A study of some oxalates and double oxalates of beryllium

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Content A STUDY
OF SOME OXALATES AND DOUBLE OXALATES
OF BERYLLIUM
A T h e s is
P r e s e n te d to
th e F a c u lt y o f th e D epartm ent o f C h e m istry
U n i v e r s i t y o f S o u th e rn C a l i f o r n i a
In 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 ire m e n ts f o r th e D egree
M a ste r o f A r ts
by
G e ra ld E . B ruce
Septem ber 1938
U M I Number: EP41503
All rights reserved
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.Q-ERALDE.,... BBUCE..............................
under the direction of h.As Faculty Committee,
and a p p ro v e d by all its m embers, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfill
ment of the requirements for the degree of
m a s te r OF a r t s
D ean
Secretary
2938. D ate...
Faculty C om m ittee
Chairman
C 21
TABLE OF CONTENTS
CHAPTER PAGE
I . THE PROBLEM AND ITS HISTORY...................................... 1
I I . REVIEW OF PREVIOUS WORK............................ 3
The e a r l i e s t w o rk ...................................................................... 3
E x p e rim e n ta l w ork t o 1 9 0 6 ........................ 4
E x p e rim e n ta l w ork o f 19 1 4.................................................. 5
D is c o v e r ie s o f 1 9 2 6 ........................ 6
I I I . EXPERIMENTAL VERIFICATIONS................................................. 8
The norm al o x a l a t e s ................................................................. 8
A n a ly s is o f o x a l a t e s .. . . . . . ......................... 8
The double o x a l a t e s ...................................................... 10
P r e c i p i t a t i o n o f p o ta s s iu m b e r y lliu m o x y la te . 13
IV. THE PHOTOCHEMICAL EFFECT OF SUNLIGHT ON
NORMAL BERYLLIUM OXALATE.................................................. 14
V. AN ATTEMPT TO PREPARE A DOUBLE OXALATE OF
BERYLLIUM AND CAESIUM.................................. 15
V I. SUMMARY AND CONCLUSIONS........................................................... 17
PHOTOMICROGRAPHS.......................................................................................... 19
BIBLIOGRAPHY........................................................... 23
CHAPTER I
THE PROBLEM AND ITS HISTORY
V ery l i t t l e work h a v in g b een done on th e o x a l a t e s and
d o u b le o x a la te s o f B e ry lliu m i n r e c e n t y e a r s , i t was deemed
a d v is a b le t h a t th e f o llo w in g s tu d y be made f o r t h r e e p rim a ry
r e a s o n s . The f i r s t o f th e s e re a s o n s was t h a t a r e a l need
f o r a v e r i f i c a t i o n o f th e w ork done on th e s e p a r t i c u l a r com
pounds a s r e p o r t e d by P a r s o n s 1 was f e l t . The seco n d r e a s o n
was t h a t th e r e was n eed ed in one so u rc e a re v ie w o f any r e
c e n t work done a lo n g t h i s s u b j e c t . The f i n a l re a s o n was
more a r e s u l t o f th e two j u s t s t a t e d a b o v e, and t h a t was t o
p e rfo rm e x p e rim e n ta l work on new p o i n t s o f i n t e r e s t a s th e y
w ere b ro u g h t o u t b y th e above v e r i f i c a t i o n and re v ie w .
P a rs o n s g iv e s u s th e p i c t u r e o f th e o x a l a t e s o f
B e ry lliu m up t o and in c lu d in g th e y e a r 1906. S in c e t h a t
tim e a p p a r e n t l y l i t t l e v/ork h a s b een done on th e s e compounds.
P o s s i b l y b e ca u se o f t h e i r l a c k o f p r a c t i c a l im p o rta n c e , t h e y
seem to have been s e t a s id e f o r th e tim e b e in g . How ever,
many q u e s tio n s and p ro b lem s c o n c e rn in g t h e i r c h em ic al b e
h a v io r and p r o p e r t i e s a re s t i l l to be a n sw e red , t o s a y n o th
in g o f many p h y s i c a l p r o p e r t i e s and c o n s t a n t s s t i l l unknown.
^ P a rs o n s , C h a rle s L . , The C h e m istry and L i t e r a t u r e o f
B e r y lliu m . The Chem. P ub. C o ., E a s to n , P a . , 1909.
2
C a r e f u l s e a r c h th ro u g h th e l i t e r a t u r e shows t h a t n o t
more th a n some h a l f a dozen a r t i c l e s d e a l i n g w ith th e o x a
l a t e s o f b e r y lliu m have a p p e a re d s in c e P a r s o n Ts b i b li o g r a p h y
was w r i t t e n t h i r t y - t w o y e a r s a g o . The Z e i t s c h r i f t f u r
A n o rg a n isch e und A llg em ein e Chemie c a r r i e d a r t i c l e s i n
1 9 0 7 ,2 1 9 1 3 ,3 and 1 9 1 4 .^ The m ost r e c e n t a r t i c l e fou n d was
5
in 1926. S in c e t h a t tim e n o th in g h a s a p p e a re d to show w ork
on th e s e compounds.
^ H au ser, 0 . , Z e i t s c h r i f t f u r A n o rg an isch e und A l l -
gem eine C hem ie, 54. p . 207. 1907.
