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SJrUDIES ON SYNTHETIC INORGANIC ION-EXCHANGERS
S U M M A R Y
I THESIS SUBMITTED FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY IN
CHEMISTRY i
- f :i9S7 BY
BALBIR SINGH
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
A L I G A R H
October, 1984 ,
STUDIES ON SYNTHETIC INORGANIC ION-EXCHANGERS
S U M M A R Y
THESIS SUBMITTED FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY IN
CHEMISTRY
BY
BALBiR SINGH
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
A L I G A R H
October, 1 9 8 4
The thesis entitled, "Studies on synthetic inorganic
ion exchangers" is comprised of 5 chapters. Chapter I is
general introduction covering the literature, to date through
availahle journals, on the subject. The emphasis has been
given on the importance ol ion exchange as an analytical
technique. Overall the introduction covers a critical review
of the earlier woiic done on inorganic ion exchangers, their
characterization, applications and main interest towards the
mechanism of ion exchange and ion exchange equilibria. Looking
for the growing interest in the physical chemistry of ion
exchange, the emphasis has been put on the thermodynamics and
kinetics of ion exchange.
The second chapter deals with the, "Ion exchange
equilibria of alkali metal ions on ferric antimonate". Because
inorganic ion exchangers have a rigid structure, they swell to a
negligible extent and, therefore, the thermodynamic studies on
Inorganic ion exchangers will be simpler than that on their
organic counterparts which have appreciable swelling. The
Influence of temperature on the ion exchange equilibria of
Li , Na , K and Rb with H has been described in this chapter o
for a temperature variation of 30 to 60 C. The thermodynamic 0 0 o
parameters, AG , AH and AS have been evaluated. The
equilibrium experiments were performed by a batch process
equi l ib ra t ing for 6 hours at desired temperatures. The exchange
Isotherms are plotted for the said ions and the r e su l t s indicate
( i i )
a d i f f e r en t i a l s e l ec t iv i ty with a revers ible exchange process
H* + n* ===± M* + H*
where M* stands for an a l k a l i metal ion and bar represents the
exchanger phase. The se l ec t iv i ty coeff ic ients have been
calculated by the experimental r e s u l t s and the thermodynamic
parameters then calculated using appropriate equat ions . The
hypothet ical data at "zero loading" have also been evaluated.
The th i rd chapter deals with the , "Ion exchange 2 - 2- 2 - 2 - - -
equ i l ib r i a of CrgO- , CrO^ , SgO- , SO^ and MnO^ with NO- on
zirconium t r ie thylamine" . The survey of the e a r l i e r l i t e r a t u r e
shows that only a few thermodynamic studies have been made on
inorganic anion exchangers. This chapter describes the
thermodynamic s tudies on a new inorganic ion exchanger, zirconium
t r ie thylamine , A simple approach has been applied using a batch
process for equilibrium based on the mass action law modified
in terms of a c t i v i t i e s . The various isotherms plot ted indicate
t h a t the bivalent anions are preferred to n i t r a t e ions by the
zirconium triethylamine exchanger. All the isotherms show
r e v e r s i b i l i t y of ion exchange whereas the s e l e c t i v i t y sequence
is
Cr^O^- > Cro2- > S^of" ) sof- ^ MnO^
The r e s u l t s of the s e l e c t i v i t y coeff ic ients indicate tha t the
( i i l >
value of s e l e c t i v i t y coef l ic ient decreases as the temperature
inc reases . The thermodynamic parameters are evaluated by the
thermodynamic equilibrium constant .
The fourth chapter describes the , "Ion exchange k ine t i c s
of t r ans i t ion metal ions on stannic oxide". Kinet ics play an
important role to study the mechanism of ion exchange. The
mechanism has been found to be a par t ic le diffusion cont ro l ,
A theore t i ca l approach based on cer ta in ca lcu la t ions has been
appl ied. The energy of act ivat ion and other parameters are "5+ 2+ 2+ 2+
evaluated. The studied ions are Fe" , Mn , Co and Zn
with H exchange. The s tudies on effect of temperature show
tha t the r a t e of exchange increases as the temperature increases .
Besides the temperature the exchange also depends upon the
pa r t i c l e diameter and time.
The las t chapter i , e , the V chapter describes the
synthesis , propert ies and applicat ions of a new inorganic anion
exchanger, f e r r i c t r ie thylamine . Ion exchange capaci ty ,
composition, chemical s t a b i l i t y , effect of heat on capaci ty ,
pH-metric t i t r a t i o n s have been studied to character ize the new
ma te r i a l . IR studies have been made t o confirm^ the presence of
various groups. Dis t r ibut ion studies for 17 common anions have
been made. The u t i l i t y of the exchanger has been explored by
achieving some ana ly t i ca l ly important separat ions .
STUDIES ON SYNTHETIC INORGANIC ION-EXCHANGERS
THESIS SUBMITTED FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY IN
CHEMISTRY
BY
BALBIR SIIMGH
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
A L I G A R H
October, 1 9 8 4
\
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W£S/S ^^CT/our
, j j r ^ADTJg^^^
vo
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1 2 S£P 1935
L86ZX
CHECKLD 19%.^^
J-agdlsn J). (Kamal M.Sc, Ph.D,
READER IN CHEMISTRY
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
AUGARH-202001 INDIA
C E H T I F T C A T L
fh le i s to c e r t i f y thot the work ecibodtGdl In t b l e
thestfi i s orlr:lnfll anil sol table for fabnlGslon for ttio
mi&td of l%«T», degree in Cbesslstry.
/C___igs->/^' 4.P,ll/4MT /
DEDICATED TO MY PARENTS
A C g N O W L L D G E M C K T
Tt I s with Itseense pleaiiurc thai T place on record ey
profound sense of grotltufle and gratefulness t o Br , J.P.Rawat
tfhose able guidance and precious suggestions T enjoyed during
the course of the worl: reported in t h i s t h e s i s .
T a® thenicful to Prof, w.nabnsan and Prof. Fahebuddio
Ahaod of the Bepcrtrspnt of Chenlntry, Mt'^nrli !!aslln Hnlvori'lty,
Allp:arti, for h i s cooRtsnt cnoouranoT^fnt an**! provWlns nccoooary
laboratory f a c i l i t i e s .
T extend ry thankP to Hr, it.P.S.Mufitavot, '^r, Maeood MB'^
cntl other research collea/^ues for the voloablo help they hove
rendered to ire durln<^ the preparation of t h i s thos lB,
My thanks are a lso due t o the Council of relent IfIc and
Indus t r i a l Research (INBIA) for f lneaolal ocelPtance,
/ BAtBin SINGH /
C U N T L N T S
PAGC
T , t i S T o r HJBLICATIuNS ( H I )
I T . LIFT OF TABLLS f l^)
i r r . LIST uF viQvms ( v i i i )
IV, CnAPTLR - I
imnonucTioN i
iSiFEIENCLS 52
V, CliAPTER - i r
ION EXCIIANCn. EQUILTBRTA OF AMCAM WCTM IONS
ON Fl.HRIC ANTIMoNATi; 39
EXPLHT^S^NTAL 4 1
Ri,SULTS 43
BISCUSfluN 64
VI , CHAPTEH - I I I
ION fcXCllANG.. LCt'TLIBHlA OF CrgO^*, Ciof*, P n ^ f ' t
SO J * AN?> ?fnoJ VTT?? NO* ON 2rifCuNIUM THILTOYL-
AMINE 72
EXK.ntIM«-NTAL 73
RLSULTS 76
DISCUSSION 96
nbFEI&KCES 102
( 1 1 )
PAGE
VXT, CilAPTLR « IV
ton LXCHATiGi; fCIHLTlCr OF TR/^STTION K.VAL lUNS
ON STANNIC OXIPE 103
EXPERIMI;NTAL to*
KESULTS 106
TIIFCUF5I0N 121
REFEnL?:CLS 127
V I T I , CflArTLR - V
SYNTHESIS, PRUPCnrTES AN^ APK.ICAT10NB OF A NL¥
IXunOANTC ANIUM L^}.AKt^U Ff-HHIC TnrcTr.YLAMlKE 128
BxrLnirn.NTAL 129
lEFULTS 130
DTSCU^FION 145
ffiJFEfjENCES 148
i l l )
L I S T g F P U B L I C A T I O N S
1 , ION EXCHANGE EQUILIBWIA BLTaiN ALKALI M.TALF ANP IiY!>!yGi-N
luNb ON ir*uN(li i) /4:vi!Jo?;AiL, A?; IKOLGA^'TC ION EiKiwicLn.
BULL.CWM.PuC .JAPAN, 57 , 2 ? ! (1994).
2 . ION EXCIl/uNGL KINETICS OF TRANSITION f&.TAL IONS ON STANNIC
OXII^L,
J,INT)IAN CIlL?I.Fi)C,, (IK rRJ£iS).
•5. ION LXCHANGP CQUILTfinTA OF Cr«oS". CiO?*, P«of", TO?" AND
^•nor WIH' NO* ON /TRCONTUM T'tT! riyj.AMIK'J .
(COMMUNTCATnl)),
h, SmrnuSTS PaonUTlEf^ AN^ APrLICATIONS OF A Nr.'J INOHGANTC
.\NT0N nxOHANG.' H, FEUniC TnTLTimJ^niKE,
(CO P-TUNTCATCP),
( Iv )
L I S T ii ¥ T A B L E S
PACK
TABU. I Tm^raO^YNAHTC PAty^>a,TLRf ON VARIOUF lON
LSCfANGL JIATLRt/XP 16
TABLL TT LQUTVALi Kl FMCTION OF L I * , Stl i :CTTVITY
a j L F F T C I . N T ? AW TIIEHMOnifNAMlC CQUILIBlltUM
CONST ANT Fyft L l * ^ * E5CHAN&L ON R R L I C
ANlH'^aNAti, %3
TABLL I I I Kt^UIVALLlh F t V C i l u r ; UF K c * , l - L ^ C i l V I i T
COLFFTCI* M 5 Ar;^ TL..rJKj?T:4AVTJ ^(^UlLTi: l l t l l
CaKfcTAST FOii Ka*-.H* KB^ILU.'GL ON FiJlHIC
AJfrriONATE %7
TABU. IV CQUIVALLia PIUCTIUS OF S * , SLUXITVITY
Cu^-FFTCILNI F AK^ f KI. U!4or»yKA^nC LQUTLIRRIUM
CONSTANT Fon !i*-i]* ExtJfiAHGi. Qi: Fi :naic
ANrifJoNATt: 50
TABif. V EqUIVAU.KT FRACTION OF Rb*, S J U - C . n i i Y
COl.rFTCl!.KT Am TI-Ln>lu' yKA?:TC EOlXLIDl'TWI
coNiTAKT r o n m'*''4i* E:a:iiAMrL OK FLRnic
ANTT?:aHATi 53
TABLL VI TOLRMO^WAMTC PABAMl.TLHF FOR Ll"*''^!* EXCOAKGE
ON FA.nine AJITTMO^ATL AT CuSSIfM TOKTC STIllHOTH
mti V A R I J U S TLMRllATUHES 57
( V )
PAGIi
TABli> VIT
TABLE V I I I
TABU: I I
TABLL X
TAHLL XI
TABLE H I
TADLL X I I I
TABU: XIV
Tift riTfU^YXAVtC r/.llA>Gli.Rf Full Na*-n* LSCLAVGl
OK FLRRIC ANTI?!uNATr AT CoKSTAKT lONIC Sini-NGTI?
AK^ VACUUS vtm PATurms
Till n»sinyN/Kic lAnAn^TLRp ron n*-n* C5CIA!:GL
OK' a?mTC AjrrTMuKATi; AT CONTTAXI' loi.'ic
FTfU-KGli. .^-n VAniOLE TLMarL'TUHES
Tr!Enr!uT ¥?:AMic i'AnA*^Tinf Fon nb*-K* EI'CAIIC::
OK FtnnTC AKTirioNATI AT COIiiT-V^T luKTC
STRl^IGTII A*P VAIlToUS TEMll.llATUnk.B
RYruTIILTTCAL T}1LmfunY!;A!1TC DATA OM, "ZCro
LOABIKG" OF TJK IO!I CXCUAKGL RE-ACTION AT 30*C
lOK CSCIIAKGL CAPACITY Of Fu?i:: A JIOMS ON
ZTr.cavTU^' TniLTr.yLAHiME
Eqt'TVAlLNT FnACTT0?:F OF Cr„o2*. SEIICTIVTTY «» 7
COLFrTCILMT? Air* TI'I l?"unY?JAHTC irVlltmWU
CoNST. KT Fun CrgoE"-NO' EXUIiANGi. OM /iinCONTUM
TnTl.TtIYLA!lT?X
UQCTVAXI-NT FRACTToKS OF CrO^"', S'LfXTlVTTY
CuLFFTCT N'TP AK' THLmionYKAMTC bQUILTBRTUM
CuNFTANT? r o n CrO?*-SOr EXC!!ANG!: ON 7.THCuNHm 4 3
TflTlTHYI AMINE EQUTVALLNT FHACTIoXS oF SO^" , SLLLCTIVITY
COLFFTOTLNTS Am THl-RMO^YKAMIC LCUILIDHIVM
GONSIANT? ron SO?".?©" EXC!!AHGL ON ^tliCoNIUH
TnirTlTLAMTKb
59
61
63
69
76
78
79
83
( VI )
PAGF
TABl^ XV
TABU: SVI
TABIX XVII
TABlii X V I I I
TABLf } a x
T/^BU XX
TABU. XXI
TABLE XXII
. 2 -EQUTVAtLMT pnACTiuKe OF ?J ) " , Si:i:.crTvnY
2 3 "
ca.»:?TANT« Fon s^a^'-No" EXCHATIGL OH
glRCONTUM Tnil TnYLA?tI>3i
CQlTVAl m FRACTIuNS OF MnoJJ, S L L L C T T V T T Y
COLFFTCl! ^Jl't Am TiiUnMu^'raAMIC Li^'UTl TUJIUM
CuKSTANtr FUH HnOj-NOl tXCUAhUL UK ^.tllCuMLM
8%
8^
95
THLiiiiXAri:;*- A; JH U M C , rri.%Uini or o . i
AS^ VAHt^l? l*,MhLaATUR2S
F 'iNr nt VAi-ii4.! A« A FCNCiio.% ur n*'i FOH
^T»rii:^KT c;*TioKf ON ^'TANNIC usre.. AT 3O ^ i^c io6
P i\Nn Dt VALU.5 Af A FUKCaoJ: Oi iTv^ FOU
nTFH.Hi;N"i OArXoKE g.V STAN>aC 0 CTHJ
AT 40 • I*C 108
F ANT) Bt VAtUtib Ai. A FUXCTI K OI' i i::.- Fun
AT 50 • i*c n o
F AN^ nt VALULS AS A FUKCTIUU uF Tl^t. FOR
niFFLRLNT CATIOK^ ON ST.VNNIC OXWh AT
60 • t C 112
P AN^ Bt VALUE F AS A FUNCTION OF FAOTICLL
Sim FOH Fe'*«ll* LXCllAKGC 0!I FT/^MnO OXTBE
AT 30 • 1*0 119
( v t l )
P.^G:
TABIX XXTTT
TABLL x n V
TABU. XXV
T*BLK KXVI
TABIX XXVtt
T ' P I , XTtVTTT
TABir \yjt
T/.Bl! !rXX
VALU? » OF T l ( c o ^ s e c ' * ) o r VAHIuUf Tu!IS
AT nTPFumiKT TI:MII:RA7UIILS OS' >rA»n:rc oxrr*:. 124
ACTTVATiuN, rrnRut-T or ACTIVATIUI: A>n n r r .
^^XKGY i>I ACTTV/TToN of **LTAI TuKt a%"
?TA>; TC OXTH., ( t o o um) 125
CONPITIUN& oi- 1'ffi.rAiva'To!. or ri-H..ic
lU*i LXCHANG! CA.\'i;TTY TJ't '^tn-rn* NT /n tuKS ! 3 1
STABTLTTY OP F» f?nTC TRTl T'Tl ^»n*:1. IN
r^TFF:^ \ t SJIV'KTS 1-53
C^PACTTV OF ^TJiiro^'ATL TONT AY ^IFFl-itLNT
T'MTMU'iUPLS 155
m VALUi F FOn •^TFn.P.' NT ANTON? TN
^TFH fi vr foLv jrrs 159
CUA\'TTTn'TVi.. S'-PA' ATTO?! OF ANIOMF ON
( v l l l )
L I S T UP F I G U H r . S
PACE
PIGURL - 1
piGum: - 2
FTGUnL - 3
PIGUKL - k
FTGUflE - 5
PiGCnC - 6
piGCnfc. - 7
PIGITX - S
Ficvru - 9
FiGurn . 10
FIGU^ - 11
ION BXCHANGJ: TSOTHEHM OF Li*.n* E*cnAr:GE
ON im>K(III) ANTIMUHATE
ION LSCliANGL l?OTIIi-mi OF N«*-1l* F.??;tV.?'GE
ON IRON (TIT) ANTI JONAfC
ION GXCTIAKGL TFOTlItHM OF K*.I1* ESCI'/NG'
ON i n o . J ( I I I ) AIJJIMONATi:
ION EXCIIAKCI. TFOTiltra! OP Hb*-4I* T.X:)rAKGE
ON i n o N ( l I I ) ANTT*!viNATi:
iOGARlinMii OF fLLLCItVITY COLPPICI'. NTF V S . '
loNIC PrUCi'IUNS OF L i * IN t.XUnA,NG.R KUFE
LOGARTVH'.b OF l^LLCl TVITY UOLFriCIl-NTS VS.
lOXIC FnAClIONfc OF NO* IN LXCHAKGLU HIASC
L^G.*.nn..::5- oi- I L L ^ U I I V I ' I Y C U L P F I U I . N T S V S .
iur;TU pa;.uTiuNs UF X* Vi ^xcnAKu..!? V-HAU:
LoGAcniPi: uF J>LU.CTIVITy COLFIICILKTS VS.
lUTaC hlu\C'ilo}ii 01 fib^ IN tXCnANGlIi PilAtL
i^xr^uA'^it:^ K.i\.:;p.\KCu OF IHL Ti!in*toT>yNAMTC
i:(;uiLin.iiL>t CONWANI-
ION LXCFIAKC.. IFOia^lW OP CFOOI -NO, EXCHANGE * 7 >
I0!i :.xj;?A;,a- i.^^i.:. rt OF c r o i V : o r UXCIIANGS * 3
ON 2ItJCo!;iLT; TUL.?uYLAHIU
45
48
51
54
56
58
60
62
66
77
80
( ix )
PACE
FIGUIIE - 12
FIGUnii: • 13
FTGU^', - 1*
FIG13FE • 20
FIGURE - 21
FIGURL . 22
ION EXCrAXG'. tSur iJ lUl uF S^o^ ' -Ko l l.K<:U..*KG». 2 5 5
ON ZinCONTU!! TllTi THYLAMIliE
loii ExcrANGJ i£jnt.n!i UF sa^^^xa" LXCHWGE
ON ZinOa"TUM Tnii.THYLAMINL
ION LXCnA!%GC T?0li'4.K:: o r •inOjJ-NOl E3JClWNGt
ON ZIFCuNTUr lUTlVYl.Amm
82
85
87
FTGUHL - 15 In OF SLU.CtlYITY COKli'ICl NT V?, uQUIVAUNT
FRACTIONS OP CrgO?" ON ZinCoNIUn Tni . . i ' !YL-
ArilKL'
FIGURE . 16 In OF SiilXCTIVTTY COEFFICIINT VS. LQtTVAU NT
F^ACTTO^T OF C « ) ? * ON ZIHCoNIC?! TRILTTIYL-
AfSlIffi
PIfiURS - 17 l a OF EJIXCTTVITY COCFFlCTLt Tr V?. CCUIVAI/. OT
. 2 -
90
91
FHACTIONS OF S^O" ON ZinCONlU?! TRTLTnYLA?n: X 92
FIGUIJE - 18 In OF SLLCTIVITY COEFFICIi;JfTS VS. E{}UIVAU NT
FRACTIOHS OF £ o | " ON ZIRCONIIT! TniCTllYI-AMlvr
FiGuni: - 19 In OF FLLCCTIVTTY COUFFICTI.NTF V S . E(}UIVAU:NT
93
F.IACTIONS o r Hnor ON ZinCOKIUTI Tnil TllYLAMTNL 9%
TEMT RATURE BtPENDLNGL OF THCItMODYNAMIC
Lq0ILTBRTUM CONSTANT 99
IIATE OF EXCIUNGi, OF T^IFFHREXT CAflONS AT
30 *C on STANNIC OXIHE 107
nATi: OF EXC'AKGL OF niFFiiRINT CATTONP AT
^0*C ON .STANNIC OXIDE 109
( X )
PAGi:
FIGUm: • 23
FIGUIE - 2*
FIGUia- - 25
FIGOflL - 26
FICiUJlL - 27
FIGURE. - 28
PIuUiJL • 29
FIGUIIL
FIGUIT.
FTGUl^
FIGL'Ku
50
32
33
FiGURi;. « 34
PTGUnc - 35(e)
(b) FlQUm • 36(&)
PIGU^ • 37
RATE OF LXUHANGi: Of T)!ff^n .JiT CATTaKS AT
50*c on PTi NNtc ^xim
BATE OF LSCIJANGi; OF nTFll.Ii.ST CATTOK? AT
60*C ON STAMKIC UXTPL
CFrLCT 01' Tii' FtnATURE ON TIIL RATI-- OF EXCHAKCi:
FOK Pe '*-! !* E3 UANGi OK FTANN'IC UXI^L
r-FFv CT OK T::MK.!?ATun:i ON TI:L d/.u OF I XCHANGE
F\)R Co^'^-H* EXCrAKGL 0 3 STANMO Oliini
LFFi-UT o r i'».>]li,fUiUIL. ON T.iL HAIi JF rjiCTlANGr
Foa :in^*-ij* EXwiANG.. 0!: BTA:;:.'TO u:;r>i
EFI.-CT ui i.rriLrAVi'ffi. on r . . a'u-i. o." IXGTUVG':
FOR Zn^*-H* EXClLvNGL ON STANNIC OXITIi:
INFLULiNCL OF PAnVICLL ll^ oN V:i> rL'vT:. OF
LXCiiAKGl. FOR Pe^'^-H* OH STATJIIIC OSl^i:
HOI OF B VS. 1 / / Fon F©'*-!!"*" AT 30*C
uiG m v£, i / r pan p e ' * , co^*, I'n^* A>m zn^*
CAI'ACIiy AF A FUNCTIuK OF T^np-llMUPu:
p{ TiTn/.iioK ouWi. mn IUON TUT. VIIYLAMTM:
EXCIIAKGLR
i.E.siiiCTHCM OF iihiii TUTCTI:YLA!:TIC
£i>PAnATIoK OF I*«ClO 2 -
FI PARATION OP Br"-Cr„0^*
S;pAnATl0N OF CI -Cr 0 ^ -2
SPARATION OF I * - ^ ) ? *
SEPARATIOK OF Br"-SO 2«
111
113
115
116
117
110
120
123
126
13*
136
13S
141
142
143
C R A P T E B - I
mrnuDUCTioN
Anslyttcnl QhemiBtry pleye an teaportKiit role tn the
s c i e n t i f i c «orW, I t in the Irey to the solution of B vorlPty
of s c i en t i f i c problens, Anslytlcnl cherolstry wltH I to
IntfTrttcclpltnary charac te r , clvce voluoble Infoneation tn
laany brf BOhei? of science an^ technolop.y. Tt «!otermlne» the
<jHOlltotlvc find quent t ta t lvc co?«pofiltlon 8n6 s t ruc ture of
chemloel syptens and! por t lc lpotcs In t^se in te rp re ta t ion of
the date obtained•
Analytlcol chemistry has two face«t ( t ) research
on(! dcvelopsjcot, an'1 (11) uplnf; rout inely se o voicing; tool
tn rcBCsrch, Industry on»t nedlclne. An nnolypt mant BB©
I t s Ejcthods, while on flnolytlc??! oheislBt hes t o Interface
with ronny different d l^c lp l lner to in t e rp re t the r e s u l t s
he obtains* For an annlyelr* some forp! of pretreat»if»nt of
schsplc I s UBuolly required po np to remove the tnterferemse
of other euhtF^tnncec, Scpflr^tlon, tn aoet of the Cfiece, I s
one of the Icsportnnt octhods of pretreetisent cod Involves
clnfisiofll and oodera techniques. The prec ip i ta t ion find
d l s t i l l e t l o n are the* cloBRlcnl techniques end ore roplooed
oerfeedly hy aodom techniques ao solvent ex t rac t ion , ton-
exchange, chro"?otography, c lcc t ro«e t r !c t t t r e t l o n p e t c .
