A STUDY OF THE HETEROGENEOUS EQUILIBRIA OF SOME AQUEOUS TERNARY AND QUATERNARY SYSTEMS INVOLVING THALLOUS-SULFATE

Citation preview

INFORMATION TO USERS

This material was p ro du ced from a m icrofilm c o p y of t h e original d o c u m e n t. While the m o s t advanced technological m eans t o p h o to g ra p h and reprod uce this d o c u m e n t have been used, th e quality is heavily d e p e n d e n t u po n th e quality of th e original su b m itte d . The following ex p la n a tio n of te c h n iq u e s is provided to help y o u understand m arkings or p a tte rn s w hich m ay app e a r on this re p ro d u ctio n . 1 . T h e sign or " ta r g e t” for pages a p p arently lacking fro m th e d o c u m e n t p h o to g ra p h e d is "Missing Page(s)". If it was possible t o obtain th e missing page(s) o r section, th e y are spliced in to th e film along w ith adjacent pages. This m ay have necessitated c u ttin g t h ru an image and duplicating adjacent pages to insure yo u c o m p le te co n tin u ity . 2. When an image on th e film is o blite ra te d w ith a large rou nd black m ark, it is an indication th a t th e p h o to g ra p h e r suspected th a t th e c o p y m ay have m oved during e x p o su re and th u s cause a blurred image. Y o u will find a good image o f the page in th e ad ja c en t frame. 3. When a m ap , drawing or ch a rt, etc ., was part o f th e material being ph o to g ra p h e d th e p h o to g ra p h e r follow ed a d e finite m e th o d in " s e c tio n in g " th e material. It is cu s to m a ry t o begin ph o to in g a t th e u p pe r left h an d c o rn e r of a large sh e e t and to c o n tin u e p ho to in g from left to right in equal sections w ith a small overlap. If necessary, sectioning is c o n tin u e d again — beginning belo w th e first row and c on tinu in g on until com plete. 4. T he m ajo rity of users indicate t h a t th e textual c o n te n t is of greatest value, how ever, a s o m e w h a t higher quality rep ro d u c tio n could be m ade from " p h o t o g r a p h s " if essential to th e u nd ersta n d in g of th e d issertation. Silver prints o f " p h o t o g r a p h s " m ay be ord ered a t additional charge by writing th e O rder D e p a rtm e n t, giving th e catalog n u m b e r, title, a u th o r and specific pages yo u wish re produced. 5. PLEASE received.

NOTE:

Some

pages m a y

have

ind istinct print.

Filmed as

Xerox University Microfilms 300 North Z e e b R oad Ann Arbor, M ichigan 48106

LD3907 1 * - W p Z 3 19E>0 Fischer, Jack, 1920p£ A study of the heterogeneous equi0 libria of some aqueous ternary and quaternary systems involving t h a l l o u sulfate. New York, 1950c 86 typewritten leaves, diagrs., tables. 29 cm. Thesis (Ph.D o ) - New York U n i v e r ­ sity, Graduate School, 1950. Bibliography: p 085-86.

3

C 5 7 6 56

c Xerox University Microfilms,

Shelf List

Ann A rbor, M ichigan 48106

THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED.

LIBRARY OP HEW YORi UiJIVXRSTTT UHIV1RSITY PEIG-HTP

A S tu d y o f th o H e te ro g e n e o u s E q u i l i b r i a o f eone Aqueous 'P ernary and Q u a te rn a ry S ystem s In v o iY in g T h a llo u s S u l f a t e

A d i s s e r t a t i o n I n t b e d e p a rtm e n t o f oher. i e t r y s u b m itte d t o t h e f a o u l t y o f t h e G ra d u a te S c h o o l o f Arts a n d

o ie a o e o f He~ York U n i v e r s i t y l a

p a r t i a l f u l f i l l m e n t o f t h e r e q u ir e m e n ts f o r t h e d e g re e o f D o cto r o f P h ilo s o p h y

by J a c k F is o h e r 1950

3he a u th o r w ish e s t o e x p r e s s h i s s in c e re g r a titu d e to P ro fe s s o r Jo h n E . K i c c i , whose th o u g h tf u l s u g g e s t i o n s an d c r i t i c i s m s e n a b le d t h e w ork t o h e c a r r i e d o u t .

a o i

%S04-UuSG4 .K.gS04-/wae in c lu d e d In th is in v e s tig a tio n .

7

A n a l y t i c a l P r o c e d u re

h l e o t r o l y t l o Anal y e e a o f Copper Tha e l e o t r o d e p o e l t i o n o f c o p p e r, on a r o t a t i n g p la tin u m c a th o d e , was p e rfo rm e d frc m a s o l u t i o n a c i d i f i e d w i t h s u l f u r i c a c id and n i t r i o a c i d , w hich h a d b e e n b o i l e d f r e e o f n i t r o g e n d io x id e .

The in s tr u m e n t u s e d f o r t h e a n a l y s i s was t h e S e r g e a n t,

S low in e l e o t r o l y t l o a n a l y z e r .

Qhe a n a l y s i s w as oheekec u s in g

w eighed s a m p le s o f e l e c t r o l y t i c "K chlbaum " c o p ie r , w hich were d is s o lv e d i n n i t r i c a c i d .

The r e c o v e r y o f t h e c o p p e r was 1 0 0 .0 $ .

I t w as f o u n d ; t h a t when t h a l l o u s io n was p r e s e n t i n a c u p r i e io n s o l u t i o n i t i n t e r f e r e d w i t h t h e e l e c t r o l y t i c a n a l y s i s o f c o p p e r,

ivhen t h e e l e c t r o l y s i s was p e rfo rm e d i n a n a l k a l i n e

s o l u t i o n a o o p io u e brow n p r e c i p i t a t e , w h ic h was m o st l i k e l y th a llic

o x i d e , was d e p o s ite d on t h e a n o d e .

w as 2 .5 am peres a t t h e s t a r t

The c u r r e n t , w h ich

c£ t h e e l e c t r o l y s i s , f e l l t o

0 . 2 - 0 .3 am peres when t h e d e p o s it io n on t h e anode a p p e a re d .

I n a c id s o l u t i o n a a l i g h t d a rk e n in g o f t h e a n o d e , a lo n g w ith m arked d e c r e a s e i n t h e c u r r e n t , was n o te d .

I t was t h u s c o n c lu d e d

t h a t t h e i n t e r f e r e n c e o f t h a l l o u s i o n w i t h th e e l e c t r o l y s i s o f o o p p e r was d u e t o an a n o d io r e a c t i o n , v h ic h c a u s e d a p o l a r i z a t i o n o f th e e le c tro d e .

The d e c r e a s e i n c u r r e n t m arkedly slo w ed up t h e

d e p o s i t i o n o f c o p p e r. Due to th e i n t e r f e r e n c e o f t h a l l o u s io n w ith t h e e l e o t r o l y t l o d e p o s i t i o n o f c o p p e r, a n d a l s o due t o t h e low p e r c e n ta g e o f c o p p e r

8

i n some o f t h e s a t u r a t e d s o l u t i o n s w hich w ere a n a ly z e d , i t was n e c e s s a r y t o u s e some o t h e r . e- n s o f d e te r m in in g c o p p e r i n t h e p re s e n c e o f th & IIiu m . I o d o a e t r l o D e te r m in a tion o f Copper She io d o ..fc tric p r o o e u u r e , a s d e s c r ib e d by l o l t h o f f a n d S c n d e ll , was em ployed.

e ig h e d s im p le s o f t h e Kahlbaum c o p p e r

w e re d i s s o l v e d i n n i t r i c a c id , fo llo w e d by n e u t r a l i s t io n w ith NE4.OII,

F iv e m l. o f g l a c i a l a c e t i c a c i d w e re a d d e d , f o llo w e d

by t h e a d d i t i o n o f e x c e s s E l .

The l i b e r a t e d i o d in e was t i t r a t e d

w ith 0.1N NarSgOg s o l u t i o n , u s in g s t a r c h a s a n i n d i c a t o r . few d ro p s o f n itr o b e n z e n e 3 viort ad d e d t o

A

r e v e n t a d s o r p t io n

o f i o d in e on th e p r e c i p i t a t e o f c u p ro u s i o d id e .

She s ta n d a r d

CuSO^.SE^O powder was a g a in a n a ly z e d u s in g th e O.IN Na^SgOg s ta n d a r d s o l u t i o n .

She i u r i t y o f t h e CvuSC^.SHgO, a s b e f o r e ,

was found t o be 99.9',. OUSO4 . 5H2 O. P o t e n t ! o a e t r i o , lo d a m e trio D e te rm in a tio n o f Copper Shallivu:. i n t e r f e r e s w ith t h e o b s e r v a t io n o f t h e s t a r c h io d in e end p o in t b e c a u s e o f t h e y e llo w g r e e n p r e o i p i t: .,te due t o a 00

i m .t io n o f 'H I and C u l.

I t w s th u s n e c e s s a ry t o

d e t e c t t h e enu p o in t o f t h e io d o w .e tric a n a l y s i s p o t e n t i o e t r i o a l l y u s in g a Beckman re e e - r c h model G- pE m e te r .

P la tin u m and c a lo m e l

e le c t r o d e s ’w ere u s e d a s th e in d ie , t o r e l e c t r o d e s . She t i t i x t i o n c u rv e f o r t h e ; o t a n t io . e t r i c c.n l y s i s i s shewn on g r a p h I .

She i n f l e c t i o n i n th e c u rv e o c c u rs a t 0 .1 9

▼0118 FOmflCM STHIC

TIXHATIOH OF COFFER

D.2 6

1.1477 g . CuSC^.eHjO

1.1474 g . CuS04 .5% 0 I ) , 2 .0

.n "

-^ KHD POINT

5 0 .6

4 0 .0 m l. Vti2s 20Z

1 ml. ■ 0.02866c* Cu80^*5Hg0

0 .1 9 7

v o lts .

S in c e t h i s v o l t a g e a l s o c o rre s p o n d e d t o t h e end p o i n t

v o lta g e o f a v is u a l t i t r a t i o n In th e ab sen ce o f th a lliu m , i t w as c h o s e n ae t h e end p o in t v o l t a g e f o r s u b s e q u e n t t i t r a t i o n s * Die 0*1 N NasSgOs s o l u t i o n s was s ta n d a r d iz e d i n t h i s m anner, u s in g t h e p r e v i o u s ly a n a ly z e d OUSO4 .5HgQ a e a s ta n d a rd * Die mtke p l o t o f t h e t i t r a t i o n c u rv e s i n t h e a b s e n c e andAp r e s e n o e o f t h a l l o u s io n i n d i c a t e s t h a t t h e t h a l l i u m d o es n o t in tr o d u c e a n e r r o r i n t h e d e te r m i n a ti o n .

Die a d d i t i o n o f a few d ro p s

o f n i tr o b e n z e n e d id n o t i-roduoe a n y d e v i a t i o n fro m t h e r e s u l t s o b ta in e d when n itr o b e n z e n e was a b s e n t , i n d i c a t i n g t h a t t h e r e w as no i n t e r f e r e n c e due t o t h e a d s o r p t i o n o f io d in e *

In th e

ab o v e e x p e rim e n t t h e c o n c e n t r a t i o n o f t h a l l o u s i o n was s o chosen t o b e o f th e o rd e r o f th e c o n c e n tra tio n o f th a llo u s io n in su b seq u en t a n a ly s e s . Die p o t e n t i o r e t r i c t i t r a t i o n was p e rfo rm e d i n a p r a c t i c a l l y o lo s e a v e s s e l .

I h e r e was a s m a ll o p e n in g i n th e

t o p th r o u g h w hich t h e b u r e t t e t i p was in tr o d u c e d .

A m ag n e tic

s t i r r i n g d e v ic e was em ployed t o m ix t h e s o l u t i o n d u r in g t h e titra tio n . Die 0.1N t h i o s u l f a t e s o l u t i o n ,u s e d f o r t h e c o p p e r

dnti/le-d

d e te r m in a tio n , was p r e p a r e d fro m b o i l e d Aw a te r, t o whioh 0 .1 gram s o f NogCOg p e r l i t e r w e re a d d e d .

D tis s o l u t i o n

was s t o r e d i n t h e p y re x r e s e r v o i r o f a n a u to : a t i e b u r e t t e , fro m w h ic h i t was d is p e n s e d .

I t was fo u n d t h a t t h e sodium

10

t h l o s u l f a t e s o l u t i o n d id n o t d e v i a t e fro m i t s i n i t i a l s ta n d a r d ­ i z a t i o n b y m are t h a n 2 o r 3 p a r t e p e r th o u s a n d i n a p e r io d o f t h r e e m onths* D e te rm in a tio n o f S t a l l i n g T h a llo u s i o n w as d e te rm in e d by t i t r a t i n g sa m p le s c o n t a i n in g TloSO^, w ith KIQg s o l u t i o n i n a s t r o n g E01 m edium, a s s u g g e s te d b y B e rry 4 ,

The p ro o e a u re u s e d was

s i m i l a r t o t h a t o f t i u i th and w ilc o x ^ , e x c e p t t h a t oarbom t e t r a c h l o r i d e was u s e d t o d i s s o l v e t h e i o d in e , w hich s e r v e d a s a n I n d i c a t o r , w h ile S m ith a n d W ilcox u s e d a m a ra n th a s an in d ic a to r*

'lha m ethod u s e d i n t h i s p a p e r i s s i m i l a r t o t h a t

o f s w i f t a n d O e rn e rS .

I n t h e i r a n a l y s i s t h e y in tr o d u c e d

IG1 p r i o r t o t i t r a t i n g t h e sam ple w ith KIQ3 s o l u t i o n .

However,

t h i s i s n o t n e c e s s a r y , a s 101 i s p ro d u c e d i n th e c o u r s e o f t h e r e a o tlo n .

S w if t and G a rn e r, i n t h e i r i n v e s t i g a t i o n , s t a t e d

t h a t t h e t i t r a t i o n s h o u ld b e p e rfo rm e d i n a n HOI medium o f 1 t o S n o rm a l, and t h a t t h e r e a c t i o n w as f a s t e s t when t h e

medium was 3 n orm al o r h ig h e r w ith r e s p e c t t o HOI. M ethod One — T h is m ethod was u s e d d u r in g t h e i n i t i a l s t a g e s o f th is re se a rc h . The sam p le t o b e t i t r a t e d was p la c e d i n a g l a s s s to p p e r e d f l a s k a n d d i s s o l v e d i n , o r d i l u t e d t o 100 m l*, w ith w a te r* F ifty to s ix ty

m l . o f c o n c e n t r a t e d HCXL w e re a d d e d .

The f l a s k

w as s to p p e r e d a n d t h e c o n te n t s w e re c o d e d by ru n n in g c o ld t a p

11

w a te r o v e r t h e f l a s k .

