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A critical study of the 8-hydro-oxyquinoline method for the determination of beryllium

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A CRITICAL STUDY OF THE 8-HYDROXYQUINOLINE METHOD
FOR THE DETERMINATION OF BERYLLIUM
A Thesis
P r e s e n t e d to
The F a c u l t y o f t h e D epartm ent o f C h e m is t r y
U n i v e r s i t y of S o u t h e r n C a l i f o r n i a
In P a r t i a l F u lfillm e n t
!
,,
^
i
o f t h e Rl eeqquuiir e m e n t s f o r t]
t h e D egree
M a ste r of S c i e n c e
by
V i t o W arren C o n s o l i
A ugust 1941
Degree n o t
g ran te d ; course
work i n c o m p l e t e
UMI Number: EP41534
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.......................... M.to....W.ai:x©n...G.QXL6Qli
.
u n d e r the d ir ec t io n o f h . A s F a c u l t y C o m m i t t e e ,
a n d ' a p p r o v e d b y a l l it s m e m b e r s , has b e e n
p r e s e n t e d to a n d a c c e p t e d b y the C o u n c i l on
G r a d u a t e S t u d y a n d R e s e a r c h in p a r t i a l f u l f i l l m e n t of the r e q u ir e m e n ts f o r the d e g r e e of
PIASTER OF ^SCIENCE
Secretary
. 19.41
F aculty C om m ittee
Chairman
TABLE OF CONTENTS
CHAPTER
PAGE
I.
INTRODUCTION................................................. ' ...........................
1
II.
PROBLEMS STUDIED................................................................. . .
4
P r e s e n t - d a y P r o c e d u r e f o r t h e D e t e r m i n a t i o n of
B e r y l l i u m i n B e r y l Ore by Means o f t h e 8H y d r o x y q u i n o l i n e Method
................................................
4
The I n c o m p l e t e P r e c i p i t a t i o n o f B e r y l l i u m
Hydroxide F o l l o w i n g Removal of Aluminum a s
O xyquinolate
............................................................................
The R e a g e n t , 8 - H y d r o x y q u i n o l i n e
. . . . . . *
8
10
A P o s s i b l e M o d if ie d Method f o r D e t e r m i n i n g
B e r y l l i u m a f t e r Removal o f Aluminum a s
O x y q u i n o l a t e ............................................................................
III.
EXPERIMENTAL WORK
...........................................
15
.
18
...............................................
18
A S e t of B e r y l l i u m D e t e r m i n a t i o n s F o l l o w i n g
t h e Customary P r o c e d u r e
D ata on t h e M o d if ie d Method f o r t h e
D e t e r m i n a t i o n of B e r y l l i u m ...........................................
19
D ata on t h e A tte m p te d L a b o r a t o r y P r e p a r a t i o n
of 8 - H y d r o x y q u i n o l i n e
IV.
............................................23
CONCLUSION................................................................................... 25
BIBLIOGRAPHY
28
CHAPTER I
INTRODUCTION
S o u r c e s and Uses o f B e r y l l i u m . ^
B eryllium i s found,
in th e United S t a t e s ,
in the Black
H i l l s of S o u t h D a k o ta p r i n c i p a l l y , a n d , o u t s i d e o f Maine and
New H am p shire, few o t h e r s p o t s i n t h e c o u n t r y have p r o d u c e d
even a c a r l o a d o f t h e o r e s o f t h i s e l e m e n t .
Most o f th e
dom estic p ro d u c tio n i s ob tained as a by-product of f e ld s p a r
and mica m in i n g .
This s i t u a t i o n has c a l l e d f o r c o n s id e r a b le
i m p o r t a t i o n f o r t h e most p a r t from I n d i a and A r g e n t i n a .
The
o n l y two c o m p an ie s i n t h e c o u n t r y which o f f e r t h e m e t a l and
its
s a l t s on a c o m m ercia l b a s i s a r e t h e B e r y l l i u m C o r p o r a t i o n
o f P e n n s y l v a n i a a t Temple, P a . , and t h e B ru sh B e r y l l i u m
C o r p o r a t i o n o f C l e v e l a n d , O h io .
I t i s most u n f o r t u n a t e t h a t t h e w o rl d o u t p u t o f
b e r y l l i u m i s no more t h a n a b o u t 750 t o n s o f b e r y l p e r annum,
b e c a u s e i t s u n u s u a l p r o p e r t i e s l e n d t h e m s e l v e s to many v a l u ­
able u se s.
G r e a t i n t e r e s t was shown i n 1938 i n t h e u s e o f
t h e e l e m e n t i n t h e v i t a l p a r t s o f a i r p l a n e e n g i n e s , due t o
t h e g r e a t h a r d n e s s o f o v e r 1 , 0 0 0 B r i n e l l w h ic h i s e x h i b i t e d
i n a s o l u t i o n o f b e r y l l i u m i n gamma i r o n .
1
M i n e r a l s Year Book. 7 48-751 ( 1 9 3 6 ) .
The p r i c e has a l w a y s been so h i g h f o r b e r y l l i u m and
i t s a l l o y s t h a t i t has s t o o d i n t h e way o f t h e i r w id e r a d o p ­
tio n .
There was, however, a d r o p o f $7 p e r pound o f c o n ­
t a i n e d b e r y l l i u m when i t went from $30 t o $23 p e r pound in
t h e y e a r 1 9 3 7 - 8 , and c u r r e n t l y i t
i s q u o te d a t $15 p a r pound
Pure b e r y l l i u m h a s a n o m in a l p r i c e of from $75 to $125 p e r
pound, a s t h e r e i s p r a c t i c a l l y no m arket f o r i t .
H i s t o r i c a l Background o f t h e A n a l y t i c a l C h e m is t r y
of B eryllium .
P o s s i b l y no o t h e r e l e m e n t has been a t t a c k e d a n a l y t i c a l l y i n so many d i f f e r e n t ways a s has b e r y l l i u m ,
g
and t h i s
i s e s p e c i a l l y t r u e o f t h e v e x i n g p r o b le m of s e p a r a t i n g i t
from aluminum.
The method most f r e q u e n t l y used in e a r l i e r t i m e s was
fo u n d ed upon t h e s o l u b i l i t y of b e r y l l i u m h y d r o x i d e i n am­
monium c a r b o n a t e .
T h is i d e a , a l t h o u g h i t was a c c e p t e d a t
t h e t i m e , r e s u l t s a l s o i n t h e p a r t i a l d i s s o l v i n g of t h e
2
h y d r o x i d e s o f aluminum and i r o n . V a u q u e l i n was t h e f i r s t
i n v e s t i g a t o r t o u s e th e method i n 1798.
S i n c e t h a t tim e ,
one method a f t e r a n o t h e r had been p r o p o s e d o n l y t o be l a t e r
g
P a r s o n s and B a r n e s , J . Amer. Chem. S o c . . 2 8 . 1589
(1906).
^ V a u q u e l i n , Ann. Chim. P h y s . . 2 6 . 155.
3
rejected .
G ib b s ,
4
i n 1864, used th e sodium f l u o r i d e p r o c e d ­
u r e to s e p a r a t e b e r y l l i u m q u a n t i t a t i v e l y , and t h i s method
5
received the approval of P ollok,
who d e c l a r e d i t to be
exceedingly sharp.
T h is i s a b r i e f o u t l i n e of t h e a n a l y t i c a l
c h e m i s t r y o f b e r y l l i u m from t h e tim e o f V a u q u e l i n to 1906.
£
At t h a t tim e P a r s o n s and B a r n e s p r o p o s e d t h e i r sodium b i ­
c a r b o n a t e s e p a r a t i o n o f b e r y l l i u m from aluminum, and t h i s
method h a s l a s t e d r i g h t t h r o u g h t o t h e p r e s e n t day, and must
be i n c l u d e d , a l o n g w i t h t h e 8 - h y d r o x y q u i n o l i n e and Gooch and
Havens
methods a s one o f th e most i m p o r t a n t .