* % ir th , F . , I b i d . , 79. p . 357. 1913.
^ P a r s o n s , C. L . , and Wm. 0 . , R obinson, I b i d . , 7. p . 8 7 .
1914.
5
Lew is and S id g e w ic k , J . Chem. S o o . (London) 1926.
p p . 1 2 87 -1302.
CHAPTER I I
REVIEW OF PREVIOUS W ORK
A lth o u g h v e ry e a r l y a tte m p ts .w e r e made t o p r e p a r e th e
norm al b e r y l l iu m o x a l a t e , i t was n o t u n t i l 1897 t h a t c h e m is ts
w o rk in g on t h i s s u b j e c t saw r e s u l t s o f t h e i r l a b o r s . In t h a t
y e a r , Rosenheim and Woge6 c o n d u c te d e x p e rim e n ts on th e o x a
l a t e s , t a r t r a t e s , m o ly b d a te s , and s u l f i t e s o f b e r y lliu m to
show t h e i r d i f f e r e n c e s fro m th e c o rre s p o n d in g s a l t s o f a l u
minum, i r o n , and chrom ium . They p r e p a r e d and a n a ly z e d t h e i r
compounds, g iv in g to th e o x a la te th e fo rm u la BeCgC^.SHgO,
w hich i s now c o n s id e r e d to be th e norm al o x a la te o f b e r y l -
7
H um . W yrouboff c o n firm e d th e s e r e s u l t s i n 1902, and l a t e r
o
P a rs o n s and R o b inson i n 1906, w h ile m aking a s tu d y o f th e
sy ste m b e r y l l iu m o x id e , o x a l i c a n h y d rid e , and w a te r , made
th e norm al t r i h y d r a t e and a l s o su c ce ed e d i n d r i v i n g o f f two
o f th e t h r e e m o le c u le s o f w a t e r , t h e r e b y fo rm in g th e mono
h y d r a t e . They c o n c lu d e d from t h e i r e x p e rim e n ts t h a t an a c i d
o x a la te d id n o t e x i s t , and t h a t th e b a s i c o x a la te was i n
^Rosenheim , A ., and P . Woge, "Uber Die W e r t ig k e i t d e s
B e r y ll i u m s , 1 1 I . Chem. S o c . (L on d o n ). 74. p . 71. 1897.
^W yrouboff, G ., flS u r q u e lq u e s o x a l a t e s de g lu e i n e , 1 1
B u l l , s o c . f r a n c . de m in . , 25, p . 71.
^ P a rs o n s , C h a rle s L . , and W. 0 . R o b in so n , ^ E q u ilib r iu m
in th e System B e ry lliu m O xide, O x a lic A n h y d rid e , and W a te r ,”
I . Amer. Chem. S o c ., 28, p . 555.
4
r e a l i t y o n ly a s o l i d s o l u t i o n o f th e norm al o x a la te and
h y d ro x id e a p p ro a c h in g th e h y d ro x id e i n c o m p o s itio n .
W ith t h i s w ork h a v in g b een c a r r i e d o n , s e v e r a l p r o
p e r t i e s o f th e no rm al o x a la te o f b e r y l l iu m w ere o b se rv e d and
r e c o r d e d . The t r i h y d r a t e d form h a s ,th e fo rm u la BeCgO^.SHgO
and th e m o n o h y d rated , BeCgO^HgO. " I t i s v e r y s t r o n g l y a c id
i n r e a c t i o n and i n c o n c e n tr a te d s o l u t i o n d i s s o l v e s 1 .8 5
e q u i v a l e n t s o f i t s own c a rb o n a te o r h y d ro x id e . I t h a s a
s h a r p , s w e e tis h t a s t e . " 9 I t i s v e r y s o lu b le in w a t e r . I t
i s p r e p a r e d by a d d in g an e x c e s s o f o x a l i c a c id t o e i t h e r
b a s i c b e r y l l iu m c a rb o n a te o r h y d ro x id e and c r y s t a l l i z i n g
th e o x a la te th e r e f r o m . Any e x c e s s o f h y d ro x id e o r c a rb o n a te
p r e v e n ts c r y s t a l l i z a t i o n . Many o f th e p r o p e r t i e s o f t h i s
compound prove to be a t v a r ia n c e w ith th o s e o r d i n a r i l y a s s o
c i a t e d w ith m e t a l l i c o x a l a t e s o f th e b i v a l e n t m e t a l s .
P r a c t i c a l l y a l l t h a t i s known c o n c e rn in g th e do uble
o x a l a t e s a t th e p r e s e n t w r i t i n g was d e te rm in e d p r i o r t o th e
y e a r 1906. I n 1855, D eb ray , a lth o u g h u n a b le t o c r y s t a l l i z e
th e norm al o x a l a t e , e a s i l y p r e p a r e d th e d o u b le o x a l a t e s w ith
p o ta s s iu m and ammonium. The fo rm u la s g iv e n w ere BeCgO^.KgCgO^
and BeCgO^.. (NH^)gCgO^. I n 1903, W yrouboff ^*9 made th e p o t a s
sium compound and s t a t e d t h a t owing t o i t s c o m p a ra tiv e
9 P a r s o n s , C h a rle s L . ,- ojd. c i t . , ( 1 ) . p . 4 2 .
lO w y ro u b o ff, G ., o p . c i t . , ( 7 ) .
