ANHYDROUS ETHFORANOIC ACID AS A CONDUCTING MEDIUM

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The P e n n s y lv a n ia S t a t e C o lle g e The G ra d u a te S c h o o l D ep artm en t o f C h e m istry

ANHYDROUS ETHFORANOIC ACID AS A CONDUCTING MEDIUM

A D is s e rta tio n by K e ith E . L o re n tz e n

S u b m itte d i n p a r t i a l f u l f i l l m e n t o f th e r e q u ir e m e n ts f o r th e d e g re e o f D o c to r o f P h ilo s o p h y J u n e 1951

A pproved:

FEB 2 4 1951 EEB 2 4 195)

ii ACKNOWLEDGMENT The a u th o r w is h e s t o e x p r e s s h i s a p p r e c i a t i o n to D r. J . H . S im o n s, u n d e r whose d i r e c t i o n t h i s w ork was I n i t i a t e d , f o r h i s s u g g e s t i o n s , h e l p , and e n c o u ra g em e n t and to D r. R7 P . Sew ard f o r h i s v a lu a b le a s s i s t a n c e I n I n ­ t e r p r e t i n g th e r e s u l t s . A lso h e w ould l i k e t o th a n k D r. T . J . B r ic e and th e o t h e r members o f th e F lu o r i n e L a b o r a to r ie s f o r t h e i r h e l p and a s s i s t a n c e I n ways to o num erous t o m e n tio n . To D r. M e rit S c o t t o f th e P h y s ic s D ep a rtm en t he w ish e s t o e x p r e s s h i s g r a t i t u d e f o r th e u s e o f th e c o n d u c t­ an c e and c a p a c ita n c e b r id g e u s e d f o r th e d i e l e c t r i c m e asu re­ m e n ts . F i n a l l y , h e w ould l i k e t o e x p r e s s h i s s i n c e r e g r a t i t u d e t o The A l l i e d C h em ical an d Dye C o r p o r a tio n f o r th e F e llo w s h ip t h a t e n a b le d t h i s w ork t o be c a r r i e d o u t .

Hi TABLE OP CONTENTS page ACKNOWLEDGMENT ........................................................................

ii

I.

INTRODUCTION ...........................................................................

1

II.

EXPERIMENTAL ...........................................................................

5

1 . P u r i f i c a t i o n o f M a t e r i a l s ............................

5

2 . D i e l e c t r i c C o n s ta n t ..........................................

11

3 . P r e p a r a t i o n o f Sam ples ...................................

19

C o n d u ctan ce B rid g e ............................................

21

5 . C o n d u ctan ce C e l l s

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

22

6 . D i l u t i o n A p p a ra tu s ............................................

23

7 . T h erm o sta t

30

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

8 . O p e r a tio n o f D i l u t i o n S ystem .....................

35

III.

RESULTS AND CONCLUSIONS ..................................................

^5

IV .

SUMMARY .......................................................................................

63

APPENDIX I

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

6^

BIBLIOGRAPHY ...........................................................................

70

V. V I.

1

INTRODUCTION C o n d u c tiv ity m e asu rem e n ts o f v a r io u s I n o r g a n ic and o r g a n ic compounds I n a n h y d ro u s h y d ro g e n f l u o r i d e h a v e ahovn t h a t d i f f e r e n t I o n i z a t i o n te n d e n c ie s e x i s t I n th e s e s o l u ­ t i o n s th a n I n o t h e r s o l v e n t s ( 1 ) .

T hese m e asu rem e n ts v e r e

u se d t o d e te rm in e th e ty p e o f d i s s o c i a t i o n t h a t e x i s t e d In t h i s s o l v e n t an d v e r e h e l p f u l i n e s t a b l i s h i n g a c i d i t y and b a s i c i t y o f th e s o l u t e s and s o l v e n t . A nhydrous h y d ro g e n f l u o r i d e h a s a h ig h d i e l e c t r i c c o n s t a n t ( 8 5 .6 a t 0 °C . ( 2 ) ) an d a low v i s c o s i t y (0 .0 0 2 5 6 p o is e a t 0 ° C . ( 5 ) ) an d so s e r v e s a s a good c o n d u c tin g medium. The c o n d u c t i v i t i e s o f s o l u t e s I n t h i s s o l v e n t v e r e a l s o fo u n d to b e d e p e n d e n t upon th e p r o to n

a b i l i t y o f th e s o l u t e t o a c t a s a

a c c e p t o r v i t h th e s o l v e n t s e r v in g a s a p r o to n d o n o r . F re d e n h a g e n an d C adenbach (4 ) s k i l l f u l l y demon­

s t r a t e d t h a t v a t e r I n h y d ro g e n f l u o r i d e d id n o t I o n iz e I n th e c u sto m a ry f a s h i o n H20 ^ H*

+

OH",

(I)

b u t a c t e d a s a p r o to n a c c e p to r h 2o

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f"

(II)

v i t h h y d ro g e n f l u o r i d e a c t i n g a s th e p r o to n d o n o r o r a c i d . On th e b a s i s t h a t h y d ro g e n f l u o r i d e b e h a v e d s i m i l a r l y I n I t s o t h e r s o l u t i o n s , th e y v e r e a b l e t o e x p l a i n th e u n u s u a l

b e h a v io r o f many o t h e r s o l u t e s i n t h i s s o l v e n t . P o ta s s iu m f l u o r i d e and s i l v e r f l u o r i d e gave v e r y n e a r l y th e same c o n d u c ta n c e s i n an h y d ro u s h y d ro g e n f l u o r i d e and w ere a p p a r e n t l y io n iz e d c o m p le te ly i n th e more d i l u t e s o lu tio n s .