F iv e iuJL.. o f C.F.C G I 4 w e re a d d e d , a ad

t h e r e s u l t a n t m ix tu r e was th e n t i t r & t o d w i t h 0*025 11 KIO3 s o l u t i o n , w h ic h was s ta n d a r d iz e !, a g a i n s t t h e s ta n d a r d Tlr,S 04 s a d s a l t * A w e ig h t b u r e t t e , w eig h ed t o t h e n e a r e s t m illi g r a m , was u s e d f o r a l l t h e t h e l l o u s io n d e te r m in a tio n s * o rd er t h a t t i t r a t i o n s , in

T h is was done l a

h io h a s l i t t l e a s t h r e e o r f a i r

g r a n s o f s t a n d a r d KIO3 w ere d is p e n s e d , c o u ld b e a c c u r a t e l y p e rfo rm e d , a s w as n e c e s s a r y i n t h e a n a l y s i s o f some o f t h e co m plexes, which, y i e l d e d s a t u r a t e d s o l u t i o n s lo w i n t h a l l o u s io n c o n te n t* The g l a s s s to p p e r e d f l a s k w as sh a k e n v i g o r o u s l y a f t e r e a c h a d d i t i o n o f KIO3 and t h e f l a s k w as c o o le d i n t e r m i t t e n t l y b e tw e e n a d d itio n s *

I t was a l s o n e c e s s a r y t o u s e g r e a t c a r e i n

t h e h a n d lin g o f t h e g l a s s s to p p e r e d f l a s k t o p r e v e n t l o s s o f io d in e v ap o r,

and s o l u t i o n i .

Thus, e a c h tim e t h e s to p p e r was

rem oved t o ad d £103 s o l u t i o n , i t was c a r e f u l l y w ashed down w i t h a s p r a y o f w a te r fro m a w ash b o t t l e * As t h e t i t r a t i o n p r o c e e d s , i o d in e i s l i b e r a t e d a n d s u b s e q u e n tly o x i d iz e d t o i o d in e m o n o c h lo rid e .

Thus, t h e

s o l u t i o n becom es d a rk brow n i n t h e m id d le o f t h e t i t r a t i o n , a n d t h e n p ro c e e d s t o bacon® l i g h t e r i n c o lo r *

At t h e end,

a l i g h t y e llo w c o lo r e d s o l u t i o n , d u e t o t h e i o d in e m o n o c h lo rid e , i s form ed*

The end p o i n t o f t h e t i t r a t i o n i s i n d i c a t e d by t h e

d is a p p e a r;in c e o f t h e p u r p le i o d in e c o l o r i n t h e c a rb o n t e t r a u c h lo rid e l a y e r .

Towards t h e end o f t h e t i t r a t i o n , g r e a t

12

o a r a m ust b e to k e n t o i n t e r n i x t h e Efc,0 a n d t h e CCI4 l a y e r s . T his i s a c c o m p lish e d by s h a k in g th e f l a s k th o r o u g h ly a f t e r e a c h a d d i t i o n o f KIO3 , M ethod Tbo — The m a jo r p a r t o f t h e r e s e a r e h was o o n d u e te d u s in g t h e F i s h e r t i t r i m © te r an d t h e Beohman r o e e a r oh m odel pH m e te r f a r t h e f a llo w in g p o t e a t i o m e tr i c a n a l y s i s . A c e l l sy stem em p lo y in g p la tin u m a n d t u n g s t e n e l e c t r o d e s was n o t u s e f u l , b e c a u s e t h e p o t e n t i a l te n d e d t o d r i f t a t t h e r e g i o n o f th e end p o in t o f th e t i t r a t i o n .

H ow ever, a c e l l sy ste m composed

o f a s a t u r a t e d c a lo m e l e l e c t r o d e and a p la tin u m e l e c t r o d e was t h e n em ployed w ith e x c e l l e n t r e s u l t s .

The t i t r a t i o n c u r v e , a s i n d i o a t e d

i n G raph 1 1 , and two sa m p le t i t r a t i o n s belcw ., i l l u s t r a t e t h e s a t * i s f a o t o r y r e s u l t s w hich r a y b e o b t a i n e d w ith t h i s m eth o d . Grams Sam ple

Grams KIO3 S o l u ti o n

Sam ple I

0.2186

2 0 .8 8 3

0 .2 1 9 0

0 .1

Sam ple I I

0 .0 4 3 9 2

4 .1 5 6

0 .4 3 5 5

0 .1

11^304

H 2SO4 Found

55

E rro r

S t a n d a r d i z a t i o n o f KIO3 u s in g m ethod I T ria l

(1 )

1 .0 0 0 gram s KlOg s o l . * 0 .0 1 0 4 9 g ram s T2.PSO4

T ria l

(2 )

1 .0 0 0 g ram s KlOg s o l . =* 0 .0 1 0 4 7 gram s

S t a n d a r d i z a t i o n o f KEO3 u s in g M ethod I I T ria l

(1 )

1 .0 0 0 gram s K I0 3 s o l . » 0 .0 1 0 4 7

T ria l

(2 )

1 .0 0 0 gram s HIO 3 s o l . * 0 .0 1 0 4 8

T T ia l

(3 )

1 .0 0 0 g r a - s KIO3 s o l . - 0 .0 1 0 4 8

TLgSQg

GRAPH I I HiHH:

POTEaTIOlfETRIC TITRATION OP TI2S04 i l £11 Hrf 1if: Jin rr- lifelifefelt 1•i!■fRT Ifeltfe rfe- It t11i t!U‘feH

VOLTS C a lc u la te d End P o i n t 2 0 .8 5 7 g . KI03 Based on v i s u a l t i t r a t i o n

0 .7 0 20.856

END POINT

20.856

GRAMS K IO . 8IANDARD SOLDHON

13

Hie determ in ate l o a was p e rfo rm e d a e i n Met lied XI, e x c e p t t h a t CCI4 was no l o n g e r n e e d e d a s a s o l r e n t f o r t h e io d in e , w hich s e r v e d ae on in d ie ? t o r *

Hie p o t e n t i a l a t t h e end p o i n t , w i t h o u r

in s t r u m e n t, was fo u n d t o h e 0 .7 8 ? o l t a , a a i n d i c a t e d on G raph I I , and t i t r a t i o n s w e re e o n d u e te d u n t i l t h i s p o t e n t i a l was r e a c h e d . As i s e v id e n t fro m G raph I I , t h e r e l a a l a r g e v o l t a g e ra n g e f o r t h e e n d p o i n t , w hich a llo w s c o n s id e r a b l e v a r i a t i o n i n v o l t a g e w ith l i t t l e e r r o r in r e s u l t s . H ie f i n a l volum e o f t h e t i t r a t e d medium wee a p p ro x im a te ly 200 .-ml..

l h u s , t h e f i n a l n o r m a lity w ith r e e p e o t t o IIGL was ap­

p r o x im a te ly 3 N orm al. D e te rm in a tio n o f S a i f a t e H ie p r o c e d u r e o f a n a l y s i s f a r s u l f a t e io n , t h a t o f p r e o i p a t i n g b a riu m s u l f a t e by t h e alo w a d d i t i o n o f a b ariu m c fe io v t^ e . s o l u t i o n t o a h o t s o l u t i o n c o n ta in in g s u l f a t e , fo llo w e d b y s e v e r a l h o u rs o f d i g e s t i o n w h lie h o t , u s u a l l y l e a d s t o h ig h o r low r e s u l t s due t o a d s o r p t i o n o f v a r i o u s i o n s 7 .

E x p e rim e n ts

w e re p e rfo rm e d t o d e te r m in e t h e a o o u re e y o f t h e s u l f a t e a n a l y s i s o f p u re s a l t s when perform ed, a c c o r d in g t o th e m ethods d e s c r ib e d b e lo w . T h h le I .

Hie r e s u L to a r e i n d i c a t e d i n

14

TAHLE I D e te rm in a tio n o f S u l f a t e P e rce n t rec o v e ry o f M ethod I Hap304

CUSO4

... s u l f a t e f o r v a r i o u s m ethods o f a n a l y s i s M ethod I I I

1 0 0 .7 16

1 0 0 .4

1 0 0 .7

1 0 0 .4

1 0 0 .9

1 0 0 .4

%

M ethod IV

100.1

£

100.0

100.8

10 0 .8

100.6

1 0 0 .4

100.8 M ethod I ID.2SO4

M ethod I I

M ethod IV

1 0 1 .9

1 0 1 .3

101.0

102.0

101.2

101.0

101.8

101.8 9 9 .8

KPSO4

9 9 .8 (NH4 ) j O4

100.1

100.1 M ethod I

To 200 m l . o f t h e h o t (a p p r o x im a te ly 85*) s o l u t i o n , 2 a i . . vaf>iol o f c o n c e n tr a te d KC1 weve ad d ed , fo llo w e d by t h e Aa d d i t i o n o f 200 a l l . htft o f Abariusn c h l o r i d e s o l u t i o n c o n ta i n in g 1 .6 gram s o f b a riu m c h l o r i d e . The sam p le was d i g e s t e d o v e r n i g h t f o r a p p ro x im a te ly e ig h t e e n h o u r s , on a h o t r l s t e , a t a te m p e r a tu r e o f a p p ro x im a te ly 9 0 * .

The sam ple was f i l t e r e d , w h ile h o t th r o u g h a medium " S e la s " o r u o i b l e , - f t e r w h ic h i t was d rle o . f o r one h o u r a t 110 ° . The o r u c i d l e

was t h e n i g n i t e d o v e r a T i r r i l l b u r n e r

to r

tw e n ty m in u te s , c o o le d i n a d e s i c c a t o r c o n ta i n in g d r i e r i t e , and th e n w e ig h e d . T h is m ethod y i e l d e d h ig h r e s u l t s f o r t h e a n a l y s i s o f sodium s u l f a t e , o o p p e r s u l f a t e and t h a l l o u s s u l f a t e . M ethod I I T h is m ethod i s t h e sam e a s t h a t o f M ethod I , e x c e p t hot

t h a t theH C l i e a d d e d to t h e s o l u t i o n a f t e r t h e Ab :riu m c h l o r i d e hot

s o l u t i o n a n d Aa u l f a t e s o l u t i o n s were m ix e d .

The r e o o v e r y o f

t h a l l o u s s u l f a t e o b ta in e d was b e t t e r th a n i n t h e p re v io u s m eth o d . *

M ethod I I I jftvo ini'., o f c o n c e n t r a t e d ECL w are ad d ed to t h e c o ld sam ple p r i o r t o m ix in g i t w ith o o l d b a riu m c h l o r i d e s o l u t i o n . The sam ple was p la e e d on a h o t p l a t e en d d i g e s t e d o v e r n i g h t a t 85 - 9 0 * .

The r e c o v e r y o f Na^SO^ o b ta in e d b y t h i s m ethod

was b e t t e r th a n by M ethod I . M ethod IV I n t h i s c a s e t h e tw o m l., o f c o n c e n tr e te u HCt w ere addud t o t h e c o ld s o l u t i o n a f t e r t h e s u l f a t e s o l u t i o n and b ariu m c h l o r i d e s o l u t i o n w e re m ix ed t o g e t h e r .

The s u b s e q u e n t

d i g e s t i o n and f i l t r a t i o n was c a r r i e d o u t a s i n M ethod I I I .

2h i s m ethod y i e l d e d good r e s u l t s f o r Nag-O 4 , K2SO4 and

(Mi 4 )r.S 04 . I n t h e above a n a ly s e s t h e w e ig h ts o f t h e BaSdg. p s r e o ip ita te s w ere o f t h e sente o r d e r o f m a g n itu d e , a p p ro x im a te ly 0 ,7 g ra m s. Ohe r e s u l t s f o r H 2SO4 w ere a p p ro x im a te ly t e n p a r t s p e r th o u s a n d h ig h , a n d t h e r e s u l t s f o r CUSO4 w ere a p p ro x im a te ly f i v e p a r t s p e r th o u sa n a h ig h . In o rd e r t o o o rre o t f o r th e e r r o r in th e s u lf a te

>n ;« ly se s i n t h e p re s a n o e o f c o p p e r end t h a l l i u m , s u l f a t e

\

a n a ly s e s w ere made on sa m p le s c a d e up o f m ix tu r e s o f Nap .^04 a n d H g S 04 , a n d o f m ix tu r e s o f NapS 04 and OUSO4 . a r e i n d i e a t so i n lia b le I I .

The R e s u l ts

Hae r a t i o o f ^ . 2^04 a e B&S04

o v e r t o t a l s u lf G t e a s BeSG4 i s p l o t t e d on G raph I I I a g a i n s t th e e r r o r in th e s u lf a te a n a ly s is .

s i m i l a r c u rv e i s draw n

i n d i c a t i n g t h e e f f e c t o f c o p p e r on t h e s u l f a t e a n a ly s e s . I n o r d e r t o c o r r e c t f o r t h e p r e s e n c e o f c o p p e r and t h a l l i u m i n s u b s e q u e n t a n a l y s e s , t h e w e ig h t o f b a riu m s u l f a t e , e q u iv a l e n t t o t h e num ber o f p a r t e p e r thousand, e r r o r i n th e a n a ly s e s , was s u b t r a c t e d fro m t h e t o t a l b a riu m a u l f a t e o b ta in e d e x p e rim e n ta l l y .

M H

0>

O

'•O

IX.

17

T am a u .K ffeo t o f T h a lliu m oai S u l f a t e M a ly a l a NafGO* as BaBO^.

E rro r P a rts /

H p.SOa

& s£ 2 £ as Bg30 a

1 .4 0 2 2

.6 4 8 3

.6 4 8 3

.6 5 6 6

1 3 .0

0 .9 8 6

1 .3 9 9 4

.6 4 7 0

.6 4 7 0

.6547

12.0

0 .9 8 8

1 .4 7 0 6

.6799

.6799

.6 8 9 0

1 3 .0

0 .9 8 7

1 .5 0 4 0

.6 9 5 4

.6 9 5 4

.7 0 2 2

10.0

0 .9 9 0

.9189

. 4 49

.1 769

.2 9 0 7

.7 1 5 6

.7 2 2 5

10.0

0 .5 8 8

.4 3 4 8

.2010

.3012

.4949

.6959

.7029

10.0

0 .2 8 6

.4332

.2 0 0 3

.5013

.7 0 1 6

.7086

10.0

0 .2 6 3

.2 1 9 3

.1 0 1 4

.3 6 0 8

.5 9 2 8

.6942

•6992

7 .4

0 .1 7 1

.1 9 7 3

.0 4 9 6

.4102

.6 7 4 0

.7 2 3 6

.7 2 6 3

3 .7

0 .0 6 8

.1 0 0 8

.0 4 6 6

.6 6 1 0

1 .0 8 6 2

1 .1 3 2 8

1 .1 3 5 9

2 .7

0.0 4 1

.0 4 9 8

.0 2 3 0

.4 3 0 6

.7076

.7 3 9 6

.7 3 2 4

2 .5

0.0 3 1

.0496

.0 2 2 9

.6 719

1 .1 0 4 1

1 .1 2 7 0

1 .1 2 9 3

2 .0

0.020

.4 2 5 1

.6985

.6 9 8 5

.6 9 9 0

0 .7

.4 1 4 3

.6 8 0 7

.6 8 0 7

.6 8 1 0

0 .4

» fc S 0 4

.3 0 5 1

T o ta l BaOOa

Bg2©4Exp ear.