5
i n s o l u b i l i t y , t h i s m ig h t be a means o f s e p a r a t i n g b e r y l l iu m
11
from i r o n and alum inum . In a l a t e r a r t i c l e he u s e s t h i s
p r o p e r t y t o s e p a r a t e b e r y l l iu m from b e r y l , p r e c i p i t a t i n g by
means o f a c id p o ta s s iu m o x a la te o r p o ta s s iu m b i n o x a l a t e , a s
i t i s c a l l e d to d a y . He added th e KHC2 O 4 t o a s a t u r a t e d
s o l u t i o n o f b e r y l l iu m c h lo r i d e and p r e c i p i t a t e d p o ta s s iu m
b e r y l l iu m o x a l a t e . T h is b e h a v io r o f p o ta s s iu m b e r y l l iu m
o x a la te h a s b een v e r i f i e d in th e r e s e a r c h d e s c r ib e d i n t h i s
t h e s i s . The d e t a i l s w i l l be g iv e n i n a l a t e r c h a p t e r .
Of th e th r e e a r t i c l e s a p p e a rin g betw een th e y e a r s
1906 and 1914, t h a t o f P a rs o n s and R o b i n s o n - ^ was th e m ost
im p o r ta n t. I t d e a l s - w i t h th e s o l u b i l i t y o f th e n o rm al o x a
l a t e , w h ic h , in th e te rm s o f th e a u th o r , i s "w o rth d e te r m in in g
. . . b e c a u se b e r y l l iu m i s th e o n ly e le m e n t o f th e second
grou p whose o x a l a t e s a re s o l u b l e . " Here a g a in i s an exam ple
o f b e r y l l iu m re s e m b lin g alum inum , and one more r e a s o n f o r
i t s b e in g th e b rid g e e le m e n t from group 2 to group 3 i n th e
p e r i o d i c sy ste m .
A f t e r r e p e a t e d f r a c t i o n a t i o n s t o g e t r i d o f a s much
o x a l i c a c id a s p o s s i b l e , th e l a s t f r a c t i o n was d iv id e d i n t o
f o u r p a r t s . Each p a r t was t r e a t e d w ith 100 grams o f one o f
H w y ro u b o ff, G ., "S u r l a s e p a r a t i o n de l a g l u e i n e , "
£ . Chem. S o c . (L o n d o n ), 8 2 , p . 605.
-* - 2 P a r s o n s , C. L . , and W. 0 . R o b in so n , ojo. c i t . (4)
6
t h e f o llo w in g l i q u i d s : .1 N. o x a l i c a c i d , .1 N. s u l f u r i c
a c i d , 1 .0 N. s u l f u r i c a c i d , and p u re w a t e r . I n t h a t o r d e r ,
t h e y d i s s o l v e d th e f o llo w in g number o f gram s o f BeCgO^SHgO:
4 3 .1 6 , 4 2 .0 8 , ---------, and 3 8 .7 2 . The o x a la te was found t o b e ,
t h e n , more s o lu b le i n , t h e p re s e n c e o f o x a li c a c i d .
T h is s o l u b i l i t y o f b e r y l l iu m o x a la te was s t i l l open
f o r f u r t h e r r e s e a r c h i n 1926 when L ew is and S i d g e w i c k ^ pub
l i s h e d t h e i r f i n d i n g s c o n c e rn in g t h i s t o p i c , a lo n g w ith o t h e r
w ork on b e r y l l iu m .
The b e h a v io r o f th e o x a l a t e , w hich i n c r e a s e s in s o l u
b i l i t y by a b o u t t h r e e m o le c u le s f o r e v e r y f o u r o f th e
ox id e a d d ed , n e e d s f u r t h e r e x p l a n a t i o n . T h is s a l t i s
p e c u l i a r i n many w ays. I t i s u n iq u e among th e o x a l a t e s
o f b i v a l e n t m e ta ls in b e in g v e r y s o l u b l e i n w a te r ( n e a r l y
30 p e r c e n t a t 2 5 ° ) . The o x a l a t e s o f m agnesium , c a lc iu m ,
s t r o n t iu m , b a riu m , z i n c , cadmium, m erc u ro u s m e rc u ry ,
s ta n n o u s t i n , m anganous m an g an ese, f e r r o u s i r o n , c o b a lto u s
c o b a l t , and nicldfe, a r e a l l v e ry s l i g h t l y s o lu b le i f a t
a l l s o l u b l e .
A n o th e r s ta te m e n t in t h e i r a r t i c l e i s t o th e e f f e c t t h a t
"The in c r e a s e o f th e s o l u b i l i t y o f th e s a l t on a d d i t i o n o f,
o x id e i s t h r e e tim e s a s g r e a t a s w i t h th e s u l f a t e o r s e l e n a te
( 1 : 1 .3 i n s t e a d o f 1 : 1 . 4 ) . "
O th e r p r o p e r t i e s t h a t t h e y e n u m e ra te d a r e s e t f o r t h
i n th e f o llo w in g e x c e r p t :
l^ L ew is and S id g e w ic k , o p . c i t . . ( 5 ) .
• ^ I b i d . , p . 3000.
