h i g h w a t e r c o n t e n t o f t h i s l a t e r p r o d u c t may b e s u s p e c t e d .
However, !CM,A.F#2 was r e j e c t e d because of the v e r y h i g h sodium c o n t e n t .
Sou thwes te rn A n a l y t i c a l Chemica ls , I n c . i s manufac tu r ing an improved
p r o d u c t (Ref . 7 ) and a sample h a s been o r d e r e d .
A n a l y s i s of Boron T r i f l u o r i d e
A c y l i n d e r of boron t r i f l u o r i d e (BF 3 a n a l y z e d u s i n g a CEC 2 l - l O 3 C mass s p e c t r o m e t e r .
t h e o n l y i m p u r i t y found. I t s c o n c e n t r a t i o n was de te rmined t o be g r e a t e r
t h a n 1 mole p e r c e n t .
#1, Matheson, C. P . Grade) was
Tr i f luo roborox ime was
Although t h e mass s p e c t r o m e t e r was e x t e n s i v e l y
6
4.
i
w m m In L n l n
b
a n V
m a a
V
M
0 C r
o m 0 . . IC\ 7 4 M
a m
0 0 M b O O 00. 0,TyyO o M o o o o * o ~ m Ln Mod44744 0 0 Lna O O b 4 m a Lnoooz
. . D . . O . . 0 . .
5
TABLE 3
IMPURITY CONCENTFLATIONS (ppm by weight) I N TMA-F
DETEZMINED BY EMISSION SPECTROGRAPHY
B
Mg
A 1
S i
Na
Ca
T i
C r
Mn
Fe
N i
cu
Ag
Sn
TMA*F #2
1200
2 60
1800
4100
250 000
400
1200
190
47
150
10
150
2 50
~~
TMAsF #2*
12 j 000
2 10
33
3500
180,000
590
9
29
6.5
TMA-F #3
5.0
53
2 5
5 .2
'CSecond b a t c h of same o rde r , d e l i v e r 2-1/2 months a f t e r f i r s t ba t ch ,
I m p u r i t y c o n t e n t s of e lements no t l i s t e d a r e below d e t e c t i o n l i m i t s
l i s t e d i n Ref . 1. .
7
p a s s i v a t e d , t h e (BOP)
i n s t e a d bc g e n e r a t e d i n s i d e t h e mass s p e c t r o m e t e r . F i s h e r , Lehmann, and
S h a p i r o (Ref. 8) r e p o r t t h a t (BOF)
250 C y and t h a t a sample of (BOF) 3 a f t e r 1 hour a t 25 C . Thus, t h e (BOF) found i n t h i s a n a l y s i s must have
been gene ra t ed i n t he mass s p e c t r o m e t e r and i s n o t a c t u a l l y p r e s e n t i n t h e
BF sample. Permanent g a s e s , such a s S i F 4, CF4, N2, 02, and SF6, were n o t
d e t e c t e d and, c o n s e q u e n t l y , were p r e s e n t a t c o n c e n t r a t i o n s l e s s t h a n 0 . 1
mole p e r c e n t , which i s t h e d e t e c t i o n l i m i t f o r t h e s e s p e c i e s ( f l u o r i n e
cannot be d e t e c t e d mass s p e c t r o m e t r i c a l l y i n the p r e s e n c e of l a r g e amounts
of bo ron tr if l u o r i d c ) .
found may n o t be p r e s e n t i n t h e sample, b u t may 3
i s n o t s t a b l e a t t e m p e r a t u r e s below 3 i s e s s e n t i a l l y decomposed (>99 p e r c e n t )
3
3
The BF w a s a l s o ana lyzed by g a s chromatography u s i n g a Halocarbon O i l
13-21 on achromasorb W column b u t t h e r e s u l t s were i n c o n c l u s i v e ; peaks
were found b u t t h e y were n o t r e p r o d u c i b l e , i n d i c a t i n g t h a t the sample
was incompa t ib l e w i t h the packing o r t h e column had n o t been comple t e ly
pa s s i v a t e d .
3
The i n f r a r e d spec t rum of BF i n a 5 - c e n t i m e t e r c e l l w i t h s i l v e r c h l o r i d e
windows c o n t a i n i n g 80 m i l l i m e t e r s of BE’ was r e c o r d e d from 670 t o 3500 cm
on a P e r k i n Elmer I n f r a c o r d , Model 137. No peaks were found o t h e r t h a n
t h o s e expec ted f o r BF
measur ing the abso rbance a t 3878 cm on a Gary 14 r e c o r d i n g s p e c t r o m e t e r
( a c a l i b r a t i o n cu rve was p repa red by measu r ing the a b s o r b a n c e of hydrogen
f l u o r i d e a t v a r i o u s p r e s s u r e s ) .
.1 3 3
(Ref . 9 ) . Hydrogen f l u o r i d e was de t e rmined by -1 3
I n a f i rs t d e t e r m i n a t i o n , u s i n g a 10 -cen t ime te r c e l l w i t h ca l c ium f l u o r i d e
windows a t a sample p r e s s u r e of 653 m i l l i m e t e r s , a peak was found f o r
hydrogen f l u o r i d e , b u t the peak h e i g h t was a p p r o x i m a t e l y t h e same a s the
b a s e l i n e n o i s e and m s a t t h e l i m i t of d e t e c t i o n . The d e t e r m i n a t i o n was
r e p e a t e d u s i n g a 10 -cen t ime te r c e l l w i t h s a p p h i r e windows and a sample
p r e s s u r e of 1495 m i l l i m e t e r s . The peak h e i g h t a g a i n was on t h e o r d e r of
t h e b a s e l i n e n o i s e . The a c t u a l 1iF c o n t e n t was t h e r e f o r e a t t h e l i m i t of
d e t e c t i o n , 200 ppm, o r l e s s .
A n a l y s i s of Phosphorous P e n t a f l u o r i d e
The o n l y i m p u r i t y found i n phosphorous p e n t a f l u o r i d e (PF
Organ ic Chemical Company, C.P. Grade) by mass s p e c t r o m e t r y was POF
c o n c e n t r a t i o n b e i n g g r e a t e r t h a n 1 p e r c e n t . A s i n t h e c a s e of BF t h e
oxygen-containing i m p u r i t y found may n o t be p r e s e n t i n t h e PF
may be g e n e r a t e d i n s i d e t h e mass s p e c t r o m e t e r . Permanent g a s e s , such a s
SiFhY CF4, N2, 0 2 , and SF, w e r e not d e t e c t e d , and hence were n o t p r e s e n t
a t c o n c e n t r a t i o n s g r e a t e r t h a n 0 . 1 mole p e r c e n t . PF canno t be de t e rmined
mass s p e c t r o m e t r i c a l l y i n t h e p re sence of a l a r g e e x c e s s of PF because
t h e major s p e c i e s g e n e r a t e d by i o n i z a t i o n of PF
a t e d by t h e i o n i z a t i o n of PF I n a d d i t i o n , f l u o r i n e canno t be d e t e c t e d
because f l u o r i d e i o n s a r e a l s o produced by t h e i o n i z a t i o n of PF
#1, R e s e a r c h 5 i t s 3'
3' sample b u t 5
b
3
5 i . e . , PF2 , i s a l s o gene r -
+ 3'
5' 5'
The a n a l y s e s of PF5 by g a s chromatography u s i n g a column of Halocarbon
O i l 13-21 on K e l F was i n c o n c l u s i v e . Peaks were o b t a i n e d b u t t h e y were
n o t r e p r o d u c i b l e , i n d i c a t i n g i n c o m p a t i b i l i t y w i t h column packing o r t h a t
t h e two columns had n o t been comple t e ly p a s s i v a t e d .
The phosphorous p e n t a f l u o r i d e was a n a l y z e d by i n f r a r e d s p e c t r o m e t r y t o
supplement t h e mass s p e c t r o m e t r i c r e s d t s . The s p e c t r i m of phosphorous
p e n t a f l u o r i d e a t 720 m i l l i m e t e r s is shown i n F ig . 1 ; it was r e c o r d e d on
a P e r k i n Elmer I n f r a c o r d , Model 137, u s i n g a 10 -cen t ime te r c e l l w i t h
s i l v e r c h l o r i d e windows. The a b s o r p t i o n peak a t 1420 cm i s due t o
POF
peaks a r e t h o s e expec ted f o r phosphorous p e n t a f l u o r i d e (Ref , 10 and 11).
A m i x t u r e of 2 0 - m i l l i m e t e r phosphorous t r i f l u o r i d e , (Ozark-Mahoning Company,
no p u r i t y g i v e n ) and 2 4 0 - m i l l i m e t e r he l ium was p r e p a r e d f o r c a l i b r a t i o n
p u r p o s e s . The abso rbance a t 860 and 890 cm-' was measured a s a f u n c t i o n
of t h e p a r t i a l p r e s s u r e of PF a s shown i n F ig . 2a. The PF abso rbance
i n t h e PF #1 sample co r re sponds t o 2 .35 and 1 . 9 0 m i l l i m e t e r s a t 860 and
890 cm , r e s p e c t i v e l y , o r a c o n c e n t r a t i o n o f a p p r o x i m a t e l y 0 . 2 p e r c e n t
(by w e i g h t ) .
-1 .
The r ema in ing and t h e peaks a t 860 and 890 cm-' a r e due t o PF 3 3'
3 ' 3
5 -1
0 s
c
5
0 0 lo c
0 - -0 0 cr, ' 0 0 0 v
, . ._._..I_
. ..
I
9 0
0 0 0 0000 c: ? c! YL?.qh
33NVWQS9V
10
I I I I I I I I I 1- I I
tn
m
N
c
1 I I I I I I I I 0 Q\ 03 b \o v\ pr\ cv c
0 0 0 0 0 0 0 0 0
33NW9UOSW
3 0
c
I I I I I I I I I . c
c \ \ I
5 E \ o
I
0
2
I c -r crl cy
0 0 0 0 0
11
The spectrum of POF
c o e f f i c i e n t s a r e avai1abl .e . The p r e p a r a t i o n of POF w i t h a known p u r i t y
i s v e r y d i f f i c u l t and an i n d i r e c t method h a s been employed t o d e t e r m i n e
t h e e x t i n c t i o n c o e f f i c i e n t .
cm i s due t o t h e s t r e t c h i n g of t h e P-0 bond. Assuming t h a t POCl and
POF have s i m i l a r c h a r a c t e r i s t i c s , t h e e x t i n c t i o n c o e f f i c i e n t of the P-0
bond should be t h e same f o r t h e s e two s p e c i e s even though the a b s o r p t i o n
f r e q u e n c y i s d i f f e r e n t due t o t h e d i f f e r e n c e s i n t h e masses o f t h e two
3 s p e c i e s . A m i x t u r e of 13 m i l l i m e t e l s of phosphorous o x y c h l o r i d e , P O C l
(Baker ana lyzed r e a g e n t g r a d e ) , and 700 m i l l i m e t e r s of he l ium was p repa red
and the absorbance was measured a t 1320 cm a t d i f f e r e n t p r e s s u r e s . The
abso rbance o f phosphorous o x y c h l o r i d e a s a f u n c t i o n of i t s p a r t i a l p r e s s u r e
i s shown i n Fig. 2b. i n PF #1 had an
abso rbance o f 0.08 (F ig . l ) , which co r re sponds t o 0.3 m i l l i m e t e r of P O C l
o r app rox ima te ly 300 ppm (by w e i g h t ) of POF
r e p e a t e d l y ob ta ined b u t some s p e c t r a showing l a r g e r amounts of POF were
a l s o found. The l a r g e r c o n c e n t r a t i o n s i n t h e s e c a s e s a r e p r o b a b l y due t o the phosphorous p e n t a f l u o r i d e r e a c t i n g w i t h t r a c e s o f w a t e r .
pOF c o n c e n t r a t i o n may a c t u a l l y be l e s s t h a n 300 ppm. The much g r e a t e r
v a l u e found f o r POF by mass s p e c t r o m e t r y i s due t o incomple t e p a s s i v a t i o n 3 of t h e i n l e t system.
h a s been r e p o r t e d (Ref . 10 and 12) b u t no e x t i n c t i o n 3 3
The i n t e n s e a b s o r p t i o n peak f o r POF a t 1420
3 3 -
3
-1
The minimum abso rbance peak f o r POF 3 5 3
T h i s abso rbance was i n PF 3 5' 3
The a c t u a l
3
The IIF c o n c e n t r a t i o n i n t h e PF de te rmined by measu r ing t h e abso rbance
of a 500-mi l l imeter sample i n a 10 -cen t ime te r c e l l w i t h ca l c ium f l u o r i d e
windows a t 3878 cm , was 800 ppm.
