Studies in the application of extraction methods to analytical chemistry

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stu d ies on th e AmxoAixcnf o? B x x tw m a s m m o m to « m O A I - 0imi.3TRY

A D is s e r ta tio n

Submitted to the Grad.us.te Faculty o f the Louisiana S tate U n iversity and A gricultural and I'eohanieal C ollege in p a rtia l fu lfillm e n t o f the requirements for the degree o f Doctor o f Philosophy in The Department o f Chemistry

by Jack Kenneth C a rlto n B .3 ,# C entenary C o lleg e, I 9^2 !i*% , L o u isiana S ta te U n iv e rs ity , 1949 Ju n e, 1951

UMI Number: DP69352

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion.

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MANUSCRIPT THESES U npublished th e s e s su b m itted f o r th e m a s te r ^ and d o cto r* s d eg rees and d e p o s ite d i n th e L ouisiana S ta te U n iv e rs ity L ib ra ry a re a v a ila b le f o r in sp e c tio n * r ig h ts o f th e author*

Use o f any t h e s i s i s lim ite d b y th e

B ib lio g r a p h ic a l re fe re n c e s may be n o te d , b u t

passages may n o t be co p ied u n le s s th e a u th o r has g iv en p erm issio n . C r e d it must be g iv e n i n sub seq u en t w r i tt e n o r p u b lish e d work* A l i b r a r y w hich borrows t h i s t h e s is f o r use by i t s c l i e n t e l e i s ex p ected t o make s u re t h a t th e borrow er i s aware o f th e above re s tric tio n s . LOUISIAMl STATE UNIVERSITY LIBRARY

AOimowL^Dam’W 13*o author w ishes to ex p ress h i s s in c e re a p p r e c ia tio n to Hr* P h ilip W. West f o r h i s ad v ice and a s s is ta n c e as d ir e c to r o f t h i s research* Ho i s very g ra tefu l to Or. J* L* !£., Erickson, Dr* Max Goodrich and Dr-. Gunther Siohorn fo r th e ir h e lp f u l su g g estio n s i n th e p re p a r­ a tio n o f t h is manuscript* So w ishes to acknowledge the f in a n c ia l Sid provided by th e O ffic e o f Naval Research. Ho a lso w ishes to acknowledge th e encouragement o f h is w ife , Mary 3&len9 to whom he la e s p e c ia lly g ra tefu l fo r ty p in g th e d i s s e r t ation * He would Ilk© to ta k e t h i s o p p o rtu n ity to ex p ress h is d eep e st a p p r e c ia tio n to h ia m other, Mrs* J* K. O a rlto n , f o r h e r h e lp and in s p ira tio n .

table of

©ohtm ps

CHAPTER X* I I*

PAOS I n tr o d u c tio n

X

An Experim ental Survey o f th e E x tra c tio n o f M e ta llic Complexes w ith O rganic S olvents

8

E xperim ental

XIX,

D iscu ssio n o f R e su lts and C onclusions

12

Bibliography

26

The E x tra c tio n o f head Io d id e w ith M ethyl Iso p ro p y l Ketone

IV ,

^2

S p e c if ic Spot T est f o r Gold IMploying Par&roa&ni lin o H ydrochloride

V, V I, V II,

7

y*>

E x tra c tio n Pi p o t f o r Spot T eat A nalysis

*>4

Summary

?5

V ita

?6

ill

U3T OF TABLES $A8&E

X. IX* XXX. IV .

PACE S o lv e n ts Uaed i n th e E x tr a c tio n itu d y

15

C o n d itio n in g Agents Used i n th e E x tra c tio n Study

16

M etal Io n s In clu d ed i n th e E x tra c tio n Study

11

E x tra c tio n s Bnploying Potassium Io d id e a s C o n d itio n in g Agent

V.

E x tra c tio n s Sftploying Assnonium T hlooyanate ae C o n d itio n in g Agent

vx.

