Jurnal B.ing Distribusi

Copyright 2004 by Taylor & Francis Group, LLC
4
Solvent Etraction E!uilibria
JAN RYDBERG* Chal"ers #niversity o$ Technology, Go% teborg,
S&e'en
GREGORY R. CHOPPIN* Flori'a State #niversity, Tallahassee, Flori'a,
#(S()(
CLAUDE MUSIKAS* Co""issariat a* l+Energie )to"i!ue, ,aris,
France
TATSUYA SEKINE

Science #niversity o$ To-yo, To-yo, .apan
4.1 INTRODUCTION
The ability o$ a solute /inorganic or organic0 to 'istribute itsel$ bet&een an
a!ueous solution an' an i""iscible organic solvent has long been applie' to
separation an' puri$ication o$ solutes either by etraction into the organic phase,
leaving un'esirable substances in the a!ueous phase1 or by etraction o$ the
un'esirable substances into the organic phase, leaving the 'esirable solute in the
a!ueous phase( The properties o$ the organic solvent, 'escribe' in Chapter 2,
re!uire that the 'issolve' species be electrically neutral( Species that pre$er the
organic phase /e(g(, "ost organic co"poun's0 are sai' to be lipophilic /2li-ing
$at30 or hydrophobic /2'isli-ing &ater30, &hile the species that pre$er &ater
/e(g(, electrolytes0 are sai' to be hydrophilic /2li-ing &ater30, or lipophobic
/2'isli-ing $at30( 4ecause o$ this, a hy'rophilic inorganic solute "ust be ren5
'ere' hy'rophobic an' lipophilic in or'er to enter the organic phase(
6pti"i7ation o$ separation processes to pro'uce the purest possible pro'5
uct at the highest yiel' an' lo&est possible cost, an' un'er the "ost $avorable
environ"ental con'itions, re!uires 'etaile' -no&le'ge about the solute reac5
tions in the a!ueous an' the organic phases( 8n Chapter 2 &e 'escribe' physical
$actors that govern the solubility o$ a solute in a solvent phase1 an' in Chapter
9, &e presente' the interactions in &ater bet&een "etal cations an' anions by
This chapter is a revise' an' epan'e' synthesis o$ Chapters 4 /by :y'berg an' Se-ine0 an' ; /by
)llar', Choppin, <usi-as, an' :y'berg0 o$ the $irst e'ition o$ this boo- /=>>20(
?:etire'(
@Aecease'(
y B)C
&hich neutral "etal co"plees are $or"e'( This chapter 'iscusses the e!uations
that eplain the etraction 'ata $or inorganic as &ell as organic co"plees in a
!uantitative "anner1 i(e(, the "easure' solute 'istribution ratio, D
solute
, to the
concentration o$ the reactants in the t&o phases( 8t presents che"ical "o'eling
o$ solvent etraction processes, particularly $or "etal co"plees, as &ell as a
'escription o$ ho& such "o'els can be teste' an' use' to obtain e!uilibriu"
constants(
The subDect o$ this chapter is broa' an' it is possible to 'iscuss only the
si"plerEthough $un'a"entalEaspects, using ea"ples that are representative(
The goal is to provi'e the rea'er &ith the necessary insight to engage in solvent
etraction research an' process 'evelop"ent &ith goo' hope o$ success(
4.1.1 The Distribution Law
The distribution law, 'erive' in =F>F by G( Hernst, relates to the 'istribution
o$ a solute in the organic an' in the a!ueous phases( For the e!uilibriu" reaction
) /a!0 ) /org0
the Hernst 'istribution la& is &ritten
Concentration o$ Species ) in organic phase
B)C
org
/4(=a0
K
A, )
/4(=b0
Concentration o$ Species ) in a!ueous phase B)C
a!
&here brac-ets re$er to concentrations1 E!( /4(=0 is the sa"e as E!s( /=(20 an'
/2(290( K
A,)
is the distribution constant /so"eti"es 'esignate' by P, e(g(, in
Chapter 21 see also )ppen'i C0 o$ the solute ) /so"eti"es re$erre' to as the
distribuend 0( Strictly, this e!uation is vali' only &ith pure solvents( 8n practice,
the solvents are al&ays saturate' &ith "olecules o$ the other phase1 e(g(, &ater
in the organic phase( Further, the solute ) "ay be 'i$$erently solvate' in the
t&o solvents( Hevertheless, E!( /4(=0 "ay be consi'ere' vali', i$ the "utual
solubilities o$ the solvents /see Table 2(20 are s"all, say <=I, an' the activity
$actors o$ the syste" are constant( 8$ the solute is strongly solvate', or at high
concentration /"ole $raction >0(=0, or i$ the ionic strength o$ the a!ueous phase
is large />0(= <0 or changes, E!( /4(=0 "ust be correcte' $or 'eviations $ro"
i'eality accor'ing to
0
y
), org
B)C
org
y
), org
K
A, )

), a! a!
y
), org
K
A, )
/4(20
&here y+s are activity coe$$icients Bsee E!( /2(2J0C( For a!ueous electrolytes, the
activity $actors vary &ith the ionic strength o$ the solution /see sections 2(J, an'
9(=(9, an' Chapter ;0( This has le' to the use o$ the constant ionic "e'iu"
"etho' /see Chapter 901 i(e(, the ionic strength o$ the a!ueous phase is -ept
constant 'uring an eperi"ent by use o$ a "ore or less inert 2bul-3 "e'iu"
li-e HaCl6
4
( #n'er such con'itions the activity $actor ratio o$ E!( /4(20 is as5
su"e' to be constant, an' K
A
is use' as in E!( /4(=0 as con'itions are varie' at
a constant ionic strength value( 8n the $ollo&ing 'erivations, &e assu"e that the
activity $actors $or the solute in the a!ueous an' organic solvents are constant(
E$$ects 'ue to variations o$ activity $actors in the a!ueous phase are treate' in
Chapter ;, but no such si"ple treat"ent is available $or species in the organic
phase /see Chapter 20(
The assu"ption that the activity $actor ratio is constant has been $oun' to
be vali' over large solute concentration ranges $or so"e solutes even at high
total ionic strengths( For ea"ple, the 'istribution o$ ra'ioactively labele' GaCl
9
bet&een 'iethyl ether an' ;< KCl &as $oun' to be constant /K
D,Ga
=F0 at all
Ga concentrations bet&een =0
9
an' =0
=2
< B=C(
8n the $ollo&ing relations, tables, an' $igures, the te"perature o$ the sys5
te"s is al&ays assu"e' to be 2JC, i$ not speci$ie' /te"perature e$$ects are
'iscusse' in Chapters 9 an' ;, an' section 4(=9(;0( Ge use org to 'e$ine species
in the organic phase, an' no sy"bol $or species in the a!ueous phase /see )p5
pen'i C0(
4.1.2 The Distribution Ratio
The 8#,)C 'e$inition o$ the distribution ratio, D, is given in the intro'uction
to Chapter = an' in )ppen'i C( For a "etal species < it can be &ritten
Concentration o$ all species containing
D
M
< in organic phase

Concentration o$ o$ all species containing
< in a!ueous phase
B<C
t,org
/4(90
B<C
t,a!
Ghen < is present in various 'i$$erently co"plee' $or"s in the a!ueous phase
an' in the organic phase, B<C
t
re$ers to the su" o$ the concentrations o$ all M
species in a given phase /the subscript t in'icates total <0( 8t is i"portant to
'istinguish bet&een the 'istribution constant, K
A
, &hich is vali' only $or a single
speci$ie' species /e(g(, <)
2
0, an' the 'istribution ratio, D
<
, &hich "ay involve
su"s o$ species o$ the -in' in'icate' by the in'e, an' thus is not constant(
4.1.3 Extraction Diagrams
Solvent etraction results are presente' typically in the $or" o$ 'iagra"s( This
is sche"atically illustrate' in Fig( 4(=a $or three hypothetical substances, ), 4,
an' C( The 'istribution ratio is investigate' as a $unction o$ the concentration
o$ so"e reactant Z, &hich "ay be pK, concentration o$ etractant in the organic
phase /e(g(, an organic aci' K), BK)C
org
0, the etractant anion concentration in
the a!ueous phase /e(g(, BCl
C0, salt concentration in the a!ueous phase, etc( The