1000

T b ta l

E f f e c t o f C opper oa : u l f a t e A n a ly s ts GuSOa

as CuS0a.5Hp0 Bg804

M pc>Qa as NarSOa BaSOa

U c ro r

T atal BaSOA

BabQx Bxper.

P a r ts / GuSQa BaSQ^ 1000 M e l ' BaOO*

7075

.6 6 1 4

.6 6 1 4

.6 637

3 .5

0 .9 9 6

7124

.6659

.6 6 5 9

.6689

4 .5

0 .9 9 6

7084

.6 6 2 2

,6 6 2 2

.6657

5 .3

0 .9 9 5

5525

.5 165

.1121

.1842

.7007

.7036

4 .1

0 .7 3 4

3527

.3 2 9 7

.2 3 1 8

.3809

.7106

.7128

3 .1

0 .4 6 3

1742

.1 6 2 8

.3339

.5487

.7 1 1 5

.7131

0 JW

0 .2 4 4

18

h e a g e p ts

T h a llo u s S u l f a t e S ta n d a r d 3 a l t A sam ple o f t h a l l o u s s u l f a t e , u s e d f o r

r e v i o u a wo Ik

i n t h e l a b o r a t o r y , was t e s t e d f o r p u r i t y a e i n d i c a t e d b e lo w .

i: s o lu tio n , o f O.OiiSM KlOg w as p r e p a r e d by a d d in g t h e r e q u i r e d am ount o f G .p . s a l t t o d i s t i l l e d w a te r#

The s t r e n g t h

o f t h e KlOg was f u r t h e r s u b s t a n t i a t e d by t i t r a t i n g t h e s o l u t i o n a g a i n s t w eighed p o r tio if e o f Ae-.-Og.

The m ethod o f a n a l y s i s was

t h e some a s t h a t u s e d i n t i t r a t i n g t h a llo u B io n w ith hTOg s o l u t i o n , a d d e s c r ib e d u n d e r m ethod I o f a n a l y s i s f o r t h a l l i u m . The v a lu e o f t h e m o l a r i t y o f t h e U O 3 s o l u t i o n , o b ta in e d by s ta n d a rd iz in g a g a in s t

'.a- O3 , i n w h ic h b o th a l i q u o t e a p o r ti o n s

o f a stan d ? r d s o l u t i o n o f

-BpOg, a s w e ll a s a w eighed p o r t i o n

o f Ae.rOg w ere u s e d , and t h e v a lu e c a l c u l a t e d fro m th e known v ieig h t o f KIO5 tn. a known volum e o f s o l u t i o n , a g re e d w i t h in one p a r t p e r th o u s a n d .

The AsrOg u s e a was O .P .

a s h a v in g a minimum p u r i t y o f 9 9 .8 Jj AsgOg.

la b e le d

T his f o o t was

ta k e n in to aocount in th e c a lc u la tio n s . The TLt'S 04 p u r i t y was a s c e r t a i n e d by t i t r a t i n g w eighed p o r t i o n s o f t h e s a l t , d r i e d a t 110° , w ith t h e s ta n d a r d KIO3 s o l u t i o n , a c c o r d in g t o m ethod I , a s d e s c r i b e d u n d e r a n a l y t i c a l p ro c e d u re .

The a v e ra g e v l u e o f f i v e d e te r m in e tio n s was 1 0 0 .1

TI 2SO4 w ith a maximum d e v i a t i o n o f + 2 p a r t s p e r th o u s a n d from *

th is V a l t / e T h i s s a l t was t h e n u s e d a s a s t a n d a r d . * Tkt. r^etn d«yi-it/e t p .y /e o o

yi

19

S o lu b ility detem in atioiB at 25* were a lso made o f t h is standard sa lt, using v a ria b le proportions o f liq u id and sa lt* H ie a v e ra g e o f s e v e r a l d e te r m in a tio n s was 5 .2 2 gram s o f H 2 SO4 p e r 100 gram s o f s a t u r a t e d s o l u t i o n .

Hi i s v a lu e a g r e e s w ith

t h e v a lu e s o b ta in e d fro m t h e p u r i f i e d co m m ercial s a l t , d is c u s s e d vitk b e lo w , andAt h e l i t e r a t u r e v a l u e s , a s i n d i c a t e d i n f a b le I I I . P re p a ra tio n o f P u re th a llo u s S u lfa te Hie TL2SO4 C .P ., a s o b ta in e d fro m B ak er, w as fo u n d to c o n ta i n b o th h a l i d e s and i r o n , and was a l s o lo w i n th a lliu m * I t w as t h u s p u r i f i e d a o c o rd in g t o t h e f o llo w in g p ro c e d u re * '10 a p p ro x im a te ly 100 gram s o f t h e com m ercial H 2 SO4 ,

a p p ro x im a te ly 50 n v l . o f c o n c e n tr a te d H2SO4 w ere a d d e d ,

'the

m ix tu r e was p la c e d i n a p o r c e l a i n c a s s e r o l e and h e a te d u n t i l t h e r e was no l o n g e r a n y v i s i b l e fu m in g .

H ie te m p a - a tu r e was

r a i s e d and th e h e a ti n g was c o n tin u e d u n t i l t h e s a l t became p a r t i a l l y m e lte d .

'Hie s a l t was th e n aL low ed t o c o o l*

A

r e p r e s e n t a t i v e sam ple o f t h e s a l t , d i s s o l v e d i n w a te r so t h a t i t w as a p p ro x im a te ly 1 $ I 2 SO4 , h a d a p h o f 2 .0 when, m ea su red w i t h a Beckman pH m e t e r .

Hie ph o f a p u re sam ple

o f HL2 SO4 , th e s ta n d a r d s a l t i n a 1 $ s o l u t i o n , was 6 . 0 . H tis i n d i c a t e d t h e p r e s e n c e o f HLHSO4 i n t h e sa m p le . Ammonium c a r b o n a te was t h e n ad d ed t o t h e c ru s h e d f u s e d s a l t and t h e s a l t was a g a in h e a te d u n t i l i t m e lte d . Hie s a l t a f t e r t h i s t r e a tm e n t was n o t w h ite , a s i t s h o u ld h av e b e e n , b u t p in k .

ao The s a l t was t h e n g ro u n d a n d r e e r y s ta L l i z e d u s in g h o t Ej 0 .

E o in g a p p ro x im a te ly 100

m l, o f w a te r , th e

i o l u t i o n was s a t u r a t e d w ith t h e s a l t by h e a t i n g i t t o b o ilin g ,

ih e s u p e r n a t a n t l i q u i d ..a s th e n f i l t e r e d ,

u s in g a s te a n fu n n e l rnsi f l u t e d f i l t e r p a p e r ,

A f te r

f i l t e r i n g , t h e s o l u t i o n w as a llo w e d t o c o a l , th e r e b y p r e c i p i t a t i n g t h e p u re s a l t , w hich w as ~h i t e .

'jh is s te p

was r e p e a t e d Tiiany t im e s , u s in g t h e M other l i q u o r t o d i s s o l v e ..o re o f th e im pure s a l t upon h e a t i n g t h e tw o t o g e t h e r .

A

brow n r e s i d u e r e g a i n e d on t h e f i l t e r p a p e r an d i n t h e l a s t p o r t i o n o f u n d iesd L v ed im pure s a l t , t o c o n ta i n i r o n ,

This r e s i d u e was fo u n d

‘ih e r e s u l t i n g s a l t was a g a in r e o r y s t e l l i z e d

i n t h e same m a n n e r. A f te r d r y in g a t 1 1 0 ° , t h e p H , o f a 1 5i s o l u t i o n o f t h e s a l t w as 5 .3 , i n d i c a t i n g none, o r a n e g l i g i b l e amount, o f foY-tKallii/iyi t h e a c id s a l t . 3he s a l t , u p o n a n a iy e is A,p rav ed t o b e 9 9 .1 TLgS04 . A n o th er b a tc h o f H a 3O4 was a l s o p r e p a r e d i n t h e same : xuicr by s t a r t i n g w i t h t h a l l o u s c a r b o n a te i n s t e a d o f t h a l l o u s s u lfa te .

I t a ls o was fo u n d t o be 9 9 ,9

$ HpSO^,.

The s a l t s p r e p a r e d i n th e ab o v e m anner were u s e a i n th e s u b s e q u e n t work in v o lv in g t h a l l o u s s u L f a t e .

21

C opper S u l f a t e B a k e r s C .P . CuSC^.BHgO c r y s t a l s w ere u s e d i n p r e p a r in g com l e x e a c o n ta i n in g c o p p e r s u l f a t e . g ro u n d i n t o a powder*

3he B a k e r 's c r y s t a l s w ere

A s m a ll q u a n t i t y , a b o u t 1 g r m , was p la c e d

on a w atch g l a s s end w e ig h e d . was no change i n t h e w e ig h t.

A f te r a p e r io d o f one h o u r t h e r e T h e r e f o r e i t was c o n c lu d e d t h a t

t h e powder w ould n o t a d s o rb o r l o s e m o is tu r e d u r in g th e o r d in a r y p e r i o d o f tim e ta k e n t o w eigh o u t a sa m p le .

He

cw der was

s t o r e d i n sc re w c o p b o t t l e s , from w h ich sam p les w ere t a k e n f< r a n a l y s i s o f f o r u s e i n t h e p r e p a r a t i o n o f c o m p le x es. I n o r d e r t o v e r i f y t h e d e g re e o f h y d r a t i o n o f th e c o p p e r s u l f a t e , a p o r t i o n o f g ro u n d CuSO^.blfrO was p la c e d i n a vacuum d e s ic c a to r c o n ta i n in g sodium h y d ro x id e a s a d o s ic c a n t. The d e h y d r a tio n o f t h e CuSO^SIfeO was a llo w e d t o p ro c e e d (a b o u t 48 h o u r s ) u n t i l t h e w e ig h t o f t h e c o p p e r s u L f a te sam ple was re d u c e d t o an e x t e n t t h a t i n d i c a t e d t h a t a n ap ­ p r e c i a b l e amount o f t h e c o p p e r s u l f a t e p e n te h y d r a te bad b e e n c o n v e rte d t o t h e t r i h y d r a t e *

A n o th e r sam ple o f t h e g ro u n d

r e a g e n t c o p p e r s u l f a t e , 6.C 510 g . , was th e n u la o e d i n a d e s i c c a t o r i n w hich t h e m ix tu r e o f GuSO^.5HpO end CuCC^.SfTgO was u s e d hb t h e d e s i d o a n t .

H e desx C C eto r was k e p t i n t h e

l a b o r a t o r y a t a te m p e r a tu r e o f 25°

±

3 *>.

H e w e ig h t o f t h e

r e a g e n t sam ple a f t e r two days

w as

f o u r m onths w a s .

From t h i s , a n d t h e c o p p e r

6 .0 5 0 8 g .

6 .0 5 1 8 g . and a f t e r

V

33 \ a n a ly s e s w h is k w e re p e rfo rm e d , i t was c o n c lu d e d t h a t t h e sam ple was

. h y d r a te d a s CU0 O4.5EgO. The p e r c e n t c o p p e r in ' g ro u n d CuS04 . 5E £0 was o b ta in e d by

e i e o t r o a n a l y s e s and by i o d i i a e t r i c a n a l y s e s . was fo u n d t o b e 9 9 .9

p pure*

3he h y d r a te d s a l t

Sam ples o f t h i s c o p p e r s u l f a t e

w ere u s e d a s s ta n d a r d s f a r c o p p e r th ro u g h o u t t h e r e m a in d e r o f th e i n v e s t i g a t i o n . Sodium , Aimaoniun and P o ta ss iu m S u l f a t e s B a k e rs 0 . 1 . sodium s u l f a t e , ammonium s u l f a t e , and p o ta s ­ sium o u L fe te w e re u s e d i n t h e p r e p a r a t i o n o f co m p le x es, i f t e r t h e i r s o l u b i l i t i e s h a d b e e n c h e c k e d w ith t h e l i t e r a t u r e v a l u e s . The s o l u b i l i t i e s o f t h e p u re s a l t s an d t h e l i t e r a t u r e v a lu e s a r e l i s t e d on T hble 111.

TABLE I I I S o l u b i l i t y o f l u r e S a l t a • D e n s ity o f

.a tu r a te d s o l u t i o n s

S o lu b ility lite ra tu re V alu es

D e n sity D e n s ity L ite ra tu s V a lu e s E x p e rim e n ta l

S a lt

S aap.

S o lu b ility E x p e rim e n ta l

H 3SO4

10°

3 .5 6 8 (TS)

3 .8 7 10

1 .0 3 1

25*

5 .2 2 2 ( I S )

5 .2 0 8 10

1 .0 4 6

1 .0 3 3 5 10

5 .2 1 8 9 45®

7 .7 3

(as)

25*

21.66

( IS )

2 1 .6 4 ^ 1

1.201

45°

3 2 .0 5

(T3)

3 2 . O '/i-

1 .3 0 8

(HH4)p304

25*

4 3 .4 0

(TB)

4 3 .45 11

1 .2 3 9

x&x>4

10 *

8 .4 1 5 ( IS )

8 . S I 13

1 .0 6 6

1 .0 7 0 6 13 1 .0 8 6 10

NB2SO4

CUS04

1 .0 6 4

25*

1 0 .7 6

(S3)

1 0 .75 10

1 .0 8 5

45*

1 3 .5 8

(as)

1 3 .5010

1 .0 9 8

25"

1 8 .5 0

(1 )

1 8 .4 9 (E )1 4

1 .2 0 6

1 8 . 4 5 ( I ) 15 I

lo d la e trio a lly

E

lle s tro ly tio a lly

TB

T o ta l s a L ts by e v a p o r a tio n

1 . 20211

1 . 21114

g e n e r a l E x p e rim e n ta l B rooedure

P r e p a r a t i o n o f Com plexes f o r T e rn a ry S y s to le The com plexes w ere p r e p a r e d by 'w eighing t h e d r i e d s a l t s a n d d i s t i l l e d w a te r d i r e c t l y i n t o dry p y re x s o l u b i l i t y t u b e s , which c o a t in e d g l a s s b e a d s and m a r b le s , a d d e d to a c t a s c ru s h in g and s t i r r i n g a g e n t s .

The tu b e s w e re s to p p e r e d

w ith d r y r u b b e r s to p p e r ^ , a f t e r w h ic h th e y w ere s h a k e n and p la c e d d i r e c t l y i n t o c o n s t a n t te m p e r a tu r e b a t h s .

E x cep t f o r

a s p e c i a l t e c h n i q u e , u s e d i n t h e KgtK^-H•■-■04-Efe0 , 25 * sy stem ) w hich w i l l b e d e s o r ib e d u n d e r t h a t s y ste m , and f o r t h e s e e d ­ in g i n t h e K a- 304- I l : o 04-E £ 0 , 25 # s y s te m , t h e oom plexes r e g a in e d i n t h e c o n s ta n t te m p e r a tu r e b a th s w ith o u t ;n y f u r t h e r h a n d lin g u n t i l t h e y w ere sa m p le d .