The rapid development of these modern techniques hns
increeeed the rcqulreraents placed in anolyt lca l lehore tor lee*
1 L
At proeont lon-csch/ns© In an sxtronely valunble
ooelytlcJ ' l technique, Tbe ton-exclionger» had a ^reat tnpoct
on anoly t lcol ohetalPtry. The use of tbepe ea to r l a l e gave
onBlyets new tsothorte for the reijalretaentfi of esaSem Ifiborato-
r l e n . Ufitng Inorganic aod orgooic exobnngers we can hcve a
(leef>er understandinj!; of geolofjlenl, freophystcnl an<l blopbyelcal
phonowcne t o ©xploln the blolostcfil process. In labora tory ,
th© appl icat ion of loa-exohanger® ho© rasa© possible the
ehrorriatojscrophtc sepet^tlon of very cospllcatcdl nettirol
f i x t u r e s . The tlrae i s rauch redfuoc^! by the uec of high
f^rforcjQnoe chroisatoKraphlc toehntqucs. Their use hns olso
been raai!e to the siolutioii of previously uneolvable probleisg,
Such OS the eeporatloo of rare earthe and recovery of rere
elemrnte. The otoialc power control l abora tor ies and eany
d i f ferent tn«!ustrial leboretor iee ere now nniKiagianble
without the uee of lon-exchonseri . The lon-exch«tt|»o
seporatlone offer fi<lvoDtages o w r the cloeslcxil t»etho<3s of
pcporatlon© (prec ipHot lon , f i l t r o t i o n etc*) for the amount
of the sample required i s sraoll, a shor ter t ine i e needed
nnA the ooBponent^ orn eubeequently be determined using
rnpid Inetruraentel or t i t r lg je t r l e aethodlB, aepid nnd accurate
de tomlnat lon of conet i tucnts of a eaaple or , contawinpnt®
of a l loyr of coraplieeted oonpoeitlans, bloloftionl fiubst^nces
and f i s e i j n proiocts of radioactive eleisenta hse beoo^ae
poRctble by the use of ioa-eschcngers, lon-ei^henge
3
chrcCTOtogrephy cca be rotstlncly siee l t o overcoi-!® IntcractlimB
and t roubles la the detensiDOttcm of tree® olecjente of
gcocbetalcrl i n t e r ee t , before optlonl or atomic RbBorptlon
&p©ctrophot«K30try and netitron cct lvot ion atialygis , Iou»
escchouge ©oterlQlis ere fiodln'* Incroosod um In gRa-chromato»
grsftiy beccuBO they offer a erect range of iHitcntiol Beloct lvl ty
through var ia t ion of the lootc forra of raoterlfil , All over
the worlil nuisorous lon-exchon'^er plnnts ore in oporetlon for
dovolopliif^ the Boporatlons of lnoit?"ntc, orgonto and biolo^tectl
mixtures. The aost Isportont cr»pllCDtlon I r ei t l l l th©
purlf loot Ion of va to r . The weter pollut ion is Inereaslijg
day by day. However, the »etbadl8 be ted on loa-excbange ore
bocoetn.T of prossletnr, encecc© when tippllee! t o t h lu f i e l d .
The use of lon-ejtchangers on large rcalc raey provide mankind
irltb pure water and nay bo useful for the coooi^ntration and
extroctlvin of thr roost Isportant asatols and raw ®at©rlal«
irhtch Is becosilttg ©oi^ and nore d i f f i c u l t to produce.
lon-exchans© «os recognised in the middle of the l e e t
century following the Inwe t lge t lons of tiro agr icu l tu ra l
oheeiiats, Thossoa and Vay wtio were study In?: the optalce of
f c r t i l l z e r B by s o i l s . They discovered t M s phenomenon by
the aase of "base exchange" In po l le , Th« ©xcbaauft Involved
equivalent quant i t ies of replaconble and roplcsJd lon«. I t
was establtdhed In 185* tha t aluslnlua s i l i c a t e s wer© 5 6 7
reeponslble for this exchange * « AccordInt to Lsaberg and
Q
wet^Bcr the matertele responsible for th i s phenoaeiion were
dGflned salQly elsys, zeol i tes , gluoonitee and titieio aciae.
Tbefle fllscoverlee led to the uee of the neturol isateriQls
for water softening. Tbe f i rs t synthetic tndastriel ion*
eachenfi:er was n^rep^red tty Ilann end Roaipler in 1^3 . Oane
was fissbitlous to recover gol5 fro?i sea water adopting t h i s
tccTtniqtie* But he could not fulfil hie aiabitiofis becf^uce
the Bflterlol of thie type availoble at that tirae proved to lie
Insdequete for the purpose. Gene, however, recognised the
prcciic"! u t i l i t y of the ion^^xohange phena^senon for water
softening uelng natural on^ eynthetic seol i tcs and clays ,
The eshoupted bed of the ion-exchanger was regenerated by
passing a concentrated solution of frodiuss or, potessiiXB
salt over tt« Becnuce of th is possible regeneration these
zeoli tes and elaye: vcre soon rcoonnlGcd l»e, zeolites ere
decotupoeed by acids and clcys rre diff icul t to b a t t l e .
To ovcrcoae these diff ieul t tos a search of stnblo lon*exohange
materials was started. In 1931 iCullgran observed that
eulpbite cellulose worUe as an ion-^jxchen'^or for the detensi*
nation of copper. An Interest iof discovery begcn In 1935
when Ad eras and HOIIECS foun' that cm8he«1 phonograph records
exhibit lon-oa«hongc proprrtloc. ffee rewnrfeehle effect led
the invontarp to the Bynthcrir of oruonlc ion-exchange resins
which had wucli bet ter properties thPn any of the previous
5
12 produots • tbO06 resins ere etcble tawards actde os^ oaey
to bandlc. The structure can he varied as deelredi therefore,
the aifflcultlfjc observed with Keolttee ©Bd cloys were rewoved
by introduction of res ins . Since then tbecc orgonic ton-
exchangers have been used both in laboratories end industries
for eoparetions, recoveries of tuetols, doionisotion of water,
concentration of electrolytes end elucidating the e»)0hani6» 13 of great raeny reacti(«i« , The epplioetions of thei^ iim»
exchange resins pn»gressed so repidly that the theory lagged
behind and could not follow the experiments*
Just tin the flpplicotionB of tlMs zeolites are l ioi ted
no are those with orgenie ion-exchnoge resins unfler cer ts in
conditions. The reotnp Br<* isnF«trble in agneous systeiRS at
hlfh tCGiperatares ©r in presence of ionisin*: radintions.
For those reasons there hes been a resurgence of interest in
inorganic lon-mxchf^nfers in recent yeare as they are unaffected
by ionieinr, radiations and are less sensitive to higher
teistxsrstures. The structure of these inorganic ion«exchangers
1P s t i ff , therefore, they are sore selective RaH suitable for
the reparation of ions on the basis of the i r different pore
Pises. They can ol«o he usei oe ionic or solecular sieves*
Botnn stable towards ioai«in«: radiat l jns , they con bo used
a*1vant6Reounly tn reactor technolo'^.y* tnorf.ante ion-exchoc^e
wenbmnee hove also rccrntly been used preferably over
0
or^®nic oo©» hcoauec of the Inorganic oeobreBeis could penslt
h i rhc r toptneraturps to he used onfl hlglier «o lec t lv l ty for
oertfiln Ions*
Th© se l ec t i v i t y of inorgjpolc ion-fitxcheo^orfi b«s ^rcn 1 %
utlilzcf! for the prcporotlor. of Ion se lect tvo c lcc t rode t •
Tb© Ion s^loottVB ©Icctrotfes htivo new hocomt' Ir.nortnat tool
for eolTlng vorlouG onalyt lcol probldii« ,
In order to anderetaad the appl ica t ions an'1 t o laprovc
afjon then , syeteaet lc fttudao^ntol stttdlos aro hetn^ purpuaded
on theec sater lGls* Thle new tn te res t in inox^enle ion-
cxchangers oay bo sold to begin in 1945* I t was chown by IS
Boy<1 t h a t oolojine eontais iog f ina l ly divided £ireoniitffi
I^O0phnte eapported on s i l i c a wool could bo used t o eepnrate
uranliin and plutonlus; fron flsGion proloct© by en ion-<schenge
process. In eddltiun to zlrconiimi phosfhote ncny other
slf3ilar sobstoncee ©ay bo preporcd by Cosblnlnrs osideis of
group IV with the soro Qcldlc osidcs of groups V end ? I
of the periodic t o b l e .
The various inorgenlo ion-eschBngors reported iipto
1963 have been cdairobly reviewed in the aonograph of 10
Amf^lett ' which has bocoxe a cloaslc in t h i s f i e l d . The
stud lea on thee© isatcriolG fpcra 1963*t059 hEve been
s»ur?r»ariEed Ipy roUf ruk an-l Voecly •" under the follcnring
heedat
1, Hydroun ortdec,
2 , Act<1lc eo l t s of tntuHlvnlent csctnls,
3 , f r l tB of het<>roi>aly6cns,
':» Ineoluble frrrocynnlttcr,
5 , Synthetic o lunlnor l l lcn too , otid
6 , Certnln other cubrtctjces e,c* eyuthotlo o - o t t t o s , est lf*t<1©t
cod alkollnc cnrtli eulrluitcs.
Mortnelcy has cunnnrlKed the theore t l en l QSfteote of
exchonge In Inorgf^nlc loa-osCtinngc ca io r t n l e \ Tho fsyntheels
OQ<t cppl tent Ions of Inorgotilc ion-eECTioogerc huvo been S2<»26 reviewed by 1/6It on • Hecoot review oa ttio eppltent lone
of lon-exchanso ho\?o tjera cdltsfl tjy Knrinrtjy aw! Ualtoa"^.
The recent tron-lr in thr f ield of lon-oatchongo have beon
fuisr:airt«ed In the Jouronl of Clirosnto^rnphy voluao 102 (197%)
ifbioh contain*; tb« pcporc prccpnto<» ot tbo th i rd synpoclua on
lon-excbange boliS at Balntonfllrc'i {noncry) Kay 28«5i»1974»
• be pepers pree.^nted wore divtfleil Into four soet lonst
(1) lon«'«xebnnse ssatcrlols , ( i l ) theory of loa-oxohnngo,
(111) ana ly t ica l appl lcot lone, an<1 (Iv) lon*oxchonso
teehnolojny*
The eynthecis of new materials hew boee reported by
niiT»«©roui autborF. defining dif ferent types of atsorplioot^
poorly c rys to l l t ao on^ c rye t a l l t eo i sn t c r l a l s . The theory of
lOR-cxchange anl the nee of lon-excbangore In l ebora to r les anfl
faotor tes Is a flauriehtiig dieolpl lQe, The anfl tent loos of
loa-dtchangore la tbo Inborntorlea a« tjorte panslble, the
ehromatosraphlc separation of very Caoplloated rai-Eturoe. The
Bolootive use o? inorganic lon-exohonger® mny rrovlrto a oecful
lEoanc to conccntrnto on-l caitrr.ct the so r t ir;:^rtr;nt tsotole
froas laborotorlo© wastes aol l o c i l conooatrfito!!! peasples. The
appl loa t ioas of lon«<«xcheago t o mma loportas t prooossee tha t
occur at hlith teraperatur©* or In the presoncc of Ionising
radta t l tm or highly oxldls lnr e»<Jia oro «eirer©ly l loltefi on
coesierolally ovallable lon*exohaage rea ln t* nowcirer, the use
of f^ynthotlc toorganio ion-exchangors c-.n be ©ode under the so
conditions*
Unt i l rocoat ly, tbc Ineoluble acid ©altc of polyvalent
netnlj? have boen obtalne:? oo golotlnous EubfstCDCos. The
zlrconiuw phonrbcto is probcbly the f l r e t and the aost at tidied
of a l l tho ton«cxcttonger». Cryetnl l lza t lon of rone of tbaii
bore liaproved the ohonlc 1 e t c b l l l t y and roproSuclbl l i ty la
the lon-ossshenge behaviour* Host of tho l^ia-eseobange iBat<?rlala
with t h o l r proportlcs ore given prevlocely *
For a oonpleto deecrlptlon of a tBOterlal a» an loa -
catchcnsor tbo followlno; rroportloe suat be ctu^lcdi
1* The lon-cschansc capaci ty ,
2 , The rofitatnnoe toTifords r c l l p an^ baees,
3* Cotipositlon,
.9
4, roteotloE58trle staatee,
5, Dlstrltjutioa of counter ions l»ct«oen solation and
exchanger phases,
(J» Thcnsodynrmice,
?• r;io<%ttoi9, ond
8, Analytleel applletatlons,
X(m«>«3 bani;e eepacitjr is one of th« »08t fusdats^ntal
Qoantltlce for charcotorlzatlon of any ion-eitQlscnge tscter ls l .
For a stroni loa-oachan^or, the capacity can resaily he
dctercjlnea fey rtlroct t i t r a t i on . Various types of cotsaeitles
c©n be cxprerBe^ in different ESonera. fho o^uilibrlns ioa-
esctienn<> cfip^^oliy for o etrung ion-oxcticnger ct<a t»e detoninedl
by direct t i t ra t ion of strong cEtloii exchanger (in K fons)
with a ntron^ bnee, Flojorlty of tlic eynthotio tnorgcnlo
ion-eschnn^crr behoves m a woolc ton-cxolicn^er endt therefore,
the airect t i t r s t l oa iP not rollafele. In thle case lon-
exchcnj^e cark'scity ie fletcnBlacd by replEcemjot of hydrogen
loaB fro?5 tl5c ejfCfecnger phate by tbe counter ions of a
Qontral salt solution end of Seterslning the eqci l ibr las ion*
oxchnngf' copaclty ie by i»B-.titratlos8, Hexitsoa lon-excbanse
cnpecity cqael to tbe nnmbere of ionogento i^ronne per
sr^ecified afaotint of lon-exchangcr stay directly be detemined
by einple oolt^si operation paeein^ tbe electrolyt ic eolutios
oyer the lon-exchenge tsaterial (in 0* fons) end t i t r a t i ng
tbe liberated acid In tbe effluent tjy a etf?nflapa bfl»e solution.
10
Alihouoh the fHire toj3-©atchnn«»e capoolty of a eo l l l l oo -
exchenger oon be detcnsinefl In »ef«ral wajrfi, o proviso t r i e
methoa"^ of:fors for laoiiy ion-^xohaagere the advantage of
r e l a t i v e l y high eccarocy and imry Rlople eqalpaont r equ l r e -
imntn for only o» aiffereoce weighing without any ana ly t i ca l 52 eh€®lcol dateni inat ion of Ion, Breal:-through Cftp^^clty I . e .
the oseful c o ^ c l t y for attllssiRj'T the colopn op^ret lana, Is
of Iraporiance when the ra te of exchange In slow* This rote
nny h^ ©low t^ct the t o t f l c i ' - rc l ty rrrr not fcc u t i l i z e d In
rn Bctuni operation. Thp ofsrntton i s (lisco-jtlntsctl a t
hrerfe-throu^h before wsftchiw th? ccwplfjtc cqnil l 'hr lun.
ThlB capeclty which IB Rtlllzfil un t i l brer!:-throu|:h occurs
i r known OR hreefe-throu'^h CfT-rclty or 'lynrnic cnj-r^lty. Tt
{•'epenar upon off rot Int con'lltlonB e.n# le lo^cr thrn tVe
er!uilthrlur» lon-exchan'^e cfi"r*c!ty.
The ioa-exchon'^e watertol taaet he stu-iloi1 for ohcfnicol
B tab l l l t y in acidic an<1 haeic wjdlo t o check I t s l i ra i t a t ionp .
Potentiostetric t t t r f l t tonp cna helpful Irt ftnflinr,
whether th** exchengcr 1B Ronoftmctionel or rclyftJact ional .
Alher t i hac ftti^le^l t i t r a t i o n curvee in ffetri l on e i r con ias
phoophote with s ide l ine eerth w»tal hydrosiflee , He observed
thct theee cu rwr ore atrongly effeote<! by hy^irolyrle of
eschan/s^er and prec ip i ta t ion of in^solnbl© pl*oei^ttto$. Ho foan<1
tha t Ca precipl tnteg on the excheagcr ot 70 ' cxchnnre.
1
*>. Sr at %n'^ exchange and Bo at 100' exchange. No exch»oge
was foiinrt with *fg(0l*>2 Pf^^Q^ly because th« bydlreted ton of
Mg*" Is v^Jty Isrgo ana t t eoiiuot penetrate In the cavity of
th0 f>xcbGni»©r, He also gitidled the forwerai ana revere©
?lo*-l[* lon-exchOBge tsotherw end fmiB^ that llc*-E* exchange
in an aQueoup eotutlon Is a tvo step proeess with part ial
phase eoltitiillty. Albcrtl ©Iso stuatoS the lon-eieoheiigG on
crystal l ine sirconltiai phospttat® pre|»ar«<! e t tber by tbe
j^fluxlng proc©aor« or by direct pii^elpitatIon prooedur© •
I t was observed tbot two isaterlols, althowrh exblbltlog
e ta i la r x-ray powder pattams, possoes different l(mH»i«hfingo
behaviour.
fo an^€ rstund the tbeoretlcxil behaviour of ton
eimbsoge, tbersiorljniGeica 1» ao ieaportaat sta^y to wljicli ooae
woric tbottld be devoted, l*wo different approaches have been
applied for th le parpose,
The f i r s t Gppmsob Is beeed on the deelgn of uioro on^
eior^ clBborato sod@ls wbieb bavo nearly liico aotuol ton
excbongere. •Jbe oppltcotlon Is straigbt fon^ord. This
ofproaoh gives ecmlquantltatlve picture to a practical
eheatlet who Is Intercstod In uodoretandlng the jihyeloal
causes of tfio fhcnas:oo0, Ilowovcsr, tbe oholeo of tho isodlol
l0 oruclAl ott'l th is a^tprmch lo loss ll&oly to sott tfy a
theoretical cbooiPt who le IntoreeteiS la o rigorous tborao-
dlynaolc trcctBttnt,
2
To the Becon<1 approach attempts hove T>ccn niodc to
cor rv l i to the o c t l v l t i e e *fltl! SCWSP eeasurablo quaa t i t l e s with
the thcrfsoflynaBjlc equations* Same of the cfiiroocbec of t h i s
kinfl nay he iaentio»ed. Vhe ear l leRi approechce wore baeod
on Gcnlompericol or ewperlcal oquatioae to f i t lo ©aparlraentnl
rcf iul ts . ITohably, the f i r s t quent l ta t lvc formatloa of
Ion cxchan/i© e«jullll)rt«i we« mnAe by Geoii using the laass
Qctlin lew In I t s slraploet fona, The foraula dW not
involw the concept of Activity coefficloti t*. This oonoeft
wnr nccoonted by KlellPnd . A eultahle choice la the %&
(prenprol t roatacat n,iron by Gatnefi & Thowo« •
Thus the aoet Isportcnt treutrient In Ion oxcbL.n6C Is
the fitudy of chesic. I equl l lbr l tw which, of eoui*co, In a
rtudy In tbcrno'JIynculco, loorgsnlc loo oxcUtin^orB offer the
dvcntagoR for tUofo otodlet. bocnufi© of tho l r rlfiiS s t ruc tu re ,
n t ' t l H l b l c cae l l i n r end t l l fforootlol s e l e c t i v i t y , iTion an
loo oscliengor In counter ion A fona i s pieced In « solut ion
of counter lua B forra, tbore wi l l be »n equl l lbr l i ;^ sot ap
for the fJlPtrlbutlon of A an«i B between the eschcn^cr ood
solut ion phcsee oocording to t h e i r s e l e c t i v i t y . This cxcbnnj»;e
(at cc}UlllbritoB) psay be reprepontcd a«j
A • B ( s q ) ^'" "•""!'' n * A (aq) . • , , ( l )
For the sake of convenience the effect of co-lons on the
1 3
ef |Qi l ibr i t^ jsay b« neglected. Th«» therpjo<!viiofflle eiiulltbrliiis
coastfnt for itHs roRCtton •acy V w r l t t t n asi
«A «B [ I ] [B] 1A ^B
whero I ivprcfcnts oc t lv t ty eo t f f fe l nt tn t^c c-rC^nn^fr pbofli'
na** :£', tho .tct Iv l ty Coefficient tn tho ac}t»coap, n'^n'^p.
The i jsr t loalar use of tbensodyncalc cqullllirlo©
eatifttufit in aa^lc to find out tho fr<!(* etiorny c: rnT**' In t (»
lon-^xchange procoefer. Tbi. lanic rrl«'»e* Ivi ty i* •'ovorBC'l
hy tbo laiferioR of froe vmyrzy ot Vw ry*"tr- i r rn l^portaot
fac to r which gives ttit' tfifar : : 1 jn about tlio : r e f e r e n t i a l
iiotafec of tfec couotf'r Ijn by the or.QUanzcr, Taotrfii"- T_ volufs i l
f t i l f foront tcr^croturct the cntfjnlpy ehr.n cp of the eyr-ten
rjajr Dleo bo cvoluotea. Tbp rut ' r l r y c^rafo In t^c profcrty
noot d i rec t ly rolutc«1 to tbc ciinn-or in the nticticrn r.n«1
f-trrn^th of bjnlf In t^c tan-e^Iuti:7,o rcoctloiifi.
ffae toB-eschsnfe r tac t ton (e«tiiatt<:w i) prov!«!©8 that
f t ruc tu rn l clit^ni'ep within the esehrngfr ore f p a l l , the roi^t
tptpyrt«nt factor litfluonelnfj tlif* e n t r o y cbnnfc tn the r^cctlon
tnvolvfni: tho osohnnno of etiurlly Qhorr.o^'^ i»3!ir. w i l l bo exf^ctodl
to roMilt fra cSioo^ier tn l ibera t ion a n t r o y noy loo play m
tni iar t int r^irt, titc ovcrcll n t ra y wi l l r e f l ec t c5ifinn<?6 in
rnnrlonnens tn tl e laf5«-ejic!i'"n"f reac t ion , tlie ^ r iv ln" forcee
14
betn»5 the tPnf'eney for the eystem to go to the eo«t probaMe,
ft fit i r thf woflt r(^n^<m s t u t o .
The toa-exchsnse cqu l l tb r to of 1.1 , Kn*, E n«w! Cm*
xms 8t«'1io^ hf Lorscn ©n l Vltnertr^ cc:! Grl nml n«vrr*€i
on omorphouc zircoaluw pliaBih.ito of vi^irioua ounpofdtlan oo^
p rope r t i e s , Heccntly, Oktctitlja r tull?© jti tW) lan-c»iicniafe
thornodyno^lCE of o lkc l t oatlanc have tiC' o v^'i'^c u!t*i noro
iltftaoi?. f-ealoryfttollIno and c ryc ta l l l ne ?dreonitm ptjospjiati} ^ .