5'
-1
P r e p a r a t i o n of A l C l /PC S o l u t i o n s 3
S o l u t i o n s r e s u l t i n g from d i s s o l u t i o n of A l C l i n PC have a t endency t o
d i s c o l o r when b e i n g p repa red , and a l s o on s t a n d i n g ,
r e a c t i o n of A l C l i n PC i s e x o t h e r m i c , and a s t r o n g d i s c o l o r a t i o n i s
o b t a i n e d i f t h e s o l u t i o n i s a l lowed t o h e a t u p o v e r a l l o r l o c a l l y when
t h e s o l u t i o n i s p r e p a r e d . It was found t h a t o n l y s l i g h t l y t i n t e d so lu -
t i o n cou ld be made by add ing t h e s o l u t e v e r y s l o w l y , g r a i n by g r a i n , u n d e r
3 The d i s s o l u t i o n
3
12
v i g o r o u s s t i r r i n g , and t h i s method had been used t o p r e p a r e A l C l /PC
s o l u t i o n s . Very l i g h t s o l u t i o n s were o b t a i n e d by p r e p a r i n g a s l u r r y of
aluminum c h l o r i d e , l i q u i d n i t r o g e n , and p ropy lene c a r b o n a t e and l e t t i n g
t h i s s l u r r y warm v e r y s lowly . This p rocedure was mod i f i ed because the
amount of condensed w a t e r i n t roduced w i t h the l i q u i d n i t r o g e n was unknown.
I n a m o d i f i c a t i o n of t h i s procedure , t h e aluminum c h l o r i d e was cooled i n
a v o l u m e t r i c f l a s k t o l i q u i d n i t r o g e n t e m p e r a t u r e , t he s o l v e n t was added,
and t h e m i x t u r e was a l lowed t o thaw w i t h r e p e a t e d p a r t i a l r e f r e e z i n g .
S o l u t i o n s which were o n l y s i i g h t i y d i s c o l o r e d were obia ine i i i n t h i s mailner
3
S e n s i t i v i t y T e s t i n g of P e r c h l o r a t e S o l u t i o n s
L i th ium p e r c h l o r a t e s o l u t i o n s such a s a r e b e i n g p r e p a r e d on t h i s program
a r e thermodynamica l ly u n s t a b l e . A p o t e n t i a l e x p l o s i v e f o r c e can be ca l cu -
l a t e d from thermodynamic d a t a acco rd ing t o R e f , 13 (nRT-method).
been c a l c u l a t e d , e . g . , t h a t 2 M LiGlO4/DMF h a s 52.6 p e r c e n t o f the e x p l o s i v e
f o r c e of TW.
It h a s
4 S e n s i t i v i t y t e s t s were performed w i t h : ! M LiClO
#2/DMF #6-3, and s a t u r a t e d LiC104 #2/AN #4-2 ( l e s s t h a n 2 m o l a r ) .
s o l u t i o n s were s u b j e c t e d t o 250 in . - lb of impact on a mod i f i ed J e t P ropu l -
s i o n Labora to ry impact t e s t e r and t o 72 i n c h e s by 2 pounds on an O l i n
Matheson d r o p w e i g h t t e s t e r .
#2/PC #2-11, 3.5 M LiClO 4 These
A l l r e s p o n s e s were n e g a t i v e .
A l though t h e s e t e s t s seem t o i n d i c a t e t h a t the above s o l u t i o n s can be
hand led s a f e l y , such s e n s i t i v i t y t e s t s a r e n e v e r comple t e ly c o n c l u s i v e .
The same s o l u t i o n s could g i v e p o s i t i v e r e s u l t s on d i f f e r e n t t y p e s o f
t e s t s ; t h e y could c o n s t i t u t e , e .g . , an e x p l o s i v e haza rd upon h e a t i n g ,
s p a r k i n g , e t c .
13
NUCLEAR MAGNETIC RESONANCE STHUCTUlML STUDIES
A l C l and L i C l i n A c e t o n i t r i l e 3
It h a s been h y p o t h e s i z e d p r e v i o u s l y (Ref .
r e a c t i o n t h a t o c c u r s i n 1 M A l C l /AN i s : 3
5 ) t h a t t h e major s p e c i e s
based on NM& r e s u l t s . S t u d i e s of t h e C135 r e s o n a n c e i n s e v e r a l LiCl f2 + A1C13 #3/AN ##4-1 s o l u t i o n s have r e v e a l e d t h e p r e s e n c e o f C l - i o n s i n a 1 1 o f
the s o l u t i o n s , even t h e 1 M A l C l /AN s o l u t i o n . The c o n c e n t r a t i o n o f C1-
i o n s h a s no t been de termined a s y e t . S e v e r a l known s o l u t i o n s were t r i e d
f o r c a l i b r a t i o n p u r p o s e s , p r i m a r i l y aqueous lIC1 of d i f f e r e n t c o n c e n t r a t i o n s ;
however, none was found t o be s u i t a b l e . The C 1 - i o n c o n c e n t r a t i o n i s
a p p a r e n t l y s m a l l compared t o the c o n c e n t r a t i o n of A l - c o n t a i n i n g s p e c i e s ,
b u t n o t n e g l i g i b l e , t h u s i n d i c a t i n g t h a t t he a d d i t i o n of A l C . 1 t o AN d o e s
n o t r e s u l t i n t h e c o m p l e t e l y q u a n t i t a t i v e r e a c t i o n shown above.
3
3
Thc C 1 3 5 da ta i n d i c a t e t h a t Eq. 1 sliould bc expressed i n a n nmondtrtl form:
- 4 A1C13 + nAN -+ (1 + 2 ) A1(AN)n+++ + ( 3 - 2 ) M C 1 4 + € c1-
where
aluminum c h l o r i d e ) .
g i v e n by (1 + :)/4 r a t h e r t h a n 1/4.
s m a l l t h i s r a t i o w i l l s t i l l be c l o s e t o 1/4.
r e p r e s e n t s t he number of moles o f C I - formed ( p e r 4 moles of
The r a t i o of c o o r d i n a t e d A 1 t o a l l A 1 i s t h e n
However, b e c a u s e c i s a p p n r c n t l y
The broadening o f the AN p r o t o n l i n e s shown and d i s c u s s e d i n R e f . 4 h a s
been i n v e s t i g a t e d f u r t h e r . S p e c t r a were t a k e n a t s e v e r a l t e m p e r a t u r e s
f rom room t e m p e r a t u r e t o a p p r o x i m a t e l y -25 C . Two of t h e s e s p e c t r a t a k e n
a t 30 and -23 C a r e shown i n F i g , 7 . A s e x p e c t e d , b o t h p r o t o n l i n e s
narrow a t t h e lower t e m p e r a t u r e which i s c o n s i s t e n t w i t h the b r o a d e n i n g
of t h e l i n e s b e i n g due t o exchange e f f e c t s ,
14
From L e f t t o R i g h t . Spec- t r u m b w a s Taken a t H i g h e r
i a . Low Temperature(-23 C) b . Room Temperature (30 C)
F i g u r e 3 . High R e s o l u t i o n P r o t o n ( H 1 ) Resonance i n 1 M A l C l /AN 3
To o b t a i n n i n Eq. 2 , the p r o t o n l i n e s i n the AN s p e c t r a due t o c o o r d i n a t e d
and b u l k AN were i n t e g r a t e d . This g i v e s t h e r a t i o of c o o r d i n a t e d t o c o o r d i -
n a t e d p l u s b u l k AN. U t i l i z i n g the r e s u l t s of R e f . 5 , which s u b s t a n t i a t e s
3' Eq. 1, the r a t i o i s m u l t i p l e d by f o u r and t h e molar r a t i o of AN t o A l C l
T h i s g i v e s a c o o r d i n a t i o n number of 6 , 2 . The l i m i t s of e r r o r i n t h e a r e a
r a t i o a r e e s t i m a t e d t o approx ima te ly +5 p e r c e n t . The e r r o r i n t h e f a c t o r
of f o u r cannot be de t e rmined b u t i s expec ted t o be s m a l l because c (Eq. 2 )
i s s m a l l . Thus , the c o o r d i n a t i o n number f o r A 1 i n AN i s de te rmined t o
be 6. This i s i n good agreement w i t h r e s u l t s f o r A 1 i n o t h e r s o l v e n t s
(Ref . 1 4 t h r o u g h 16).
+++ ,
+++ .
B o a d l i n e A127 NMB. S p e c t r a .
s e v e r a l 1 M A l C 1 3 #3/PC #2-12 s o l u t i o n s c o n t a i n i n g d i f f e r e n t c o n c e n t r a -
t i o n s of L i C l #2 u s i n g t h e b r o a d l i n e s p e c t r o m e t e r . These s p e c t r a a r e
shown i n F i g , li. Chemical s h i f t measurements u s i n g a 1 M A l C l aqueous
s o l u t i o n i n t h e i n n e r t u b e of a c o a x i a l t u b e specimen show t h a t t h e l e s s
i n t e n s e l i n e i s t h a t due t o t h e c o o r d i n a t i n g A 1 c o n t a i n i n g s p e c i e s . These
d a t a have been ana lyzed i n t h e same manner a s t h a t r e p o r t e d p r e v i o u s l y
(Ref .
c e n t r a t i o n o f t h e c o o r d i n a t i n g A 1 s p e c i e s a s a f u n c t i o n o f L i C l concen-
t r a t i o n i s shown i n Fig. , 5 . The r e s u l t s a r e v e r y s i m i l a r t o t h o s e
o b t a i n e d for t h e LiCl + A l C l /m s e r i e s . Thus, the f o l l o w i n g ma jo r 3 s p e c i e s r e a c t i o n o c c u r s i n t h e A l C l /PC s o l u t i o n a s w e l l :
The A127 s p e c t r a have been r e c o r d e d f o r
3
5 ) f o r t h e LiCl + A l C l /AN s o l u t i o n . A p l o t of t h e r e l a t i v e con- 3
3
(3) -
4 A1C13 + n PC-+Al(PC) , +++ + 3 A1C14
The A127 s p e c t r a w e r e o b t a i n e d a l s o f o r 0 .1 M A l C l #3/PC #2-12.
shown i n F ig . 6 . 1 M A l C l /PC) t h e s p e c t r a were r e c o r d e d much s l o w e r w i t h h i g h e r g a i n and 3 l o n g e r time c o n s t a n t . The s p e c t r a show t h e same c h a r a c t e r i s t i c s a s t h o s e
o b t a i n e d from t h e 1 M A l C l /PC, namely, two a luminum-con ta in ing s p e c i e s
w i t h r e l a t i v e i n t e n s i t y of 3 t o 1. From t h i s r e s u l t it a p p e a r s t h a t the
aluminum-containing s p e c i e s p r e s e n t i n 0.1 M A l C l /PC d o n o t d i f f e r f rom
t h o s e i n 1 M A1C13/PC.
