The Detection and Determination of Antimony by Means of Rhodamine

Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1951 The Detection and Determination of Antimony by Means of Rhodamine B William Cornelius Hamilton Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Part of the Chemistry Commons Recommended Citation Hamilton, William Cornelius, "The Detection and Determination of Antimony by Means of Rhodamine B." (1951) LSU Historical Dissertations and Theses 7975 https://digitalcommons.lsu.edu/gradschool_disstheses/7975 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons For more information, please contact gradetd@lsu.edu THE DETECTION AND DETERMINATION OF ANTIMONY BY MHN.NS OF RHOBASHtlE B A D is s e r ta tio n Subm itted to th e G raduate F a e u lty o f th e L ouisiana S ta te U n iv e rsity and A g r ic u ltu r a l and M echanical C ollege in p a r t i a l f u l f il l m e n t o f th e req u irem en ts f o r th e degree o f D octor o f Philosophy in The Departm ent o f Chem istry by W illiam C ornelius Ham ilton B S F n k lin and M arshall C o lleg e, 19A2 M.S L ouisiana S ta to U n iv e rs ity , 1950 June 1951 UMI Number: DP69353 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 UMI Dissertation Publishing UMI DP69353 Published by ProQuest LLC (2015) Copyright in the Dissertation held by the Author Microform Edition © ProQuest LLC All rights reserved This work is protected against unauthorized copying under Title 17, United States Code ProQuest ProQuest LLC 789 East Eisenhower Parkway P.O Box 1346 Ann Arbor, Ml - 1346 MANUSCRIPT THESES U npublished th e s e s subm itted f o r th e m a s te r 's and d o cto r* s d egrees and d e p o site d in th e L ouisiana S ta te U n iv e rs ity L ib ry a re a v a ila b le f o r in sp e c tio n * r i g h ts o f th e author* Use o f any th e s is i s lim ite d by th e B ib lio g p h ic a l re fe re n c e s may be n o ted , b u t p assag es may n o t be copied u n le ss th e a u th o r has given perm ission* C re d it must be g iv en in subsequent w r itte n or p u b lish ed work# A l i b r a r y which borrows t h i s t h e s is f o r use by i t s c li e n t e l e i s ex p ected t o make su re t h a t th e borrow er i s aware o f the above re s tric tio n s * LOUISIANA STATE UNIVERSITY LIBRARY 119-a ACKNOWLEDGMENT The a u th o r w ishes to e x p re ss h is s in c e re a p p re c ia tio n f o r th e ad v ice and p a ti e n t a s s is ta n c e o f D r P h ilip W* W est, who d ir e c te d t h i s In v e s tig a tio n * He i s a ls o g r a t e f u l to Dr* K G Keen, Dr* G* Lee, and Dr* A I Le Rosen f o r t h e i r h e lp f u l s u g g e stio n s, and to Mr* Hans S u te r f o r th e a s s is ta n c e and advice which he gave H is h e a r t f e l t thanks go to h is w ife, C lau d ia, f o r h e r c o n s ta n t and f a i t h f u l encouragement* ii TABLE OF CONTENTS Page I II III IV V V I INTRODUCTION REVIEW OF TUB LITERATURE EXPERIMENTAL DISCUSSION OF RESULTS AND CONCLUSIONS STOIARY 33 36 BIBLIOGRAPHY A il 38 LIST OF TABLES T able I Page Scope of I n te r f e r e n c e S tu d ie s 14 II D ata f o r C o n c en tratio n Curve (F igure 3) ằ ã ô 20 III Data f o r C o n c en tratio n Curve (F ig u re 4) 22 Iv LIST OF FIOORLS Figure Pag© 1* L ig h t A bsorption Curves ô ô ã ã A bso rp tio n Curves f o r S e v e l C o n c en tratio n s o f Antimony * • * , • , * * ằ ô ã ã 3* C o n c en tratio n Curve A, C o n c en tratio n Curve • • 5* C olor S t a b i l i t y o f Antimony-Rhodarainâ B Complex 6* ã ã ã ã ã ã * 17 ô 21 ã • • • • • • 2A E f f e c t of Acid C o n cen tratio n Upon O p tic a l D en sity • • 26 7, E f f e c t o f Io d id e C o n cen tratio n TJpon O p tic a l D en sity * * 27 E f f e c t o f Rhodamine B C o n cen tratio n Upon O p tic a l D e n sity • • • • • , • • • • • # • • 28 Polarograia© o f V arious Antimony S o lu tio n s • • 32 9* v • • ABSTRACT A method f o r th e d e te c tio n and d e te rm in a tio n o f antimony has been developed, based on th e e x t r a c t a b i l i t y o f antim ony ( I I I ) a s th e io d id e i n to benzene* The benzene e x tr a c t i® su b seq u en tly re a c te d w ith an aqueous s o lu tio n o f Khodamine B, th e v i o l e t complex o f antim onyRhodamin© fo rc in g in th e benzene la y e r As a sp o t t e s t f o r antim ony, th e procedure i s s p e c if ic and s e n s itiv e P o te n tia l in te r f e r e n c e s a re removed by c o n d itio n in g th e t e s t s o lu tio n w ith sodium e u l f i t e and u re a not c ritic a l* The t e s t c o n d itio n s a re A complete study ©f in te r f e r e n c e s has been made The l i m i t of i d e n t i f i c a t i o n I s microgram o f antimony a t a c o n c e n tra tio n l i m i t of Is 300,000 The spectrophotom © trie p ro ced u re, based on th e same r e a c tio n s , p e rm its th e d e te rm in a tio n of microgram q u a n titie s of antimony* The method I s p r a c t i c a l l y s p e c i f i c , bism uth i n te r f e r i n g on ly i f p re s e n t In h ig h c o n c e n tra tio n s An in te r f e r e n c e study of the same scope as above h as been made The r e l a t i v e a n a ly s is e r r o r f o r te n micrograms o f a n t i ­ mony i s t 5*0$ Th3 c o n d itio n s o f a c id ity and re a g e n t c o n c e n tra tio n s have been s tu d ie d and have been shown to have wide ran g es o f to le r a n c e The c o lo r formed i s s ta b le f o r a t l e a s t th re e and o n e -h a lf h o u rs A p o laro g p h ic study o f the mechanism in d ic a te s t h a t antimony i s e x tr a c te d i n th e t r i v a l e n t s t a t e vi INTRODUCTION In re c e n t y e a rs th e d e te c tio n and d e te rm in a tio n o f sm all amounts o f antimony has come to he a m a tte r of c o n sid e b le p r a c t i c a l im portance* Antimony, which has been known sin c e a t l e a s t 3000 B C , i s w idely d i s t r i b u t e d , bo th i n n a tu re and in man-made products* Many thousands o f pounds o f i t go each y e a r in to th e p ro d u ctio n o f hard le a d (12% a n t i ­ mony), used in th e p ro d u ctio n o f sto g e b a t t e r i e s , b u l l e t s and shrapnel# I t i s an im p o rtan t c o n s titu e n t o f b e arin g m etal and o f type m e ta l, and w id e ly used a s a pigment in th e p a in t and ru b b e r in d u s trie s * I t s com­ pounds a re o fte n used In th e tre a tm e n t o f t r o p i c a l d is e a s e s , th u s f r e ­ q u e n tly n e c e s s ita tin g i t s d e te rm in a tio n In b io lo g ic a l samples* D e sp ite th e s e f a c t s , th e tra c e chem istry o f antimony h as n ev er been w e ll developed The w r i t e r , upon observing t h a t microgram q u a n ti t ie s o f antim ony ( I I I ) a s th e io d id e could be e x tra c te d i n to benzene, h a s c a r r ie d o u t th e p re s e n t stu d y i n an a tte m p t to a m e lio te t h i s s itu a tio n * 34 ap p ly in g th e technique o f e x tr a c tio n , s p e c i f i c i t y has been a tt a i n e d The g r e a t s i m il a r it y o f th e a b so rp tio n curves ob tain ed on th e one hand by e x tr a c tin g I r i v a l e n t antim ony a s the Io d id e in to benzene, and r e a c tin g i t th e re w ith Rhodamine B, and on th e o th e r by re a c tin g p e n tav a le n t antim ony i n aqueous s o lu tio n w ith Rhodamine B and c h lo rid e io n , in d ic a t e s t h a t th e c o lo re d compounds formed a re c lo s e ly s im ila r i n n a tu r e No evidence f o r th e s tr u c tu r e of t h i s compound had e v e r been found by p r i o r i n v e s ti g a t o r s , although a tte m p ts had