Thcf intf»rprete(1 tb© therRO«l3Fna!3lc paroset<»r» lo fomn of
jitfture of tho feornlln?! between the cl&all ©otal Ion aod the
n r t r l s . Doetple ©tu^Uct the excuaoge of C© , Sr , Co
«i3if r.B" Ions tsltl. by^rof^on hatli a t o lc ro sri'l isasro ooncf^ntra-o
t tone Invflf! over n roni^p of tc»«reKitttr© (5*70 C) on zlreonyl
r»»io<^nhnte. Th© excnsnfc^ e^ollllirttia sttidles of Ce -— n
ond 00?* — n* " have he©® »i»<!e l»y Ravarcc on crjrptel l ine
atrcofilR*! fho«nhat©# nocently th© Ion eschnngp c<iatllbrl0
oil cobalt (TT) hexncynoferrete(IT) have been isaflo by Cerente (KB
rtfi'^ Ailnrovlc'^'^* S l s l l a r ettt*?fcg bivc e l BO been rcfortefl am 56 tiylroup Ktroonlo, Gnlon ©schatigor, by McncolloB • The
thcnsoflynnialcfi of lon-oxcbooge oa aeo l i t ep bav© bofm r«*.6o
with 0 grea te r ©stoat. R«M,Bcrrcr, U.S.Sherry anti AJ^for
^ta^lofl tho offoct af tenporoturc on loQ-excJinaio with
fUffercdt Eeoll tes In various cat Ionic f o m s , Ctioy onlcniatedl
tho tbortsodyaoslc ',»Qrcaotc»rc, TIiormsKlynct^tc eiu'J!leF! to r
a l k a l i ao tu l s anfl olUullne ccr tb i?etnl© on forrSO tintteoitcte ''"^
15
an4 titoblfiis arscnoto were raoie In our l abora tor leo . Some
of tLo oquilibriucs Btu<1lefi on different ion c:sc:icnto taatoriolB
with verloufj pyateen anfl t b o l r far»reterp ere p;*v^n ^n Table T,
£/.
I ;n
o M
2 $
o
f
•J:
O
X
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19
Studlofi hav© also been nadc towards the thorrao^lynBwlcs
of flnloti eschangc on Inoi^onlc Ion ejcehongeris. The r e v e r s t b l H t y
of Br^-NO* ©schange on hydlroue sslrconia was deisonetrated by
^rou«"^. The thersso^lyfiaBsles of Cl ' -Nul , Cl^-SCfl" and PCN^-NoI
exchange on hydrous Klrcontun oxide was otudtcd by Nancollnei ^ fid PaterBon • The tneehenter? for Ion exchotige capaci ty afypeart
SI t o bo hlubly spec i f i c , iluirarac and Trtanj atudted the
thfJTtaodyno'Silcs of CI and fH>- fron solution and KO- frotu 6 ft
hydrous ziroonta at 25 -90 C, Thotwodynaralc quaatitlcf! (AG , O 0
Alf and AS ) can be coloulated by ovaluatlsr, thcrnsodynnwlo
©qulltbrlu»n Gonetont,
The UPC of stxed aolvcnt ayrteras lllio oethnnollo water
changes AG and ohanixe« AH and A S of the exchange of CI
for NO- In hydrous s t rcania and thus the s e l e c t i v i t y constant
i s affected* s e l e c t i v i t y reversal occors by incroosing the
concentration of ejethenol in the ©Ixture above a ce r ta in l e v e l ,
Mtsak and Mikhail studies! the thensodynanics of N0-/C1 ,
Mor/Br* and KOl/SCN* exchanges in hydrous c e r i a , Se lec t iv i ty
reversa l of monovalent anicme do (Kscur in the weak base
hydrous oKl'tes l ike ce r l a and s i roon la , Ccrtoln rsodels l ike
Liseo"non raodel «ay throw eone llijht on the phonw^ena involved
In onion exchonse of hydrous oxides but ce r ta in fac tors l ike
non-couloR)bic e l e c t r o s t a t i c a t t r a c t i o n s and osido entropy
chftni^es have been ignored In t n i s raodel, r>ycr and Malik
20
cotsrsentea on the thorsol and ohealcel e t o b i l l t t e s and
se loo t iT l t t e s of oorrtscrcially avatleble inorganic anion
©xch8n|»ero with the help of exchange Isothcnae for the ions
sofj*", KoI , CI", Br* and T*". Hygtaretle loops mere ohtaincd
in the anion exchange ieothcrms obtained for the exchange of
NO "/CI**, K0r/5CN*, F0 j7Cl* and ^ J I V ^ C N " on hydrous
thoriun oxide " ,
Althounh thcrcjo^ynasalCB ie a powerful tool for
inv«>«ttcaling thf» con' l l t i inf a t e r u l l l b r t u n . However, ! t Ip
Intorosted only in the i n i t i a l and f inal s t a t e s of a syateis
and i t does not eonsidor about the mechanif^n of tho change of
one fitote to the other and the time re^ioircd thereon* Slnct loe
tnkoB theffe foot or § Into conptderat ion.
The teinettoe of etnplo horoocenooufi chcnicnl react ions
Ir? piovcmcd by the rote of the reaction def5ondtn«» upon the
concentrotiona of the reectantR
sA • yB ' ' ) Product
n « Jt. CAl^jD]^
where !t iu the r a t e constant , [A] and [O] arc the concentration
of reactin,'5 specior end x and y are orders of th<> react ion with
respect to A and B ropj»»ct!vely«
2 I.
loo-excbfioge, however, t s sojESWhot d i f ferent froai »uch
chcralcal react ions* In the f i r s t caee tcwi'-exchoiig& Involves
the t ransport of tons froen solution Into ©xohanger phese an^
vlco-versa . Ton«->«schan!?cri9 cons t i tu te a d t f feront phase than
the eoltitlon phase on^ hence the process le heterogeneous.
Second!ly, In lon-cxchongo proceoe coions have no part to play
in the overal l reaction iscchanifiaf!, only the counter ions ere
re«ponplblc for th i s procesu, L lee t roneu t ra l l ty in each phaaa
and at a l l tleies la to be s a t n t a l n e ' * Thus the norther of
charges carr ied hy tho counter lone of one type Into the
ejEChonger phase raupt be equal t o the number of charges earrle<!
by the o tbr r type of counter tons loovln'! tho exchenrv«r phase
Into the eolutlon phase, at the earse t ime. This coupling of
flowc of th** enter ing on<*5 lenvln'r ions s t e p l l f l o s the t rentnent
of lon-.cxchan(»e t : lnet lc«.
Ion-exchange procoee thna can be coaaidercd aa tsade up
of following atepat
1 . Migrotlan of counter ion A fron lon«exQhanger pa r t i c le in to
the f l l o B'^hcrca to the p a r t i c l e ,
2 . {Migration of counter Ion A frora the fllra Into the so lu t ion ,
3 . Migration of counter ion B free the solut ion in to the f i l e ,
%• Tfigretion of counter loo B fron the fllra into the par t i c le*
Since the rate in dotorntnca by the clot^ert s t ep . I t Is
Ireportcnt to canslder n i l these a tepa.
9 2
Three <Stetlnot type® of k ine t ic processes may be
ccmeldcred la an lon-cschongo proceoiij
(1) Intor-«llftaston of counter lonii In the ft?1horent fllra, the
ftliB (liffutilan control*
(S) In tc r -a t f fus l jn of counter Ions In tttc Ion exehaii^er l t « e l f ,
the pa r t i c l e dlffuslun c o n t r o l .
(3) Che«tcol eschonge reaction bett^ceo the two typcB of counter
ions .
I t i s on Important point to note that of a l l the exchonice
telnet Ice which hove appeared In the l i t e r a t u r e t o dntc , none hoe
been Phown to be controlle^^ by the chenlc i l eschoof^e rooct lon.
However, I t Is not purprlnlnn tjhen stronr: ocl<1 and ctrons bnee
exchflngers are uec'! whore the coanson counter lv>n6 do not fora
the oheialcol bon<! with the flxe^l lonogenlc group but i s somswbet
retanrltchle when there le a conplcs fortsfltlon. Even In such
CQBee the k l n e t l c a l l y elow c t rp woe found to be pa r t i c le
dlllfuslon ana not cherlcol eschonce renct lon . Purthef»ore
the re te deters lnlng Btep s l so dopon^r upon esperlts^otal
eondltlons* Borne tbeore t iee l cn^ pract ica l approcchee can be
opplled t o decliS© the Tsechnnlre of lon*eschQafi[o r a t e .
Jlechokl flntf Wood^* have sa^lo the f i r s t ser ious attempt
on the Itlnetlc etudlefi of lon-cxc.iange* They hove etutllcd the
reootiou rote with which lone frosi solutions ere resoved by the
soll<f ion-exoh@ng€r or convereely the ra te with wr ich tho
o 3
©xcfjoni crble taac are roleaeefl fron tb? cschnnger. Boyd et a l ,
bavo la ter on stu^ica artoetlcs of tnetal Ions upon the rcntn b^ads
on?! bavG given a olcar anaerBtooain- about th© norticle anfl film DO
diffusion pheaosiefio which govern the tcm»€xohaoge, n^lchenherg
conflrsotf thot at ht«"b concent ret lono the rate In laa«i«M>aciit
of Ingolnr Ion (particle diffastuo), while at low concentration
the revorso ie t ru® (fllt3 diffof^iun). Haacollaa ' started the
kinetics of Ka*-fl* exohcng® o/n eryRtolllno sirconinai phoephate.
The rate of exchange ie i n i t i a l l y fast ana ttirn becocot BIO«»
fsug'^sating a change in cryetal structnra, Fo^e ai«! Klkinai'
etudicd the kinetics of loa-excbange hetwcon alkal i E^tala
ftn«! siircorjlu'*! antlronato in I! torn at 25 C# They found that
thr rati* of the reaction incrcoaeB with the otOEJlo ntieber of 91 the cntion, Altierti ft a l . have observed that the* rota of
cizchcnc'* decrcofcn fro?^ Be to Sr and thot It is r^rt toularly
low for Mff ion. Since thr energy of hydration of given M ion
decrone^p wttb i t s crystal l ine reditie^ i t i s lifeioly that the
lower exchange rote of M tr. related to t te relat ively larger
hydration onerfy, "fheroforc, i t 1« diff lcat t for the large 2+ hydroted •!?» to dtffiifie in the re t icular etruoture of Eireonitm
f.hof5pbBte phapet havln* low interleyer distances,
92 Costantino et el# hove studied the self diffusion
of ^a* and K* ions on ulcrocrystale of Zr(KaH)4)2«3K2C) and
21r(KK) ),3HgO and aodifle<1 the Fick's equation to take into
24
acGOttut th© jion-anlfot^alt ty of th«' par t ic le else* The cijuotloii
obtained hove heeo eiapl^red In o stuffy of self dllffasioo ra te of
N8 and R tone in the above es^hanger*
lucently Iclsietlc ©tu^ic® on toortiaiilo ton t^ieahnnfiere
were node In our l ahore to r los . A felnettc study of eatchung© of
cptlotie Ag*, Mg^*, Ca^*, ?r^*, Ba^*, y-^* OHJS fh^* was a.i3«e on 95 tantalups erconete , The neehantsa «©B controlled hy p«rt1ole
dtffttstoa* Th© felnetics of exehonge reactioii@ of Ag y -n , S* &• 'S* ^^
Ca , Rg , h& cintS Th lono on Iroo(ITT) antteonat© has hees
stuifi©a a t different temperatHmt # fh t o e e h e o t ^ of oattiwi
©xehcrtgo h iiB hccn th© p»r t t c le ^iffitsi^m control whtch le
conflrrer! hy cer ta in plots* r<inetlc paretyctor© hove boon
cralijfttca, Fl»?il0r «t«^l©p on etanntc arfeaoto for !?«*, Zn**,
' g , C« , Cs et!« Al* haw oleo h«»eii wed©^*', Tb©
applicat ion of nnch 8tu«!l#o on clays wes e l so nade by etudylfiff
k ine t i c s of ?n ©jtchniif,© o» •Sodlim T»lcfelte * ^ , The
npchpfilcn hae been foundl t o b# s fllrs diffusion e^atrol*
K:in€»tie p©reB©ter» has a l so been CTsltsetcd*
The a is t r tb t t t ton of en Ion between the cxct^aager anfl
eolat ion phOBOP t s © ec«Eiire©ent of ©elect Ivi ty , df ten , the
lon-esehf*ger te&es ap o t r t a l n lonis in prefcttsooc t o the oth«»r
present coitnter lons# Thla s e l ec t i v i t y may depi?nd| nalnly n ^ n t
( t ) Bonnan po ten t i a l , (11) sieve ae t l an , and ( t i t ) cofsplcx
formation* Th© Bclect lvl ty In an Inportant fac to r t o atti«1y the
L, 0
eeparations. On the basis of distribution coeffictente
I t In possible to predict the separatiun of oao ion froa
the other. Tbe difitrlbation eoefflcient i s of value en a
procticol guide to the eeparotion proccJiirc*; in c^rosf.tonrcphy.
The dletrlbutioo eoefficirnt for en ion A le |»iveo by
na AsQuat of cation (A ) preeent in eHChongor p^ose g
Amount of cation (A ) present in solution ^aee ral*
* * • • • ( « )
The general ucc of dletrlbntion coefficnt IfJ node In
clutitm technicjues used In eeparotlona. The rate at which i jas
tsjve lo ion-exchanffc chr(»r.fltography le proportional to the i r
dlDtribution coefficient*
Analytical ion exchcn^^e eicficrl»«»ntB a«j best carried out
to set the condltf jne in vhich the solutions ere d i lu te , loedlnf,
i s lour, {m^y less then S-IC! of tot s i ion exchange capacity)
end n:d l0 thereby nearly conetent. The lnor""nic ion-^xchangers
have found auiMsrous itsportast enalytioel appl loot ions as
categorized belowt
{ i ) Purification of sobetaaoes on a large scale,
( i i ) Separatl>n of one ion froa the other on a sraell ion-
excheager colui^,
( i l i ) ton-^xohange pof^r ehrocatographic eeporsstionSt
{ iv) ClcctrophoresJe,
2G
( v) lon-easshflager for gBB chro-noto^rophy,
( v i ) Poll*! e ta ie separottone,
( T 1 1 ) S|«>clfic Ppot t e o t s ,
( v t t l ) Uee of lon-cxcfeonger bctv^f to locoto th<» <*n«! point In
t i t r a t i o n , aad
( tx) Us© of l»m ©elective electrolCB,
PurltlQBtion on e large ecale can be '-ad© by naeslng
the eaiaple solution through tfeo lan-03tchooner bode vbleti toke op
oc r ta ln taatorlale In preference of o tbc r s . The exchesger bed
cnn "be rojeneroteil Into ru l t rb le for" by con^?r'nttoaol r«othofls.
The technique con ol6o ^ ut 11 Iced t o recover t recep of
clrncntr . frtR^ the d i l u t e colut lone. The oletajnts proGont In
tonic fom ore cxchenccd by erulvnl«^nt CEtount of the eouotor loo
present 1B tho cschOREor» The c l e c r n t s con be eltrtcd fror:* the
exchoncer by eul teble e l e c t r o l y t i c rcegont .
Xon-earchGttge l e , «riih very fev exccptlous, a reversli»le
process* The s jetel l ic lane ere exch»tii;ea 6talchlo":setrlC0lly
with hydrogen tons la e^mhenger i^ase en<3 the a e t e l Ions een be
determined Ind i rec t ly by the appllcotlon of exchonge react lonet
where n repreronts the e t ruct i i ra l uni t of the ion-cschoorer, on«l
r end ?r ore the cot lone tcte*nf» pert In the loQ««j;change • A
o 7
s i n i l a r i^thodl oan bo adapted for the replocomjnt of eoione by
hydroosyl tons stolobto'tsetrionlly.
Jon-^xchcnfie bee roeolved the motat d i f f i c u l t problea In
elsc*ntcol ODalysis i . e . ccpurntlon of typtoral cos^paaients having
etfsilar onuugb proper t i e s . Colur'n chror.fttofcraphy Is Talttobley
fiocc tbc ©abetoficost separated arc col lected f jaant l tc t lvcly .
Since tfeo c rys tn l l tno loa-cschnB^erB hBve eavltl©8 of
def in i te Biz0^ thoy olao poEcttrr Ion sieve p roper t i e s , fhe
counter lunf hnvin'j lnrf»er i ^d l l than the boles la the cavi ty
enn not ponotrfite mi therefore , they coo be ceparntcd froia
thoeo ct^ollcr lone wtjlcb crn oscl ly en ter Into tha cev l ty .
fhcs© geporottonn Koro f i r s t cchleved by Clearflel '1 on slrconltaa
pbaghote c rye t r l e and ore Bmmorized belovs
Zlrconiim phoeptisto and onhy«1rour ffictol enl t vore heated
In a plottnuia dli^» The esohanse react ion toljlng plPce le
roprpccnted by the following equetlons
r(nru )g.PgO • 2/x ?ici ) ^^^-'h/js ^^^kh * * ^ * "2^
"TioQ nine chloride or bafnlurj chloride were exchanged a net? phase
was obtained tJhloh f^rslstod to eboot 2/3 of t o t a l ccpacfty of
e:2cbQnit«'»r, Thone wWr* ran-^oc of nctol coatont f o n l n " the eawe
ntrtiw'tur? I'idlcpte that so l id oolutlone of cottoti v l t b l n c r y s t a l
l a t t i c e are for^ln«, ?ho fact that a var ie ty of oa t l jn type
28
gives the sea© phases (olraoat l«1eiitlc«l tn terplanor epeoing
but d i f ferent In t ens i t i e s ) Inilcat©!? tha t the c ry s t a l lattlo*?
rt^^jnlne r tn t« ^Ith tlio ca t ions occupying e l s l l a r oxcliang© s i t e s .
This in unll^o the bchcviour of Elrconlasi phoe|^5atc cxchcnglng
l«*n0 In aqueous e l ec t ro ly te solution where tbe l a t t i c e exponas
by the laoveraent of the (I-zirconItio phosphate layers t o
aecomBNNficito hydrate^ oatlonfli. The e la t ion of eaticms v i t h
d i lu te acW solutions provort the i^enoreenoii a« ioo-exchiinge,
th© oaticme coul^ also he ronovea hy contacting the exchange
phasefi with gaeeoue hydrogen chlorl<^e,
Sor« 1 jo-oxchnn^e sopcrotluns were nleo achieved. A
solut ion cotjtnlninr! f-quol per ts of l l thltaa chloride and ccosluo
chlorliSe woe cvaporoted to drynofin and the dry snl t Rlr tore wne
"roMod tOKOthorwIth o(»slrcoalii^ phoBphoto. On hcotln^ the
nlxturo ot 125 C lithium exchani^cd lenvlnf cronlitn bccouoe
the cnvl t ioe are lori^o enough to imrf^it a oofet^ of shoot 2-6 A.
ThuB Cs should be ejsclodod os wns observed esTierlncntnlly.
However, very few l i t e r a t u r e ie available oa loa-exchange
in CTolten s a l t , Alber t ! and Al lu l l i t rea ted iooHsscfcancc on
osorphoun zirconlam phoephoto in c^olten n i t ro tee* They found
t h a t llthl«Ri ion in g rea t ly preferred over potosBltao lone
by the eschmger .
Albert l elBO tsttidtcd thr» fspeolflc conductance of
anorpho««t 2lreor>lu« phowphftte In t l , !lo , K and CP* forras
29
over tho ronr^e 2»40^' eonverslons, Tbo ep©ctflo contactotseo
of hi*' oud CB forse vaf. found to flecreoeo with percent
coaveTBijn while tha t of the Na aw3 K* foitis f l r r t locroosep
ood thon deer<*ace0 as conf«rslan proceeds, A t en t a t i ve wod©!
wac propotod t o explain the otiterved i^eiiomenoii*
Tho profmrotloa of on enlao excho.cfre ronin with good
cheolcol nn-l thomol o tnb l l t t j ' roaatns on outstan^lnp pro!)Ion*
The mitjn exctinnre rer-lnfi ore* fswolly proparefl t>y Introtluclng
on flftjlne o r smonlu*? nruupto."; np a sawrc© of noeltlvo touo^enic
rjroap Into nolyntyrcnedlvenyl bonsene copolyror thruu,"!! a
Prio-lol-Crofts eijii«l<'nsfltlao, Tho co "!!soo loa oschon,*!ore ore
b«8<»d on t r i e t h y l n a l n c , Atj Icornnntc fjulon caohonfcr can bo
prepnw^l by Intro^luctnr' trletfcylaTjlnc group i a t o the hyaroup
oxtde of 0 t r l va lon t or t c t r a v n l m t netc l i ons . The iS!alno
'^.ronp ooy a lso cct os n chclatiti'^ nroop t o ce r t e ln ofitlone nod
hencf euch « rsoterlsl raey ho useful la tt?o ^ cy© (1) as nQion
©jrchanf^e, and ( I t ) a c h o l r t l o r eschaoi^er*
A Dew oheloitnn raotorlnl, tttantuaCTV) Otothonolnntne,
hoo been preponJd by codif icat ion of hydrous t i t ac luB oxide ' ,
A nov cleeB of Ion exchange ree tos wat developed hy
Gregor in 1952 hy suhtt l t i t t l i ig a chelate group in a highly
oroselinlced hydrocai^on ciatr tx, Sliwe then tsoiiy eubstences
&iio«?{} fis ohelottn?? itm eaehanijer have been described in the
l i tera*ttre# Tn theee types of exchongerB the use of chentcal
30
react ions can also be con^ldorad to ploy on liapartant r o l e .
The chelattn«r ton excfefsn e P'Stertnls bei eve rlitee true lon-
exohangcr© and the functlotiol ^raup Is e chela t ing groap which
1P fixed within the a a t r t s . Parraatlon of a cainplex with a
r e t a l Ion 1© en extswple of a ouonllRfttioii can^pound in which
tho donor of loan unlr of e lec t rons I s the ca'»'pl«ir 8f*cfit
and! the ocntrol wctnl ion forp?s a coorfllnnte covnlent bofi»
with l t» Foraatlon of the eo'^plex depcnflB tipan the s t a h l l l t y
oanstunt of the chelate foiii«!sd,
A ler'^.c nunbor of prococsee for the preparation of
cbclntlng Ion oschcngers hovo been ci ted in the l i t e r a t u r e in
the recent pos t . They ore baee* nolnly OQ condensation,
palynerlssatlon or ed«Htljn polynorizatlon eiul IntrocJuctlon of
cholRtliiG fonetlon c i t h e r during polycerlzatlon or attoching
a f t e r polynterlzotloB,
Varied physical forws Fiay thus be obtained with soch
0 wide reose of preperat lons . Further the nature of che»9ic€il
acl^lltlons i s ba©e«1 on the introduction of wide range of
!aaterlnlfi# Chelntlng ejtchengerp thus hove dcslrcblo proper t ies
of high capaci ty , high s e l e c t i v i t y , k ine t i c s an^ high li^ohenlcal
strength«
The presfnt work 1P undertafren t o otudy the ion exchange
ermlllbrlQ of a l ' ta l l netnl lans on fer r ic ontlnanote end
thnt of ce r t a in anions on o new sirconiun trlftliylflnino onion
31
exchanger* Kinetics for the t r ans i t i on laetal ions Is done on
stannic oxide, A new anion exchanger, f e r r i c triethylaralne
hnp been synthesized anfl the materlnl has been studied for
I t s ion exchaniie capaci ty , jAi t i t r a t i o n , M values, chemical
find thertnal s t a b i l i t i e s . Certain Important separations of
the anions are achieved on the colutan of the wa te r lo l .
