Synthesis of some New Inorganic Ion Exchangers and their Applications in the Analysis of
Organic and Inorganic Substances of Pharmaceutical Importance
DISSERTATION SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS
FOR THE AWARD OF THE DEGREE OF
M^^ttX of $ililQ£(Qpt)P IN
APPblED CHEMISTRY
BY AbKA GUPTA
DEPARTMENT OF APPLIED CHEMISTRY FACULTY OF ENGG. & TECHNOLOGY
ALIGARH MUSLIM UNIVERSITY ALIGARH (INDIA)
1991
,0y' ''-• //'V
/ / -
DS1718
H:GOPAL VARSHNEY M. ic. Ph. D.
READER DEPARTMENT CF APFUED CHEMISTRY
Phone : (Of f . ) 0571-0042
FACULTY OF ENGG. a TECHNOLOGY ALIGARH MUSLIM UNIVERSITY
ALiGARH-202 002 llNDIAj
jum 1 , 1991
TO WIIOM IT MAY CONCERN
T h i s i s t o c e r t i f y t h a t t h e v;oiic ojahocliecl
In t h i s t h e s i s ie t h e o r i g i n a l contr lhufc Ion erf
the candidate
/ K.G.YAU;;H:EY
SESIDKNCE : SHANTI SADA S. PAKKi SARA!. ALIGARH -202 001
C O N T E N T S
PAGE
ACKNOWLEDGMENT ( i )
LIST OF TABLES ( i i )
LIST OF FIGURES ( l i i )
CHAPTER - I
INTRODUCTION 1
REFERENCES 14
CHAPTER - I I SYNTtlESIS AND aiARACTERIZATlON OF
ANriMONir(v) ARSE NO SILICATE CATION
EXaiAMJER
INTRODUCTION 18
BXPERmEITTAL 19
RESULTS AND DISCUSSION 45
REFERENCES kS
ACKNOWLEDGMENT
Aclcno^jledging g r a t i t u d e at t h e end of a t a s k wel l
accomplished i s an e x l i i l a r a t i n g e x p e r i e n c e . Alone i t hecomes
d i f f i c u l t t o achieve our goa l s because we not only need
educa t iona l guidance but a l so moral support which i s r ece ived
frot; t h e v a r i o u s sources around u s ,
I wish t o o f f e r w thanks t o Dr , K.G.Varshney (Reader)
fo r h i s exce l l en t gu idance , cons tant support and t r u s t throughout
the course of t h i s s t u d y . I am a l s o thankfu l t o Prof , K,C.Singhal ,
Prof, K.T.Nasim and Prof , M,Ajmal f o r providing t h e r e sea r ch
f a c i l i t i e s .
Thanks a r e a l s o due t o Dr . A,A.Khan (Lec tu re r ) f o r h i s
kind h e l p and coopera t ion and t o ny s e n i o r s for t h e i r a f f e c t i o n a t e
and f r i e n d l y behav iou r .
I have no words t o express my i n f i n i t e g r a t i t u d e t o ny
p a r e n t s fo r t h e i r b e n e d i c t i o n s and cons tan t support during t h e s e
s t u d i e s . I a l s o warmly acknowledge ny b r o t h e r s and s i s t e r s who
c o n t r i b u t e d a l o t with t h e i r a f f e c t i o n and moral support t o me.
/ ALKA GUPTA /
( i )
LIST or TAffi S
m*
1
4 ION EifitsiAiCf'' CM^crrr A!® AKPEAHA?? ' or
hmimm^) mspm^x%.\^M^. AFPRR HPATI^O TO
VAiifoiTs Timppw'nTfws pcm o?f iwtm fcm h m«??«? 23
5 cfVRCf or i iUAwr oo?JORsrRA3n»N ON tw IOH
6 »N RxaiAicr. csiimcn^ or mstmm^)
An^»>SlLIOMT IPOl VARIOUS ITTAL 90UniW?fe 38
7 goiAjniLifY (»• hmrmw^) AiisRi«siLiovr IH
iixffi!nrm' SOIM: : E?S 3Q
9 sa fAums w smr KTTAL mm OH ANTBIUIVCV)
9 x-HAT POKTmn fiwrmcrio!? DATA ptm omrsiJAiftir
10 izmitr aBtABATio!® OF iKTAi. mm kmtmm mi
Aiimio!«r(T) Aaas^msiLioiTi? 35
<u)
hmtmmt9) AIIS^KOSILIC^W^ OPTION sicHA?orB %
CATXUW |?aaKA»Ea XH VAfllUJS AL^LX If'TAI, im?au a i B S S9
K GOUAN&EIi AT TABIOUS ySHI^IlAyimES 36-37
a W?A OJHVr E\m AM?B'^JK(V) A£iaE?*#aliaa 4 a\4lw>;
7 x-HAY DxnmAOTXO!! PAfTimH Or Amummiv)
AR3BJ»SlLiaa!m JHO
Oa(IT) Ofl A!TO^?«'(V) An^msTf^OAT?^ <^ril«»3B lit
9 A nisr?oc{iAii sfQf^xii} mm son BisaiMCT? CAS^^cxf ii?s o r
l i EPTEOSr o r HBATXm UN rUE XOH WSmM^Vi Ql£AOm
op VAiUaiS ION R^OJAMlFas Va
(iU)
c II A y T. n R - I
m I II i i i i It I M l
for t?»e atnclcnt t o perform expertc^mts «o thot h<? t^/ o'^tnln rn
twaronoBs of tho sc lMi t l f lo ciethaO oml heeow^B la ia i l lnr uith t!ip
le^.tool patb tha t atioaia b«» followod In forisln" a t?ioorv'»
Anoly t i i^ l ebttwAQtry 1» a branch of ctiCHBlstiy irtild: aeai-s -. rit*
tho anolyois of the subs tances . I t I s often oorril.*c>r«»i] t o bo n
©otlrely B^rvta^ a c t i v i t y thot la Intontletl to provtOf* q^oTltatlvp
ovoluotlon and quantitotivf* ossasrs of oubtdttod a a r r l o a . In
inUtiotrial s l t t i t i g s onolyals I s Inoroasi^igly tM?iiii* roqi i roa IT
eaiFinoora and aoor©ostofrly \rf ninmlntBi, AnolytlfstJl i^'i^ytnintB,
thus , have t o osplaln tho t^ocslGal tmnoforwatloM taEjl 5r placf
In El nivoa react ion t o engineers thrtnic'^h i^icciicnl ui.sc.ni -IUOJ;,
AQQlytlool isothaOB xmy bo both inatrat;«ital . and ii'jti-i..^\rittmitoU
Althoijf.h the forr/»r have o groot |)otositlal in thf? ciujf>r.•
tc»<^aolor:y, th© l a t t o r tmvo t h e i r cntti iKportonoo 'Jjoont; >•• of t-uo
reasons , F i r u t l y , thoy oro dhioarx^r oml sooursUly, thr?:. -iorn t-r-
baais otajKlardloatiori of any tnotnic:<*at anj hmicp nr< .•.?;'/
Quporlor in aconmcy,
Th<» variotss amslytlonl ewt.hoaa w!slc4i ar« rwu-iro'tv 'IB^^C
for scparGtlon of sat^stancoe ar«> ti!!r> followlrif'S
( i ) C3hrOEat0f?;rB|Jliy
(2) Ton ©a rfianfi;©
(3) ?*r©olpltottoo
(4) fiolvont c::stroQtlon
(5) '^Icetroiieposltlon
(6) Mo lys is
(7) - l e o t r o c^irocsnt^rartsy.
Out of t!»ea<i ©©thotls, t^nroBEStc^.ropI^ I3 th^ wovt
©^©natvely uaoi] v e r s a t i l e and stepl<? tec^miqao, l a l t i i - a iy , ao
th© tiaiio sogKcats, th© t®eCinlq«o was UIJCHJ for tli<» ai*;x^nation of
ooloarea eob3t««o«»9# But no«-a-d€©^s I t ia useJ. for botJ:; tfi€»
©olourea oaa oolourleso sulistanc^a, f t crasi ti«» uti'J.i;'.<>{=.;. to
s«]^r©te a l l ty^Mss of Ea>l©oulos nrarU^C i'roBs t'w small'"ssi (l' ,.[)_„,.•;
to th© l>lgEeat (S^'rotoia, aaoloie aoi t la) , TIIKS lasat ^>i;:.u.; fiociot
footuriii of ttJf tc<}fmlao<» t s tha t ttif* rjuaatit i^a -i:, rirr/l " a . i ' .
d ie ts ls ts , I t a ortgtuti tor was a lluaslao Ijotaatst Meioc? ')•M',; t /i
t?ho, in 19OG aoc»ia.«tt5tolly a?»|ioratm'l o»d isola tPu iljc .r .r-r' -p. o-n,
yellow pL-^c^Rto of d i loroi t iy l l Isy oolucvn ttusors-tiosi tityo<^tio(rrOi :•<.)- .
