THE EXTRACTION OF TIN FROM ITS ORES AND

THE PREPARATION AND BEHAVIOR OF CERTAIN

P M E SALTS OF TIN.

by

Harry Borden M a r s h a l l

A Thesis submitted f o r the Degree o f

MASTER OF ARTS
i n the Department

CHEMISTRY

The U n i v e r s i t y of B r i t i s h Columbia
A p r i l - 1931.
 TABLE OF CONTENTS

INTRODUCTION.

I. EXTRACTION OF TIN FROM ITS ORES.

1. Occurrence of Samples.
2. D i s i n t e g r a t i o n of G a s s i t e r i t e .
3. D i s i n t e g r a t i o n of Stannite.
4. P u r i f i c a t i o n of C a s s i t e r i t e T i n .
5. P u r i f i c a t i o n o f Stannite T i n .

II. THE STABILITY OF STANNIC OXIDE.

I I I . THE DETERMINATION OF TIN AS CAESIUM CHLOROSTANNATE.

1. P r e p a r a t i o n of Stannic C h l o r i d e .
2. P r e p a r a t i o n o f Caesiian 0hloride.
r

3. Method.

IV. SOLUBILITY OF CAESIUM CHLOROSTANNATE.

 ACKNOWLEDGMENT

I wish to express my greatest appreciation

and thanks to Dr. E.H. Archibald, who has

not only provided many materials necessary

i n t h i s i n v e s t i g a t i o n but has also gladly

given every possible assistance and advice.

 THE EXTRACTION OF TIN FROM ITS ORES AND
THE PREPARATION AND BEHAVIOR OF CERTAIN
PURE SALTS OF TIN.

INTRODUCTION.
The existence of isotopes has explained a great many-
d i s c r e p a n c i e s i n the theory of atomic s t r u c t u r e . I t has also
d e f i n i t e l y s e t t l e d the v a l i d i t y o f the whole number r u l e f o r
the atomic weights of the elements. Henee any experimental
work whieh w i l l corroborate the existence o f i s o t o p e s , w i l l
be o f great importance i n strengthening the proof of the
atomic Theory.
1
F. W. Aston, by u s i n g the p o s i t i v e ray spectograph, and
p l a t e s of i n c r e a s e d s e n s i t i v i t y to p o s i t i v e rays, has found
i t p o s s i b l e t o d e f i n i t e l y prove that a group of eight l i n e s ,
corresponding approximately t o atomic weights of 116, 117,
118, 119, 120, 121, 122, 124, was due t o T i n . I t i s extremely
l i k e l y that these eight i s o t o p e s do e x i s t i n the case of t i n ,
but as y e t no d i r e c t chemical evidence has proven t h e i r
existence.
One method of a t t a c k i n g t h i s problem i s t o determine the
atomic weight of t i n i n i t s d i f f e r e n t ores. Due to extremely
d i f f e r e n t g e o l o g i c a l formation there may be wide v a r i a t i o n s
i n the concentration of the isotopes i n these d i f f e r e n t ores.
Such a v a r i a t i o n might be detected by separate atomic weight
determinations of the t i n i n the d i f f e r e n t samples.
 T h i s was the o r i g i n a l problem attempted. However, the
e x t r a c t i o n of t i n from i t s ores proved to c o n s t i t u t e a
problem i n i t s e l f , and t h i s t h e s i s w i l l deal l a r g e l y w i t h
t h i s p a r t of the work, together w i t h the preparation of pure
t i n from the m a t e r i a l e x t r a c t e d .

Considerable work has been c a r r i e d out towards evolving

a convenient and g e n e r a l l y a p p l i c a b l e method of a n a l y s i n g
t i n ores. This search has brought f o r t h many methods of
d i s i n t e g r a t i o n and may be b r i e f l y reviewed under two headings:
A. Reduction methods i n which the oxide i s reduced
to m e t a l l i c t i n .