4G i b b s , Am. J . S c i . .
( 2 ) , 37, 3 46.
^ P o l l o k , T r a n s . Roy. D u b l i n S o c . ,
(2),
139 ( 1 9 0 4 ) .
6 P a r s o n s and B a r n e s , l o c . c i t .
7Gooch and Havens, Am. J . S c i . ,
( 4 ) , j4, 111.
CHAPTER I I
PROBLEMS STUDIED
P r e s e n t- d a y P ro ced u re f o r the D ete rm in a tio n o f
B e r y l l i u m i n B e r y l Ore by Means of t h e
8 - H y d r o x y q u i n o l i n e Method.
The method a s recommended i n t h e l i t e r a t u r e
QQ
*3
fo llo w s:
0 . 7 - 0 . 8 gram o f t h e a g a t e - g r o u n d o r e i s f u s e d f o r 25
m i n u t e s i n a p l a t i n u m c r u c i b l e w i t h 5 grams o f sodium c a r b o n ­
ate.
When p e r f e c t l y c o o l ,
t h e m elt i s t r a n s f e r r e d to a
400-ml b e a k e r o r e v a p o r a t i n g d i s h ,
tr e a te d c a u tio u s ly w ith
h y d r o c h l o r i c a c i d , and i s d e h y d r a t e d f o l l o w i n g t h e c u s t o m a r y
p ro ced u re fo r the d e te r ra in a tio n of s i l i c a .
In o r d e r t o r e c o v e r a n y b e r y l l i u m which m ight have
been c a r r i e d down i n t h e s i l i c a d e h y d r a t i o n , t h e s i l i c a i s
i g n i t e d i n a p l a t i n u m c r u c i b l e , and t r e a t e d w i t h h y d r o f l u o r i c
acid .
The o x i d e s which r e m a i n b e h in d i n t h e c r u c i b l e a r e
t h e n f u s e d w i t h p o t a s s i u m b i s u l f a t e f o r a b o u t 25 m i n u t e s ,
d i s s o l v e d i n h y d r o c h l o r i c a c i d and t h e r e s u l t i n g s o l u t i o n
added t o t h e o r i g i n a l f i l t r a t e
from w hich s i l i c a was removed.
8K o l t h o f f and S a n d e l l , J . Amer. Chem. S o c . . 5 0 . 1900
( 1 9 2 8 ).
9 H. B. Knowles, J o u r . of R e s e a r c h . U. S. N a t ' l . B u r e a u
o f S t a n d a r d s , 15,, 87 ( 1 9 3 5 ) .
The combined f i l t r a t e s w i l l now c o n t a i n a l l
the bery lliu m
from t h e sa m p le .
B eryllium ,
t o g e t h e r w i t h aluminum,
i r o n and o t h e r 3rd
and 4 t h group e l e m e n t s , a r e f r e e d from c a l c i u m and magnesium
by a s i n g l e p r e c i p i t a t i o n w i t h ammonium h y d r o x i d e w h ic h i s
added t o t h e a l m o s t b o i l i n g s o l u t i o n u n t i l a f a i n t but p e r ­
f e c t l y d i s t i n c t o d o r o f ammonia p e r s i s t s .
The p r e c i p i t a t e
o f combined h y d r o x i d e s i s f i l t e r e d o f f and washed w i t h Z%
ammonium c h l o r i d e s o l u t i o n , w h ic h has been r e n d e r e d j u s t
a l k a l i n e t o l i t m u s by t h e a d d i t i o n o f ammonium h y d r o x i d e .
The h y d r o x i d e p r e c i p i t a t e s a r e d i s s o l v e d w i t h 25 ml
o f h o t , 6N h y d r o c h l o r i c a c i d ,
the f i l t e r
b e i n g w e l l washed
a f t e r w a r d w i t h h o t w a t e r , and t h e n t h e s o l u t i o n i s d i l u t e d
to a volume o f a b o u t 400 m l.
15 ml of ammonium a c e t a t e
s o l u t i o n (2 0 0 g r a m s / l i t e r ) , and 1 ml o f b r o m c r e s o l p u r p l e
i n d i c a t o r ( 0 . 1 gram o f t h e dye d i s s o l v e d i n 3 . 7 ml o f 0 . 0 5 N
sodium h y d r o x i d e and d i l u t e d t o 250 ml) a r e a d d e d .
liq u id
The
i s now t r e a t e d w i t h 6 N ammonium h y d r o x i d e u n t i l
d i s t i n c t l y p u r p l e and t h e n ,
from a b u r e t t e , a r e added 50 ml
o f 8 - h y d r o x y q u i n o l i n e s o l u t i o n (made by t r i t u r a t i n g 10 grams
o f t h e s o l i d w i t h 23 ml o f g l a c i a l a c e t i c a c i d and t h e n
d i l u t i n g to 200 ml w i t h d i s t i l l e d w a te r a f t e r making s u r e
t h a t a l l of t h e r e a g e n t has gone i n t o s o l u t i o n ) .
The m i x t u r e
i s h e a t e d t o b o i l i n g and b o i l e d g e n t l y f o r a m i n u t e .
I t is
t h e n a l l o w e d t o c o o l to 60°C whereupon t h e aluminum o xy-
6
q u inolate is f ilte r e d
o f f and washed w e l l w i t h c o l d w a t e r .
The p u r e aluminum o x y q u i n o l a t e i s y e l l o w b u t ,
i n an o r e
s a m p le , w i l l be more o r l e s s d a r k e n e d , d e p e n d i n g upon t h e
amount o f i r o n p r e s e n t .
The f i l t r a t e from t h e rem oval of aluminum i s now
t r e a t e d w i t h 6N ammonium h y d r o x i d e u n t i l t h e odor o f ammonia
i s c l e a r l y p e r c e p t i b l e , a l lo w e d to c o o l t o room t e m p e r a t u r e ,
and t h e p r e c i p i t a t e d
b e r y l l i u m h y d r o x i d e i s f i l t e r e d o f f on
o p en -te x tu re a s h le s s f i l t e r paper.
I t i s washed w i t h
ammonium a c e t a t e s o l u t i o n made j u s t a l k a l i n e by t h e a d d i t i o n
o f ammonium h y d r o x i d e .
To make c e r t a i n o f t h e t r a n s f e r o f
ev ery tra c e of b ery lliu m hydroxide,
a r e r i n s e d down w i t h a l i t t l e h o t ,
th e b e r y l l i u m i s r e p r e c i p i t a t e d
the s id e s of th e beaker
6N h y d r o c h l o r i c a c i d , and
i n t h e b o tto m o f t h e b e a k e r
by a s l i g h t e x c e s s o f d i l u t e ammonium h y d r o x i d e .
The b e r y l l i u m h y d r o x i d e f i l t e r
is tran sferred
to a
p o r c e l a i n c r u c i b l e w hich h a s been weighed w i t h i t s c o v e r .
The p a p e r i s s l o w l y burned o f f w i t h t h e c r u c i b l e u n c o v e r e d .
Then t h e c r u c i b l e i s c o v e r e d w i t h t h e c o v e r i n v e r t e d and
h e a t e d a t t h e h i g h e s t t e m p e r a t u r e o f t h e F i s h e r o r Meker
b u r n e r f o r 45 m i n u t e s , c o o l e d i n a d e s i c c a t o r o v e r f r e s h l y
con cen trated s u lf u r ic acid o r,
better yet,
"D ehydrite".
F u r t h e r h e a t i n g i n 15 m inu te s t a g e s i s c o n t i n u e d u n t i l con­
s t a n t w e i g h t i s shown.