E x tra c tio n s HJaploying H ydrochloric Acid as C o n d itio n in g Agent

V II.

m

23

E x tra c tio n s Employing p y rid in e as C ondition­

25

in g Agent

iv

ABSTRACT? A Bystem&tio i n v e s t i g a t i o n has boon mads o f th e e x tr a c tio n , o f m e ta l­ l i c s a l t s and complex®© by o rg an ic so lv e n ts *

The c o n d itio n in g ag en ts

employed in this su rv ey in c lu d e d a th y lo n e d i a n in e , ©thylcnodiam inet© tra& c© tia s o ld , rcanr&tol, h y d ro c h lo ric a c id , potassium iodid© , ammonium th ie c y a m t® , p y r id in s, p e r c h lo ric a c id , a c e tic a c id and malonio acid*

Th© s o lv e n ts

used w ere n -b u ty l c h lo r id e , petroleum e th e r , benaene, n~arnyl a lc o h o l, c h lo ro ­ form , m ethyl iso p ro p y l kotano, iso p ro p y l e t h e r , butyraldehyd© , carbon t e t r a ­ c h lo r id e and e th y l a o e ta te *

.Methyl iso p ro p y l koton© and butyr&ldehyd©

were found to be vory good s o lv e n ts f o r th e e x tr a c tio n o f m e ta llic com plexes. Only th o se s o lv e n ts used which co n tain ed oxygen were found to e x t r a c t th e complexes in c lu d e d i n t h i s study*

S ev eral e x tra c t!o n e war© d isco v ered

w hich hold prom ise fo r a p p lic a tio n i n q u a l i t a t i v e and q u a n tita tiv e a n a ly s is * The e x tr a c tio n o f lo ad io d id e w ith m ethyl iso p ro p y l fcoton© has boon th o ro u g h ly in v e s tig a te d a s a p a r t o f th o se studio©*

I t has boon found

t h a t when le a d s o lu tio n s a re t r e a te d w ith a la rg e excess o f potassium io d id e and a d ju s te d to th e proper a c i d i t y , lead io d id e can bo e x tra c te d w ith m ethyl is o p ro p y l k etone *

The e x tr a c tio n perform ed i n t h i s manner

was 91% com plete in a s in g le pace*

I n te rf e re n c e s wore k e p t a t a minimum

through th e u se o f a p re lim in a ry e x tr a c tio n which was a p p lied a f t e r t r e a t ­ in g th e aqueous s o lu tio n w ith ammonium tin.ocyanato and h y d ro c h lo ric a c id . Hie p e r a ro s a n ilin o h y d ro c h lo rid e t e a t fo r gold was ren d ered s p e c if ic f o r t h a t m etal by e x tr a c tin g an a c id ic aqueous s o lu tio n of a u r ic c h lo rid e w ith e th y l a c e ta te *

In t h i s manner, gold was se p a ra te d from th e platinum

m e ta ls , a group which c o n s titu te d th o p r in c ip a l in to rfa ra n c © in th e

v

d e te c tio n o f gold*

A fte r th e s e p a ra tio n o f phases th e organ!o la y e r was

evaporated* ta k e n up w ith a few drops of w ater and a p p lie d to th e re a g e n t on Spot t e s t paper*

The t e a t was found to be s e n s itiv e to [3 ge^maa o f gold*

A d ev ice was needed f o r th e ra p id ex tr& o tlo n o f sm all volumes o f aqueous s o lu tio n s w ith o n ly a few drops o f o rg a n ic s o lv e n t.

An e x tr a c tio n

p i p e t was designed and p rep ared and hao carved quit© w ell i n t h i s c a p a c ity .

nrrRODUOTXon The u se o f e x tr a c t! o n te ch n iq u es a s a moans o f e f f e c ti n g a n a ly tic a l s e p a ra tio n s h as f o r many y e ars provided th e chem ist w ith a very u s e f u l t o o l , and e s p e c ia lly i n re c e n t y ea rs have th e s e tech n iq u es become g e n e ra l­ l y popular*

The in c re a s e d i n t e r e s t i n t h i s f i e l d can be a t t r i b u t e d i n p a r t

t o th e ap pearance o f a c o n s id e ra b le number o f e x tr a c tio n d e v ic e s , such m th e c o u n te rc u rre n t e x tr a c to r s d isc u sse d a n n u a lly In th e review a r t i c l e s o f O rsig ( 6 , 7 , 8 ) f and th e development o f numerous c o lo r im e tr ic proced­ u re s based on th e e x tr a c tio n o f o rg a n ic -m e ta llic complexes ( 15 , 35# 24, 27, 52)*

The e x tr a c tio n o f in o rg a n ic complexes a ls o ho ld s many i n t e r e s t ­

in g p o s s i b i l i t i e s , and th e a p p lic a tio n s o f th o se e x tr a c tio n s to a n a ly tic a l s e p a r a tio n s , a s w ell as to c o lo rim e tric p ro ced u res, a re to be found th ro u g h o u t th e l i t e r a t u r e .