The s i z e s o f t h e com plexes u s e d w i l l

b e i n d i c a t e d on t h e i n a i v i d u s l d ate, s h e e t s f o r e a c h s y ste m . C o n s ta n t Tem p a r e t u r e B a th s B a th s : n i n t a i n e d a t 10®, 25® and 45® c e n t i g r a d e w e re em ployed i n t h i s r e s e a r c h .

The te m p e r a tu r e r e g u l a t o r s u s e d

wer^. o f t h e m e rc u ry , t o l u e n e t y p e .

B o th . a g n e t i c and t h y r a t r o n ,

e l e c t r o n i c r e l a y s w e re em ployed, i n c o n ju n c tio n w ith t h e m e rc u ry , t o l u e n e r e g u l a t o r s , a s t h e r m o s t a ts to m a in t i n th e b a t h s a t t h e i r r e s p e c t i v e te m p e r a tu r e s , j* 0 .0 4 * .

The tu b e r a c k s , i n t h e b a th e ,

w ere r o t a t e d c o n s ta n t ly s o t h a t t h e s o l u b i l i t y tu b e s w ould be i n v e r t e d s e v e r a l tim e s a m in u te .

25

M ethod o f S am p lin g Tfabes The s o l u b i l i t y t u b e s w ere remove; fro m t h e r e v o l v i n g r a o k s a n d w ere p la o e d i n a v e r t i c a l p o s i t i o n in t h e b a th s .

This was

done t o a llo w t h e b u lk o f t h e s o l i d s to s e t t l e t o t h e b o tto m o f t h e t u b e s , w hich o c c u r r e d r a p i d l y w ith t h e c o u p le r s a o f t h e s y a ta u s s t u d i e d .

A d r y , c a l i b r a t e d p i p e t t e , w hose t i p had

b e e n c o v e re d w ith f i l t e r p a p e r, f a s t e n e d t o t h e p i p e t t e w ith a ru b b e r b a n d , was lo w e re d i n t o t h e s o l u t i o n i n t h e s o l u b i l i t y tu b e .

F o r t h e sy ste m s a t 10* and 2 5 * , t h e p i p e t t e a u s e d w ere

a t room t o u p e r a t u r e .

F o r t h e sy ste m s done a t 4 6 " , t h e p i p e t t e s

w ere p r e h e a te d t o a fe w d e g r e e s above 45° p r i o r t o s a m p lin g . T h is was done t o p r e v e n t su d d en c o o lin g o f th e s a tx ira te d s o l u t i o n a n d h e n c e p r e c i p i t a t i o n o f s a l t s w i t h in t h e p i p e t t e s , u n c tio n was a p p li e d t o t h e p i p e t t e and i t was f i l l e d t o t h e p ro p er le v e l. T reatm ent o f t h e Sem ule and D e te rm in a tio n o f T o ta l S o lid s

■ w h i m .

—

i.

n -in n

ii

ii

..i—

---------

------------- ---------

-

-

-

,

| i ' r i i-

■

in

-

i— i ii

The sam ple was t r a n s f e r r e d t o a p r e v i o u s l y w eighed w eigh­ in g b o t t l e .

I n t h e c a s e o f t h e 10* an d 25* sy ste m s th e b o t t l e s

w ere em pty, b u t f o r t h e 45* sy ste m s 10 m l. o f d i s t i l l e d w a te r , a t room te m p e r a tu r e , w e re ad d ed t o eao h w e ig h in g b o t t l e , p r i o r t o i t s o r i g i n a l w e ig h in g .

This was done t o c o o l down t h e 45®

sa m p le s upon t r a n s f e r , t o m in im iz e e v a p o r a tio n l o u s e s .

A fte r

t h e l i q u i d s a m p le s w ere t r a n s f e r r e d t o t h e w e ig h in g b o t t l e s , th e y w ere w e ig h e d .

C o r r e c t io n s w ere made f o r b u o y an cy , a n d t h e w e ig h ts

an d t h e d e n s i t i e s o f t h e sa m p le s w ere d e te r m in e d .

26

The w e ig h in g b o t t l e s w ere t h e n p la c e d i n a n 65° ovsn u n t i l th e r e m in in g s o lid ap p e red

. d ry .

The sa m p le s,

e x c e p t f o r t h o s e c o n ta in in g ammonium s a l t s , w ere d r i e d a t 110* u n t i l th e y no l o n g e r shoved any I c e s i n w e ig h t.

These

s o l u t i o n s , c o n ta i n in g ammonium s a l t s , w e re d r i e d s lo w ly a t 85*.

A f te r t h e s a l t s a p p e a re d d r y , th e y w e re k e p t f o r an

a d d i t i o n a l 24 h o u r s i n t h e 86* o v e n .

T his was done to p re v e n t

d e c r e p i t a t i o n a n d c re e p in g o f t h e s o l i d up t h e w a lls o f t h e b o t t l e , w hich o c c u rs when t h e s a l t s a r e d r i e d l a p i d l y above 100°.

The ammonium s a l t s w e re th e n p la c e d a t 1 1 0 * , a s w ere

t h e o t h e r sum p i e s , a n d h e ld t h e r e u n t i l t h e y came t o c o n s ta n t w e ig h t.

Simone*® whowed t h a t t h i s m ethod o f d r y in g ammonium

s u l f a t e s a l t s was a d e q u a te . A f t e r d r y in g , th e s a l t s and w e ig h in g b o t t l e s w ere w e ig h e d , a n d i n t h i s m anner t h e t o t a l s a l t was o b t a i n e d .

c o n te n t o f t h e s & tu r r te u s o l u t i o n s

The s o l u b i l i t y d e te r m i n a ti o n s o f t h e p u re s a l t s

w ere a ls o made i n t h i s m anner.

The s a l t s o b ta in e d fro m th e

t o t a l salt.deterim netiffjs,w ere s u b s e q u e n tly d i s s o l v e d i n d i s t i l l e d w a te r a n d a n a ly z e d f a r t h a l l i u m , a s p r e v i o u s ly d e s c r i b e d .

27

T e rn a ry System s

The t e r n a r y syeteEiB t h a t w are i n v e s t i g a t e d w e re o f t h e ty p e i.sado up o f w ater 1 s a d two s a l t s . an io n in common.

The two s a l t s h av e

T hus, n o t m ere th a n t h r e e com ponents a r e

n e o o a s a ry t o e x p r e s s t h e c o m p o s itio n o f any p h ase of t h e sy s te m , b ility

The sy ste m s ware s tu d i e d by d e te rm in in g th e s o lu ­ r e l a t i o n s among t h e v a r io u s com ponents in v o lv e d i n

ue.ah is o th e r m , w hich i s a t-.o d im e n s io n a l r e p r e s e n t a t i o n o f t h e s y s te m a t c o n s ta n t te m p e r a tu r e . The system * w ere s t u d i e d a s c o n d e n se d system s^® ; t h a t i s , o nly th e l i q u i d and s o l i d p h a s e s w ere c o n s id e r e d . The t o t a l p r e s s u r e i n any one com plex was a p p ro x im a te ly one at! o s p h e re .

How ever, th e v a r i a t i o n i n t o t a l p r e s s u r e h a s

little

e f f e c t on t h e e q u ilib r iu m v a p o r p r e s s u r e o f a com plex.

Heme,

th e s o l u b i l i t y o f t h e s u i t e in v o lv e d i s e f f e o t e e v ery

little

by c h a n g e s i n th e a tm o s p h e ric

ren su re.

I t s h o u ld be

n o te d t h a t , a lth o u g h t h e t o t a l p r e s s u r e o f t h e sy ste m m y be c o n s t a n t , t h e v a p o r p r e s s u r e o f t h e syster.; i s v a r i a b l e . V a rio u s c o m p le x e s, c o n ta in in g d e f i n i t e m o u n ts o f com ponents, w e re p r e p a r e d a s p r e v io u s ly d e s c r i b e d u n d e r th e g e n ­ e ra l e x p .r i r e n t a l p ro ce d u re .

The c o m p o s itio n o f a n o r i g i n a l comp­

l e x , and t h e c o m p o s itio n o f t h e s a t u r a t e d s o l u t i o n , a t e q u il ib r i u m ,

28

f i x e d tw o p o i n t s on a t i e l i n e o f t h e t r i a n g u l a r d ia g ra m , r e p re s e n tin g

a p a r t i c u l a r i s o t h e r m . I n o r d e r t o d e te r m in e

t h e s o l i d p h a s e , a t e q u ilib r iu m w i t h t h e s a t u r a t e d s o l u t i o n , t h e t i e l i n e mas a l g e b r a i c a l l y e x t r a p o l a t e d t o t h e b a s e o f th e t r i a n g l e to o b ta in th e s tilt p ro p o rtio n s o f th e s o l i d p h a se. Ih u s, f o r th e v a rio u s is o th e m s s tu d ie d , th e s a tu r a te d s o lu ­ t i o n c u rv e s en d t h e p o s s i b l e s o l i d p h a s e s a t e q u il ib r i u m w i t h t h e s a t u r a t e d s o l u t i o n s were a e t- m i in e d .

I h i s s y s te m was i n v e s t i g a t e d a s d e s c r ib e d u n d e r t h e g e n e r a l p r o c e d u r e , e x c e p t t h a t t h e com 1 exes m ere s e e d e d

ith

a v e ry s m a ll am ount o f s o d i m s u l f a t e d e e a h y d r a te a f t e r th e y h ad b eaa i n t h e c o n s t a n t t e n p e r a t u r e b a th f o r tw e n ty f o u r h o u r s . I t mas n o te d t h a t t h e s o l u t i o n s h a d t o be s a t u r a t e d w ith t h e sodium s u l f a t e , p r i o r t o t h e s e e d in g w ith t h e d e e a h y d r a te , i n o r d e r t o i n i t i a t e t h e p r e c i p i t a t i o n o f t h e d e c a h y d r e te i n t h e s a t u r a t e d s o l u t i o n s o f t h e com plexes i n w h ic h t h e d e e a h y d r a te was a s o l i d

ch ase a t e q u il ib r i u m .

I h i s sy ste m i s s im p le , s o l u t i o n s w ere fo u n d .

in t h a t no compounds n o r s o l i d

Ih e s o l i d p h a s e s t h a t can e x i s t

at

e q u ilib r iu m w ith s a t u r a t e d s o l u t i o n s o f t h e sy stem a t 25* e re HgSO^ and NagSC^.lOKgO. The a l g e b r a i c e x t r a p o l a t i o n s o f t i e l i n e s t o NagSO^lOKpO g iv e v a lu e s , a s shown i n I h b le XV, w h ich i n d i c a t e d t h e p r e v i s i o n

o f th e a n a ly tic a l p ro ce d u re ,

'Die t h e o r e t i c a l , o r c a l c u l a t e d ,

v a lu e o f HgO i n IJapL'O^j.lOHgO i s 5 5 ,9 3 jO.

The e x p e rim e n ta l

v a l u e s , c s o b t a i n e d from com plexes 1 , ii and 9 , d e v i a t e from t h i s by l e s s th a n two p a r t s p e r th o u s a n d , c a l c u l a t e d v a lu e fro m t h e

e; n v a l u e o f t h e t h r e e e x t r a p o l a t i o n s

i s l e s s t h a n one p a r t p e r th o u s a n d . obtain® ;; a s

'Hie d e v i a t i o n o f t h e

Good r e s u l t s w ere a ls o

a r e s u l t o f th e e x t r a p o l a t i o n s ;;ude t o 'JHl£: O4

a s t h e s c d id p h a s e , a s s e e n i n com plexes 1 0 ,4 , 5 and 6 , w here t h e e x t r a p o l a t i o n e r r o r c a n b e l a r g e r , due t o t h e s h o r t n e s s o f t h e segm ent o f t h e t i e l i n e from t h e s o l u t i o n c u rv e t o t h e com plex p o i n t , a s com pared t o t h e l e n g t h o f t h e e n t i r e tie lin e .

The v a lu e s o b t a i n e d f o r t h e i n v a r i a n t p o i n t s ,

com plexes 7 and 8 , a r e a l s o s a t i s f a c t o r y . I h e a t t a i n .e a t o f e q u ilib r iu m was a s s u r e d by t h e a g re e m e n t o f th e r e s u l t s o f t h e f i r s t s a m p lin g s w ith t h o s e o b ta in e d fro m th e sem e t u b e s , a f t e r th e y h ad r e a n i n e d i n th e b a th f a r a n a d d i t i o n a l ...e rio d o f tim e . I t was th o u g h t t h a t t h i s sy stem ^w o u ld re s e m b le t h e Agpi.O4-KarSO 4.-EgO, , 25* sy stem s tu d i e d by E i o e l and Simons i n which s o l i d 's o l u t i o n s w ere fo u n d . A so.

H ow ever,9 t h i s wee n o t

I h e o t h e r As y s te m s s tu d i e d i n t h i a reseex*ch a r e a l s o

d i f f e r e n t from t h e s i m i l a r s i l v e r sy ste m s s t u d i e d by R ic c i and S im ons.

B u s l a c k o f s i m i l a r iso m o rp h ic c h a r a c t e r

may be c i t e d e s b e in g i n d i c a t i v e o f t h e d i s s i m i l a r i t y o f

30

s i l v e r and t h a l l i u m .

These two m e ta ls i n t h e i r p lu s one v a le n o e

s t a t e - a r e o f t e n com pared.

V a r ia t io n s i n i o n ic s i n e s and c r y s t a l

s t r u o t u r e may make a d e o id e d d i f f e r e n c e i n t h e f o rm a tio n o f s o l i d s o lu tio n s .

That t h e r e i s same e v id e n o e o f s i m i l a r i t y betw een

s i l v e r a n d t h a l li u m i s shown in th e f o r m a tio n o f s o l i d s o l u t i o n s betw een s i l v e r s u l f a t e and t h a l l a u s s u l f a t e i n t h e b i n a r y sy ste m s a s fo u n d by Sokolov^-7 , a t t h e te m p e r a tu r e c f th e m o ltin g r .o in ts , w hich a r e t ? i and t i l r e s p e c t i v e l y . The c ry , t e l r a d i i , a c c o r d in g t o Pauling**®, o f sodium and t L u l l o u s io n s a r e 0 .9 5 and 1.44.1® r e s p e c t i v e l y .

Both sodium

and t h r l x o u s s u l f a t e c r y s t a l s e r e o r th o r h o b i c .

However,

a s India* t e a by w ln c h e ll2? , t h e i r a x i a l r a t i o s , a : b : c , a r e d iffe re n t.

The a x i a l r a t i o f o r sodium s u l f a t e i s 0 .5 9 8 :1 :1 .2 5 2

end f o r t h a l l o u s s u l f a t e i t i s 0 .5 5 5 : 1 :0 .7 3 3 .