7
I t ( b e r y lliu m o x a la te t r i h y d r a t e ) i s a l s o a lm o st
u n iq u e among b e r y lliu m s a l t s i n n o t fo rm in g a t e t r a -
h y d r a te b u t o n ly a t r i h y d r a t e * These f a c t s c l e a r l y
i n d i c a t e t h a t i t i s n o t a norm al o x a la te * F u r th e r
p e c u l i a r i t i e s t h a t we have fo u n d a re (1 ) th e conduc
t i v i t y , w hich even a t v=513 i s b a r e l y a q u a r t e r o f
t h a t o f th e s u l f a t e , and a t g r e a t e r c o n c e n tr a ti o n s
f a l l s t o a b o u t a s i x t h , show ing t h a t (assum ing th e
io n ic m o b i l i t i e s t o be a b o u t th e same) th e number o f
io n s form ed i s o n ly a b o u t a q u a r t e r o f t h a t p ro d u ced
by a norm al b i - v a l e n t s a l t ; and ( 2 ) th e in c r e a s e in
s o l u b i l i t y o f th e s a l t on a d d i t i o n o f o x id e i s t h r e e
tim e s a s g r e a t a s w ith s u l f a t e o r s e l e n a te . . • ;
f i n a l l y (3) th e f r e e z i n g p o i n t e x p e rim e n ts show t h a t
th e number o f m o le c u le s ( in c lu d in g io n s) in th e s o l u t i o n
i s n o t much l e s s t h a t i t would, be w ith a norm al s a l t .^ - 5
I t i s t o be g e n e r a l l y c o n ce ed e d , t h e n , t h a t th e s o - c a l l e d
norm al o x a la te o f b e r y lliu m i s in r e a l i t y an abnorm al s a l t .
The f o u r t h c h a p t e r r e c o r d s an e x p e rim e n t c a r r i e d on c o n c e rn
in g th e p h o to c h e m ic a l e f f e c t s on b e r y lliu m o x a la te t r i h y d r a t e
w hich f u r t h e r b e a r s o u t th e s ta te m e n t j u s t made*
^ L e w i s and S id g e w ic k , lb id *. p* 3001*
CHAPTER I I I
EXPERIMENTAL VERIFICATIONS
As h a s b e en s u g g e s te d , th e norm al o x a la te o f b e r y l
liu m c o u ld be p r e p a r e d b y s a t u r a t i n g e i t h e r th e b a s ic c a r
b o n a te o r th e h y d ro x id e w ith o x a li c a c i d and c r y s t a l l i z i n g .
B oth ways were t r i e d and fo u n d s u c c e s s f u l . An a tte m p t was
made t o c r y s t a l l i z e th e compound w i t h a l i t t l e o f th e c a r
b o n a te i n e x c e s s . As had been th e c a se w ith th e h y d ro x id e ,
no s a l t would fo rm . T h is showed th e n e c e s s i t y o f h a v in g
o x a li c a c i d in e x c e s s .
The o x a la te c r y s t a l l i z e s in v e r y t i n y c r y s t a l s , form
in g a scum o f w hat a p p e a r to be t i n y flo w e rs on th e s u r fa c e
o f th e c o o lin g m o th er l i q u o r . I f t h a t l i q u o r i s d i s t u r b e d
o r sh ak en to a s m a ll d e g re e , th e " f lo w e r s ” th e n s i n k to th e
b o tto m o f th e c o n t a i n e r where th e m ain body o f c r y s t a l s i s
fo rm in g . I f th e a c i d i s to o much i n e x c e s s , th e lo n g ,
n e e d l e - l i k e c r y s t a l s o f o x a li c a c i d w i l l be fou n d in te r m in g le d
w ith th e b e r y lliu m o x a l a t e . W ith r e p e a te d f r a c t i o n a t i o n s ,
th e a c i d can be e li m in a te d to a l a r g e d e g re e , a lth o u g h n e v e r
e n t i r e l y s o . T h is i s why t h e s a l t c a n n o t be a n a ly z e d w ith
any d e g re e o f a c c u ra c y by t i t r a t i o n a g a i n s t s ta n d a r d perm an
g a n a te s o l u t i o n . I t c an be a n a ly z e d s u c c e s s f u l l y by d e t e r
m in a tio n o f th e b e r y l l iu m c o n te n t i n th e d r i e d s a l t .
T here a re two sim p le m ethods o f p ro c e d u re in a n a ly z in g
f o r b e r y lliu m i n t h i s compound. One i s to d i s s o l v e th e
o x a la te and p r e c i p i t a t e b e r y l l iu m h y d ro x id e by means o f
ammonium h y d ro x id e . The f i l t e r i n g i s slow b e ca u se o f th e
v e r y g e l a t i n o u s p r e c i p i t a t e , som etim es m aking t h i s m ethod
lo n g and drawn o u t ev en th o u g h t h e r e a r e v e r y few s t e p s .
The o t h e r m ethod r e s t s upon th e o x a l a t e ’ s p r o p e r t y
o f b e in g c o n v e rte d t o th e oxide a t 350° C. I t i s a v e r y
sim p le m a t t e r to w eig h o u t a sample i n t o a w eighed c r u c i b l e ,
h e a t a t 350° f o r s e v e r a l m in u te s , a llo w to c o o l, and w eigh
th e r e s i d u e . I t i s a p p a re n t a t o n c e, how ever, t h a t t h i s
p ro c e d u re i s o n ly a p p li c a b l e t o d e te rm in in g th e p u r i t y o f
th e o x a l a t e . The above p r e c i p i t a t i o n p ro c e d u re v/ould have
to be u se d i n a m ixed sam p le.