This i s 3
Because o f t he much lower s i g n a l ( o n e - t e n t h of t h a t f o r
3
3
16
w
a. No L C 1
0
- 0
N
8
I
0
b. 0.25 X LiCl c . 0.50 X h C 1 a. 0.70 H ~ c i
Magnetic F i e l d 1s 7.17 Kgouse and Inerasacs From Lef t t o Right . h.0 Linea ID Each Spectrum are i Separated by Approximately 0 . 8 gausa
Figure 4. A127 Nuclear Magnetic Resonance in 1 M A l C l /PC Containing Various Concentrations of L i C l 3
THE R E L A T I V E P O P U L A T I O N S WERE v) W DETERMINED FROM THE PEAKS O F
THE D E R I V A T I V E CURVES OF T H E - V W L v)
- SPECTRA SHOWN I N F I G . 4. c3 THE S O L I D L I N E I S A T H E O R E T I C A L - z L I N E BASED ON THE ASSUMPTION
'
T H A T A L L C 1 - FORMS A l C 1 4 . I- s - n rz 0 0
LL 0
z 0
I-
I- W u I 0 V
W > I-
0 .15-
- 2 = 0.10
- 2 0.05, rz
0 0.2 0.4 0.6 0.8 1
CONCENTRATION OF L i C l , MOLAR
0
Figure 5 . Approximate I t e l a t i v e P o p u l a t i o n s o f Coord ina t ing ,11 S p e c i e s i n 1 M A l C l /PC a s a Funct ion o f Added L i C l 3
18
J - 8 . . ' ._ ...
UI W .
I
Kgauss and Increases From Left t o Right. The Separation of the Two Lines i s Approxi-
-- I -8. _I , - . .."_- ~ - - I _n--" . I
I - - . _ _ _ _ _ _ .
1
1 I
8 " . i -_ -_-...-_ --. * -
Figure 6.. A127 Nuclear Magnetic Resonance i n 0 . 1 M A l C l /PC 3
19
1 High R e s o l u t i o n H1 NMR S p e c t r a . PC $42-6 and 1 M A l C l
The H 3 o r d i n a t e d Pc as w e l l as b u l k PC.
t a i n t h e r a t i o of c o o r d i n a t e d PC t o c o o r d i n a t e d p l u s b u l k PC.
t h e resu l t s of t h e A127 s p e c t r a a n a l y s i s and t h e i n t e g r a t i o n r e s u l t s , t h e
c o o r d i n a t i o n number f o r Al'" i n PC i s 6.3. f o r A l f + + i n PC i s i n agreement w i t h t h e c o o r d i n a t i o n number of A1
AN and o t h e r s o l v e n t s ( r e f e r t o p r e v i o u s d i s c u s s i o n ) .
The h i g h r e s o l u t i o n H s p e c t r a of pure
#3/PC #2-6 have been shown p r e v i o u s l y (Ref. 4 ) . 3 1 spec t rum of t h e 1 M A l C l /PC specimen e x h i b i t s peaks due t o CO-
These peaks have been i n t e g r a t e d t o ob-
U t i l i z i n g
A c o o r d i n a t i o n number of 6 +++ i n
The spectrum o f n e a t p ropy lene c a r b o n a t e (PC #2-12) h a s been s t u d i e d f u r t h e r
unde r h i g h r e s o l u t i o n c o n d i t i o n s . The complexi ty of t h e spec t rum s u g g e s t s
t h a t the chemica l s h i f t s and c o u p l i n g c o n s t a n t s a r e q u i t e s i m i l a r i n magni-,
t u d e . This s i t u a t i o n r e s u l t s i n a v e r y complex s p e c t r a l p a t t e r n i n which
a s imple p a t t e r n canno t be a s s i g n e d t o e a c h t y p e of r e s o n a t i n g n u c l e i .
However, t h e s p e c t r a l f e a t u r e s due t o r e sonance of t h e me thy l p r o t o n s a r e
w e l l removed from t h e r i n g p r o t o n s i g n a l s . For t h e pu rpose of d e t e r m i n i n g
c o o r d i n a t i o n number, t h e s imple p a t t e r n due t o t h e me thy l g r o u p p r o v i d e s
a l l t h e n e c e s s a r y i n f o r m a t i o n . For t h e s t u d y of p o s s i b l e p a r t i a l po lymer i -
z a t i o n o r d e g r a d a t i o n r e a c t i o n of p ropy lene c a r b o n a t e u n d e r t h e i n f l u e n c e
of aluminum s p e c i e s , a f u r t h e r i n v e s t i g a t i o n of t h e s p e c t r a due t o the
r i n g p r o t o n s may be advan tageous .
CuCl and LiCl i n Dimethyl Formamide 2
The h i g h r e s o l u t i o n p r o t o n s p e c t r a of t h e s o l u t i o n s of CuC12 #2 i n DME'
#5-2 w i t h v a r i o u s amounts of L i C l # 2 added have been o b t a i n e d o v e r a
6-month p e r i o d . The i n i t i a l s p e c t r a were r e p o r t e d i n R e f . 5 . The l i n e
p o s i t i o n s and s h a p e s have been observed t o change c o n t i n u o u s l y and appa r -
e n t l y a s y m p t o t i c a l l y over t h a t t ime. I n a d d i t i o n , t h e v i s i b l e c o l o r of
t h e s o l u t i o n s h a s g r a d u a l l y changed. The f r e s h l y p r e p a r e d s o l u t i o n s r a n g e
i n c o l o r from g r e e n f o r n o L iC l t o orange f o r 1 and 2 M LiC1. On s t a n d i n g ,
t h e g r e e n s o l u t i o n s become r e d d i s h orange w h i l e t h e o range s o l u t i o n s retnain
20
f a i r l y c o n s t a n t .
t o y e l l o w immedia te ly f o l l o w i n g p r e p a r a t i o n b u t became c o l o r l e s s i n a
few d a y s . An e x p l a n a t i o n of t h e p r o c e s s e s o c c u r r i n g on t h i s l o n g time
s c a l e h a s n o t y e t been f o r m u l a t e d . It i s presumed t h a t t h e d i f f e r e n t
c o l o r s a r i s e f rom d i f f e r e n t copper complexes. The e x a c t n a t u r e of the
chemica l env i ronmen t s i nvo lved and the mechanism f o r the c o n v e r s i o n of
copper s p e c i e s a r e s t i l l undetermined . The changes a r e a l s o unknown.
A 0 . 1 M s o l u t i o n of CuC12 #2 i n DMF #5-2 was obse rved
P e r i o d i c moni-tpring of t h e
h a s r e s u l t e d i n t h e f o l l o w i n g group of o b s e r v a t i o n s :
spec t rum d u r i n g t h e t ime p e r i o d of i n t e r e s t
1. The s p e c t r a of f r e s h l y prepared 1 M CuC12/DMF s o l u t i o n s c o n s i s t
of two v e r y broad l i n e s , one from t h e s i x me thy l g r o u p p r o t o n s
and one from the s i n g l e a ldehyde- type p r o t o n .
a . A d d i t i o n of L i C l r e s u l t s i n d e c r e a s e d l i n e w i d t h of b o t h
l i n e s .
b . The s e p a r a t i o n between t h e l i n e s d e c r e a s e s w i t h added LiC1.
2 . All s p e c t r a l f e a t u r e s d e c r e a s e i n l i n e w i d t h w i t h t i m e .
3 . The d o w n f i e l d , s m a l l e r , broad l i n e s h i f t s toward t h e s t r o n g e r ,
u p f i e l d l i n e and as -ymptot ica l ly approaches 304 Hz which i s the
v a l u e of the s p l i t t i n g observed i n n e a t DMF. T h i s i s shown i n
F i g . 7 . With 2 M LiCl added, t h e i n i t i a l s p l i t t i n g i s q u i t e
c l o s e t o the f i n a l v a l u e and o n l y a s l i g h t sha rpen ing o f t h e
l i n e h a s been d e t e c t e d .
4 . A f t e r s e v e r a l months, a sma l l peak a p p e a r s f a r d o w n f i e l d . The
s p l i t t i n g i n c r e a s e s w i t h t i m e and a s y m p t o t i c a l l y approaches a
p o s i t i o n which i s dependent on t h e L iC l c o n c e n t r a t i o n a s shown
i n F i g . 8 .
The p r e c e d i n g r e s u l t s have r e q u i r e d a r e v i s i o n of t h e i n t e r p r e t a t i o n of
the s p e c t r a p r e s e n t e d i n F i g . 3 of R e f . 4 . The two l i n e s found i n
f r e s h l y p r e p a r e d 1 M CuC12/DMF appear t o be due t o t h e a ldehyde and
methyl p r o t o n s r a t h e r t h a n due t o a d i s t i n c t i o n between c o o r d i n a t e d and
b u l k DMF.
2 1
s .)
7 f c o u A w w
a z K
w w
- n o
- k 2 2 z
k-
k . . z 00--4 W 0
- 0 u
o n n
d " 0 9
z o a 0 0
8 hl <
az J 0 I:
a
c
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3 u LL 0
z 0
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t- z w u 2 0 0
- d
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0
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0 < 0
-0 -
0 0 0
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22
o a 0
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o a I
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O a1 o-a+- o a
0 .
o < 0
0 (
0 I 0
a 0
a C
a
-0-a- o a 0 0
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o a
0
0
--o 0 0
0
0
0
-0 0
0 0-
0
I
O
8 h
L c V
A LL 0
.-
rr
0 x 4 c .. h( c
V 3 0
LL 0
o a o o z 0 0 - - t- m o o . I-
0 0 - N 2 . . I- Z W u z 0 u I 0 0 0 0
a - a 4
m --rrl
\L
0 - w 0
- E
-ii
c 0 - - w v)
YS - a
ZH ' U I H S
These o b s e r v a t i o n s s u g g e s t t h a t the s o l v e n t i s i n i t i a l l y r a p i d l y exchanging
i n t h e s o l v a t i o n s p h e r e of a pa ramagne t i c s p e c i e s . The changes i n p o s i t i o n
and l i n e shape a r e c o n s i s t e n t w i t h t h e f o r m a t i o n o f a s p e c i e s i n which t h e
s o l v e n t i s s h i e l d e d from t h e pa ramagne t i c e l e c t r o n . Evidence t h a t t h i s
s h i e l d i n g is l i k e l y due t o t h e c h l o r i d e i o n i s p rov ided by t h e smal le r s h i f t s
observed with added LiC1. The s m a l l e r s h i f t o c c u r s b o t h i n i t i a l l y i n the
broad l i n e d i s p l a c e m e n t and i n t h e p o s i t i o n of t h e s m a l l peak f a r downf ie ld
i n t h e l a t e r s p e c t r a .