been made to so The w r i t e r 1s p o la ro g p h ic I n v e s tig a tio n seems to show stro n g evidence t h a t th© antimony in th e benzene e x tr a c t i s in th e t r i v a l e n t s t a t e Curve •A** i n F ig u re i s th e curve d e sc rib e d by K o lth o ff and Lingane (3 ) f o r antim ony ( I H ) in N s u l f u r i c a c id Curve WBW in d ic a te s th e e f f e c t o f having antim ony ( I I I ) p re s e n t a s the io d id e complexj th e de­ com position p o t e n t i a l o f th e antim ony i s so s h if te d t h a t th© re d u c tio n b e g in s Im m ediately upon th© a p p lic a tio n o f p o t e n t i a l to the system Io d id e io n , i t should be n o te d , i s p re s e n t h e re in c o n sid e b le e x c e s s I n curve *C% where th e e x tr a c tio n has been perform ed, i t i s noted t h a t a g a in th e decom position b e g in s im m ediately b u t t h a t th e s te p h e ig h t o f th e cu rv e i s c o n sid e b ly g r e a t e r In t h i s case io d id e i s n o t p re s e n t i n e x c e s s , having presum ably been e x tra c te d only in th e s to re h i ora©t r i e r a t i o re q u ire d by th e antim ony te tra io d id © complex I n curve "D" an e x ce ss o f io d id e was added to th© s o lu tio n a f t e r th© e x tra c te d benzene la y e r had been fla s h e d o f f T his excess of lodid© should be q u ite c lo se to t h a t e x is tin g in curve W B% and th e s i m il a r it y o f th e magnitude o f th© s te p h e ig h ts in MDB and ”BM in d ic a te s t h a t t h i s i s dependent upon th© amount o f excess io d id e p re s e n t 35 While benzene has been v ery fr e q u e n tly used to e x tr a c t m e ta llo - o rg a n ic complexes, th in ap p ears to be th e f i r s t tim e i t has been used I n an a n a ly tic a l procedure to e x tr a c t an In o rg a n ic compound o r complex, Th© f a c t t h a t th e e x tr a c tio n f a l l s o f f sh a rp ly when th e ic d id o /a n tin o n y m olar r a t i o becomes l e s s th an lO tl i s w ith o u t obvious s ig n if ic a n c e j c e r ­ t a i n l y antim ony does n o t p o ssess a c o o rd in a tio n number o f ten* fto r does th e Rhodamine B/antim ony m olar r a t i o f o r maximum o p tic a l d e n s ity g iv e any c lu e a s to th© n a tu re o f th e co lo red compo nd formed* The e f f e c t o f th e a c i d i t y upon th© e f f ic ie n c y o f e x tr a c tio n i s n o t s u r p r is in g , t h i s b ein g th e r u l e r a t h e r than th e exception* As to th© procedure i t s e l f , th e re i s much to recommend i t* Th© f a c t t h a t th© antimony © p re s e n t i n th e t r i v a l e n t s t a t e i s a con­ s id e r a b le advantage* Maren ( 35 ) has shown r a t h e r c o n c lu siv e ly t h a t i n o x id iz in g antim ony ( I I I ) t o antimony (V) a c e r ta in amount o f a n t i ­ mony (IV) w i l l p robably be formed T his nchem ical e n ti t y 11 a s Maren c a l l s i t , i s n e a rly im p o ssib le to o x id iz e , alth o u g h i t i s e a s i l y reduced w ith s u l f i te * Maren was a b le to circum vent t h i s d i f f i c u l t y only by u sin g p e rc h lo ric a c id a s an o x id a n t, a s te p which many a n a ly s ts p r e f e r to avoid* A c e r t a i n tedium I s involved i n e x tr a c tin g th re e tim e s, b u t t h i s i s more than compensated f o r by th© immense g a in in s p e c i f i c i t y The c o lo r s t a b i l i t y , th e adherence to B eer1© Law, th© wide p e rm issib le c o n c e n tra tio n ran g es o f a c id , iodld© , and Rhodamine B, the low c o s t and s t a b i l i t y of th e re a g e n ts , and the accuracy and p re c is io n o f th e method a l l recommend i t s w idespread adoption* SUISaRY 1* A s p e c if ic sp o t t e s t procedure f o r th e d e te c tio n of antimony h