B. S a l i f i c a t i o n methods i n whieh advantage i s taken o f

the a c i d p r o p e r t i e s of stannie oxide i n the formation
of a l k a l i stannates.
A. Reduction Methods:
C o r n o u a i l l e s f i r s t used carbon as a reducing agent f o r
2
t i n ores. The process has been studied by l e v o l and Moissenet,
4
but i t i s best described by B e r i n g e r . He a l s o suggests the
a d d i t i o n of a l i t t l e powdered f l u o r spar to a s s i s t the f u s i o n
of r e f r a c t o r y s l a g s .
The method of r e d u c t i o n i n hydrogen or i l l u m i n a t i n g gas
5
i s due to Hampe, but has been described i n some d e t a i l by
6 ,7
Parry. Fawns considers i t the most p r a c t i c a l method of
reduction.
Reduction w i t h potassium cyanide has been used by
6 8
a s s a y i s t s f o r some time. P a r r y and Bayerlein-Essen have
o u t l i n e d t h e i r methods of a n a l y s i n g t i n ore w i t h t h i s reagent.
 3
9
a. M. Henderson has found that t h i s method of f u s i o n i s out
10
of the question f o r low grade ores. 0. Boy ascribes this
i n e f f i c i e n c y f o r low grade ores to the presence of sulphur
or s i l i e a , and m o d i f i e s the procedure by f i r s t r o a s t i n g to
remove sulphur, and then b o i l i n g w i t h h y d r o f l u o r i c a c i d to
remove s i l i e a .
B. S a l i f i c a t i o n Methods:
F u s i o n w i t h sodium carbonate and sulphur to form soluble
11 12
sulpho-stannates, has been worked out by G o l i c k and C o r t i .
13
J. Gray has found t h i s to be an accurate method, but describes
i t as " d i r t y , tedious, and slow." This conclusion has been
a f f i r m e d by S. Fawns who also adds that f o r t h i s reason the
method i s never used.
14
E. ?. Pearce suggested the use of sodium hydroxide f o r
the d i s i n t e g r a t i o n of t i n ores and worked out a scheme of
a n a l y s i s based on t h i s method of f u s i o n . The present accepted
method i s a s l i g h t m o d i f i c a t i o n of Pearce's o r i g i n a l procedure
15 16
and i s c a l l e d the Pearce-low method. R.J. Morgan also uses
the a l k a l i f u s i o n method f o r d i s s o l v i n g t i n ores and f i n d s that
consistent r e s u l t s are obtainable using t h i s process. J. Gray
has obtained accurate r e s u l t s f o r low grade ores w i t h sodium
hydroxide whereas potassium cyanide i s e n t i r e l y u n r e l i a b l e .
9

G. M. Henderson used sodium peroxide instead of the 13

g r e a t l y increased. The peroxide was a l s o discussed by J . Gray
hydroxide and found that the speed of the a n a l y s i s was
who claims i t s advantage over the hydroxide i s only i n
s p e c i a l cases, as when chromite i s present.
 4

EXTRACTION OF TIN FROM ITS ORES.