32
1. Mazzocotelll , Asbroglc, Pranchc, Roberto, ncnd.Soo.Ttal.
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17. N,L8ltshralnarflyanalah, Mcrlirone Electrodeo, Aoadeotc Prose,
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32. J,Tnc«e^y, "Analytleol Applleati ms of Ton-Kxctiangers*,
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35
47. L.H.Baestlc, Ti.nys and T),VaB T»©yofe, J.Tnorg,Nucl,Chein,,
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3B
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37
7fl. E,?^,I.«r«>e!i end tf.A.Cllley, J.Tnorg.Nuct.Chen,, 30, 2S7
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(t9R4)«
CH A P T £ n • II •ti-mrTT-iinnii •) I [ii.i i i . ._ -rrr n n m - i irmiirr^
lON-CXCIIANa EQUTLIBRTA OF AI.KALJJCTALIONS
ON FtoniC ANTIMONAtE
39
Bqallt!)ria Hetveon loB-exehengere «ni eolutionet is
being »tiiat®d wttli great Interest* The «ar l l0r sta^ftee
were mmHe on tnarganlc lon^txebaiigers• Stu«!l©ii on orgatite
iofi-exohasge resins vere sm^e ©ft«r It beeause of late
Inv^fitloii of tbeaa realna* tnorgantc lon-exchanTera miell
to negltsjtble extent, andl, tberefore, the theiniO)33^a«los of
lon-excbaiige on tbeae raaterlolff will be sirapler than on the i r
organic coanterparts where swelling Is ciulte appreciable, fn
recent yeare severnl theorlet of ion-exchaogc equilibria bawe
been developed and triet ' on a nitmber of liiorganlo ion*
estchangera. The lon^exobange eQuilibrlsm atUiSiee on anorphoue
slrconitxtE! phosphate of Tarioot o<^poaltione end properties i 2
hawe been reported by Laraen anfl Vlesers ami navarao for
alisall metal ions, Sose adwlrable stogie® of ion-ejpjhange
tberBo^jmaaict on ee^sl-crystalllne and crystal l ine ztrconloa
f^osphate h&ym been ©ade by A«phlett, Albert I , Honcollas an«!
^yer at different teoperaturee with various c rys ta l l ln i t l e s
of tisaterlal for M , Na , K , Cs and Rb ^"^t K.Abe, tarsen
on<S Cllley perforstert the eiadlee of loa-exehaoge efiatllbrltm
on antlsoalc acl5, xlrconlttn phosphate ^ an« eerlnai 14 11 i^
phosphate respectively. Baetsle*"' ao^ Wavaroc*** reported
tbe loo-exehanie ecfullibrta for Ca *, Sr , Ce'** aort Eo
with hydrogen i<ais at n tenj^ratere range 5*70 C os zlrconyl
pbosf^ate. He also stusllei the effect of tesperatitre on
io«-e3ichcii|tc fcr Co *, Sr *, Ba * and ha^* on polyantlnonic
0
17 acid at eonetent tonic strength •
This ohApter desorlhee the influence of tetEiperatare
on the ton-exchfloge e<iulllhri«ai of Li*, He » K end Rh* with
n on ferric entlmoitate at constant ionic tttrongth within «
the teisperatcire rang© fross 5© to 60 C» A nirople approach
ho« heen appliea nwi the thtrmo^fjnaanio par»i»eter« ore
calOQlated.
* J.
• • T i M i j i . . . . I . II I. II r 11—••iiULi
ferric n i t r a t e (B,l?,n,,Tn?fts) and autiisoiiy pcntachlorlde
(B,T»,ru,Eiigloa£l) were pse3, t o prepare the eolut loa of nattisony
pet}t00til9ride one 1ftre of tiyflrachlarlo acid kK vae prep^rei to
a fitandar^ flastc:. About SOO a l of t h i s solut ion Is takeiii In a
boaker anil th© stgpul« of mtimony peiito«lilorid€ and the benteor
eoat^ilain^ the %M fey<Jrochlorlc a©i<S were cooled t o about 2 C
by fMittlag tlies! ia aa icebath* Aatltsoay peataobloridle fro»
tbe eapule waa added slowly la tb© lee cooled hn HCl with
regular t t l r r l a g by n ^laes rod la e ft^anlag cbaraber. Thl t waa
traaeferred t o a oae l i t r e itaadarfl flask aad ®ade opto tbe
mmrk with %M HCl. This prejiared solution was about 0ǤM, To
prepare O.IM aattmoay pentaehlorlde solut ion, 125 e l of t b l a
aolotlcm vofs taicen la a oae l i t r e atoiidard flask aad isad® apto
tbe wBtt with %M flCl» All other reaieota oae«1 were of
/)tnalaH grade*
The aolotloae of f e r r i c a l t r a t e sod aatinony penta-
chloride were prepared ia de»laera l la td water and 4iM hydro
ch lor ic acid reapect lvely ,
gyntheala of f e r r i c ( I I I ) aBtlBoaate
Ferr ic entligoBete was ©yathcalzed a© reported earl ier*®
by mixing 0»1M eoluttons of I ron (TIT) a t t ro te noa enttisony
pCRtfiChlortde* ftm sero pH of the f i n a l eo lo t ion was
©flj[tt8te<i l»y adfiiag asjKoiiia so lu t ion aropwltse w i th constant
shaking, fbe pro(5«et woe nllowe<3 t o stand f o r 2^ bourt*
I t w®s f i l t e r e d , waehed wi th deialaeraltsBod water sntf dr ied
tn a teisperatttre coatrolle<l 0¥©B at 40 C« fhe profluet
lirolcedlowiii i n t o s i ia l l pert I d e e when itm^vee^ In water. The
mater ie l was eonverted In to H* forta by treotraoiit wi th m
n i t r i c 0Cld f o r 2% hottrt w i th oecasionel Bhaktnc aoi i n t e r -
la l t tent ehanftng the ecld» A l l the tamplep were sgitln e
drte^a Bt *0 C.
Prooei3ttrB
the ©dui l lbr i ins «xperiffient» were perfor«»1 by sbolclng
20 ©1 »ol»t lon eontaining bydroeblorle mei& so l t i t i ^a ®B*
afif iraprleto fflteall i ^ tJ i l eolttttooa bar lo^ con»tf*nt los ic
strength 0.10 In ttopperefl contenl f lasks* To t h i s 0.5 m
of ©xcfeanfer i n hydrc^en form wes &Me(i end f lasks wews sbaken
tfeoroughly i n a terai^ratorc oontrolledi «hiJk©r fo r 6 hours at
d©filr©a tei9|»er8tares, Experttsents sbowed that ec|uilibriass was
attoineiS w l t b l n t b i e pofio^ «o^ alt i iaotcp fro^. stipemotant
eolnt lone were analyeed f o r hydrogen ton© conccntratlcii i by
t l t r n t i n g I t against etandard NaOH ao lo t loa .
43
ffi.SUI.T5
Tbe excliange leotherae for various ca t l aae at different
teraperattiree are plotted to Figures 1 t o 4 ,
Til© r«6uH0 of ionic freotlons of ae to l Ions, s e l e c t i
v i t y eoeff lol imts and thcnsodjmealc cqoililirluira CQuetante are
given in feblee TI to V,
lOSIC FRACflaHS OF Li* , SElXCTIVirY COEFFTCILHTS ANT?
TlE RMOn KAMTC EQUTl lUnlUM CaNSTAKTS FuR Ll*-H*
EJSCMKCL on FLRRTC ANtlMaNAfE
' " ' '" 4 ' '"• ' "•" "" I '"""""" ' t '
I >'W»»IW — » • M M I I W I I W — H —
(a) Ll^-ff* at 50 • I ' c
0.001%
0.0932
0.1932
0.2862
0.3769
0.%722
0.5605
0.6559
0.7*89
0.8419
0.9302
0.0016
0.0282
0.0483
0.0984
0.1250
0*1983
0.2S16
0.3150
0.3630
0.4150
0.4983
0.5028
0.4927
0.4254
0.3642
0.3266
0.2590
0.1654
0.1568
0.1291
0.1047
0.0745
0.0769
4 4
(tal»l« IT continued)
\ i
0.0050
0,0955 0.1911 0.2600
0.5793
0.6029 0.6582
0.7512 0*8442
0.9525
0.0020
0.0979 0.1978 0.2908 0.3S1%
0.4768
0.6052 0.6605 0.7535 O.S%65 0.9349
(%) Ll*-H* at
0.0017 0.0216
0.0317 0.0617 0.1183 0.1817 0.2650
0.2983 0.3483 0.3983 0.4816
(o) tl^-K*^ at
0.0010 0.0150 0.0151 0.0651 0.1117 0.1652
0.2483 0.2817
0.3317 0.3817 0.4650
^
40 • t*C
0.5028
0.4927 0.4142
0.3599 0.3049 0.2514
0.1605 0.1482
0.1151 0.0921 0.0672
50 • l*C
0.5048
0.4889 0.4126 0.3478 0.3012
0.2476
0.1535 0.1416 0. t088 0.0!J04
0.0605
""I" ""•""'" '•"'" " " '""""""
0.0634
0.0499
4 5
IK L .
C o r w K
1-0
c o
o
*c
c
>
X 30°c Backward 0 30' C Forward
•71 /
/
/
0 '8 | - A 50'>c
1-0 0-2 0-4 0-6 0-8
iJJ Equivalent Ionic fraction of L i * in solution ( X , . )
FIG.l ION EXCHANGE ISOTHERM OF Li"*"-H* EXCHANGE ON IRON (III) ANTIMONATE
46
(Te!»le IT continued)
\ i
0.0020
0.0979
©•i978
0.2817
0.38J5
0,4792
0.6075
0.6S29
0.7559
0.9*88
0.9372
\ i
(d) ti*-4'* at
0.0010
0.0150
0.0151
0.0650
©•1099
0.1*85
0.2317
0.2651
0.3151
0.3650
0.*4S3
^
60 • Tc
0.5048
0.4B84
0.%112
0.34%7
0.2971
0.2%32
0.1«k>2
0.13a*
0.1016
0.0872
0.05**
a
0.0*19
'i 1
fABU: T i l •WW**- WjliMwM>i|[»Mlw*WlilMM
laNTC Pf ACTIONS OF No'*', milJbCTTVTTT CUI FFtCtrj.TS i\Kf>
TIttflMMWNAMtC EQUTHBimiM CaKSTAM'F Fur !3a**fl*
% »
0.0031 0.0900
O.U55
o,3n^ 0.5766 0.47%4 0.5720 0.667R 0.7656 0.8567 0.9249
0.0051 0.0922 0.t«?7^
0.2e35 0.3789 0.4767 0.5725 0.6700
0.7656 0.8567 0.9249
%e
(a) Ne*^i* at
0.0015 0.0869
0.1256 0.1521 0.2036 0.2219 0.2606
0,S?995 0.548*
0.3700 0.4528
(to) Na*«.n* at
0.0013 0.0S69 0.1252 0. t515 0.2024 0.2204
0.2573 0.2950
0.3451 0.566?? 0.449S
\
30 • I ' c
0.7718 0.7622
0.6307 0.5149 0,3^57 0.3159 0.2649 0.1929 0.1302
0.09Sg 0.0726
*0 4. 1 C
0.771B 0.7394
0.5625 0.4684
0.3055 0.2569
0.2316
0.1647 0.1235 0.0936 0.0686
0 .04 f ^
0.0354
48
o z
I X
c o
X
O
z
c o o o
c o
c
>
1 .0
0 . 8
0 . 6
^ 0.4
0.2 -
Z. 0 . 0 D cr
X 30°C Backward • 30°C Forward a 40°C o 50°C A e o ^ c
0 . 0 0.2 O 4 0.6 0.8 1.0
Equivalent Ionic fraction of Na* In solution (Xj^ )
FIG.2 ION EXCHANGE ISOTHERM OF N a * - H*
EXCHANGE ON IRON (IK ) ANTIMONATE
/ 0
(Table TTI conttnuefl)
• . . • • (c) m -»I at 50 •, t C
0,0031
0,0S<^1
0.1905 0.2758
0.3^12
0,%790
0,57*5 0,672%
0.7357 0.^612
0*92%9
0.0031
0.03<fe?
0 . t 5 7 5
0 . i '45t
0.36*7
0.4ftl3
0.57*5
0.67*6
0.770?
0,S635
0.*?2*9
0.0015 0.0959
0.12*0
0.1510
0.2011
0.21R6
0.2555 0.2*>38
0 . 3 * 1 *
0 .35 t2
0.*2*9
(«) M0*a«* a t
0.0013 0.0676
0.1163 0.1*52
0.1836
0.20S6
0.2*10
0 ,2%2
0.3389
0.3*73 0.*2*$
0 .7701
0.7155
0.5319
0.*263
0.2669
0.2365
0.1^79
0.1353 0 . 0 9 1 *
0.0«*38
0.0507
60 4- 1*C
0.7701
0.7196
0 . 5 3 ^ 0.3S02
0.29*1
0.2**3
0.1*65
O.l lOl
0.0751
0.0690 0.0382
0.031*
0.0217
50
7Ann. IV
I0r4IC FiUCTTaKS OP K*, a ; i i CTTVTTY Cu! frTG-^ TTS .'im
THi.RMaT YNAMTO EQllltlBnTUM CONSTANTS FUR ll*-il*
ESCHANGJ,: ON FERRTC ANTTnoKAlC
\ - \ ^ 'a
(a) S*-H* at 30 • t*C
0.00^2
0.0695
0,15S2
0,2512
0.3516
0.3989
0.«B5*
0.6360
0.7315
0.8225
0.9112
0.007*
0.1270
0.21*52
0.2667
0.5^55
0.3610
0.*091
0.^571
o.4sn9 0.5532
0.6357
(b) K*-^*
3.S2%2
3.7133
2.2609
1.5SW7
0.9732
0.8513
0.7339
0.3511
0.3274
0.2671
0.1685
at 40 1*C
0.3646
0.0042 0.0072 3.e017
0.0695 0.1270 3.7083
0.1605 0.1996 2*0533
0.253'5 0.2500 1.4481
0.3670 0.3292 0.S464
0.4517 0,3448 0.6387 0.3005
0.4954 0.4093 0.7162
0.6382 0.4408 0.3468
0,7338 0.4726 0.3050
0.S248 0.5369 0,2462
0.9155 0.6175 0.1528
51
I X
o» C
r o X C9
c o o o
o "c o
c
>
cr
1-0 X 30 C Backward o 30°C Forward
40°C * 50°C • 60*^0
•71
/
0-061 0-0 0-2 0-4 0-6 0-8 1-0
Equivalent ionic fraction of K^in solution (X^)
FIG.3 (ON EXCHANGE ISOTHERM OF K* - H *
EXCHANGE ON IRON ( I I I ) ANTIMONATE
52
Motile TV oonttnaed)
\ % % a
(«) K*^n* at 50 • l**c
0.00^4
0.0718
0,1605
©•2558
0.3561
0. 562
0.5472
0.6405
0.7583
0.8271
0*9135
0.0069
0.111%
O.I6I9
0.2431
0.3130
0.3423
0.3766
0.4246
0.4401
0.5207
O.6I75
4 - (a) K -H
3,7514
3.7235
2.0533
1.44S1
O.0S38
0,7307
0.499s
0.3095
0.2736
0.2270
0.1328
at 60 • 1 C
0.2697
0,0044 0.0068 3.7514
0.0713 0.1114 3.7235
0.1605 0.1619 2.0533 0.253s 0.2104 1,44'?1
0.3561 0,3019 0.8238
0,4561 0.3123 0.7307 0.2228
0.5495 0.3603 0.'i616
0.6248 0.4083 0.4228
0.7406 0.4739 0,2577
0,8370 0.5044 0,1982
0,9148 0.6012 0.1266
53
TABLE y
IONIC FRACTIONS OP rm*, «;r!r.cTTVTTT Ciiznnotr.ms Aim
TiTEHKOnYKAMTC K<}UII IBniUM CUJISTAm'i F J - I Ilb*-R*
ESCllANGi: ON R;anTC AKTItluKATIi
' k' ^ ' 'i i ' "
(a) Rb -H* at 50 • 1*C
©•0078
0.0030
0,1750
0.2695
0.5231
0,%567
0.5556
0.6^81
0.7427
0.8552
0.9277
0.0073
0.0832
0.1753
0.2738
0.364C
0.4610
0.5599
0.6502
0.6«76
0.8352
0.9277
0.0066
0.1562
0.25SO
0.2837 0.37S5
0.4325
0.4457
0.5187
0.5725
0.6474
0.7285
2.1962
2.0451
1.5714
1.2758
1.1882
0.9066
0.6379
0.5S51
0.'i639
0,3622
0.2738
(b) ail*-!!* at 40 I'c
0.0066
0.1471
0.2241
0.2687
0.3362
0.3986
0.4012
0.4762
0.5380
0.6262
0.7012
2.1906
2,0451
1.4414
1.2513
0.9377
0.8261
0.5263
0.5326
0.4579
0.3418
0.2529
0.5970
0.5141
a. I X
54
o» c o
JZ U X
c o o o
c o
c
o > 3 cr UJ
FIG
1-0
X 30°C Backward A 30°C Forward o AO**C 4 50°C • 60°C
/
0 0 0-2 0-4 0-6 0-8 1-0
Equivalent ionic fraction of Rb* in solution (Xpj^)
4 ION EXCHANGE ISOTHERM OF Rb"*-H""
EXCHANGE ON IRON ( I I I ) A N T I M O N A T E
5o
(Table V c<mttnu0d)
(c) m> -41 at 50 • 1 C
0«0073
0,0S30
0,1771
0,2760
0.3663
0.463t
0.5598
0,G523
©•7470
0,8373
0.929s
0,0073
0,0830
0.1771
0.2700
0.3663
0.4658
0.5641
O.G5%5
0.7470
0.8575
0.929s
0.0066
0.1471 0.2241
0.2697
0.3362
0.3615
0.4587
0.4698
0.53BO
0.6130
0.6941
2,1906
2.0451
1.3803
1.2014
0.8762
0.7475 0.526S
0.4345
0.3076
0.3255
0.2370
(«) Hb*«4!* at 60 • 1*C
O.OOS6
0.1471
o.ni74
0.2687
0.5267
0.3525
0.4314
0.4732
0.52* 9
0.6250
0.6942
2.1^6
1.9441
1.45SO
1.1576
0.8322
0.7523
0.5154
0.470s
0.3537
0.2399
0.2075
0.4481
0.3991
56
- 0-AO
- 0 - 8 0 -
1-20
- 1 - 6 0
- 2 - 0 0
- 2-AO
- 2 - 8 0
- 3 - 2 0 -
0 . 0 0.1
• 30°C
* SO 'C o 60°C
0 . 2 0.3 0.4 0.6
^ U *
FIG.5 In OF SELECTIVITY COEFFICIENTS
VS. IONIC FRACTIONS OF L i * IN
EXCHANGER PHASE
C 7
Tho ploie of In HL vii* lonio fraoticm of cation in
«xclsnn/»©r pfmre arc pr( B<?nte' In Fl/^ur^® 5 to fl# The
thomo^fynenlc equillbrtufs con«tnn*» c«lcalat««1 fror* tbese plots
are given In Tables Tt to V.
o
The values of eath®!]^ oliange ^fl , fre© cjoergy chen^o, e »
^G ond entropy change AS , wer© ealoulnted, Bifulte of
these thenso^^Qfeile peraaetere are given In Table® VX to IX,
TiSiiiKonYNAjjTc pAfiAm.TEns FOR LI"*"«H'*' KXCHANO:
QVi H.HR1C AHTfm;N/*TE AT QorAlMU luNIC
Srn.KGlU AT VARIulS T^*]Fi:nA1KICS
TliosraotTynftwic pQronKstcrs
^a
z^G* (:M/nole)
^ n " (K.J/8Jole>
e AS (J/i?!ole/^©??ree)
» «
30 j ^ 1 C
0.08
§•50
77.62
• 0 • o * 0 * 1 C 5 0 * 1 C
0»0G 0*05
7.20 8.10
17.06
77.^3 77,75
• •
60 ^ 1 C
0*0%
8.78
77.60
u 8
it:
1-00
0-00
- 1-00
- 2-00
- 3-00
- A - 0 0 -
- 5 - 0 0 -
o 30 C
• 50°C
J L 0-0 0-1 0-2 0-3 0-4 0-5 0-6
FIG.6ln OF SELECTIVITY COEFFICIENTS
VS. IONIC FRACTIONS OF Na* IN EXCHANGER
5:1
TABLL VII
TiiEn»ionYN.iHic PAnA?FTr.ns Fon Ne'*'-ti* EXCI:AN(E
ON FEnniC ANTtNONATE AT CONSTANT lOHIC
Srm.NGTH AT VABlat/S f£MH«;RATl/IffiS
o o o «
ThermcylyiiO'ntc 3 0 j ^ l C 4lOJ^lC 5 0 j ^ l C 6 0 < ^ t C pcrcnoters — — -.
K 0,05 0.04 0,03 0,02 a
Z^G* (KJ/iBolc) 7»69 8,7* 9.61 tO*66
A n * (KJ/male) 22.17
Zxs" (J/oole/«egree) 98.55 93.76 98.40 98.58
60
2-50 -
1-50
0-50 -
- 0-50 -
- 1 - 5 0 -
-2-50 -
- 3 - 5 0 -
F I G J In OF SELECTIVITY COEFFICIENTS VS. IONIC FRACTIONS OF K* IONS IN THE EXCHANGER PHASE
61
TADLC VXII
fHLJI^O^.YKA^:tC PMmiTUih FOR K*^'^ ESCll-ftNGE
ON PtHRTJ ANTrriuN'ATL AT CONSTAOT TOHXC
STHKTZGTH AT VARIuOS TEMICUATUBES
TTiiciTio^ynaBit© ]\o reenter©
(^J/nolo)
• • 30 • 1 C
mm
0.57
2.%
%0 1 C
0.50
1 J 50 • 1*C
mm
0,27
3,55
60
0,
e ^ t C
,22
.18
z^l! (O/oole) 13.85
« AS (j/a5ol©/<lef»ree) 5^.14 54.29 5 3 . ^ 54.14
62
1-40
0-60 -
0-20-
0-20 -
c - 0 - 6 0 -
-1-00 -
- 1-40-
-1-80 -
0-0 0-1 0-2 0-3 0-4 0-5 0-6 0-7 0-8
FIG.8. In OF SELECTIVITY COEFFICIENTS VS. IONIC
FRACTIONS OF Rb* IN EXCHANGER PHASE
63
mmmmmmtammmmmmmmm
OH Fi HRTC ANTT?fa\*ATE AT CUI.'STANT lUJJlC
STRl.KGTU AT VARIOUS TCMmilATUlCS
'• "•" '• " 'i " " ' 't 1 ' ^ — i * © • o
fbcit^o^lyuaptlc 3 0 j | ^ l C % 0 * , 1 C 5 0 * ^ t C fiO^lC poreisotorfi "" — — —
K 0*60 0 .51 0A5 0,kO a
A o ' (KeT/ffiole) 1.31 1.7% 2.17 2 .56
AH* {KJ/mU) 11.09
A ? * <J/Bjole/i«gree) ^0 .90 ^ . 9 9 1 M . 0 3 3 %0.971
ii<l»Mwi<»i»W«B
6 > 't
mscussioK
Forrlo antlnonote In hydro'jen for-s t»ehavos os o
vjnuprotic week acid . The excbnn?;© with monovalent Ions on
fe r r i c imtinonate can be reproponted by the following equations
nn* • M* -" •> HM* • n* . , . ( i )
Ton-exohooRC process, b«lnf» s tolchlosjetr lc , wi l l ftlve
e-ROunt of hydrogen ion l iberated equivalent to tbe metal Ion
iy ) taken by the exchanf^er. Such en exchQnu fi I s pre«ente<!
in TnblcB TT to V and plotted In Fip^uree 1 t o *i in the forw
of lon-exchonge Ifothems for the forward and backward prooeeetea.