I t i s w ith th e e x tr a c tio n o f in o rg a n ic complexes

t h a t t h i s in v e s tig a tio n i s p rim a rily concerned. B efore embarking upon a d is c u s s io n o f th e exp erim en tal work and th e r e s u l t s o f t h i s i n v e s tig a tio n I t n ig h t be w e ll to d isc u s s th e v a rio u s c la s s e s o f e x tr a c tio n s and th o u ses to which th e y have been put* G e n e ra lly , ex tr a ctio n s can be c l a s s i f i e d acco rd in g to th e fo llo w in g categories*

liq u id - liq u id , liq u id - s o lid , 11quid-g a s and s o lid -gas*

Be­

cause t h is stu d y was Gonflnod to liq u id -1 1 quid system s only b r i e f m ention w i l l be mado o f tho o th e r c l a o s if l c n t i o n s . Probably th e most f a m ilia r type o f liq u id - li q u id e x tr a c tio n being employed In a n a ly tic a l c h em istry i s t i n t in whioh a p a r t ic u la r component o f an aqueous m ix tu re i s e x tr a c te d i n to an o rg an ic s o lv e n t w ith tho form­ a tio n o f a h ig h ly co lo red o rg a n ic phase which l a th e n r e a d ily adapted to («

(2)

ft p h o to m etric a n a l y s is .

In auoh ft iaann®r c o b a lt can bo rioter mined, a f t e r

t r e a t i n g I t w ith a.mmonium th io o y a n a ta and e x tr a c tin g i t w ith arsyl a lc o h o l (1 8 , 19, 38)*

th e blu© c o lo r o f th e th lo o y a n a tc complex i s s u f f i c i e n t l y

in te n s e to p ro v id e an e x c e lle n t means o f do to r a in in g c o b a lt colorim etric** a lly .

S im ila r ly , i r o n can be e x tr a c te d as th e th io o y a n a to complex by a

m ixture o f amyl a lc o h o l and e th y l e th e r ( 55 > 55) I th e blood re d c o lo r o f th e o rg a n ic phase i e th e n measured p h o to m e tric a lly a f t e r th e s e p a ra tio n o f p h a se s,

The tM ooy& nate o f molybdenum can be e x tr a c te d by normal b u ty l

a c e t a t e w ith th e fo rm ation o f & redd!sh-brovm co lo r*

A c o lo r im e tr ic do*

torrid.nation o f molybdenum based on t h i s e x tr a c tio n has boon re p o rte d by James ( 15)*

O o lo rim o trio procedures have been developed f o r th e dotorn&n-

a t i o n o f b ism uth, b oth as th e th io e y a n a to complex ( 5^) and as th e io d id e complex (1 2 ),

I n th e form er procedure amyl a lc o h o l was employed as s o lv e n t,

and i n th e l a t t e r a 5*1 m ix tu re o f amyl a lc o h o l and e th y l a c e ta te wm u sed . One o f th e more o u tsta n d in g examples o f th e u se o f e x tr a c tio n tech n iq u es i n c o lo r im e tr ic procedures i s th e d e te rm in a tio n o f chromium by e x tr a c t* i n g th e b lu e p er chromic a c id and Treasuring th e i n t e n s i t y o f th e b lu e e x t r a c t . Amyl a c e ta te has been used in a procedure re p o rte d by Bishop and Dwyer (1 )• There a re two p r in c ip a l advantages o f employing an e x tr a c tio n procedure i n c o lo r im e tr ic a n a ly s e s .

F i r s t , i n many oases th o d e s ire d component la

se p a ra te d from 'color masking o r r e a c tio n maoking in te r f e r e n c e s 5 and second, sm all amounts o f m a te ria l can bo e a s i ly c o n cen trated from r e l a t i v e l y d i lu te s o lu t i o n s ,

dxcept fo r th e o ilm ln a tio n of c o lo r masking in te r f e r e n c e s , th e

a d v a n ta g e s l i s t e d above a re m a n ife st i n a l l procedures employing e x tr a c tio n

te c h n iq u e s ,

The second group i s com prised o f e x tr a c tio n s whloh can bo u t i l i s e d a l s o t o i s o l a t e a d e s ire d component w ith o u t depending upon th o develop** mont o f a c o lo r*

th o im portance o f suoh a g e n e ra l s e p a ra tio n tech n iq u e

I s becoming in c r e a s in g ly a p p a re n t, and by employing © xtr& otlon in con** ju n c tio n w ith complex! ng ag en ts many o f th e q u a l ita tiv e and q u a n tita tiv e a n a ly s a s ©f m etallic* io n s could bo g r e a tly improved w ith re g a rd to sen­ s itiv ity *