In s p i t e of t h e r e p o r t e d a c c u r a c y o f t h e 8 - h y d r o x y -
q u i n o l i n e method, a s shown by t e s t a n a l y s e s i n t h e o r i g i n a l
papers c ite d ,
t h e f a c t r e m a i n s t h a t r e s u l t s o b t a i n e d by th e
method i n com m ercial l a b o r a t o r i e s a r e f a r from s a t i s f a c t o r y .
O c c a s i o n a l l y th e r e s u l t s a r e a l i t t l e
to o h i g h , b u t f r e ­
q u e n t l y v a l u e s f o r b e r y l l i u m o x i d e a r e o b t a i n e d w h ich a r e
f a r below t h e t r u t h .
T h is s u g g e s t s e i t h e r r e t e n t i o n o f
b e r y l l i u m by t h e aluminum o x y q u i n o l a t e , o r i n c o m p l e t e p r e ­
c i p i t a t i o n of b e ry lliu m hydroxide in th e l a s t s te p of the
an aly sis.
M ention o f p o s s i b l y i n c o m p l e t e p r e c i p i t a t i o n o f
b e r y l l i u m h y d r o x i d e i s made by Knowles,^® who s u g g e s t s t h a t ,
as a p re c a u tio n ,
it
i s w e l l t o add a few d r o p s o f ammonia
s o l u t i o n to t h e f i l t r a t e and a l l o w i t
to s t a n d 24 h o u r s .
In
t h i s way a few f l o c k s o f b e r y l l i u m h y d r o x i d e a r e su ppose d t o
be r e c o v e r e d .
However, t h i s d o es n o t a c c o u n t f o r t h e l o s s
o f a s much a s 20 % o f t h e t o t a l b e r y l l i u m i n a sam ple, and
l o s s e s o f t h i s o r d e r have o f t e n been f o u n d , a c c o r d i n g t o P.
H. M .- P . B r i n t o n , * ^ who f i n d s t h e method u n r e l i a b l e u n l e s s
the f i l t r a t e
from t h e b e r y l l i u m h y d r o x i d e i s f r e e d from
*
o r g a n i c m a t t e r by t h o r o u g h o x i d a t i o n , a f t e r w hich t h e r e s t
of t h e b e r y l l i u m can be p r e c i p i t a t e d by ammonium h y d r o x i d e .
C o n v e n t i o n a l t r e a t m e n t w i t h s u l f u r i c and fum ing n i t r i c a c i d s
w i t h p e r c h l o r i c a c i d f o r o b s t i n a t e c a s e s , was found to be
10H. B. Knowles, l o c . c i t .
■^P. H. M .-P . B r i n t o n , P r i v a t e Com m unication.
8
successful,
th o u g h tim e - c o n s u m i n g .
The d e t a i l s of t h e O xi­
dation follow :
The f i l t r a t e
i s e v a p o r a t e d t o a volume of 50-75 ml and
r i n s e d i n t o a 300 ml K j e l d a h l f l a s k .
s u l f u r i c a c i d a r e added c a r e f u l l y ,
n i t r i c ac id (Sp. G r. 1 .5 0 ).
7 ml o f c o n c e n t r a t e d
f o l l o w e d by 2 ml of fuming
The i n c l i n e d f l a s k i s h e a t e d
o v e r a s m a l l f l a m e u n t i l a volume o f a b o u t 20 ml i s a t t a i n e d ,
a t w h ic h p o i n t t h e s o l u t i o n i s a l l o w e d t o c o o l , and 2 ml more
o f t h e fuming a c i d a r e a d d e d .
p e a t e d once o r t w i c e more.
be n o t i c e a b l e .
If n o t,
T h i s t r e a t m e n t s h o u ld be r e ­
A c o l o r l e s s s o l u t i o n s h o u ld t h e n
t h e c o l o r c a n be d i s c h a r g e d by a d d i n g
3 ml 60# p e r c h l o r i c a c i d and c o n t i n u i n g t h e h e a t i n g .
The c o l o r l e s s s o l u t i o n , w hich may s o l i d i f y on c o o l i n g ,
i s d ilu te d w ith w ater,
t r a n s f e r r e d t o a b e a k e r and f i l t e r e d
t o remove t r a c e s o f s i l i c a w h ich w i l l u s u a l l y be f o u n d .
clear f i l t r a t e
The
i s t h e n t r e a t e d w i t h a s l i g h t e x c e s s o f am­
monium h y d r o x i d e , and b e r y l l i u m i s d e t e r m i n e d a s b e f o r e .
The amount found h e r e i s added to t h e f i r s t
batch in c a lc u ­
l a t i n g t h e p e r c e n t a g e of b e r y l l i u m o x i d e i n t h e sa m p le .
The I n c o m p l e t e P r e c i p i t a t i o n o f B e r y l l i u m Hydroxide
F o l l o w i n g Removal o f Aluminum a s O x y q u i n o l a t e .
In t h e f i l t r a t e ,
qu inolate,
a f t e r rem oving t h e aluminum a s o x y ­
t h e i n s t r u c t i o n s f o r t h e d e t e r m i n a t i o n of b e r y l l i ­
um p r e s c r i b e p r e c i p i t a t i o n a s h y d r o x i d e by t h e a d d i t i o n of
9
ammonium h y d r o x i d e and t h e n d e s t r u c t i o n o f t h e o r g a n i c m a t t e r
w hereupon more b e r y l l i u m h y d r o x i d e w i l l be r e c o v e r e d .
T h is phenomenon i s n e v e r e n c o u n t e r e d when d e a l i n g w i t h
s o l u t i o n s o f b e r y l l i u m c h l o r i d e c o n t a i n i n g no o r g a n i c m a t t e r ,
th e p r e c i p i t a t i o n o f the hydroxide being a b s o l u t e l y q u a n t i ­
ta tiv e .
F u r t h e r m o r e , d i r e c t t e s t s have shown t h a t when
e i t h e r t h e 8 - h y d r o x y q u i n o l i n e o r t h e ammonium a c e t a t e a l o n e
is p resen t,
i n c o m p l e t e n e s s o f p r e c i p i t a t i o n i s n o t en­
countered.
However, when b o t h t h e s e r e a g e n t s a r e u s e d ,
a c c o r d i n g t o t h e r e q u i r e d c o n d i t i o n s f o r t h e aluminumberyllium s e p a ra tio n ,
failu re
to d e s tr o y the o rg a n ic m a tte r
may r e s u l t in t h e l o s s o f a s h i g h a s 2.0% o f t h e t o t a l
b e r y l l i u m c o n t e n t o f t h e s a m p l e . 1^
At t h e tim e of w r i t i n g of t h e a r t i c l e by H. B.
Knowles, 1 ^ v e r y l i t t l e a t t e n t i o n was p a i d t o t h i s e r r o r and
the a u th o r contented him self w ith the statem ent t h a t ,
instances,
i n some
t h e p r e c i p i t a t i o n o f b e r y l l i u m h y d r o x i d e m i g h t be
delayed and, fo r t h i s re a s o n ,
i t was a d v i s a b l e to t r e a t t h e
f i n a l f i l t r a t e w i t h a few d r o p s o f ammonia and p e r m i t i t t o
s t a n d f o r 24 h o u r s .
M. Frommes14 a l s o a d v i s e d t h i s .
As to
the cause of t h i s u n c e r t a i n t y in th e 8 -h y d ro x y q u in o lin e
12P . H. M .-P. B r i n t o n , L o c . C i t .
1
H . B. Knowles, L o c . C i t .
*4M. Frommes, Z e i t . fftr a n . Chemie, 9 3 . 287 ( 1 9 3 3 ) .
10
scheme, ev e n t o d a y t h e r e i s no c o n c r e t e e v i d e n c e .
The R e a g e n t ,
8-H ydroxyquinoline
S t r u c t u r e and S y n t h e s i s o f O x i n e .