These r e s u l t s indlcnte thftt S shaped ourvea are obtained for
M , Nu , K anf fib lone with different s e l e c t I v l t l e a and the
exchRngG i r revers ib le in a l l these cases ea th*» forward
praccrs iPotheros Cu>incl'1e with the bac&werd proccas Isotherms.
The preference of Li end Na i s leHser than for H'*' t o f e r r i c
en t inonate . At low cunccnt re t ions of K the uptnJio io ell«;htly
oorc thnn that of H but ot hl^h conccntrnttona the upta'ce of
K Is IcGSor than tha t of 11 • Nearly 8or»e trend In observed
with nb except thnt at low conc<»ntrntlon{3 the r e l e t lvo uptalte
of lb If r l iPb t ly nsoro op cci-'pared with thnt of T • Thle
uptake, tlicro^'ure, followe the trend ts%* Na ( 1.1 ( ^f <( Hb*
at low concentra t ions . For on o%'ernll corptirlRon the equ l l tb r luo
conptnnt wi l l be helpful .
Go
The eelectlvity coefficient, l^ , for lon-exchaiiga
reaction (eqaetloa 1) Ic calculated ef. follotJOi
^n » 1'^ ' - X "T^ . . . (2) *C h X ?!
in
whQi Xjtj i s the eculTdle&t fraotloa of oetol in tbe exchonger
^ a s o , Xj, Bad JLjt the e<|»lvaleiit freettim of bj^rogeo and aetal
tn th© eolotton jdiascg rcepccttrely. j ^ *otl 4^ tfee ac t iv i ty
ooefftoicnta of hyarofce mid raotal r t tpectively in th© eolntloit.
For at luto ooiMtcBtrattoiiP tb© rat io --— ntiy ha tclEeo og unity*
The valuea of ^ ot different oonccistratioiie cna
different tCQi^tratttf^c or. presented in Tables TI to V Indicot©
thot ^ <fecr«aiice with rie© in nctal ion cooocatratios. X,
oleo «ccr©ae©8 with r t rc la teiapernturG as well*
ffce thcrnoaynonic ©f|«illbriii!«j omiiitast, K i« oalonlated
follo»lnr! the expression Riireo by Galncfi & Thoisas
in K^ m (Z^ • Z^) • In KQ dX j . . . (3)
th© thcnsc^ynamio ©quilibriois conetont, K cnlcoleted followlBg
the ccjuation (3) (Toblos VT to TX) end tho Flgoros 5 to S
rcvonl that a lkat i cietals at a l l the tcnporctores ranging
from 30 to 6^ C however^ the degree of (selectivity decrease©
66
B>j U)
6 - ) /
an conpored t a thet of at lower tooperatur©s* A conparotive
otudy of K volues at different tetsperaturos for different 8
a lko l l r c t o l lone reflects the s e l e c t i v i t y order of ©Ikall
oc t a l Ions as Ma* ( LI* < K* < m*. e
The standard free energy of exchenisfe, /s^G I s ccleulijtedl
froia the therBJoflyncmic ef lol l tbr lur conetont K^, ueing the &r\U&ti9Q
AG e « -—-;- ^^ ^a * • • ^*^
where R l e the gas constant , the Z. an^ Z_ ere the velctieiee ' A H
of competing ionic speciee, T i s the ahpolute teCTpersturo.
The resJilte (Tables VT to IX) Indicate that daring the exchange
of a lka l i metBl lona over f e r r i c antinonate in hydrogen forp,
the free energy change la posi t ive over a l l the tenpern tures .
At a l l the temperatnf^e these oschonRes a r c , the re fore ,
nanapuntancous. This i s aleo supported hy the vloif that la
n* forD the ion exchanger hchoves as a wealj acta which la loos
ionlised aa co-iparod to i t s aolt i,©« the tendency t o prefer
11* as car^porcd with altcali reetal Ions should bo e f f ec t i ve .
The standard enthalpy chanre, AH , hca hcen ©valnatea
fror! the plot of lo?» It against - (Pin. 9)» The reeuU©
glvinrt (Tohlee VT to TX) poRltlve enthnlpy chnnfc indicate
that the reaction i s endotherrlc or in o ther raeans the hlndin^
68
enei^y of one atoffl of o lbol l psjtal t s hif^her than that of one
oto« of hydrogen.
The Btnndart ontropv change, A s Is then oalculoted
followln^T the c?suatlon
A G " n A H " - T A S * , , , ("J)
The poeulte of entropy change (Tobies VT to TX)
produce o oarkahle effect on the ton-exchflnge nechantfin. The
gain In entropy IndlcoteB the l e s se r order produced in the
fttr 'cnl rcuctlon rlurin/^ allroll ^e ta l Ions t r s n c f e r t o f e r r i c
cnt tnonatc . The entropy chunge inoludee two reac t ions , one
which occurs In the Interphase and o ther In the eolut ton ,
Tn,'!;olnr of Ions frora solution to the solid phase resultfi In o
lesp ordered s t ructure to the a lka l i wetol ione in the f!atrls
which recul ta in the Dohilization and IncrcsBe In the dORrec
of freedon of a lka l i nete l tons in the oxchon^'cr pliase, t^hloh
contr ibutes a Increase in ontrupy. Further, the passage of
hydrogen ionc frora solid t o aolutlan frtioso roeul te In l e s s e r
orderin'T of water ani a fur ther incroceo in entropy which ore
in occorlance ifttb th<» dutoo on nioblun arsenate and f e r r i c 21
antinonato •
The hypothetical tbcrraodyiiatiic data in in f in i teo lno l
concentration wore calculated for in te rp re ta t ion of the
s e l e c t i v i t y of the aKcali csetol in the t r ace orotrnts on
\^:i
ir<wi(TTT) BUtlwonnte ond fo r co«i>Rrlson with those da t a
oDtnlnefl with o the r exchangore . The V8luc6 ofiln -^o^x. —> 0
,'*r'"» ohtnlne^ hy eartra '^olating t o ss^ro loedlnft—^of ttie
-;lljr^ll nptnlfi on FlrurcB 5 t o 8, Pron ttieso voluoD the
hypothet lci^l thcrrso'lynorjic dnta wt?re cnloulnt<»«1 by the
?t«pnQr t n j o t n o n t e r for the o v e r a l l cqul l lbr iuc* oonst tmt*
The accuracy of th«for voluon ssay be h t i h f r thon thof!C of the
l e t t e r . The c e l c u i e t e d (/^If )Z _^ . voluco Ind loo tc t h o t
t h e r e tfi no entha lpy chnn^e In the r eac t f jn whc n taotol Ion
c a n c f n t r a t i o n In tho aul id phace opprjieheP t o s o r j over thp
n n ' i r e range of te-^pcrnturcr., Uhtlc t h r (AT )* ._^
t n c r c a r o e with inert o ' l n g t an lc r o d l l of ol l jol l c o t r l c o rc fp t
f^r Rh*. HypothetlCiil dota on "soro loa<!lng^ of tho Ion e
oxch •n'-e nt 30 C a r c ^Ivt^n in t ' ab lc \ ,
HYPOTHE rTC M r.I..ftMO' YS.\MTC n;.TA UN •Zi.PU LOAT>TKG"
Of T!t» TOIJ EXOJIAKG; IIL/.aVTUH AT 3 0 C
LI %'o K^ Rh
l a , • * * ^ » )
-©•35 - 1 . 5 0 - 2 , 0 0 -1 .25
''%^0^'''^'^'''^''' o,m 3.79 5.06 3.16
0.00 0.00 0.00 0.00
-1 -2 .90 -12 ,50 -16.70 -I0,%ft
>WMWl.1"Wl>Hi
70
1. ii,M,Lar8©n Qnd P.n.ViBecrs, J.Hiy.Cbeffl., 6k, t73ii (I960),
2 . T.Gal and A.Uuvarec, nul l .Dor ls Tn6t,Kucl«Sci«, 13, 1
(1902).
3 . G.K,Kai50allae and B»V,K.R«A,Tllak, J.Inarg.Huol.Chera,,
31 , 36^3 (1969).
4 . i;,Tarraca, J.Tnorg.Nuol.Chem,, 31 , 1189 (1960).
5 . C,n,Aiaphl0it, P.Batoii, t.A.McTionel QmJ A.J .Mll ler ,
J.Tnorg.NttCl.CbOB,, 26, 297 (196*).
6 . J.P.norUln, G.H.Nancollns onfl R.Petcrcian, J.Tnorf.NucLChewi,,
26, 305 (1964).
7« Y.Hoeegowa, .T.Tcorg.Nucl.Clieia,, 38, 319 (1976).
v9, S.Alluli and S.A.iraefJUcci, J.Inarg.Nucl.Cltcn., 39, 659
(1977).
9 . A.Clearfleia, u,L«T>uaEl, j .v .Garoes out! A.F.T^cdlna,
J.Tuors.Kucl.CheB,, 3^, 329 (1972),
10. ?l.Abe, rcenjlro Yofiblgaef.kl o»d Takachl Suglurc, J . I no rg .
Nucl.Chcta., 42, 1753 (1980).
1 1 . U.Costantloa, J.Tiiorj^«Hacl,Che@., 41 , 1041 (1979).
12. M./b«. J,7norn.Nucl,ChcD,, 4 1 , 85 (1979).
13 . M.Abe and Kezufuya fu(lah, J.Tnorrc.Hucl.Chea., 42, 1051
(19S0),
14. E,?4.Latfien and U.-\,Cllley, J.Tuors.Nucl.Cheu,, 30, 2f?7
(1968).
15 . L,niiQi?telc, J.Tnarg.Nucl.ChCEj., 25, 271 (1963).
7 i
16. Alcte8on<lar,T,J,Ruvarac, J,Chroajatoj»r., 60, 235 (1971).
17. I..M,Roet8le au^ T>,Huys, J.Toorg.NtMrl^Chea,, 30, 539 (I96fi).
18. J.P.Uiwat and i>,K.Stngh, Anal.Cblw.Aota., r*7t 157 (1976),
19. S.Harvle and V.P^lcarefc, Private CotSTnuiilcotlotJ, (1968),
20. M.cjurer.hl, J.P.Rawat ana A.F.Gupta, J.tn^.Chatn.foc.,
LVTIT, 855 (19fil)»
2 1 . J.P.Rawat and FC.r.S.Mafetawat, J.InorR.Nucl.Chcia.,
43, 2121 (19S1).
22. V.Abe, J.Tnorg.Nucl.Ghera., %1, 85 (1979).
C H A P T E R - TTI
ION EXeilAHO: EQUTLIBRIA OF Cr«0^*, CfO?*, S«0?*, Sof* AHB ... . . .. _. .,2 / . % * . 2 5 * 4
^fnO" WITH NOl OK ZIHCOKICM TRmUlYLAMlNE 5_ .._ 3
7 :
Tn reeent years a ausbor of Inorgonlc ion-^exchaagere
hov© been cynthoolzcTi nnlnly for ana ly t ica l separa t ions ,
Denldeu the ^ev©luT»?5ent of BOW •noterlcls anfl t h c t r ©ppllcatlone,
IntereiJt hau ol$?o bepa tleveloped In the phyelcol cheratetry of
ton e.TChnngo In t e r r p of tbonso^ynoplcr anfi t r lnctlce of Ion
oxclinnge, Tberaa^lynanlcp tJeuls with the stufly of ton exchani^e
cn«lllhriu«! while the fclnettes '!e?ilp with wechantflip of exchansje.
Ton oschrmge ersuil ibria on cst lan cschJ5na:crG have been ctuStct!
to f5 Irr-rer extent then thot of anion exchanffcrfl. Only a few
thcr^o^ynn??lc ^tu-lier ? .'vc boon pajle on Inor^enic anion
exch^nrors. The eouillbrlufs s tudies were started with the
n sphoterlc PobBtoncer l l^e bytr jus sslrcoala ond byffrous 5
c*»ria , H'nfthariP on the s e l ec t i v i t y am! r e imre ib i l i t y of the 6 2-
contrercicily avfiilnblo inox^nnlc anion 03scb«an:ere for ?0. ,
KoT, Cl", Br" and T* hoB a l so been g l ren . Thersodynatatcp of
inco"!pleto exehsnge during sorption of netnl co«3plexe«« by anion 7
e^chnn'^errs have oleo bijon st»Jled «
Thorraodynflf^ic stUfHop an o new lnor;?«nlc onijn exchnnptcr,
BlrconlufR t r le thylenino arc mio^arlzed tn t h i s chontor, t»hich
Qeror1b«s the Influence of te-nporoturc of the ion exchange
eno l l lb r l a of ^r^O^", Cr^>|', ^2'A'* ^ 4 " ^"' ^^^^k ^**^' ^^5
a t 0 constant tonic Btreng[th» A nipple approach hne been
opplt'*'' end the therno' lynrdc paranetcrs are co lcu le tod .
73
Reagoats
JJlrconiurs oxlchlortSe (B,T»,f!,) and triethyloialne
(E.Merck) were ueed. All other rccitcnts wore af Anelan
grofle.
Syntboste of zircon I uta trtethylarotne
Tt W0S prepare*^ by mixing O.IK eolution of zirconium
oxycMorldle an*! trlethylaffllno in the ro t l o l j 2 , Preclpltet©
thus (rfbt£''ln0d vfts *tej)t etnitdlnr for 2^ hours fit ro«wa
t©oper«tur@, Preofpttote woa fllterefl on^ wachec! with
<1c»alnorGllEo^ wotor eosf drledl at the tctnporoture controlled
a t 40 C. The arte?! cold nro«1uct was Its^ersed In wo t o r , the
proiluct brofcoffown Into cnoll pieces* The raoterlsl wes
convertCi'! Into n i t r a t e forn by keeping In 2 Rolor sodturj
n i t r a t e solution for 2h hours anrt In to rn l t t en t ly roplnclnr^
the eapomotent l iquid with a fi^eh solution of eodlup! «
n i t r a t e . Sample wns we^hed eof! <!rledl again ot «iO C In the
oven. The par t lc leo were then elevcd t o get the products
of requlr«*f1 JJISC,
Proco<1nre
The Biaterlal (50-100 sseeb) wee convertc<3 t o other
snlunlc fonae by placing the laoter l"! In a colursn ©nd panBlnc
7-1 t
l.OM fiota^ipiuf? or RO iura su i t s of the respective onlans un t i l
the eoncrntrotlon of not an In the oluent oni effluent WOR
l«!«^nt!onl. The s«'Dplo vios wrshO'l with demlneraltzo^ wnter
u n t i l I t WHS free tVijn anlu»e, drlefl GW^ rtorfd In the
rtopper©d t jo t t l e .
Ton exchange capacity
Ton exchange Cfipacltles «ere ^eteralnerl hy botch
procees, 0.5 S «f ^^^ exchaoRor wars shaken for S^ hour©
with 50 ml of 2M eoiUura a l t r a t o solut ion In the sstoppcrod
flflstss. Cont(>at of the flacte w«s fi l tercfl and t i t r a t e d
for fftfferent anions.
Equilibrium gtadios
The enullthrlttw experisientfi were p^rforr^eA by taking
?0 R1 solution contolnlng sodtlui-) a potcsplur, n i t r o t e solut ion
cxvl appropriate anljn solut ion• The ionic ctrcnjijth of the
to t a l content was Irept O.IO in tho ntoppcred oonicol flaH&a,
To th lo 0,2 g of tho exchani^er in n i t r a t e fora wao added and
flnrkf. wcr® ehalten thoroughly in o temperature control led
shaker far 2^ hours at deeirod tcfsperaturtse, experiments
rhowed tha t cqulllhrl'tm was attained within t h i s period end
a l iqu j tea fron sapematant solutions «ero analysed for anions,
7.')
mmmmmmmmmmmmmmw imiHi i i i—i—WWt
For HJvers lbt l l ty esperlaente were perforroed by
equl l lb ra t tng the exchfinner In the pfirtlculer anionic form
with flodium n i t r a t e nolution at 30 C*
7r,
BbSULTS
The resu l t s of the ion excheni^e capacity for chro^oto,
«!lchrosjflte, 8ulphi»te, tl^loculrbate an«t pors^orcinatQ are
prceented in Table XT,
XAUU XI
ION LXCIIANG?. CAPACTTY UF luJn ASTuNS
UK ZinCOHTUM inTlTIIYl^MTNE
Anion Salt usedl Ion exohenge Ton ezchaiir^e capacity of oepaetty of enlvinio fons c i t r a t e forw of ejtchanger of ©xoheni^er
imen/g) if^f./p)
2 -k
2 -k
2 -
Mnur
PotRSflu® dichroE-flte
Potaaelora chro«toti»
Sodiuci pulpbate
Fo<11i«5j thlopulpbnte
PotenFlura pcrcouRcnat©
2*00
1,62
i .1%
0.56
l , 5 t
l .SS
i . 6 i
1«06
0,55
t . 51
The cxchnn^e isotherms for various anions a t d i f ferent
tenjperaturet ar© plotted in Figures 10-i%»
The res t t l t s of equivalent fraet ions of anions^ s e l e c t i v i t y
coef f ic ien ts an?! ther®o«1jrn0oic equilihriUQ oonstante «r© i^ivea
i^ Tables XTt-jnrT,
\
"1
(
tn O n a L.
c o
JO O X
C o c O ^ »*<
c o • J
o O L.
C
>
'5
10
0-8
0-6
0-4
0-2
'if o 30 Backward • 30** Forward
00 ao 0-2 0-4 0-6 0-8 1-0
Equivalent fraction of anion in solution ptiase X
FIG.10 ION EXCHANGE ISOTHERM OF
DICHROMATE IONS ON ZIRCONIUM TRIETHYLAMINE
\(\\ i j f
k i^'tay-jf >^-.'Z
7S
TABLL XTT
EQUTVALLKT FSACTIgHS UF Cr^a!!", Si-LLClIVtiT CuLFFTCTi.KTH AH-^ 2 7
2 7 3 ON zrncoNiuri THfhfmiAmm^
iiiwiWHii I •Mi».wiiiiiwn&«>—w>*'M» IIft Ml w mmmmMmmmmmmmmmmm
0.0000 0.00*2 0.0078 0.0416 0.0769 0.1259 0.1795 0.2152
0.2955 0.3A72
0.0000 0.0042 0.00@S
0.0532 0.0810
0.1316 0.1850 0.22^8 0.2912
0.3565
0.1950 0.3780 0.5620 0.6666 0.76CO 0.0140 0.8580 0.8'?20 0.9260 0.9400
(H) CrgO^^-NO*
0.1950 0.3780
0.5517 0.6584
0.7560
0 . ^ 1 6 0.S322
0.8775 0.9100
0.9246
326.20 230.72 153.44
132.47 146.20
159.85 119.95 181.60 259.80 320.44
at 45 • l^'c
326.20 230.72
152.46 134.22 148,58
180.74
102.55 147.26 175.00
£38.67
170.2«
64.07
7;l
(Tabic XTT continue'f)
"cr^ol"
0.0000 0.0042
O.Ot58
O.O^tg
0.0^79 0.13«2
0.1982
0.2407 0.2990
0.3758
(c) CrgO^-
0.1940
0.37S0
0.5%20 0.6666
0.752*
0.78*0
0.8280
0*8720
0.8960
0.91%5
— r""'
•NO* at
TAIilB
C
60 • 1*C mm
3S6.21
230.72
142.35 132.47
150.40
90.45
97.09
128.13 126.94
219.77
XITI
If ""
39-25
rf}UTVM..NT FnACTIaNS OF CtO^*, SEI£CTTVTiy Ou.FFTCT. NTS Am
THK ?ma? rvAMT(; EcifrtTonTUM const AUTB pa a cjo?*«4ror ExciANCt
(o) CrO^*-lloJ Bt 30 •. 1*C
0.0000 0.04<I8
0.1124
Oa512
0.2152 0.2704
0.3200
0»3550
0.4106 0,5054
0.2364
0.3745 0.4516 0.5344
0.6180
o.sn^^ 0.7446
0.845*9 O.B772
0.5874
34.45
17.39
10.53
11.75 12.12
14.01
16.50 4 1 . S2
49 .14
25.98
26.31
80 0) (A O
a
c a
JO o X
c o *c o
c o o o
c o > '5 cr UJ
IK
1-0
0'8
0-6
0-4
"35^ .f^^---"':::"'^
UN
0 30 Backward • 30° Forward
A 60°
0-0 00 0-2 0-4 0-6 0-8 1-0
Equivalent fraction of anion in solution phase
FIG. II ION EXCHANGE ISOTHERM OF CHROMATE IONS ON ZIRCONIUM TRIETHYLAMINE
81 (Table KTTT Continued)
^'ciO?" ^rof*" ^o ^o k
ih) Crol^-mZ at 45 i. 1*C
0,OOf92
0.0665 0.12^6
0.1773 0.2352
0.2848
0,3362
0.37^1
0.li369 0.5162
O^oihn
0.0772
0.1338
0.1900
0.2559 0.3000 0.3512
0.3990 0.^616
0.523^
0.2146
0.3694
0,4605 0.4262
0.6067
0.6755 0.736S
0.8350 0.86S4
0.S740
33.70
13.36
9.14 9.78
10.85 11.44
1*.70
32.23 35.80
18.97
(c) CxO^*-IK) at 60 • 1 C
0.2652
0.3655
0.4545
0.5247 0.5919 0.6666 0.7220
0.3110
0.8522
0.9355
3 2 . ^
10.02
8.57 8,02
7.69 9 .79
11.21
2 1 , ^ 23.64
13.43
21.04
17.6a
o a
c o
JZ
X
C O C O
c o
u D
c
>
s cr
\V<^>^^^
71 4 r
/
,^A--A'
0 30 Backward • 30° Forward A A5° A 60*
X
0-8 1-0 0-A 0-6
X
Equivalent f ract ion of anions in solution phase
FIG. 12 ION EXCHANGE ISOTHERM OF THIOSULPHATE IONS ON ZIRCONIUM TRIETHYLAMINE
83
TABLL XTV
LCUTV.^L: ."1 FfL CTT01«' ur fa?*, stLccTiviTY CUI.PFTCTI.NTS Am k •
TU .pyj'^rs^yio hqvnjBnwH CUX-STANTS FOR sa?%Hor EXGMANCH. * 3
(»> so J* ^ o l at 30 • 1*C • l »« I I m i l i C I I I l l mi l
0.<K>55 0.0140
0.0333 0.0628 0.1350
0,235« 0.3202
0.4177 0.4906 0,6045
0.1526 0.2576 0.348a
0.4777 0 . ' J 8 9 0
0.5173 0.5555 0.5990 0.5722 0.6150
(b) ?o^ -NO^ at
38.24 32.46
23.09 24,51 10,38
5.53 4.06 3.02
1.65 1.07
45 • 1*C
0.0068 0.1366 30.76 0.0250 0.2470 21.05 0.0446 0.3165 14.86 0.0825 0.4011 15.07 0.1466 0.4528 9.13 0.2429 0,4B90 4.39 0.3260 0.5582 5.15 O«4204 0.5607 2,38 0.5050 0.5679 1.42 0.6173 0.6065 1.04
5.59
4.16
84 (Table 5ETY caa t l nued )
0.0068
0.0245 0.0722
0.1051
0.1656
0.2350
0.5366
0.4254
0.5111
0.6200
0.1243 0.S28S
0.2686
0.3455
0.4227
0.4555
0,5600
0.5350
0.5624
0.5892
t
fABtl^
K C
23.53 15.01
5.99
6.15
6.87 3 .89
2.06
1.92
1.37
0.81
JkV
r " " • " - •"
n
2.73
EOUIVAl. NT Ff ACTluy.'- <iV SgU^*, Si.LtXTIVIfY Cu..Fi TCT- m AWR
f 1 a.!Wy^¥!JAHIC KqiJTIIHilTUM CuUhfAH'xii FuU 8 - 0 $ * ^ ^ ^ SXC!*A! GE « 3 3
X 2 -•
i .2-t
e
" " • » ' • " — "
K
(o) SgU^*-NO* St 30 4 1*C
0.0042 0.3745 226.01
0,01^6 0,5924 184.67
0.O42S 0.7494 255.44
O.ltSg 0.8228 165.75
O.S355 0.7S12 40.55
0.31S4 0,7156 12.95 *^*^*
0.4S40 0.6490 4.10
0.4852 0.6004 2.05
0.5764 0.6550 1.71
0.67S2 0.7000 1.24
85
O
CL
cn c o n u C9
c o c o
c o
u O
c
o >
cr HI
1-0
I K
0 30 Backward • 30° Forward
0-0 0-0 0-2 0-4 0'6 0-8 1-0
Equivalent fraction of anions In solution phase
FIG. 13 ION EXCHANGE ISOTHERM OF SULPHATE IONS ON ZIRCONIUM TRIETHYLAMINE
8G (Table XV oontinuedl)
2 3
0.0152 0.0368
0.0517 O.l^^O
0.24Q5 0.3266 0.^30$ 0.^922
0.5S99
0.7172
0*0355 0.06^2 0.0630
0.1615 0,2355 0.339* 0.4590 0.%S50 0.61%S
0.7«10
2^3
ih) fgof'-HU*
0.3^5© 0.5537 0.7058 0.7990 0.7524 0.6990
0.6055 0.5733 0.61fi9 0.7192
(c) Sjol'-^IO*
0.301%
0.5115 0.6789 0.7670
0.7215 0.6777 0.5700 0.5494 0,5895 0.7252
S
at 45 • 1 C mm
211,78 154.90 198.04 153.87 36,00 11.95 4.44
1.97 1.62 1.20
0 lit 60 •, 1 C
194,41 1S7.74 151.40
145,47 34.81
11.70
4.48 1.89 1.56
1.17
a
13.88
11.19
87 C9 U) O r. a t_
c o n o X
C
o "c o I X
c o o o
c
>
UJ
10
0-8
0-6
0-4
0-2
0-0
o 20" Backward 30° Forward
10 0-4 0-6
X
Equivalent fraction of anions in solution phase
FIG.I4 ION EXCHANGE ISOTHERM OF PERMANGANATE IONS ON ZIRCONIUM TRIETHYLAMINE
0 0
TABLE XVI
IJ )UTVAL. :;T fJIACTIUMS UP Mik)J, SLLBCTTVnY CuLFMCT. NTS AW
OH HHQiinth^ THTi T-^l-A^lNl.