as been d ev elo p ed , baaed on th© e x tr a c tio n o f antimony ( I I I ) a s th e io d id e complex i n to benzene, and consequent re a c tio n o f th e e x t r a c t w ith a s o lu tio n o f Rhodamine B Th® re a c tio n p roduct I s formed in th© hen- gene l a y e r , to which i t Im p arts a c h a r a c t e r i s t i c color® T his procedure w i l l d e te c t w ith c e r t a i n t y a s l i t t l e a s microgram of antim ony, a t a c o n c e n tra tio n o f I t 300,000 S p e c if ic ity i s gained by th e a d d itio n o f u re a and sodium s u l f i t e , and by v ir tu e of th e e x tr a c tio n procedure* Based on th e c r i t e r i a o f s e n s i t i v i t y , s e l e c t i v i t y , ease of perform ance, n o n - c r i t i c a l n a tu re o f t e s t c o n d itio n s , and c o s t, s t a b i l i t y and a v a il­ a b i l i t y o f re a g e n ts , i t ap p ears su p e rio r to any t e s t y e t re p o rte d f o r th© d e te c tio n o f antim ony On th e b a s is o f th e above r e a c tio n , a spectrophotom etrxc proce­ d u re has been d ev ised f o r th e e s tim a tio n o f microgram q u a n titie s o f antim ony Antimony ( I I I ) , in 1*3 s u lf u r ic a c id i s re a c te d w ith p o ta s­ sium iodide* The r e s u l ta n t io d id e complex i s q u a n tita tiv e ly removed from th e aqueous phase by e x tr a c tio n w ith th re e su c ce ssiv e p o rtio n s of benzene The benzene e x tr a c t i s re a c te d w ith an aqueous s o lu tio n of Rhodamine B, th e c o lo re d r e a c tio n product being formed in th© benzene l a y e r , which i s removed, d ilu te d to volume, and measured a t 560 m i l l i ­ m icrons* I n t e r f e r i n g io n s , i f p re s e n t, can be s u c c e s s fu lly e lim in a te d by tre a tm e n t p r i o r to e x tr a c tio n Bismuth i s th© so le ex cep tio n to t h i s , and I t s in te r fe re n c e even a t a r a t i o to antimony of 100s1 I s 36 37 n o t se rio u s* At 10 raicrograms of antim ony th e r e l a t i v e a n a ly s is e r r o r o f th© procedure i s fuCfo* The s t a b i l i t y o f th e c o lo red compound has been studied* The con­ d i t i o n s of a c i d i t y , io d id e c o n c e n tra tio n , and Rhodamine B c o n c e n tra tio n n e c e ssa ry f o r th e su ccess o f th e procedure have been defined* A* A sp e c tro g p h ic survey o f the e x tr a c tio n in d ic a te s t h a t bism uth i s th e only o th e r m etal e x tra c te d under th e c o n d itio n s given* 5* P o la ro g p h ic s tu d ie s g iv e evidence t h a t th e antimony i s o re s e n t i n th e benzene e x t r a c t 5jei th e t r i v a l e n t s ta te * BIBLIOGRAPHY I* C a i l l e , M, and V ie l, B* A new re a c tio n o f th e a lk a lo id s and th e p re p a tio n o f th e io d o s tib n a te s o f th e s e su b sta n c es in th e c ry s ­ t a l l i n e s ta te * Compt* rend* 176, 1156-59 (1923) C A* 17s 2289 (1923) C la rk e , S* G*, New method f o r th e c o lo rim e tric d e te rm in a tio n o f sm all q u a n ti t ie s o f antim ony and t h e i r se p a tio n from tin * A n a ly s t, 53, 373-9 (1928) C A 3369 (1928) 3* D avidson, J , P u lle y , G f f., and C a s s il, C* C* D eterm in atio n of antim ony in t a r t a r em etic spray resid u es* J* A ssoc, O f f i c i a l Agr* Chem, 21, 314-18 ( 1938) C, A, 32s 5988 (1938) 4, D av ies, W C* Scheme f o r q u a li t a t iv e a n a ly s is employing sp o t t e s t s , J Chem, Ed* 17 j 231-4 (1940) C A 34* 4685 (1940) 5, D obbins, J , T, and S o u th ern , J A* Semimicro scheme of q u a lita tiv e a n a ly s is J Chem* Ed* 19s G„ A, 37s 479-82 (1942) 47 (1943) 38 39 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i n phenols -with antim ony p o n tac h lo rid e P h a rs Z e n ir a lh a lle 75s C A 28s 13 £9, 50 (1934) 1955