The r e a g e n t ,
8 - h y d r o x y q u i n o l i n e ( a l s o known by t h e name 8 - Q u i n o l i n o l
(C h e m ic a l A b s t r a c t s ) an d , more p o p u l a r l y , o x i n e ) was f i r s t
p r e p a r e d by Z . H. S k r a u p ^ f o l l o w i n g t h e mode o f s y n t h e s i s
w hich b e a r s h i s name.
substance,
The r e a g e n t i s d e r i v e d from t h e p a r e n t
q u i n o l i n e , by t h e s u b s t i t u t i o n o f an OH gro u p i n
t h e 8 - p o s i t i o n , a c c o r d i n g to t h e f o l l o w i n g s e t o f s t r u c t u r a l
form ulae:
Hvo«oxY
N
OH
Oxine may t h e r e f o r e be c o n s i d e r e d a h e t e r o c y c l i c
t e r t i a r y a m in o p h e n o l o r a h y d r o x y d e r i v a t i v e o f t h e t e r t i a r y
h e t e r o c y c l i c a m in e , q u i n o l i n e .
The method o f p r e p a r a t i o n of 8 - h y d r o x y q u i n o l i n e g i v e n
b y . B e i l s t e i n 1_A c o n s i s t s i n d e h y d r a t i o n o f g l y c e r o l t o form
a c r o l e i n through the a c tio n of c o n c e n tra te d s u l f u r i c a c id ;
u
Sft.
CMC
c 1*
C H
j
. 0 H
+
•»
_______________________
152I. H. S k ra u p , Wiener M o n a t s h e f t f t i r Chemie, 3^,53® ?
(1881).
-------------------------------------------------• ^ B e i l s t e i n , e t a l . , Handbuch d e r o r g a n i s c h e n Chemie.
4 t h E d . , XXI. 91 ( 1 9 3 5 ) .
11
c o u p l i n g of t h e a c r o l e i n w i t h t h e o - a m i n o p h e n o l ;
and c o m p l e t i o n of th e r i n g c l o s u r e by oxygen from t h e a r s e n i c
acid an h y d rid e.
2-*
_ tii a
w r*
V a r i o u s Uses f o r t h i s R e a g e n t .
8-H ydroxyquinoline
i s a w h i t e , f l u f f y powder, w h ic h , when d i s s o l v e d i n a s o l v e n t
such as g l a c i a l a c e t i c a c id ,
t u r n s t o a deep o r a n g e s h a d e .
The t h e o r y upon w h i c h o x i n e i s su ppose d t o p r e c i p i t a t e
m e t a l s i s c a l l e d t h e c h e l a t e - l i n k a g e t h e o r y and i n v o l v e s t h e
follow ing conception.
When a m e t a l l i c i o n r e a c t s w i t h a
s o lu tio n of 8-hydroxyquinoline,
th e hydrogen of th e h y d ro x y l
g r o u p i s r e p l a c e d by m e t a l , t h e number of moles o f o x i n e
r e q u i r e d b e i n g d e t e r m i n e d by t h e v a l e n c e o f t h e m e t a l i n
questio n .
Now, due to t h e c l o s e p r o x i m i t y of t h e n i t r o g e n
to t h e h y d r o x y l g ro u p i n t h e 8 - p o s i t i o n ,
t h e r e i s t h o u g h t to
e x i s t a f u r t h e r e l e c t r o n i c a t t r a c t i o n of t h e n i t r o g e n f o r
t h e m e t a l , c a u s i n g a s u p e r f i c i a l bond between i t and t h e
m etal.
S i n c e t h i s b e n d i n g - a r o u n d o f t h e n i t r o g e n to h o ld on
t o t h e m e ta l i s i n t h e shape o f a c r a b ' s claw , t h e name
" c h e l a t e " h a s been d e r i v e d .
The t h e o r y i s f u r t h e r b o rn e o u t
12
by t h e f a c t t h a t h y d r o x y l d e r i v a t i v e s o f q u i n o l i n e w i t h t h e
s u b s t i t u e n t i n p o s i t i o n s o t h e r t h a n t h e 8 t h do n o t p r e c i p i ­
t a t e elem ents q u a n t i t a t i v e l y .
The f o l l o w i n g s t r u c t u r a l
f o r m u l a e a r e g i v e n to p i c t u r e t h e c h e l a t e t h e o r y i n t h e
r e a d e r ' s m ind:
Oxine
-g- Magnesium
Magnesium O x y q u i n o l a t e
8-H ydroxyquinoline ranks as ex trem ely im p o rta n t w ith
o r g a n i c r e a g e n t s w hich a r e u se d i n i n o r g a n i c a n a l y t i c a l
chem istry.
There i s p r o b a b l y no o t h e r compound o f i t s t y p e
t h a t h a s been used t o d e t e c t and d e t e r m i n e so many m e t a l s a s
oxine.
P o s s i b l y t h e f i r s t u s e f o r 8 - h y d r o x y q u i n o l i n e was
f o r t h e d e t e r m i n a t i o n o f magnesium i n am ounts u n d e r 1%*
This d e t e r m in a tio n i s c a r r i e d o u t i n s t r i c t l y a l k a l i n e
t i o n (pH g r e a t e r t h a n 7 ) .
solu­
Depending on t h e c o n d i t i o n s o f pH,
8 - h y d r o x y q u i n o l i n e h a s bee n p u t to u se i n d e t e r m i n i n g a l u m i 17
num, i r o n , c a l c i u m , and even b a r i u m .
The work o f B erg
has
bee n u n d o u b t e d l y t h e most v a r i e d
in re g a rd to the a p p l i c a ­
b i l i t y o f o x in e a s a p r e c i p i t a n t f o r m e t a l s .
lft
w o r t h y a r e t h e p u b l i c a t i o n s of Hahn.
A ls o n o t e -
17R. B e rg , Z e i t . f tlr a n . Chemie, 7 1 , 2 3 , 171, 321,
369 ( 1 9 2 7 ) ; 72, 177 ( 1 9 2 7 7 7 7 6 , 191 ( 1 9 2 9 7 ; 81, 1 ( 1 9 3 0 ) .
18F . L . Hahn, e t a l . ,
I b i d . . 71, 122, 225 ( 1 9 2 7 ) .
13
I n t h e s e p a r a t i o n o f aluminum from b e r y l l i u m , t h e
s o l u t i o n must be d e f i n i t e l y on t h e a c i d s i d e (pH a b o u t
4 . 5 - 5 . 0 ) , w hich i s a c c o m p l i s h e d by t h e u s e o f t h e ammoniaammonium a c e t a t e b u f f e r p r e s e n t a t t h e ti m e of s e p a r a t i o n .
3.
8
P r o c e d u r e f o r S m all L a b o r a t o r y P r e p a r a t i o n of
- Hyd r o x y q u i n o 1 i n e .
The c o s t of
8
-hydroxyquinoline is r a th e r
h i g h , a b o u t $ 2 . 9 0 p e r 100 gram s; so , a l i t t l e
t h o u g h t was
g i v e n t o t h e q u e s t i o n o f s m a l l - s c a l e p r e p a r a t i o n of t h e
reagent.
The mode o f s y n t h e s i s f o l l o w e d i n t h i s p h a s e o f th e
work was a m o d if ie d S k ra u p m ethod, a s g i v e n i n a n a r t i c l e
on s t u d e n t p r e p a r a t i o n s o f compounds i n t h e h e t e r o c y c l i c
s e r i e s . 19^
The r e f e r e n c e f o l l o w e d i n t h e p r e p a r a t i o n i n v o l v e d
a c t u a l l y two d i f f e r e n t s y n t h e s e s ;
F irst,
o - n i t r o p h e n o l i n t o o - a m in o p h e n o l a n d ,
the c o n v e rs io n of
second, the condensa­
t i o n o f t h e l a t t e r w i t h a c r o l e i n ( fr o m t h e g l y c e r o l ) to form
the desired product,
8
-hydroxyquinoline.