^any o f th e m etal c h lo rid e s a re e x tr a e ta b le from h y d ro c h lo ric

©old s o lu tio n u s in g d ie th y l e th e r (25)*

I t has been re p o rte d t h a t f e r r i c

c h lo r id e i s ex tract& d b e t t e r and over w ider ran g es o f c o n c e n tra tio n when iso p ro p y l e th e r i s used as s o lv e n t (9) * Uranium and thorium n i t r a t e s have been e x tr a c te d by e th y l e th e r (22)*

Sine i s e x tr a c te d by e th y l o th e r as

th e th io c y am t e i n th e d ith is o n e d e te c tio n o f aims re p o rte d by Vanes s i ( 56 ) * Mercury can bo determ ined g ra v im o trio a lly a f t e r e x tr a c tio n o f th e io d id e by e th y l e th e r (1?) * The e x t r a c t i s ev ap o rated and th e mercury weighed as m ercu ric io d id e *

Thallium l a s e p a ra te d from le a d , s i l v e r and

bism uth by e x tr a c tin g th e bromide w ith b u ty l a c e ta te (20) * Sold can be s e p a ra te d from th e platin u m mot a i n -hy e x tr a c tin g th e c h lo rid e in to e th y l a c e ta te ( 1 6 ) .

P e a tc v a le n t antim ony may b® s e p a ra te d from t r i v a l out a n t i ­

mony by e x tr a c tin g a h y d ro c h lo ric a cid s o lu tio n o f thon© io n s w ith i s o p ro p y l e th e r ( 1 0 ).

" a n ta v a le n t antim ony i s e x tr a c te d alm ost 100$ w hile

t r i v a l e n t antim ony i s l e s s th an 2% e x tr a c te d . A t h i r d group which in v o lv e s two i real so l bl© 11 q u id s, b u t whloh dooe n o t r e p re s e n t tr u e e x tr a c tio n , lo one in which a p r e c i p i t a te i s formed and i s g ath e re d a t th e i n t e r f a c e when an o rg an ic s o lv e n t l a shaken w ith t h e aqueous s o lu t i o n ,

Examples o f tho u se o f ouoh methods a re found both

w

i a q u a l i t a t i v e and q u a n tita tiv e a n a ly s is .

Ammoniaoal s o lu tio n s o f z in c » when

t r e a t e d w ith r e a o r o in a l, produce a b lu e p r e c i p i t a t e .

Th© d e te c tio n o f aino

i n low © o neentrationo i s f a c i l i t a t e d by sh ak in g th e aqueous s o lu tio n w ith e th e r , which cau ses th e p re c ip itn t© to ©ottl® a t th e i n te r f a c e (2 fj),

Mercury

i s d e te c te d by th e v i o l e t p r e c i p i t a t e produced on th e a d d itio n o f cryogenius s e n s i t i v i t y I s in c re a s e d when benaen© i a added and th e p r e c i p i ta te i s c o l l e c t ­ ed a t th e i n t e r f a c e ( 2 ) ,

N ickel i a d e te c te d as th e dimethylglyoxim© complex

w ith oaxisHim s e n s i t i v i t y whan th e aqueous s o lu tio n o f th e p r e c i p i t a te i s shaken w ith carbon t e t r a c h l o r i d e , th u s c o lle c tin g th e p r e c i p i ta t e a t th e I n t e r ­ fa c e ( 1 4 ) .

S ilv e r and c h lo rid e d e te rm in a tio n s by th e Volhard. method may employ

benzene a s a c o l l e c t i n g a g e n t to p re v e n t th e I n te r f e r e n c e o f th© s i l v e r c h lo rid e p r e c i p i t a t e i n d e te c tin g th e end p o in t o f th e t i t r a t i o n ( 5 ) .