B r o a d l i n e H1 and Li7 s p e c t r a have a l s o been r e c o r d e d i n some o f t i i e se
spec imens a s a f u n c t i o n of r ad io - f r equency power 2 weeks a f t e r p r e p a r a t i o n .
The purpose of t h e s e e x p e r i m e n t s was t o d e m o n s t r a t e t h e e f f e c t of the para-
magne t i c s p e c i e s on t h e r e l a x a t i o n t imes of t h e s e r e s o n a n c e s . A s e x p e c t e d ,
t h e s a t u r a t i o n b e h a v i o r of t h e H r e s o n a n c e s i n DMF c o n t a i n i n g L i C l and
CuCl d i f f e r s from t h a t i n n e a t DMF. The l i n e s a t u r a t e s less r e a d i l y i n
t h e DMF c o n t a i n i n g CuC12 a s a r e s u l t of i n c r e a s e d r e l a x a t i o n v i a i n t e r -
a c t i o n of p r o t o n s w i t h t h e s p i n of t h e pa ramagne t i c s p e c i e s . However, t he
s a t u r a t i o n b e h a v i o r of t h e Li7 l i n e i n 1 M L i C l + 1 M CuC12/DM.F i s t h e same
a s it i s i n 1 molar l i t h i u m c h l o r i d e s o l u t i o n (LiC1 #!!/Dm #5-2). T h i s
s u g g e s t s t h a t t h e r e l a x a t i o n of t h e L i r e s o n a n c e i s n o t a f f e c t e d by t h e
paramagnet ic s p e c i e s . Thus f a r , t h i s r e s u l t i s n o t e x p l a i n e d . It may
be due t o " s h i e l d i n g " of t h e Li+ i o n s from t h e pa ramagne t i c s p e c i e s by
coord ina ted m o l e c u l e s s u r r o u n d i n g the pa ramagne t i c s p e c i e s , and/or mole- '
tules coord ina ted by t h e L i i o n s , o r because the pa ramagne t i c copper
s p e c i e s have s t r u c t u r e s s i m i l a r t o CuCl -(n-2) w i t h t h e pa ramagne t i c
e l e c t r o n i n t h e c e n t e r of the s t r u c t u r e . The h i g h r e s o l u t i o n H s p e c t r a
of 1 M LiCl/DMF do n o t show c o o r d i n a t e d peaks ; however , L i i o n s a r e
expec ted t o c o o r d i n a t e l e s s s t r o n g l y t h a n A 1 i o n s r e s u l t i n g i n a much
h i g h e r exchange r a t e . High exchange r a t e s would p r e c l u d e t h e o b s e r v a t i o n
of coord ina ted peaks a t room t e m p e r a t u r e .
1
2
+
1 n
f .
+++ ,
24
PHYSICAL PROPERTY DETERMINATIONS
S o l u b i l i t y Measurements
The s o l u b i l i t y d a t a c o l l e c t e d d u r i n g t h i s r e p o r t p e r i o d a r e p r e s e n t e d i n
Tab le 4 . The samples were prepared b a s i c a l l y i n t h e manner d e s c r i b e d i n
R e f . 3. Copper c o n t e n t s o f the samples d i l u t e d w i t h w a t e r were measured
by a tomic a b s o r p t i o n . The d a t a p re sen ted r e p r e s e n t , t h e r e f o r e , t h e s o l u b i l i t y
of copper i n t h e s e s o l u t i o n s and d o n o t y i e l d any i n f o r m a t i o n conce rn ing the
f a t e of t h e f l u o r i d e i o n s .
The s o l u b i l i t y of CuF2 i n t h e pure s o l v e n t s DMF and PC was v e r y low. It
was i n c r e a s e d t o a g r e a t e x t e n t by t h e a d d i t i o n o f LiClO o r LiC1. This 4 can be e x p l a i n e d by t h e p r e c i p i t a t i o n of L iF a c c o r d i n g t o
CuF + 2 L i C l = CuC12 t 2 LiF 2
and
CUE' + 2 LiC104 = Cu(C104)* + 2 L i F 2
(4)
(5)
No d a t a a r e a v a i l a b l e f o r t h e s o l u b i l i t y of copper p e r c h l o r a t e . Copper
c h l o r i d e h a s a h i g h s o l u b i l i t y i n DMF, and it i s s i g n i f i c a n t t h a t the
s o l u b i l i t y of CuF2 i n 1 M LiCl/DMF d o e s n o t a p p e a r t o depend on the
t e m p e r a t u r e and f u l f i l l s the s t o i c h i o m e t r i c r e q u i r e m e n t s of Eq. 4 . The
s o l u b i l i t y of CuF2 i n 1 M L iCl + 0 .075 M A l C l /DMF a p p e a r s t o be s i g n i -
f i c a n t l y lower t h a n i n 1 M LiCl/DMF.
r e a d i l y , a l t h o u g h a p r e c i p i t a t i o n of a s p e c i e s c o n t a i n i n g copper and
aluminum may be a p o s s i b i l i t y .
3 An e x p l a n a t i o n canno t be g i v e n v e r y
The s o l i d r e s i d u e o b t a i n e d by p r e p a r i n g the s a t u r a t e d s o l u t i o n of CuF2
i n 1 M LiCl/DMF was examined a s shown s c h e m a t i c a l l y i n F i g .
of CuF2 #3 was added t o 15 m i l l i l i t e r s of 1 M LiCl#2/DMF #5-l. p o r t i o n of t h e r e s u l t i n g mix tu re was c o l l e c t e d and a n a l y z e d ; i t c o n t a i n e d
1.53 mmoles of copper ( a s much copper a s c o n t a i n e d i n 0.16 gram of CuF2)
and 14 .7 mmoles l i t h i u m , probably p r e s e n t i n t h e form of LiF. C o n s i d e r i n g
t h e l i m i t e d accu racy o f t h e p rocedures i n v o l v e d , t h e p r e c i p i t a t i o n of L iF
a c c o r d i n g t o Eq. 4 a p p e a r s t o be q u a n t i t a t i v e .
9. One gram
The s o l i d
x x b n . . X K
M a lnln . . m
a3
I n 0 Lno n o I n 0 I n 0 In m a N a a a a a a a N
rl 4
I
$ 0
+ !2 n
2 % 4 4 u u 3 3 E E d rl
START :
15 M I L L I L I T E R S 1 M L i C i I D M F
1 GRAM C u F 2
A N A L Y S I S : ASSUMED T O BE PRESENT:
1 . 5 3 MMOLES Cu
(CORRESPOND1 0.16 GRAM c ~ F ~ 1 - q . - NG TO
~- x 1 - 1 4 . 7 MMOLES L i -- -:/I
/ I -_
(AS COMPARED TO 1 5
SOLUT I ON) MMOLES L i I N ORIGINAL'
CuF2 + 2 L i C l = C u C l z + 2 L i F
0.5 M CuC12/DMF
L i F (+ SURPLUS CuF2)
F i g u r e 9 . Examinat ion of P r e c i p i t a t e Obta ined i n D i s s o l v i n g CuF i n 1 M LiCl/DMF 2
27
The s o l u b i l i t y of CuCl
found p r e v i o u s l y i n pure DMF (1 .30 M a t 25 C , a c c o r d i n g t o R e f . 3 ) and
i n 1 M LiCl/DMF ( 1 . 0 4 a t 25 C , a c c o r d i n g t o R e f . 3 ) . c e r t a i n n o n r e p r o d u c i b i l i t y r a t h e r t h a n a r e a l e f f e c t e x i s t s ; t h i s i s n o t
unexpec ted c o n s i d e r i n g t h e long-term changes observed i n CuCl /DMF samples , 2 because t h e p r e p a r a t i o n of t h e samples invo lved t r e a t m e n t f o r pro longed
p e r i o d s under somewhat v a r y i n g c o n d i t i o n s .
i n 1 M L iCl + 0.075 M A l C l /DMF was h i g h e r t h a n 2 3
It a p p e a r s t h a t a
Heat of S o l u t i o n
The LKB c a l o r i m e t e r was checked o u t and c a l i b r a t e d . V a l u c s r e p r o d u c i b l e
t o w i t h i n l e s s t h a n 1/2 p e r c e n t were o b t a i n e d f o r the c a l o r i m e t e r c o n s t a n t ,
and h e a t of s o l u t i o n v a l u e s a g r e e i n g w e l l w i t h t h o s e i n t h e l i t e r a t u r e have
been measured ( d u r i n g a n o t h e r program) f o r t h e d i s s o l u t i o n of K C 1 i n w a t e r .
The h e a t produced by t h e breakage of t h e sample ampoule was found t o be
n e g l i g i b l e .
Measurement of Vapor P r e s s u r e s
A g a s - s a t u r a t i o n method a s d e s c r i b e d i n R e f . 1 7
p r e s s u r e s . The a p p a r a t u s i s shown i n F i g . 10. N i t r o g e n i s bubbled t h r o u g h
was used t o measure v a p o r
the s a t u r a t o r which i s immersed t o t h e l e v e l of t h e g l a s s wool wad i n t o a
cons t an t - t empera tu re m i n e r a l o i l b a t h . The n i t r o g e n i s s a t u r a t e d w i t h the
s o l v e n t , and t h e s o l v e n t i s c o l l e c t e d i n a l i q u i d n i t r o g e n t r a p . The con-
n e c t i o n between s a t u r a t o r and t r a p i s m a i n t a i n e d above t h e t e m p e r a t u r e of
t h e cons t an t - t empera tu re b a t h , i f n e c e s s a r y by means of h e a t i n g t a p e s .
The g a s f low i s measured by a soap bubble f lowmete r . To minimize t h e
e r r o r caused by e v a p o r a t i o n of wa te r i n t he f lowmete r , a 2 : l m i x t u r e of
g l y c o l and g l y c e r o l c o n t a i n i n g approx ima te ly 7-1/2 p e r c e n t of U l t r a w e t
60L was used . T y p i c a l n i t r o g e n f l o w r a t e s were 1 t o 2 ml/ sec .
The v a p o r p r e s s u r e d a t a o b t a i n e d t o d a t e a r e l i s t e d i n Tab le 5 . Al though
f u r t h e r checks on t h e r e p r o d u c i b i l i t y of the method s h a l l be made, the
28
- N I T R O G E N __t ~
S O L U T I ON---<
+
FLOW METER
- -
u SATURATOR
F i g u r e 10 . Appara tus f o r Measuring Vapor P r e s s u r e s by Gas S a t u r a t i o n Method
T B L E 5
VAPOR PRESSURES
S o l u t i o n
PC jf2-12
PC #2-12
PC &-11
PC $2-11
1.00 M LiC104 k2/PC #2-11
1.00 M LiC104 #2/PC #2-11
0 .125 M T M A ~ P F ~ # i /pc #-ii
DMF ff5-2
DMF #5-2
DMF #5-5
DMF #5-2
DMF #5-5
1.00 M hC104 #2/DMF' #5-1 1.00 M LiC104 #2/DMF #5-1
1.00 M LiC104 #2/DMF #5-l
1.00 M LiCl #/DMF #5-l
1.00 M LiCl #2 + 0.075 M A1C13 ff3lDM.F #6-2
AN #4-2
1.00 M LiC104 #2/AN #4-2
Temperature, C
25 L "5
60
60
60
60
25
60
25 25
25
60
60
25 25
60
60
25
60
25
25
~ ~~ ~~
Japor P r e s s u r e ,
__ mrn Hg
0 .082
0.056
0.803
0.796
0.657 0.663
0 .062
0 .52
3.96 4.10
3.79
26.7
25 .9
3.18
3.14
22 .6
23.55
3.32
22.80
89 . O
79 .4
Average Vapor ? r e s s u r e Va lues ,
mm &
0.80
0 . 6 6
3 .95
26 .3
3.1G
r e s u l t s g e n e r a l l y a p p e a r t o be a c c u r a t e w i t h i n 1 t o 2 p e r c e n t .
o b t a i n e d w i t h p ropy lene c a r b o n a t e a t 2 5 C v a r y t o a g r e a t e r e x t e n t and
no ave rage v a l u e i s y e t cons ide red r e p r e s e n t a t i v e ; i n t h e s e e x p e r i m e n t s ,
t h e vapor p r e s s u r e was v e r y l o w and t h e amount of s o l v e n t c o l l e c t e d was
s m a l l , t h u s i n c r e a s i n g e x p e r i m e n t a l e r r o r s . However, t h e vapor p r e s s u r e
of AN i s h i g h , and t h i s r e s u l t w i l l be rechecked t o v e r i f y t h a t complete
s a t u r a t i o n was o b t a i n e d .