In the f i r s t s te p ,
the o - n i tr o p h e n o l i s reduced to
t h e c o r r e s p o n d i n g a m in o p h e n o l by t h e a c t i o n of a m i x t u r e of
sodium s u l f i d e - s o d i u m h y d r o x i d e .
O t h e r m etho ds of r e d u c t i o n
w ere, a c c o r d i n g t o t h e a u t h o r s , u n s u c c e s s f u l .
^ W a g n e r and Sim ons, J . Chem. E d . , JL3, 265 ( 1 9 3 6 ) .
14
The se cond s t e p was c a r r i e d o u t i n a 500 ml r o u n d bottom ed P y re x f l a s k .
The o - a m i n o p h e n o l , g l y c e r o l ,
su lfu ric
a c i d , and a r s e n i c a c i d a n h y d r i d e were i n t r o d u c e d , and t h e
m i x t u r e was g e n t l y b o i l e d f o r f i v e h o u r s w i t h a l o n g r e f l u x
condenser.
A f t e r a l l o w i n g t h e m i x t u r e to c o o l t h o r o u g h l y ,
i t was n e u t r a l i z e d , p r i n c i p a l l y w i t h sodium h y d r o x i d e s o l u ­
t i o n , and f i n a l l y w i t h sodium c a r b o n a t e s o l u t i o n u n t i l t h e
effervescence ceased.
The l i q u i d was t h e n s t e a m - d i s t i l l e d ,
th e w ater in the co n d en ser being run o u t o c c a s i o n a l l y in
o rd e r to p re v e n t the s o li d
the tu b e .
8
- h y d r o x y q u i n o l i n e from c l o g g i n g
The u s e o f a Hopkins t r a p , a l t h o u g h n o t m e n tio n e d
in the fo reg o in g p u b l i c a t i o n ,
measure.
i s a v e r y good p r e c a u t i o n a r y
The d i s t i l l a t e was c o o l e d , f i l t e r e d on a Buchner
f u n n e l , and the s o l i d o x i n e washed w i t h i c e w a t e r .
I f th e
p r o d u c t does n o t m e lt w i t h i n a d e g r e e o r two o f i t s c o r r e c t
m e ltin g p o in t (76°C),
i t s h o u l d be t a k e n up i n t h e l e a s t
p o s s i b l e amount of warm a l c o h o l ,
t h e n p r e c i p i t a t e d by p o u r i n g
t h i s s o l u t i o n i n t o a f a i r l y l a r g e volume o f c o l d w a t e r .
It
was t h e n c o o l e d , f i l t e r e d o f f a s b e f o r e , and p r e s s e d o u t on
a porous p l a t e to d ry .
The c h e m i c a l , when d r y ,
s h o u l d be
p r o t e c t e d from t h e a c t i o n of l i g h t by b e i n g p l a c e d i n a
brown b o t t l e .
S t a b i l i t y of S o l u t i o n s o f
C o n s i d e r a b l e P e r i o d s o f Time.
8
- H y d r o x y q u i n o 1in e o v e r
Inasm uch a s i t
i s n e c e s s a r y to
p r o t e c t s o l i d o x i n e from t h e a c t i o n of l i g h t by p a c k a g i n g i t
i n brown b o t t l e s ,
t h e d o u b t had a l w a y s a r i s e n w h e t h e r i t was
a d v i s a b l e to p r e p a r e l a r g e q u a n t i t i e s of
8
-hydroxyquinoline
s o l u t i o n i n ad v a n c e o r t o s i m p l y make a l i t t l e
a c id a s needed.
K o l t h o f f and S a n d e l l
PCi
up i n a c e t i c
state th e ir p re fe r­
e n c e f o r a n a c e t i c a c i d s o l u t i o n of t h e r e a g e n t r a t h e r t h a n
a n a l c o h o l i c o n e , b e c a u s e t h e f o r m e r " w i l l k e e p f o r a w ee k ".
In o r d e r to s e t t l e t h i s
i m p o r t a n t q u e s t i o n once and
f o r a l l , Dr. B r i n t o n f u r n i s h e d me w i t h a b a d l y d i s c o l o r e d
sample o f o x i n e s o l u t i o n , w h ic h he had made up f o u r y e a r s
ago by t h e c o n v e n t i o n a l method o f d i s s o l v i n g i n a c e t i c a c i d .
T h i s was u se d on
8
sa m p le s o f t h e same b e r y l o r e , w h ich had
p r e v i o u s l y been a n a l y z e d and whose c o m p o s i t i o n was d e f i n i t e l y
known, a n d ,
in no i n s t a n c e was t h e r e a n y e v i d e n c e t o i n d i c a t e
t h a t t h e aged s o l u t i o n had l o s t i t s s t r e n g t h a s a s e p a r a t i n g
a g e n t f o r t h e aluminum from b e r y l l i u m .
5.
A P o s s i b l e Mod i f i e d Method f o r D e t e r m i n i n g B e r y l ­
liu m a f t e r Removal o f Aluminum a s O x y q u i n o l a t e .
Out o f t h e
many a t t e m p t s on t h e p a r t o f t h e a u t h o r t o f i n d a n a l t e r n a t e ,
s h o r t e r p r o c e d u r e by w h ic h t o c a r r y o u t t h e
8
l i n e s e p a r a t i o n of aluminum from b e r y l l i u m ,
the fo llo w in g
method was d e v e l o p e d :
pn
K o l t h o f f and S a n d e l l , L o c . C i t .
-hydroxyquino­
16
F i r s t of a l l ,
much ti m e and u n c e r t a i n t y i n t h e i n i t i a l
d e c o m p o s i t i o n o f t h e o r e was overcome by f o l l o w i n g Huns a k e r ' s 21 method, u s i n g sodium p e r o x i d e i n a n i c k e l c r u c i b l e .
T h is mode o f d e c o m p o s i t i o n h a s two g r e a t a d v a n t a g e s .
In t h e
f i r s t p l a c e , d e c o m p o s i t i o n o f t h e o r e i s made more c e r t a i n by
the s u b s t i t u t i o n of th e s tr o n g e r a l k a l i ,
sodium p e r o x i d e ,
f o r t h e sodium c a r b o n a t e , and t h e tim e o f f u s i o n i s r e d u c e d
from 25 m i n u t e s t o l e s s t h a n 5 m i n u t e s .
S e c o n d l y , i t i s un­
n e c e s s a r y to u s e t h e e x p e n s i v e and o f t e n u n a v a i l a b l e p l a t i n u m
w ire f o r the f u s i o n .
When t h e p e r o x i d e method was employed
by H u n sa k e r, he was n o t f o l l o w i n g t h e
8
-hydroxyquinoline
scheme b u t t h e P a r s o n s and B a r n e s p r o c e d u r e ,
bicarbonate s e p a r a tio n .
inv o lv in g the
In t h e l a t t e r c a s e , t h e r e was no
need f o r w o rr y a s t o w hat e f f e c t t h e n i c k e l d i s s o l v e d from
th e c r u c i b l e would h a v e .
I n t h e o x i n e m ethod, how ever, be­
f o r e n i c k e l c o u ld be u s e d ,
i t was n e c e s s a r y t o c a r r y o u t
c e r t a i n e x p e r i m e n t s to p r o v e t h a t t h e r e would be no n i c k e l
p r e s e n t in th e f i l t r a t e
fo r the d e te rm in a tio n of b ery lliu m
and w h ic h m ig h t e a s i l y be a b s o r b e d by t h e g e l a t i n o u s h y d r o x ­
ide.