IPhe ls«y f<^tar€!>s of l-!»f 8w«»tt'a t^eitnlque w«»r« the api-lleotlO;, oi
tfj© cdacture an a tmrrof^ tnttityl sjone and i t a ap^^lor'-R'^n\ ari
etiromnto^nsr^ ty " tfi«» app"*-lent ion of o fr»3?i BO^vr-rt, "•l*t-; r^«i-v ,
bus, howe^ror* tji»!i»0 05Oclifi<»ii1 in EsotF;- w iya r«stu1tir¥': ir- '?.•'><* diff'»r*^-'t
tyi>«6 of dhroRato^rojiiy, as DOEmsriaevl In Tab'lo-i .
Ion «isahaii{',«» Qlirois3atE^,rsfliy in th© terc; ?3»c»=-a \/'=jf>!-.i ion
f*z^imw,<? ploys an IriJortatit ro1.«» in the c^-irosi50rcr,ro::-f:.le prfxifs-J .
fh0 loti ©ai ian -!-© la i t e r t a l »ay bo orgaoie or iaon",rint<; in na tu re ,
Aa ton <»^chan^e material lo tisu oao whid» oontoi:u> aor;* lonorrr . ' -
rroiir'9 tn I t s E a t r l s csoaoiatinr!, of a hinh lEOleeulor \tr^i' n
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P 2
12
-> 3 O'-* c*a,» 4M S C
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o a
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E it ?€ o o or:* p c > G IN ^ !*
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c o > ti«
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t:, c
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fmi^imt^ i s RMierall!/ e t t r l b i i t o t l t o ThotsiJOoo (2 ) , nn l '.fay (3) -wrso
r«»I»c«^«cl i n t^5^ t h s t irfien a s M l i s tr«fltf»<S wi t ' ' 0lthr»r ataesonltw
atslft^tc o r eE«ioni«ci oai^oaat© ©ost of tti© aE?csanio 1 - nii'^or^ml anc
oaloiuEs r f t l eased . I t wao lat<»r |>rcrred !)?;• ^ic^iom (4 'I ttiat t h e
o a s o r p t l o a of lows trot- graima natci'r by c l a y s Qotrntitn'^'-e n
rftveralblf* recioti(»3.
OotrsKiif^rcial dc*velo;iCJ<*iSt of t l ie ion <»30hc«ir:?''5*y ^^'^ ' tj atxii^
00 yoai'S latf?t' whon O-ans (5) SF'3thrf8i2S€*<i saat^^rlaia fr^jt: olGy, iiarK-
and sotliuB oartiOfmt«!, Howevory n o t a r a l uooli toi* G^ •I; .:•: :rc--'rj&;.> •
wniro the* f i r s t t o T)< «»aEt•c»n8lv« ls'• usou mi an inv'.nstrlnl aor.if^, v^r
f i r s t opi)lio«tiof3 of ion essi!lia!a5,or woa for t h o i«r{,o;H^' o... a u i t o a i ;^
wa t e r , y/hcu.} o a l c i u o waa rmviOvoa frue; wa te r anu ow Cir-ivr l^nt nr-t!:jL!*
of aodiut; r e l o a s e d , DcOauBe of t h e l i t d t o C e«;ciit;.i!;/- oa , . - e i ty JI
t h e sjotiaral a o o l i t o s t oQuipneot haa t o be IQIT:«> nui. rorr 'aorat lot)
v#fy f requent ^ i t n soStPuitig of o largfif q u a n t i t y aS' Imr.. t??^*rr
was r o ^ i i l r c ^ .
In 1933 Ailacsj a:)Q nolc^<»s ('j) ayot?;©BiK<^'! tj)c s'ir-.^t
r«stnoaci t v n e of o cntio^'- ©iiohnnf^^r fror- i'45<»rJO'l nni^ fort'rt'»:'r»':' • !f,
f.«tfflr, n»Moe"tlo sjyothcoljml r ^o in s frut;: polystyrrr^c (7 , 7'IJO
polys tyrouo r<»sta6 havt? a h igh ciimrdo.l and i:5eo!ionio:'l -.it-ntiiUty
in a d d i t i o n t o th<» wtiJ© i)?? raa?'0 of t ' s ^ i r Q;>rlic«'-:!l'Ut,y,
Tlio fundot^ntol i - r inc tp tos a?ji.t©rlyl::t^ o i l to^? cifha-i- '
nppl icnt tor ia s r ^ ' b a a ^ a on a f<nj slc^i^lo f a c t a l a v o ' v i r: c' o o:ie^'>?v-^
rpoot iOKa sijo!' a s I
( i ) Pt|i.iivaleiice or eaobaaj-e.
(2) Self^otivity or a f f i n i t y praferfi'ctoej-i of tsjo escii^^ti/or for -JVi^^
l<m relative? t o onotijer, iiioliKlivr: eaoca iu wlu ju tiie cllfff^ri,.;
affinities® of t!j<? iOH6> are laadifiea. lay tlu-" a-je of e-jr - ir^^ir^-
(3) SK}n;>0;j &scluci(m • ffJc? a b i l i t y of tfin $'03i:i £0 (\;ic^ : := lov
but not , in --oaeiral, undlsooelatetl siiljgtaneoa•
(%) ' cr<»#*ninf»; ^fftHSt - 1*fj*> I n s b H t t y of ^fir^r lnrf»o lonn or
polyptors t o IKJ aliaorbiSil t o an DfiproetsMic? c??rt;«>nt.
(5^ 1)1 fformless In ritgi^tion ftitcs of 3l>sor1W-i •i.ib-ito. : ** ..: oi/i
s oolu^D prlesarity o r©flootl«m of Mtfrnrmm^s ia .- ?fi? 5' ,v%
(6) Tontc laQbillty m a t r i e t e t l t o tiw oaw!fesi>p®«i.)?t Um- an<l
co^mter loos only.
Ion KSC3lJi:>r» o la solid&i Ics tho |>raef*a;;} in ^itich '•';»o'jnrii;'- v
loas af l iU" enlarge taltea plaee Ij^tweon tuu iJfKi;-]! ; . o.ie of ,;?U; h
la Q l lqa id and tlm Othnr i0 a s o i i J ( i . e# ly .. osclUia'; *'-;-: (S ; ,
eontaot witfi a solution eontoloitif; B lojus, tben t:-:o e.io'mi- r* ;'"o:,?'-"
sjay T>*» rov>r€*ofnt-0d tiy
{n«r i«dio*3t«>s the? nolia fijaoo ©«•.! "^ atanas for t!ir> -- '.ri : .V
Ion eadumigo 18 o revorsibl© i^roceea ami an cKioilibrtuii
l a nvfsitUBlly sot up In whleh aoise of the ; iotis, i n l t l liy ijr^o t
'alUMi © ayotem coaaigta o l a solut ict i oontaialtir- ii^Hfr 't i Imc.
in e<}uilit»riaiti with the so l id eaichanger i?hoa<? tlnr>r<! Is ; i>r'5»f(»rf»«-
t i o l G-sehonge of ions 1? tho. esdbani^er, f h l s i>ros'C»rty u ' fchc
int<»rtat i s fmovn as •Solect lvl t j r" irtiic^ i& of th»> fundf«>ntnl
ieport(B)0€! in a l l i t s a p j l i o t l a i s . I t tt©t<>xiE:lnos trio 'iftcl'H«*v
of G prooess in uhlob tlu© ion ei:icrf>0ti(;er i s t o rocovor itma frur r
d i l u t o solut ion oiia onac with xHiich the tooa oaii :>o aubuoiiuoatlv
rensoved fror; tfer ©xohanc^r ffinsi*. Tt al-' o Ht»t r^rtjinr:} tb •
roadlncss with wJjidi two or core aubstcjjocis, furtlHi iJ»is> of tlv^
l i k e diixr^.e, oon bo soparoted liy ion ojsohnt^.e obrotatu rait iy,
Tbc s« loo t iv i ty of a i^ i*^ o-Mrfiair,**' i e Ittflutsaceu t^ tlir mifcurr*
of tbi? eaMjhfflnslag iona mich oa o!iar?,e, siase i>olarlaablllt.v jmd
t iydmtian. In d i l u t e 90luti-t?a ions OMnyttvi e hlfrher (^icfrr^.o a *?*
s t rcoc ly re to ined Iw t he o2eoh£ifi «gr tban the ioos of a Xmif*r olmv'*^.
For eaaiaplff in Dowr>3f»50f tfer* rfitimtions are in t he or«if»rif
file sf t leet ivi ty a l so itior*aes«s with ttm ineroase in tlip a tocio
nuB^^r of t h e icms in tho snts^ pc^rlodie group such ant
• • 4 • 4-Li ^C ^^ -^ J ' < '- - < C»
B« <;r ^ ^C! Ga <: 3r <^ Wo <^ fm
P < CI < ! * < ; I
7
For i « i s of tfe« »a«» valeaey Imt aiffermut iMrioJie croui-
tli« aeleertlvlty ean b© a|.'t*rOwa«3etiHl troa t h e i r ao t tv l t y coftf-fi-inni!