I t i s th e re fo re ,

n o t s u r p r i s i n g t h a t s o l i d s o l u t i o n s do n o t form b etw een sodium and t h a l l o u s s u l f a t e .

The c r y s t a l r a d i i o f sodium and s i l v e r

io n s a r e 0 ,9 5 a n d 1 .2 6 r e s p e c t i v e l y .

I n v ie ., o f t h e io n s i z e s ,

one w ould n o t e x p e c t t o f i n d s o l i d s o l u t i o n s b e tw e e n sodium s u l f a t e and s i l v e r s u l f a t e .

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

fo iv .e d from s i l v e r s u l f a t e m d sodium s u l f a t e a t 25 an d 3 5 ° , a s fo u n d by u i c o i an d lim o n s ^ - . As p o in te d o u t by R ic c i and Sim ons, "The c o n tin u o u s s o l i d s o l u t i o n o b ta in e d b etw een s i l v e r s u l f a t e a n d .o dium s u l f a t e i s n o t s u r p r i s i n g in view o f th e s i m i l a r i t y o f t h e i r

31

c ry s ta l s tr u c tu r e s .

B oth a r e o rth c i'h o m b ic , and. t h e a x i a l

r a t i o s , a : b : c , g iv e n byV /j«koff2 e f o r s i l v e r s u l f a t e a r e , 0 .5 7 0 : 1 :1 .2 3 5 , w h ile f o r sodium s u l f a t e t h e v a lu e s a r e 0 .6 0 0 : 1 :1 .2 6 1 .

U in c h e il* ^ g i v e s f o r sodium s u l f a t e t h e

v a lu e s 0 .5 9 8 :1 :1 2 5 " . I t i s i n t e r e s t i n g t o n o t e ( s e e G raph IV) t h a t t h e i n c r e a s e d c o n c e n t r a t i o n o f H 2SO4 i n th e s a t u r a t e d s o l u t i o n has l i t t l e ran g e

e f f e c t on t h e s o l u b i l i t y o f Ife^-O^.IGE- O in t h e

of c o n c e n tr a tio n s i n w hich t h e d e e a h y d r a te a lo n e i s

th e s o lid p hase.

H ow ever, t h e r e i s u j e r k e d In o x •.ase i n

t h e s o l u b i l i t y o f 'ilr .O4 , upon i n c r e a s i n g th e c o n c e n t r a t io n o f NagSO^, i n t h e r e g i o n w here U p O4 i s t h e s o l i d p h a s e in e q u ilib riu m . w ith s a t u r a t e d s o l u t i o n .

H i s l a t t e r b e h a v io r

s u g g e s t s , b u t does n o t pit>ve, th e f o r m a tio n o f a com plex io n .

f i

32

TAEL& IV NapSQa-SL^GOa-HpO. 25*

Ib b e No,

O r i g in a l Complex W t.'jT

QrSOd 100.0

—

Nap. SO4 —

S a t u r a t e d S o l u ti o n W t

TL' - O4 5.222

100.0

Pe n a l t y

S o l id P h a se

NapSO^ —

1 .0 4 6

21.66

1.201

1

1 .4 1 2

2 6 .1 1

1 .7 6 5

2 1 .5 9

1 .2 1 9

B 5 5 .8

% SgO

z

3 .5 0 6

2 5 .9 8

4 .3 6 0

2 1 .5 6

1 .2 5 6

B 5 5 .9

17

9

5 .4 7

2 5 .3 7

6 .5 9

2 1 .5 0

1 .2 9 0

B 5 5 .8

7

7 .9 8

2 7 .9 9

8 .4 2

2 1 .3 4

1 .3 1 5

A + B

8

1 3 .9 9

2 1 .9 7

8 .4 8

2 1 .3 3

1.3L 3

A ♦ B

10

1 4 .9 9

1 6 .9 8

8 .2 7

1 8 .3 4

1 .2 7 5

A 100.35t»

4

1 2 .4 6

1 5 .2 1

8 .0 6

1 5 .9 5

1 .2 4 5

A 100.0

5

1 4 .9 7

9 .9 8

7 .3 2

1 0 .8 7

1 .1 7 8

A 9 9 .6

tv

S

1 9 .4 9

4 .8 8 5

6 .2 4

5 .6 9

1.112

A 9 9 .9

n

A ■ H ; S0 4 B •

Nap;S04 . 10Kp,0

Minimum tim e i n b a th — 7 d a y s Maximum tim e i n b a th ~ 3 S d ay s A pproxim ate t o t a l w e ig h t o f com plexes — 20 gram s

ft

n zt tv

33

TABLE 7 MarSQA-TLySCA-H-O, 45°

O r i g in a l Complex Ttibe No.

wt.

H-gS04 Nar;304 100.0 —

s a t u r a t e d S o lu tio n

wt. ft

%

100.0

S o l i d P h a se

H 2SO4 Na*. SO4 7 .7 3

«*«*

D e n s ity

—

—tm

1 .0 6 4

3 2 .0 5

1 .3 0 8

1

4 .9 6

3 9 .8 9

5 .7 4

3 0 .4 2

1 .3 6 2

C 9 9 .9 ft Na£S 04

7

7 .5 0

3 7 .5 0

8 .4 6

2 9 .5 7

1 .3 9 9

G 100.2

n

2

10.02

3 5 .0 7

1 0 .9 5

2 8 .7 5

1 .4 3 4

0 9 9 .3

tt

8

11.68

3 2 .4 3

1 1 .0 4

2 8 .7 8

1 .4 3 5

3

1 8 .0 2

2 7 .0 0

1 1 .0 5

2 8 .8 0

1 .4 3 4

A* 0 A♦ c

4

2 0 .0 3

1 6 .9 6

11*41

2 2 .1 1

1 .3 5 6

A 100.1 5i a .g S 04

10

1 7 .9 4

1 6 .9 6

1 1 .3 2

1 8 .3 9

1 .3 0 8

A 100.8

ft

5

2 0 .2 2

1 3 .0 7

10.86

1 4 .6 5

1 .2 5 4

A 100.6

t?

6

2 0 .0 2

7.00

9 .6 2

8 .0 0

1 .1 6 6

A 1 0 0 .6

A - SLgSO^ 0 * lIagS 04

Liintmun t i n e i n b a t h — 7 days iJaxiniua tim e i n b a th - - 3 8 d a y s A p p roxim ate t o t a l w e ig h t o f com plexes — 20 gram s

J

! * 1

.

34

N arS0A-TlrSG4~Hr'0, 45° Ih iB sy ste m v;as i n v e s t i g a t e d a t a te m p e r a tu r e above th e t r a n s i t i o n p o in t o f Na^SC^.lOIigO, t o d e te r m in e i f t h e r e would be any m crked v a r i a t i o n from t h e system a t 2 5 ° .

As was t h e

c a s e a t 25®, th o s y sta m a t 45* was a l s o s im p le .

'Ihe d i s c u s -

s i o n , a s a p p lie d t o e r t r a p o l o t i c a s t o t h e s o l i d p h a ses i n t h e 25* s y s te m , i s a ls o a p p li c a b l e t o t h e sy ste m a t 4 5 ° . C o n tr a r y t o th e r e s u l t s a t 2 5 e t h e r e i s a d e c r e a s e i n t h e s o l u b i l i t y ( s e e G raph V) o f NapS 04 a s t h e H 2SO4 c o n c en ­ t r a t i o n i s c o n s id e r a b l y i n c r e a s e d , a s would n o r m a lly be e x p e c te d , due t o t h e com on io n e f f e c t .

H ow ever, t h e r e i s

a g a in a m arked i n c r e a s e i n t h e s o l u b i l i t y o f H?;:S04 as ft-'2*04 i s a d d e d .

'H iis, a s a t 25 * , i s p ro b a b ly due to

com plex io n f o r m a tio n o r t o mo e o t h e r f a c t o r c o n t r i b u t i n g t o t h e n o n - i d e a l i t y o f th e s o l u t i o n . H pSOfl.-(MI4 ) i 04.-E r 0 » 25° I n t h i s s y s te m , o s i n t h e o t h e r s in v o lv in g s o l i d s o l u ­ t i o n s , t h e a tta in m e n t o f e q u il ib r i u m was s lo w .

A minimum t i .e

o f s i x t y days i n t h e c o n s ta n t te m p e r a tu r e b a th y i e l d e d r e s u l t s whioh wer>.. re p ro d u c e d when t h e s . - e tu b e s w ere sa m p le d , e f t e r h a v in g b e e n a llo w e d to rear, a in i n t h e b a th a n o th e r t h i r t y d a y s . G raph VI i n d i c a t e s t h a t th e s o l i d

phase i n e q u ilib r iu m

w ith s a t u r a t e d s o l u t i o n s i s a s o l i d s o l u t i o n ,

'ihe s o l i d

s o l u t i o n i s c o n tin u o u s , a n d t h e e x t r a p o l a t e d t i e l in e .; a .i 0 d i s t r i b u t e d e v e n ly a lo n g th e s o l i d s o l u t i o n l i n e .

I

(BUFB V II

(■ 04)2804 - TI2SO4 - HgO, 26 C

1.0

LIQUID

0.6

0.6

0.0

MOLE FSACTIOH

1.0

80LID

iii

'•••I mSSI !m »**•§?• *•••) »•«(
••• • • • • • « ••••1

••••••••••••••) HIMMMI MMIHIM (ItMf*f•


» •» •(» ■ » •!••••••

(H a4)2S 04 - T l2 8 0 4 -

MOSS VBACTIOI (IB 4)|S04

SOUS

26 0

35

The p l o t o f t h e m o l e f r a o t i o a o f H -S O 4 l a t h e l i q u i d p h a s e , a g a i n s t t h e m ole f r a c t i o n o f H?. UO4 i n th e e b l i d p h a s e , y i e l d s a o u rv e on G raph V l l

y vdiich i s o f t h e Ixoozebocan Type I 1 8 .

S x p e r to e n t a i l y i t would, be extre,-,.i.ly d i f f i c u l t t o c i s c e r n w h e th e r o r n o t t h e o u rv e c r o s s e s t h e d ia g o n a l l i n e a t low c o n c e n t r a t io n s o f t h a l l o u s s u l f a t e , a s w ould b e t h e o a s e i f s o lid s o lu tio n .

i t w ere a Type I I

Ih e f e e t t h a t t h e o u rv e i n G raph V I I d o e s n o t

c r o s s t h e d i a g o n a l , i n t h e e x p e r im e n ta l r a n g e , i n d i c a t e s t h a t t h e r e i s no p o i n t o f minimum v a p o r p r e s s u r e o f t h e s a t u r a t e d s o l u t i o n s i n t h e s y s te m . H i l l , P u rh a

and S i o o i ^ d e r iv e d a n e q u a tio n t o r e p r e s e n t

th e d i s t r i b u t i o n , in th e s o l i d end l i q u i d p h a ses, o f s a l t s in

K (

s y s te m s i n w hich s o l i d s o l u t i o n s a r e fo rm e d . w h ere H , and

/ jg ) &

e q u a l t h e m ole r a t i o s o f t h e io n s B/B* i n th e

l i q u i d and s o l i d p h a s e s r e s p e c t i v e l y ,

B and B* r e p r e s e n t t h e

i n te r c h a n g e a b le i o n s i n t h e s o l i d s o l u t i o n s .

Ih e d i s t r ib u t io n

r a t i o , &*/£hyJyti>f p o i n t T, 1 8 ,5 1 gram £Ap e r 100

Thus,

gras& o f s a t u r a t e d s o l u t i o n , i s

n o t t h e p o i n t o f minimum s o l u b i l i t y .

Ho .e v e r, i t i a t h e

p o i n t o f maximum v a p o r p r e s s u r e a lo n g t h e s a t u r te d s o l u t i o n c u rv e R -;., and t h e e v a p o r a tio n p a th s on th o s a t u r a t e d s o l u t i o n c u rv e w i l l r o v e a«ay from T. I f one e v a p o r a te s a s o l u t i o n ,

..hose c o m p o sitio n , i s

r e p r e s e n t e d by p o in t P, t h e c o m p o s itio n w i l l Change a lo n g t h e d o t t e a l i n e i n t h e d i r e c t i o n o f t h e a rro w u n t i l p o in t s i s r e a c h e d . At t h i s p o i n t t h e s o l u t i o n w i l l become s a t u r a t e d , s o l i d ft w i l l p r e c i p i t a t e and one d e g re e o f f r e e ,om w i l l be l o s t . upon f u r t h e r e v a p o r a tio n , w i l l p o in t ft i s r e a c h e d .

The s o l u t i o n ,

o v e a lo n g t h e c u rv e f t- 3 u n t i l

, . t t h i s p o i n t , a second s o l i d D w i l l p r e ­

c i p i t a t e , a n o th e r d e g re e o f freedom in l o s t and th e s o l u t i o n becom es i n v a r i a n t ( e s a c o n d e n se d is o th e r m a l s y s te m ) .

The

s a t u r a t e d s o l u t i o n w i l l r e t r a i n a t ft u n t i l e l l t h e w a te r h a s *

f

fct)rD//oo^.

61

e v a p o ra te d , l e a v in g t h e two s o l i d s

D a,.d h , whose s a l t

p r o p o r tio n s a r e r e p r e s e n t e d by t h e p o in t Y. S i m i la r ly i f th e i n i t i a l s o l u t i o n i s r e p r e s e n t e d by p o i n t 0 , th e s o l u t i o n c h a n g e s a lo n g t h e d o t t e d l i n e u n t i l a t U s o l i d i; p r e c i p i t a t e s .

'Hie s a t u r a t e u s o l u t i o n

,* ili now v a r y a lo n g t h e c u rv e U-Ve i n t h e d i r e c t i o n o f t h e a rro w u n t i l t h e i n v a r i a n t p o in t

is re a c h e d .

In th is

p r o c e s s th e l i q u i d mgty o a ss th ro u g h a r&xlnum o f w a te r c o n te n t, b u t i t w i l l alw ay s ch an g e in t h e d i r e c t i o n o f d e c r e a s in g v a p o r p ressu re.

A t 1 a se c o n d s o l i d p h a s e ,

( M l ^ J g S O ^ p r e o ip i ta t e s .

She s o l u t i o n f i n a l l y d r i e s up t o y i e l d a m ix tu re o f CUSO4 . (HH4 ) 2^ 04 . 6KpO (1} and r e p r e s e n t e d by t h e

o in t 1.