T h e r e f o r e , a s e t o f o r e sa m p les was r u n u s i n g n i c k e l
f o r t h e d e c o m p o s i t i o n , and i t was n o t e d t h a t w h a t e v e r n i c k e l
did n o t pass in to th e f i l t r a t e
from t h e ammonia p r e c i p i t a ­
t i o n , a l o n g w i t h t h e c a l c i u m and magnesium, was c o m p l e t e l y
2 ^Hunsaker,
'’Rapid Method f o r B e r y l l i u m , " M a s t e r ' s
T h e s i s , U n i v e r s i t y of S o u t h e r n C a l i f o r n i a , J u n e , 1933.
1?
t a k e n c a r e o f by t h e o x i n e r e a g e n t i t s e l f .
T h is was e a s i l y
p r o v e d by d e s t r o y i n g a l l o r g a n i c m a t t e r i n t h e f i n a l f i l t r a t e
and t h e n t e s t i n g f o r n i c k e l by t h e u l t r a - s e n s i t i v e d i r a e t h y l g ly o x im e r e a g e n t .
I n no i n s t a n c e was a t r a c e of n i c k e l t o
be f o u n d .
The second c ha nge i n p r o c e d u r e w h ic h t h e a u t h o r found
to be r e l i a b l e was a m o d i f i c a t i o n o f t h e manner i n w h ich t h e
o r g a n i c m a t t e r p r e s e n t i n t h e b e r y l l i u m f i l t r a t e was d e ­
stroyed.
I n s te a d of p r e c i p i t a t i n g
t h e b e r y l l i u m i n two s t e p s ,
and c o m p l e t e l y d e s t r o y i n g t h e o r g a n i c m a t t e r by r e p e a t e d
e v a p o r a t i o n s w i t h s m a l l amounts o f fum ing n i t r i c a c i d ,
whole f i l t r a t e
the
( w i t h o u t f i r s t p r e c i p i t a t i n g t h e b u lk of
b e r y l l i u m h y d r o x i d e ) was t r e a t e d w i t h 30, ml o f fuming n i t r i c
a c i d and e v a p o r a t e d down to h a l f i t s o r i g i n a l v o lu m e ; i . e . ,
from 600 t o a b o u t 300 ml.
The b e r y l l i u m may t h e n be p r e c i p i ­
t a t e d by t h e c a u t i o u s a d d i t i o n of ammonium h y d r o x i d e u n t i l
s l i g h t l y a m m o n ia c a l.
it
A f t e r a l l o w i n g t o s t a n d f o r 20 m i n u t e s ,
is f i l t e r e d o f f .
The two f o r e g o i n g p r o c e d u r e s ,
then,
co n stitu te a
method w hich h a s seemed to t h e a u t h o r t o work o u t q u i t e
s a t i s f a c t o r i l y and w hich r e p r e s e n t t h e s a v i n g of many h o u r s
of t e d i o u s work.
CHAPTER I I I
EXPERIMENTAL WORK
A l a r g e amount o f p r e l i m i n a r y e x p e r i m e n t a l w ork, a l l
t h e d e t a i l s o f w h ic h need n o t be r e c o r d e d , had i n d i c a t e d
t h a t s o m e th in g a b o u t t h e c o m b i n a t i o n o f ammonium a c e t a t e and
8
-hydroxyquinoline in t e r f e r e d ,
i n a v e r y i r r e g u l a r way, w i t h
t h e c o m p le t e p r e c i p i t a t i o n o f b e r y l l i u m h y d r o x i d e .
The o r e s
a n a l y z e d in e a c h of t h e f o l l o w i n g e x a m p le s were o f e x a c t l y
t h e same c o m p o s i t i o n ;
A S e t o f B e r y l l i u m D e t e r m i n a t i o n s on Ore
F o l l o w i n g t h e Custom ary M ethod.
BeQ C o n t e n t
Sample No.
1
2
.
12.15#
11.97#
.
12 . 11#
12 . 21#
3.
4.
Average
1 2 . 1 2 # BeO
R e s u l t s of N e g l e c t i n g t o D e s t r o y O r g a n i c
M a t t e r in t h e F i n a l F i l t r a t e .
Sample No.
BeO C o n t e n t
1.
2.
4.04#
5.81#
11.82#
9 .02#
6.83#
11.14#
3.
4.
5.
6.
m
E f f e c t o f R e a g e n t s I n v o l v e d on B e r y l l i u m
C hloride S o lu tio n .
B e r y l l i u m o x i d e was d e t e r m i n e d i n 25 ml of e a c h of
t h e f o l l o w i n g b e r y l l i u m c h l o r i d e s o l u t i o n s , w i t h no r e g a r d
f o r t h e d e s t r u c t i o n of t h e o r g a n i c m a t t e r p r e v i o u s to t h e
p r e c i p i t a t i o n of b e r y lliu m h y d r o x id e :
1.
8
- H y d r o q u i n o l i n e A lo n e .
Volume o f Oxine Used
W e ig ht of BeO/85 ml
0 ml
5 ml
10 ml
0 . 1 0 3 6 gm. ( S t a n d a r d )
0 . 1 0 3 3 gm.
0 . 1 0 5 7 gm.
0 ml
5 ml
10 ml
0 . 0 9 2 7 gm. ( S t a n d a r d )
0 . 0 9 2 2 gm.
0 . 0 9 2 5 gm.
0 ml
5 ml
10 ml
0 . 0 3 0 4 gm. ( S t a n d a r d )
0 . 0 3 0 5 gm.
0 . 0 3 0 2 gm.
2.
Ammonium A c e t a t e Alone ( 2 0 ^ ) .
Volume of A c e t a t e Used
0
5
10
15
ml
ml
ml
ml
W e ight of BeO/25 ml
0.0 3 0 4
0.0302
0.0305
0.0303
gm. ( S t a n d a r d )
gm.
gm.
gm.
20
3.
Ammonium A c e t a t e P l u s Oxine
15 ml A c e t a t e P l u s
________ Oxine_______
10
10
20
20
ml
ml
ml
ml
BeO/25 ml
__________
0 .0 6 7 6
0.0328
0.0207
0.0461
True S t r e n g t h of S o l u t i o n
g m .^
gm.
gm.
gm.
0 .0 5 5 6 gm.
/ 2 5 ml
U n s u c c e s s f u l M o d ifie d M e thods.
Q u ite a l a r g e number o f m o d i f i c a t i o n s were t r i e d
in
o r d e r to t r y t o overcome t h e extre m e i r r e g u l a r i t i e s e v i ­
denced by t h e f o r e g o i n g e x p e r i m e n t s .
A few o f t h e s e w i l l be
c i t e d here along w ith the a n a l y t i c a l r e s u l t s o b ta in ed through
t h e i r u s e on b e r y l l i u m c h l o r i d e s o l u t i o n s , whose t r u e c o n ­
c e n t r a t i o n s had been p r e v i o u s l y d e t e r m i n e d .
1.
T r e a t m e n t w i t h B rom ine .
25 ml of b e r y l l i u m c h l o r i d e s o l u t i o n had added t o i t
10 ml of o x i n e s o l u t i o n p l u s 15 ml o f a c e t a t e s o l u t i o n .
ml o f bromine were t h e n a d d e d ,
10
i n t h e hope t h a t t h e o r g a n i c
m a t t e r would be t a k e n o u t a s a bromo d e r i v a t i v e .
t a t e d id form a n d , a f t e r s t a n d i n g f o r
1 0
A p recip i­
m i n u t e s , was
* I t i s i m p o s s i b l e to e x p l a i n t h i s r e s u l t ,
included in the i n t e r e s t of com pleteness.
but i t
is
21
f i l t e r e d o f f and w e l l washed w i t h a c i d u l a t e d w a t e r .
The f r e e
bromine i n t h e f i l t r a t e was e x p e l l e d by b o i l i n g w hereupon
t h e s o l u t i o n was made am m oniacal w i t h ammonium h y d r o x i d e .