1. Occurrence of Samples.
Tin occurs i n Nature i n three forms: (1) as C a s s i t e r i t e
or stannic oxide, (2) as s t a n n i t e , the combined sulphides of
Iron, Copper and T i n and (S) as n a t i v e T i n .
By f a r the most abundant source of t h i s element i s
C a s s i t e r i t e and hence t h i s mineral has been studied i n some
detail. Stannite occurs u s u a l l y i n much smaller q u a n t i t i e s
and o f t e n i n small proportions along w i t h the oxide. It i s
very seldom used as a souree of T i n not only because of i t s
r a r i t y but a l s o because of i t s low t i n content. Hence i t
has not been studied i n the same d e t a i l .
Hence i n e f f e c t i n g the d i s i n t e g r a t i o n of the mineral,
the methods already i n use i n connection w i t h C a s s i t e r i t e
were t r i e d , and s i m i l a r ones i n the case o f the Stannite.
The sample of C a s s i t e r i t e r e f e r r e d to was obtained
from the Consolidated Mining and Smelting Company, from
t h e i r S u l l i v a n mine, at Kimberley, B. C. I t had bein
concentrated from t h e i r t a i l i n g s and was a f a i r l y r i c h ore.
A sample of Stannite was obtained from the Snowflake mine,
s i t u a t e d twenty miles n o r t h o f Revelstoke. I t was taken
from a quartz v e i n and was of low q u a l i t y .
These two ores seemed to f u l f i l l the conditions l a i d
down above as to d i f f e r e n c e i n conditions of formation.
 5
2
The D i s i n t e g r a t i o n of O a s a i t e r i t e Sample.
The methods of t r e a t i n g C a s s i t e r i t e are v a r i e d and have
17 13
been aiseussed by H. M i l o n and R. Fouret, and J. Gray.
The t i n oxide may be reduced by carbon, hydrogen,
i l l u m i n a t i n g gas, z i n c or potassium cyanide. Of.these carbon
and cyanide were t r i e d . The f i n e l y ground ore was w e l l mixed
w i t h powdered charcoal and placed i n a p o r c e l a i n c r u c i b l e
w e l l l i n e d w i t h the reducing agent. The dross was heated t i l l
redness and kept at t h i s temperature f o r ten minutes. On
c o o l i n g the reduced t i n was found to e x i s t i n very small
p a r t i c l e s which had to be separated by s l u i c i n g .

The cyanide method was next t r i e d and since the r e s u l t s

obtained i n t h i s ease were most s a t i s f a c t o r y , the p u r s u i t of
a b e t t e r method was discontinued. A 25 gram sample was w e l l
mixed w i t h an equal quantity of Potassium Cyanide and placed
i n a 3 i n c h p o r c e l a i n evaporating d i s h . On both top and bottom
of the mix was placed a l a y e r of pure cyanide. The c r u c i b l e
was heated, slowly at f i r s t and then more r a p i d l y , u n t i l the
whole mass had fused. The temperature was f i n a l l y r a i s e d to
a b r i g h t red heat and then the c r u c i b l e and i t s contents were
allowed to c o o l g r a d u a l l y . The whole operation required
about t h i r t y minutes. The melt was then leached out w i t h
water and the m e t a l l i c t i n button found on the bottom o f
the c r u c i b l e .
I t has been noted above that the Pearce Low method of
f u s i o n w i t h Sodium Hydroxide gives the most accurate r e s u l t s ,
e s p e c i a l l y w i t h low grade ores, and seems to be the best method
 thus f a r suggested. While the cyanide f u s i o n i s not an
accurate a n a l y t i c a l method, i t i s r e l a t i v e l y most e f f e c t i v e
i n the s e p a r a t i o n of the t i n from other constituents and f o r
t h i s reason was adopted.

3. The D i s i n t e g r a t i o n of Stannite.
Very l i t t l e study has been made of the d i s i n t e g r a t i o n
of s t a n n i t e ores. A c c o r d i n g l y those methods which are
s u c c e s s f u l i n f u s i n g C a s s i t e r i t e , were also t r i e d w i t h stannite
with varied results.