T h e ir i o n i z a t i o n was e q u i v a l e n t to t h a t e x p e c te d

o f a b in a ry e l e c t r o l y t e .

H ow ever, s a l t s o f o t h e r a c id s

(p o ta s s iu m n i t r a t e , s i l v e r n i t r a t e , and p o ta s s iu m a c e t a t e ) d id n o t b eh av e a s b in a r y s a l t s a s th e y do i n aq u e o u s s o l u ­ t i o n s b u t gave c o n d u c t i v i t i e s i n d i c a t i n g tw ic e t h a t num ber of io n s .

S in c e h y d ro g e n f l u o r i d e i s assum ed t o p la y th e

r o l e o f a p r o to n d o n o r , th e b e h a v io r o f th e s e s a l t s was a c ­ c o u n te d f o r by th e r e a c t i o n s KNO3 AgNO}

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(IV ) 2F“

(V)

w hich i s e q u i v a l e n t to s a y in g t h a t n i t r i c and a c e t i c a c i d s a r e b a s i c o r p r o to n a c c e p to r s i n r e l a t i o n to h y d ro g e n flu o rid e . T h ese r e a c t i o n s i n d i c a t e t h a t th e f r e e a c id i s f i r s t form ed and t h a t i t a c t s a s a p r o to n a c c e p t o r .

T h is

f i t t e d v e r y w e ll f o r n i t r i c a c i d , b u t w ith a c e t i c a c i d b o th o f th e f o llo w in g r e a c t i o n s a r e p o s s i b l e CH3COOH +

H F^C H ^C O F

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(VI)

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p".

(V II)

R e a c tio n (V I) v o u ld g iv e c o n d u c t i v i t i e s o f th e same m a g n itu d e a s t h a t o f v a t e r s in c e a c e t y l f l u o r i d e I s n o t Io n ­ iz e d I n th e a c i d s o l u t i o n .

H ow ever, s o l u t i o n s o f a c e t i c a c i d

d id n o t g iv e th e same c o n d u c ta n c e s a s s o l u t i o n s o f v a t e r .

It

was fo u n d t h a t s o l u t i o n s o f a c e t i c a n h y d rid e g av e th e same c o n d u c ta n c e s a s a c e t i c a c i d s o l u t i o n s .

S in c e th e fo rm e r I s

known to u n d e rg o th e r e a c t i o n (ch 5c o o ) 2o

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(V III)

th e a c e t i c a c i d m u st I o n iz e a s shown ln x m a c tio n ( V I I ) . B a s in g t h e i r c o n c lu s io n s on th e f a c t t h a t a c i d s w hich v e r e good c o n d u c to r s I n h y d ro g e n f l u o r i d e v e r e p r o to n a c c e p t o r s , i t v a s p o s s i b l e t o e x p l a i n th e low c o n d u c t i v i t y o f s u b s ta n c e s a s t r i c h l o r o a c e t i c a c i d , p h e n o l, o x a l i c a c i d , and fo rm ic a c i d on th e g ro u n d s t h a t th e y v e r e s t r o n g a c i d s . T h e r e f o r e , th e y h a d l e s s te n d e n c y t o a c c e p t p r o to n s from h y d ro g e n f l u o r i d e . S i m i l a r l y , th e c o n d u c ta n c e o f compounds su c h a s a c e to n e , e t h y l e t h e r , an d a l c o h o l s v a s e x p la in e d on th e b a s i s t h a t th e y a c t a s p r o to n a c c e p t o r s I n h y d ro g e n f l u o r i d e .

T h is

a g r e e s v e i l v i t h th e k n o v le d g e an d s t r u c t u r e o f th e s e com­ p o u n d s.

T hey seem t o a c t a s s t r o n g b a s e s I n th e s e s o l u t i o n s

and i f th e c o n d u c t i v i t y m easu rem en ts a r e s i g n i f i c a n t , b e g in t o a c c e p t a se c o n d p r o to n a t h ig h d i l u t i o n .

H en ce, i t I s s e e n t h a t th e p r o p e r t i e s o f a p o l a r s o l v e n t d ep en d n o t o n ly upon th e d i e l e c t r i c c o n s t a n t o f th e medium, b u t a l s o on th e s o l v e n t s a b i l i t y t o a c t a s a p r o to n donor o r a c c e p to r.