J0
Fig. 4.1 Li!ui'5li!ui' 'istribution plots( /a0 The 'istribution ratios D $or three 'i$$erent
substances ), 4, an' C, plotte' against the variable Z o$ the a!ueous phase( Z "ay
represent pK, concentration o$ etractant in organic phase /BK)C
org
0, $ree ligan' ion con5
centration in the a!ueous phase /B)
C0, a!ueous salt concentration, etc( /b0 Sa"e syste"s

sho&ing percentage etraction IE as a $unction o$ Z( D an' Z are usually plotte' on
logarith"ic scale(
range o$ D is best "easure' $ro" about 0(=L=0, though ranges $ro" about
=0
J
L=0
4
can be "easure' &ith special techni!ues /see section 4(=J0(
8n "any practical situations, a plot li-e Fig( 4(=a is less in$or"ative than
one o$ percentage etraction, IE, &hereM
IE =00D N/= + D0 /4(40
Such a plot is sho&n in Fig( 4(=b $or the sa"e syste" as in Fig( 4(=a( ,ercentage
etraction curves are particularly use$ul $or 'esigning separation sche"es( )
series o$ such curves has alrea'y been presente' in Fig( =(9(
) convenient &ay to characteri7e the S5shape' curves in Figs( =(9 or 4(=b,
&here the etraction 'epen's on the variable Z, is to use the log Z value o$ J0I
etraction, e(g(, logBCl
C ( The pK
J0
5value in'icates logBK
+
C $or J0I etrac5
tion( This is sho&n in Fig( 4(= $or 'istribuen's ) an' 4(
2
Oery e$$icient separations are o$ten nee'e' in in'ustry, an' a single e5
traction stage "ay be insu$$icient( The 'esire' purity, yiel', etc( can be achieve'
by "ultiple etractions, as 'iscusse' in Chapter P /see also section =(20( 8n
the 'esign o$ separation processes using "ultistage etractions, other etraction
'iagra"s are pre$erre'( 6nly single stage etraction is 'iscusse' in this chapter,
&hile "ultistage etraction is 'iscusse' in the secon' part /Chapters PL=40 o$
this boo-(
4.2 THERMODYNAMICS OF EXTRACTION SYSTEMS
Etraction $ro" a!ueous solutions into organic solvents can be achieve' through
'i$$erent che"ical reactions( So"e "ay see" very co"plicate', but usually oc5
cur through a nu"ber o$ rather si"ple steps1 &e assu"e this in "a-ing a "o'el
o$ the syste"( The sub'ivision o$ an etraction reaction into its si"pler steps is
use$ul $or un'erstan'ing ho& the 'istribution ratio varies as a $unction o$ the
type an' concentration o$ the reagents( 6$ten these "o'els allo& e!uilibriu"
constants to be "easure'(
)s solute, &e consi'er both nonelectrolytes /abbreviate' as ) or 4, or5
ganic or inorganic0, an' electrolytes /e(g(, as "etal5organic co"plees, "etal
ions ren'ere' soluble in organic solvents through reactions &ith organic anions
)

an' &ith a''uct $or"ers 40( The syste" o$ e!uations sho&n later is only
vali' as long as no species are $or"e' other than those given by the e!uations,
all concentrations re$er to the free concentrations /i(e(, unco"plee'0, an' activ5
ity $actors an' te"peratures are constant( Further, &e assu"e that e!uilibriu"
has been establishe'( 8t "ay be note' that the use o$ e!uilibriu" reactions "ean
that the reactions ta-e place in the a!ueous phase, the organic phase or at the
inter$ace, as is illustrate' in the net ea"ples, but 'o not sho& any inter"e'i5
ates $or"e'1 this in$or"ation can be obtaine' by -inetic stu'ies, as 'escribe' in
Chapter J, or by 2$ingerprinting3 techni!ues such as "olecular spectroscopy(
4e$ore a 'etaile' analysis o$ the che"ical reactions that govern the 'istri5
bution o$ 'i$$erent solutes in solvent etraction syste"s, so"e representative
practical ea"ples are presente' to illustrate i"portant subprocesses assu"e' to
be essential steps in the overall etraction processes(
4.2.1 Case I: Extraction of ran!" #itrate
b! $%%uct &ormation
This is a puri$ication process use' in the pro'uction o$ uraniu"( The overall
reaction is given by
#6
2Q + 2 KH6
9
+ 2 T4,/org0 #6
2
/H6
9
0
2
/T4,0
2
/org0
/4(J0
&here T4, stan's $or tributylphosphate( The organic solvent is co""only -ero5
sene( 8n Table 4(= this etraction process is 'escribe' in $our steps( 8n Table
9
2 2 ;
i
e
e
Table 4.1 Sche"atic :epresentation o$ the Kypothetical Steps in #/O80
Etraction by T4, an' Their )ssociate G
i
o$ :eaction
Secon'
First step step Thir' step Fourth step
6rganic phase T4, #6
2
/T4,0
2
/H6
9
0
2
/T4, + 'iluent0
2+
)!ueous solution 2 KH6
9
+ #6
2
2+
#6
2
/H6
9
0
2
+ 2T4,
+
/KH6
9
+ #6
2
K
2
60
+ #6
2
/H6
9
0
2
+ 2K T4, #6
2
/T4,0
2
/H6
9
0
2
#6
2
/T4,0
2
/H6
9
0
2
Start Final G
=
> 0 G
2
> 0 G
9
0 G
4
0
G
ex
< 0
4(=, the sign o$ the $ree energy change, G
0
, in each step is given by !ualita5
tively -no&n che"ical a$$inities /see Chapter 20( The reaction path is chosen
beginning &ith the co"pleation o$ #/O80 by H6

in the a!ueous phase to $or"
the uncharge' #6
2
/H6
9
0
2
co"ple /Step =0( )lthough it is -no&n that the $ree
uranyl ion is surroun'e' by &ater o$ hy'ration, $or"ing #6 /K 60
2
+
, an' the
nitrate co"ple $or"e' has the stoichio"etry #6
2
/K
2
60
;
/H6
9
0
2
, &ater o$ hy'ra5
tion is not liste' in E!( /4(J0 or Table 4(=, &hich is co""on practice, in or'er
to si"pli$y $or"ula &riting( Ko&ever, in a!ueous reactions, &ater o$ hy'ration
can play a signi$icant role( )s the reactive oygen /bol'0 o$ tributylphosphate,
O,/6C
4
K
>
0
9
, is "ore basic than the reactive oygen o$ &ater, T4,, &hich
slightly 'issolves in &ater /Step 20, replaces &ater in the #6
2
/K
2
60
;
/H6
9
0
2
co"5
ple to $or" the adduct complex #6
2
/T4,0
2
/H6
9
0
2
( This reaction is assu"e' to
ta-e place in the a!ueous phase /Step 90( Adduct formation is one o$ the "ost
co""only use' reactions in solvent etraction o$ inorganic as &ell as organic
co"poun's( /HoteM the ter" adduct is o$ten use' both $or the 'onor "olecule
an' $or its pro'uct &ith the solute(0 The net process is the etraction o$ the
co"ple /Step 40( Even i$ the solubility o$ the a''uct $or"er T4, in the a!ueous
phase is !uite s"all /i(e(, D
T4,
very large0, it is co""on to assu"e that the
replace"ent o$ hy'rate &ater by the a''uct $or"er ta-es place in the a!ueous
phase, as sho&n in the thir' step o$ Table 4(=1 $urther, the solubility o$ the
a''uct #6
2
/T4,0
2
/H6
9
0
2
"ust be "uch larger in the organic than in the a!ueous
phase /i(e(, D
#6 /T4,0 /H6 0
=0, to "a-e the process use$ul( 6ther inter"e'iate
2 2 9 2
reaction paths "ay be conte"plate', but this is o$ little signi$icance as G
0
'epen's only on the starting an' $inal states o$ the syste"( The use o$ such a
ther"o'yna"ic representation 'epen's on the -no&le'ge o$ the G
0
values as
they are necessary $or vali' calculations o$ the process(
The relation bet&een G
0
an' K
e
is given by
o o
G
e
G
i
RT ln K
e
/4(;0
K K K
K
#
e
4
6"itting &ater o$ hy'ration, the e!uilibriu" constant $or the net etraction pro5
cess in E!( /4(J0 is K
e
, &here
[
#6
2
/H6
9
0
2
/ T4, 0
2
]
org
K
e

[
#6
2Q
]
[
KH6
]
2
[
T4,
]
2
/4(P0
2 9 org
The extraction constant, K
e
, can be epresse' as the pro'uct o$ several e!uilib5
riu" constants $or other assu"e' e!uilibria in the net reactionM
2
e i 2, H6
9
A: 2,TP AC
/4(F0
&here
2,H6
9 is the complex formation constant o$ #6
2
/H6
9
0
2
, an'
2,T4,
the
$or"ation constant o$ the etractable #6
2
/H6
9
0
2
/T4,0
2
co"ple $ro" $ro"
#6
2
/H6
9
0
2
an' T4,( K
A:
an' K
AC
are the distribution constants of the un!
charged species, the reagent an' the etractable co"ple, respectively(
K
e
'eter"ines the e$$iciency o$ an etraction process( 8t 'epen's on the
2internal che"ical para"eters3 o$ the syste", i(e(, the che"ical reactions an'
the concentration o$ reactants o$ both phases( The latter 'eter"ine the nu"erical
value o$ the distribution factor for the solute, &hich $or our ea"ple is
D
B#C
tot,org
#6
2
( H6
9
)
2
(T4, )
2
1
]
org
/4(>a0
B#C
2Q
2 n
1 tot,a!