A small sample of f i n e l y ground ore was b o i l e d w i t h aqua

r e g i a f o r sometime but was not attacked.
Potassium n i t r a t e i s a powerful o x i d i z i n g agent and i s
often used s u c c e s s f u l l y f o r t h i s purpose. I n order to test
out the method, f i f t e e n grams o f ore and an equal quantity
of the n i t r a t e were w e l l mixed and placed i n a f i r e c l a y
c r u c i b l e o f two hundred c c . capacity. An upper and lower
l a y e r of pure potassium n i t r a t e was used and the c r u c i b l e
heated g e n t l y i n a muffle furnace u n t i l f u s i o n . The temper-
ature was then r a i s e d and maintained at red heat f o r t e n
minutes longer. On eooling the charge was found to have
changed somewhat i n color and appearance, and had become
extremely hard and b r i t t l e . I t was found to be very d i f f i c u l t
to remove by mechanical means, i . e . , w i t h hammer and c h i s e l ,
and could not be d i s s o l v e d by any of the ordinary a c i d s
or aqua r e g i a . Therefore t h i s attempt was considered
unsuccessful.
 7
The Cyanide f u s i o n was used i n a manner s i m i l a r to that
o u t l i n e d above. When the cyanide was leached out with water
i n the customary manner, the f i n e l y d i v i d e d ore came out as
w e l l , s t i l l i n the form of a f i n e black powder. The ore had
not been attacked. The duration of the heating p e r i o d a f t e r
f u s i n g d i d not seem to a s s i s t the process of reduction.
I t has been already noted that the sodium hydroxide
f u s i o n i s the standard method of d i s i n t e g r a t i n g and analysing
Cassiterite. About t h i r t y grams of broken Sodium Hydroxide
was mixed w i t h f i v e grams of f i n e l y d i v i d e d ore and the
mixture fused f o r h a l f an hour i n a p o r c e l a i n e r u c i b l e .
The melt was f i r s t softened w i t h water and then with HC1.
The ore d i d not d i s s o l v e even on b o i l i n g .
18
J.H. Walton and H.A. Scholz found that many r e f r a c t o r y
substances could be e a s i l y decomposed by f u s i o n w i t h Sodium
Peroxide. Their experiments included a Titanium T i n ore.
This method as a p p l i e d to C a s s i t e r i t e has been h i g h l y
13
recommended by Gray.
I n g e n e r a l , even where the sodium hydroxide f u s i o n i s
s u c c e s s f u l , the peroxide has been found to produce a surer,
safer, and more complete fusion, f o r not only i s a better mix
p o s s i b l e , but the combined e f f e c t of an o x i d i z i n g and
s a l i f i c a t i o n agent i s obtained.
Accordingly twenty-five grams of ore were w e l l mixed
w i t h an equal quantity of Sodium Peroxide and the mixture
t r a n s f e r r e d to a f i r e c l a y c r u c i b l e . I g n i t i o n of the mix
was obtained by heating gently i n a muffle furnace f o r three
 8

or four minutes. The molten mass was allowed to cool somewhat

and was then poured c a r e f u l l y i n t o about s i x l i t r e s of water.
V i o l e n t e b u l l i t i o n took plaee at f i r s t , but soon subsided.
The remainder of the melt was e a s i l y chipped from the c r u c i b l e
and added to the s o l u t i o n . This mixture s t i l l appeared
p a r t i a l l y undecomposed but on a c i d i f y i n g w i t h HC1 and
warming, complete s o l u t i o n was obtained, y i e l d i n g a c l e a r
yellow l i q u i d . To remove s i l i e a t h i s s o l u t i o n was evaporated
u n t i l the l a r g e Jfcl which p r e c i p i t a t e d , became quite v i s c o u s .
The mixture was then d i l u t e d , and the s i l i c a separated by
decantation. The s i l i e a was then f u r t h e r extracted with
d i l u t e H y d r o c h l o r i c a c i d u n t i l the s o l u t i o n obtained was no
longer y e l l o w .

This method of f u s i o n has proven to be quite s a t i s f a c t o r y

f o r the d i s i n t e g r a t i o n of s t a n n i t e ore. I t i s exceedingly
r a p i d and r e q u i r e s only a r e l a t i v e l y small amount of f u s i n g
material. Since the m a t e r i a l i s to be l a t e r p u r i f i e d , another
important feature i s to be noted. No f o r e i g n material which
would be d i f f i c u l t to remove l a t e r on, i s introduced.
4. P u r i f i c a t i o n of C a s s i t e r i t e T i n .
The metal i s obtained from the cyanide f u s i o n i n the
form of a shiny button. A l l the cyanide i s f i r s t c a r e f u l l y
d i s s o l v e d out w i t h water and the metal then d i s s o l v e d by
warming i n HC1. The t i n i s p r e c i p i t a t e d from t h i s s o l u t i o n
as the sulphide by passing i n hydrogen sulphide gas, i r o n
and other group (3) metals remaining i n s o l u t i o n . The
 9