Many o f th e p r o p e r t i e s o f v a t e r h av e

b e e n e x p l a in e d b y I t s a b i l i t y t o a c t I n e i t h e r c a p a c i t y . H ydrogen f l u o r i d e a c t s c h i e f l y a s a p r o to n d o n o r . T h ere a r e many r e a s o n s t h a t make a n h y d ro u s h y d ro ­ g en f l u o r i d e u n d e s i r a b l e f o r c o n d u c t i v i t y m e a s u re m e n ts . I s a d i f f i c u l t c h e m ic a l to h a n d l e . te m .

It

I t r e q u i r e s a m e ta l s y s ­

Many compounds c a n n o t be r e c o v e r e d u n ch an g ed fro m I t .

T h u s, a d i f f e r e n t s o l v e n t o f th e same ty p e I s d e s i r a b l e . I t v a s v i t h t h i s I d e a I n m ind t h a t th e v o r k d e s c r ib e d h e r e v a s u n d e r ta k e n . E th f o r a n o lc a c i d a p p e a r e d t o be s a t i s f a c t o r y I n many r e s p e c t s t o c o n d u c t th e same ty p e o f v o r k .

I t Is a

s tr o n g a c i d ( h a v in g an e q u i l i b r i u m c o n s t a n t o f a b o u t 0 .3 I n v a t e r ( 3 ) ) , I s n o n -o x id iz in g , h a s a v i s c o s i t y c lo s e to t h a t o f v a t e r (0 .0 0 8 7 6 p o is e a t 2 5 °C . (5 ))> I t s d i e l e c t r i c co n ­ s t a n t I s f a i r l y h ig h (^W.7 a t 25° C ., t o be d e s c r ib e d l a t e r ) , I t m e lts a t - 1 5 .2 5 ° C . ( 5 ) , b o l l s a t 7 1 .1 ° C . ( 6 ) , and d o e s n o t a tta c k g la s s .

The l a t t e r p r o p e r t i e s make I t I d e a l f o r

m a n ip u la tio n I n s i d e a g l a s s vacuum sy ste m t o p r e v e n t I t s e x p o s u re t o m o i s t u r e .

EXPERIMENTAL P u r if ic a t i o n o f M a te ria ls E th f o r a n o lc a c i d . —C rude e t h f o r a n o i c a c i d was o b ta in e d b y t r e a t i n g some c ru d e ammonium e t h f o r a n a t e w ith c o n c e n tr a t e d s u l f u r i c a c i d an d d i s t i l l i n g o f f th e m ore v o l a t i l e a c i d . The d i s t i l l a t e , a m ix tu re o f a c i d and v a t e r , v a s th e n f r a c ­ t i o n a t e d y i e l d i n g a f r a c t i o n o f p u re a c i d an d a f r a c t i o n o f c o n s t a n t b o i l i n g m ix tu re w h ich i s 7 9 *^ p e r c e n t a c i d an d 2 0.6 p e rc e n t v a te r (5 )• To rem ove th e a c i d i n th e c o n s t a n t b o i l i n g m ix tu r e , th e b a riu m s a l t o f th e a c i d v a s p r e c i p i t a t e d v i t h b a riu m c a rb o n a te .

The m ix tu re v a s e v a p o r a te d t o d r y n e s s on a steam

b a t h , an d th e r e s u l t i n g w h ite h a r d s o l i d p u l v e r i z e d t o a f i n e p o v d e r an d f u r t h e r d r i e d a t 110° C . i n a d r y in g o v e n . T h is p o v d e r v a s t r e a t e d v i t h c o n c e n tr a t e d s u l f u r i c a c i d , and th e e t h f o r a n o l c a c i d rem oved b y d i s t i l l a t i o n . The a c i d fro m t h e s e d i s t i l l a t i o n s v a s com bined and d i s t i l l e d i n one o f th e l a b o r a t o r y f r a c t i o n a t i n g c o lu m n s. B .p . 7 1 .0 ° C ., r e p o r t e d 7 1 .1 ° C . ( 6 ) . S in c e a c i d o f h ig h p u r i t y i s n e e d e d f o r d i e l e c t r i c and c o n d u c ta n c e m e a su re m e n ts, th e a c i d v a s f u r t h e r p u r i f i e d by f r a c t i o n a l c r y s t a l l i z a t i o n .

R ie a c i d v a s s e a l e d w ith a

s m a ll am ount o f c o n c e n tr a t e d s u l f u r i c a c i d ( t o rem ove t r a c e s o f v a t e r ) i n t o B u lb I ( F i g . 1 ) .