#6
2
1
]
+
#6
2
(
H6
9
)
n
]
2n
8n the a!ueous phase &e have inclu'e' the #6
2
/H6
9
0
n
co"plees but eclu'e'
the #6
2
/H6
9
0
2
/T4,0
2
co"ple, because the concentration o$ the last co"ple
in the a!ueous phase is negligible co"pare' to the other t&o( 8n 'ilute solutions,
2+
the nitrate co"ple can be neglete' co"pare' to the $ree #6
2
8n the latter case the # 'istribution e!uals

[
KH6
]
2
[
T4,
]
2
concentration(
/4(>b0
D
#
K
e 9 org
6$ the reaction steps, only the $irst three have values o$ G
0
> 01 ho&ever,
the large negative value o$ the $ourth step "a-es the overall reaction G
0
nega5
tive, thus $avoring the etraction o$ the co"ple( The $irst step can be "easure'
by the 'eter"ination o$ the 'initrato co"ple in the a!ueous phase( The secon'
is relate' to the 'istribution constant K
D,T4,
in the solvent syste"( )lso, the
$or"ation constant o$ the a!ueous #6
2
/H6
9
0
2
/T4,0
2
can be "easure' /$or e5
a"ple by H<: on
9=
, o$ T4, in the a!ueous phase0( Thus, G
0
can be 'erive'(
4.2.2 Case II: '!nergistic Extraction of ran!" Ions
b! Che"ation an% $%%uct &ormation
Solvent etraction is a po&er$ul techni!ue in research on "etal co"plees( Con5
si'er a "etal co"plee' by a chelate co"poun' /see Chapter 90, &here the
chelate is a &ea- organic aci'( For ea"ple, the uranyl ion can be neutrali7e'
by t&o TT)

/)ppen'i AMJe0 anions to $or" the neutral #6 /TT)0 /K 60 2 2 2 2
co"ple( This co"ple is etractable into organic solvents, but only at high
concentrations o$ the TT) anion(
) large a''uct $or"ation constant increases the hy'rophobicity o$ the
"etal co"ple an' thus the 'istribution ratio o$ the "etal( This is co""only
re$erre' to as a synergistic effect( Figure 4(2 illustrates the etraction o$ the
#6
2
/TT)0
2
co"ple $ro" 0(0= < KH6
9
into cycloheane( 4ecause the linear
6R#R6 group is believe' to have $ive to seven coor'ination sites, &here only
Fig. 4.2 Synergistic etractionM Aistribution o$ #/O80 bet&een 0(0= < KH6
9
an' "i5
tures o$ thenoyltri$luoroacetone /TT)0 an' tributylphosphate /T4,0, or tributylphos5
phineoi'e /T4,60, at constant total "olarity /BTT)C
org
plus BT4,C
org
or BT4,6C
org
0(02 <0 in cycloheane( /Fro" :e$( 2(0

9
9

n
p
$our are occupie' in this co"ple, the uranyl group is coor'inativaly unsatu5
rate'( )t the le$t vertical aes o$ Fig( 4(2, the $ree coor'ination sites are occu5
pie' by &ater an'Nor H6
, only1 an' the #/O80 co"ple is poorly etracte', log

D
#
about =( Ghen T4, or T4,6 /tributylphosphine oi'e?0 Bboth in'icate'
by 4C are a''e' &hile BKTT)C + BC is -ept constant, the D
#
value increases to
about ;0 $or T4, an' to about =000 $or T4,6( )t the pea- value, the co"ple
is assu"e' to be #6
2
/TT)0
2
4
= or 2
( The 'ecrease o$ D
#
at even higher BC is 'ue
to the correspon'ing 'ecrease in BTT)
C, so that at the right vertical aes o$

Fig( 4(2 no #/O80ETT) co"ple is $or"e'( For this particular case, at "uch
higher nitrate concentrations, the #/O80 is co"plee' by H6

an' is etracte'
as an a''uct co"ple o$ the co"position #6
2
/H6
9
0
2
4
=L2
, as 'iscusse' earlier
$or Case 8(
The pri"ary cause $or synergis" in solvent etraction is an increase in
hy'rophobic character o$ the etracte' "etal co"ple upon a''ition o$ the a'5
'uct $or"er( Three "echanis"s have been propose' to eplain the synergis"
$or "etal + chelan'@ + a''uct $or"er( 8n the $irst suggeste' "echanis", the
chelate rings 'o not coor'inately saturate the "etal ion, &hich retains resi'ual
&aters in the re"aining coor'ination sites an' these &aters are replace' by other
a''uct5$or"ing "olecules( The secon' involves an opening o$ one or "ore o$
the chelate rings an' occupation by the a''uct $or"ers o$ the vacate' "etal
coor'ination sites( The thir' "echanis" involves an epansion o$ the coor'ina5
tion sphere o$ the "etal ion upon a''ition o$ a''uct $or"ers so no replace"ent
o$ &aters is necessary to acco""o'ate the a''uct $or"er( )s pointe' out be$ore,
it is not possible $ro" the etraction constants to choose bet&een these alterna5
tive "echanis"s, but enthalpy an' entropy 'ata o$ the reactions can be use' to
provi'e "ore 'e$initive argu"ents(
The KTT) + T4, syste" can serve to illustrate the "ain points o$ ther5
"o'yna"ics o$ synergis"( The o"erall extraction reaction is &ritten asM
<
n Q
Q n KTT)/org0 Q p T4,/org0

</TT)0 /T4,0 /org0 Q p K
Q
/4(=0a0
Ge assu"e that the $irst step in the etraction e!uation is co"pleation in the
a!ueous phase
#
+

# n Q
< + n TT)
</TT)0
n
/a!0 + n K /4(=0b0
lea'ing to the $or"ation o$ the uncharge' co"ple </TT)0
n
, &hich i""e'i5
ately 'issolves in the organic phase 'ue to its high hy'rophobicityNlipophilicity
</TT)0
n
/a!0

</TT)0
n
/org0
/4(=0c0
?T4,6 /C
4
K
>
0
9
,6, see )ppen'i A, ea"ple =;, at the en' o$ this boo-(
@$heland or chelator is the chelating ligan'(
9 =9
9 2 9 9 2 =2
The a''uct $or"ation reaction in the organic phase /the 2synergistic reaction30
is obtaine' by subtracting E!s( /4(=0b0 an' /4(=0c0 $ro" E!( /4(=0a0M
</TT)0
n
/org0 + pT4,/org0

</TT)0
n
/T4,0
p
/org0
/4(=0'0
Ther"o'yna"ic 'ata $or the etraction reactions o$ E!s( /4(=0a0 an' /4(=0c0
allo& calculation o$ the correspon'ing values $or the synergistic reaction o$ E!(
/4(=0'0( <easure"ents o$ the reaction
#6
2
/TT)0
2
/org0 + T4,/org0
#6
2
/TT)0
2
T4,/org0
/4(==0
at 'i$$erent te"peratures gives log K J(=0, %
0
>(9 -. "ol
=
, T&
o
20(0
-. "ol
=
(
8n another eperi"ent, it &as $oun' $or Th/TT)0
4
Th/TT)0
4
/org0 + T4,/org0
Th/TT)0
4