^hoae s a l t p r o p o r tio n s s r e

TAHLA XV OuS04>(Ha4)£S04-il£Q,. *8« Caven. a n d L S ito h e ll23

l& p e r lm e a ta l S a t u r a t e d S o l u ti o n

S a t u r a t e d S o l u ti o n CuSQ^

O11SG4 vvt.^

(HHa J t SOa S o lid «/t »c/o P h a se CU-SO4 . 5E2 O

1 8 .5 0

(NH4)£ G0-4 ■it./:

1 8 .3 7

*■“■

1 8 .8 2

1.02

p

—

1 8 .9 3

1 .2 6

*t

—

—

1 8 .9 5

1.66

tt

—

—

1 9 .0 8

1 .9 1

ft

»«■

—

1 9 .3 2

3 .0 1

n

——

—

1 9 .7 1

5 .2 9

CuS04 .5E20+ CUSO4 . (NH^SOi.GBgO

1 7 .3 4

5 .8 1

1 6 .8 7

5 .8 7

1 5 .7 0

6.20

Tt

1 0 .1 4

8 .3 8

ft

7.46

9 .8 2

If

—

—

5 .3 9

1 9 .4 9

5 .3 7

CUSO4 . (N E 4 )g S 0 4 .6 ^ 0 —

««•

1 0 .1 5

8 .3 7

—

—

7 .4 1 6

ft

—

It

6 .2 0 3

1 .2 4

2 9 .5 6

tl

—

0 .7 4

3 3 .3 6

It

0 .4 6

4 2 .8 3

n

CUSG4 . 0 .3 8

—

1 0 .1 2

—

1 1 .2 4 —

—

—

(1 2 1 4 )': 0 C 4 .6 1 .; 0

4 3 .0 6

4 3 .3 9

—

—

ft

—

—

1 9 .4 4

1 0 .7 9

6 .6 8

—

(N Ii4 )rS 0 4

0 .3 5 4

4 3 .3 0

0 .3 6 6

4 3 .3 1 4 3 ,4 0

65

au.-::Q4.-K--S04.- i;fO, E5° (Qpiven anu l i l t c h e l i ^ ) Caven a n d M it c h e ll a l s o i n v e s t i g a t e d t h e sy ste m CufX>4KpEC^-HpO a t 2 5 ° , w hich K i l l h e u s e d a s p a r t o f a q u a te r n a r y s y s te m .

'B its e y s te ja was t a b u l a t e d (lia b le AVI) and p l o t t e d

(G raph AVI) i n t h e s a n e m anner a s t h e p re o e d in g s y s te m .

As

i n t h e rr e v io u a sy ste m a d e v i a t i o n o f t h e minimum, s o l u b i l i t y p o i n t , o n t h e c u rv e r e p r e s e n t i n g s a t u r a t e d s o l u t i o n i n e q u i l ­ ib riu m w ith th e d o u h le s a l t h y d r a t e , fro m t h e p o i n t r e p r e s e n t i n g t h e s o l u b i l i t y o f t h e d o u b le s a l t ,

was e x p e o te a b e c a u s e o f t h e

s i m i l a r i t y o f t h e tw o s y s te m s .

B ie r s was no i n d i c a t i o n o f t h i s

from Cavcn and E i t o h e l l ’s d a t a .

B i e r e f o r e , t h r e e e x p e rim e n ta l

e o m p le x ee , w hose s a t u r a t e d s o l u t i o n s l a y w ith in t h i s r e g io n , wer~ a n a ly z e d .

These v a lu e s - r e l i s t e d on I h b le AY u n d e r t h e h e a d in g

S s p e rim e n ta l.

A minimum s o l u b i l i t y v a lu e w hich i s n o t c o i n c i d e n t

w ith t h e v a lu e o b t a i n e d f a r t h e s o l u b i l i t y c f t h e d o u b le s a l t h y d r a te , was o b ta in e d .

Mb i n th e p r e v io u s s y s te m , t h e s h i f t i n t h e moacimvni

i s i n d i c a t i v e o f non i d e a l i t y i n t h e s o l u t i o n .

64

la'-jxm ;jri OuJC4»Ivc

5*

Gaven and l i t o h e l l ^3 S a tu ra te d S o lu tio n OuSQa. wt.Vs 1 8 .3 7

KSsOa

uttja —

1 8 .3 9

.SO

1 8 .4 9

.2 7

1 8 .6 4

1 .2 0

1 8 .7 9

1 .5 3

S a t u r a t e d S o lu tio n S o lid P h a se CuSD4 .5H£G

CuSOa Wt.fe 1 8 . 5C

**

—•

«

—

"

2 .0 6

1 9 .4 3

3 .0 4

CuS04 .5H£0* CuS04 .XgSQ4 .6EgQ

1 8 .9 7

3 .0 9

CuSO4 i 2.gSO4 . 6HgO

1 4 .9 2

3 .7 0

"

1 2 .7 1

3 .9 2

"

5 .2 2

5 .1 7

"

5 .0 0

5 .4 6

”

"

—

—

1 9 .1 6

4 .9 3 6 4 .2 9 5

6 .4 7

1 .7 1

9 .2 8

1 .0 3

1 1 .2 3

0 .8 5

1 0 .8 9 1 0 .3 3

—

"

1 8 .9 6

3 .4 1

K2SQ^. .v’t.y?

"

CuS04 .Iu S 0 4 »6EgO+ k » so 4

3 .0 9

5 .3 8 1 5 .7 0 3

3 .4 1 5

6 .3 4 6

1 .2 9 4

1 1 .0 5

" Kf.'304

~

1 0 .8 1

Ih e o r i g i n a l d a t a o f Caven a n d i i i t c h e l l a j e i n m o le s p e r 100 gram s Eg 0 .

w ir\- Sc

65 (^ t e r n a r y System s Herthod o f

tu d y

One s t a r t s o u t w ith a ’l i x t u r e o f tw o known s o l i d a lia s e s o f a t e r n a r y sy stem a t e q u i l i b r i a . , w ith a s a t u r a t e d s o l u t i o n , an i n v a r i a n t s o l u t i o n o f a t e r n a r y s y s te m .

A f o u r t h com ponent ( s o l i d ) i s ad d ed ,

and t h e s y s te m , whioh i s now a q u a t e r n a r y one, i s a llo w e d t o come to e q u il ib r i u m .

Hie p o in t r e p r e s e n t i n g t h e e q u ilib r iu m s a t u r a t e d s o l u ­

t i o n w i l l now l i e

on e c u rv e w i t h in t h e t e r n a r y d ia g ra m .

A f te r sa m p le s

o f th e s o l u t i o n a r e a n ly a e ri, more o f th e f o u r t h com ponent may b e added t o o b t a i n a new p o i n t on t h e c u rv e .

T his ra y be r e p e a t e d i n g r a d u a l s t e p s ,

i n o r d e r t o m a in ta in th e p r e s e n c e o f t h e kno.»n s o l i d s a s p h a s e s , u n t i l a t h i r d s o l i d p h a se p r e c i p i t a t e s . v a ria n t.

At t i i s p o i n t t h e s o l u t i o n becom es i n ­

I f th e f o r e g o in g p r o c e d u re i e r e p e a t e d f a r a l l th e o t h e r i n ­

v a r i a n t p o i n ts o f th e t e r n a r y s y s te m s , vdiioh a r e p a r t o f th e q u a te r n a r y s y s te m , i t i s p o s s i b l e t o d e f i n e e l l th e c u rv e s r e p r e s e n t i n g th e s u r f a c e b o u n d a rie s of t h e

Q u a -te rn a ry sy s te m , p r o v id e d t h e sy. t e n i s s im p le .

Hie c o n d e n se d q u a te r n a r y is o th e r m o f a s y s te m , e o n s i t i n g o f ..a te r a n d t h r e e s a l t s w ith e common io n , i s u s u a l l y r e p r e s e n t e d a s a r e g u l a r t e t r a h e d r o n w ith Hr 0 a s i t s u p p e r a p e x .

I f t h i s te tra h e d ro n

c o n ta i n s a p la n e s e c t i o n , p a s s in g th ro u g h t h e HgO ■p e x , on w hich a l l c o m p o s itio n s o f l i q u i d s and s o l i d s i n e q u il ib r i u m may b e r e p r e s e n t e d i n term s o f KjjO e n d tw o o th e r s u b s ta n c e s (one o r b o th b e in g d o u b le s a l t s ) fo rm in g th e b a s e o f th e t r i a n g u l a r s e c t i o n , t h i s s e c t i o n i s known a s a q u a s i - t e r n a r y s e c t i o n o f t h e co n d e n se d q u a te r n a r y i s o th e r m . w i l l be r e f e r r e d t o a s a " q u a s i - t e r n a r y s y s te m " .

Ifcis

.e o tio n

From a s tu d y o f a q u a s i”

t e r n a r y sy ste m one c a n o b t a i n in f o r m a tio n c o n c e rn in g one o f t h e s u r f a c e s o f a qu! t e r n a r y s y s te m .

Xhis i s p a r t i c u l a r l y u s e f u l when t h e compounds o f th e

66

t e r n a r y s y s te m s, c o n s t i t u t i n g t h e s i d e s o f th e q u a te r n a r y p y ram id , f o r ' s o l i d s o l u t i o n s . P r e p a r a t i o n o f Com plexes o f th e Q u a te rn a ry System s Com plexes f o r t h e q u a te r n a r y s y s te m s and t h e q u a s i t e r n a r y s y s te m s w ere p r e p a r e d by p la c in g w eighed q u a n t i t i e s o f t h e com ponents i n

r e f e r t o gram s o f t h e s a l t d e te r ; in e a p e r 100 g r t '. s o f s a t u r a t e d s o lu t i o n *

The d e n s i t i e s w ere o b ta in e d i n t h e sam e

t h e p r e v io u s t e r n r y s y s te m s .

anner as in

67 Jan eo k e P ro j e c t io n One o f t h e v.ay;. o f r e p r e s e n t i n g o qu; t e r n a r y sywtem a s o rile n e f i g u r e , w hich . peaces

o f the t r ia n g u la r b ase o f th e . risra r e p r e se n t th e pure s a l t rr

coupon© a t; •

The p o in t s , cu rv es

nd s u r fa c e s o f th e Ja n e o k e

■risiii are an alogou s to t h e p o in t s , cu rves -nd s e r ia c e s o f th e r e g u lv r te tr a h e d r o n . Graph j j J i s a p e r s p e c tiv e draw ing,

ade to s c a l e , o f

t h e s o li d f ig u r e r e p r e s e n tin g t h e q u o ttr n -r y ay tern.

'Ihe cu rv es

and s u r fa c e s • r t la b e le d w ith sym b ols, re r e s e n t in g t h e s o l i d o r s o l i d s w ith v.hioh th e y are s a tu r a t e d .

DISSORII'ITUH OF itfi.'BOOLO OH GHAPH iQtl

A ...

G11SO4 .S llgO

B ...

OU3 O4 . 'IlgFO ^. 6IF 0

C ...

HI g SO4

D ...

(UK4 ) • SO4

E . . . GuS0 4 .(KH4 )pS0 4 . 6I^-.0 33 . . S o lid . S o lu tio n T . . . O n e fo ld s a t u r a t e d s o lu tio n . c u rv e i n t h e t e r n a r y sy s te m s Q, . . .

'iVvofold s a t u r a t e d s o l u t i o n c u rv e i n t h e q u a te r n a r y sy s ts n .

Qs . . O n e fo ld s a t u r a t e d s o l u t i o n s u r f a c e i n th e q u a te r n a r y eye t e n

* S o l i d p h a s e s i n e q u i l i b r i u m w ith s a t u r a t e d s o l u t i o n s . 9 P h a se s added t o p re v io u s com plex.

'Urns, D (u n d e r P h a se s Added, lh.be

r e p r e s e n t s t h e p h a se added t o com plex I ( a f t e r i t was a n a ly z e d ) t o o b t a i n com plex IA

s i m i l a r l y A (u n d e r P h a se s mdded, lU be IB 4 )

r e p r e s e n t s t h e p h a se t o o b t a i n com plex 13 4 .

dded to com plex IB 3 ( a f t e r i t was .m a ly z e d )

69

table xvxi OuSOa- H Tube No.

p SQa- ( m u

S a tu ra te e l S o l u ti o n ■it. p

I p.SOa-L rO, 25*

'fo HrO

CUS04

TLpSO* (HH4 ) 2SO4

I

1 8 .7 0

2 .8 1 0

I* *

1 8 .9 0

2 .4 2 9

0 .8 6 1

7 7 .8 1

“

l

1 8 .6 6

2 .4 %

0 .8 7 3

IB--;

1 8 .9 1

2 .3 4 1

IB 3

1 6 .7 0

I3 4

1 9 .1 2

IIIB

1 9 .4 4

IIIA

1 9 .48

IIIB i

—

* S o lid P h a se

° P hases Added

D e n s ity

H ae Pay.«

—

1 .2 3 6

A+SSBE

-0

1 .2 4 6

14 d

7 7 .7 7

tt

D

1 .2 4 8

14 d

1 .2 8 6

7 7 .4 6

n

D

1 .2 5 1

21 d

1 .7 1 3

3 .2 3 6

7 6 .2 7

SS.BE

B+H

1 .2 2 5

14 d

1 .6 1 8

2 .7 3 4

7 6 .5 3

A^SS. BO-

A

1 .2 5 6

11 d

5 .3 9 8

—

A+B

—

1 .2 4 7

12 d

—

3 .3 7 1

«.»

H

—

1 .2 4 6

9 d

1 9 .4 6

0 .2 4 6

5 .0 2 0

7 5 .2 7

A+S3.BE

G

1 .2 5 6

12 d

IIIB 2

1 6 .2 2

1 .0 7 2

4.6 2 9

7 8 .0 8

SS5BE

C+H

1 .2 2 3

14 d

IIIA x

1 9 .4 4

0 .3 2 1

5 .0 0 7

7 5 .2 3

A+S3.DSS

0

1 .2 5 6

27 d

IIIA -

1 9 .3 4

.6 7 3

4 .439

7 5 .5 5

n

0

1 .2 6 1

14 d

1 8 .5 7

1 .0 0 7

4 .1 0 5

7 6 .3 2

1 .2 4 7

26 d

iiia

3

—

s s . rd

a +c +e

'liable AVTI c o n tin u e d on p a g e s 70 and 71

70

M LE x m S a t u r a t e d S o l u ti o n Ih b e g o . '" " " "".JtV'jfr ""

C ant *d

% H- 0

OUSU4

H ;-S0 4 (BH4) 2 S0 4

1 .8 6 3

5 .6 4 9

1 .7 6 2

5 .7 6 0

11%

1 .6 9 4

IIB g

S o lid P h a se

P hases Added

D e n sity

TSLtiie Days

1 .0 7 0

—

D

1 .0 7 6

13 d

9 2 .49

®+o

1 .2 2 6

9 1 .2 5

SS.BC+ 3S.BL

5 .9 7 1

2 .7 6 1

8 9 .5 7

w

D

1 .0 9 0

13 d

1 .6 3 4

6 .1 9 5

4 .2 9 6

8 7 .8 7

ft

D

1.101

19 d

ID s

1 .6 3 4

6 .2 6 0

4 .6 7 8

8 7 .4 3

n

D

1 .1 0 4

25 d

IIB 4

1 .3 2 3

7 .0 9 9

1 3 .2 3

7 8 .3 4

ft

;D

1 .1 6 6

19 d

11 %

1 .5 4 2

6 .4 9 1

8 5 .4 2

w

C+A

1 .1 1 9

27 d

IVB

0 .3 5 4

—

4 3 .3 0

5 6 .3 5

C

1 .2 4 7

12

d

IVA

0 .3 6 6

tmm

4 3 .3 1

5 6 .3 2

0

1 .2 4 5

13

d

I7AX

0 .3 7 9

4 0 .5 4

5 6 .5 6

c

1 .2 6 1

27 d

0

1 .2 6 5

15

c

1 .2 6 7

21 d

c

1 .2 5 6

18 d

c

1 .2 5 5

14 d

0

1 .2 5 5

18

c

1 .256

27 d

II -l

i i a

2 .5 1 6

—

6.546

b

+ e

«

SS.BC+ s

s

. b e

IV %

0 .3 7 5

3 .1 3 7

3 9 .5 3

5 6 .9 6

0 .4 6 1

5 .3 0 ?