A f t e r e v a c u a tin g th e s y ste m ,

o u tg a s s ln g th e l i q u i d , an d m ix in g th e tv o com ponents

UUMA




Inni)

v h lc h ca n be r e a r r a n g e d I n t o th e form A*

(XXXIII)

P u o sa an d K rau s (22) d e v e lo p e d a g r a p h i c a l m ethod v h lc h to o k c a r e o f th e s e e f f e c t s b y s u c c e s s iv e a p p r o x im a tio n . F u o ss (20) fo u n d t h a t by th e sim p le e x p e d ie n t o f s u c c e s s iv e s u b s t i t u t i o n o f E q u a tio n (XXXIII) b a c k i n t o i t s own c o r r e c ­ t i o n te rm , 1 -

c ^ /c T

/ A 0 , th e l a t t e r c o u ld b e r e p la c e d by

th e r e l a t i o n F (Z ) - 1 - Z (1 - Z (1 - Z ( e t c . ) “ ^ J ^ ) “*

(XXXIV)

i n w hich

z-

S^rt/V o)"1 -

§ J A o)-* y i0 0 0

i

w ith k th e s p e c i f i c c o n d u c ta n c e o f th e s o l u t i o n .

(xxxv) F u o ss (20)

t a b u l a t e d v a lu e s o f F(Z) f o r 0 ^ Z £ 0 .2 0 9 , by i n t e r v a l s o f .0 0 1 , so t h a t 7

c a n b e c a l c u l a t e d b y th e r e l a t i o n

7 - A / A 0P(Z)

(XXXVI)

The therm odynam ic i o n i z a t i o n c o n s t a n t o f th e s o l u t e i s g iv e n b y th e r e l a t i o n k -

c y 2£ --

(XXXVII)

w here f I s th e a c t i v i t y c o e f f i c i e n t o f th e io n s o b ta in e d from th e D ebye-H dckel e q u a tio n ( 2 3 ) , assu m in g t h a t th e a c t i v i t y

c o e f f i c i e n t o f th e a s s o c i a t e d io n p a i r s i s o n e . C om bining E q u a tio n s (XXXVI) and (XXXVII), th e f o l ­ lo w in g r e l a t i o n i a o b ta in e d

A p l o t o f F (Z )/A . a g a i n s t c A .f 2/P (Z ) s h o u ld be l i n e a r and h a v e an I n t e r c e p t o f l/A - o and 8 alop© of 1/K ( A0)2 .

T hese p l o t s f o r t r i - n - b u t y l am ine and p o ta s s iu m

e t h f o r a n a t e a r e shown i n F ig u r e s 13 an d 1 4 .

The d i e l e c t r i c

c o n s t a n t , d e te r m in e d e a r l i e r , o f 4 0 .7 find th e v i s c o s i t y o f O.OO876 p o is e ( 5 ) w ere u s e d f o r th e c a l c u l a t i o n s . K d e te rm in e d from

A 0 and

th e s e p l o t s a r e shown i n T a b le X I I .

The

l i m i t i n g c o n d u c ta n c e o f t h e s e two s a l t s d e te rm in e d b y I g n o r in g th e s o l v e n t c o r r e c t i o n a r e more n e a r l y a l i k e n u m e r ic a lly th a n when th e s o l v e n t c o r r e c t i o n i s c o n s id e r e d . The e q u i l i b r i u m c o n s ta n ts o b ta in e d fro m th e s e p l o t s (T a b le X II) show t h a t t r i - n - b u t y l ammonium e t h f o r a n a t e an d p o ta s s iu m e t h f o r a n a t e a r e d i s s o c i a t e d i n e t h f o r a n o i c a c i d to th e same e x t e n t a s weak b a s e s a r e i n a n aq u eo u s s o l u t i o n . F u o ss (2 0 ) s t a t e d t h a t p l o t s u s in g E q u a tio n (XXXVTIl) s h o u ld be l i n e a r a t v a lu e s l e s s th a n 3*2 x 10 w here D i s th e d i e l e c t r i c c o n s ta n t o f th e s o l v e n t .

-v.

A p p ly in g

t h i s e q u a tio n t o th e d i e l e c t r i c c o n s t a n t o f th e s o l v e n t , we f i n d t h a t t h e p l o t s s h o u ld be l i n e a r a t v a lu e s o f c l e s s th a n 0 .0 2 2 n o r m a l.

The p l o t s o f t r i - n - b u t y l am ine and

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p o ta s s iu m e t h f o r a n a t e ( F i g . 15 an d 1*0 b eg an t o d e v i a t e from l i n e a r i t y a t c o n c e n t r a t i o n s a s low a s 0 .0 0 0 5 n o rm a l to 0 .0 0 0 5 n o r m a l.

T hese v a lu e s a r e c o n s id e r a b ly lo v e r th a n

a n tic ip a te d . S in c e th e d i e l e c t r i c c o n s t a n t o f n itr o b e n z e n e i s n e a r th e one t h a t ve m e asu red f o r th e a c i d , an d s in c e a c e t i c a c i d i s a s i m i l a r ty p e s o l v e n t , a co m p ariso n o f c o n d u c tiv i ty m easu rem en ts made i n t h e s e s o l v e n t s v i t h o u r m easu rem en ts in e t h f o r a n o i c a c i d (D i s 4 0 .7 , in g .

^

i s 0 .00876 ( 5 ) ) i s i n t e r e s t ­

T h is c o m p a riso n i s shovn i n T a b le X II .