T4,/org0
/4(=20
the correspon'ing valuesM log K 4(>4, %
o
=4(4 -.("ol
=
, T&
o
=9(P -.(
"ol
=
(
4oth #6
2
/TT)0
2
an' Th/TT)0
4
have t&o "olecules o$ hy'rate &ater
&hen etracte' in ben7ene, an' these are release' &hen T4, is a''e' in reac5
tions E!s( /4(==0 an' /4(=20( The release o$ &ater "eans that t&o reactant "ole5
cules /e(g(, #6
2
/TT)0
2
2K
2
6 an' T4,0 $or"e' three pro'uct "olecules /e(g(,
#6
2
/TT)0
2
T4, an' 2K
2
60( There$ore, & is positive( Since T4, is "ore
basic than K
2
6, it $or"s stronger a''uct bon's, an', as a conse!uence, the
enthalpy is eother"ic( Kence, both the enthalpy an' entropy changes $avor the
reaction, resulting in large values o$ log K(
4.2.3 Case III: (aintaining (eta"
Coor%ination #umber
) gui'ing principle $or the solvent etraction che"ist is to pro'uce an un5
charge' species that has its "ai"u" coor'ination nu"ber satis$ie' by lipo5
philic substances /reactants0( For trivalent lanthani'es an' actini'es /Ln an' )n,
respectively0, the ther"o'yna"ic 'ata suggest a "o'el in &hich a''ition o$ one
"olecule o$ T4, 'isplaces "ore than one hy'rate "oleculeM
)n/TT)0 /K 60
T
4,
)n/TT)0
/T4,0/K 60
4,
)n/TT)0
/T4,0
/4(=90
This sche"e o$ steps re$lects the ability o$ so"e "etals, li-e the trivalent actin5
i'es an' lanthani'es, to vary their coor'ination nu"ber1 since the trivalent Ln
an' )n "ay go $ro" > to F an', $inally, bac- to >( The last step re$lects the
operation o$ the thir' "echanis" propose' $or synergis"(
Th/TT)0
4
can be 'issolve' in 'ry ben7ene &ithout hy'rate &ater( The
values o$ the reaction o$ E!( /4(=20 in the syste" areM log K J(4;, %
o
9>(2
-. "ol
=
, T&
o
F(0 -. "ol
=
S
=
( The negative entropy is un'erstan'able
as the net 'egrees o$ $ree'o" are 'ecrease' /t&o reactant "olecules co"bine
to $or" one pro'uct "olecule0( Ko&ever, the %
o
value is "uch "ore negative(
These e!uations 'o not provi'e co"plete 'e$inition o$ the reactions that
"ay be o$ signi$icance in particular solvent etraction syste"s( For ea"ple,
KTT) can eist as a -eto, an enol, an' a -eto5hy'rate species( The "etal co"5
bines &ith the enol $or", &hich usually is the 'o"inant one in organic solvents
/e(g(, K BKTT)C
enol
NBKTT)C
-eto
; in &et ben7ene0( The -inetics o$ the -eto
enol reaction are not $ast although it see"s to be cataly7e' by the
presence
o$ a reagent such as T4, or T6,6( Such reagents react &ith the enol $or" in
'rier solvents but cannot co"pete &ith &ater in &etter ones( KTT) T4,
an' T4, K
2
6 species also are present in these synergistic syste"s(
Ko&ever, i$ etraction into only one solvent /e(g(, ben7ene0 is consi'ere', these
e$$ects are constant an' nee' not be consi'ere' in a si"ple analysis(
8n section 4(=9(9 &e return brie$ly to the ther"o'yna"ics o$ solvent e5
traction(
4.3 OVERVIEW OF EXTRACTION PROCESSES
<any organic substances as &ell as "etal co"plees are less etracte' $ro"
a!ueous solutions into organic solvents than epecte' $ro" si"ple consi'era5
tions such as the a"ount o$ organic "atter in the solute or their solubility in
organic solvents( Such substances are hydrated /see Chapter 90( <ore basic
'onor "olecules can replace such &ater, $or"ing a''ucts( For the "ost co""on
oygen5containing a''uct "olecules, the e$$iciency o$ the replace"ent 'epen's
on the charge density, also re$erre' to as basicity, o$ the oygen ato"s( The
se!uence in &hich these 'onor groups are able to replace each other is
:CK6 < :
2
C6 < :
2
6 < :6K < K
2
6 /:60
9
,6
T :
HC6: /:60
2
:,6 < :
9
,6
&here ' stan's $or organic substituen'( 8n Chapter 9 the basicity &as presente'
in $or" o$ donor number( The larger the 'i$$erence bet&een the 'onor nu"ber
o$ &ater an' the a''uct $or"er, the larger the a''uct $or"ation constant( 6$ten
the 'onor property has to be rather strong, &hich is the case $or "any phospho5
ryl co"poun's /li-e T4,, T4,6, T6,6, etc(0, because the concentration o$
K
2
6 in the a!ueous phase is very large /o$ten >J0 <0, even though K
2
6 is only
a "o'erately strong 'onor(
Table 4(2 gives a survey o$ the "ost co""on etraction processes( 8n
general, Type 8 etraction re$ers to the 'istribution o$ nonelectrolytes, &ithout
/)0 or &ith a''uct $or"er /40( Type 88 re$ers to etraction o$ /"ainly organic0
aci's, Type 888 to the etraction o$ "etal co"plees, an' Type 8O to the special
/but co""on0 use o$ solvent etraction $or evaluation o$ $or"ation constants
Table 4.2 Sy"bolic Survey o$ Fun'a"ental Li!ui'5Li!ui' Aistribution ,rocesses
a
Type (5A )onelectrolyte extraction
b
Solute ) etracte' into organic phase /solvent0
)
/E!uilibriu" governe' by the Hernst 'istribution la&0

Solute is the nonelectrolyte ) in &ater
)
Type (5 )onelectrolyte adduct formation and extraction
c
)''uct )4 in organic phase /plus eventually 40
Solute ) an' a''uct $or"er /or etractant0 4
Type ((5A Extraction of nonadduct organic acids
)ci' an' 'i"er /an' possible poly"ers0 in organic phase
)ci' 'issociation in a!ueous phase
4 )4
/0
) + 4

)4
K)

K
=
U2K
2
)
2
+ ( (
(
K)

K
+
) +
Type ((5 Extraction of acid as adduct
)ci' a''uct /an' aci' an' a''uct $or"er0 in organic phase
K)4 /
0 4 /+0 K)
/0 /0
)ci' 'issociation in a!ueous phase
K)4
4 + K)

K
+
+
)
Type (((5
'
Extraction of saturated metal complex
Heutral, coor'inatively saturate' "etal co"ple in organic phase
<etal
co"plee'
)
<
7+
+ 7)

<
)
7
<
)
7
Type (((5$ Adduct extraction of unsaturated metal complex

Coor'inatively saturate' "etal co"ple in organic phase /an'
40
For"ation o$ saturate' "etal co"ple trough a''uct $or"er 4
e
<
7
4 <)
7
4
b
/0
+ 7) + b4

<) 4
b
7
Type (((5D *i+uid anion exchange extractions
+ + p
6rganic phase &ith anion echanger an' "etal co"ple
:HK L /:HK 0
p
<L
n

7+ + + p
<etal &ith co"pleing anions L

an' organic a"ine
< + nL + p:HK L /:HK 0
p
<L
n
Type (((5E Extraction of ion pairs, and other unusual complexes
+
8on pair C
+
)

/an' counter species0 in organic phase
C
=
)
2
= 2
)!ueous cation C
+
an' anion )

associate' into ion pair C
+
)
C
=
)
=
+
C
2
)
2

C )
2
+
C
2
)
=
= 2 = 2
+ + + +
=
Type (, %ydrophilic complex formation and sol"ent extraction
Coor'inatively saturate' "etal co"ple in organic phase
7+
<)
7
7n
For"ation o$ etractable an' nonetractable co"plees
< + 7) + nV <)
7
+ <V
n
a
The organic phase /sol"ent, diluent0 is assu"e' to be 2inert3 /sha'e' area0( The a+ueous phase /nonsha'e' area0 is unspeci$ie', but "ay
contain various salting agents, not consi'ere' here(
b
) nonelectrolyte solute is 'enote' ), an electrolyte solute is assu"e' to be the cation <
7+
an' anion )
, L
, or V
(
c
The extractant /or reactant0 is 'enote' )

/$ro" acid K)0, or ligand L
, an' by 4 /$or adduct0(

'
Type 8885) /'enote' Class ) in $irst e'ition o$ this boo-0 is closely relate' to an' covere' by Type 85)(
e
8$ 4 is un'issociate' K), the sel$5a''uct <) /K)0 "ay be $or"e'(
7
#
n
#
$or hy'rophilic co"plees( )n arro& &ithin parentheses suggests a reaction o$
secon'ary i"portance( 6ur three ea"ples are all o$ Type 8885C, but contain
also ele"ents o$ Type 85) /the 'istribution o$ T4,0 an' 885) /the 'istribution
o$ the &ea- aci' KTT)0, though the presence o$ un'issociate' aci' /KTT)0 or
the aci' a''uct /T4,5KTT)0 is not 'iscusse'( 8n evaluations o$ eperi"ents,
all "olecular species present an' all e!uilibria "ust be ta-en into account, as
'e"onstrate' subse!uently $or a nu"ber o$ cases(
Solutes containing "etals can $urther be classi$ie' accor'ing to the type
o$ ligan'1 ) re$ers to the "ai"u" coor'ination nu"ber o$ the "etal relative
to the ligan'M
Class A: Type <V
)
( /HoteM Ge generally assu"e that the ligan' is "onova5
lent(0 ) s"all nu"ber o$ al"ost purely covalent inorganic co"poun's that
are etracte' by nonsolvating organic solvents( )s these co"plees are
nonelectrolytes an' al"ost as inert as the solutes o$ Type 85), they are
treate' Dointly in section 4(4(
Class B: Type <)
#
( Heutral coor'inatively saturate' co"plees $or"e' be5
t&een the "etal ion an' a lipophilic organic aci'( This class contains
the large group o$ "etal5organic chelate co"poun's( For "onbasic aci's
$or"ing bi$unctional chelates, # )N2( They belong to the etraction Type
88854, treate' in section 4(F(
Class C: Type <)
#
4
b
or <L
#
4
b
( These Type 8885C co"plees are 'iscusse' in
section 4(2( They are neutral co"plees $or"e' bet&een the "etal ion an'
ligan's )

or L
, &here the neutral co"ple <) or <L is coor'inatively

unsaturate' /) > # or 2#0 an' acts as an acceptor $or uncharge' organic
co"poun's /a''ucts 0 containing lipophilic 'onor groups( 8$ the syste"
'oes not contain any 'onor "olecules , the &ater o$ hy'ration "ay be
replace' by un'issociate' K) /assu"ing the ligan' )

to be a 'issociation
pro'uct o$ K)0, at least at high K) concentrations1 the <)
#
/K)0
x
co"5
plees are re$ere' to as self5adducts( 4oth types o$ co"plees are 'is5
cusse' in section 4(>(
Class D: 8on pairs, consisting o$ the "etal boun' in an anionic co"ple /e(g(,
<L
#
n
, &here n > #0 an' one or "ore large organic /usually "onovalent0
cations /sy"boli7e' by :HK
+
01 the etracte' co"ple is &ritten /:HK0
<L
n
( These co"plees are treate' in section 4(=0(
n#
Class E: <etal co"plees that 'o not $it into these categories1 e(g(, other types
o$ ion pairs an' chlatrate co"poun's /see section 4(==0(
)ll "etal ions in &ater are hy'rate', an' at higher pK "ost o$ the" also
hy'roly7e( 8t can be 'i$$icult to 'istinguish bet&een the hy'roly7e' an' the
co"plee' species, as &ell as their sel$5a''ucts( For such syste"s, plots o$ D
<
against B)
C at various pK an' total concentrations o$ BK)C sho& three types o$