3 4 .9 5

5 9 .2 8

Ft

i v

IVB3

0.487

5 .3 9 4

3 4 .5 6

59 .5 6

f?

IVAg

0 .5 9 1

6 .1 4 5

3 0 .9 2

6 2 .3 4

It

0 .5 9 5

6 .1 8 1

3 0 .8 8

6 2 .3 4

«

0 .6 0 1

6 . 2 Q1

3 0 .7 9

6 2 .4 1

17

i v

b

a

e

3

IVA4 Q u S ( ‘4 . 5 H

^ 0

(NH4 )?S04

—

. A

CUSO4 .

..

.

CUSO4 .(N H 4)sS0 4 .6E g0. E

B

E

•

S 0 4

. 6 H

g

0 ..

e

. .

.

E r S04 Babl© XVII c o n tin u e d can page 71

d

d

S o lid S o l u ti o n .

1 •

EgO

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

»

71

m n u -.v ii coat *a Gu SOa- xi-'3 0 a- ( illA ) r SCA-HpO, 25* D a ta f o r J e n e c k e P r o j e c t i o n S a tu ra te d

S o l u ti o n Tube No.

CUSO4

B . 2 SO4

(HU4 )s i

S a tu ra te d S o lu tio n . v /i. p e r Ib ta l* S a l t s CuS04

TI 2SO4

ilffl4 ) 'S 04

1 3 .0 6

—

II

2 4 .8 0

7 5 .2 0

__

IA i

8 5 .1 7

1 0 .9 5

3 .8 8

I lA i

2 0 .1 4

6 5 .8 4

1 4 .0 1

%

8 4 .8 6

1 1 .2 1

3 .9 3

11%

1 6 .2 5

5 7 .2 7

2 6 .4 8

IBr

8 3 .9 1

1 0 .3 9

5 .7 1

1192

1 3 .4 8

5 1 .0 9

3 5 .4 3

IB 3

7 7 .2 2

7 .8 8

1 4 .8 9

1103

1 3 .0 0

4 9 .7 9

3 7 .2 1

IB 4

8 1 .4 6

6 .8 9

1 1 .6 5

IIB 4

IIIB

7 8 .2 7

—

2 1 .7 3

IIB g

IIIA

7 8 .4 0

—

2 1 .6 0

IVB

0 .8 0

—

11 %

7 8 ,6 9

0 .9 9 4

2 0 .3 0

IYA

0 .8 9

—

IH B g

7 3 .9 9

4 .8 9

2 1 ,1 2

iv Al

0 .8 7 3

5 .7 9 3

9 3 .3 3

111%

7 e ,4 9

1 .3 0

2 0 .2 2

19%

0 .8 7 1

7 .2 8 8

9 1 .8 5

H IA S

7 9 .0 9

2 .7 5

1 8 .1 5

ira £

1 .1 3

1 3 .0 4

8 5 .®

IIIA s

78 .41

4 .2 5

1 7 .3 3

I7 3 3

1.2 0

1 3 .3 4

8 5 .4 6

iv a ?

1 .5 7

1 6 .3 2

8 2 .1 0

m

3

1 .5 8

1 6 .4 1

8 2 .0 1

IVA4

1 .6 0

1 6 .5 0

8 1 .9 1

1 0 ,5 8

•

6 .1 0 9

CD

8 6 .9 4

8

I

4 4 .5 2

6 1 .1 1 4 4 .9 0 9 9 .2 0 9 9 .1 1

TABL& ,.7111 Q u a s i-T e rn a ry S ystem

Tdbe Ho, 1 X 2 X

O rlg i n a l Complex CuSOa qfej.TpSO^ Tlp'SOd.

S a tu ra te d S o lu tio n Cu SQa (m u T ^so a. H g 3 0 a

1 1 .8 5

1 0 .1 5

9 .8 1 2

—

2 1 .6 6

—

—

1 8 .5 5

1 1 .9 0

9 .7 a

.3 8 0 5

9 ,9 8 3

—

1 8 .29

2 1 .5 3

Y

0 .5 0 1 3

1 1 .4 3

— — 9 .0 6 5

5 .0 1 1 5

7 .8 5 3

0 .2 1 5 7

—

6 .5 1 9

1 .5 7 9

55. 5 1 .1 4 0

—

—

1 4 .3 9

—

—

4 .2 7 0

2 .8 9 0

8 3 .£ > 1*116

4 .5 1 8

2 .0 7 8

7 .5 7 9

6 .0 2 1

—

9 .4 2 6

Y

9 .9 7 6

—

—

3 .6 0 5

7 .5 6 4

2 .6 8 8

3 .5 1 9 0 .9 0 1 8

— 0 .8 7 2

X

1 .9 5 1

—

—

1 .9 2 7

X

9 .9 5 5

—

~

6 .2 4 5

2 .4 0 9

—

7 .6 1 5

1 .8 7 1

—

10.02

—

—

—

—

X . . . Cu S04.(H H 4)2S04 Y ...

—

8 .2 8 4

—

y

25. T t 1 .1 5 4

3 .8 0 7

7 .2 6 3

9 .9 7 4

7

0 .5 9 9

—

—

X

6

1 .1 5 5

0 .7 8 8

—

Y

6 .7 8

—

2 .0 0 1

1 6 .0 3

0 .1 6 4

—

Y

X

6 .2 7 5

1 .1 5 7

1 7 .2 3

—

1 .5 2 0

8 .3 6 9

7 .8 0 5

2 0 .0 1

9 .9 7 6

—

P e n a lty

ss»

9 .5 2 9

X

4

GuSO0« £ 5 *

CuSO4.a2.g8O4

— 4 .7 4 5

5 .6 4 0

9 6 . 4 1 .0 7 7

1 .0 7 2

--

SS. . . . S o l i d S o lu tio n ft OUSO4 . H Time i n b a th . . . 2? days

2

SO4

73

CuSOA-Ug.SOA-LfSQA-HaOf j>5° Ih© p r e p a r a t i o n o f t h e com plexes a n d t h e a n a ly s e s of t h e sy s te m , w i t h r e s p e c t to flo p p er, t h a l l i u m and t o t a l s u L f a t e , ware p erfo rm ed I n t h e same m anner a s t h e p r e v io u s q u a te r n a r y sy s te m . H ie d a te f o r t h e v r i o u s i n T able X E i.

j

o i n ts on Graph XXII a r e l i s t e d

The c u rv e s b etw een p o in ts V and V I I , a n d t h e c u rv e s

between. p o i n ts VI end V I I I a r e c o n tin u o u s . m inim a w ith r e s p e c t t o w a te r c o n te n t ,

However, t h e y have

'ih e re i s a ls o a minimum

p o i n t i n t h e t e r n a r y s y s te m

a t 25*.

As i n th e

p re v io u s qu t e r n a r y s y s t e , t h e r e e x i s t s c o n tin u o u s s o l i d s o lu ­ t i o n s b e tw e en t h e compounds CuSO4 .K2 SO4 . 6EpO an d CUBO4 . H£SG 4 . 6h g 0.

The s o l u t i o n c u rv e o f t h e q u a s i - t e r n a r y s y s te m , a s

i n d i c a t e d on G raph X X III, s u b s t a n t i a t e s t h e vtreoence o f th e s o l i d s o l u t i o n s i n t h e q u a te r n a r y s y s te m .

2h e c u r v e i s n o t

c o m p le te b e c a u s e , t h e compound CUSQ4 . UgoC^GKpO i s in c o n -

(tihl*)CK)

g ru e n tly s o lu b le .

I h e r e i s a l s o a minimum o f w a te r o o n te n t A)

a s se e n o n G raph X X III, in t h e s a t u r a t e d s o l u t i o n c u r v e o f t h e q u a s ia t e r n a r y s y s te m .

H ie m inim a, i n t h e t h r e e c u r v e s ,

p ro d u c e o c o n tin u o u s d e p r e s s io n in th e s a t u r .- t e d s o l u t i o n s u r f a c e and a s a d d le p o in t on t h e r id g e betw een th e h y d ra te d do u b le s a l t s , a e s e e n on G rip h XXTV.

I h e o o n to u r l i n e s on

Graph X_-.IV w ere o b t e i n e d i n t h e same

m anner a s t h o s e o f t h e

p r e v io u s q u a te r n a r y s y s te m .

Graph XXV i s s i m i l a r t o Graph XX,

3

i

CO

CO

i

ORAPB XXV

(MAPH XXVI

SOLID s o u m o x DISTHIBOTIOB

UOLE FBACTIOH CuS04 .T 1 2S04

&

III

10 ll) the lull

l iq u id

0.0 MOU PHACTIOS CuS04 .T 1 2804 IX SOUD I '

I

*I

0«804 .T12S04-CuS04 .(KH4)2S04- ^ 0 , 26 U

Cm»04 .T12804-CuS04 . I 2804- ^ ,0 , 25

o f t h e p r e v io u s q u a lv m .iy s y s te ra . A fao lid p e rs p o o i'iv e d raw in g was n o t :.ad e o f t h i s e y stc e i. I t v o u ld bo s i m i l a r t o th e s o l i d p e r s p e c t i v e d ra .-ia g o f t h e p r e v io u s s y s te m , e x c e p t f o r t h e p r e s e n c e o f t h e m inim a. S o lid S o lu tio n D i s tr i b u ti o n , in t h e Q u a s i-T e rn a ry .Systems 2he s o l i d s o l u t i o n d i s t r i b u t i o n i n t h e two q u a s i - t e r n a r y

s y ste m s war© s t u d i e d in t h e sam e m anner a s t h e s o l i d s o l u t i o n s s ir ip le o f t h e p r e v i o u s ,,te r n a r y s y s te m s . 'ihe p l o t o f t h e m ole f r a c t io n o f

0 U...O4

.UpRO.}. in t h e

l i q u i d p h a s e , a g a i n s t th e m ole f r a c t i o n o f OUSO4 . H 2 SO4 i n t h e s o l i d p h a s e , y i e l d s c u rv e s on G raph 2X71, w hich i n d i c a t e s t h a t t h e s o l i d s o l u t i o n s fo u n d i n t h e q u n s i - t e r a a r y s y s te m s a r e o f t h e R oozeboau ly p e I .

75

TABLE XIA CuS04.-E . rS04-K p.S0a “H?.0. 2 5 ”

TUbe No*

S a t u r a t e d S o lu t io n Vit. %

£ EgO

CuS04

a 2S04

1 8 .7 0

a . 610

1 8 .7 7

2 .6 1 2

0 .4 2 2

7 8 .2 0

Ve

1 8 .9 0

2 .1 2 8

1 .0 7 4

V3

1 9 . OS

1 .5 6 0

V1IA

1 9 .1 6

S o lid P hase

P hases Added D e n s ity

Time Days

IfeBQ* —

1 .2 3 6

A+SS.Dii

B

1 .2 4 4

53 d

7 7 .9 0

B

B

1 .2 4 9

35 d

1.702

7 7 .7 2

It

B

1 .2 5 1

13 d

—

3 .0 9 0

7 7 .8 7

—

1 .2 4 6

27 d

V IlA i 1 9 .2 3

0 .2 2 9

2 .7 2 0

7 7 .6 2

A+SS.DE

G

1 .2 4 7

a? d

v m £ 1 5 .9 0

0 .1 7 3

3 .3 0 5

8 0 .6 2

3 3 . DE

C+A

1 .2 0 7

Id d

7 i i a 3 1 5 .5 7

0 .5 1 2

3 .1 0 9

8 0 .8 1

«

C

1 .2 0 4

15 d

V I 1% 1 9 .aa

0 .2 4 8

2 .6 7 8

7 7 .8 5

A+SS.DE

G

1 .2 4 5

30 d

VIIBg 1 9 .1 7

0.563

2 .5 3

7 7 .7 4

«

C

1 .2 4 9

as d

V V1

A ...

A+B

CuSO^.SEgO

A+B

D ...

CUSO4 . TL^SG^IfeO

B . . . E£S 04

£1 . . .

GuJbO^.oE^O

0 ...

S S .. . S o l id S o lu tio n

Ti.£ S04

H . . . HgO Tfebl e

a I a.

on page 76

76

TABLE XIX (c o a t *d) 25°

CuSO^ 1

Tube Ho*

S a tu i'a te d S o l u ti o n Wt* L f~ OU.SO4

B.OS04

S o lid P h a se

■&

lim e P h a se s Added D e n s ity Days

K2 S04

—

1 .0 9 7

27 d

C

1.119

17 d

ft

G

1 .1 2 5

33 d

8 5 .1 7

n

C

1 .1 3 2

20 d

9 .7 0 9

8 5 .1 4

n

C+E

1 .1 3 2

20 d

4 .3 0 7

9 .6 7 7

8 5 .1 0

n

C+H

1 .1 3 3

8 d

0 .9 1 2

4 .5 0 3

9 .5 6 1

8 5 .1 2

n

C+E

1 .1 3 4

15 d

VIIIA 4

0 .9 2 7

4 .5 6 8

9 .4 1 3

8 5 .0 9

n

C

1 .1 3 1

—

VI

1 .8 6 3

5 .6 4 9

S+D

—

1 .9 1 0

5 .5 8 4

0.3 7 9

9 2 .1 4

Viz

1 .4 1 7

5 .0 3 6

3 .5 1 0

v iz

1 .0 3 9

4 .9 3 0

7 .2 7 2

1 .2 9 4

—

1 1 .0 3

8 7 .6 8

X+B

VIHAi

1 .0 7 8

2 .5 0 7

1 0 .2 6

8 6 .1 4

SS.DX+ SS.BC

Y III^

1 .0 0 5

3 ,2 9 4

9 .9 9 0

8 5 .7 1

VIIIBg

0 .9 3 3

4 .2 0 8

9 .6 8 6

VIHB 3

0 .9 2 6

4 . 220

VIIIAs

0 .9 1 1

VIIIA 3

7IIIA

A ...

OUibO^. 5B.jp0

B . . . A2 SO4 C ...

—

TL; 204

—

—

—

B

1 .0 7 3

53 d

9 0 .0 4

. SS.B0+ Si5.ES •?

B

1 .0 9 3

40 d

8 6 .7 6

19

B

1 .1 1 9

21 d

D . . * C11SO4 . 'H 0SO4 . 6HgO

E . »• iS. . .