Greater the a c t i v i t y ooeffleiietit, tbe g rea t e r l a tho © ofaiisig??
potent io l* targo ions , 01 r^jially tfee organic oaes, art' aft ©a
oasorb©a atr<xif:l$? but f u l l e3<*(4Hi © oapaolty laey not. l><" obs^j-V'Oti,
t a genera l , tlio higher i t s iJOlarlaalJlllty eua low«»r Itt-n a^s r c* of
hydi^ t ton , the laore atroiigl^r ti/lll ao ion be a«l»orbcd. Vor eatai-u.'lA,
th© adsorption tnerms^m trots 14 t o Ca in Ktil<*i a^^prec of
byarat ion d«»orenai0g in tb.e aarse' (Ure«tioij# Also, tli.- rwiar lsat im^-/
iaoreasoo with oij Inoreasc In th*» atoiBtc ni»j#>€r,
The? natur© of th© oatc iaHftor oiao atfmjts tlv-^ »<^lfiitivlty
in two ways i t l a effectml \sy tli<? tiaturo of the funt^iE'-i^jtal <';rotr|.=
and tli<» «3ef re© of cross llnJalqg of tin* e3Lcitii^t^'.m^» "jio's-nor'Ars
eontais ing woa^ly aclcUo asViJ t*«>a!i:ly tioolc grouj-tj ar«'' hlrjity
9i*l0Ctlv© toworda hyarof^oo loan maX hyavo^l lo;-is»
Tb^ ion oawhat^ip t«<3^jnlque l a b<»ooc3li9f" poi'ulor -lay ir/ ir*v
bf!-cau3<» of i t s v e r s a t i l i t y ©ti-u a t ep l lo tey in a|>oratlan, .rhf»
oquipeitont roquiroa la 3lCu>3^ « i;loa;^ «.ul,3€» or a IrtSFr tt*"- \r!ildi l =
c i©«:' and readi ly oval l t ibio. Hoot of t?if> ion «?soijsuv.:<;* i?«» Jor«»tlwn;;,
oao be L-erfort^il usii-if oeiall OOIUMVS* And ol:":o, s-.m '>,';coi,l<>fic
seporsitlor»i o n bo ac^sieved tijtjit ^ ar<? Dot pcmoibie -jy ti-.-
oomret?tional d i i i t t l l n t i a i ricytiioaa t>(ioat.53<> mmll cJi-ini;; are
egtjivolf^nt to s tarrro nnt^t^r ox oqt i l l ibra t iaso l.f", tiU-urotlOi'Vi
p l a t en . Tb«» laost strictft^^ faotaro of thlf? t<*<#5nt--::nj 1 •• t?»a?: i t
onij 0ort)lnp (soslly with o t h ' ^ isod«*riK oDalytlonI t<*o;iJI ;:H»S t?ur*" <v
3pf?otroiiiOtor«*try, poloro^rcii^uy arsu !3fH>t t<*s6t. I» tn^ H'»l'! o*
8
Inorgonlo dietJlstry i t Qcm ootmine with raaioc^ti*ic tc»d5niMn<^4?,
On tti« tMUdig o t t h e i r 09ei|>O3ition oad oat ore i o i 0Ji^iQ:r<^
ttaterials tse^ bo o l o s s i t i e a as orgauiQ atul loott ionic. urgonic
x'Qsias or« superior In tUeir (^eoioc^l tm<k esociiatilci I a t a b i i i t y ,
ioo easdianr.© r a t e and v o r s o t l l l t y * However, s incf the^/ doeoti'O .
a t oleirated tec:p<*rotQr<?o aa^ mickrr strotjf? rod la t i cna , an lDtf>r<?9^
In inorganic ion eatc^nafrora was revived• At proacnt t$j< occjr •
tti«»tr ot;n posltto?i lo t h " f io l a of ion © i>|jiitif.p oUros. fiti^nr^l^w
(0 -*9) , <iytrt^<»tlc ioortrmite tor? est^Qvmmm lam'' 'i "' e?n«-"i .t -f?»a
in to t\it> folTowinf? 0lx •"fi'' <5i! ** f,rou|>sf
( l ) Insoliiblo o d d OQltsj oi polyvolmit cietola.
( I I ) ilydroas oiiiaeo of i>olyvalent pe ta l s*
( i l l ) Bolts of h«*teropoly ooltls,
( tV) Inaolubl© hf*3acyonof*»rrfit09(TT )•
( V) iyutl ir t lc oluclno o i l lent eo ,
( V I ) Miooellanooui5 iaorRonic €txeiinnf',er& f> f, M^^roarbi-o ao^t
ami potaBfilfTD fjolyiitioait^otos,
Inaoluble aciti sa!.ts of i>olyvalptat ewtals a r - '•.;::: icot
Ijy cot:fblntM :. ttj'- osldm-i of ciitio;- I I I , IV, V arKi VI o:' ::h- IKTI->•.: u
tal>le. Such laritoriala hove iKjno i>rei'Uroc iij'' i.,.i.;x ;; t - • ; ;uric,
orsonlo, raalyljctio, t u t f o t i o , aati twtiic aoU vuua. ic acl t t '
airootiliaa, tit«nit!F;, t i t i , thoriuri, ccrivjK-., irur;, ehrut,;l'.5t:., niu;l.nr;,
t an to luc , btats-ttb, nioizol, colmlt e t c . Onr tacl:; c»?. uc:.^i . w'l r; •>'•••
on tho aa l t 3 of ix^lyvnl*^)^ tTrrtals BH tliej- ;>a3£iotr c-u 'ti LJoli>jiootv?r/
t<m «5a8cliinnr;«» ivopipyttos.
9
stttdifiNa wi t eHn l Ijoth iB th€» otorphoo« {»if} oxyatnl l inp fortm^
I t ba© t>««o us<ia t o var ious f t e l a s , spec i a l l y , the oaon r f t r i t !
{l>-2l)» I t boo a l so t>o«ii uQoa in t!i© portaMt* rwnal d i a l y s i s
(22)• Present ly , t t t}«iiig as«<i to a<pt©ii«»it9 (23 i f^fr i/!5icli a
|«it«»nt bas lM?c« granted* l^esajrcmes of Inorgwinic ion e::ic?'.snf ?aPQ
are a l so Important froci th@ Inaua t r io l point of vim i2k).
Antieorroslve uaa i t lvos havo hfim prc^imreiS frot iaorganie ion
exdiaQg(*re, A tiJin e^ct^t of easeljang^r pr?^i^roa l? / US'DOUV and
n<m£Q (25) «^iieii «h«ai pieced orotaad a s t o c l tulw* 1113* 1: 0.1 in fcho
cartU oota oa ^irot^ctor* aooont eppl ioot ioas of liiorgcjiic too
easoiiaiigcrG iaolaao the onalyola of gtiarcjacoutioals, drtt a, rooiia,
a l loys and |>eatlcitloa (26-31) soc© spot tcjGt ©etiioOs bovo ols^o
boeo a0volop©a (32) for t^^ quiefe iil«otifIc&tion o£ c ^ a l iotm.
The Qpplieotiofia of 1cm ©att^Joagors In th© fi i ' lu of
Heilletne aad rharKooeittlC!! to iua t ry a re v o r l ^ anc poiiy, Thr>
r(>«siiral of a©tc»torioao Ions tiy ©axSieof o la tm «»srtat>ll9hr><i t:'ract,le'
for tb0 roDOvol of h?»«vy isotnla, T!i<» laost ooff'CK>n Iti U!i< r-rf-*
Ofiganle e28dlifu:3 f>re iriiloh !iy thf?t?o<*lv<?a do ntat tn<i'i€fo finy tOKie
MBilfestation ana a re oasl ly roiaoveKl froc: the t)CM^ throit-h nurvxil
c^anoels lacaat for tbo pwrpose*
Tho CIIOMOOIB as©4 as E^dlOifseQ requi re hip;f> l?*vola af
staodanlQ of iiurity 03i>oolally trfioti th<^ latonaea ro':,ttc» oi'
aac?inl3tratioa i s |:«irontor®l« Ai^ l e r ^ r l t y la the i'ort-. ot hixtvy
dcftolG ^ U d t arf» ut tlinoa uaaal oontactitierrttj csjy aof?»at il)r> vf^y
imrpoae of trcatia^fit ami oa the otUor Uaau caaso (iau^fv: •-« o«?»a3
10
t s ^ i r i t i e s . 'Slip "b^st taunvm ia€*ttioc1s inoXudo the r'>j:javn« of i3<»tal
l a i s ty oaBdKan lssf th««i with tti«? not haxwfal &n«m« ' tx^ pr<;>«f>><t
stuxiy Is an attoisrt fa thtn d4s*etl<m« AntieiOHy(tO ar'T^ogtllORt*
luin Tx?(si fo\md ealootlvo for Zn" nad Fcf" onvi t h i t ?5pl-otlvlty
rjE sr find i tn tis© in rtnuovlRg ^e©e ioos t?I:t!.di oowlti '«- ??tv-t»>!; lroT>Ie
ID aoce rlmiTciccs^itle®! foitailetlooa. I t tt> prop»J9cu to stas^' the
tostieltt'-, Tjorth ao«te a«'2 cforcwio, to tli^ c":p<*rli3< jt;•• :i cir.icyil
Itlso rat/Edoe to esto?)li8h the naiiglii of oafr^ty follotrtaf; oitil/
pas*ont crj 1 aclciinistrat ion •
fbo ali^ of tti«oo 8tuki&(!io i s to explore f?irt M«r ti.u;-
pos8lMllti«« of G^mthDsiei^^ oater ia l of br^t^r ia» esuskianp^o
oSiarac3teri0tio9 and s t o b i l i t y . Aatieioay sa l t s hove rcKJolvcxl
ettcntlmi r^5C«it1y (3!H^i) i ffa Iiavo g^ona iprOEdaiai': oliorotAr-
i s t ios* Pr!O0'i3f of t h l 3 , £intiwx3^^) arsnnosillcntn is: ')o<»
tri(tHl wiiiofc 13 n asw tnorganlei ion oaotoancor oml roar.rtao'-'Q ,r?;ooo
ion oaEoiiaui e bolmvlour. Xta sytitheaig, ^^mvacitt^rizntim. aue
asuilytieal ain>liootioii9 are iU»oerib@i1 ia cliai>tor XX*
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14
3 , viQTfJ.f • and aflgr,J«, Agr»soo,Et)gl*« JUL* '^^ ( i 8 5 0 ) .