curvesM /a0 $or the si"ple chelate <)
n
, /b0 $or the sel$5a''uct <)
n
/K)0
b
, an'
/c0 $or the /"ie'0 hy'roi'e <)
n
/6K0
p
see Fig( 4(9( 8t shoul' be note' that the
"ie' <)
n
/6K0
p
co"plees inclu'e the <)
n
+ </6K0
p
co"plees( )s "ie'
co"plees are "ore 'i$$icult to 'eter"ine, they are less o$ten 'escribe'( Ko&5
ever, it is i"portant to reali7e that i$ "etal hy'roy co"plees are $or"e' an'
not correcte' $or, the result o$ the investigation can be "islea'ing( ) test o$ the
syste" accor'ing to Fig( 4(9 rapi'ly establishes the type o$ "etal co"pleation(
4ecause "etals 'i$$er in si7e, charge, an' electronic structure, no t&o
"etals behave eactly the sa"e in the sa"e solvent etraction syste", not even
$or the sa"e class o$ solutes( Hevertheless, there are syste"atic tren's in the
$or"ation an' etraction o$ these co"plees, as 'escribe' in Chapter 9( Kere,
the e"phasis is on "o'els that give a !uantitative 'escription o$ the etraction
&ithin each type or class(
8n the subse!uent 'iscussion, the $ollo&ing si"pli$ications are "a'eM
=( The systems beha"e -ideally,. i(e(, the activity $actors are assu"e' to be
unity, unless speci$ically 'iscusse'1
2( The metal extracted is in trace concentrationM B<C
t
BEtractantC
t
, as this
si"pli$ies the e!uations1
9( The reactants are at "ery low concentrations in both phases(
These are great si"pli$ications in co"parison &ith the in'ustrial solvent
etraction syste"s 'escribe' in later chapters( Hevertheless, the sa"e basic reac5
tions occur also in the in'ustrial syste"s, although activity $actors "ust be intro5
'uce' or other a'Dust"ents "a'e to $it the 'ata, an' the calculation o$ $ree
Fig. 4.3 Etraction curves $or various types o$ "etal chelate co"plees, &hen log D
<
is plotte' against $ree ligan' ion concentration, p) logB)
C, or against BK)CBK
+
C
=
(
Fro" such plots, the general type o$ "etal chelate co"ple "ay be i'enti$ie'M /a0 type
<)
n
, /see also Fig( 4(=001 /b0 type <)
n
/6K0
p
/K)0
r
, /see also Figs( 4(=4 an' 4(9001 /c0
type <)
n
/6K0
p
, /see also Fig( 4(=>0( /Fro" :e$s( 9a an' 9b(0
Solvent
,er"ittivity
Venon :a'on 4ro"ine 8o'ine
Keane =(>= 4= F0 =4(J 9;
Carbontetrachlori'e 2(24 9J J> 2F F;
Chloro$or" 4(>0 9J J; 9P =22
4en7ene /5bon's0 2(JP 2P JJ FP 9J0
Hitroben7ene 94(F =4 2= 4= =PF
&ourceM :e$( 4(
ligan' concentrations are "ore co"ple( So"e o$ these si"pli$ications are not
use' in later chapters(
4.4 EXTRACTION OF INERT MOECUES !TYPE I"A#
Kere, an' in later sections, &e begin &ith sa"e -in' o$ rectangular $igure to
in'icate the type o$ etractionM to the right &e in'icate the 'istribution o$ the
solutes in a t&o5phase syste" /the organic phase is sha'e'01 the syste" is also
brie$ly 'escribe' by the tet to the le$t, an'Eo$ courseEin 'etail in the "ain
tet(
Solute A etracte' into organic phase /solvent0 A
/Hernst 'istribution la& $or regular "itures an' solventsM0
The non5electrolyte solute A in &ater A
8$ the solute ) 'oes not un'ergo any reaction in the t&o solvents, ecept $or the
solubility cause' by the 2solvation3 'ue to the nonspeci$ic cohesive $orces in
the li!ui's, the 'istribution o$ the solute $ollo&s the Hernst 'istribution la&, an'
the e!uilibriu" reaction can be 'escribe' either by a 'istribution constant K
D,A
,
or an /e!uilibriu"0 etraction constant K
e
M
)/a!0

)/org01
K
A,)
K
e
B)C
org
NB)C
a!
/4(=40
K
e
al&ays re$ers to a t&o5phase syste"( The measured distribution ratio $or
the solute ), D
)
, e!uals K
D,)
, an' is a constant in'epen'ent o$ the concentration
o$ ) in the syste"( 6nly 2eternal3 con'itions in$luence the K
D,)
value( 8n
2eternal3 con'itions &e inclu'e the organic solvent, in a''ition to physical
con'itions li-e te"perature an' pressure(
The noble gases an' the halogens belong to the sa"e type o$ stable "olec5
ular co"poun'sM :u6
4
, 6s6
4
, GeCl
4
, )sCl
9
, SbCl
9
, an' KgCl
2
( The si"plest
ea"ple is the 'istribution o$ the inert gases, as given in Table 4(9( The larger
Table 4.3 Aistribution :atios o$ So"e Gases 4et&een 6rganic Solvents
an' 0(0= < HaCl6
4
at 2JC
Solute
:n is etracte' "ore easily than the s"aller Ve, because the &or- to pro'uce a
cavity in the &ater structure is larger $or the larger "olecule( The energy to
pro'uce a cavity in nonpolar solvents is "uch less, because o$ the &ea-er inter5
actions bet&een neighboring solvent "olecules( Energy is release' &hen the
solute leaves the a!ueous phase, allo&ing the cavity to be $ille' by the hy'ro5
gen5bon'e' &ater structure( Thus the 'istribution constant increases &ith in5
creasing inertness o$ the solvent, &hich is "easure' by the 'ielectric constant
/or relative per"ittivity0( The halogens 4r
2
an' 8
2
sho& an opposite or'er 'ue
to so"e lo& reactivity o$ halogens &ith organic solvents( Oery inert solvents
&ith lo& per"ittivity, such as the pure hy'rocarbons, etract inert co"poun's
better than solvents o$ higher per"ittivity1 conversely, li!ui's o$ higher per"it5
tivity are better solvents $or less inert co"poun's( <olar volu"es shoul' be
use' $or accurate co"parisons1 such 'ata are $oun' in Table 2(= an' in :e$( B;C(
8n ben7ene, the 'istribution constant 'epen's on speci$ic interactions be5
t&een the solute an' the ben7ene pi5electrons( Table 4(4 sho&s the i"portance
o$ the volu"e e$$ect $or the "ercury hali'e ben7ene syste" /Cl<4r<80(
#n'issociate' $atty aci's /K)0 behave li-e inert "olecules( Figure 4(4
sho&s the 'istribution /D
K)
K
D,K)
0 bet&een ben7ene an' 0(= < HaCl6
4
o$
$atty aci's o$ 'i$$erent al-yl chain lengths /C
n
, n = to J01 the 'istribution con5
stant $or an aci' &ith chain length n is given by the epression log K
D,K)
2(;
+ 0(;n( Si"ilar correlations bet&een K
D,K)
an' "olecular si7e or chain length
are observe' also $or other reagents /e(g(, nor"al alcohols0(
For organic solutes, not only the si7e but also the structure is o$ i"por5
tance( Table 4(J gives 'istribution constants $or substitute' oines( Ghen the
substitution increases the si7e o$ the "olecule, the 'istribution constant in5
creases( The variations &ithin Table 4(J an' position o$ the substitution in the
oine "olecule re$lect structural e$$ects( Table 4(; sho&s 'istribution constants
$or 5'i-etones( The increasing K
D
&ith "olecular si7e $or the series acetylace5
tone, ben7oylacetone, an' 'iben7oyl"ethane, re$lects the 'ecreasing solubility
in the &ater phase, "ainly governe' by the increase' energy necessary to over5
co"e the solute5solvent interactions $or the larger etractant "olecules in &ater(
Thenoyltri$luoroactetone has a greater hy'rophilic character than the other 5
'i-etones 'ue to its 6R an' FR ato"s, &hich interact &ith the &ater "olecules,
Table 4.4 Aistribution Constants $or <ercury
Kali'es 4et&een 4en7ene an' 0(J < HaCl6
4
Solute Log K
D
Solute Log K
D
KgCl
2
0(>; KgCl4r 0(42
Kg4r
2
0(=J Kg8Cl 0(2F
Kg8
2
=(P> Kg84r 0(P>
&ourceM :e$( J(
:eagent pK
a
log K
A,K)
6ine >(P 2(P
25<ethyloine =0(0 9(4
J5<ethyloine >(> 9(9
J5)cetyloine P(F 2(F
4,P5Aichlorooine P(4 9(>
P,P5Aiio'ooine F(0 4(2
J5Chloro5P5io'ooine P(> 9(>
a
)!ueous phase 0(= < Ha
2JC(
l6
4
1 organic phase chloro$or" at
&ourceM :e$s( Fa, b(
Fig. 4.4 Aistribution constants K
A,K)
o$ $atty aci's as a $unction o$ the nu"ber n o$
carbon ato"s in the al-yl chain /$
=
is acetic aci'0 in the syste" 0(= < HaCl6
4
Nben7ene(
/Fro" :e$( P(0
Table 4.$ Aissociation, K
a
, an' Aistribution, K
D,%A
,
Constants $or Substitute' 6ines
a
C
: is C CK
2
C :
W
is thenoyl, K
9
C
9
SC
XX XX
4
Table 4.% Aissociation K