The s a l t s i n

n itr o b e n z e n e (D i s 5 4 .9 ( 2 4 ) , 7^ i s 0 .0 1 8 1 1 (2 5 )) a r e from th e d a ta o f W itsch o n k e an d K raus ( 26) , and th e s a l t s i n a c e t i c a c i d (D i s 6 . 2 ( 2 7 ) , ^

i s 0 .0 1 1 2 1 ( 28) ) a r e from th e

d a ta o f W e id n e r, H u tc h is o n , and C h an d lee (2 9 )• A p l o t o f th e f i r s t t h r e e s a l t s shovn i n T a b le X II i s shovn i n F ig u r e 1 5 .

The t a b l e and th e p l o t shov t h a t th e

b e h a v io r o f t r i - n - b u t y l ammonium e t h f o r a n a t e i n e t h f o r a n o i c a c i d i s s i m i l a r to t h a t o f t r i - n - b u t y l ammonium io d id e and t r i - n - b u t y l ammonium p l c r a t e i n n itr o b e n z e n e s in c e a l l th r e e b eh av e a s v e a k e l e c t r o l y t e s .

Ve v e r e u n a b le t o m easu re th e

c o n d u c t i v i t y o f two s i m i l a r s a l t s i n e t h f o r a n o i c a c i d , t e t r a n - b u t y l ammonium p i c r a t e an d t e t r a - n - b u t y l ammonium i o d i d e . The fo rm e r v a s n o t s o lu b l e i n e t h f o r a n o i c a c i d and th e l a t t e r d i s s o l v e d v i t h th e l i b e r a t i o n o f a g a s , p re su m a b ly h y d ro g e n io d id e .

60 TABLE X II

0

COMPARISON OP SAWS IN DIFFERENT SOLVENTS S a lts

S o lv e n t

Ao

K x 1©5

A o7^o

9 .3

.602

(C4H9)3NHI

C6 H5NO2

5 3 .3 3

(ClvH^jNH P i

C6H5NO2

2 8 .8 5

19

.522

(C4H9)5NHOOCCF5

CF3 COOH

3 6 .2 2 8 . 8*

40 31*

.317 .240*

CF5 COOH

CF5COOH

2 9 .4 3 8 .5 *

(CH3 ) 4NCI

CH5COOH

1 3 .2

.62

.1 4 8

KCl

CH-xCOOH

1 0 .0

.10

.1 1 2

2 .3 1 .4 *

.2 5 8 .337*

* No s o lv e n t c o r r e c t i o n a p p l i e d A d is c r e p a n c y o c c u r s , h o w ev er, when W a ld e n 's r u l e (5 0 ) I s a p p l i e d .

W a ld e n 's r u l e s t a t e s t h a t th e p r o d u c t

A© Ijo 18 8 c o n s t a n t f o r one s a l t I n d i f f e r e n t s o l v e n t s . I h i s r u l e ca n a l s o h e a p p l i e d to Io n s an d h a s b e e n sh o v n to be r e l a t i v e l y In d e p e n d e n t o f te m p e r a tu r e (2 1 ) an d d i e l e c t r i c c o n s t a n t (22) o f th e s o lv e n t f o r l a r g e s e m e t r i c a l i o n s .

The

v a lu e s shovn I n T a b le X II f o r th e s a l t s I n n itr o b e n z e n e a g r e e v e i l v i t h v a lu e s o f s i m i l a r s a l t s i n th e l i t e r a t u r e .

The

v a lu e s o f A.0 7f0 f o r t *10 s a l t s i n e t h f o r a n o i c a c i d a r e l o v e r , an d th o s e i n a c e t i c a c i d a r e c o n s id e r a b ly l o v e r .

A ssum ing

t h a t th e v a lu e s o f A 0 and 97 o a r® c o r r e c t , th e io n s i n th e s e a c i d s m u st h a v e m o b i l i t i e s much l o v e r th a n w ould be a n t i c i ­ p a te d .

(C^Hg)

30

HO

0

No

•

Wi t h

•

(C^HgJ^NHI

•

(C^ Hg J^NHPi

CCC F

in

ethforanoic

acid

solvent cor rec tio n solvent co r r e c tio n in

nitrobenzene

in n i t r o b e n z e n e

F igure

20

LH

10

I

01

02

03

■ ■ ■ I

.04

.05 /c

■ ■ • '

.06

■ ■ .

I

07

•

■ .

i

.08

X. .

1

09

.1 1 . J

T h is w ork h a s s u g g e s te d some i d e a s f o r f u r t h e r r e ­ s e a r c h v h lc h I t n i g h t be I n t e r e s t i n g t o e x p r e s s a t t h i s t i n s I t h a s b e e n d e m o n s tra te d t h a t w a te r , d i - n - b u t y l e t h e r , an d t r i - n - b u t f o r y l n i t r i d e a r e p o o r c o n d u c to rs i n a n ­ h y d ro u s e t h f o r a n o i c a c i d , b u t t h a t t r l - n - b u t y l am ine an d p o ta s s iu m e t h f o r a n a t e a r e c o n d u c to r s .