p r e c i p i t a t e was f i l t e r e d , washed, and d i s s o l v e d by warming

w i t h ammonium p o l y s u l p h i d e . When copper i s present i n large
q u a n t i t i e s , i t i s d i s s o l v e d to a small extent by t h i s reagent,
but there was no i n d i c a t i o n of i t s presence i n the sulphide
as i t appeared , b r i g h t yellow and p e r f e c t l y homogeneous.
The ammonium sulpho stannate was then f i l t e r e d and the stannic
sulphide r e p r e c i p i t a t e d by a c i d i f y i n g the f i l t r a t e w i t h d i l u t e
hydrochloric acid. The large yellow p r e c i p i t a t e obtained was
washed f r e e o f a c i d and then treated i n a beaker w i t h eonc.
N i t r i c Acid. Small pieces of yellow amorphous sulphur were l e f t
u n d i s s o l v e d even on warming. These were f i l t e r e d o f f , washed
and r e j e c t e d , the wash water being added to the main s o l u t i o n .
The s o l u t i o n of the t i n i n n i t r i c a c i d was then evaporated
almost to dryness, a c l e a r transparent j e l being obtained.
This j e l gave a f i n e white f l o c c u l e n t p r e c i p i t a t e of metastannio
a c i d when a g i t a t e d w i t h a large excess of water. Dilute
n i t r i e a c i d was added to increase the s o l u b i l i t y of any
i m p u r i t i e s and the p r e c i p i t a t e most conveniently f i l t e r e d by
decantation. Antimony forms a corresponding pentoxide which
however i s i n s o l u b l e only a f t e r i g n i t i o n . Hence t h i s
procedure should remove the l a s t p o s s i b l e traces of any
impurities.

To obtain the t i n i n a m e t a l l i c form, the p r e c i p i t a t e

(H Sn0) was d i s s o l v e d i n concentrated hydrochloric acid,
2 o
3
d i l u t e d , and e l e c t r o l y s e d . As Platinum i s d i s s o l v e d somewhat
by nascent c h l o r i n e , i t was necessary to s u b s t i t u t e some
other r e s i s t i v e m a t e r i a l which i s not attacked, f o r an anode.
 Tantalum metal i s not attacked, by aqua r e g i a or
c h l o r i n e , hence would be quite u s e f u l f o r the purpose. A
t h i n s t r i p , one mm. i n width and t e n cm. long was obtained,
and was s u b s t i t u t e d f o r the anode, and a f i n e platinum rod
used as cathode. The tantalum however, on imposing an E.M.F.,
was found to take on an i r i d e s c e n t blue f i l m of the oxide,
which was quite impervious to the passage of the current. I t
i s remarkable that the current was found t o pass i n the
opposite d i r e c t i o n w i t h the tantalum serving as a cathode.
A s p e c t r o s c o p i c a l l y pure carbon electrode, f i f t e e n cm.
long and one h a l f cm. i n diameter was obtained from Adam
H i l g e r L t d . , and s u b s t i t u t e d f o r the anode. I t was found
to be very s a t i s f a c t o r y and r e s i s t e d the a c t i o n o f the
c h l o r i n e quite w e l l . The platinum rod was again used as
cathode.

The t i n deposited i n s h i n i n g l e a f l e t s which were

i o l l e c t e d d a i l y and stored i n d i s t i l l e d water. To obtain i n
a more compact form the c r y s t a l s were placed i n a p o r c e l a i n
boat and fused i n a current o f pure dry hydrogen. A shiny
m e t a l l i c button was obtained. This completed the p u r i f i c a t i o n .
The hydrogen f o r t h i s purpose was prepared by the action
of zine on s u l p h u r i c a c i d and was p u r i f i e d by passing through
a s e r i e s o f wash b o t t l e s containing concentrated a l k a l i , and
over hot copper gauze.
 11

5. The P u r i f i c a t i o n of Stannite T i n .

The percentage of t i n i n t h i s ore i s very much lower

than i n the C a s s i t e r i t e . Hence the procedure had to be
modified considerably, as c e r t a i n separations used i n the
preparation o f pure t i n from C a s s i t e r i t e can not be used
where there i s only a small q u a n t i t y of t i n , and much l a r g e r
q u a n t i t i e s of other elements.