CUSO4 . ilc; SO4 . 6Ep 0 s o l i d S o lu t io n s

H . . . BjpO

'Ih b le XIX c o n tin u e d on p ag e 77

77

UTiHLB XIX. (C ont *d) CuSOA-ELRSOA-grSOA-HpO. 25°

Data f o r J a n e o k e P r o j e c t i o n

Tube No.

V

S a tu ra te d S o lu tio n . vft. > p e r T o ta l S a l t s GUSO4

H r S 04

8 6 .9 4

1 3 .0 6

Tube Mo.

CuS04

Iv;:;S04 —

S a tu ra te d S o lu tio n - t . ft pear T o ta l S a l t s

v im

2lgS 0 4

1 0 .5 0

% S 04 8 9 .5 0

86 . 1 G 1 1 .9 8

1 .9 4

v i i i a -l

7 .7 8 6

1 8 .1 1

7 4 .1 1

V;

8 6 .5 2

9 .6 3

4 .8 6

V U IB j^

7 .0 3

2 3 .0 5

6 9 .9 1

V3

8 5 .3 7

7 .0 0

7 .6 3

VXIIBg

6 .2 9

2 8 .3 8

6 5 .3 4

VIIA

8 6 .7 1

—

1 3 .2 9

V IIIB 3

6 .2 3

2 8 .4 5

6 5 .3 2

V I I /^

8 6 .7 0

1 .0 3

1 2 .2 6

VXIIag

6.12

2 8 .9 2

6 4 .9 7

VIlAg

8 2 .0 5

.8 9 3

1 7 .0 6

v iiia 3

6 .0 9

3 0 .0 7

6 3 .8 4

VIIA 3

8 1 .1 3

2 .6 7

1 6 .2 0

VIILA4

6 .2 1 8

3 0 .6 4

6 3 .1 4

V II^

8 6 .7 7

1 .1 2 4

1 2 .0 9

VI

2 4 .8 0

7 5 .2 0

—

VIIBg

86.11

2 .5 3

1 1 .3 6

VI1

2 4 .2 9

7 1 .0 2

4 .8 2

VIj

1 4 .2 2

5 0 .5 5

3 5 .2 4

VI 3

7 .8 4 7

3 7 ,2 3

5 4 .9 2

V1

77jS. Q u a s i-T e rn a ry . ,y..tei

Tube Ho. 8

.Jt.

Cu. X>4 .lip . Oa-CuSOayTlpltodrK:-0 ,2 5 °

G ccrdex O rig in a l GufX-4 apSQa HrXOa

S a tu r u t ed C«SP-4 % * 4

7 .1 6 1

4 .9 3 6

7 .8 1 6 ~

't,

S o l u ti o n ^£004

3S.

D e n s ity 1 .0 9 3

5 .3 8 1

1 0 .3 2 9

7 .9 0 1

8 .3 5 8 .7610

4 .8 6 5

5 .1 4 2

0 .3 6 8

8 .8 9

i .in . 1 .0 9 3 i;* Q Oont

1

1 6 .0 1

y

1.002 10

2

7 .6 7 1

9 .8 5 2

— 7 .8 4 7

1 .5 2 3

1 5 .0 3

Y

2

7 .4 4 1 1 4 .0 5

y

7 .4 6 9 1 0 .8 0

Y

7 .3 3 4

2 .2 8 8

5 .7 4 2

4 .9 2 6

0 .6 7 5

15.81 1 .0 9 4

4 .7 1 4

0 .9 8 0

2 4 .2

1 .0 9 5

3 .9 5 0

3 .4 2 0

2 .4 7 5

5 7 .3

1 .0 9 2

6 .5 5 3

—

2 .7 6 8

3 .1 1 5

7 4 .5

1 .0 8 8

0 .4 6 8

5 .1 4 9

9 6 .1

1 .0 7 3

5 .6 4 0

9 6 .4

1 .1 3 4

4 .6 5 8 9 .0 3 2

—

1 .2 9 0 5 .6 3 6 7 .2 9 3 ——

——

9 .6 0 13

4 .7 6 3

0.8G8

3 .0 1 1

12

—

9 .4 3 8

2 .0 0 5 11

0 .4 8 4

3 .2 5 8 3 .6 4 9 7 .5 0 9

3.548,

Z

6 .9 9 1

0 .3 9 3

Y

9 .9 8 9

4 .1 0 0

15

2 .8 6 9

0 .5 2 0 7 .5 6 8

2

0 .9 9 6

2 .7 5 5

Y

9 .9 6 1

6 .7 7 7

16 Y

2 . 407

—

7 .6 1 5

1 .8 7 1

1 0 .0 2 . . . CuS04 . 04 y . . . 0u >o4 ■n * ^c 4

88 . . . .

S o l id S o l u ti o n > CuSO^.'H 0SO4 Ti e in b o th . . . 35 days

78 TABLE XXI 3GI.IL SCLU'IIuL Li13 'IlilBUTIGK Gu30/|. TJ.'; 3O4.—CuSOa . (HE4 ) ?■304.-H;:' 0 , 25'

Tube Ho.

M ole F r a c t i o n OuSO^. TI^SO^ I n L iq u id

ilo le I n a c t i o n OuSO*. !!■- 80 4. I n S o l id

a

.0051513

.0309

3

.0 1 9 6 8

.132

4

.05961

.352

5

.1505

.6 9 0

6

.5e73

.9 2 2

GuSO*. TLr-S0AaCu3GA

0a -I L 0 , 25*

9

.0891

.162

10

.158

.2 7 3

11

.221

.389

12

.497

.7 2 8

13

.6061

.0 5 3

15

.8 3 0 3

.9 8 0

3he m ole f r a c t i o n in t h e l i q u i d i a b a a e d on t o t a l s a l t s .

79

I s o th e r m a l e v a p o r a tio n s O F ig u re 4 i s a s c h e m a tic J a n e c k e p r o j e c t i o n , r e p r e s e n t a t i v e o f e q u a te r n a r y a y s te u s i m i l a r t o t h e tw o q u a te r n a r y s j s t e a s which w ere in v e s t ig- t e d .

F or t h e ;u rp c e e o f d is c u s s in g t y r.ic o l

is o th e r m a l e rr-ra r; t i o n s , c e r t a i n re g io n © , s u r f a c e s , a n d s p e c i a l r e g io n s a r e l i s t e d on f i g u r e 4 .

The c u rv e s on f i g u r e 4 r e p r e s e n t

s o l u t i o n s n a tu r e te n w ith two s o l i d s o l i d p h a se s a r t

lia s e s .

On c u rv e I - J th e

A and a s o l i d s o l u t i o n a lo n g l i n e D -k.

On

c u rv e G-F t h e s o l i d p h a s e - e r e u s o i i d solution.tfL ong 0 - 1 and a s o l i a s o l u t i o n a lo n g 1 .ne C-B.

The s u r f a c e s on f i g u r e 4

r e p r e s e n t s o l u t i o n s s a t u r t e d w ith only one p h a s e .

S u r fa o e I

(3 ,C ,D ,F ) r e p r e s e n t s s o l u t i o n s s a t u r a t e d w ith a. s o l i d s o l u t i o n a lo n g B-C.

S u r fa c e I I ( G ,H ,F ,J ,I ) r e p r e s e n t s s o l u t i o n s s a t ­

u r a t e d 'w ith a s o l i d s o l u t i o n a lo n g D -h.

S u r fa c e I I I ( A , I , J )

r e p r e s e n t s u s o l u t i o n s a t u r a t e d w ith A.

Hie c o u rs e o f

ev u p o r t i n a , d u rin g w hich t h e l i q u i d and s o l i d p h a se s a re a t e q u il ib r i u m , w i l l b e d is c u s s e d . D uring is o th e r m a l ev p o x t t i o n s , s o l u t i o n s a lw a y s change i n th e

i r e c t i o n o f d e c r e a s in g v a p o r ; r e s o u r e .

The d i r e c t i o n s

o f d e o ro a a m g v a r o r p r e s s u r e - r e t h e srir.e in b o th q u a te r n a r y s y s te m s .

tit .th e

T h e r e f o r e , f i g u r e 4 i s cii l i c a b l e t o

b o th s y s te ra s . I f a s o l u t i o n , 'whose s a l t ■r e p o r t io n s l i e w i t h in R egion I ( B ,C ,’0 ,£.) i s e v -r.o r t e d , th e f i u a l s o l i d

.i x tu r e w i l l c o n s i s t

ISOTHERMAL EVAPORATION

R egion I T r a p e to id R egion I I T ria n g e S u rfe o e l BCOHF S u rfa o e 11 gHFJI S u r f a c e l l l A IJ S p e e la ) R egion 1 S p e c i a l R egion 2

BCDE ADE

HFE

DQH o

5i

A.

The errews in d iv a te th e d ir e c tio n of deoreaoiitg vapor p ressu re

FISURE 5

—t

F

e

»

79-A

o f tw o s o l i d p h a s e s , w hich a r e s o l i a s a b . t l o n e . p r o p o r t io n s o f th e c o n s t i t u e n t

The

iih y u ro u e s u i t s o f one

s o l i d s o l u t i o n . . i l l be r . pi-osexited by a p o in t on th e l i n e CD, a n d th o s e o f t h e o th e r s o l i d s o l u t i o n ( h y a r o te d ) on t h e l i n e D -ii.

I f n s o l u t i o n , .h o s e s u i t p ro o r b io n a

l i e w i t h in r e g io n I I (a ,D ,L ) i s e v a p o r a te d , t h e f i n a l s o l i d m ix tu re w i l l c o n ta i n ;.ur e A and a n o lid s o l u t i o n o f h y d r a te d s a l t s

U and A, whoso s a l t p r o p o r t io n s a r e r e p ­

r e s e n t e d by a

o i n t on 1 . ne '0 -ii.

a s o l u t i o n i n R eg io n I

m u st d r y up on c u rv e F-G, w hich i s t h e o n ly c u rv e i t w i l l rea c h . J-I,

B ut, s o l u t i o n s i n R egion I I m ust d r y up on c u rv e Those s o l u t i o n s i n s p e c i a l r e g i o n 1 f i r s t r s o c h

o u rv e F-G, th e n le a /W J it, e n d f i n a l l y r e a c h c u rv e J - I . S in c e t h e r e i s no i n v a r i a n t p o in t s a t u r a t e d w ith t h r e e s o l i d s , no s o l u t i o n y i e l d s a m ix tu re o f t h r e e s o l i d s on e v a p o r a tio n . The f i r s t p h a se w hich

i l l b e d e p o s it e d upon p e rfo rm in g

a n is o th e r m a l e v ep o r t i o n , w i l l depend upon w hich s u r f a c e o f s a t ­ u r a t e d l i q u i d i s f i r s t n e t w i t h , when th e s o l u t i o n becom es s a t ­ u ra te d .

'ih u s, i f t h e s a l t p r o p o r tio n s o f a n u n s a t u r a t e d s o lu t i o n

a r e r e p r e s e n t e d by a

- o in t w i t h in t h e b o u n d a rie s o f s u r f a c e I (13CGHF),

t h e f i r s t s o l i d p h ase t h a t w i l l p r e c i p i t a t e w i l l b e a s o l i d u t i o n on l i n e B-C.

s o l­

I f t h e p o i ;t i t w i t h in t h e bounds o f s u r f a c e

I I ( G ,E ,F ,S ,I ) th e f i r s t s o l i d phase t o

r e o i p i t a t e w i l l be a

s o l i d s o l u t i o n a lo n g D - l, and i f t h e i n i t i a l p o i n t l i e s w ith in t h e bounds o f s u r f a c e I I I ( A ,I , J ) , t h e f i r s t s o l i d p h a se t o p r e c i . i t ; t e v. i l l b e A.

80

T y p ic a l is o th e r m a l evapoi" t i o n s o f .s o lu tio n s whose s a l t p r o p o r tio n s ai e r e p r e s e n t e d by p o i n ts i , 4 w i l l now be c o n s id e r e d . hen a lr e a d y become

R, o,

% on F ig u r e

Tr* l i e s on a l i n e th ro u g h Pg and

It, i s f o r t h i s r e a s o n t h a t

when th e s a t u r a t e d

s o l u t i o n r e d i e s l g a se co n d s o l i d s o l u t i o n pg p re o i m i t a t e s . I h e s a l t p r o p o r t io n s o f t h e t o t a l m a lts p r e s e n t , a r e s t i l l y\0w t6-*n*+ffc r e p r e s e n t e d by p o in t ?•, ,.h io h l i e w ith in t h e t r i a n g l e ah o se /(

th e

FI GU R E

a p e x e s P « , pj:., a n d p ;', r e p r e s e n t t h e e q u ilib r iu m p h a s e s . Upon f u r t h e r ev ap o r- t i c n t h e l i q u i d p h a se

V% • nd t h e s o l i d

p h a s e s p£ and p£ w ill e h qge i n t h e d i r e c t i o n o f t h e a rr o w s . In th e

r o c e s s , t h e q u a n t i t y o f t h e l i q u i d d im in is h e s a s t h e

q u a n t i t y o f th e s o lid .- i n c r e a s e s . th e d i r e c t i o n o f t h e orrov.'s,

As th e t r i a n g l e ...oves i n

c o .ies t o

b e c r o s s e d ( o r sw e p t)

by t h e l i n e c o n n e c tin g t h e . 01 i d s , and a t t h i s p o in t t h e qu; n t i t y

o f t h e l i q u i d becomes z e r o .

Thus, t h e l a s t tr> oe

o f s o l u t i o n w i l l d is a p p e a r e t Pg l e a v i n g a m ix tu ro o f s o l i d s o l u t i o n s P 3 aud pg, whose a e i t p r o p o r t io n s a r e r e p r e s e n t e d by t h e p o i n t F ^ . S im ila rly

-e may t r e e t h e c o u rs e o f t h e e v a p o r a tio n ,

s t a r t i n g w ith p o in t Qq o a f i g u r e 6 . Qp t h e s o l i d

h a s o s a r e qp a n d q * .

Qg s o l i d p h a se qg d i s a p p e a r s .

-hen t h e l i q u i d r e a c h e s ..hen t h e l i q u i d i..a c h e s

'Ihe s o l u t i o n now moves a lo n g

t h e d o t t e d l i n e and i s s a t u r a t e d w ith cue p h a s e , a s o l i d s o l u t i o n b etw een qg a n d q,^.

hen th e s a tu ra te d s o lu tio n

r e a c h e s Q4 a n o th e r s o l i d p h a se ; u r e A p r e c i p i t a t e s .

Uhe

s a t u r a t e d s o l u t i o n no.- moves a lo n g t h e c u rv e a f tw o f o ld s a tu ra tio n .

vhen

eoiries t o be sw ept by t h e l i n e c o n n e c tin g

s o l i d A a n d t h e s o l i d on A-H, t h e l i q u i d v a n i s h e s . a t Qg l e a v ­ in g a m ix tu re o f tw o s o l i d p h a s e s , p u r e A and 3o l i d s o l u t i o n q5 , whose s a l t p r o p o r tio n s a r e r e p r e s e n t e d by p o in t

00

UJ

M