a
an' Aistribution Constants K
A,K)
$or 5Ai-etones1
)!ueous ,hase 0(= < HaCl6
a
log K
A:
:eagent /solute0 pK
a
C
;
K
;
CKCl
9
CCl
4
)cetylacetone, ))1 CK
9
: CK
9
F(P; 0(P; =(9; 0(J=
4en7oylacetone, 4Y)1 CK
9
: C
;
K
J
F(P4 9(=J 9(;0 2(F=
Aiben7oyl"ethane, A4<1 C
;
K
J
: C
;
K
J
>(9J J(94 J(40 4(J=
Thenoyltri$luoroacetone, TT)1 :: CF
9
;(9 =(;= =(F4 =(J4
6 6
a
6rganic phases 0(= < in solute1 2JC(
&ourceM :e$( 4(
lea'ing to a re'uction in the 'istribution constant( Thus, either the si7e e$$ect
relate' to the &ater structure or the presence o$ hy'rophilic groups in the solute
'eter"ines the general level o$ its 'istribution constant(
4.$ EXTRACTION OF ADDUCT"FORMIN&
NONEECTROYTES !TYPE I"'#
)''uct A in organic phase /plus evt( 0 A
/0
Solute ) an' a''uct $or"er /etractant0 A +

A
The etraction o$ a solute ) "ay be i"prove' by its reaction &ith another
solute /2etraction reagent3, or extractant0, 4, $or"ing an adduct compound,
)4( This occurs through che"ical interaction bet&een ) an' 4(
4

4/org0
) Q 4

)4
K
D ,
B4C
org
NB4C /4(=Ja0
K
ad
B)4CNB)C B4C /4(=Jb0
&here K
a'
is the adduct formation constant /in the a!ueous phase0
)4

)4/org0
K
D , )4
B)4C
org
NB)4C /4(=Jc0
an' K
D,)4
the a''uct 'istribution constant( The etraction constant $or the overall
reaction is
a'= org org org

0
o
)/a!0 Q 4/org0

)4/org0
an' also
D
)
K
e
B4C
org
K
e
B)4C
org
NB)C
a!
B4C
org
K
D ,)4
K
a'
K
D
,4
/4(=J'0
/4(=Je0
For the etraction reaction it "ay su$$ice to &rite the reaction o$ E!(
/4(=J'0, though it consists o$ a nu"ber o$ "ore or less hypothetical steps( )s
"entione', e!uilibriu" stu'ies o$ this syste" cannot 'e$ine the in'ivi'ual steps,
but supple"entary stu'ies by other techni!ues "ay reveal the vali' ones( E!ua5
tion /4(=J0 in'icates that the reaction ta-es place at the boun'ary /interface0
bet&een the a!ueous an' organic phases( Ko&ever, it is co""on to assu"e that
a s"all a"ount o$ 4 'issolves in the a!ueous phase, an' the reaction ta-es place
in the steps
)/a!0 + 4/a!0 )4/a!0 )4/org0
These e!uations allo& 'e$inition o$ a 'istribution constant $or the species )4,
K
D,)4
Bsee E!( /4(=Jc0C( Aistribution constants can also be 'e$ine' $or each o$
the species ), 4 an' )4 /K
D,)
, etc(0 but this is o$ little interest as the concentra5
tion o$ these species is relate' through K
e
( ) large K
e
$or the syste" in'icates
that large 'istribution ratios D
)
can be obtaine' in practice( )s sho&n in E!(
/4(=J0, the concentration o$ 4 in$luences the 'istribution ratio D
)
(
Consi'er $irst the etraction o$ hea$luoroacetylacetone /KF)0 by T6,6
by Ea"ple =, an', secon', the etraction o$ nitric aci' by T4, /Ea"ple P0(
The principles o$ volu"e an' &ater5structure e$$ects, 'iscusse' $or the solute )
in section 4(4, are also i"portant in the 'istribution o$ the a''ucts(
Ea"ple =M Etraction o$ hea$luoroacetylacetone /KF)0 by trioctylphospine
oi'e /T6,60(
)bbreviating KF) /co"p( structure Je, )ppen'i A0 by K), an' T6,6
by 4, &e can &rite the relevant reactions
K)/a!0

K)/org0
K BK)C NBK)C
D
/4(=;a0

A org 0
K)/org0 + 4/org0

K)4/org0
K Z BK)4C NBK)C BC /4(=;b0
K)/org0
+
24/org0

K)4 /org0
K
Z BK)4 C NBK)C BC
2
/4(=;c0

2 a'2 2 org org org
assu"ing that 2 a''ucts are $or"e', K)4 an' K)4
2
, the latter containing 2
T6,6 "olecules( E!uation /4(=;a0 'enotes the 'istribution o$ 2unco"plee'
K)3 by D
o
( Co"bining these e!uations yiel's
D D
=
= + K
a'=
B4C + K
a' 2
B4C
2
/4(=;'0
Figure 4(J sho&s the relative 'istribution, log D D
=
, o$ hea$luoroace5
tylacetone as a $unction o$ the concentration o$ the a''uct $or"er T6,6( KF)
o
org org
Fig. 4.$ :elative increase, DND
o
in etraction o$ hea$luoroacetylacetone /KF)0 into
heane $ro" 0(=< HaCl6
4
at pK 2, at 'i$$erent concentrations o$ the a''uct trioctyl5
phosphine oi'e /T6,60 in the organic phase( The $itte' curve is DND = + =0
4(22
BT6,6C + =0
P(J=
BT6,6C
2
( /Fro" :e$( >(0
is a "o'erately &ea- aci', &hile T6,6 associates strongly &ith hy'rogen5
bon' 'onors in nonpolar solvents li-e heane( The constants &ere 'eter"ine'
to log K
a'=
4(22 an' log K
a'2
P(J=( Thus even at "o'erately lo& T6,6
concentrations, the 2'i"er a''uct3 'o"inates(
4.% EXTRACTION OF NONADDUCT OR&ANIC ACIDS
!TYPE II"A#
)ci' an' 'i"er /an' possibly %A

=
U2 %
2
A
2
+
( ( (
poly"ers0 in organic phase
)ci' 'issociation in a!ueous phase /%
+
A%0

%A

%
+

+
A
/an' protonation0
Tables 4(JL4(P an' Fig( 4(; list organic aci's co""only use' as "etal
etractants( Ghen the aci's are not protonate', 'issociate', poly"eri7e', hy5
'rate', nor $or" a''ucts, the 'istribution ratio o$ the aci' K) is constant in a
given solvent etraction syste"M
K)/a!0

K)/org0 S
D ,K)
BK)C
org
NBK)C
D
K)
/4(=P0
This is sho&n by the hori7ontal tren's in Fig( 4(;, $or &hich E!( /4(=P0 is vali'1
i(e(, the 'istribution constant K
D,K)
e!uals the "easure' 'istribution ratio( Ghen
)ci' 'iluent
b
S /<0
c
log K log K
Salicylic aci' Chloro$or" 0(=P 2(> 0(J
Cup$erron Chloro$or" 0(4 4(2 2(9
F5Ky'roy!uinoline /oine0 /6[0 Chloro$or" 2(;9 >(F
'
2(;;
AMo CCl
4
E >(;; 2(=F
)cetylacetone /))0 4en7ene F(FJ 0(PF
AMo Chloro$or" E E =(9;
AMo CCl
4
E F(;P 0(J=
4en7oylacetone /4)0 CCl
4
E F(9> 2(F=
4en7oyltri$luoroacetone /4TF)0 CCl
4
E ;(09 2(9>
Thenoyltri$luoroacetone /TT)0 4en7ene J(2P ;(9 =(;
AMo Chloro$or" E E =(F4
=5Hitroso525naphthol Chloro$or" =(9J P(; 2(>P
Ai/25ethylheyl0phosphoric aci'
$
<ono/25ethylheyl0phosphoric aci'
n56ctane
n56ctane