From the h y d r o c h l o r i c a c i d s o l u t i o n of the ore, the

t i n was p r e c i p i t a t e d as the sulphide along w i t h other group
(8) metals, the most serious of these being antimony and copper.
This p r e c i p i t a t e was f i l t e r e d o f f , washed, and then warmed
w i t h ammonium p o l y s u l p h i d e . Instead of l e a v i n g the copper
behind as expected, quite a l a r g e quantity of i t passed i n t o
solution. This was i n d i c a t e d by the dark c o l o r of the sulphide
p r e c i p i t a t e obtained by a c i d i f y i n g the s o l u t i o n of ammonium
sulpho-stannate w i t h d i l u t e h y d r o c h l o r i c a c i d . The process
o f d i s s o l v i n g i n ammonium polysulphide and p r e c i p i t a t i n g w i t h
h y d r o c h l o r i c a c i d was repeated, but there was s t i l l considerable
copper present. Consequently the p r e c i p i t a t e was dissolved
by warming i n d i l u t e n i t r i c a c i d , the sulphur residue f i l t e r e d
o f f , and the s o l u t i o n evaporated to dryness. On d i l u t i n g and
a g i t a t i n g the residue w i t h water, a white f l o c e u l e n t p r e c i p i t a t e
of metastannie a c i d appeared. By evaporating to dryness, i t
was found that some of the antimony was rendered i n s o l u b l e
by being converted to the pentoxide. The evaporation had to
be c a r r i e d that f a r because of the small quantity of t i n

j
 IE

present. However, by t a k i n g up the residue i n a i l u t e n i t r i c

a c i d , the copper and other metals form soluble n i t r a t e s , while
the t i n and antimony remain quite i n s o l u b l e . The antimony
was then separated by t a k i n g advantage of the f a c t that t i n
can not be p r e c i p i t a t e d i n a s o l u t i o n of a c e r t a i n a c i d
c o n c e n t r a t i o n i n which the antimony i s r e a d i l y p r e c i p i t a t e d .
The i n s o l u b l e residue obtained on evaporation w i t h n i t r i c
a c i d was d i s s o l v e d i n concentrated h y d r o c h l o r i c a d d , and
the s o l u t i o n d i l u t e d w i t h f i v e times i t s volume of water.
The antimony was p r e c i p i t a t e d by s a t u r a t i n g the hot s o l u t i o n
w i t h hydrogen sulphide. The t i n was then obtained as yellow st
stannic sulphide by almost n e u t r a l i z i n g the f i l t r a t e with
ammonium hydroxide, d i l u t i n g , ana s a t u r a t i n g the c o l d s o l u t i o n
w i t h hydrogen sulphide.

II. THE STABILITY OF STANNIC OXIDE.

The atomic weight of t i n has been determined by several

19
Investigators by means of the r a t i o Sn: SnOgjwithout exception
the values obtained by them have been too low, due to
absorption of a i r on so l a r g e a surface. In order to
determine the accuracy of the method as a means of estimating
t i n , the temperature of drying and s t a b i l i t y of the oxide to
heat treatment was i n v e s t i g a t e d .
A small button of C P . t i n , weighing approximately one
gram was f i l e d to remove surface oxide and etched w i t h
dilute hydrochloric acid. I t was then washed w i t h d i s t i l l e d
water, d r i e d , and c a r e f u l l y weighed. The metal was converted
to the oxide "by warming i n cone, n i t r i c a c i d , the excess o f
a c i d being c a r e f u l l y evaporated when the metal no longer
remained. The r e s i d u e when d r i e d at d i f f e r e n t temperatures
gave the f o l l o w i n g r e s u l t s .