"Mno •Sfno^ ' e «.
(a) MnoJ[-Kor ot 30 •, 1 C
0.0700
0.1500
0.2*50
0.3200
0.4100
0.46^
0.5550
0.5950
0.6300
0.6800
0.0700
0.1586
0.2495
0,3249
0.4190
0.4S13
0.5504
0.6100
0.64S7
0.6950
0.0800
0.1300
0,1566
0,2133
0.2600
0.3600
0.3«66
0.5466
0.7066
0.0600
(1^) jasoJ-»«*a^ at
0.0800
0.1105
0.1470
0.1722
0.2177
0.521S
0.3568
0,4375
0.3290 0.«*2«2
1.15
0.0467
0.5718
0.5761
0.5056
0.6471
0.5053
0.9205
1.4144
2.8907
45 ^ 1*C
1.05
0.64
0.44
0.41
0.39
0.46
0.43
0.62
0.88
'•£0
1.18
0,'59
8.9
(table XYT oonttnued)
^I^J^ ^I5f>j
0.0750 0,1650
©•2550
©•3300
o»%3mj
©•5000
0.!!:750
0.6350
0*6725
0.70CK3
(e) Mi^^-ICo" at
0.0666
0.0933 O.ltOO
0,1466 0*1566
0,2667
0.3365
0.3600 0.525S
O.SOO0
e 60 jf 1 C
o.asoo 0.5SO9
0.39S3
0.34S7 0.50^0
0.3635 0.358%
0.3235
0.3S37 1.71*2
0.7*
fhe pl&%B of la 5t- vernum ©Qtilvslent f r ac t l oa of em loo
la exchanger fhmm arc prescot©^ In Figures 15-19. The
thereotfynasic enal l lbrt ina csmtieot© calculoted f r * » these p l o t i
©r© glvoQ 1« Tablei XTT-XVT.
The resultss of entropy eljnn.^o AT^ , f ree caci^y ctinngo
A 0 sn<t ©ntropv ehBn^e A 5 tri>r© Galeatated. The reetilt© o f
these tberso^jmsfBlo porimeterfj are glWB to TaTsle Tf?l#
90
c
0-0
XCr207"
FIG.15 Ln OF SELECTIVITY COEFFICIENTS VS. EQUIVALENT FRACTIONS OF
Cr20.7 IN EXCHANGER PHASE
91
o
c
5 -0 -
4-0
3-0
2 0 -
1-0-
0-0
\\^ ^ v
- \^
1 1
J/
,
0 0 0-2 OA 0-6 0-8 10
x c r o ^ -
FiG.I6 Ln OF SELECTIVITY COEFFICIENTS
VS. EQUIVALENT FRACTIONS OF C r O
IN EXCHANGER PHASE
2-4
32
FIG. iV Ln OF SELECTIVITY COEFFICIENTS VS. EQUIVALENT FRACTIONS OF
S2O3IN EXCHANGER PHASE
0
o a: c
6-0
\ s \ N
\
3-0
2 - 0 -
1-0-
0 - 0 -
- 1 - 0
\
t
• % ^V^ < .
:!2^ 0-0 0-2 0-4 0-6 0-8 1-0
Yso^
FIG.ISLn OF SELECTIVITY COEFFICIENTS VS. EQUIVALENT FRACTIONS OF SO^ IN EXCHANGER PHASE
2-
't
c
0-A 0-6
F(G.I9 Ln OF SELECTIVITY COEFFICIENTS VS. EQUIVALENT FRACTIONS OF MnO^ IN EXCHANGER PHASE
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95
3r>
r>TycursTuK
Th© Ion estcbonge cqui l t l i r to with c e r t a i n ton exchoogers,
csnfte l a l ly t»art!:ciBic Ion exchangers cf*a he stud I d by the
epT>ticMtion of •asss-octlan lav ao^Ufied In t e r s e of a c t i v i t i e s .
Tar the eschengcr In n l t r o t f fora and solut ton havla* !i!onavnl«»nt
counter Ion x" at &f!«lll^«"iw'^ th© oxcbrnge raey bo represented net
^0^ * X^,^) ^=± X~ ^ K03^^^) . . . . (1)
nn-l t o r btvoleni counter ton
The therp'o^ynr-'le eoulllbrtuw eonotant for the cbov©
rrnct lanp mmy b«» wri t ten, for un 1-on 1 volant eatchcnge eej
^x- °No: [X"][KU:) fr fro:
^Ko 'x* (^3][ri Uo^h'
en<l for unl-blvalont osci-nn^o osj
(V-)(\-o:)' i x ^ i U . / i^'-f>^; K^ m g— A - ^ o g- £— , ^ 2. ^^ (4)
where I r e p r e e n t c ac t iv i ty Coefficients In thr exchnn^^er f*ose
8B^ f the no t lv l ty co3filcl«»nt In the oqucaur phnce.
3 ;
An examination of tbe ton exchenge tnottioirsB
Ftgurcc lO-H shoifs tbflt thft tr.at^cr^? nre above tbo diai^onQl
excfpt for Mno2 ln*?lcptinp thot blvelent antone are strongly
'^rrfcrre'f tn comnurfsun to n i t r a t e by the slrconiuo t r lot! ' .y l -
Bvninc exchrnger, Tbe a f f in i ty for the anlonc ^ecroasQe as
the teaperature InereaRet, Ftgurea tO-1^ ehow that a l l the
etu<?lcfl Inothersfi! wen* revers ib le trberene the so loc t lv l ty
soffuence tjon
Tf fC« If? the se l ec t iv i ty coef f ic ien t , then Tor iini-nntTal»»nt o
eatchaope
"^x" ^ o l f Mu^ o ~0 - • ^ « . . . . (5)
\* - X
nrwl for unt-blvalent exchange 2
g^ • ^—^ - d , «i . . . . (6)
where ^ Q - fl«^ X---1n the enutvalent frPCtion of cotsipctlns
onions in pxchrnr^er n»irfe, X„-- en5 r —the effuivelent fract ions
of the n i t r a t e and conpctini: anion in solution nhare renp^ctfvely,
i •Kti" '^^^ f v* • ***** *^®*^^**y coefflelentft of n i t m t e and th©
cof"ncttn«r onion ref8r«^ctlv<»ly in so lu t ion . The ac t iv i ty
(
coef f ic ien ts of the anions In solotloii phase wero oalculatea
us lag 1i«%y©-Hucfeel effuatlcm
f>
Ion f^ * •""•'•"""•'""• "' • " • • • » « ( 7 )
1 • B fl|V7"
Where A ©rwS B are ctjijstant?!, o. the Ion size paroiaoter, ^ the
toate strcR^th sa<3 2f C^ ar^e or the lais I . Tb© v«ltiep of A aiKl R
at Bfjpropri«te te»p«*r'tureB are token fran the tnblep aliren
©flrlier * •
Tb^ res t t l t s of the «eloct tv l ty c a c f t l c l e n t s
( tables XTT-XVT) Indlc.it© t ;at nn the tccsptrature increases
thi» v&lut 9f the fiplectlvity Ca#ffi.el*nt ii&Qn^nmiB, The r<»pu1t«»
: lottti^i (Ft^s , 15-19) rove 1 t!,at thr Reluct ivi ty coef io l^nf
i -Joen nat rcaain canstant nt a l l with thi^ vary tan cane«»ntra-
H >np of DO fair- i la rolutJon, aod, there fare, S eh«ul<* toe
eiflculated.
ir , the thor5*>s1ynn«lc €»f!Ulllbritin constant cr.n M 10
ahtoliioil acoariSl»«* ta Oolnes emA Thap««! , frats tl:e eqn&iioni
t I n PC„ • C^ - - ? v . - ) • In I al • , . . (8)
X
Tho vfilttcB 0f thcrtaalynjwta equilibrium coast.-ot mrv
CHtctil&to4 hy lntc£:r.itlan umler the curvep of FlgurcR 15-19
applyfn^ en.iatlan S, Varintloii of In K wllh loaainn* " v * *
glvoo In Figures 15-19* The voluor of the chanfiot in
9.9
o
0 - 0 -
107 T
FIG.20 TEMPERATURE DEPENDENCE OF THE THERMODYNAMIC EQUILIbRIUM CONSTANT-
l O G
thermiMlynaiBic quant l t tes are celculotcfl tron tbe respect tve
tltor^O'^ynonio oqull lbrlun constnatfi OP tollQitBt
A G " • - nf la Kg • . . . • (9)
a (In K ) AH a - R S-. (10)
d (t/T)
ona AF* » (All** - A G " ) / ? (11)
e
A n is obtained fror Pl,«;uro 20 (ospr««Bin;', tlie r e r i o t i o a
of In If wtth 1/T). The r««»ultf» InfJtcate thnt ^urtng th-»
pTCtiPn"© of onljnP over rircontira trf^thyla'^fne to n l t r n t e forra,
XYif frrc tnr-rgy ct«nn«'e fr negative in n i l cceer cxuf 'pt for ^t&T
ft htf»?'cr tonyncrftturof, Tt revcnl'- tt^nt for blv?'l^nt antono
the oxchftife procern In ppontancoor nij^ I P !n rceorflr.nc^ wltli,
pit'Jnly, on c:!''i'r«Te r e l n t i j n e . However, for nonoval'-Bt ntsl jm
eTOhpn-'p i?lth ^n^r tli« chnrpc b 'lnr^ « rf I t r.ny diencnfl on othor
fRctorn,
The rcpultts (Table XVTT) giving cnthalry change ^n fsll
the eitchonp^ reactiunB ImHoote thot procrsn te csothorr tc
l , e , tbo blrKflnf cnor^ry of u;w fsolpcule of coopetln^! onion l**
lower thon the two or»t >nr of n t t r ' ^ tc , Thur t l ^ n l t r n t e Ion In
leeB t i g h t l y bouiw!? to the zlreoelupj trlctbylnstine no t r i s thnn
any of the other wnlunn *tiKUcd,
10
Th® fouults of entropy choagei; given t e Telile XVTT
In.Ucetc thPt 'luring the foryerd rQactlon the oo-«pttlttg
anl .nlc epecice ere raare orderly arr«ngec1 tfe::a t h r t of n l t r n t e
foi-n of Klrconltia t r i e t h y l o a t n e .
102
i* K,^,Krnvs^ n .O.Phl l l lpp , T,A,Corl''an Fn^ J.'^'.Johrjfon,
rroc,Tiit«Conf.?*<?aceful Uees, Atcmtc Kner'^r, C-eoevo,
Vol. 2S, p . 3 t ' .N. (1959),
? , G.H.rJnncollas and R.Potersan, J»Tnorf;,T?ucl.Cheis«,
29, 565 (1967).
3 . /..Ruverac are! M.T.TrtonJ, Jf«Tnof^,Uucl,Chett», 3^t 3S93
(1972).
4 . ?Usak,S.Z., G!!onelry,!r,F», J.Chem.Tcchnol.Rlotechnolt,
32, ?« 3 (19*^2).
5 . N,i!/:isc!r on* b .M.^H&ball, J,Tnorg,riacl.Ch<»a,,
^ 3 , 1903 («9'?1).
6 . A.'^ycr Rji'l K,A/!allk, J.TnarR.Nacl.Cbeo., ^ 5 , 2975 (19=^1).
7» Boric,I. .I. , (l'#F«*^»n,), Ion Obracnl tonore t r ia Lcninfrndf,
3 , i3 (1992).
8, CG.^^anov, !?,G.Bates, Vf.j.'fftwer end! ?«r,Acrec, J .Ar ,
Chop.Soc., 65, 1765 (19*3).
< . IT.rrceper ftnrf r . fernondo, "Tonic Fqu l l lb r ln in Analyt ler l
ChewlPtrf*, John vi ley cu^ Pone, I n c . , Now York (1966).
10, rr.!,,Gninef! r.in! P.C,Thoja08, J.Cheia.Rjy., 21 , 71% (1953).
C H A P T E R - I f '"• • • ' — ' ' " ' ' " • ' " " ' »
ION EXCHANg:; ICTH£TTCS OF THAKStTtQK mtAt lOHS
m STANNIC wXTRE
103
Tncrenttng studies on analyt ica l appl icat ions of
sjmthetic inorganic Ion ejcchAngerti show th« great laportonce
of thes© fitilietancee. The ne«r materials of fori now oppoi inni t tes
in th© l i eW of 8«porati<wa teienee* Beside® the <!evelopient
of noi* mater ia ls and t h e i r appl icat ions i n t e r e s t has a lso been
flev^loper! t o ntuAy th t BechanisiB of Ion axohange* Kinetics
plays an iraportant role t o etody the aechani@@ of Ion exchange.
Kinetic s tud ies on Ion enchamcc were isainly s tar ted by Nacho^ 1 2
end Woofl • MRncallas en S Fetersun deserthe^ the f in^ntitative
Bieastiressent on hy*frau» thor le an^ z i r con ta , Bume stujflef* on
k ine t i c s of ion exchange an lnoin|«ntc Vm (&xch»i!Rers have been
reported recently ", To understand the roechenisw of ion
exchon^e on granules af stannic oxide, s tudies are suKsjarlxed
in t h i s chapter . Rxperitsjpntol and t heo re t i ca l approaches
have been used to show the rate of diffusion through the
p a r t i c l e s . The energy of act ivat ion and other parameters are
ca l cu la t ed .
104
%%B.mmm Ah
l^oi^ratc
Stanntc cblort^e pentahydrot© (Toland) 6«kllita hydroxl'l©
(E,M©rk> were aeert. All oth«r nJRgents wer® of «o«laR.
Fynthpel* of etsnntc oxl^e
s tannic oxWe was prepared by latxlag 0.05^f aquuoos
solution of fitaanlc chloride an?? so^tuw hydroxtdle u l th oonstniit 10 fthaklsji ta the voluw© r a t i o l j2 , On itflnding for 24 hours
at roo« t««p«retttre, the wlilte gelattnous p rec tp l t e te «ettl««!
dawn. I t W8© flltere«l off, i«a«hea with dc^tnerallzed water
aiw! ffrliMl at %0 C in an oven. The «!rt®«f product tiroke <1OWB
t o fine parttcleswhen ItKserfiert In water, wasbedl with water and
converted In H forw by t««s#rslan In 2H n i t r i c acid for
2% hoars* I t w«» agnln wafshe'i with dewlnerallied water t i l l
free froai ac!d and f ina l ly dried at k(i C In on oven,
Kinetic TReaeoreisente
Rate of exchange were ^eufitsred by llislted bath
teehnl<|ue. Stannic oxide was ground well In order to l ive
pa r t i c l e s of different mash size (50-tOO> 100-15to, 150-200
and 200-300) • Pert te les of we««h elKe (50-100) were ased for
various s tudies unless otherwise Btated, Solutions af eat lone
wew teken In stoppered eonlcfll flf^elte and thereoeteted at
105
required temperature, \fhtin the retfuiro^ tewperatww «8s reached
a v.elghed oraount of the exchanger (0,2 g) wae silded ©nd the
floBlcs were theroui^hly shaken* After approprtcte In te rva ls
the contents of flasks were ftltera«f using ^'hataan No» 4
f i l t e r paper, fhe Ion exohanffo diffusion stusHes tjere conancted
at 30 G, 40 C, 50 C and 60 C with + 1 C v a r l a t t o n ,
Stuflled cat ions Fe-' , Co , Mn and Zo wore t i t r a t e d
with ETVTA,
106
msvvrv
The P valttCfi oa a function of tlwe ore coloulotod arnS
corroppoodinf^ Bt valufn are glv«»ii by Rlechenberg , The F
and Bt values for Fe '* , Co *, MB*"* ftnd Zn * at tour «!iffer*»nt
tetaperotares are given In Tableu XVTIT-STT,
TABI.1 KVYIT
F AKn Bt VALUES AS A FUNCTIUN OF TTMf Fan TlTFFEmAT
CAftONS ON PTANN'TG UXTTIE AT 30 • l"c
t , ffllB
£
5 10
15
2
5 10
15
2
5 10
15
2
5 10
15
1
P
0.%2
0.61
0.77
0.«7
0.32
0.^6
0 .65 0.7%
0.32
0 .50
0 .69
0 .79
0 ,23 0 .38
0.50
0.61
1
Bt
3- •
0 .20
0 .50
0 .98
1.5* 2 ^ •
0.10
0.25 0 .60
0 .85
Co -41
0.10 0.30
0.70
i.to 2* •
Zn -11
0 .05
0 .15 0 .30
0 .50
t
t, nln
Cxcbenfl;©
20
25 50
60
Excbeni^e
20
25 30
60
Exchonffe
20
25 30
60
Exobanffe 20
25 30
60
1
F
0.93
0 .95
0 .97 1.00
o.si 0.86
0 .89 0 .90
0.S5 0 .90
0 .93
•*
0 .69
0.7% 0.76
«»
1
Bt
2 .12
2.5% 3.16
* •
1.15 1.50
1.70
1.80
l.%0 1,80
2.10
""
0.70
0 .85
0 .95 «»
107
O) c o JO O X UJ
O c o
o o
Time (min)
FIG.2I RATE OF EXCHANGE OF DIFFERENT CATIONS
AT 30*C ON STANNIC OXIDE
108
TAHLL XTX
F AND Bt YALUKS AS A FUNCTTUK UP TTML FOR niFFERLNT
CATIUNS ON STANMC U KtnE AT 4 0 • I'^C
t , iQll l
2
5 10
15
2
5 10
15
2
5 10
15
2
5 10
15
—!'- " -"" P
0.46
©•63 ©•81
0 .89
0 .38
0 .50
0.67 0 .79
0 .38
0 .56
0.71 0 .80
0 .23 0,k6
0.61
0 .71
«
Bt
« 3* „ •
0.25
0.55 1.20
1.75
0 .15 0 .30
0 .65 1.05
Co ^
0 .15 0 .40
0.75 3.10
« 2* „ •
0.10
0 .25 0 .50
0 .75
t
t ,1! (D
EsOhCfi.i^o
20
25 30 60
20
25 30 60
Exchange
20 25
30
60
20
25 30
60
• (
F
0 .93
0 .97
0 .98
0 .84
0 . 8 9
0 .92 •»
0 .88
0 .92 0 .94
« i
0 .78
0 .83
0 .87
•
t • "
Bt
2.25
2.90
3.45 mm
1.35 1.70
2.00 « i
1.65 2.05 2.40
1.00 1.30
1.55 tm
109
c o Si O X llJ
O c o o o I -
10 15 20
Time (min )
FIG. 22 RATE OF EXCHANGE OF DIFFERENT
CATIONS AT 4 0 ' C ON STANNIC OXIDE
110
TABLr XX
P AW Bt VALULP AS \ RNCTToN OF TIME FuH n i F R H l N T
CATIONS ON STANNIC JXJ^t AT 50 • 1 *C
t,niD
2
5 10
15
2
5
10
19
2
5 10
15
4 .
5 10
15
•"> " ' " '"
F
0.50
0,67
0.85
0.91
QM
0.59
0.72
0.85
0.42
0.61
0 .78
0.S5
0.52
0.^6
0.61
0,71
T -Bt
Fe "P.
0.30
0 .65
1.30
1.90
0 .20
0.^5
0 .80
1.30
0 .20
0 .50
1.00
1.42
0 .12
0 .26
0 .53
0 .75
-IF— t f ^ l n
ExchOttRO
20
25
30
60
20
25
30
60
20
25
30
60
Exchange
20
25
30
60
— J — ,
F
0.955
0.975
0.990 4m
0.88
0.92
0 .9*
0 .90
0.9h « k
^m
0.78
0«83
0*87 «•
Bt
2.65
3.25
4 .11 « k
1.65
2 .00
2 .40 <M»
1.94
2.36
-
1.03
1.34
1.55 «»
Hi
c O
J : o X
"o c o o o
0 10 15 20 25 30
Time (min)
FIG.23 RATE OF EXCHANGE OF DIFFERENT CATIONS AT 5 0 ' C ON STANNIC OXIDE
1 1 2
P A?in Bt VALUES AF A FUNCTTUN UF ?TX. FOR BTFFLm.KT
CATTUN!? UN STANMTC UXinU 'iT 60 • l*'c
t^nln
2
5
10
15
2
5
10
15
2
5
10
15
2
5
10
15
1
F
0.53
0.72
0.S6
0.9^
0.%2
0.59
0.72
0 .83
0.^6
0.61
0 .78
0.87
0.32
0.50
0.65
0 .76
T - - " ' Bt
3 ^ *•
0.35
0.80
1.50
2.30
0.82
0.45
0 .84
1.35
Co •«
0.25
0.52
1.05
4.55
0*14
0.32
0.65
0 .95
.. ^.
t j d l n
Esrtrtianfice
20
25
30
60
20
25
30
60
Escbanse
20
25
30
60
20
25
30
60
-""V — " 1
P
0.97
0 .98
1.00
0 .88
0.92
0.94 tm
0.92
0 .96
1.00
0 .81
0.86
O.SO
0.96
( ' • " " • " • • " ~ - "
nt
3.00
3.75
-
m»
1.65
2.06
2,44
2.13
2.72
-
1.24
1.45
1.80
2 .70
113
c o o X HI
o c o 4-'
o o
0 10 15 20
Time (min)
25 30
FIG.24 RATE OF EXCHANGE OF DIFFERENT
CATIONS AT 60 "C ON STANNIC OXIDE
1J4
The values of F at dlfff»irent tltaefl en<! tenpcr»turee
©ro preeentctJ In Figures 21-2^, Tho Dt r s luee os o fttnctton
of tlrn? for various cot tons at different tenperotaree are
plotted in Fiparet 25-28»
Th« effect of p a r t t e l e t l ze on klnetioB of l« i exchange
for fo«r different pa r t i c l e otaee were ]Wjrforwc«S. The r^Kults
of r on*' Bt values o« a function of por t l c lc B|»e for Fe -II
eschnn'te ot 30 j ^ 1 C ore given In Tabic XXTT, The Bt valucc
OSS B function of tlRje for Fe -ft* esohonge ot 30 •; 1 C for
four d i f ferent par t tc lo slzoe are plotted In Figure 29.