=(4
=(9
e
9(44
E
Ainonyl naphthalene sul$onic aci'
4
a%
K (
S
Table 4.( ,hysical ,roperties o$ So"e Co""only #se' )ci'ic Etractants
a
6rganic
org a A:
a
The a!ueous phase is "ostly 0(= < HaCl6 at 2JC(
b
The choice o$ organic 'iluent only a$$ects the 'istribution constant, not the aci' 'issociation
constant(
c
org
is solubility in < in organic solvent(
'
Log K J(00(
e
a=
$
Ai"eri7ation constantM log K 4(4P1 see also section 4(;(9(
K) is use' $or the etraction o$ a "etal, K
D,K)
is abbreviate' K
A:
, $or the distri5
bution constant /o$ the un"o'i$ie'0 reagent /or etractant0(
Figure 4(Pa sho&s the e$$ect o$ a!ueous salt concentrations on the D
K)
value o$ acetylacetone at constant total K) concentration an' pK( The salt has
t&o e$$ectsM /=0 it ties up K
2
6 "olecules in the a!ueous phase /$or"ing hy'rate'
ions0 so that less $ree &ater is available $or solvation o$ K)1 an' /20 it brea-s
'o&n the hy'rogen bon' structure o$ the &ater, "a-ing it easier $or K) to
'issolve in the a!ueous phase( Figure 4(P sho&s that the $or"er e$$ect 'o"inates
$or HK
4
Cl &hile $or HaCl6
4
the latter 'o"inates( Ge 'escribe the increase o$
the 'istribution ratio &ith increasing a!ueous salt concentration as a salting5out
e$$ect, an' the reverse as a salting5in e$$ect(
Figure 4(Pb sho&s D
K)
$or the etraction o$ acetylacetone into CKCl
9
an'
C
;
K
;
$or t&o constant a!ueous HaCl6
4
concentrations at pK 9, but &ith varying
concentrations o$ K)( )cetylacetone is in$initely soluble in both CKCl
9
an'
C
;
K
;
1 at BK)C
org
> <, about >0I o$ the organic phase is acetylacetone /<
&
=000, so the $igure 'epicts a case $or a changing organic phase( Figure 4(Pb also
Fig. 4.% Aistribution ratios calculate' by E!( /4(220 $or acetylacetone /K))01 ben7oyl5
acetone /K4)01 be7oyltri$luoroacetone /K4TF)01 an' oine /F5hy'roy!uinoline,
K6[0, in the syste" 0(= < HaCl6
4
NCCl
4
, using the $ollo&ing constants( /Fro" :e$s(
Fa, b(0
K)) K4) K4TF) K6[
log K
A
0(J= 2(F= 2(9> 2(=F
log K
a
F(;P F(9> ;(09 >(;;
log K
aK
E E E J(00
in'icates 'i$$erent interactions bet&een the acetylacetone an' the t&o solvents(
8t is assu"e' that the polar CKCl
9
interacts &ith K), "a-ing it "ore soluble in
the organic phase1 it is also un'erstan'able &hy the 'istribution o$ K) 'ecreases
&ith 'ecreasing concentration /"ole $raction0 o$ CKCl
9
( C
;
K
;
an' aro"atic sol5
vents 'o not behave as 'o "ost aliphatic solventsM in so"e cases the aro"atics
see" to be inert or even antagonistic to the etracte' organic species, &hile in
other cases their pi5electrons interact in a $avorable &ay &ith the solute( For
acetylacetone, the interaction see"s to be very &ea-( The salting5in e$$ect is
sho&n both in Figs( 4(Pa( an' 4(Pb(
4.).1 Dissociation
)ci's 'issociate in the a!ueous phase &ith a 'issociation constant K
a
) org
a
a
+
K) K
Q
+
)
K BK
Q
CB) C NBK)C /4(=F0
The 'istribution ratio incorporates the K
a
$or etraction o$ aci's, K), asM
D BK)C /BK)C + B)

C0
K
D ,K)
/= +
K
a
BK
Q
C
=
0 /4(=>0
8n'e ) in'icates that the 'istribution ratio re$ers to the concentration o$ all
species o$ ) in the organic an' in the a!ueous phase( 8n Fig( 4(; the 'istribution
o$ the 5'i-etones is constant in the higher hy'rogen ion concentration range
/lo&er pK0 &here they are un'issociate'( 8n the higher pK region, D
)
beco"es
inversely proportional to the hy'rogen ion concentration 'ue to increase in the
concentration o$ the 'issociate' $or" o$ the aci' )
, in agree"ent &ith E!(

/4(=>(0
The free ligand concentration, B)
C, is an i"portant para"eter in the $or5

"ation o$ "etal co"plees /see Chapter 9 an' section 4(F0( 8n a solvent etrac5
tion syste" &ith the volu"es , an' ,
org
o$ the a!ueous an' organic phases,
respectively, B)
C is calculate' $ro" the "aterial balanceM

&here
log B)

C log K logBK
Q
C + log /m
K), t
N ,
org
0 log
/
/4(20a0
= Q =
/ K
D ,K)
+ , ,
org
+ K
a
BK C ,
,
org
/4(20b0
m
K),t
is the total a"ount /in "oles0 o$ K) /reagent0 a''e' to the syste"( 6$ten
= o
m
K),t
,
org
is abbreviate' BK)C
org
, in'icating the original concentration o$ K) in
the organic phase at the beginning o$ the eperi"ent /&hen BK)C
a!
00( Ghen
,
org
, an' pK pK
a
, / = + K
D,K)
( Fro" E!( /4(200 it can be 'e'uce' that
B)
C increases &ith increasing pK, but ten's to beco"e constant as the pK value
approaches that o$ the pK
a
value( 8n the e!uations relating to the etraction o$
"etal co"plees, K) is o$ten i'entical &ith reagent :1 the in'ees "ay be
change' accor'ingly, thus e(g(, K
D,K)
K
A:
( /HoteM Oarious authors use slightly
'i$$erent no"enclature1 here &e $ollo& re$erence )ppen'i C(0
4.).2 *rotonation
)t lo& pK, so"e organic aci's accept an etra proton to $or" the K
2
) co"5
ple( This lea's to a 'ecrease in the D
)
value at pK < ;, as sho&n in Fig( 4(;M

Fig. 4.( Aistribution ratio D
K)
o$ un'issociate' acetylacetone( /a0 Aistribution bet&een
ben7ene an' a!ueous phase containing 'i$$erent inorganic salts1 2JC( /b0 Aistribution
bet&een CKCl
9
/upper curves0 or C
;
K
;
/lo&er curves0 an' a!ueous phase 0(= an' =(0 <
in HaCl6
4
as a $unction o$ BK)C
org
( The uncertainty at the lo&est D values is t= $or
CKCl
9
an' t0(2 $or C
;
K
;
( /Fro" :e$( =0(0

2
2

2
2
'i 2 2 org org
) org 2 2 org
+
K) + K
Q

K
)
Q
K
aK
BK)CBK
Q
C NBK )
Q
C /4(2=0
4ecause K
2
)
is ionic, it is not etracte' into the organic phase, an' thus the
'istribution ratio beco"es
Q =
D
)
BK)C
org
/BK
2
) C + BK)C + B) C0
= Q
Q = =
Z K
A,K)
/K
aK
BK C + = + K
a
BK C 0
/4(220
as illustrate' in Fig( 4(; $or oine(
4.).3 Dimeri+ation
Figure 2(= illustrates a nu"ber o$ orientations by &hich t&o linear aci's "ay
$or" a 'i"er( The partial neutrali7ation o$ the hy'rophilic groups lea's to in5
crease' solubility o$ the aci' in the organic solvent, but is not observe' in the
a!ueous phase( The 'i"eri7ation can be &ritten asM
2K)/org0

K )
/org0
K BK ) C NBK)C
2
/4(290
The 'istribution ratio $or the etraction o$ the aci' beco"esM
D /BK)C + 2BK ) C 0/BK)C + B)

C0
=
= =
Z K
D ,K)
/= + 2K
'i
K
D ,K)
BK)C
a!
/= + K
a
BKC
0 /4(240
The last ter" can be epresse' in several 'i$$erent &ays( 4ecause the 'istribu5
tion ratio D
)
re$lects the analytical concentration o$ ) in the organic phase, the
'i"er concentration is given as 2BK
2
)
2
C, although it is a single species /one
"olecule0( Figure 4(F illustrates ho& the 'i"eri7ation lea's to an increase o$
aci' 'istribution ratio &ith increasing a!ueous aci' concentration( For propionic
aci' logK
a
4(FP, logK
D,K)
=(>0 an' logK
'i
9(=4 in the syste"( The e5
traction increases as the si7e o$ the aci' increases( ) 'i"eric aci' "ay $or"
"onobasic co"plees &ith "etal ions, as is illustrate' by the $or"ulas in )p5
pen'i AM=4 bL', $or the </K/AEK,0
2
0
9
an' #6
2
//AEK,0
2
0
2
co"plees( The
situation "ay be rather co"ple( For ea"ple, at very lo& concentrations in
inert solvents, 'ial-ylphosphates /:60
2
,66K act as a "onbasic aci', but at
concentrations >0(0J < they poly"eri7e, &hile still acting as "onobasic aci's
/i(e(, li-e a cation echanger0( The 'egree o$ 'i"eri7ationNpoly"eri7ation 'e5
pen's on the polarity o$ the solvent B==bC(
4.).4 ,!%ration
8n solvent etraction, the organic phase is al&ays saturate' &ith &ater, an' the
organic etractant "ay beco"e hy'rate'( 8n the etraction o$ ben7oic aci', K47
/)ppen'i AM20, it &as $oun' that the organic phase containe' $our 'i$$erent
Fig. 4.) Aistribution ratios /$ro" botto" to top0 o$ acetic /C
2
0, propionic /C
9
60,
butyric /C
4
0, an' valeric /C
J
0 aci's /carbon chain length C
n
0 bet&een carbon tetra5
chlori'e an' &ater as a $unction o$ the aci' concentration in the a!ueous phase, BK)C
a!
(
/Fro" :e$( ==a(0
speciesM the "ono"er K47, the "ono"er hy'rate K47 K
2
6, the 'i"er K
2
47
2
,
an' the 'i"er hy'rate K
2
47
2
/K
2
60
2
( 6nly by consi'ering all these species is it
possible to eplain the etraction o$ so"e "etal co"plees &ith this etractant(
4.( EXTRACTION OF ACIDS AS ADDUCTS
!TYPE II"'#
)ci' a''uct /an' aci' an' a''uct K)4
/
+ %A0
$or"er0 in organic phase /0 /0
)ci' %A 'issociating an' $or"ing K)4
a''uct in a!ueous phase