U nfortunately,
t h e f o l l o w i n g e r r o n e o u s r e s u l t s were o b t a i n e d ,
a n d , b e i n g low,
i n d i c a t e p r o b a b l e a b s o r p t i o n o f b e r y l l i u m by
the o rganic p r e c i p i t a t e :
a.
0 .0 8 3 9 gm. BeO/25 ml
b.
0 . 0 7 0 1 gm. BeO/25 ml
c . True s t r e n g t h — 0 . 1 0 1 3 g m ./2 5 ml
2.
P a r t i a l D e stru c tio n of
O rg a n ic M a t t e r .
The b e r y l l i u m c h l o r i d e s o l u t i o n was t r e a t e d
in the
same manner a s b e f o r e b u t now s u b j e c t e d t o p a r t i a l d e s t r u c ­
t i o n o f t h e o r g a n i c m a t t e r p r e s e n t p r e v i o u s to p r e c i p i t a t i o n .
1 0
ml o f c o n c e n t r a t e d n i t r i c a c i d and
1 0
ml o f fuming n i t r i c
a c i d were added t o t h e s o l u t i o n , w h i c h was h e a t e d up to
a b o u t 80°C.
The s o l u t i o n t h e n t u r n e d b l a c k a n d , when i t had
c o o l e d down, t h e s o l u t i o n was c a u t i o u s l y made am m o n ia c a l.
I n t h i s c a s e t h e e r r o r was a p o s i t i v e o n e , a s f o l l o w s :
a.
0 . 1 0 6 2 gm. BeO/25 ml
b.
0 . 1 0 2 7 gm. BeO/25 ml
c . True s t r e n g t h — 0 . 1 0 1 3 gra./25 ml
The b e r y l l i u m c h l o r i d e s o l u t i o n ,
m a t t e r , was a l s o t r e a t e d
c o n tain in g organic
i n s e v e r a l o t h e r ways, a l l o f them
22
■ u n s u c c e s s fu l.
In one i n s t a n c e ,
c y l i n d e r was p a s s e d i n ,
s u l f u r d i o x i d e from a
i n t h e hope t h a t th e i n t e r f e r i n g
s u b s t a n c e , w h a te v e r i t m ig h t be, would be r e d u c e d .
T his,
ho w e v e r, l e a d s t o a s t i l l more i n c o m p l e t e p r e c i p i t a t i o n o f
th e b e r y l l i u m h y d r o x i d e .
I n a n o t h e r c a s e , magnesium was
employed i n t h e form o f a s o l u t i o n o f magnesium c h l o r i d e i n
o rd e r to p r e c i p i t a t e the ex cess o x in e ,
but the u n c e r t a i n t y
o f i t s s u b s e q u e n t re m o v a l f o r c e d i t t o be g i v e n u p .
The
c o n t a m i n a t i o n i n t r o d u c e d by i t s u s e i s shown i n t h e f o l l o w i n g
data:
BeO C o n t e n t / 2 5 ml
gm.
0 . 0 7 9 8 gm.
0 . 1 0 1 1
0 . 0 5 5 6 gm. — True C o n c e n t r a t i o n
D a ta on S u c c e s s f u l M o d if ie d Method.
The r e s u l t s o f u s i n g t h e m o d i f i c a t i o n i n p r o c e d u r e ,
a s g i v e n on page 17, were q u i t e s a t i s f a c t o r y , and r a n a s
fo llo w s:
1.
On B e r y l l i u m C h l o r i d e S o l u t i o n s .
25 ml of b e r y l l i u m c h l o r i d e were p r e p a r e d i n t h e same
way a s in t h e u n s u c c e s s f u l m e th o d s;
i. e.,
15 ml o f 20#
ammonium a c e t a t e p l u s i n c r e a s i n g am ounts o f o x i n e .
However,
t h e o r g a n i c m a t t e r was t a k e n c a r e o f by t h e method h e r e
proposed.
23
S e t No. 1
Volume o f Oxine
W eight o f BeO
5 ml
10 ml
15 ml
0 . 0 3 0 0 gm.
0 . 0 3 0 3 gm.
0 . 0 3 0 1 gm.
True Amount — 0 . 0 3 0 4 gm. BeO/25 ml
S e t No. 2
5 ml
10 ml
15 ml
0 . 0 3 0 1 gm.
0 . 0 3 0 5 gm.
0 . 0 3 0 2 gm.
True Amount — 0 . 0 3 0 4 gm. BeO/25 ml
2.
On A c t u a l Ore Samples,
Sample No.
BeO C o n t e n t
1
2
3
4
A verage
12.09#
1 2 .1 7 #
12.12#
12.16#
1 2 . 1 3 # BeO
D ata on t h e A t t e m p t e d L a b o r a t o r y P r e p a r a t i o n
of
1.
8
-H ydroxyquinoline.
C o n v e r s i o n o f o . - N i t r o p h e n o l i n t o o - A m in o p h e n o l.
Reagent
o-nitrophenol
sodium h y d r o x i d e
su lfu r
sodium s u l f i d e
w ater
Q uantity
Weight of Y i e l d
# Y ie ld
40 gms.
1 2 gms.
1 0 gms.
80 gms.
1 0 0 ml
28 gms.
90#
24
2.
S y n t h e s i s of
Reagent
o - a m in o p h e n o l
glycerol
AS2 O5
Cone. H2 SO4
8
-H ydroxyquinoline.
Q uantity
25 gms.
54 gms.
9 gms.
44 gms.
W e ight of Y i e l d
^ Y ield
5 grams
15%
CHAPTER IV
CONCLUSION
1.
The Value o f t h e
8
- H y d r o x y q u i n o l i n e Method a s
C o n t r a s t e d w i t h O th e r W id e ly Used Schemes f o r
t h e S e p a r a t i o n of B e r y l l i u m from Aluminum.
I n e v a l u a t i n g a p r o c e d u r e f o r t h e s e p a r a t i o n o f two
elem ents,
all,
two p r i n c i p a l p o i n t s come t o o n e ' s min d.
i s t h e s e p a r a t i o n u se d a b s o l u t e l y q u a n t i t a t i v e ,
F i r s t of
espec­
i a l l y w i t h o u t too much r e g a r d f o r s t r i c t e x p e r i m e n t a l c o n ­
d itio n s?
S econd, how much tim e i s i n v o l v e d i n c a r r y i n g o u t
th a t sep aratio n ?
As r e g a r d s t h e f i r s t
issue,
the
8
-hydroxyquinoline
method g i v e s a p r e c i p i t a t e w h ic h i s of t h e b e s t t y p e a v a i l ­
a b l e f o r many r e a s o n s .
I t i s extrem ely in s o lu b le under th e
c o n d itio n s of a n a ly s is ,
f i l t e r s e a s i l y , and n o t b e i n g o f a
g e l a t i n o u s or c o l l o i d a l n a t u r e ,
c a n be t h o r o u g h l y washed
w i t h c o l d w a t e r and i s n o t a p t to r e t a i n b e r y l l i u m by a b s o r p ­
tio n .
Furtherm ore,
the a c e t i c a c id in the s o l u t i o n of the
r e a g e n t i n c o m b i n a t i o n w i t h t h e ammonium a c e t a t e c r e a t e s a
s t r o n g enough b u f f e r t h a t ,
p r i o r to the s e p a r a t i o n ,
i f one h a s used to o much ammonia
there is l i t t l e
chance t h a t t h i s
w i l l c a u s e an i n c o m p l e t e p r e c i p i t a t i o n o f th e aluminum o x y q u in o late.
26
Due to t h e n a t u r e o f t h e aluminum oxyquj.nol a t e , t h e
s e p a r a t i o n may be c a r r i e d o u t q u i t e r a p i d l y and t h e p r e c i p i ­
t a t e washed f r e e from b e r y l l i u m i n l e s s t h a n 45 m i n u t e s .