In th o io d o m etric

d e te rm !n a tio n o f selenium , benssono i s added to g a th e r th e reduced selenium a t th e i n t e r f a c e to p re v e n t i t s in te r f e r e n c e in th e p e rc e p tio n o f th e end p o in t o f th e t i t r a t i o n (^1) • The e x tr a c tio n o f a p a r t i c u la r component from a c o lid m ixture by an o r ­ g an ic s o lv e n t p ro v id es a method o f s e p a ra tio n which i n many case s i s q u ite s e le c tiv e .

G e n e ra lly , th e tec h n iq u es involved a re tim e consuming, r e q u irin g

th e conversion, o f th e d e s ire d c o n s titu e n t i n t o th e s a l t f o ra i n which i t i s e x tr a c te d .

I n apit© o f t h i s l i m i t a ti o n , s o li d - liq u i d e x tr a c tio n s o f f e r a

means o f s e p a ra tin g some io n s whloh aro d i f f i c u l t to s e p a ra te by othor means* Lithium can be a e p a re tc d from sodium and potassium by e x tr a c tio n of tho anhy­ drous c h lo rid e s w ith arayl a lc o h o l ( 2 1 ).

The a l k a l i and a lk a lin e e a r th bromides

can be s e p a ra te d in to two groups by e x tr a c tin g tho dry re sid u e o f thect© s a l t s w ith amyl a lc o h o l ( 4 ) .

Lithium , calcium , stro n tiu m and magnesium com prise

one group w h ile th e o th e r members c o n s ti tu te th e o th e r group.

Lithium s te a r a te

0) o*n be determined tur b idim etrioa 11 y due to i t s I n s o l u b i l i t y i n amyl a lc o h o l, in which th e oth er a lk a li m etals are s o lu b le (^6)#

M ille r and Tr&ves (21)

rep ort th e sep a ra tio n o f calcium and sodium from potassium by th e e x tr a c tio n o f th e ir p erch lo ra tes by amyl a lc o h o l, potassium p e rc h lo ra te b ein g in s o lu b le in the a lc o h o l.

Aluminum n i t r a t e con be s e p a ra te d from b ery lliu m n i t r a t e

by e x tr a c tin g th e s o lid mixture o f th e s e s a l t s w ith amyl a lc o h o l.

B eryllium

n itr a t e i s so lu b le i n t h is s o lv e n t, whereas aluminum n i t r a t e i s n o t (5) • The e x tr a c tio n o f a p a r t i c u l a r component o f a gaseous m ix tu re by p assin g th e m ixture over a s o lid adsorbent i s a f a m ilia r la b o r a to ry p r a c tic e which ex em p lifies the s o lid -g a s type o f e x tra c tio n #

The u ses o f calcium c h lo rid e

and as sa r i t s i n a d s o rp tio n t r a i n s to remove w ater vapor and carbon d io x id e , r e s p e c tiv e ly , a r e good exasaplaa o f th e eolld-*gas e x tr a c tio n system ( 29 ) . The a n a ly sis o f gaseous m ix tu res by means o f th e G reat a p p a ra tu s (*P) p ro v id e s the b e s t example o f th e liq u id -g a s e x tr a c tio n system .

An a lk a lin e

p y ro g a llo i s o lu tio n i s used to e x t r a c t th e oxygen from a gaseous m ix tu re o f known volume, and potassium hydroxide s o lu tio n i s employed to e x t r a c t carbon d io x id e from tho m ixture.

Oar bon monoxide i s e x tr a c te d by moans o f a so lu ­

t io n o f cuprous chlorid e# From th o p reced in g p aragraphs th o im portance and u s e fu ln e s s o f e x tr a c tio n te c h n iq u e s i n a n a l y t i c a l s e p a ra tio n s con r o a d ily bo s e e n .

Th® stu d y re p o rte d

i n th e fo llo w in g pages i s th e r e s u l t o f a sy ste m a tic in v e s tig a tio n which was mad© i n an e f f o r t to o b ta in in fo rm a tio n re g a rd in g tho e f f ic ie n c y o f com® o f th e s o lv e n ts which have n o t boon e x te n s iv e ly employed I n e x tr a c tio n p ro ced u res, and to d is c o v e r, i f p o s s ib le , some e x tr a c ta b lo in o rg a n ic and o rg an ic s a l t s o f complexes which m lght fin d u se In a n a ly tic a l determ ination© *

The s o lv e n ts

(