%• istat>om,n«, Awi«Fti:f9iiE«ai^«, i^og. 126 (185a)«
5« G«ii8»n«, Jatii««pr«fia»««;«cit«Lmidte0afi8ti U, Jg, 179 (lf)05).
6« A^«StB«A* and notcMiSfF.t.,, J«ii>«»Ob«e,XDa,, ^ , 1? (1955K
7» AloeUo,D«0«, !I.S«I*at«its, £ , 366, 00? (»«o<»et>'*r 36,i9Mi)»
», 566, OOS (D«o««ii>er a6,19%4)*
8 , H«lft«rlcli,!P., noo-f awlsfi«ig«", KoOraw Hill nook Co.,
lm* mM Tofit (1962)*
9« AiBI3til«tt,0»B*t <»lBoeg&QlQ Son BaBOlutiigMrs" el»»vler, London
(196%)•
10, Gt«flrfi#l<l,A«, Htaiioolla£i»Cr«!l« and Blossitir.,^MU, iv.
J«A«K«rliisfs3r «id TJIarotw, •lon- aE iaiif?© and Solv**Rt
fiartitictiott". Vol. j[, Ob. 1» Marcel OeUcer, JJew Yaik (1973).
11, 6l€iarflaia,A« (Ed.), noorganlc Ion Rjcf mtitjc l^aterlals"*
C»0 i¥os», Xno,, D00& Baton, FtorlOo (19B&).
12» Qar<i9hl,l*oheln eptd Var^hnQy.K^, (Editors), "Inoir:? Uc Ion
f xdtiasigers in Chcolo^l Analysis*, CSIC i^rao tno«e Hoea Baton,
norlOa (1991 )•
15* V«a«ly,V, acid l»©feflrek,V,, ^alaoto, j ^ ia%5 (l*T72».
!%• AllMMrtljG, an*! €Soato«tlno,!J., J,0hro!9atof,r,; jOg. *> (l97% U
15. Waltoti,n,f., A»al.Ohe»«, ^ , 39SR (197%).
16. WoUon,H.F., ibid. , 12, 52W (19?6)»
17. WaUon,II.P., iM«. , ^ , 56H (1978).
15
18, Hloiio(il,N. and Fletoiier,w,J)«, froaa,AD..fliiol»soc., ^ , 46
( I960) .
19. Hlo!m©l,!J„ S t e r l i n g , P . F . imd Oohcm,!., mjorsaaies, §g ( t % 3 ; .
20, ntrfaroo,A« and Tollo,A.» "IJarla ICidric* Just .?lucl,soo,no; ort.,
1 BE - 452 (1962).
S I . A?irlancl,=5, «ntl C*irT<*son,G., .I.Iaor«i,''^JOt.Oteci,, ^ , G' S*)
(1971).
22. Goraon,A., Bett©r,O.S, , Or©pnT»auo ,:M,, M a m t s , ! . , « s-nt^f, -u*
l fo^o l l , f ? .n , , T r a n s . A c S o c v r t l . l o t .Organs, J2» -'^'^' (t971 U
23 . H%o,K., S£nfada,Y., Kunu!)e,K, find Daf5ohl,K., Jamm r it Ant.
7317, 810 (1973).
24. RQjaii,!C«S., Bol«8,B.B., CaselOjA.J. and nrt^m&n^3«l,,
D(*salinotlo», 2» -27 (1966). 25 . frfsbotly,!. and Ronay,D., Tlung, fe l . jos , 3327 (1972)*
26. VarQhney,!C.G., Agrawal ,s . , Var0hnoy,K, miu Anwar,s.,
J .Liq .a i rora i tonr . , 8 ( ^ ) . 57D (l9S5).
27 . VarsLnc3y,S:dCf., Agrawal,B, oad Vars lm^,K. , A a a l . l ^ t t . ,
J6 (1^9), 685 (15^3).
28 . Varohni«y,K.C,, Agroual ,S. , Vor0lin^,!C., i^arrre,ti. ruui flani.-.,,
Iiadiocli©o,nQdloanal.I.??tt., 58(3)• tht ( l 9?3 i .
29 . Varshnry,.?{.(»., Varshnt^j'^K. aod Agrawnl,3. , s«»p.;.oi, ;>o^.mt?i,.
18(10). 005 (1983).
30. Vfir9hn<sy,K.G., AgTUwolj^^, and VorghnWi'.TC.. JJ(,ix>»''^'ror€ttO'^r<,.,
7(1) . er»l (1984).
3 1 . Var3hn«y,FC.G., A{T.rawal,s, and Vnr3hi}f*y,K., I M d , , 6 ( S / ,
1555 (I9f?3).
16
32« Varahfi^jKWt*., Itanl^s*, Aawar, :-» ana ^amtTEsa^u,, An I ,Lett ,>
^8 C M G ) , 2033 (1985 )•
55* At»©,M, onil n o , T . , milt .Oh«?!.«^o©,Japan, M , 333 ^1 »''' ^ U
34. Abe.r , and n o , T . , l M d „ %i, 2366 (196??).
3 5 . Ab ,W# and I t o , T . , IJlpi^n Kagalcu ^iOaahi, 52* **' ^ il'>j6)*
36. Baet8l«,Li41, and Oi^g.f)., n<»lg.latent, o49, 7 i6 ^ 1 6 ' ) ) ,
37 . Be l ln9knyo ,F^ . , fJilltolnQ,*^»j\»., onU nun<»vo,r.!i., fZ'uM: iu
?Saufe, SSSn, N«>orRiiKntrr, 12, 1631 (1970).
38« Sovl!:av,rv,G», r3ellD«kaye,I'^»A, and ftatepuvo,'\,.A , , ' 1U: ,K!I IE,
I, 9% (1976).
39 . noc<*kl,n. and l^ laer , !S .n . , Hnaio,ailB.Aota, 20, «:<1 (1973 .
^ 0 , Grir,rovo,N*y,, Hiliol* - k l l l j n . r , , n©linsI:ayo,I » » -MU
i toa l i l aa . I . I . , Flr,.IQilE., 2, 79 (l^^Sl).
4 1 , VDraluiey,IC^«, 3lianao,l3,, Uonl ,3 , aaa iroE5oaau,A,, r ' . , , o i s
T©obuol., jy[, 1527 (1902-83).
4 2 . Abe,?% and I t o , ? . , rit!ll,(^ec«SOo.JoriQn, 5 ; , !J33 (1 i6' )«
'#3. Ab©,?U ami I t o . f . , I M d . , ^ , 2366 ( l % R ) .
hh» Ab^,>1, ood XtO,T,, FfllptOiJ !£D|;foku i'*08u;ii, ^ , 11?^ Cl%6)*
<i5. na^^tsT^.LJI. ond F'(i:v'9,ru, nf^ld^l'^tmtt, Gfi9. 7'*6 (J% J.
S.ssfi, M«org^ot#r, Jt£, 1G31 (1976).
^ 7 . Novlkov,})^,, nellnskayo,! .A., Matf*rona,T^*A., l i z . v h l c , ,
II, 9* (1976).
40 , Boc©lcl,n, and I^l9«»r,tC.n,, Haaio.Ctilr^Acto, 22, "1 (t^>?j .
h9m Ortcrovtuw.S. , Nlkol»'-4{3llT,D.r., Bolln8liaynsF.A, :i=ui
Ko-^hina,!.?,, Fla.SIUia., 2, 79 (1981).
50, Rawat,J.V. and S i n g h , J , I , , Chroi?«tagro;lJio, ^ , 1 ' (l<)?;'h
17
51. aw£jt,j.}** ma s iagh. j . i . , Ami.diiis,, ^ , 58? ( i9%; ,
52, Taiiaon,s,Kr. and Gi l l , J*S« , Talanta , 12, 1355 <1>72 .