R e s u l t s
Measurement of D i f f u s i o n C o e f f i c i e n t s by t h e
P o r o u s Di sk Method
D i f f u s i o n c o e f f i c i e n t s a r e b e i n g determined by t h e method of Wal l ( R e f . 18
t h r o u g h 2 0 ) . The p rocedure i n v o l v e s f i l l i n g an evacua ted porous p o r c e l a i n
d i s k w i t h t h e s o l u t i o n t o be s t u d i e d , and t h e n suspend ing t h e d i s k from one
arm of a n a n a l y t i c a l b a l a n c e on a f i n e w i r e , i n a l a r g e volume of pu re
s o l v e n t . Measurement of t h e a p p a r e n t w e i g h t change of t h e d i s k a s a
f u n c t i o n of time a l l o w s t h e d e t e r m i n a t i o n of t h e d i f f u s i o n c o e f f i c i e n t
from t h e e q u a t i o n :
where W ( t ) i s the a p p a r e n t w e i g h t of t h e suspended d i s k a t t ime t , W(m)
i s the w e i g h t a f t e r e q u i l i b r i u m has been r e a c h e d , D i s t h e d i f f u s i o n
c o e f f i c i e n t , and Q! and b a r e c o n s t a n t s .
C a l i b r a t i o n r u n s w i t h a s o l u t i o n o f known d i f f u s i o n c o e f f i c i e n t a l l o w
t h e d e t e r m i n a t i o n of t h e a p p a r a t u s c o n s t a n t , a. Appara tus c o n s t a n t s were
d e t e r m i n e d u s i n g s t a n d a r d 1.5 M KCl/%O - %O (D = 1.87 x a t 2 5 C ; R e f . 2 1 ) f o r two recommended Micro-Porous F i l t e r D i s k s (2 by 1/4
i n c h , No. 10 p o r o s i t y ) , o b t a i n e d from S i l a s F l o t r o n i c s .
f o r t h e c o n s t a n t s of t h e two f r i t s t o be used were = 6.49 cm and
% = 6.59 cm
2 -1 cm s e c
The a v e r a g e v a l u e s -2
1 -2 , r e s p e c t i v e l y .
31
The d i f f u s i o n c o e f f i c i e n t s de te rmined a r e p r e s e n t e d i n T a b l e 6 .
1.00 M LiCl #2/DMF #6-1 1.00 M LiCl #2/DMF #6-2
1.00 M LiCl #! + 0.075 M A1C17 #3/DMF #6-2
TABLE 6
DIFFUSION COEFFICIENTS, D , OF DIMETHYL FORM.4MIDE ELECTROLYTES AT 25 C
DMF #6-2
Mixture of DMF #6-1, 6-2, and 6-4
Mixture of DMF #6-3 and 6-5
D i f f u s i o n Zoef f i c i e n t ,
1 cn? sec-
7 . 2 8 x lo-‘ 7.30 x
5.76 x
5.99 x
5.72 x
D i f f u s i o n C o e f f i c i e n t Lverage Value
cm2 sec-1
7.3 x lo-6
5.9 x lo-6
* U n d i s t i l l e d , s p e c t r o g r a d e m a t e r i a l
I n a l l f i v e r u n s , p l o t s of l o g [ W ( t ) - ~ ( c o ) ] vs t ime gave r e l a t i v e l y
s t r a i g h t l i n e s i n d i c a t i n g t h a t Ey. 3 w a s b e i n g f o l l o w e d . Approximate ly
1.5 l i t e r s of s o l v e n t were used i n e a c h d e t e r m i n a t i o n and a l l measurements
were made a t 2 5 *0 ,02 C.
D e t e r m i n a t i o n of D i f f u s i o n C o e f f i c i e n t s
bv ChronoDotent iometrv
Chronopotent iomet ry i s b e i n g used t o d e t e r m i n e the d i f f u s i o n c o e f f i c i e n t
of copper i n 1 M LiC1o4/DMF and 1 M LiCl/DMF.
been conducted on t h e r e d u c t i o n of copper i n t h e s e s o l u t i o n s . F i g u r e 11
shows a chronopotent iogram f o r the r e d u c t i o n o f CuCl,, i n 1 M LiCl/DMF.
The wave f o r the r e d u c t i o n of CuC12 i n 1 M LiClO /DMF i s s i m i l a r . The
copper wave i s w e l l d e f i n e d and t h e t r a l l s i t i o n time may be d e t e r m i n e d
w i t h good p r e c i s i o n . A t e n t a t i v e v a l u e f o r t he d i f f u s i o n c o e f f i c i e n t
of c o p p e r ( l 1 ) i n 1 M LiCl/DMF i s 1.1 x cm / s e c . T h i s v a l u e i s
P r e l i m i n a r y s t u d i e s have
x-
4
2
-2.5
h LL SI a
ai 2 .- A
3i -2.0 0 I
P)
\ cn
v
ai
a a v) > v)
5 0 > - - 1 . 5 -I
t- z w I- O L
a -
- 1 .o 0 5 10
T I M E , SECONDS
I ~
1
Figure 11. Chronopotentiogram of 0.01 M2CuC12 in 1 M LiCl/DMF; the Current Density is 1.6 ma/cm
t e n t a t i v e because a s i g n i f i c a n t amount of w a t e r may have been absorbed
by t h e s o l u t i o n d u r i n g t h i s p r e l i m i n a r y s t u d y , and t h i s amount of w a t e r
may change the d i f f u s i o n c o e f f i c i e n t .
A second wave a p p e a r s a t more c a t h o d i c p o t e n t i a l s . T h i s wave i s s m a l l e r
t h a n t h e copper wave and r e p r e s e n t s t h e r e d u c t i o n of w a t e r .
c u r r e n t d e n s i t i e s , two a d d i t i o n a l wavesappea r a t 0 and -400 m i l l i v o l t s .
The quarter-wave p o t e n t i a l o f t h e f i r s t wave i s t h e same a s t h e o p e n - c i r c u i t
p o t e n t i a l of a copper e l e c t r o d e i n t h i s s o l u t i o n .
t o oxygen because t h e s o l u t i o n was d e a e r a t e d w i t h n i t r o g e n and because t h e
r e d u c t i o n p o t e n t i a l f o r oxygen i s -200 m i l l i v o l t s .
A t much lower
The waves a r e n o t due
The r e d u c t i o n of coppe r ( I1 ) d o e s n o t appea r t o p r e s e n t any problems, and
a more a c c u r a t e d e t e r m i n a t i o n of t h e d i f f u s i o n c o e f f i c i e n t w i l l be made.
Measurement of D i e l e c t r i c C o n s t a n t s
F o r d e t e r m i n a t i o n of t h e d i e l e c t r i c c o n s t a n t , K~ , measurements made a t
microwave f r e q u e n c i e s of 8.5 and 2 5 Gljz w i l l be e x t r a p o l a t e d t o low f r e -
quency .
H a r r i s and O'Konski (Ref . 22) f o r h i g h p e r m i t t i v i t y l i q u i d s h a s been
adopted, (Ref. 4 ).
A somewhat mod i f i ed v e r s i o n of a t r a n s m i s s i o n method used by
Microwave Method D e s c r i p t i o n . The method i s based on d e t e r m i n i n g t h e
phase s h i f t and d e c r e a s e i n a m p l i t u d e of a wave when i t t r a v e l s t h o u g h
a d i e l e c t r i c sample.
t r a v e l i n g i n d i r e c t i o n T2 t o T1 ( F i g . 1 2 ) i n t e r f e r e s w i t h t h e sample
wave.
VSWR)* a r e t h e n measured w i t h and w i t h o u t the sample i n p l a c e .
d i f f e r e n c e i n minimum p o s i t i o n , t h e phase s h i f t , C , of t h e sample wave
i s o b t a i n e d , Measurement of t h e VS\flls a l l o w s c a l c u l a t i o n of Q , the
d e c r e a s e i n a m p l i t u d e .
A r e f e r e n c e wave of f i x e d phase and a m p l i t u d e
The r e s u l t i n g s t a n d i n g wave p o s i t i o n (minimum) and a m p l i t u d e ( o r
From t h e
"Voltage s t and ing wave r a t i o
cc W U 4 n VI
4
2
F, I-
= W I- W
I: cz ? W
n W I u L
W > 3 a = z o - I -
N n u I- z w
I - W WJ n a k
I
cz W z 3 I-
I I
s U
h
c m e cz
0 I- 0
4 N 0 v) >
..
L n
co + m a =r +-, W Cn W
35
A computer program h a s been used t o c a l c u l a t e Q and C from assumed K‘
and K ” v a l u e s ( K = K ’ - i K ” ) .
Q and c a s e r i e s of i n t e r s e c t i n g c o n t o u r s of K’ and K ” (Ref .22 ) . These
g r a p h s a r e u s e d f o r d e t e r m i n i n g K’ and K ” . The computer program makes
p o s s i b l e r a p i d c a l c u l a t i o n of Q vs C g r a p h s f o r v a r i o u s c e l l w i d t h s .
T h i s y i e l d s g r a p h s t h a t show f o r c o o r d i n a t e s
The p r e s e n t s e t u p ( F i g .
The m o d i f i c a t i o n s a r e a s f o l l o w s :
matched ( i .e . , do n o t have r e f l e c t i o n c o e f f i c i e n t s < O . 5 p e r c e n t ) and (2)
a f e r r i t e i s o l a t o r i s used t o a b s o r b waves r e f l e c t e d from the f i l l e d sample
c e l l . I n Ref . 22 an i r is was p o s i t i o n e d i n t h e r e f e r e n c e arm t o p r o v i d e
f o r c a n c e l l a t i o n of t h e r e f l e c t e d wave (Ref .
pu rpose , t h a t i s , t o p r e v e n t c o u p l i n g between t h e two arms . Using mod i f i . .
c a t i o n No. 2 , no c o u p l i n g between r e f e r e n c e and sample waves could be
d e t e c t e d .
12) d i f f e r s from the a p p a r a t u s d e s c r i b e d i n R e f . 22.
(1) a t t e n u a t o r s T1 and T a r e n o t f u l l y 2
4). Both have the same
F i g u r e 12 shows o n l y t h e 8 . 5 GHz equipment . The 2 5 GHz s e t u p i s s i m i l a r
e x c e p t t h a t t h e E-H t e e i s r e p l a c e d by a d i r e c t i o n a l c o u p l e r .