This i s d e f i n i t e l y i n c o n t r a s t t o t h e P a r s o n s and B a r n e s
method,
i n w h ic h t h e s o l u t i o n h a s to be s a t u r a t e d r e p e a t e d l y
w i t h COg, i n o r d e r t o e f f e c t a h a l f - w a y q u a n t i t a t i v e s e p a r a ­
t i o n , and i s c e r t a i n l y f a r l e s s t r y i n g and s a f e r t h a n t h e
Gooch and Havens p r o c e d u r e ,
c a l l i n g f o r t h e u s e of d i e t h y l
e t h e r , an e x t r e m e l y in f la m m a b l e s o l v e n t , and t h e g e n e r a t i o n
o f hydrogen c h l o r i d e gas in a l a b o r a t o r y .
The
8
- h y d r o x y q u i n o l i n e method h a s t h e f i n a l a d v a n t a g e
o f e n a b l i n g t h e a n a l y s t e i t h e r to w e ig h t h e aluminum i n a
s u i t a b l e form o r to d i s s o l v e i t
i n a c i d and t i t r a t e
the
r e l e a s e d o x i n e w i t h s t a n d a r d p o t a s s i u m b ro m ate s o l u t i o n .
2.
S i m p l i c i t y and Time S a v i n g o f t h e M o d if ie d Method.
The o n l y p o s s i b l e i n c o n v e n i e n c e i n v o l v e d i n t h e o x i n e
d e t e r m i n a t i o n o f b e r y l l i u m i s i n t h e v e r y l a s t s t e p , and
t h a t i s th e t e d i o u s mode of t h e d e s t r u c t i o n of o r g a n i c
m atter,
covered.
i n o r d e r t h a t a l l t h e b e r y l l i u m h y d r o x i d e may be r e ­
The sodium c a r b o n a t e f u s i o n , a l t h o u g h n o t a c t u a l l y
c o n n e c t e d w i t h s e p a r a t o r y method,
i s a l s o somewhat u n c e r t a i n .
The r e t e n t i o n o f b e r y l l i u m i n t h e s i l i c a
i n amounts g r e a t e r
t h a n t h a t o f aluminum i s u n d e r i n v e s t i g a t i o n i n a n o t h e r
lab o rato ry .
27
For t h e s e r e a s o n s ,
th e a u th o r has a t te m p te d to p u t
t o g e t h e r t h e two a l t e r n a t e p r o c e d u r e s o f u s i n g th e n i c k e l
c r u c i b l e s i n s t e a d o f p l a t i n u m and of f o l l o w i n g a s h o r t e n e d
scheme f o r d e s t r o y i n g t h e o r g a n i c m a t t e r .
ficatio n
The f i r s t m odi-:.-
i s a b s o l u t e l y c e r t a i n of b e i n g f r e e from e r r o r ,
and
t h e second i s , a c c o r d i n g t o a l l t h e e x p e r i m e n t a l d a t a now a t
h an d, r e a s o n a b l y c e r t a i n o f a c c u r a c y , and s h o r t e n s th e tim e
r e q u i r e d f o r t h e f o l l o w i n g d e s t r u c t i o n o f o r g a n i c m a t t e r from
3 h o u r s t o l e s s t h a n an h o u r .
The a u t h o r t h e r e f o r e s i n c e r e l y h o p e s t h a t t h i s modi­
f i e d method may p ro v e i t s w o r t h i n t h e f u t u r e and come more
and more i n t o g e n e r a l u s e .
3.
L a b o r a t o r y P r e p a r a t i o n of 8 - H y d r o x y q u i n o l i n e
v e r s u s P u r c h a s e o f t h e Commercial P r o d u c t .
I t was hoped, when t h i s r e s e a r c h was begun, t h a t
t h e r e m ight be a s u i t a b l e method t o a v o i d p a y i n g $ 2 . 9 0 p e r
100 grams o f o x in e r e a g e n t , a n d , f o r t h a t r e a s o n , t h e o r g a n i c
p a r t o f t h i s work was u n d e r t a k e n .
A f t e r g o i n g t h r o u g h a l l t h e s t e p s n e c e s s a r y t o g e t to
th e f i n a l p r o d u c t and t h e n n o t i n g t h e u n c e r t a i n t y and v e r y
low y i e l d s o b t a i n e d by t h e s m a l l s c a l e S kra u p s y n t h e s i s ,
the
a u t h o r f e e l s t h a t i t i s v i r t u a l l y i m p o s s i b l e to a v o i d p u r ­
c h a s i n g t h e c o m m e r c ia l r e a g e n t .
BIBLIOGRAPHY
BOOKS
M i n e r a l s Yearbook 1939, U. S . D e p t , of t h e I n t e r i o r , B u r e a u
o f Mines, p p . 7 4 8 - 7 5 1 .
S c o t t , S t a n d a r d Methods o f A n a l y s i s . 5 t h E d . , V o l . 1, New
Y ork: D. Van N o s t r a n d C o ., p p . 7 9 7 - 8 , 8 0 0 - 0 1 .
W i l l a r d and Furman, E l e m e n t a r y Q u a n t i t a t i v e A n a l y s i s , 3 r d Ed
New York: D. Van N o s t r a n d C o ., p p . 4 0 6 - 0 9 .
PERIODICALS
B e rg , R . , Z e i t s c h r i f t ftlr a n a l y t i s c h e Chem ie, 7 1 . S3, 171,
321, 369 ( 1 9 2 7 ) ; 7 2 , 177 (1927> ; 76, 191 ( 1 9 2 9 ) ; 81, 1
(1930).
Frommes, M., Z e i t s c h r i f t ftlr a n a l y t i s c h e C h e m ie. 9 5 . 287
(1933).
G ib b s , Am. J . S c i . . ( 2 ) ,
37, 3 46.
Gooch and H avens, Am. J . S c i . ,
( 4 ) , 4,
111.
Hahn, F . L . , e t a l . . Z e i t s c h r i f t f t t r a n a l y t i s c h e Chemie. 7 1 .
122, 225 ( 1 9 2 7 ) .
Knowles, H. B . , J o u r n a l of R e s e a r c h , U. S . N a t i o n a l B u rea u
o f S t a n d a r d s , .15, 87 ( 1 9 3 5 ) .
K o l t h o f f and S a n d e l l , J o u r n a l o f t h e A m e r ic a n Chemical
S o c i e t y . 5 0 . 1900 ( 1 9 2 8 ) .
P a r s o n s and B a r n e s , J o u r n a l o f t h e Amer i c a n C h e m ic al S o c i e t y
2 8, 1589 ( 1 9 0 6 ) .
P ollok,
T r a n s . Roy. D u b l i n S o c . .
(2),
139 ( 1 9 0 4 ) .
S k ra u p , Z. H . , W iener M o n a t s h e f t fttr Chemie. j3, 536 ( 1 8 8 1 ) .
V a u q u e l i n , Ann. Chim. P h y s . . 2 6 , 155 ( 1 7 9 8 ) .
Wagner and Simons, J o u r n a l of C he m ic al E d u c a t i o n . 1 3 , 265
(1936).
29
BIBLIOGRAPHY ( C o n t i n u e d )
REFERENCE WORK
B e i l s t e i n , e t a l . , Handbuch d e r o r g a n i s c h e n Chemie, 4 t h E d . ,
B e r l i n : V e r l a g von J u l i u s S p r i n g e r , XXI. 91 ( 1 9 3 5 ) .
THESIS
H u n sa k e r, "R apid Method f o r th e D e t e r m i n a t i o n o f B e r y l l i u m , "
M a s te r's T hesis, U n iv e rsity of Southern C a lif o r n ia ,
J u n e , 1933.
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