O r i g i n a l weight of Sn button* 0.9923 grams.

Atomic
Weight of Weight
Sn0 2 Calculated.
A f t e r drying i n the oven f o r
two hours, at 150 degrees.
1.2743 11.6
A f t e r d r y i n g i n the oven f o r
twenty-four hours at 150 degrees. 1.2643 116.73
A f t e r h e a t i n g w i t h a b l a s t lamp
f o r h a l f an hour
1.2632 117.21
A f t e r heating w i t h a b l a s t lamp
f o r another h a l f an hour.
1.2623 117.60
A f t e r heating w i t h a b l a s t lamp
f o r another h a l f an hour.
1.2619 117.78

I t can thus be seen from these measurements that

prolonged heating tends to decrease the amount of a i r
absorbed, but i t i s doubtful whether a p e r f e c t removal of
the absorbed gases can be a t t a i n e d .

III. THE DETERMINATION OF TIN AS CAESIUM CHLORO STANNATE.

T i n forms several complex c h l o r i d e s with the a l k a l i

metals, of which the caesium chloro stannate i s i n s o l u b l e .
As the o r i g i n a l object of the i n v e s t i g a t i o n was to determine
the atomic weight of t i n i n i t s d i f f e r e n t ores, the p o s s i b i l i t y
of u s i n g the formation of t h i s s a l t as a method was considered.
The method was i n v e s t i g a t e d i n the f o l l o w i n g manner.
P r e p a r a t i o n of Stannic C h l o r i d e .
A small button of t i n corresponding to about one gram
was f i l e d u n t i l a l l the surface l a y e r had been removed. It
was then etched i n d i l u t e h y d r o c h l o r i c a c i d and washed i n
d i s t i l l e d water. A f t e r drying and d e s s i e a t i n g , the button
was a c c u r a t e l y weighed. I t was then d i s s o l v e d i n a covered
beaker i n concentrated h y d r o c h l o r i c a c i d w i t h gentle warming,
and the stannous c h l o r i d e o x i d i z e d by passing i n c h l o r i n e ,
the temperature of the l i q u i d being kept as low as p o s s i b l e
by running water. Previous t e s t s have shown that a corresp-
onding q u a n t i t y of t i n can be o x i d i z e d i n t h i s manner i n
h a l f an hour, so i n the present case one hour was considered
as s u f f i c i e n t .
P r e p a r a t i o n of Caesium C h l o r i d e .
The caesium used f o r the purpose was obtained from
Dr. E.H. A r c h i b a l d i n the form of caesium sulphate. I t had
o r i g i n a l l y been used f o r the determination of the atomie
weight of caesium. To convert t h i s m a t e r i a l to caesium
c h l o r i d e the c a l c u l a t e d weight of r e c r y s t a l l l z e d barium
c h l o r i d e necessary was added to i t . The p r e c i p i t a t i o n was
c a r r i e d out i n a t o t a l volume of two l i t r e s and both s o l u t i o n s
were kept hot during the mixing. A f t e r s t i r r i n g and d i g e s t i n g
the p r e c i p i t a t e f o r sometime, i t was f i l t e r e d o f f and the
f i l t r a t e of caesium c h l o r i d e evaporated to a small volume.
To remove p o s s i b l e traces of sulphate, the caesium chloride
was r e p r e c i p i t a t e d from the s o l u t i o n by s a t u r a t i n g i t w i t h
HC1 gas. The c r y s t a l s , a f t e r washing and drying were ready
f o r use.
 Method.
A s l i g h t excess of the c a l c u l a t e d amount of caesium
c h l o r i d e was weighed up and d i s s o l v e d i n twenty-five c c . of
water and added a l i t t l e at a time to the stannic c h l o r i d e .
The caesium chloro-stannate came down as a f i n e white
precipitate. I t was f i l t e r e d o f f and washed w i t h pure water
i n a tared Sooch c r u c i b l e , which had been prepared w i t h an
asbestos mat. The c r u c i b l e and i t s contents were then d r i e d
i n an oven f o r s e v e r a l hours at 150G, and weighed.
The f i r s t r e s u l t s c a l c u l a t e d from the r a t i o Sn:0s SnGl
o fl