53» Q«r0»l!l,lf,, iaiiKiT,n. an<l nat*iore ,n ,5 , , Tnlmitr% j ^ , 137T
(1972).
55* Quir©sbl,M», Vorahot^slCwG, anU Fat ten ,^ ' . , J.CSjrorrit o r r , ,
162, ^ ^ (1979).
56. nowafc,J.P. ana Sln^h,!>.K., An«1 .CIili!J.Aota, 62, 157 ( 1 ^ 6 ,
57 . Tli lna,P.S, and fliridal.T.K,, J .Mqu ia (3iror=iito r , , 2» "73
(1980).
58 . Gui:ita,J.J\, Nowellt^.V,, Qort»slil,r. ana G«i*c,.A.> »,
J.Inorg.Tftiel.Oiita.. hO, 9i5 (1978).
59. '^tiro3M,ru, f&ic5ar,v. orjo afttira,!^., *l.airu»«tonT., 22» 3">t
(1972).
6 0 . QureshlfK., Gupta,J«P. and ^artaQ,V*, AauLCtiiOBj., ^ , 19< l
(1973).
6 1 . QttreslJljH. ana StUfiDr,?., J.Oieis.f^ot}.(A)» 1408 (i!)7 J.
6 2 . •'juresUljF. and Skur<ar,V., a.airO!satof*r., ^ , ' J31 Cl';7i )•
G3. if>©,A.rc. and 1>00,S,K., GhrofiatograilUo, 1^, 35^' ( I ' r ^O.
6%. t.«»iP«*r1©,tT., l,«»f#1>or<», J .Pol l ,Soc .?3i l» .Pr . , J2» ' " (l*>7G).
6 5 . rpu.'r,o,J,n. aud Klklmll ,T. , Oarp't.fJeiid^Aena.Hcl. (J 'nrls),
S o r . C , S, 26^ (1967).
6 6 . Mathow,,!., TaBdon,S.N., J*Rddiaai»il.Cli0fit., ^ , "!''» <l<)75 .
6 7 . Be,A»!t. end Cbakraborty,! ' . , 3*»|3H,s©l.Te<jlmol., jy^, i io9 1'?*
6 8 . msnPva,T,N., F l l l t0 laa ,F*A, , Bclioateaya,!-*^ • oua 'ija<*3ls.;Hr)n,
O.V., lonns^l OtHtoo lonoc^tr lyo, £ , 13 (1979>.
0 B A r y B B >. ly
18
Altlioiieii a liucge i»uriM3ty of iiun^euni: ion oatoUat ;en»
have hctn i^teveamC and atuOidd 00 far (1)^ there IQ s t i l l a
need to li«v« «Bt«rials pott8««@&£ig gooo i€NS «soiiflti ,o b^ripviour
ond tMtt«r stability* rtifthur, thf ^ ahottia lie oenfui in
poilation vttKliQai* ABtiseeer salta hava roeeived attontion a®
i>K>f|{8iiio ioe «aetibai3«tai li<»ofitia«> of th«rir good otal)tiity atio
ese«llc«it ion QOMIIOIIIIO betuivii»ir <3*9)« Th«^ havt also lio«i
praparad in oxyatollina {tJiaaos ^icth bava e omi i tieiairi,' ,
aalaetirtty for albalina aarths (10*24)• Antitaam^^^ s i l i cate
baa alioira a graoit proatlsa aa &a iaorKania ion asabai^t^r anu on
«iS)attf»tiTa attu^ liao Isa B parfomad mi tba various »sp^crts of
thla vatarial la oor lotjoratoriaa (25 )•
The praa«3it at04^ la aiead to profiara aos^ other aiitiisicmy
Tiaaed Ion astahaagare pooaaaaiag good ion emttimie^ oSiox^eteristics
for thair po8ail»la aaa ia cHonriroitei ital atudiaa* An a result
m^loaci8r(V) araaiM>oili<mta htm ^toea sQratbaaiaaa liilc^v iio&a^&tim
a good ion OJiatiaaga eai^aoliy tusd tbarc&l atabll ity, Folio^ioB
Pm^^ aiisa^ris<9 a datailad atad^ tm tbia octarinl in ror^tirC to
ita ayotbaaiat dbtaraotarisatioo and analytiaal ai^liootioos*
19
pcmi^mimh
Rgaganta
ailloctte w«r«» oMain<>d from t4>l>o»<B«?«Jl«» (Xodia)
Appoitittio
ApporctttiG osoa la t h i s sttk^ ar# gtvcai betovt
S I . Stud io anm and Its Ho^el/ ld^Q
stuoies
3* OolorlE^jtiy
4. T^^./fe.Tjl.
5. :«»aay diffract ion
jfl Mier , tlodol I*I-10, ' l l o o (louta .
Sp«et roptKit oeflt or •
caUiri fbenaobolQiHJo Kotlel 112050),
R i l l i j * X-Oay aiffrooitoii aait wlti FO-H: CC target •
Pra|>aratloa of the rtmgent aolutlooe
Daoleiolar solutions of oodiuei Reto-«111oetir» ana oramwt^
wero praparea in aet!tn#rall2©cl water (CIW) and -» nolsttion (o.lt*
of potoasiuis i;;yro«mtif9onato wao proparad In 5«SM HCI .
20
S^fnth—ia of th» too »aMt>BBgc Bftt#rtatl
A nmiber of omsplM of niitl«oiQrfr) arscnooHlcntf* v«»re
l>r«par<KI iQr vizlc^ the solationfl of soaiiua arsenate, {idtassiuir
pjrroantliDOoate mta Bodivm o«ta<->8i11«3t« to aiffercHit volune rotior
88 given in TablD»3* Tbe iG of tlio r eea l t i i ^ gel was fii ocl In tt:r
range O-i by addli% lHJJSti solotion with ooostatit sttrrin?T. Vl^»
gel thus obtained was teept for 2k hoara at rooir tc Bp rf!* s>rp
(r^30 C) end f lHerea Uy auotlon* The excess of self was rirraov^d
ly waahlng with W^ t i l l the |ir of tb© t#a»hln was 5 b**for» aryin
in an a i r oiren at %5 ۥ The arted gel was then piit in Tif / to
ohtaln grontileo of imlfom also, soitahle for <»>lni!«2 ois^ratlons.
They were oonverted Into th© ii - fore lay treating tUtis if HND«
for £^ hours with oo<moloool ^laUlng on the hauls of i t s na -Ion
onihcaiee oapaolty, oppeorance and api«ir<Hit a tab l l l ty In nolda an.;
beaea* Soisple A*3 vos oeleoted for a l l studies*
Ion P,a6obooge Oopaolty U»e,o , )
The ion essdliaei e capaelty ( i . e . o . ) trae d<«t<*r^aod b ' thr^
oolaan prooeaa* Omi f mis of the e3(«*ionfr«»r 0! - torr^) of aoiforp
oeob^alze (5O»i00) was plaoed to a glaaa tube bavins an Internal
dloeseter 1 oc and f i t ted with glass wool at the bottor , Ttm
ooluon lenii!);th was oprroxtwitely 1.5 oo. 250 BBI of m ?tei»^
oolntlon was paaaed thro«B»h i t issalntalnli^ a v«ry slow flw# roto
(0.5 m Btn" ) and the effluent was t i t r a t e d againat a ataudonl
(O.IK) SBKKI aoluttoti. The He -loo eatohtam^ caix^oltics of tfjp
varlooa sacfples ta t©r«« of the islXllequiv»lent iwr aw (.rac nr.-
given in Table 5 .
ii
I s
s
o
tt
I
Iff ^5
§ O
5
I o
8"
i
VI
«4
O o VI
o
a
o o
o • o o
T t T
22
s«v«rot t.O g |x>rti(m8 of tht» SSCRPIP (A-O) t**»rA tiftet«»f]
at mirlous t©iBp«*«tiir«o to a matfle furaaooi* for tm(> hmir ©aot ,
Th« ton escdaiange oapecity was a0t<>nslQiNl oo obovc by th^ cfottim
process a l t e r eooltflg them to T9om t«fssH*r8t«r©« ftje rcoaltB
or© gtvfo tn Toblp 4*
Effeoft gf Eloact Ootie«atrati<m on tli0 lorn Raghange Oa^jaclt^
•Tho ©stimt of ©Ititlon vs@ focniia to a«|K»o<3 urwn th«» ooiio«rj-
t n t i o n of tht* eluant* n^nc© a flsed volt«i'« (25^ til - o- the* ^m.
notutioa of ratylm eoncentrotioos (0«2, 0.4, o ^ , o,e, 1,0, 1,2,
1»4K) wero pasood thro«p;I} tho ooliun ooeftalattig l.C r ot the
exeiiaiiger la the n -fore msd tlie efftuent was t t tn i tou w^,aiu»t i?
stanOara alkal i (0*jj! Nfedl) solotion for the 11 -lorao f»iwtp«l out.