T e t r a a l k y l ammonium

s a l t s s h o u ld be good c o n d u c to r s I n e t h f o r a n o i c a c i d s in c e th e y h a v e b ee n sh o v n t o be s tr o n g e l e c t r o l y t e s i n n i t r o ­ b en zen e ( 26) v h lc h h a s a co m p arab le d i e l e c t r i c c o n s t a n t . H ence, a compound su ch a s t e t r a - n - b u t y l ammonium e t h f o r a n a t e s h o u ld b e a s tr o n g b a s e I n e t h f o r a n o i c a c i d .

I f I t v e re ,

th e c o n d u c ta n c e o f I t s s o l u t i o n s w ould g iv e a more r e l i a b l e v a lu e A o and a b e t t e r e v a l u a t i o n o f A 0 ^ o * The c o n d u c t i v i t y o f a s a l t o f a v e a k e r a c i d th a n e t h f o r a n o i c a c i d su ch a s p o ta s s iu m a c e t a t e v o u ld be I n t e r e s t lu g s in c e I t s I o n i z a t i o n m ig h t be e x p r e s s e d by one o f th e e q u a tio n s CH3 COOK ?=± K*

+

CH3COO"

CH3 COOK +

CF5COOH ;==£

CH3COOK +

2CF5COOH ^

(XXXIX) +

K1- +

CH3COOH +

CH500aH2+

CP5COO-

+

(XL)

2OF3COO'. (XLI)

I f th e s o l v e n t v e r e a s u f f i c i e n t l y s tr o n g p r o to n d o n o r , th e n e i t h e r E q u a tio n (XL) o r (XLI) v o u ld be e x p e o te d .

I f th e

a c e t a t e Io n v e r e o n ly b a s ic enough t o a c c e p t one p r o to n (XL)

th e c o n d u c ta n c e m easu red v o u ld be t h a t o f p o ta s s iu m e t h f o r a ­ n a te .

C o n d u c ta n c e s l a r g e r th a n t h i s v o u ld i n d i c a t e t h a t a n

a d d i t i o n a l p r o to n v a s a c c e p te d (X L I).

I f th e s o lv e n t v e r e

n o t a p r o to n d o n o r, p o ta s s iu m a c e t a t e v o u ld be e x p e c te d t o i o n i z e a s sh o v n i n E q u a tio n (XXXIX).

T h is b e h a v io r i s p r o ­

b a b ly l e a s t e x p e c te d s in c e e t h f o r a n o i c a c i d i s a s t r o n g e r a c i d th a n a c e t i c a c i d .

By m e a su rin g th e c o n d u c t i v i t y o f

s o lu tio n s o f s tr o n g e r a c id s o r s o lu tio n s o f s a l t s o f s tro n g e r a c i d s i n e t h f o r a n o i c a c i d , i t v o u ld be o f i n t e r e s t t o se e v h e t h e r an a c i d s tr o n g enough t h a t th e s o lv e n t v o u ld b eh av e a s a p r o to n a c c e p to r m ig h t b e fo u n d . The an o m alo u s b e h a v io r o f th e d i e l e c t r i c c o n s t a n t o f e t h f o r a n o i c a c i d v i t h te m p e r a tu r e i n d i c a t e s t h a t th e l i q u i d i s h ig h ly a s s o c ia te d .

S in c e th e m ethod u se d t o m easure th e

d i e l e c t r i c c o n s t a n t i s n o t th e m o st d e s i r a b l e f o r l i q u i d s v i t h a h ig h s p e c i f i c c o n d u c ta n c e , i t v o u ld be i n t e r e s t i n g t o c h e c k t h e s e m easu rem en ts v i t h one o f th e more r e l i a b l e m ethod s ( h e te ro d y n e b e a t o r re s o n a n c e m ethod) v h e re p o l a r i z a ­ t i o n d o e s n o t in f l u e n c e th e m e a su re m e n ts.

The a s s o c i a t i o n

o f th e a c i d c o u ld th e n be i n v e s t i g a t e d b y m ethods su ch a s X -ra y d i f f r a c t i o n o f th e l i q u i d o r v a r i a t i o n o f s u r f a c e t e n ­ s io n v i t h t e m p e r a tu r e .

The e x t e n t an d ty p e o f d i s s o c i a t i o n

v o u ld be I n t e r e s t i n g s in c e th e b o i l i n g p o i n t o f e t h f o r a n o i c a c i d i s c o n s id e r a b ly l o v e r th a n v o u ld be e x p e c te d f o r a h ig h ly a s s o c ia te d l i q u i d .

A d d itio n a l in f o r m a tio n m ig h t be

g a in e d fro m a s i m i l a r s tu d y o f p r o p f o r a n o ic a c i d an d b u t f o r a n o lc a c i d , th e n e x t h i g h e r members o f th e hom ologous s e r i e s .

63 SUMMARY 1 . The d i e l e c t r i c c o n s ta n t o f e t h f o r a n o i c a c i d and i t s v a r i a t i o n w ith te m p e r a tu r e w ere m e a s u re d .