A f t e r h a v in g d r i e d th e sam ple a t 100° C. f o r f o r t y -
e i g h t h o u r s , an a n a l y s i s was made a c c o rd in g to th e second
m ethod j u s t m e n tio n e d . S in ce th e o x a la te c o u ld n o t be
e n t i r e l y f r e e d o f o x a li c a c i d , th e p e rc e n ta g e o f b e r y lliu m
d e te rm in e d by th e a n a l y s i s w ould be s l i g h t l y l e s s th a n t h e r e
t h e o r e t i c a l l y sh o u ld be in th e compound. T hen, t o o , i f th e
t r i h y d r a t e had n o t been a l l d e h y d ra te d to th e m onohydrate
form , th e e x p e rim e n ta l v a lu e s v/ould a g a in be l e s s th a n th e
v alu e p re d e te rm in e d on th e b a s i s o f th e fo rm u la w e ig h t o f
th e compound.
On th e a ssu m p tio n t h a t p u re b e r y lliu m o x a la te mono
h y d r a t e , BeCgO^.HgO, was th e m a t e r i a l ta k e n f o r a n a l y s i s ,
th e p e rc e n ta g e o f b e r y lliu m s h o u ld ru n v e r y c lo s e to 7 .8 4 .
10
A n a ly s is gave 7 ,8 1 and 7 .8 3 w ith an a v e ra g e o f 7 .8 2 p e r c e n t
b e r y l l iu m in th e compound. I t m ust be conceded t h a t th e s a l t
was a l l in th e m onohydrated fo rm , a s t h i s ag re em e n t can be
c o n s id e r e d a s a b s o l u t e , w i t h in th e l i m i t s o f a c c u ra c y o f th e
m ethod o f a n a l y s i s . T here i s a l s o l i t t l e d o u b t t h a t th e
s a l t a s i t c r y s t a l l i z e d o u t o f th e s o l u t i o n was th e t r i h y
d r a t e d form , a lth o u g h a n a l y s i s was n o t made a t t h i s p o i n t .
P r e p a r in g th e d o ub le o x a la te s o f b e r y l l iu m w ith th e
a l k a l i m e ta ls i s v e ry f a s c i n a t i n g b e ca u se t h e y c r y s t a l l i z e
o u t in b e a u t i f u l c r y s t a l fo rm s, e a c h w ith i t s own c h a r a c
t e r i s t i c p a t t e r n . T h is i s s t r i k i n g l y shown i n th e p h o to
m ic ro g ra p h s a t th e end o f t h i s t h e s i s .
The m o n o b ery lliu m d oub le o x a l a t e s a re a l l p r e p a r e d by
a d d in g th e c o n s t i t u e n t p a r t s i n s o l u t i o n , i n th e r a t i o o f
t h e i r m o le c u la r w e ig h ts , and c r y s t a l l i z i n g from t h i s s o l u
t i o n . The d i b e r y l li u m compounds, on th e o t h e r h an d , n e c e s
s i t a t e th e use o f b e r y lliu m h o d ro x id e and th e a c id o x a la te
o f th e d e s i r e d m e ta l. I n o t h e r w o rd s, i f p o ta s s iu m b e r y l
liu m o x a la te was w a n te d , b e r y lliu m o x a la te and p o ta s s iu m
o x a la te would be c r y s t a l l i z e d o u t t o g e t h e r . I f th e d i b e r y l
liu m o x a la te o f p o ta s s iu m was th e p ro d u c t s o u g h t, a c i d
p o ta s s iu m o x a l a t e , o r p o ta s s iu m b i n o x a l a t e a s i t i s f r e q u e n t
l y c a l l e d , w ould be s a t u r a t e d w ith b e r y l l iu m h y d ro x id e and
16
c r y s t a l l i z a t i o n c a r r i e d on . R osenheim and Woge i n 1897
^ R o s e n h e im and Woge, 0 £ . c i t . . ( 6 ) . p . 71.
11
c o u ld n o t g e t r e s u l t s by so sim p le a p r o c e s s , b u t bad t o
s a t u r a t e a t th e b o i l i n g p o i n t , d i l u t e som ewhat, and a llo w
t o s ta n d u n t i l th e e x c e s s b e r y l l iu m h y d ro x id e was d e p o s ite d
o u t o f th e s o l u t i o n . By f i l t e r i n g and e v a p o r a tin g o v e r s u l
f u r i c a c i d , t h e y were a b le t o o b t a i n c r y s t a l s o f th e d i b e r y l
liu m o x a l a t e s .