2 o
gave a value f o r the atomic weight of t i n whieh was much too
high, i n d i c a t i n g that the weight of the p r e c i p i t a t e was
correspondingly low. Moreover, on evaporating the f i l t r a t e
and wash water a number of c r y s t a l s s e t t l e d out. As the
f i l t r a t e should contain nothing but a s l i g h t concentration of
caesium c h l o r i d e , i t was concluded that the low r e s u l t s could
be a t t r i b u t e d to the s o l u b i l i t y o f caesium ehlorostannate.
Two more determinations were made taking greater
precaution to decrease an e r r o r due to s o l u b i l i t y and more
accurate values were obtained. This j u s t i f i e s the assumption
that the e r r o r i s due at l e a s t i n part to s o l u b i l i t y .
As very l i t t l e work has been done on t h i s compound i t
was considered necessary to obtain more d e f i n i t e information
on i t s s o l u b i l i t y i n v a r i o u s concentrations of h y d r o c h l o r i c
a c i d and caesium c h l o r i d e . Such information would enable us
to s t a t e more d e f i n i t e l y whether t h i s method i s s u i t a b l e or
not f o r atomic weight determinations, and i f so, the most
s u i t a b l e concentration f o r p r e c i p i t a t i o n . Accordingly, t h i s
has c o n s t i t u t e d another phase of the i n v e s t i g a t i o n .

IV. THE DETERMINATION OF THE SOLUBILITY OF CAESIUM

CHLORO ST ANNATE.

Apparatus.
I n order to a g i t a t e the s o l u t i o n s at a constant
temperature u n t i l the e q u i l i b r i u m of s a t u r a t i o n was obtained,
a g r a n i t e k e t t l e of f o r t y l i t r e s capacity was nearly f i l l e d
w i t h water and covered w i t h a t h i c k l a y e r of f e l t to prevent
radiation. The water was maintained at constant temperature
by a tungsten lamp which was c o n t r o l l e d by a thermostat and
o o
relay. The temperature remained w i t h i n .05 of SO with t h i s
apparatus. Pyrex t e s t tubes of twenty-five c c . capacity
were used and rubber stoppers which had been p r e v i o u s l y b o i l e d
f o r s e v e r a l hours w i t h ammonium hydroxide.
Method of Determination.
To the tubes were added twenty-five c c . of s o l u t i o n , and
somewhat more of the caesium chlorostannate than would
d i s s o l v e i n that p a r t i c u l a r concentration. The s a l t was
prepared as i n the determinations above. The rubber stoppers
were then wired i n and the tubes attached to the s t i r r i n g
apparatus and rotated f o r twenty-four hours.
In order to determine how much of the s a l t had d i s s o l v e d ,
the t e s t tube was placed i n the bath so that the top just
stood above the water. A f t e r the excess s o l i d had s e t t l e d
to the bottom, the l i q u i d was drawn up i n t o the c a l i b r a t e d
p i p e t t e and two t e n c.e. p o r t i o n s withdrawn. The t i p of the
p i p e t t e was prepared by t y i n g a f i l t e r paper around i t w i t h
a small piece of s i l k thread. I n t h i s manner the p o s s i b i l i t y
of s o l i d p a r t i c l e s being drawn o f f was e l i m i n a t e d .
The twenty c.e. p o r t i o n s of l i q u i d were c a r e f u l l y
evaporated i n small p o r c e l a i n c r u c i b l e s , and the amount
d i s s o l v e d taken as the weight of the residue obtained on
evaporation.

The r e s u l t s as f a r as they have been c a r r i e d at the

present time are given i n the f o l l o w i n g t a b l e .
 BIBLIOGRAPHY

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