The d i e l e c ­

t r i c c o n s t a n t i n c r e a s e d w ith i n c r e a s i n g te m p e r a tu r e w hich i s I n v e r s e to th e n o rm a l b e h a v io r o f d i e l e c t r i c c o n s ta n ts o f liq u id s . 2 . The c o n d u c t i v i t y o f d i l u t e s o l u t i o n s o f t r i - n b u t y l ammonium e t h f o r a n a t e and p o ta s s iu m e t h f o r a n a t e was m easu red i n e t h f o r a n o i c a c i d a t 2 5 °C .

T hese compounds w ere

shown to be weak b a s e s i n t h i s s o l v e n t . 3 . The c o n d u c t i v i t y o f d i l u t e s o l u t i o n s o f t r i - n b u t f o r y l n i t r i d e , d i - n - b u t y l e t h e r , and w a te r w ere m easu red i n e t h f o r a n o i c a c id a t 2 5 °C .

T hese compounds w ere p o o r con­

d u c t o r s show ing t h a t th e y d id n o t p o s s e s s b a s i c p r o p e r t i e s in th is s o lv e n t.

i

APPENDIX I C a l i b r a t i o n o f A p p a ra tu s B u lb s F an d G. —B u lb s P an d G ( F i g . 10) w ere c o n s tr u c te d from 15 mm. P y re x tu b in g b y s e a l i n g 5 mm. P y re x tu b e s on b o th e n d s . C a l i b r a t i o n m arks v e r e s c r a tc h e d above and below th e b u l b s . E ach b u lb v a s s e a le d a b o u t 5 cm. b elow th e lo w e r c a l i b r a t i o n m ark an d s u p p o r te d v e r t i c a l l y i n a 125 m l. E rle n m y e r f l a s k . The b u lb s w ere f i l l e d w ith c le a n and d r y m e rc u ry u p to th e lo w e r c a l i b r a t i o n m ark an d w e ig h e d .

The to p o f th e m e rc u ry

m e n isc u s to u c h e d th e lo w e r c a l i b r a t i o n m ark .

E ach b u lb was

th e n f i l l e d w ith d i s t i l l e d w a te r u n t i l th e b o tto m o f th e l i q u i d m e n isc u s to u c h e d th e u p p e r c a l i b r a t i o n m ark .

The

b u lb s w ere a g a in w e ig h e d , and th e w e ig h t o f th e w a te r d e t e r ­ m ined b y d i f f e r e n c e .

The volume o f e a c h b u lb was c a l c u l a t e d

from th e d e n s i t y o f w a te r a t th e te m p e r a tu r e o f c a l i b r a t i o n . The r e s u l t s a r e shown i n T a b le X I I I . TABLE X II I VOLUME OF BUIBS F AND G Volume o f B u lb F

Volume o f B ulb G

6 .0 9 7

5 .1 0 7

6 .0 9 6

5 .1 0 8 5 .1 0 6

A v.

6 .0 9 7 * .003

5 .1 0 7 t

.003

B ulb XY. —B ulb XY ( F i g . 10) c o n s i s t e d o f a 25 m l. P y re x b u r e t s e a l e d above a b u lb w hich was a b o u t 40 m l. i n v o lu m e.

F o r th e

c a l i b r a t i o n , a s to p c o c k was te m p o r a r ily a t t a c h e d a t th e b ase o f B u lb Y (P ig * 10) an d th e volume o f d i s t i l l e d w a te r d e ­ l i v e r e d from th e b u r e t and fro m th e b u lb w ere w eig h e d . T a b le XIV shows th e volum es o f th e b u r e t and b u lb c a l c u l a t e d from th e d e n s i t y o f th e w a te r w eig h e d . TABLE XIV VOLUME OP BUI£S X AND Y Volume o f B u ret X

Volume o f B u lb Y

A v.

5 9 .1 6 0

2 4 .9 0

5 9 .1 8 6

2 4 .8 7

5 9 .2 4 6

2 4 .9 0

5 9 .2 0 * .03

2 4 .8 9 * .02

A c h e c k o f th e b u r e t made by w e ig h in g one m i l l i ­ l i t e r p o r t i o n s o f w a te r a t a tim e showed th e e r r o r t o be e q u a l l y d i s t r i b u t e d o v e r th e ra n g e o f th e b u r e t .

I f th e

m e rc u ry l e v e l i s a t th e lo w e r c a l i b r a t i o n m ark ( th e one below B u lb Y ( P i g . 1 0 ) ) , th e volum e, V, o f l i q u i d i n B u lb XY ( P i g . 10) i s g iv e n b y th e r e l a t i o n V - 5 9 .2 0

+

(2 5 .0 0 - R ) (0 .9 9 5 6 )

w here R i s th e l e v e l o f l i q u i d m easu red i n th e b u r e t . S e c tio n s H . I . and J . — S e c tio n s H, I , an d J ( P i g . 10) a l l w ere c a l i b r a t e d b y m e a s u rin g th e le n g th o f a s lu g o f m e rc u ry a t a p p r o x im a te ly one c e n t i m e t e r i n t e r v a l s an d th e d i s t a n c e o f

th e s lu g from a

c a l i b r a t i o n m ark a t th e b a s e o f th e tu b e

o v e r th e le n g th

o f th e t u b e .