115
CD
10 30 40 20
t (min)
FIG.25 EFFECT OF TEMPERATURE ON
THE RATE OF EXCHANGE FOR
Fe^^-H*^ EXCHANGE ON STANNIC OXIDE
116
CD
4-0
3-0
2-0
1-0
0
-
-
/r ,
y /
1 1
/60°C
/ / 40°C
^y 30°C
1
0 10 20 30
t (min)
40
FIG.26 EFFECT OF TEMPERATURE ON
THE RATE O^ EXCHANGE FOR
CO^-H" " EXCHANGE ON STANNIC OXIDE
117
3 - 0 -
2 - 0 -
co
1 - 0 -
FIG.27 EFFECT OF TEMPERATURE ON
THE RATE OF EXCHANGE FOR
Mn^'*'-H*EXCHANGE ON STANNIC OXIDE
118
CD
3 - 0 -
FIG.28 EFFECT OF TEMPERATURE ON THE RATE EXCHANGE OF FOR
Zn^*-H'"EXCHANGE ON STANNIC OXIDE
lis
TABU: xm
F ANP » t VALUES AE A rUKCtlON OF IWRTTCU, M ^ . FuR Fe^^^-fl*
EXGHANOI. ON STAMENtC OXl^L AT 50 • 1*C
tfCslQ
2
5 10
15
2
5
to 15
2
5 10
15
2
5 10
• ~ T - " "
F
0.46
0«61 ©•78
0,*»B
0.50
0 .65
0.82
0 .89
0 .53 0 .69 0 .85
0 .93
0 .56
0 .7S
0 .89
- T — r Bt
For pert lc lo
0.25 0.50 1.02
For part ic le
0.50 0 . ^
1.20
1.75
For nart lc lo
0 .35 0 .70 1,42
2.1J&
UF part ic le
0.40
1.0%
1.75
tytnln
0 l s e 100 }m
20
25 30
0m
20
25
30 •
1 r
I
0 .92
0.955
0 .97
0.9%
0 .97 .
-
s l«e 42.85 i »
20
25 30
filEe :50 pe
15 20
25
0 .96 0 .98
mt
mm
0 .96
0«9@ 4n>
f •
Dt
2.05 2.65 5.16
2.35 3.00
wm
tm
2.65 3.^0
-
2.S0 3.75
•
120
CD
4 - 0 -
3 - 0
FIG.29 INFLUENCE OF PARTICLE SIZE ON THE RATE OF EXCHANGER
FOR Fe^'*'-H^ON STANNIC OXIDE
e 100 u m , A 6 0 u m , 0 42 '85um, A 30um
12 IJISCUSSTUN
To enaure pa r t i c le d t f tus ian ffioohamtsffl a etu«1y af
conccntrfitlon effect OQ the rat© of exchange for Te^*'4i* et
30 ;• 1 C was carr loa out , Sl»co the l a l t t a l r a t e of oxclianijo
for Pe'"*"-!!* 1» proportioQfil to Pe^* too eonocntratfoit at
concent lot ions ( O.OIM while at conosntrat lons ) OAH I t Is
Inflepenslent of concentrattum, the s tudies were oeae for
ooncentrations g rea te r than O.IH,
The extent of reaotton (P) le defined am
p m ^^ eatonnt of exohBOge at t t g e t the asoiint of ©sehnnGR ot Inftntt© t ine (equl l thr lua)
The ra laee of f at tllff©r«»nt tlfse Intervole and
' l l ffcrent tenp«rot«ref» were obtained for Pe , Ito" , Co*" ewf
Zn" -H exehongea an*1 are plot ted In Fl^uree 21-2A(* I t la
cl<».ir froBi thp r e s a l t s tha t aa t he teisperatare Increaaee frous 0
30 to 60 C the ra te of ton eschange el^o loereoseB, This la
flue t o the fact that with Incrcosinn teapcrature isK>bllity of
iona increaaee, Tbeac reaul tP also inrtleate tha t I n i t i a l l y
the uptake of iona la r ap id . The uptake of ion deoreaaes
with increase in tlrae. These reaul ta ore anolosoua with t ha t 12 of Heliher an<! Marlcovitles ,
As the rnte determining step lo exohsnge through the
12:
ton exchanger p a r t i c l e , the follot/lng equatlvwn In voll«!
I? -. 1 J L . V exp («o- Bt)^
where
B « A^ B ! / / » ( t )
r , the raaiui* of the i;«>rttole, TII i s the effect ive diffusion
ooefflct**at of twa IOHB underKolnir exchange u l t h l a exchfmgcr 13 phBfic " and t le the tlrae^
Valuep of Bt oe a function of P eay he calculated as
tfibuluted hy Relchenhern, The typlcwl Bt irarRus t plots et
different tei«peret«re^ proponteft In Teh lee XVIII-XTX and
plotted In FlfjureB 25-28 show that the rote of exchanjjie 1»
' l i r ec t ly proportional to the tcrapernture, Tn « l l caaes the
p lo t s Bt ver!?up t are e t ra lpht l ince peaaln^ throuif»h the
orli:?ii. t h t a Indlcatofs that the rote deterroiulng step is
diffusion throuffh the eschnofer p e r t t c l e t at a l l temperatures
etu'^ted.
The pa r t i c l e BIEC hat? a parked effect on the ra te of
eschange. A plot of Bt voraufJ t at four d i f fe ren t par t i c le
roi l t l Flpure 29 end a plat of B afalnst l / r WQP node In
Pl?:urc 30 which also coaes the s t r a igh t l ine Indicating tha t
123
(/)
m O «~ X
CO.
0 20 40 60 80 100 120
1/r^X10"''m"'^
FIG.30 PLOT OF p VS. I/r^ FOR 3+ o
Fe" AT 30 C
rat© of eaohnng© Is invereely proportional t o the pnr t i c le
Tbo otfUotlQn (1) Is uscfl for tho oaloulfttlon of the
<* if fuel an coefflci'^nt (Hi) , Tbe valoee ere given In Table XXTTT,
The llnofir re le t lanshlp lictween log Dl oo^ 1/T K (Ftg, 31)«
<»nafelj?g the calculct lon of the energy of ao t l ra t lon (Ea) for
tho e<»lf dlffusian of oetione t o be oaloulatcd from Arrfctenloos
oquGiioa
Ot • Do exp (-Ea/ST) . • . • • (2)
VALUt OF rst (cn^ eec"*) uF VARIuu? l u x s AT '>irFum:KT
J ^ 1 ^—^ * ' ^ ^ ^ Cfttlon 30 ' c 4iO*C 50 *C 60 "c
Fe
Co
Mn
Zn^*
'^^ 1.698 * 10**^ 2.04 X 10**^ 2.29 x 10*"*^ 2.57 x 10**^
.^* 1.20 X 10**^ i . « X 10"*^ 1 .58x10**^ 1 . 6 9 x 1 0 " * ^
^* 9.77 X 10**' 1.14 X 10"*^ 1.31 X 10"*^ 1.41 x lO"*^
6.31 X 10"* ' 7.58 X 10*^' 8.51 x l o " * ' 9.77 Jt lO"* '
The act ivat ion encrfl;y of the cation se l f ftiffaalon
process rof lec t f the e&m with which oatlun pns'co through the
1 ">
ejeobaogur. Th© ireliie of ae t lvat lon enerp.y ( t a ) tor dtffererjt
cetlonf are giv^n in Table XTTV, Caloaletlim of ^o eart
BQbetitttttoB In ewa t ton (3) ^iveet entrafrf of aotlT«*ttan ( AS )
Do • '2,72 a^ fef/b cxp (AS*/«) • • . • (3)
irhere d in the tonte J tap distance eqtjal t o 5A , k I s tfee
Boltsesra constnitt ei|«Ql to 1.3S s 10 J U jROle , h t s • •
Ple{icte*8 oonetant ®ii5 T Mas 275 K:. The valwee of AO «ere
o%tafti©a fro® the r^lmn of Ba ©iw! ZlsS , which ere given 1B A *
Tst>lo xiiv» More Beg«tlip® vBloes of A S t o rtlvalent Ion* 1%
ore imologous to th«» faigraticwn through «©olites and the »
valnee of t o , ! o on<J A S give soorly s l e t l o r p c t t e m t o thet 'y « Q
obf^'lued with other Inorfsnlc loo essehangtrs • * , mmmmmmmmmimmmimiimmm
Sltr DIFFt'FION CULFFTCT:J»TS, tmUGY Ul' ACTIVA1I0M, F-NTnijrV OF ACTTVATTuK Mm FS-i. LJILRGY OF ACTTVATIy?: Of H^f Al. TONS
OK Sf AKNIC a.XT^ (lOO jaa)
M e t a l fiQ tF S*^ E© As* Ao*
F«^*
Co^*
KB
2*
t.69 X SO"^®
3.16 X 10*"
4.36 X JO***
6.91 X 10"**
11,^
S.05
9.%1
It .70
-85»%2
•202.04
.94.71
•^•^.S
37*35
69.25
3§.10
59.25
126
tM I E Q cn o
12-20 A . ^
10 /T°K
F(G.3I LOG Di VS. I / T FOR 3+ 2+ 2+ 2 +
• Fe ; 0 Mn ,A Co j A Zn
127
1. P.C.NacUdfl on^ Vocwf, J.ABj.Ch©ra.?oo., 66, 13^0 ( l ^ W ) .
2 . GJl.HatiCQllos cn-l H«Peterson, J.lQorg.Kocl.Cheai.^
22, 259 (I96t)*
3 . ?^y1v!0 J .narvle PD-I G.n.Hnncolles J,Tnors«?!ucl,Che!a.,
30, 273 (1968).
4 . A.nyer and r.T.OCon, I b M . , 33, 3t53 (t971)»
5 . A.nyer ana j . s . G l l l , ll»ia,, 39, 665 {1977).
6 . !Curt Buncl, t b M . , 39, tO'i5 {«977),
7 . J .P.Rwat and P.P.ftitnd, J.rfeye.Cheig,, m^ 1384 (1976).
8 . J.P.Rawat and T>»x,Fingh, J.Tfioi^.Huol.Cticia., kOp 897
(1978).
9 . j .P.nawet end M.A.rCbnn, J.Tuorg^Nticl.Chera., 42, ^ 5 (1979).
10. J,T>,T)attaia6an and M.J.FuUer, J.tnorg.Nucl.Cheisi,, 30, 1083
(1968)•
1 1 , n.Helohentien;, J,Ai?t,CheBi.Soc., 75, 589 (1953).
I S . Carlo Holther-^lrguln ens! G^Her^ovttos, J.Fhyr.CheiB.,
67, 2263 (1963).
13 . fl/t.Bowcr, n.r.BarthalOKKK* onrl L.V.C.H^sc*, J,I^tys.CbQta.
SalldR, 12, 21 (1961).
i%, Turee me '.'.Rtenon, 111, J . rhy.Cboo. , 65, 1021 (1961).
C H A P T E H - V
SYNTIESIS, PROPERTTKR ANT APPLICATTONS UF A NLW THORGANTC
ANION EXCHAKGLH. FKKRIC TRIETllYLAMINS
128
In the continued effor t to syntheslae o new tnorganlc
nnlon earchanger bese«1 on a e t a l hy^roxtfleB with aaino group*
only 0 few Itlce aralno ethyl phosnhf>te derlvntlve of alpconluia
hUR been s tudied . Some a a t c r l a l of t h i s kind have been t r i ed
ta our l abora to r i e s , Aluj^tntum tr te thanolantne was found 2
t o behave as anion exchanger • Thorlma triethonoloisfne ««? m 3 chela t ing i j n exchanger hag a lso beon studied , The studiee
on thoriuia»tricthyl0Tn^ne and zirconiusj t r l e t h y l a o l a c ,
pave the way to develop some new ton eschnnglng mater ie ls of
t h i s type to be u t i l i zed for sose ana ly t ica l ly Inportont
separat ions on the bas is of t h e i r anion exchange behaviour and
for forptlan of metal ions on the bas is of t h e i r chelatlnit
a c t i on . Therefore, the 6tudic@ arc extended to synthesize
another material of thin kind, f e r r i c t r le thyla ta ine . The
mater ia l has been studied for i t s anion exchange capaci ty ,
d i s t r i b u t i o n of different anions t o oeaeure s e l e c t i v i t y .
Composition s tudies and T,R, s tudies arc made to charaeter ize
the exchanger.
129
Apparatus
An e l e c t r t c ter^tx^raturo controlled STGu ahnker, Baueoh
antl Loab spectronlc 20 (U.P.A,) and Elico pH raoter noHel
Ll-10 (Indie) were uced for shakint^ purposo, spect roj^otonetr lc
detcrpslnotlon on<3 pit tscanurereente respec t ive ly ,
KeagentB
Ferr ic n i t r a t e (B.»>,H,) and tr lethyloi t lne (CJIerclc)
were iissd. The o ther chenlcols were of analyt lcol grade,
Syntbeels
Ferr ic t r le thy lan lne was prepared by islxlnr; a O.IM
solution of f e r r i c n i t r a t e rnd O.IM t r le thy laa tno In the volurae
r a t i o of I t^ (Table XW), Any a l t e r a t ion In the r a t i o of the
reagentB e i t h e r rceal ted In the dleapt^arancc of the p rec ip i t a te
o r the yield was l e ce . Red prec lp l to tc thus fomofl was feept
etaodlng at room tenperatur© for 24 hours* The p rec ip i t a t e woe
f i l t e r ed and washed «l th delonlzed water* I t wee then dried
ot 40 C, The dried product was cooled a t roota tonperoture for
12 hoars* The dried eaaterlel on l©ii?crslan In water broke down
In anal l p ieces . Again a f te r drylnjj the eschangor wae converted
In the desired anionic form by t r ea t ing the exchanger with IM
solut ion of d i f ferent anions*
130
O
MM*
>-3
'J
'd
^ w
i o < E-»
O
(/, ; j
•» _-' 8< O « H ^
E ^ < 11 .<**,. •-• { -
< c < ^ k " *
.?: e« <JH "5
^. O H
i: fe p O
t
I
a o o'v. O £ <S C*
C M O g
o
o g o
s
c e o
o o
o
C
o
C3
I
O C
u u
fiD
o 4»
a •» •H
a «*« 0 £ c. o iR
9 •» C3 4* W 4
{& <H o 1 o. 0 s
o «« s ^ «« c. •-• o £ o. 0 &:
(S
a c 6 IS
o «; > • » K N
o o • i ' & o4 tS
O
tt A» P
0 4* Q •» ^ a v<
e» o u r». a 0
x: •» <
Ss a o
§£ a
49 C. «r c. 4,* a
•r* <c -r*
>« a / : a. p IS
+» (X
o ss
rk
© «
c o ©
T. r
© o • •
O G
<H t»
04 in
tA m
^ (A
L-\ til
O u<
f». i / j
131 BSiiSULTS
/nlon eagchop^e eopeclty
The anion exchange capacity of f e r r i c trlethyla-nine
cxchnnger viae Hetermlneti hy coluran ptctbod. The eolon exchanger
welr.hlng one grew woe tnfecn in a g lass coltnsm soagarlns 20 cm
lonj* awS 0.6 ow dlaRcter with o nloee wool supnort . The
capacity was calculated for d i f ferent aalone ns'^ely, ch lor ide ,
hrotnWe, iodide, dlchronote, ohrooate an< sulphate by converting
the exchonser in the recjolred fom vl th so^lun or potarplarn s a l t s
of refjulred anions. The colussn was washed with iflelonized water .
The cluent used was l?t so^lus n i t r a t e . The e lu t lon rote wa«?
fixed at 0.5 ial/©lnute. Table XXVI (jlves a vie'* of the exchange
oapac i t i e s for a i f fc ren t anions*
TABtL iXVt
ION CXCnAKGE CAPACITY OF FLHEIC Tnii-TIIYLAMINC
FOR T>IFF1:.R. KT ANIOKS
J , ,
Sl« Anions S a l t s tofeen Capacity No» (ffleq/gm)
0,160
0.130
0«105
0.74
0.62
1.
2 .
3 .
4 .
5.
6 .
Chloride
Broride
Tod id©
Bichroraate
Chrowate
Pulphate
Podlura chloride
Potasrlun bronide
Potae«?l«'« iodide
Potssplu*^ dlchrcmate
Potassiun chronate
Eodlun BUlphate
132
Coaposttlon
1 gr©' of fe r r i c trlethylanjlne was dloftolvefl tn 50 o l of
crjueren**** TTeetlnf was avoided for prcpartn*^ eolotioQ, I t wee
then tsR^o upto thft rark In 100 ml stondardl flnek wltb deionized
t^ator. The amount of Iron(TTT) present In tbo Baraple wae
^ctcrulned by taking one lal of tho eolation In tho bea&er and
t l t r o t i n ' t I t against KBTA using PAN Indlcntor , The t o t a l atnount
of Iron (TIT) present in the eaiaple was calculated for lOO ml,
runnt l ta t ivo de tcr r lna t lon of t r i e thy let3lne In another portion 4
of t!je PCrsMe xiaa done Bpectrophotoraetrlcplly by nlnhydrln ,
Iron ant! trlethylarjln© were found to be present In the r a t i o of
1 J 3 tn the exchanger,
Cheiaiool s t a b i l i t y
To check the ohenlcol s t a b i l i t y of the eschanf;cr
f e r r i c t r l e t ^ y l a e l n c , 0#5 n» c^ **»e ©acchan/iier was sbaj^en with
di f ferent rolventP for foor hours . The amount of f e r r i c present
in the supernatant liquid was dcterralned by t i t r a t In" a knotm
V3l«'!io of the solution against tWA ao^ the asiount of t r l e t h y l -
anlne was detereined spectronhotonetr lcal ly In another earaple
by nlnhydrln. Table ^XVtT gives the s t a b i l i t y of exebauf^er In
d i f fe ren t solvent syote-ts.
133 TABLL XXVII
STABILITY OF FLHiiic TRii:Tr.yLAHiM: IN T1TFF. \.:7T toh\K ^^rs
S I , No.
Solvpnt syetcns Solttlillity
(t?g/50 ral)
Perrle
00
00
00
oa 15.00
1.50
00
50.00
15.00
IS.20
Trlethylaeln*
00
00
0.01
0.05
51.00
4.20
00
fl5.20
50.00
52.i|0
1. '^elonlzefl water
2, Sodiun n i t ra te (IM)
5 . So^lua hj' 'IrosWe (2? )
4» Armonlvm hyrtronl^^f (l*f)
5* nyrtrochloric acid (0,10*f)
6. Poralc ecl<! (O.lOM)
7. Methyl alcohol
8. Sulfuric acta
9. Nitr ic acid (oaO'O
10. Acetic aolrt (O.IOM)
Thermal trcetment
l^iffcrent aaaples of ferric trlethylaelne were heated
in the furnace for 6 hours. The anion exchange canaclty for
diehronote Ions for the exchanger ferric tr lethylaslne at 6© C, o o • o
100 C, 150 C, 200 C and 500 C were (fotersfjlned reaimctlvBly
134
E
e
O < Q. <
100 200
TEMPERATURE(°c)
300
FIG.32 CAPACITY AS A FUNCTION OF TEMPERATURE
135
(Table XXVIIT), Tn Figure 32 anion excbange capacity (fordl-
chronot© Ions) were plotted against toaperaturo,
TABU: XXVIIT
CAPACITY OP ^TCHfyj'ATE lONS AT DIFH-RLhT TEMKlHATUrffiS
P I . No,
Temperature o
(C)
Capacity
(EMsq/gra)
1.
2,
3.
5,
40
60
loo
150
200
300
1.48
1.48
1.20
1.00
O.SO
0.78
Potent lopietrie s tad les
pil t l t r o t i o n s of the oxchonger fe r r ic t r i e thy laeilne were 5
perfomcd by Topp and Pepper aethod • 0.5 gtn socple of f e r r i c
t r le thylewlne t^ae shaken In 250 a l conical flBwk v l t h O.OlM TTCl
and O.OlM polutton of sofllu-n c h l o r i d e . The voluae of hoth the
6olutl:»i was kept 50 ml in each cose . Each flop's was then
ei iul l lbratcd for four hours end then pR of each solut ion was
detcrnlned by pT! r e t c r . Figure 33 f ives the curve for the
pn t i t r a t i o n .
o
in
_ to
- to
CC UJ o Z <
I u X UJ UJ z
>^
in (*)
o CO
to CM
o CM
O I S *— o o M-
o ^ E 3 "o
2 < _J > T
LiJ
DC
h-Z o cr
oc O U-
> cr D O Z g <
h
a
CO CO
O
Hd
137
T»n, studies
For cheracter lz log loo exohenger, T#R» s tudies were made,
T.n, epectruo of f e r r i c trletbyle»ninp were perforT",e4 by uslni^
KBr dllBC, Plpure Jk shows the fif^eotrum,
T)l8trl1?utlon 9tM>11i p
K& velues for anions were deterwlned by bach process,
1 ral of 0#5'^ anionic solution and 49 ral of the solution In which
fCd values of the exchcngor were to be checlcod, wrro nddod In a
250 ral erlonweyer flaek* 0,5 gn of the exchanger wcf then added
In the flPiRteP. TheBe flwpfee were then ehe^en for k honrr In a
ahnker for obtalnlnn co?nplete etittlllbrlisti. The onions le f t In
solution wore then deterralned. Total ewount of anions were a l so
deterr lned without equl l lbra t icm. KA •a lues cnn be calculated
by uslnc the formula
T*P Voluise of the solut ion F height of the exchani;er
where T s Tn l t i a l voluce of t l t r c n t before equ i l ib ra t ion , and
P o Final volune of t l t r c n t a f t e r equ i l i b r a t i on .
K:d values in deiontzed water an^ different Rolar solat lone of
fiO(<iuT hydroxide are reported in Tr.ble XXTS:.
to
o o 00
o o o
13^
o o CM
o o > x-~
o o
o o 00 *"
o o o CM
o o in CM
o o o CO
O o in CO
<-^
1
6 (J
L.
E 3 C ^ >
o ^
a: UJ O z < I u X UJ u z 5 <
> X
UJ nr h z o QC
U. o 5 D h-U LU CL C/)
(T •
o o o
CO
o LL
( 0 / ^ ) a D U D ^ I U J S U D J i
139
TABLE XXTX
Sd VAhm:S KOH fTFis.n, KT . NljXf^ IN '^IF*-:..! .>JT ?Jl.V!.NTS
SI. No.