C o r r e c t i o n s f o r R e f l e c t i o n s ,
n e g l i g i b l e r e f l e c t i o n c o e f f i c i e n t s ( - 2 . 5 p e r c e n t ) .
and mipimum p o s i t i o n d i f f e r e n c e s a r e c o r r e c t e d f o r t h i s by s u b t r a c t i n g
t h e e f f e c t o f t h e s m a l l a m p l i t u d e waves r e f l e c t e d toward the p robe ( a s
shown by t h e curved a r r o w s i n F i g .
have been a l s o programmed on t h e computer . To o b t a i n t h e c o r r e c t i o n s
needed , t h e r e f e r e n c e and t h e sample waves e a c h a r e measured s e p a r a t e l y .
A t t e n u a t o r s T1 and T2 have s m a l l b u t n o t
The measured VSWRs
12) . These c a l c u l a t i o n s (Appendix A)
A t t e n u a t o r T1 r e f l e c t s a l s o a p a r t o f t h e wave t r a n s m i t t e d t h r o u g h the
sample. The r e f l e c t e d component r e a c h e s the r e a r f a c e of t h e c e l l , where
i t i s a g a i n r e f l e c t e d ( i f t h e c e l l c o n t a i n s l i q u i d w i t h a h i g h K ’ ) and
t h e n a d d s t o t h e t r a n s m i t t e d wave.
between two measurements and s u b s e q u e n t l y a v e r a g i n g the r e s u l t s a l l o w s
c a n c e l l a t i o n of t h e r e f l e c t e d weve (Ref .
Moving T by a d i s t a n c e of x /4 1
23).
36
A s i m i l a r d i sp l acemen t of t h e i s o l a t o r p reced ing t h e c e l l compensates f o r
secondary r e f l e c t i o n s a s s o c i a t e d w i t h t h a t component.
The changes made by a p p l y i n g t h e r e f l e c t i o n c o r r e c t i o n s depend on t h e K '
and K" v a l u e s of t h e sample. A t 8.5 GHz it h a s v a r i e d from -3 t o +12 pe r -
c e n t f o r K' and -12 t o 32 p e r c e n t i n K ! ' . S h i f t i n g t h e a t t e n u a t o r T
appeared t o e f f e c t a l e s s t h a n 5 p e r c e n t change i n K' and a -10 p e r c e n t
change i n K " .
1
T e s t R e s u l t s .
o b t a i n e d a t 8.5 GHz f o r 5 0 , s p e c t r o g r a d e me thano l , and AN#4-2 a r e pre-
s e n t e d i n Table 7 . Each of t h e s e was o b t a i n e d by employing t h e q u a r t e r
wave leng th s h i f t t e c h n i q u e f o r c a n c e l l i n g r e f l e c t i o n s from T The w a t e r
r e s u l t s a r e w i t h i n t h e expec ted -*5 p e r c e n t accu racy . The d i e l e c t r i c
c o n s t a n t , K ' , of methanol i s a c t u a l l y lower t h a n v a l u e s f o r which t h i s
microwave method i s b e s t s u i t e d . Use of a t h i c k e r c e l l and r e d i s t i l l a -
t i o n of t h e me thano l sample should y i e l d b e t t e r agreement . S i n c e l i q u i d s
hav ing w e l l known K' and K" v a l u e s b o t h i n t e r m e d i a t e between t h o s e of H 0
and methanol a r e n o t a v a i l a b l e , a c e t o n i t r i l e h a s been used f o r t e s t i n g
pu rposes . For AN t h e measurements were r e p e a t e d by s h i f t i n g t h e i s o l a t o r
by a q u a r t e r wave leng th . The r e s u l t s were e s s e n t i a l l y the same a s i n
Tab le 7 . by e x t r a p o l a t i n g t h e d a t a from 30, 40 , and 50 C t o 24 C .
i s approx ima te ly 14 p e r c e n t h i g h e r and f u r t h e r work i s i n p r o g r e s s u s i n g
d i f f e r e n t c e l l t h i c k n e s s e s (Ref , 23) t o r educe e f f e c t s due t o t h e mica
windows and t h e r e b y i n c r e a s e t h e accu racy .
T e s t i n g h a s been i n p a r t d e s c r i b e d ( R e f s . 4 and 5) . R e s u l t s
1'
2
The l i t e r a t u r e v a l u e s (Ref . 2 7 ) f o r comparison were ob ta ined
OW K ' v a l u e
The a p p a r a t u s f o r measurements a t 25 GHz h a s n o t been a s e x t e n s i v e l y
checked o u t a s t h e lower f requency a p p a r a t u s . The c r y s t a l r e s p o n s e law
h a s n o t been de te rmined a s y e t . Tes t ing f o r coup l ing between t h e sample
and r e f e r e n c e arms h a s been made. No s i g n i f i c a n t coup l ing was found.
I f p r e s e n t , such c o u p l i n g would lead t o l a r g e e r r o r s . A l so , p r e l i m i n a r y
e x p e r i m e n t s u s i n g a rough , 0 .255-cent imeter - th ick t e s t c e l l were made
on H20, s p e c t r o g r a d e methanol , and AN #4-2. The K' and K" o b t a i n e d
37
( e x c e p t K ’ f o r methanol) a r e a l l w i t h i n 16 p e r c e n t o f the l i t e r a t u r e d a t a .
Further work i s b e i n g conducted on making r e p e a t r u n s w i t h a t t e n u a t o r ( T ) and i s o l a t o r d i s p l a c e m e n t t o c a n c e l o u t secondary r e f l e c t i o n s . Sample
c e l l s of d i f f e r e n t t h i c k n e s s e s w i l l be used t o improve the a c c u r a c y .
a t t a i n a b l e a c c u r a c y may approach +5 p e r c e n t a l s o w i t h t h i s s e t u p .
1
The
TABLE 7
DIEUXTRIC CONSTANT TEST RESULTS AT 8.5 GHz (24 C)
L i t e r a t u r e V a l u e s
d , V , Sample cm GHz K ’ K” K ’ K”
H20 0.383 8.49 63.9 29.2 64.9 27.5
Me O B 0.383 8.49 8.05 9 .8 8.85 8.95
AN#4-2 0.383 8.49 35.6 9 . 0 31.3 8.2 L
R e f e r e n c e
24
25, 26
27
APPENDIX A
REFLFCTION CORRECTIONS FOR DIELECTRIC CONSTANT MEASUREMENTS
i W ) X 4/% E1(x) = H. e - R R e
-i ( 1/2) x E2(x) = e ?2 ( e
0 1 0
- R2e e
- R2e e -ix2
q6 - i(1/2) x E;(") = e
= E ( X ) + E (x )
= E ( X +n) + E ( x +n)
= E (x ) + E i ( x 4 )
= E ( X +~ + Ei(x4+n)
3 ,min 1 3 2 3
3,max 1 3 2 3
E
E
4,min 1 4
4,max 1 4
E
E
The r e f l e c t i o n c o e f f i c i e n t s H
m a t i o n s from the measured s t a n d i n g wave r a t i o s :
and R a r e c a l c u l a t e d by s u c c e s s i v e a p p r o x i - 0
The p h a s e s 9 and q a r e o b t a i n e d from 6
d( 1 E3,min()2 = 0 and d ( I E 4 , m i n dX = 0 , r e s p e c t i v e l y ,
4 dx 3
The a m p l i t u d e d e c r e a s e ( Q ) i s RR whereas t h e phase s h i f t ( E ) i s u!p?6. 0 These a r e t h e n used t o r e a d o f f K ' and K" from the computed g r a p h s .
39
The symbols a r e :
4 R = r e f l e c t i o n c o e f f i c i e n t s ; Ro f o r composi te wave E
E = e l e c t r i c f i e l d s f o r t h e waves ( E ’ r e f e r s t o t r a n s m i t t e d sample
and I1 f o r E 3
wave)
S u b s c r i p t s
1 = r e f e r e n c e wave
2 = sample wave
3 = composi te wave w i t h empty c e l l
4 = composi te wave w i t h f i l l e d c e l l
x = d i s t a n c e s (:!;TTz/Xg ) w i t h s u b s c r i p t s d e s i g n a t i n g the minima of
i s minimum of wave x3 t h e c o r r e s p o n d i n g s t a n d i n g waves, i . e .
w i t h empty c e l l .
40
WORK PLANNED FOR NEXT QUARTER
PREPARATION OF ELECTROLYTES
Work on t h i s phase w i l l be performed e s s e n t i a l l y on a r o u t i n e b a s i s .
STRUCTURAL STUDIES
Some work w i l l be performed on the LiCl + A l C l /DMF system and on d i l u t e
L i C l + A1C13/AN. Most of t h e e f f o r t w i l l be devo ted t o DMF sys tems con-
t a i n i n g L iCl and copper h a l i d e s , u t i l i z i n g b o t h EPR and W.
t o i n i t i a t e work on the TMA-F + BF /PC and TMA-F + BF /DMF sys tems.
3
It i s planned
3 3
P E S ICAL PROPEETY DETERMINATIONS
D e t e r m i n a t i o n s of p h y s i c a l p r o p e r t i e s w i l l c o n t i n u e . S o l u b i l i t y , conduct-
a n c e , s o n i c v e l o c i t y , vapor p r e s s u r e , d i f f u s i o n c o e f f i c i e n t , and t r a n s f e r e n c e
measurements w i l l be supplemented. The f i r s t h e a t of s o l u t i o n v a l u e s and
d i e l e c t r i c c o n s t a n t s w i l l be de te rmined .
41/42
1.
2 .
3 .
4 .
5.
6.
7.
8.
9 .
10.
11 0
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October 1966.
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R e p o r t , by R . K e l l e r , J. N . F o s t e r , J. D . Ray, and J. 3. S u l l i v a n ,
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R e p o r t , by R. K e l l e r , J. N . F o s t e r , J. F. Hon, and J. M. S u l l i v a n ,
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REPORT DISTRIBUTION LIST FOR CONTRACT NO. NAS3-8521
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National Aeronautics & Space Administration Washington, D. C. 20546 Attention:
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Instrument Research Division
(3)
45 . ..