The m easu rem en ts v e r e

made v i t h

a c a th e to m e te r t h a t c o u ld be r e a d to 0 .005 cm. S in c e

th e volume o f th e s lu g re m a in s c o n s t a n t , i t s

le n g th v a r i e s i n v e r s e l y v i t h th e volum e i t o c c u p ie s i n th e tu b e .

H en c e, i f a p l o t o f 1 /L (L i s th e le n g th o f th e s lu g )

a g a i n s t h , th e d i s t a n c e from th e c a l i b r a t i o n m ark I s m ade, th e a r e a u n d e r a sm ooth c u rv e d ra v n th ro u g h th e p o i n t s r e p r e ­ s e n t s th e volume o f th e t u b e .

T h is p l o t f o r S e c tio n J ( F ig .

10) I s sh o v n i n F ig u r e 1 6 . The volume o b ta in e d from th e c u rv e b y g r a p h i c a l i n te g r a tio n , h o v e v e r, i s in a r b i t r a r y u n i t s .

The r a t i o o f

th e a c t u a l volume o f th e s lu g t o th e i n t e g r a t e d volume o f th e s lu g v a s d e te r m in e d and u se d a s a c o n v e rs io n f a c t o r to c o n v e r t th e i n t e g r a t e d volum es i n t o m i l l i l i t e r s .

T h is con­

v e r s io n f a c t o r f o r S e c tio n J ( F i g . 10) v a s 0 .1 5 2 ^ 2 .

The

a c t u a l volum e o f th e s lu g v a s d e te rm in e d fro m i t s v e l g h t and th e d e n s i t y o f m e rc u ry a t th e te m p e r a tu r e o f c a l i b r a t i o n . S in c e th e m easu rem en ts v e r e made v i t h th e tu b e s s u p p o r te d v e r t i c a l l y , a c o r r e c t i o n v a s a p p l i e d t o t h i s volume f o r th e tv o m e n is c i o f th e s l u g .

The volume o f e a c h m e n isc u s v a s

c o n s id e r e d to b e o n e - h a l f a n e l l i p s o i d o f r e v o l u t i o n v i t h th e semlma j o r a x i s e q u a l t o th e r a d i u s o f th e tu b e and th e sem lm ln o r a x is e q u a l t o th e h e i g h t o f th e m e n is c u s .

The

i n t e g r a t e d volume v a s ta k e n a s th e a v e ra g e o f f i v e volum es d e te r m in e d a t f i v e d i f f e r e n t p o s i t i o n s o f th e s lu g i n th e tu b e

The volum es o f one c e n tim e te r le n g th s o v e r th e e

le n g th o f th e tu b e v e r e d e te rm in e d b y g r a p h i c a l i n t e g r a t i o n . T hese v o lu m e s, i n a r b i t r a r y u n i t s , v e r e c o n v e r te d to m i l l i ­ l i t e r s b y m u l t i p l y i n g b y th e c o n v e r s io n f a c t o r .

The t o t a l

volum e, V, a t a h e i g h t , h , above th e c a l i b r a t i o n m ark and th e volume o f one c e n tim e te r in c r e m e n ts , & V, a r e g iv e n i n T a b le XV.

TABLE XV VOLUMES OF SECTIONS H , I , AND J TT

S e c t io n H V AV

S e c tio n I T ■~AV

S e c tio n 3 ... " 'V " ■ ■" AV

■

0

.00000

.01091

.0000

.1028

.0000

.1037

1

.01091

.01091

.1028

.1027

.1037

.1035

2

.02182

.01094

.2055

.1026

.2071

.1031

5

.03276

.01098

.3081

.1025

.3102

.1024

4

.04374

.01106

.4106

.1024

.4127

.1017

5

.05480

.0 1101

.5150

.1023

.5145

.1016

6

.06581

.01095

.6155

.1020

.6160

.1024

7

.07676

.01102

.7175

.1018

.7183

.1035

8

.08778

.01110

.8191

.1020

.8217

.1044

9

.09888

.01111

.9212

.1019

.9261

.1048

10

.10999

1 .0 2 3 1

.1013

I .0309

.1050

11

1 .1 2 4 4

.1009

1 .1 5 5 9

.1049

12

1 .2 2 5 5

.1007

1 .2 4 0 8

.1046

13

I . 326O

.1004

1 .3 4 5 4

.1042

14

1 .4 2 6 4

.1002

1 .4 4 9 6

.1037

15

1 .5 2 6 6

1 .5 5 5 2

.1035

16

I .6567

.1038

17

1 .7 6 0 4

.1044

18

1 .8 6 4 8

.1048

19

1 .9 6 9 6

.1044

20

2 .0 7 4 0

.1038

21

2 .1 7 7 8

.1036

22

2 .2 8 1 4

.1034

22

2 .3 8 4 8

.1033

91

74

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