A xsaximm glutton was ofeigervotl yiith 1«2M eonomitratlon of th<?
eluant a« Is evta^nt frois fal>l<i 5 antl Fii^ur© 1#
^«^n<»y ^ ^ n < ^ ^ r •J
The oolusn eontaioia^ 4 g of tb© laatttrlal In H fonn was
oltxtod vi th 0 11! ^Ii>« «oltttlOB tiavlng tlifl staadartl flat; iiJtc a«
above and ocfveroi 10 lail fraotlona of the «ffla«at worf* oollectwi
QOd t i t r a t e d for the H -loius roleasod. fli*» to t a l volrjrr^ «os f 1 w ?
as 250 «!• W10 fftiKlsr reveals that abotst 50 ©l of tho r»l lairt l >
neeOed to oo£;pl«rtely leaoh out the H -long frot; thp collide.
Figure 2 shmtu the eltttloo be^avloor of the extitksmR^v*
23
4r
4*
I
!
f o
^
g Y 16
III
P 411
8 K 8 S S S & ^ S
I 8 j( R « S $ S I • • • • • • «
«H v4 v( *^ O <H O
6 ^ <tf
ir\ p o Q * s S S g g S 8 8
« ® o * c
24
mm,,! v.tf9et of ol-oant ^towtmtmtjm ma <n« too «mfibem9 mvfmiiy
^ * (H) (aM»q/a»yg) wjur-w I •laaMani
1 . 0.S 1*36
a . 0,% tA2
«• 0.8 t . ^
$• 1.0 i , 62
7 . !•% 1 .1WI
•*»HK<NMIII1M«WMWHMI
9 5
2.0
1.8
S 1-6 CO
_ )
Q^ 1 . 2 X
0.8
I 0.6
O./i
0.2
0.0
-O
± ± ± ± 0.0 0.2 O.A 0.6 0.8 1.0 1.2
MOLAR CONCENTRATION OF NQNOJ -1 .4
F I G 1 - CONCENTRATION PLOT OF ANTIMONY ( V ) ARSEN05ILICAT CATION EXCHANGER
1.0
3 0.8 < _1 UJ a t^O.6
u. o
^ 0.^ o £
2D
0.2
CO 20 ^0 60 80 100
VOLUME OF EFFLUENT (ml) 120
FIG.2- HISTOGRAM SHOWING THE ELUTION BEHAVIOUR OF ANT IMQN- ( ' Af?SENOS(LICAT£ CATION EXCHANGER
?7
ten ^^tdtkBtt^ff Oapaclty for ntffftrffnt Wotat I<m#
Ion 0sclioni»e oopoolty of tUo etatcnrial was also at>t«»t^in««^
!?y pQssing iilfforeat wrtal ion oolat toaa throi^h th?' eaioliaiii ^^r
ooliatn in tlie B • fo re t)y tb© pethoa ac«oril»«a atwave. T!ip r©*iaito
a re iiucxs^rlzed in Tat>l<» 6*
lil T i t ro t iona
fH t i t r a t i o n s wer© performed W the tmtdi prtKsosj iwia' th<^
Bothotl of Topp ana Pepi>4*r (26)• 500 w? por t ions of the ,'t;«c*ionr«*r
in tb© H - f o r e wmre j>l0o©a in eaotJ of thfi several 25f> cl ootilo 1
flnaUe followed l^ eqaiisotcir oolu t ians of a l k a l i umial cKilortaf^s
ond t t i e l r fijraru^dos in d i f ferent volac« r a t i o s , tac* f iaol VOIMCC
boing 50 cid t o caniotain tu® ionic s t r e i ^ t h oonatont . I tie |#i of tr r
soltitimi was rooorded a f t e r <v35illibriuE omi woe plottotl orniant f r.
c l l l i oqu lva l ea t of tbe iMf-tons eaded. The r e s u l t s or^ v>h(nm
in f t cure 3 ,
Chawieal s t a M l t t y
The a o l u M l l t y of antit«>ny(?) »rsc»oo-ciilJoi?t«? i« vaH-Oiii*
solvonts woD aeterKloeu fty tii© e^thoa slvoo bc»los#i
250 nj por t ions of the iaet©rlol w©r« kPi-t wit?? :?n t?? Q^
the solvent for £^ f>0?ir!:5 at roc?c: tOEJiOratur© wlti: Inter&ittoiat
sfmkiisg^ AntHsony tiaa Uotercdnoa qajsntltotivc'ly in tJif» aupor-
natnnt l iquid a a follows:
t o tho 2 rsl portion of ttse? ahovp solutlcm -/«»rf ;?»]
1»6 Bl of 18N HgSO, and 5 c^ of KX roogcat ( i i . 2 p. of Ki * ;> ?/ ot
28
Metal sol tit ions loii ost^utnge oapocity
L i d l.<te
Badg 2.2
2d
12.0
0.5 r o J.5 2.0 m moles of OH ions added
FIG.3- pH TITRATION CURVESFOR ANTIMONY ( V ) ARSENOSiLlCATE CATION EXCHANGER IN VARIOUS ALKALI METAL HYDROXIDES
30
osoorMc oetfl In 1^0 m watpr), Tti© oolour mo amt*lop»i} wm
dilnte^l to 10 ©l witJi BW' In a atandtoi^ vol?>Ei««trIe fioH" ami !*•?*»
atjsorbano© irao isoasured; a t t e r af3 ©iaut«i6 at 420 aa ap;.mst o
reagosl blank (27)* tti« aooiatt of aatieiony foimd tn thf» vorlo?ui
solvents after tli© aliove treotKient oro givfm In TQIJIO 7,
IB Stodioa
^ o tu »pectTQ Of aotimoayiv) orsonoaiUoatc •»<?r tsketi
by the fEBr ul3c ieeth<Kl eifei ort> ahmm In Pl^jire 4 .
Ylier8x?gitryiE3gtrie Annlysia
F'l^.uros 5 and 6 show tisc "WlA ana Dai/\ cnirv^s fur Jt>.s<j( /t jf-
the effect of beotlt^, an the nater la l*
200 m tMirttoiiii of ttio o^ohon^rer in the H'»forn wore sliok-r'n
for f«*r fdmttes in ttO m of th© oetal eototton tn a4ff<»r*mt Eio<iir
and then x^ote eoltitimi wao kept for 3% hours'adjustirvr th© tn l t io t
cetol Ion c^me<;ntr8tioti at 3f of the to ta l Ion ox<*innf»<» oat^affit-'
of the ton oaKshaiieer* The eacrtal ions in the oolutl.Hie T?fforc aiiti
a f ter equilibrluci were aetartntned by the <mA (38) t i t r n t i w a ,a
the distribution ooefftoients ( M ) were oeleulnted t^' t!jf> fore:*il.o
«M « ^ . | <«a/6)
Where
I " InliiQl vol;it2e of fiyiA aaea
F » Final volure of Ri)TA uoea
0 1
• * fotal Yolune of the sotulliiii (nl)
li *» KaoG of title •sGohiixiser (g)«
tlM 8a iralooo for i% netol ions IA differeot oolvefrts arfi
eiwmi in Table 6«
Figaro 7 slHMf6 tbo j»*rsiy tUffraotion pat torn of anticoiayCv)
orsonosiliooto. foblo 9 w/msaariA^t ttm f^oiats of tho»c atttOlos*
Sopoimtioo aoiiioyoa
Qoseil <Hi the (llistritmtioit »t?>ai«»8 ©cm sr»i/ajr0tio!i3 of EKntal
Ions were trl94« As a rooolt, tha Moaxy oi poratloras ©»«*$ as
sr<ir)»Z»(fT) ana llB{ll)-Oa(ir) birr© hem\ aobi^od oa viho-^ la
Plguro 8« The Oetaito of the oeixsratloos ore f ives in fable 10,
32
SolaMlit^
1
^ »
U
2*
5.
4 .
5.
6.
7.
8 .
9.
10 .
11*
of satiBoaytv)
Soivcmie {25 ffil)
m nmy 3! mo-m na SH HCI
4t! HCI
IK HgSO^
»J IlgHO^
3H !9a!»^
SH fCND-
o.jif fbm
C.H! ?«^0!1
aracwioot 1. ieat«
^
in diff«pettt 8olv«at8
Sl5 dl!>;JOly^r«<i
im)
i . 5
3.25
S0.i>5
50.68
n*25
9,25
£3*27
0.75
1.25
30.62
18.25
«
I
a 6
«4
8
1 8
S
4* 8
%
8
I a
I
B
o a
®.8
o a
§ r is O K
1
8
«)
9 e 8 :i
II
I II I f'*!! s
8 0 i 4 r <B
<i4 V4
i n 11 g § 4P
^ I ^ v< <rv «<
^ § ^ I *» cj ei v5
33
I I 8 I;
l l l l l § S l l l g §
o
o
I I I §g § S o o o c o o VS V\ V\ Kb CD VS •< IfS %f» \ 5 vS Cv
I o
o
% 8
8
*
£ 1 1 1 ^ 1 ^ 1
8 S 9. O r- c CD S 4*
II I II « I Q O O Q i»N r \ lA \fi *• ift o vs
l l l l l l l l l VO
O
»>« H Hi
S Xai^ ^ a ^ ' • w '
3 8
M M Ml M M M
M M M M H M M M
s i i ^ ^ i r ^ ^ « « ^ < « ^ «»^ »«•• «n^
« ( C 3 l f ^ 4 > i n \ 0 t < » C D e v C *4 CI ••t v* * *
1 ^ ««•
I i
q o o g o o o o o c o o c |
limmfrii •
JHity P9wamt Oiffyttotim tet« for oiy»tailtti«
onttBOByCv) are<nio>Uloot»
S I , No.