N a t i o n a l A e r o n a u t i c s 8i Space A d m i n i s t r a t i o n Langley Resea rch C e n t e r Langley S t a t i o n Hampton, V i r g i n i a 23165 A t t e n t i o n : M. B. S e y f f e r t (MS-112)
I n s t r u m e n t R e s e a r c h D i v i s i o n
N a t i o n a l A e r o n a u t i c s ei Space A d m i n i s t r a t i o n Langley Resea rch C e n t e r Langley S t a t i o n IInnpton., V i r g i n i a 27365 A t t e n t i o n : S . T . Pe t e r son /Har ry Riclrcr
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N a t i o n a l A e r o n a u t i c s & Space Admini s t r a t i or1
L e w i s Resea rch Center. 21000 Brookpark Road C l e v e l a n d , Ohio '111115 A t t e n t i o n : 11. J . Scliwartz (Ms 500-202)
Nat ior ia l A e r o n a u t i c s 8r Spac e Admini s t ra t i on Lewis Resea rch C e n t e r 21000 Ilrooliparlr Road C l e v e l a n d , Ohio 4 4 l j 7 A t t e n t i o n : D r . J . S . Fordyce (MS 702-1)
N a t i o n a l A e r o n a u t i c s Ir Space Admin i s t i -n t Lon L e w i s Resea rch C e n t e r 21000 Broolrpnrlc Road C l e v e l a n d , Oh io 44175 A t t e n t i o n : J . E;. D i l l e y (IE 500-700)
N a t i o n a l A e r o n a u t i c s & Spa"' Adiiiini s t r t i l , 1 0 1 )
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K a t i o n a l A e r o n a u t i c s h Space Admini s t r a t i on Lewis R e s e a r c h C e n t e r 21000 Brooliparlr Road C l e v e l a n d , Ohio 44135 A t t e n t i on : R o b e r t B. King (YS 500-202)
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?i at i ona 1 A e r onau t i c s 8r Spa c e A dcli n i s t ra t i on George C . Marshal Space F l i g h t Cen te r H u n t s v i l l e , Alabama 35812 A t t en t i on : Ph i 1 i p Yo ung b 1 o o d
N a t i o n a l A e r o n a u t i c s & Space A d m i n i s t r a t i o n George C . Flarshal Space F l i g h t Cen te r I I u r i t s v i l l e , Alabarua 35812 A t t e n t i o n : R i c h a r d Boelime (B ldg . W 3 W 3 B )
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P r o p u l s i o n & Energy Sys tems Branch (Bldg. 16, S i t e 1)
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Gemini P r o j e c t O f f i c e
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N a t i o n a l A e r o n a u t i c s & Space A d m i n i s t r a t i o n Manned S p a c e c r a f t Cen te r Houston, Texas 77058 A t t e n t i on: R i c h a r d Ferguson (EP-5)
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P i o n e e r P r o j e c t
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B i o s a t e l l i t e P r o j e c t
J e t P ropu l s i on L a b o r a t o r y 4800 Oak Grove D r i v e Pasadena , C a l i f o r n i a 91103 A t t e n t i o n : A i j i U c h i y a m
Department of t h e Army
U. S . Army E n g i n e e r R & D Labs. F o r t B e l v o i r , V i r g i n i a 22060 A t t e n t i o n : E l e c t r i c a l Power Branch (SMOFB-El')
Commanding O f f i c e r U. S . Army E l e c t r o n i c s R & D Labs. F o r t Monmoutli, New J e r s e y 07703 A t t e n t i o n : Power Sources D i v i s i o n (SELM/PS)
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48
U. S. Army Research Off ice Box CM, Duke S t a t i o n Durham, North Caro l ina 27706 At t en t ion : D r . Wilhelm Jorgensen
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AMCRD-RSCM-T-7
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AMCRD-DE-MO-P
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20760
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k ’ l i g h t V e h i c l e Power Branch .
Re r o Pi- o p u l s i on L a b o r a t o ry \ $ r i g h t - P a t t e r s o n Air Force Base, Ohio 45433 A t t e n t i o n : James E. Cooper
A i r Yorce Cambridge R e s e a r c h Lab. (CRFE) L. G . IIaiiscorJ F i e l d Bedf o r d , Evlassacliusetts 01731 A t t e n t i o n : D r . Richard Payne
l l e a d q u a r t e r s , U . S . A i r Fo rce (AmR-AS) Vas l i i ng ton 2 5 , D . C . A t t e n t i o n : Major G . S ta r l rey
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Rome A i r Development C e n t e r , ESD G r i f f i s A i r F o r c e Base , New Yorlr A t t e n t i o n : Franlr J. N o l l u r a (RISSFI)
13442
Othe r Government Agencies
N a t i o n a l Bureau of S t a n d a r d s Wash ing ton , D. C . 20234 A t t e n t i o n : D r . K . J . Harner
O f f i c e , DDR&E, USE & BSS The Pentagon Washington, D. C . 20310 A t t e n t i o n : G . B. Wareham
M r . Donald B. Hoatson Army Reactors , DRD U. S. Atomic Energy Commission Washington, D. C. 20545
I n s t i t u t e f o r Defense Analyses R & E Support D iv i s ion 400 Army-Navy Drive A r l i n g t o n , V i r g i n i a 22202 A t t e n t i o n : M r . R. Hamilton
I n s t i t u t e f o r Defense Analyses R & E Support D iv i s ion 400 Army-Navy Dr ive A r l i n g t o n , V i r g i n i a 22202 A t t e n t i o n : D r . George C . Szego
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Indus t ry
Aerojet-General Corporation Von Karman Center Bldg. 312, Dept. 3111 Azusa, Ca l i fo rn ia At t en t ion : M r . Russ Fogle
heronut ronic D i v i sioii Phi 1 c o Corporati on Ford Road Newport Beach, Ca l i fo rn ia 92660
Aerospace Corporation Pos t Off ice Box 95085 L o s Angeles, Ca l i fo rn ia 90045 At t en t ion : Library
Aerospace Corporation Systems Design Divis ion 2350 East E l Segundo Boulevard E l Segundo, Ca l i fo rn ia At t en t ion : J o h n G . Kr i s i l a s
A 1 1 i s 41ialmer s Manufacturing Co . 1100 South 7Otli S t r e e t Milwaukee, Wisconsin 53201 A t t e n t i o n : D r . P. Joyner
American Univers i ty Mass. & Nebraska Avenues, N . W. Washington, D . C . 20016 At t en t ion : D r . R. T . Foley,
Chemistry Department
Ar thur D . L i t t l e , Inc. Acorn Park Cambridge, Massachusetts 02140 A t t e n t i o n : D r . E l l e r y W . Stone
Atomics I n t e r n a t i o n a l Divis ion Nor th American Avia t ion , Inc. 8900 De Soto Avenue Canoga Park, Ca l i fo rn ia 91304 At t en t ion : D r . €I. L. Recht
B a t t e 1 1 e Memoria 1 I n s t it u t e 505 King Avenue Columbus, Ohio 43201 A t t e n t i o n : D r . C . L. Faust
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B e l l Telephone L a b o r a t o r i e s , I n c . Murray H i l l , New J e r s e y 07971 A t t e n t i o n : U. B. Thomas
The Boeing Company P. 0. Box 3707 S e a t t l e , Washington 98124
Borden Chemical Company C e n t r a l Research L a b o r a t o r y P. 0. Box 9524 P h i l a d e l p h i a , P e n n s y l v a n i a 19124
Burgess B a t t e r y Company Foot of Exchange S t r e e t F r e e p o r t , I l l i n o i s 61032 A t t e n t i o n : D r . Howard J. S t r a u s s
C & D B a t t e r i e s D i v i s i o n of E l e c t r i c A u t o l i t e C o l . Conshohocken, Pennsy lvan ia 19428 A t t e n t i o n : D r . Eugene W i l l i h n g a n z
C a l v i n Co l l ege Grand Rap ids , Michigan 49506 A t t e n t i o n : P r o f . T . P. D i r k s e
C a t a l y s t Research C o r p o r a t i o n 6101 F a l l s Road B a l t i m o r e , Maryland 21209 A t t e n t i o n : J. P. Wooley
Chem-Cell Inc . 150 Dey Road Wayne, New J e r s e y 07470 A t t e n t i o n : P e t e r D. Richman
Delco Remy D i v i s i o n Genera l Motors C o r p o r a t i m 2401 Columbus Avenue Anderson, I n d i a n a 46011 A t t e n t i o n : D r . J . J . Lander
Doug las A i r c r a f t Company, I n c . Astropower Labora to ry 2121 Campus Drive Newport Beach, C a l i f o r n i a 92663 A t t e n t i o n : D r . Carl Berger
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I
I
Dynatech Corporation 17 Tudor S t r e e t Cambridge, Massachusetts 02138 At t en t ion : R. L. Wentworth
Eagle-Picher Company Post Of f i ce Box 47 J o p l i n , M i s s o u r i 64802 At t en t ion : E. M. Morse
Elg in Nat iona l Watch Company 107 Nat iona l S t r e e t E lg in , I l l i n o i s 60120 At t en t ion : T . Boswell
E l e c t r i c S torage Ba t t e ry Company Miss i l e B a t t e r y Div is ion 2510 Louisburg Road Rale igh , North Carol ina 27604 At t en t ion : A. Chrei tzberg
E l e c t r i c S torage Ba t t e ry Company Carl F. Norberg Research Center 19 West College Avenue Yardley, Pennsylvania 19068 At t en t ion : D r . R. A. Schaefer
Electrochimica Corporation 1140 O'Brien Drive Menlo Park, C d i f o rn i a 94025 A t t e n t i o n : D r . M o r r i s Eisenberg
Electro-Optical Systems, Inc. 300 North Hals tead Pasadena, C a l i f o r n i a 91107 A t t e n t i o n : M. K le in
W a r t Manufacturing Company
Har t fo rd , Connecticut 06101 A t t e n t i o n : D r . W . P. Cadogan
BOX 1620
Engelhard I n d u s t r i e s , Inc. 497 DeLancy S t r e e t Newark, New J e r s e y 07105 A t t e n t i o n : D r , J . G. Cohn
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D r . A r t h u r F l e i s c h e r ri66 S o u t h Center S t r e e t Orange, New J e r s e y 07050
Genera l E l e c t r i c Company R e s e a r c h & Development C e n t e r Schenec tady , New York 12301 A t t e n t i o n : D r . R . C . Ostl ioff
(Bldg. 37, Room 2083)
Genera l E l e c t r i c Company M i s s i l e & Space D i v i s i o n S p a c e c r a f t Department P. 0. Box 8555 P h i l a d e l p h i a , Pennsy lvan ia 19101 A t t e n t i o n : E. W . Kipp , Room T-2513
Genera l E l e c t r i c Company B a t t e r y P roduc t s S e c t i o n P. 0. Box 114 G a i n e s v i l l e , F l o r i d a 32601
Genera l E l e c t r i c Company R e s e a r c h & Development Cen te r Schenec tady , New York 12301 A t t e n t i o n : D r . €1. L iebha f sky
Genera l blotors C o r p o r a t i on Defense Research L a b o r a t o r i e s 6767 I I o l l i s t e r S t r e e t S a n t a Barba ra , C a l i f o r n i a 93105 A t t n : D r . J . S. Smtlro/Dr. C . R. R u s s e l l
Gene ra l Telephone & E l e c t r o n i c s Labs. Bays ide , New York A t t e n t i on : D r . P a u l Goldberg
Globe-Union, I n c . 900 East Keef e Avenue Milwaukee, Wiscons in 53201 A t t e n t i o n : D r . Warren Towle
Globe-Union, I n c . 900 East Keefe Avenue Milwaukee, Wiscons in 53201 A t t e n t i o n : D r . C . K. Morehouse