Only th e p r e p a r a t i o n o f th e m o n o b ery lliu m compounds
was a tte m p te d f o r t h i s p a p e r . The f i r s t o f th e s e t o be p r e
p a re d was p o ta s s iu m b e r y l l iu m o x a l a t e , BeCgO^K^CgO^ The
c o n s t i t u e n t s c r y s t a l l i z e d o u t in l o u s t r o u s c r y s t a l s a s r e
c o rd e d b y R osenheim and Woge. When th e compound was a llo w
ed t o c r y s t a l l i z e on a g l a s s s l i d e and o b se rv e d u n d e r th e
m ic ro sc o p e , th e c r y s t a l form s a p p e a re d t o be l e a f - s h a p e d
and o f t e n a p p e a re d on a stem in t y p i c a l d e n d r i t i c fo rm . In
o t h e r fo r m a tio n s th e l e a v e s would r a d i a t e in a flo w e r p a t
t e r n , and i n s t i l l o t h e r c a s e s , a s i s o l a t e d u n i t s . These
" f lo w e rs " a p p e a re d i n u n d e s c r ib a b le a r r a y s o f c o lo r when
s u b je c te d t o p o l a r i z e d l i g h t . The p i c t u r e on page 19 shows
th e b e a u t i f u l c r y s t a l fo rm s o b ta in e d .
An a n a l y s i s was made on th e p o ta s s iu m b e r y lliu m
o x a la te f o r p o ta s s iu m u s in g p e r c h l o r i c a c id t o p r e c i p i t a t e .
On th e b a s i s t h a t th e sam ple was p u re BeC^O^.KgCgO^, th e
p o ta s s iu m sh o u ld ru n 2 9 .7 $ . A sam ple o f th e unknown y i e l d e d
2 9 .0 $ . The d is c r e p a n c y i s e a s i l y a c c o u n te d f o r in th e fa c e
^ L o c . c i t .
12
o f th e i m p o s s i b i l i t y o f r i d d i n g th e sam ple e n t i r e l y o f o x a li c
a c i d , and a l s o th e r e m ig h t have b e e n a s m a ll amount o f e i t h e r
o f th e s i n g l e o x a l a t e s c r y s t a l l i z i n g o u t w ith th e double
o x a la te i f one o r th e o t h e r happened t o be i n s l i g h t e x c e s s
due t o i n a c c u r a te m easurem ents a t th e tim e th e y were p la c e d
i n th e same m ix t u r e ♦ The r e s u l t was c lo s e enough, how ev er,
t o e s t a b l i s h th e f a c t t h a t p o ta s s iu m b e r y lliu m o x a la te had
been p r e p a r e d .
F o r a seco n d p r e p a r a t i o n o f a double o x a la te w ith
b e r y l l iu m , some sodium o x a la te was added to b e r y l l iu m o x a
l a t e and c r y s t a l l i z a t i o n a llo w e d t o ta k e p l a c e . As a r e s u l t ,
t i n y c r y s t a l s o f sodium b e r y l l iu m o x a la te h a v in g th e fo rm u la
BeC2 O 4 .Na2 C2 O 4 .H2 O form ed on th e b o tto m o f th e c o n t a i n e r .
The p i c t u r e on page 20 show s, u n d e r h ig h m a g n i f ic a ti o n , th e
c r y s t a l form v e ry c l e a r l y .
A n o th er d o u b le o x a la te o f t h i s s e r i e s t o be p r e p a r e d
was th e ammonium b e r y l l iu m o x a l a t e . I t s fo rm u la i s
BeCgC^.(NH4 ) 2 C2 O 4 . I t fo rm s lo n g n e e d l e - l i k e c r y s t a l s l i k e
th e ammonium o x a la te (se e p . 2 1 ) b u t n o t n e a r l y so l a r g e or
p e r f e c t a s th e s i n g l e o x a l a t e .
A r a r e r d o u b le o x a la te o f b e r y l l iu m was p re p a r e d
u s in g ru b id iu m o x a l a t e . S in c e th e ru b id iu m c o u ld o n ly be
o b ta in e d a s a s u l f a t e , i t had t o f i r s t be c o n v e r te d to th e
o x a la te b e f o r e a tte m p tin g th e d o u b le o x a l a t e . T h is was
a c c o m p lish e d by p r e c i p i t a t i n g th e s u l f a t e w i t h b a riu m
13
h y d ro x id e , l e a v i n g th e s o lu b le RbOH. The f i l t r a t e was e v a
p o r a t e d to d ry n e s s and d i s s o l v e d in o x a l i c a c i d , from w hich
th e ru b id iu m o x a la te was c r y s t a l l i z e d . From h e r e , th e two
o x a l a t e s , HbgCgO^ and BeCgO^, w ere p la c e d in th e same c o n ta in e r
and c r y s t a l s o f BeCgO^.RbgCgO^formed.
The f i n a l c o n f ir m a tio n f o r t h i s t h e s i s was th e s t a t e -
ment o f V/yrouboff-L O t h a t p o ta s s iu m b e r y l l iu m o x a la te c o u ld
be p r e c i p i t a t e d by a c i d p o ta s s iu m o x a la te from b e r y lliu m
c h l o r i d e . Some d ry b e r y lliu m c a rb o n a te was d i s s o l v e d in
h y d r o c h lo r ic a c i d and a h o t s o l u t i o n o f a c i d p o ta s s iu m o xa
l a t e v/as a d d e d . Upon c o o lin g , a c r y s t a l l i n e p r e c i p i t a t e
form ed v e r y r a p i d l y and s e t t l e d to th e b o tto m o f th e con
t a i n e r . The c r y s t a l form was e x a c t l y t h a t o f th e c r y s t a l s
o b ta in e d by th e d i r e c t c r y s t a l l i z a t i o n m ethod, h a v in g a
more compact m ass, h ow ev er. T here v/as no d o u b t t h a t th e
s u b s ta n c e form ed was p o ta s s iu m b e r y l l iu m o x a l a t e .