Anton« Kd
»'ater NaOH NeOH Neon Naon
{10"*M) (10*'^) (lo'^M) {10"*M)
1.
2.
3,
^ .
5,
6.
?•
8,
9.
10.
!!•
12.
13.
U .
15.
16.
17.
ChlorWe
BrouHe
Iodide
nic'ironote
Chraaate
Tbiocyanoto
Thiosulfaie
lodote
Broaatc
Arecnnte
Chlorate
Eulfate
Sulfate
rersulfote
Forrocyanlde
riiosphatc
Areenlte
too
6k
101
T.A.
T.A.
220
253
14^0
1670
3*50
1290
224
1200
233
533
T.A.
T.A.
81
57
Bk
T.A.
3666
129
150
ikhO
286
34SO
1120
205
1250
150
533
1890
T.A.
41
23
47
T.A.
1800
52
91
280
86
1300
295
114
234
67
138
54
560
32
12
10
8
10
85
08
15
70
536
280
114
43
50
27
40
420
13
5
01
4
7
00
02
10
52
51
115
42
12
30
12
02
40
140
Separations
Owinf, to the lorgo differences In .01 values t o r d i f ferent
anlann, wany analy t ica l ly lusportent separatlone of anions were
t r i ed and euccesefully achieved. The colu-me having: a height of
30 CMS end d lane te r 0 » ^ on f i t t ed with the glaas wool in the
l o t t o s r e re used. 2,0 z^ of ^^^ rxchenger havlnr» 150»200 meuh
^l ie in n i t r a t e forsa wac cl'ted Into the COIU"T3. Yhf* 'fixture
of anion Bolutlt«ifi wae added In the coluna t o r iepora t lon . The
solution 'ins allowed to tr lc&lc tlown slowly through tho column*
The solution wa*- rerentedly Daseod throy.h the colu^an to enrurc
co'-iplctc cl0orption of anions. These anions were cdeorhad at
tho top of the cjichanser bed. The anljaf were then eluted by
opnrarJ*l«*tc e lu t inp rc r ' r rn t . The acotint of anljnr verc then
dcjtenlno'i by standard "sothads, Fcparatlons of Crul" trom T",
CrgOl* frsT' Dr*, FoJ* fross T " , CrgOl" fron Cl" , CrajJ* frosj Br"
•jcre nucccssfully achieved. The olutiou carves for each set of
Eeprratlon are shown In Flfturo 35» Tabic XX\* glvee a view of
i tuantl tat lvc separation of onl^n on fe r r ic t r i e thy laa«lne
c o l u m s .
o CM
O o CM
O CO
o CM
O CD
O IT) CO
o
141
I r-
o 00
o >*
o o vt CM
O CM
O C£> "
O CM
E
c Q>
2 ^
« o Q)
6 D
o >
•
' 'sT O L.
o 5 0 cr l i .
1 »—1
LL o ^ O h-< DC < Q. UJ (/)
* » - ^ D
-^
o .^ L. u 2 o QC
£_
CD
l i -
O z o h < cr < a i i j
to
^"^ n *-^
(iLU) jUDj;)) wtO-0 *o auunjOA
c o
o 6
E ZJ
o >
2-00
1-60
1-20
0-80
O' O
0
( a )
CI"
1 ^ ^
H2O
t ^'2°l'
\
\
\
\
i 1 i H .
0
1-20
0-80
0-AO
40 80
142
120 160 200
80 120 160 200
Volume of effluent (ml)
F(G.36(a)SEPARATION OF Cl" FROM Cr20y
(b) SEPARATION OF l " FROM 504'"
143
c o
o o
£ D
o >
2-00
1-60
1-20
0-80
0-AO
0
] \ Br"
l\ ] \
1 \ 1
1 ^
H2O
1
CrO^-
1 1 40 80 120 160 200 240
Volume of effluent (ml)
FIG. 37 SEPARATION OF Br" FROM CrO^"
TABLL XXX
QUANTlTATTVi: B.VhUATlon OF ANTONF OK
n-RRTC TnTi.Y!iYI.A!ftNU CoLUMNF
144
S I . TJo.
1.
2 ,
3 .
h.
5.
t
Mixture
t -
C i O ^
Br*
Cr^o;*
CI*
cr^a- -
T*
FO^
Br"
c r
T 1 Cluente
10 71 Naon
10* K M^Tl
io**M nm\
10**K KaOH
•4 10 M Ni H
lo* M i:mn
10"*M McDII
lo'Sf Naan
10*Sf Naon
10**>f NaOH
Eluate
(iBl)
110
110
110
100
90
110
100
90
110
110
1 <
laBdod
(rag)
5.588
6.6234
6.1607
14,70092
1.917
14.70092
5.589
2.40
6.1607
6.6234
1
Amount found
(rag)
5.5245
6.5072
6.0408
14.4S473
1.S46
14,48473
5.461
2.256
6.0408
6.5072
f
"' Error
1.15
1.75
1.94
1.47
3.70
1.47
1.27
6.0
1.94
1.75
145
Th© re su l t s of Tabic JDHT Rhot? tha t for ca plote
n rec ip l t a t i an to occur, f e r r i c n i t r c t o to trlcthylo-nlno r a t i o
nUBt ho fecpt iihm '.lifin forr lc t r l e thy lan lne in H forta was kept
in oontftct wltfe a solut lan of codlun n i t r a t e no releaeo of H*
wos obj?ervod» nigb value of loo exohenge ccpoclty towards
aichroirotc ion (1.48) I s in accortlr.nce with tbc r c r o l t s of
r.lrconlQ • The or^er of cepccity for halldoe I s CI* ) Br"* ) T",
Tbc ion exchan/!e copnclty of the exchoni^rr dreror rcs ns the
ionic r a d l l of the halidc Incrpflses. For other Ionic ercctos < Saw 4 P«»
cepaclty docreeses In the order Cr^Ol ) CrO^ ) F). » The
ejichsngor fe r r ic trlothylfir»ine ehowe enlon esc»inr";;c copccity
flue to the proeencc of -N - group.
The r e s u l t s presented in Tnblc lOrvtTI give the effect
of tenperoture on the capacity of cschcnger* The onpeolty
rtecreoses with the Increase in t cnnera tu rc . M h lcher tempera
t u r e s the water wolocules on-l oalnc lolcoulcc cr^ los t froa the
eschanrer anfl thereby rtecrconlnE the capaci ty .
The r©«jaltP of e x p o s i t i o n 8tu:!lcs r^oti tha t Iron (TIT)
an3 trlcthylftfstne are present In the nolor r r t i o of l s3 In the
exchanger. The r e s u l t ? of notent lonctr lc t i t r a t i o n cnrve
plot ted In Flpure 33 reveal thot the exchenfcr IroR(TTT)
t r le thylnnino behaves ne a mono functional Qschrnr<^r,
146
The lnfra«td epeotrun of f e r r i c t r l c thy la^ lna in
Figure 3* shows the obBorptlon peaks at different vnluoc of
wave nuDhere ae given belovt -I (o) .A brood peak ranging fron 3300-3550 era in «3u€ to the
-on 8tretchtn?T v l b r a t l o n t ,
(h) A strong pcBi at 1380 Oai~ la due t o C-N vtbra t loae and
C<i4l beodlng vibrat ions*
(c) A isedlu?? peak l i e s at 2950 era* due to C-^ otretehlng
vlbrntlon8»
(a) A stron/» C-C stretchinr; vibrat ion i s ob£.orvn<^ In the
frof»ucncjr range of 1620-1660 CEB* •
(a) A pscdlun C-N bendlni;; fre<iuoncy l i e s In the frequency range
of 1070-1080 Cifl* .
(f) A nedluw pen!t In the frequency range of SOO-G'iO era" i s
observed due to the isetol oxygen bend Ins v lb ro t ion .
I t Ifi oHltc c l c s r tl:0t the cxcti::ns;cr f e r r t c - t r * o t h y l -
nninc contalnf, ootno c w' Jp ^-^^ t *? netnl osygen bond* I t
oonflrrn tha t In tho forrnt ion of thin type Oi eatcliaiscr the
Dwlnc 1 P lncornor«»ted with t^e cc to l oxlt!c forraln': tb© matrix*
The d i s t r ibu t ion bohovlour of anlonn (Tabic XXTX)
Inilicotee tha t the fC1 values wore hlfjh whrn <!oioni20d i»'ater
•JQP used 06 a ncdlun, t l lptr ibut lon velnoo were l e s s when
sodluta hydraxl«'«e solution t^cs used for ftu'^lor. and they deereaso
as the conoentration of sodlii© hydroxide rolutlcm t.as increased.
147
Being a veBk onion eacchanser, f e r r i c t r lothylswlne has a
hl(»h a f f i n i t y for Ijyflrosryl loow, hence anlans otner thon
hyircrtyl Ion showed Iccc uptc!ie In the prepence of hyilroxyl
lone*
Owln« t o the lorf,e differences In the a ie t r lbut l t ra
rrilimfs of vorloue nnlonr nony ana ly t ica l ly lr'»>ortRnt sepurntions 2 - • 2 - •
were t r l o d . Separation of CrOj frtn T , Cr„0« fr«r Dr , RjJ fra-n T , ^^0^7 ***o^ ^ ^ * C ^ J ^^^'^ Br were suoeesBfwlly
nchleved (Tohle XXX). Those ropul t r r i m shotf c Ui Ii s e l e c t i v i t y
toi#ar«5r CrO^* onfl Cr^al" CE pre-^lctcd by Tohlc :i,x>.
148
1» L.Hayo» J.Inorg.Kucl.Cheo,, ^ 3 , 400 (19S1),
2 . J,I\l!Gwct, K.Iqbcl and Kceoo'l Ales, Annoll ^1 ahlnlcn
(in pr©6e),
?• J.P.Rowot and ^faeood Alcta, Annnll I>1 Cbt-iiCQ {Tn proes) .
4 . Sn«ll ,F«n, , Fnell .C.T, and Snell,C»A,, Color lnotr lc rjctho<1e
of anolyBlo, Vol. IIA, T>,Van.Noptronfl Co. Ino , , rHacoton,
H , J . , n . 683 it959)*
5 . ToppjN.E. and Popper, SC,U,, J.Cbcrs.foc., 3295 (19^9)«
26 © 1984 The Chemical Society of Japan Bull. Chem. Soc. Jpn., 57, 271—271 (1984) [Vol. 57, No. 3
Ion Exchange Equilibria between Alkali Met"Is and Hydrogen Ions on Iron(III) Antimonate, an Inorganic Ion Exchanger
J. P. RAWAT and B. SINGH
Depaitment of Chemistry, Aligarh Muslim University, Aligarh-202001 India
(Received July 19, 1982)
Ion exchange equilibria of alkali metal ioiib (Li"", Na", K' and Rb ' ) 'H ' systems have been studied at 30, 40, 50, and 60 °C; on iron(III) antimoiialc as a cation exchanger. The exchange isotherms have been measured for both forward and backward reac'tions with solutions of ionic strengtii 0.1 by the batch technique. The isotherms showed S-shapcd curves for each exc' ige system except Li' Tl*. Selectivity coefficients vary with the
ec|uivalent fraction {X\\) of the alkali metal ions in the exchanger and give linear functions against Xy^ in the range from 0—0.40. The selcctivit\ .sequence shows Na^ < L i ' < K ' < R b ' . 'I'hc overall thermodynamic data arc evaluated.
Syntliclic inorganic ion cxrhangcr.s have been developed in recent years. The primary aim of most of tlic studies done in this field has [)een to achieve the separations. Besides the preparation of new materials and their applications to tlie separations interest lias also been developed towards the study of ion exchange equilibria on these materials. Because of their thermal stability, their rigid structure and consequently negligible swelling, the ion exchange equilibrium studies at different temperatures on these materials will be simpler than on organic ion exchange resins which swell quite appreciably and are prone to thermal instability. The contributions of Larsen Vissers,!' Ruvarac,^^ Amphiett,^' Alberti,^^ Xancollas & Dyer^' are noteworthy in this fieTd. • Recently Abe and Sudoh""') described the ion exchange equilibrium studies on antimonic acid for the systems of transition metal ions/H'*" and from these results the appropriate thermodynamic data were derived.
The influence of temperature on the equilibrium between alkaline earth metal ions and hydrogen ion on tantalum arsenate has been described in our earlier paper.*) Similar studies on the equilibria between alkaline earth metal ions and sodium ion on iron(III) antimonate have also been described.^' The ion exchange characteristics of iron(III) antimonate are of considerable interest since it behaves as a cation exchanger with different selectivitics for cations.^"'
Limiting our attention to series of ions belonging (o the OTne group of the periodic table, that is having the same valency and similar electronic structure, we can study the effects of ion size and hydration upon equilibria eliminating the problem of the influence of eletronic and valency differences. Alkali metal ions can be taken as models for metal ions since they have univalent positive charge. Furthermore, they form inoic bonds and the effect of complex formation can be avoided.
Exper imenta l
The iron(III) antimonate was prepared as desci'ibed jjre-viously.
Determination nf Maximum Uptake of Alkali Metal Ion<: on Iron(III) Antimonate. A 0.1 mol dm •' solution of alkali metal chloride was passed continuously through the iron(III) antimonate column in H*- form until the change in concentration of the alkali metal ion was negligible between the influent and effluent. The equivalent fraction of H' and
M' in iron(TlI) antimonate was calculated on the basis of total exchangi: capacity.
hn Exchange EqtiiUlnia. In the forward rcaction.s the iron(III) antimonate (0.5 g'> in H* form was immersed in 20 cm'' of a mixed solution of varying ratio of alkali metal chloride/hydrochloric acid in the conical flasks with intermittent shaking at 30±1, 40±1 , 50± 1 and 60±1 ''C. The ionic strength in the mixed solution was adjusted to 0.1 with hydrochloric acid.
In the reverse reactions the ion exchanger iron(III) antimonate in the respective alkali metal forms corresponding in weight (0.5 g in the hydrogen form) was immersed in the 20 cnr' of the mixed solution of alkali metal chloride/ hydrochloric acid at an ionic strength of 0.1.
Theoretical Aspects. The ion exchange reactions of the univalent alkali metal ions/H"" exchange systems on iron(III) antimonate can be represented by the following expression;
H+ : M ' :;=± M*- + H+, (1)
where the bar refers to iron(III) antimonate phase and M+ is the alkali metal ion.
The corrected selectivity coefficient of the above reaction can be defined as:
(2)
where K^ is the corrected selectivity coefficient. X<i and
Xji arc the equivalent fractions of the metal and H+ in the exchanger phase, respectively. X^ and X^f are the equivalent fractions of exchanging H+ and M' in the solution phase, respectively. 7,1 and >>,( the activity coefficients of hydrogen and die metal in solution respectively. For dilute concentrations the contribution of the activity coefficient ratio (;',, y^j) may be taken as unity.
The thermodynamic equilibrium constant JTa can be calculated using the simplified form of the expression given by Gain.s and Thomas (II) :
In K, -- r In K^dXyi. (3)
The change in the free energy of the ion exchange reaction, AC^ was calculated from the thermodynamic equilibrium constant A'l using the expression:
AG" - -RTlnK,. (4)
The standard enthalpy change, AW° has been calculated from the plot of log/fa against 1/T.
The standard entropy change, AiS"" is then calculated by the relation:
AG" - A / / ' - TAS° (5)
March, 1984] 11
I 0
0 8
0 6
0 i.
0 2
0 0
« 3 0 ° C BACKWARD O 3 0 C FORWARD » < 0 * C
/ ^ ^ ^ ,
a. IX '_ I 0
0 0 0 2 0 4 0 6 0 8 1 0
Equiv i l tn t ionic f r i c t i o n of L i * in solution ( X L , I
Fig I Ion exchange isotherm of Li+-H+ exchange non(III) antimonate
0 8 -
0 6
0 4
0 2
X 3 0 ° C BACKWARD a 3 0 ° C FORWARD O A 0 ° C
= 0 0 02 04 06 0 8 10
Equivalent ionic frac tion of Rb* in solution ( Xp^)
Fig 4 Ion exchange isotherm of Rb+-H+ exchange on iron (III) antimonate
1 0 « 3 0 ° C BACKWARD • 3 0 ° C FORWARD * 4 0 ' C
0 8 |- o 5 0 ° C 4 6 0 ° C
0 6
0 «
o 0 2
; 0 0 0 0 0 2
Equivalent ionic f ract ion of Na'in solution I X/yj^l
Fig 2 Ion exchange isotherm of NaT-H+ exchange on iron(III) antimonate
- I 2 0 -
- I 6 0 -
-2 4 0
- 2 8 0 -
- 3 2 0
0 0 01 0 2 0 3 0 4 0 6
X L I *
Fig 5 Logaiithms of selective!) coefficient vs ionic fi actions of Li* in exchanger phase
I 0
0 8
0 0
« 3 0 C BACKWARD 0 3 0 ° C FORWARD ' 4 0 !c
^ 0 0 0 2 0 4 0 6 O S 1 0
Equivalent ionic fraction of K* in solution (Xk I
Fig 3 Ion exchange isotherm of K+-H+ exchange on iron (III) antimonate
Resul t s and Di scuss ion
The equilibrium was attained for the forward and backwaid ion exchangee leactions within 6 h shaking
The ion exchange isotherms for the systems Ll+/H^, N a ' / H ^ , K II , and R b ' / H ' in a temperature lanq-c of 30—60 C aie sliown in Figs 1 to 4 Ion exchange isotherms ]ia\( been used to lepiesent graphically experimental data peitment to ion competition (at diffeient concentration latios)
For Li-''H+ and \ a /H*, the isotherms showed that the exchange docs not go to completion although cntciing cation is initially piefeired and the degiee of exchange givis a value lower than unity Foi K /FI and Rl) /FI the cnteimg cations show a selectivit) icveisal with mcieasing equivalent fiaction in the exchangci The isothttms foi the leveise exchange aie performed onlv at 30+1 °C and can be plotted
28 J . P. RAWAT and B. SINGH [Vol. 57, No. 3
TABLE 1. THERMODYNAMIC PARAMETERS ON IRON(III) ANTIMONAIL AT AN IONIC STRENGTH
OF 0 . 1 AND V A R I O U S TEMPERATURES
Alkali metal ion
Li+ Na+ K^ Rb+
30 °C
0.08 0.05 0.37 O.fiO
A'a
40 °C
0.06 0.04 0.30 0.51
50 °C
0.05 0.03 0.27 0.45
60 °C
0.04 0.02 0.22 0.40
30 "C
6.50 7.69 2.56 1.31
AG7kJ
40 °C
7.20 8.74 3.15 1.74
equiv"'
50 °C
8.10 9.61 3.55 2.17
60 °C
8.78 10.66 4.18 2.56
AH7kJ equiv-^ 30—60 °C
17.06 22.17 13.85 11.09
A57J equiv-i deg-i
77.60+0.17 98.40±0.35 .54.14±0.18 40.98±0.23
TABLE 2. HYPOTHETICAL THERMODYNAMIC DAT.V
ON "ZERO LOADING" OF THE ION EXCHANGE
REACTION AI- 30 °C:
InK,
kj equiv^'
A//%„.^ A J JJ,-™
J equiv^'
Li'
- 0 . 3 5
0.80
0.00
- 2 . 9
N a '
1..50
3.79
0.00
- 1 2 . 5
K
- 2 . 0 0
5.06
0.00
- 1 6 . 7
Rh'
- 1.25
3.16
0.00
- 1 0 . 4
1.00
0.0 0
-1.00
'^ -2.0 0 c
- 3 . 0 0
- 4 . 0 0
- 5 . 0 0
\ ^
-
-
-
V O 3 o ' c
) R \ \ * 60*C
% \
1 r 1 1 1 .
0 0 01 02 0 3 0.4 05 0.5
Fig. 6. Logarithms of selectivity coelHcient vs. ionic fractions Na+ in exchanger pha.se.
on tlie cuves of the isotherms for the forwared exchange (Fig. 1 to 4). Thus ilie ion exchange reaction'^ are reversible throughout the entire range ol' the com-l^osiiions siudied.
The selectivity of the cxciiangcr can he measured in terms of 7\',,, whlcli is the quantitative measure of the jjrefernce of the exchanger for one ion over another in sohuion with it. The In A',, vs. A\[ which is rcferiTd to as Kielland plot gave fairly straight line for all systems at lowei" values of A' (Figs. ,') to 8). ^I'he linear Kielland pl<jt was also observed for the alkali metal ions H systems on ciystalline antiiiionic acid.
The ihermodynamic equilibi'iiim constant A' was evaluated from Eg. 3 by assuming tliat the relation
between In A',, vs. Zj, remains unity over entire range
0.0 0 1 0 2 0.3 0« 0.5 0 6 0 7
Fig. 7. Logarithms of selectivity coefficients vs. ionic fractions of K+ ions in the exchanger phase.
Fig. 8. Logarithms of selectivity coefficients vs. ionic fractions of Rb in exchanger ohase.
0 to I of A\|. The A / / ' and A^"" showed a corresponding change in their values with the change in temperature since the plots of log A'„ r'.f. 1/7" showed fairly good linearity over the ritire range of temperatures studied. The thermodynamic selectivity scries was found to be:
Na < Li- < K* < Rb-.
liilerpielatwn of llie Seleclirily in /lie Infinitesimal Con-
March, 1984] i9
3 00 3 05 3 10 3 15 3 20 3.25 3 30
Fig. 9. Temperature dependence of thermodynamic equilibrium constant.
centration of the Alkali Metals. The hypothetical thermodynamic data in infinitesimal concentration were calculated for interpretation of the selectivity of the alkali metal in the trace amounts on iron(III) an-timonate and for comparison with those data obtained
jj/jj^h other exchangers. The values of (In JfJA^,->0 were obtained i)y extrapolating to "zero loading" (7) of the alkali metals on Fig. 5—8. From these values the hypothetical thermodynamic data were calculated by the similar treatment as for the overall equilibrium constants. The accuracy of these values may be higher than those of the latter. The calculated {AH°)X^->0 values indicate that there is no enthalpy change in the reaction when metal ion concentration
in the solid phase approaches to zero over the entire range of temperatures. While the (A^ ' ' )Zj ,^0 increases with increasing ionic radii of alkali metals except for Rb^.
The Authors are thankful to Prof. W.Rahman, Head, Department of Chemistry, Aligarh Muslim University, Aligarh. One of the authors (B.S.) is thankful to C.S.I.R., New Delhi for financial assistance.
References 4
1) R. M. Larsen and D. R. Vissers, J. Phy. Chem., 64, 17,32 (1960).
2) I. Gal and A. Ruvarac, Bull. Boris Kidric Inst. Niicl. ScL, 13, 1 (1962).
3) C. B. Amphleti, P. Baton, L. A. McDonald and A. J. Miller, J. Inorg. Nud. Chem., 26, 297 (1964).
4) G. Albert! and U. Costantino, J. Inorg. Nud. Chem., 36, 653 (1974).
5) G. H. Nancollai and B. V. K. R. A. TiUak, / . Inorg. Nud. Chem., 31, 3643 (1969).
6) M. Abe and K. Sudoh, J. Inorg. Nud. Chem., 42, 1051 (1980).
7) M. Abe and K. Sudoh, J. Inorg. Nud. Chem., 43, 2537 (1981).
8) J. P. Rawat and P. S. Thind, J. Indian Chem. Soc., LVII, 819 (1980).
9) J. P. Rawat and K. P. S. Muktawat, J. Inorg. Nud. Chem., 43, 2121 (1981;.
10) J. P. Rawat and D. K. Singh, Anal. Chim. Ada, 87, 157 (1976). 11) G. L. Gains and H. C. Thomas, / . Chem. Phys., 21,
714 (1953).