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Gould-National B a t t e r i e s , I n c E n g i n e e r i n g & R e s e a r c h C e n t e r 2630 U n i v e r s i t y Avenue, S. E. M i n n e a p o l i s , Minnesota 55418 A t t e n t i o n : D. L. Douglas
G u l t o n I n d u s t r i e s A l k a l i n e Bat-kery D i v i s i o n 212 Durham Avenue Metuchen, New J e r s e y 08840 A t t e n t i o n : D r . R o b e r t S h a i r
Grumman A i r c r a f t OPGS, P l a n t 35 Be thpage , Long I s l a n d , N. Y. A t t e n t i o n : Bruce C l a r k
Hughes A i r c r a f t C o r p o r a t i on C e n t i n d a Avenue & T e a l e S t r e e t Cu lve r C i t y , C a l i f o r n i a 90230 A t t e n t i o n : T . V. Garvey
Hughes A i r c r a f t C o r p o r a t i o n Bldg. 366, M. S . 524 E l Segundo, C a l i f o r n i a 90245 A t t e n t i o n : R. B. Robinson
Hughes R e s e a r c h Labs. Corp. 7011 Mal ibu Canyon Road Mal ibu , C a l i f o r n i a 90265 A t t e n t i o n : T . M . Hahn
I T T F e d e r a l L a b o r a t o r i e s 500 Washington Avenue N u t l e y , New J e r s e y 07110 A t t e n t i o n : D r . P. E. L igh ty
I T T R e s e a r c h I n s t i t u t e 10 West 3 5 t h S t r e e t Ch icago , I l l i n o i s 60616 A t t e n t i o n : D r . H. T . F r a n c i s
Institute of Gas Technology State and 34th Street Chicago, Illinois 60616 Attention: B. S. Baker
Johns Hopkins University Applied Physics Laboratory 8621 Georgia Avenue Silver Spring, Maryland 20910 Attention: Richard Cole
Jolms-Manville R & E Center P. 0 . Box 159 Manville, New Jersey 08835 Attention: J. S. Parkinson
Leesona Moos Laboratories Lake Success Park, Community Drive Great Neck, New York 11021 Attention: Dr. H. Oswin
Livingston Electronic Corporation Route 309 Montgomeryville, Pennsylvania 18936 Attention: William F. Meyers
Lockheed Missiles & Space Company 3251 Hanover Street Palo Alto, California 94304 Attention: Library/Dr, G. B. Adams
Lockheed Missiles & Space Company Dept. 62-30 3251 Hanover Street Palo Alto, California 94304 Attention: J. E. Chilton
Idaho State University Department of Chemistry Pocatello, Idaho 83201 Attention: Dr, G . Myron Arcand
i I
Mal lo ry B a t t e r y Company 60 Elm S t r e e t Nor th T a r r y t o n , New York 10593 A t t e n t i o n : R . R. Clune
P. R . Ma l lo ry & Company, I n c . T e c h n i c a l S e r v i c e s L a b o r a t o r y I n d i a n a p o l i s , I n d i a n a 46206 A t t e n t i o n : A. S. Doty
-
P. R . Ma l lo ry & Company, I n c . Nor thwes t I n d u s t r i a l Pa rk B u r l i n g t o n , M a s s a c h u s e t t s 02107 A t t e n t i o n : D r . P e r Bro
P. It. Ma l lo ry & Company, I n c . 3029 East Washington S t r e e t I n d i a n a p o l i s , I n d i a n a 46206. A t t e n t i o n : T e c h n i c a l L i b r a r i a n
Marquard t C o r p o r a t i o n 16555 S a t i c o y S t r e e t Van Nuys, C a l i f o r n i a 91406 A t t e n t i o n : Dr. H. G . K r u l l
M a t e r i a l R e s e a r c h C o r p o r a t i o n Orangeburg , New York A t t e n t i o n : V. E. A d l e r
Melpar T e c h n i c a l I n f o r m a t i o n Cen te r 3000 A r l i n g t o n Boulevard F a l l s Church, V i r g i n i a 22046
Midwest R e s e a r c h I n s t i t u e 425 V o l k e r Boulevard Kansas C i t y , M i s s o u r i 64110 A t t e n t i o n : D r . B. W. Beadle
Monsanto R e s e a r c h C o r p o r a t i o n Bos ton L a b o r a t o r y E v e r e t t , M a s s a c h u s e t t s 02149 A t t e n t i o n : D r . J. 0 . Smi th
N o r t h American R o c h e 1 1 Corpora t ion Rocketdyne D i v i s i o n 6633 Canoga Avenue Canoga Park, C a l i f o r n i a 91303 A t t e n t i o n : L i b r a r y
N o r t h American Rockwell Corpora t ion 12214 Lakewood Boulevard Downey, C a l i f o r n i a 90241 A t t e n t i o n : Bur ton M. O t z i n g e r
D r . J o h n Owen P. 0. Box 87 B loomf ie ld , New J e r s e y 07003
Power In fo rma t ion Cen te r U n i v e r s i t y of Pennsy lvan ia Moore School B u i l d i n g 3401 Market S t r e e t , Room 2107 P h i l a d e l p h i a , Pennsylvania 19104
P h i l c o Corpora t ion D i v i s i o n of t h e Ford Motor Company Blue B e l l , Pennsylvania 19422 A t t e n t i o n : D r . P h i l l i p C h o l e t
R a d i a t i o n A p p l i c a t i o n s , I n c . 36-40 3 7 t h S t r e e t Long I s l a n d C i t y , New Yorlc 11101
Radio Corpora t ion of America A s t r o D i v i s i o n Hights town, New J e r s e y 08520 A t t e n t i o n : Seymour Winkler
Radio Co'rporat ion of America P. 0. Box 800 P r i n c e t o n , New J e r s e y 08540 A t t e n t i o n : I . Schulman
Southwes t Research I n s t i t u t e 8500 Culebra Road San An ton io , Texas 78206 A t t e n t i o n : D r . J a n A 1
Sonotone Corpora t ion Saw M i l l R ive r Road Elmsford , New York 10523 A t t e n t i o n : A. Mundel
Texas I n s t r u m e n t s , I n c . Me ta l s and C o n t r o l s D i v i s i o n 34 F o r e s t S t r e e t A t t l e b o r o , Massachuse t t s 02703 A t t e n t i o n : D r . E. M. J o s t
60
Sprague Electric Company 87 Marshall Street North A d a m , Massachusetts 01247 Attention: Harold F . Phillips, Jr
Texas Instruments, Inc. 13500 North Central Expressway Dallas, Texas 75222 Attention: Dr. Isaac Trachtenberg
Thomas A. Edison Research Laboratory McGraw Edison Company Watchung Avenue West Orange, New Jersey 07052 Attention: Dr. P. F. Grieger
TRW Systems, Inc. One Space Park Redondo Beach, California 90278 Attention: Dr. A. Krausz
(Bldg. 60, Rm. 929)
TRW Systems, Iiic. One Space Park Redondo Beach, California 90278 Attention: M r . Richard Sparks
T R W Inc. 23555 Euclid Avenue Cleveland, Ohio 44117 Attention: Librarian
Tyco Laboratories, Inc. Bear Hill Hickory Drive Waltham , Massachusetts 02154 Attention: W . W . Burnett
Union Carbide Corporation Development Laboratory Library P. 0 . Box 6056 Cleveland, Ohio 44101
Union Carbide Corporation Parma Research Laboratory P. 0 . Box 6116 Cleveland, Ohio 44101 Attention: Library
61
U n i v e r s i t y of C a l i f o r n i a Space Sc ience L a b o r a t o r y B e r k e l e y , C a l i f o r n i a 94720 A t t e n t i o n : D r . C . W. T o b i a s
U n i v e r s i t y of Pennsy lvan ia E l e c t r o c h e m i s t r y Labora to ry P h i l a d e l p h i a , Pennsy lvan ia 19104 A t t e n t i o n : P r o f . J. O ' M . B o c k r i s
U n i v e r s i t y of Toledo Toledo , Ohio 43606 A t t e n t i o n : D r . A l b e r t i n e Krohn
Western E l e c t r i c Company S u i t e 802, RCA B u i l d i n g Washington, D. C . 20006 A t t e n t i o n : R. T . F i s k e
West inghouse E l e c t r i c C o r p o r a t i o n R e s e a r c h & Development Cen te r C h u r c h i l l Borough P i t t s b u r g h , P e n n s y l v a n i a 15235 A t t e n t i o n : D r . A. Langer
W h i t t a k e r Corpora t ion 3850 O l i v e S t r e e t Denver , Colorado 80237 A t t e n t i o n : Borch Wendir
W h i t t a k e r Corpora t ion NARMCO Research & Development D i v i s i o n 12032 Vose S t r e e t Nor th Hollywood, C a l i f o r n i a 91605 A t t e n t i o n : D r . M. Shaw
Yardney E l e c t r i c C o r p o r a t i o n Y a rdney Bui 1 d ing 40-52 Leonard S t r e e t New Yorlc, New York 10013 A t t e n t i o n : D r . George D a l i n
Naval Ordnance Systems Command Energy Conversion and M a t e r i a l s D i v i s i o n Washington, D. C I A t t e n t i o n : M r . B. Drimmer
62
American Oil Company P. 0. Box 431 Whiting, Indiana 46394 Attention: Dr. R. J. Flannery
Sandia Corporation Division 1323, Sandia Base Albuquerque, New Mexico 87116 Attention: Dr. S. C. Levy
63
PROPEXTIES OF NONAQUEOUS ELECTROLYTES
Expenditures (March 22, 1968)
Contract No. NAS 3-8521
Prepared for
NASA Lewis Research Center
Cleveland, Ohio
APPROVED: K. €I. Mueller Manager Physical and Engineering Chemistry Research Division
The e x p e n d i t u r e s and commitments d u r i n g t h e p e r i o d
from F e b r u a r y 19 t o March .22 , 1968 were:
1080 man-hours
$17,787
The t o t a l e x p e n d i t u r e s and c o m i t m c n t s up t o
F e b r u a r y 18, 1968 were:
13,340 man-hours
$211,327
UNCLASSIFIEXI
ORIGINATING A C T I V I T Y (Cornorate aurhor)
Rocketdyne, a Division of North American Rockwell
California 91304 Corporation I 6633 Canoaa _Avenue, Canoga Park,
U. R E P O R T S E C U R I T Y C L A S S I F I C A T I O N
UNCLASSIFIED 2b. G R O U P
a D E S C R I P T I V E N O T E S (Type o f report and Inclusive dates)
7.. T O T A L N O . O F P A G E S
73
Summarv ReDort (20 S e D M e r 1967 to 19 March 1968)
Keller, R.; Foster, J. N.; Hanson, D. C.; Hon, J. F.; Kalman, 0 . F.; Muirhead, J. S.; Sullivan, J. M.
5 A u THORIS I ( F i r s t name, middle in l t la l , last name)
76. N O . O F R E F S
77
I R E P O R T D A T E
19 April 1968 Id. C O N T R A C T O R G R A N T N O .
NAS3- 8 5 2 1 b. P R O J E C T N O
C .
d.
10 D I S T R I B U T I O N S T A T E M E N T
I ! S U P P L E M E N T A R Y N O T E S
R6754-6 Ob. O T H E R R E P O R T N O I S I (Any other numbers that may be assigned
this report)
NASA CR-72407
1 2 . S P O N S O R I N G M I L I T A R Y A C T I V I T Y
National Aeronautics and Space Administration, Lewis Research Center, Cleveland, Ohio
3 A B S T R A C T
Studies of aprotic electrolytes based on three solvents: dimethyl fomamide, and acetonitrile, were continued. Characterized components
were used to prepare the electrolyte solutions.
containing lithium chloride, aluminum chloride, and cupric chloride were performed
utilizing nuclear magnetic resonance. solubilities, vapor pressures, diffusion coefficients, and dielectric constants.
propylene carbonate,
Structural studies of electrolytes
The physical properties studied include
UNCLASSIFIED Secu ri tv Clv s si fica t inn
1 N c v 6 5 1473
Wonaqurous E l e c t r o l y t e s
A p r o t i c E l e c t r o l y t e s
Propylene Carbonate
Dimethyl Foimainide
Ace t o n i t r i l e
L i t h iim C h l or i d c
A luminim Ch 1 o r i de
Cupr ic Chloride
s i 1
R O L E -- W T
L I N K c
R O L E -
W T
UNC T d S S IF TED Security C l a s s i f i c a t i o n