^ U y r o u b o f f , G ., £ £ . c i t . , (1 1 ).
CHAPTER IV
THE PHOTOCHEMICAL EFFECT OF SUNLIGHT
ON NORMAL BERYLLIUM OXALATE
S in c e i t had a lr e a d y b e en shown t h a t b e r y l l iu m oxa
l a t e a c t s a b n o rm a lly i n c e r t a i n w ays, th e q u e s tio n came up
a s t o w h e th e r th e s u n fs r a y s w ould have any e f f e c t upon i t ,
a s i s th e c ase w ith o x a la te s o f o t h e r d i - v a l e n t m e t a l s .
T h is e f f e c t i s a b r e a k in g down o f th e o x a la te w ith an e v o lu
t i o n o f c a rb o n d i o x i d e .
A s m a ll amount o f th e b e r y lliu m o x a la te was suspend ed
i n v /a te r and th e n p la c e d i n th e d a rk f o r f o r t y - e i g h t h o u r s ,
b e in g o b se rv e d a t i n t e r v a l s . As w ith o t h e r o x a l a t e s , no
r e a c t i o n c o u ld be seen d u rin g t h i s tim e . Then i t was p la c e d
in d i r e c t s u n l i g h t f o r e i g h t h o u r s , and a g a in o b se rv e d f o r
any r e a c t i o n . T h is r e a c t i o n w ould be shown b y t i n y b u b b le s
o f carb o n d io x id e a s i t was e v o lv e d . No r e a c t i o n c o u ld be
s e e n . So h e r e , a g a in ,, t h i s o x a la te p ro v ed i t s a b n o rm a lity
a s compared w ith o t h e r s o f i t s k in d .
CHAPTER V
AN ATTEMPT TO PREPARE A DOUBLE OXALATE
OP BERYLLIUM AND CAESIUM
H aving found no r e c o r d o f a double o x a la te o f b e r y l
liu m and c a e siu m e v e r h a v in g been p r e p a r e d , an a tte m p t t o
p re p a re t h i s compound w ould prove v e ry i n t e r e s t i n g . S in c e
th e d o u b le o x a l a t e s o f th e o t h e r a l k a l i m e ta ls were a l l
p r e p a r e d b y c r y s t a l l i z a t i o n , t h i s compound sh o u ld be no
e x c e p tio n to th e r u l e , b u t sh o u ld c r y s t a l l i z e o u t i n th e
same m anner. W ith o n ly a v e ry l i m i t e d am ount o f caesiu m
a v a i l a b l e and t h a t in th e s u l f a t e form , th e p ro c e d u re was
a s d e s c r ib e d b elo w .
As i n th e c ase o f ru b id iu m s u l f a t e , th e c ae siu m
s u l f a t e was t r e a t e d w ith b a riu m h y d ro x id e and b a riu m s u l
f a t e p r e c i p i t a t e d . The f i l t r a t e c o n ta in i n g th e caesiu m
h y d ro x id e was e v a p o r a te d t o d ry n e s s and d is s o l v e d in o x a li c
a c i d , from w hich c ae siu m o x a la te v/as c r y s t a l l i z e d *
S e v e r a l o f th e l a r g e s t caesiu m o x a la te c r y s t a l s were
d i s s o l v e d and added to a d i s s o l v e d q u a n t i t y o f b e r y lliu m
o x a l a t e . The r e s u l t i n g m ix tu re Y/as e v a p o r a te d somewhat and
allo v /ed t o c o o l, w hereupon a c r y s t a l l i n e s u b s ta n c e form ed
in th e l i q u i d . P i c t u r e s were made o f some o f t h i s m a t e r i a l ,
su p p o s e d ly caesiu m b e r y l l iu m o x a l a t e .
16
A r a t h e r h a s t y a n a l y s i s was r u n on some o f th e d r i e d
c r y s t a l s and r e s i d u e , h u t due to an a p p a r e n t la r g e e x c e s s o f
th e b e r y lliu m o x a l a t e , e x p e r im e n ta l r e s u l t s d id n o t check
v e r y c l o s e l y w ith th e t h e o r e t i c a l p e rc e n ta g e o f b e r y lliu m
in th e compound on th e b a s i s o f a sup posed fo rm u la o f
BeCgO^.CSrjCgO^. L arge am ounts o f w a te r o f h y d r a t i o n , s in c e
caesiu m i s h i g h l y h y g ro s c o p ic i n many o f i t s compounds, may
a ls o have cau se d th e d i f f e r e n c e .
On th e b a s i s o f th e above fo rm u la , th e p e rc e n ta g e o f
b e r y l l iu m in th e compound sh o u ld be 2.0% . The a n a l y s i s
r e s u l t e d i n 3.9%. T h is r e s u l t shows t h a t t h e r e m ust have
b een some caesiu m b e r y l l iu m o x a la te p r e p a r e d , in s p i t e o f
th e l a r g e d i f f e r e n c e .