80 ^MinfiriiFMMM'iWJMK'i*^ i«^MKinvu--<»ui»"'
d valuos
! •
2* 5» 4 . 5 . 6* 7 . 8 . 9 ,
10. n. 12, 13. 14 « 15. 16. 17. 18 . 19 . 20» S i .
12.514 15.72© 14 .^Si 14.687 14.797 14.950 15.151 15.281 15.409 l<i.055 37.485 28*490 08.819 29.553 29.729 25.037 50.592 ^ . 1 7 1 3^.679 50.729 59,296 55,49%
loe 14% 30B
890 2% ^ 4 276 232 130 140 300 3%2 374 350 310 f?72 ioa 112 112 104 124
7.0738 6.4503 6.083% 6.0312 5.*je68 5.92(50
5.0553 5.7963 5.7r><.>2 5.^2t>3 3.2% »1 3.13^!9 3.0979
3.''- > l
2.9*1%5
2. 2.8693 S.5867
1.55^5 1,5837
b
I 1
SI
£1
I I e
91
S
I
I
s
s
8 if
CftI
S R ft S
rx s B V! 1 • o
<m •
P
n S »
i •
c
o •
1?
o* IS 13
i • O
•^ • i
o* 6 K
§ • *<
C «
^
fi a
1* 0 05 68
^ 0)
1? INI
i &
s •
4r
3 •
1 i n
8
M
It H
C4
36
60
40
20
0
60
AC
20
UJ 0
o
I") 1 -
?.o
0
60
40
20
AT 400 C
AT 200 C
\
AT TOO C
AT 45 C
X 4000 3000 2000 1900 18001700 1500 1300 1100
WAVE NUMBER cm"^ 900 7C0 6SC
FIG. ^ ' I R SPECTRA OF ANTIMONY (V) ARSEN05ILICATE CATlON tXCHANGER AT VARIOUS TEMPERATURES
-J 7
60
AO
20
0
go
60
^0
20
AT TOGO C
AT 800 C
AT 600 C
± ± J-
AOOO 3000 2000 1900 1600 1600 UOO 1200 1000 WAVE NUMBER cm"^
800 70G 6S0
FIG. A Contd . - I .R . SPECTRA OF ANTIMONY (V ) ARSENOSILICATE CATIOr\ EXCHANGER AT VARIOUS TEMPERATURES
38
0 80 160 2A0 320 400 4B0 550 6A0 720 800 880 960 10^0 TEMPERATURE (C)
FIG. 5- THERMOGRAM OF ANTIMONY (V) AR5EN05ILICATE CATION EXCHANGER
3 9
_L I J L
FIG J
20*C llrfc 200*C 21^C 3t9*C iW*C t67'c S6fC6«*C68fc 7fiScbo/c8»'
TfiMPERATURE ( *C ) ^
J T A CURVE FOR ANTIMONY (V) ARSENOSILICATE CAflON EXCHANGER
4
o <
u LLl i —
<
<J1
o
<
U J
U J
cc CD UJ O
CP C N *
1 j
! 1
>• z: o 2 f—
<
o z: cr UJ 1 , ,
-a
o
A i l S N B i N l
r^ t ^
< cr LJ- UJ
> • <
< X
> X X UJ
1
r O u_
z o
Q =0 OlM HNO3
b-O.lOM HNO3
0 20 AO 60 80 100 120
< UJ
LL
O CO
a "6 E 0.6
QA
0 2
0.0
U
Mn ( I I )
1 I
~< )
\ • 1 ^
/ 1
1- b-D ^
Cd (I I )
Q rO.IM HCIO^
b= l.OM HCIO^
^ — S 1
)
20 ^0 60 80 100 VOLUME OF EFFLUENT ( m l ) —
FIG. 8 - SEPARATION OF Sr ( I I ) FROM Zn (I I ) AND Mn 11} FROM Cd ( I I ) ON ANTIMONY (V) AR5EN05IUC AT:. COLUMNS
4 ^
/h
2 . U -
cn 2.2
f 2 , 0
2: o 1 — •
z.
>-I -
< CL <
V8
1.6
1.2
1,0 LLl
< ^ z O . 8 <
5o.6 ui
zO.A o • — •
0.2
OOL
c CL <
X) CO
X)
LEGENDS
S b P ; ANTIMONY (V ) PHOSPHATE
S b S r ANTIMONY (V ) SILICATE
S b A « , rA^iTIMONY ( V ) ARSENOSILICATE
ZAS .-ZIRCONIUM ( I V ) ARSENOSLICATE
SnAS .-TIN ( I V ) ARSENOSILICATE
CAS rCHROMIUM ( I I I ) ARSENOSILICATE
Sn A .-TIN ( I V ) ANTIMONATE
S n A A . - n w ( I V ) AftSENOANTIMONATE
C/1
ISJ
CO < c
CO
< < c
CO
CO
<
INORGANIC IGN E.XCHANGERS
FIG.9-- A HISTOGRAM SHOWING THE ION EXCHANGE CAPACITIES OF VARIOUS INORGANIC ION EXCHANGERS
4:.
X Q-
LEGENDS I
O TIN (IV ) A N T I M O N A T L }
• ANTIMONY (V) PHOSSPHATEJ
ANTIMONY (V) ARSENC -SIL i C /i ^ £
\ I 0 0.2 O.L 0.6 0.8 1.0 1.2 1./ , 1.6 18 2.0 2.2 2.A 2 6 :
m moles of OH" CTKS cxcidccL -- ^
FiC 10-EQUIL!BRiUM pH T|TRATlO-J CURVES OF VARIOUS INORGANiC ION EXCHANGERS
uo LEGENDS
# - ANTIMONY ( V ) PHOSPHATE
O - ANTIMONY (V) SILICATE
4 - ANIIMONV (V ) ASSENOSILICATE
6 — ZIRCONIUM (IV) ARSENOSICATE
^ - TIN ( I V ) AR5EN0SIL1CATE
- CHROMIUM (1)1 ) ARSENOSILICAIE
X — TIN { IV ) PYROANTIMONATE
200 AOO 500 800
TEMPERATURE( "c
T O O O
f^lG.11-EFFECT OF HEATING ON THE I .E.G. OF VARIOUS ION EXCHANGERS
^ b
Aa tii«e« sttiOlds revml tbe toongonio Ion exohonGf r
ViTepmiMt& !•€»• fisl'icKMlS^ (7) ar8<»ioallleate to a oat ion exetiongor
vith «B ton «a6tfiiiig(» «ftp»ttttsr of 1«6S eeq/dxr g for Na ions. On
eottpttrini tfei« too ^oimiiiSe eameity of this mittorial vtti) otbor
tnos^anio ion «aaetuxa^0r9 i t i s tfb»0rrod ttiai i t lias n ix^ttf^ ion
oxohongo eepeei^ ttioii otli«r aeterials of this olosu e^c^pt
«iiti«o«Qr(v) liUMibate iittd tin(IV) Mttisxmate (Figure 9)« On
liootit^ i t ot aiffor<M>t tocrpofotoros for on« hour eadti it tiraa
Qh&erw^ ttmt tliis aetorial Itmm i t s ion taaima^^ o&pacity not
•«ry olmrply* It retoisMi i t s i«e«Q* npto about 6cXc on hc»attt^
to 600-800 C» fli© wet ©rial i s , thtis, highly atoble tliena^lly.
fba ooneaiiti^ti<:m aurvo <Pigara i ) aboirs tlie Qo intic
ion oaEc bonge oopaoit^r of tho eaterial with the oltiant ootiofstitratioa
of rN iH* X» tlila roai>ect tli« ent^rlai bdiavea aiedlor to othm-
mtariala of tbia olaas* Tlie elution etsnre (Figur*! 2) lilustratc^s
tb© atrooc; ion oxobaago babavioar of antiexxiyCv) arsonosiiiooto,
Only 25 to 50 &i of tbe eiiiatft ia naa adi to o0Gu4et<!«ly imioit out •4-
tba n -iaoa frocs a oaa c,rms oolitmn of tb© eetarlai noiar a c Morc ..
aotuticm aa an ataant«
Tbe fit titfaticxi curve (Figur© 3) inaicotfte the KOOO-
ftmotioaol babavioar of thta scitarial* As it ly wiiom fror
this ourro tbe asabanger aorfaea ia bigbly aeiaie to oatur?»