The m icro sco p e gave no c lu e a s t o c r y s t a l fo rm , a s
can be se en i n th e p h o to g ra p h on page 22 . They a p p a r e n t l y
were so sm a ll a s t o r e n d e r them u n d i s c e r n a b l e , even u n d e r
th e m ic ro s c o p e .
CHAPTER V I
SUMMARY AND CONCLUSIONS
W ith a v e ry d e f i n i t e need f o r such a s t u d y , th e f o r e
g o in g work was do ne. A g a th e r in g t o g e t h e r i n t o one so u rc e
o f a r e v ie w o f th e more im p o rta n t work done on t h i s s u b j e c t
up t o th e p r e s e n t tim e w ould c e r t a i n l y be u s e f u l . E x p lo rin g
i n to new f i e l d s c o n c e rn in g th e s e compounds w ould s u r e l y be
p r o f i t a b l e .
Work on th e o x a l a t e s and doub le o x a l a t e s o f b e r y lliu m
came to an a p p a re n t s t a n d - s t i l l a f t e r th e y e a r 1906. B ut
some re c o rd e d s tu d y was made a b o u t 1914 and 1926. O ther th a n
t h i s , l i t t l e advance h a s been made, and th e s u b j e c t h a s b e en
in a s t a t e o f r e s t f o r s e v e r a l y e a r s .
The o x a l a t e s a re a l l made by a p r o c e s s o f c r y s t a l l i
z a t i o n . They a re w h ite , c r y s t a l l i n e s u b s ta n c e s , b e in g v e r y
s o lu b le i n w a te r . They p o s s e s s c e r t a i n i n d i v i d u a l c h a r a c
t e r i s t i c s w hich d i s t i n g u i s h one fro m th e o t h e r , b u t g e n e r a l l y
th e y a re v e ry much a l i k e . The n o rm al o x a la te o f b e r y l l iu m
does n o t r e a c t p h o to c h e m ic a lly a s do o x a l a t e s o f th e o t h e r
d i - v a l e n t m e t a l s .
Up t o th e p r e s e n t tim e , a l l o f th e double o x a l a t e s
w ith th e a l k a l i m e ta ls had been p r e p a r e d w ith th e e x c e p tio n
o f caesiu m and ele m e n t No. 87. B ut now th e caesiu m compound
h a s been p r e p a r e d , v e ry l i k e l y th e l a s t i n t h i s s e r i e s .
18
The o x a l a t e s o f b e r y lliu m a p p a r e n t l y have no p r a c t i
c a l v a lu e * O u tsid e o f p o s s ib l e use in a n a l y t i c p ro c e d u r e s ,
th e y a r e o f l i t t l e consequence* T h e ir c h i e f i n t e r e s t l i e s
i n th e f a c t t h a t t h e y r e a c t a b n o rm a lly , and th o u g h th e y
occupy o n ly a s m a ll and i n s i g n i f i c a n t p l a c e , t h e y a r e n e c e s
s a r y to com plete th e g r e a t s t r u c t u r e o f c h e m is tr y .
PHOTOMICROGRAPHS
* ■
r \
n
r .
k
L i
1 5
r .
BeC 2 04 .Na2C 2 0 4 .H20
U
u
Ha2 C2 ° 4
I
21
1 %
BeGgG^.RbgCgO^
r .
CssC2°4
22
(kh4 ) 2c2 o4
BIBLIOGRAPHY
Lew is and S id g e w ic k , "The S o l u b i l i t y o f B e ry lliu m Oxide in
S o lu tio n s o f i t s S a l t s ." J . Chem. S o o ., London, 129,
128 7-1302, 1926*
P a r s o n s , C h a rle s L . , The C hem istry and L i t e r a t u r e o f B e r y l
liu m . The Chem. P ub. C o ., E a s to n , P a . , 1909.
P a r s o n s , C h a rle s L . and W. 0 . R o b in so n , "E q u ilib r iu m i n th e
System B e ry lliu m O xide, O x a lic A n h y d rid e, and W a te r,"
£• Amer. Chem. S o c . , 2 8 :5 5 5 -5 6 9 , May, 1914.
R osenheim , A. and P . Woge, "Tiber d ie W e r tig k e it d es B e r y l
l iu m s ," £ . Chem. S o c . , London, 7 4 :7 1 , 1897.
W irth , F . , "Uber d as O x a lat und A c e ta t du B e r y l l e r d e ,"
Z e i t s c h r i f t f u r A n o rg an isch e und A llgem eine Chem ie,
8 7 :7 - 8 , 1914.
W yrouboff, G ., "S ur q u e lq u e s o x a l a t e s de g l u c i n e ," B u l l .
s o c . f r a n c . de m in . , 2 5 :7 1 , 1902.
W yrouboff, G ., "S u r l a s e p a r a t i o n de l a g l u c i n e , " £ . Chem.
S o c . . London, 8 2 :6 0 5 , 1906..

Asset Metadata

Creator Bruce, G. E (author)

Core Title A study of some oxalates and double oxalates of beryllium

Contributor Digitized by ProQuest (provenance)

Degree Master of Arts

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

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Language English

Advisor [illegible] (committee chair), [illegible] (committee member), Smith, Frank J. (committee member)

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Rights Bruce, G. E.

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Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

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