(l«i • 2 for tb© aiepla oolt aotuticm). fha fti increases shari ly
&a^ beeoaMm nearly iO on aoaiag 1*5 sgaMilaa of Qfl^-iona, The
aaiabangar aurfboa ahows a taater asctfianga of fl -ions uiti; Li
4b
OS eampar^ to tti«» Na or S tans* It tm^ he ilui» to i% mp,hf^T
taydrettea vsdli of this ton aa QO£q[)Qr«d to the let ter ones* 1*110
ion excbonge eapoolty oolotilat«a from tbe pn t i tr»tlo» mirv^
oorrespQNDils nearly to the o:xperii!tentQl iralae oiitainea \xy tlii?
eoltaao i)roo«»s for Bia ions* noe«ver, for the a l ^ l i n o eortlis
(Ca % Ba^*, sr^*) the i««*o« i* btgher thm for t&e ol?snli oetals,
th« !Me being an except ion* It way tie dtoe to e l i l^er iotilo rodii
of the a i r l i n e eorthe* The high oeidio eurfaoe oeoee to be a
geaeFQl dharteetertsties of inofigenlo ton €PCehotir,ers of tbis OIQSS.
as Is eleer froo Figure 10«
The M oti^lea iroveal (29t!^) tb<? preaence of th-> vtirlo«<j
sroupe Iti antioongrCv) eraeooelUoote* 1!he laetel-ojis^en ana metal **1
€1! stretohine honas «re ohterred at TOO «• • The absorption bonti
ol^erved at^-^ 900-10© ow* ahows the pree«<«oe of aroeoate ^ roiip
in the anterial* The aietol'Kiavigen atretotitng ylhrotione also
absoil) in this range* The pi aaeooe of Si-O-si open chains or rinr^
in the fltroeture anil the 3i-0l! atretobing •ibratioos aro eviaeticed
hjr the absorption hands near 1100 m* sod 3300 em Tutm^B
reapeetlvely* The hana& at IO50 ana i6<K) mT are the oheroot^tl;)*
t i e s of al l ieote group* nMettml wster noieoules ai jo absorb at
1600 on in addltiofi to the uaaal renge of 5300 on*** The heat
treotnont given to the veterial vealtene theae bands obvloaaly
be^ioae of the reoovol of the eai^emal water eoleotlles. Flgur<f» ^
^o«rs tho Tarioua banda at different temperatures*
The 38-ray studies reveal the ory»tallln<» natur*^ of th<»
Koterlel as ahotm in PlRure 7* Table 9 eaooorlBes tb*» d-valaea.
k.f /
«ie t t ierml ottxdiee (TlgoirM 5 mna^ d) indiont© the uaoisl
bdbaviour o£ tbe ion eaabeag«r ia*epfir«a io tU«M»« a t o n o s . 'Siio
f i r9 t d«flaalioa in th© fGA ounro et^^lOO C la do© to the rewov 1
of the eari fimal «ot«r coleeules miidb MKfounto for th«> v^tfjpt. lom, m
Of nearly 17^« A further weight loas upto 560 C is do** to th(>
eoQdffieatiosi prooeaa golag on in the cAteriat . Ww?> wel7i-t b- cocof
eoQStant thereofter «e only the reetdit© is nothlnr* f»ttt thf» vari' ^nr.
ostidee o M a i n ^ t The V^A earre (fi@ore 6) indioatoo on entiothprrt'
peak at 118 C oonftrtsiJXJ tlac welgfit loeo an<* to th« loss of
es temal water etoleeolea* ftie broad eoa veok o icotb rmiic ^ <»ak9
erotma 350 a»a %87 C are <lue to the eosn^eneatian proo^as »?ilol*
i s a tf3ecii<K)l diaogo oo<mrriii^ in the i3cit<>rial» Sino th^
<K>t po8itiOQ studies are s t i l l io prot^^resa tlic fonsolo of the
oater ia l <^as>ot lie proposed at t h i s stage* GociixirQtiir^ footiurr G
of the various ae te r ia l s of th i s oloss on heating or<> glv^n in
Figure i i«
Ibe distr ibution stuOles reveal tim solootivity of
aatiooayCv) arsenosilioate for the varitnis tietQl iu!£ C 'oblo Q),
OB tbo basis of these studios sotae binaiy seporotlms were aofilovf?
oa the oolutm audi as 3r(tX)*eo(Xl) and l!a(IT}-oa(ll). Biis
i l l u s t r a t e s tho analytiaol pote^itial of the taotorl^A. f&hi& lO
otnaaarises the sa l ie i^ fei^tures of tho sepomtioue. riovmrer, thf^
ful l pot««}tial of the vnterial ecm be (lacploree only aft*»r tbp
(letnilea s t t i ^ in trhti^ tiire«stion iihioh i s in i^rogress*
48
<1) Ol6arfleld,A* (Bd«)f ^tmn&mie Km Estobcaige Materials**
C*lt*C«l¥es9 !»«•, Bo«e Baton Floriao (198c)»
<2
(3
<%
(5
(6
(7
<8
(9
(iO
(18
(13
( U
(15
(16
Ab««R« mid ttO,f«„ BaU*(li«s«SO«»<fopo», 4|^ 333 {l%9).
Abe,M. and Ito,¥.« IMd., M> ^^^ (1958).
AI>e,M» and Ito,T«« lappow KuRofta Saashl, ^ , 117% (t%6).
!Ki«t8l<»,t«I!. ana I!«sr«,»,, B^lg^Patent, ^9« T i (l'359>,
"BelttmkayQfTJimt l!ntt8la£ii,t>*A« a»a a«»i rva,7*H., T: i Mmtl.
Miuk SSSR, SeoniJlater, | 2 , 1631 (1975 )•
Ilafiilkov,B^*, BelLlas&eQra,F*A« and Matorava,?«A«« i^.K^itr,,
i , 94 (19%).
Boeeicl»B» and Liii»(»r,K«i(Uy !iadlo«Cfcie«Aotd, j ^ , 51 (1973 u
Grl£rova,II«S», !lllEOl*Skill,B.F,, f>aliiiafj:ay&,F«A» am
tt»liloa,Xa.« riB«8l)ie^«, £, 79 (1981)*
Aba,lf. and Ito.f . mp-. on Sasaka Easehl, a^ 1259 (1963).
Ito^T* and A!>e,M«v ^ ^ ^ ^ Untlotial Haatlog of «ki|> n as<»i! on2
Soelety, Ja^ua Oii ciaeol society, Toloro, Atjstr. i . 5S, April
(19S8).
Aba tf* and l to , t ,„ mppoii Kagaku ZaasVii, 82, 117^ (1966),
tafatwra.J., (Xmpt.nma^t ^ 0 , 5575 (1965).
htdelfvre,3» and OtqnairdyO.^., Aoad.Sol.i*aria, 260, G Hi
(1963).
Ito«t8te,r4j7«, D<!!rotc«P«Van., Hii7s,0. and <5a€'fy,ft,« T A'C,
ATC Aee«89lcni !*»• 7613f fiap.Nb. BIG n67 (1964).
Ba«tale,Ljn[., Desr<&,D*Va»» tlays,D. and Ou<»iy,A,, 04.\ c» AT c
Aooaastott I*», 3871, aap. Jto. nm 2497C (1975).
^9
(17) t.aplt»Uil,A.N. oad Tatov^ljV.F., au.KhtE., g, IV (1%9).
(18) Lapltaicll,A,N, ana TalEavyl,T.F*, ser*imiin«Nbirir., ^, 57
(1971).
(19) Qttro«hljll. aoa Klttur,V«, J.Ctoroiaatoer*, ^ ^31 (1971).
(20) Qttro8hl,M. ana lBawir,V., IMd,, §2» '51 (1972).
(21) Abe lf.r CtiitTg&mr,H*t Tou l M. a»tl Fuktaraoto.lC., s«1v< nt
©xfcn.XiKi Pawn., ?(l»g), 149 (1985).
(S2) Al>©,ll. and !fO!xnni Parakl, B»ll*€ber.»3oc*<lnpan, ^ - '812
(19B5).
(25) Ab«,lf. and HeQraslUtK*, solv<mt exttm^toa I'xoti., I,, )2 (19<^5>.
(S%) lte90er)TarliE«A«lC«, Slcitior,V« ana 9s^lB,sat)eh«Tallb«, J.Cbcr .
Soc.Pafe., 2, 123 (19S3).
(29) Var )Uf9 ,EdC«, Sliarea,Ui», ilaiil^Slmi ana PrmsQilaSfA., Ser.sel .
T*HSb., U s 1527 (1982-85).
(96) Topp,K«!'. ana P#pp9r,K«w., J»aieiB«Boo«, 3299 (I9«i9;.
(87) Simdell,&«B«, »O>lori&i0trlo D«itereiiuitloo of fxtio< a of MotniG'*,
Tol« III , P« 266» Zateraoloneo Pabllshara, Xoe.Netv York
(1959).
Belly,C«N., S€i)C3ldt»a*U« otul Tmn^Sf J.OIOE,- due , J6, 5 •515
(1959).
(39) Godsden,J»^«, *Iiifrar«d spoctro of Minerals cind Rolntad
fnocisaale Oonpotaids**, R*J,Aofo»l Lta. (BUSSC^X), I • 36 (1975).
( ^ ) lloo,C«H»r!,» €h««!teol Applleatlona of Infrnr^m si^^o+rosaoy
(AoadeMo i r««a, ItVeur Tor&), P. 288 (1965).