+ %A

K
+

+ A
The solubility o$ organic aci's in &ater is 'ue to the hy'rophilic oo5 an'
hy'roo5groups o$ the aci' that $or" hy'rogen bon's &ith &ater "olecules( 8$
the hy'rogen ion o$ the aci' is solvate' by a 'onor organic base, 4, in the
b

b
a
organic phase, the a''uct 4LK) is li-ely to have "uch greater solubility in the
organic phase(
4.-.1 .ea/ 01rganic2 $ci%s3 ,$
8n etraction o$ &ea- organic aci's /abbreviate' K)0 $ro" aci'ic a!ueous solu5
tions, the concentration o$ un'issociate' aci', K), ecee's the concentration o$
its 'issociate' anions, )
, as long as pK > pK( The aci' "ay then act as a''uct5

$or"ing nonelectrolyte1 see section 4(J an' Ea"ple =(
4.-.2 'trong 0Inorganic2 $ci%s3 ,L
To avoi' con$usion &ith &ea- organic aci's, strong inorganic aci's are 'enote'
by KL( <ost strong aci's are co"pletely 'issociate' an' both cations an'
anions are hy'rate' in a!ueous solutions even at pKs as lo& as 0( The hy'ration
"a-es the" lipophobic an' al"ost insoluble in inert organic solvents( The hy5
'rogen ion is a Le&is aci' /Chapter 90 an' is solvate' by strong organic /'onor
or base0 "olecules, such as those in Table 4(F /e(g(, alcohols, ethers, -etones,
esters, a"ines, phosphoryls, etc(0( This results in greater lipophilicity, an' the
aci' beco"es "ore soluble in inert organic solvents( The structure o$ these
2solvate' hy'rogen salts3 is not &ell -no&n, but "ay be represente' sy"boli5
cally by K4
+

L
, &here 4 re$ers to the a''uct $or"er or the solvating solvent1 b

"ay have a value o$ =L4(
The or'er o$ etractability changes &ith a!ueous aci'ity, but in general
$ollo&s the or'er KCl6
4
KH6
9
> K8 > K4r > KCl > K
2
S6
4
/see Table
4(F0( Since the hy'ration energies o$ the aci's $ollo& the opposite or'er,
'ehy'ration is an essential step in the solvent etraction process( This or'er o$
aci's has a practical signi$icanceM aci's higher can be replace' by the aci's
lo&er in the se!uence1 e(g(, KF an' KH6
9
are etracte' $ro" aci'ic stainless
steel pic-ling &aste solutions into -erosene by a''ition o$ K
2
S6
4
/see Chapter
=4 o$ this boo-0(
The etraction o$ "ost aci's is acco"panie' by etraction o$ &ater( 8n
the etraction o$ KH6
9
by T4, into -erosene, "any 'i$$erent species have been
i'enti$ie', several o$ &hich involve hy'ration( The ratio o$ aci'Ma''uct is not
very pre'ictable( For ea"ple, KCl6
4
apparently is etracte' into -erosene &ith
=L2 "olecules o$ T4,, KCl into ethylether &ith one "olecule o$ ethylether,
etc( )lso, the etracte' aci' "ay 'i"eri7e in the organic solvent, etc( Ea"ple
2 illustrates the co"pleity o$ the etraction o$ KH6
9
by T4, into -erosene(
)ssu"ing that 4 is al"ost insoluble in the a!ueous phase, the e!uilibriu"
reaction can be &ritten in t&o &aysM
=( The interface extraction model assu"es that K) reacts &ith 4 at the inter$ace(
Thus
K)/a!0 + b4/org0

K)4
/org0
/4(2Ja0
9
b org org
Table 4.) 4asicity /Electron ,air5Aonating Ten'ency0 o$ So"e 8ons
an' <olecules /' is an al-yl or aryl group0
asicity of some common anions
relative to the /har' type0 actini'e cations
Cl6

< 8

< 4r

< Cl

< H6

< SCH

< acetate

< F
4 9
asicity of some organic molecules
a b c
)"ine co"poun's :
9
H < :
2
HK < :HK
2
< HK
9
)rsine co"poun's :
9
)s
,hosphine co"poun's :
9
,
6o5co"poun's

'
Carbonyls
e $ g
,hosphoryls
/:60
9
,6 < :/:60 ,6 < : /:60,6 < : ,6
)rsenyls : )s6
h
2 2 9
i
:CK6 < :
2
C6 /:
2
6 < :6K < K
2
60
D - l "
Sul$uryls /:60
2
S6
2
< :
2
S6
2
< /:60
2
S6 < :
2
S6
n o
Hitrosyls :H6
2
< :H6
Substitutions causing basicity decrease of oxo compounds
/CK
9
0
2
CKE < CK
9
/CK
2
0
n
E < CK
9
E < CK
9
6E < ClCK
2
E
aLc
Tertiary, secon'ary, an' pri"ary a"ines(
'
tri5' phosphate(
e
'i5'5' phosphonate(
$
'5'i5' phosphinate(
g
tri5' phosphine oi'e(
h
arsine oi'e(
i
ether an' hy'roo co"poun's(
D
sul$ates(
-
sul$ones(
l
sul$ites(
"
sul$oi'es(
n
nitro co"poun's(
o
nitroso co"poun's(
&ourceM :e$( =2(
Since BK)C
a!
an' B4C
org
are easily "easurable !uantities, it is co""on to 'e$ine
the etraction constant K
e
$or this "o'elM
K
e
BK)4 C BK)C
=
B4C
b
/4(2Jb0
2( The organic phase reaction model assu"es all reactions ta-e place in the
organic phase( Thus one assu"es
K)/org0 + b4/org0
K)4
b
/org0
The e!uilibriu" constant $or this reaction is
/4(2;a0
= b
K
a', b4
BK)4
b
C
org
BK)C
org
B4C
org
/4(2;b0
) org b org
e= org org
org
K
2
&here K
a',b4
is the /organic phase0 adduct formation constant( The 'istribution
ratio o$ the aci' in this syste" beco"es
D /BK)C + BK)4 C 0/BK)C + B)
=
B4C
b
0 N/=
+
K BK
Q
C0 /4(2;c0
Z K
D ,K)
/= + K
a',b4 org
a
E!uation /4(2Jb0 beco"es i'entical to E!( /4(2;b0 i$ K
e
is replace' by K
D,K)
K
a',b4
( E!uilibriu" "easure"ents 'o not allo& a 'ecision bet&een the t&o reac5
tion paths(
Ea"ple 2M Etraction o$ nitric aci' by pure T4,(
<any "etals can be etracte' $ro" nitrate solutions by T4,( 8n those
syste"s it is i"portant to account $or the KH6
9
5T4, interactions( The net set
o$ e!uations &ere 'erive' by B=9C an' are believe' to be vali' $or the etrac5
tion o$ KH6
9
at various nitrate concentrations into 90I T4, in -erosene( )b5
breviating KH6
9
as KL, an' T4, as 4, an' inclu'ing hy'ration $or all species
&ithout speci$ication, one 'erives
=( The $or"ation o$ an aci' "onoa''uctM
K
Q
+ L

+ 4/org0

KL4/org0
/4(2Pa0
For si"plicity, &e &rite the a''uct KL4, instea' o$ K4
+
L
( The etraction
constant is
K BKL4C BKC
=
BLC
=
B4C
=
/4(2Pb0
2( The $or"ation o$ a 'iaci' "onoa''uctM
2 K
Q
+
2 L

+
4/org0

/KL0
4/org0
/4(2Fa0

2
K
e2
B/KL0
2
4C
org
BKC
2
BLC
2
B4C
=
/4(2Fb0
9( 8on pair associationM

K
Q
+ L

K
Q
L
/4(2>a0
ass
BK
Q
C BL

CNBK
Q
L

C /4(2>b0
This reaction only occurs un'er strong aci' con'itions, an' the e!uilibriu"
constant "ay be <=(
4( The 'istribution o$ nitric aci' is then given by
D Z /BKL4C Q 2B/KL0
4C
Q ( ( ( 0/BL
R
C Q BK
Q
L
R
C0
R=
/4(900
H69 org 2 org
J( Further"ore, the 'i"eri7ation o$ T4, in the organic phase "ust be ta-en
into accountM
2 4

4
B4 C NB4C K
/4(9=a0
2
'i 2 org org
/4(9=b0
yiel'ing the total concentration o$ T4, in the organic phase
BT4,C
B4C + 2 K B4C
2
/4(920
org,t org 'i org
org
;( The 'istribution ratio in ter"s o$ only BK
+
C an' "ono"eric B4C
can then
be epresse' by
D K
=
B4C /K + 2 K BK
Q
C
2
0 /4(990
H69 ass org e= e2
8n this e!uation it is assu"e' BK
+
CZBL
C /electroneutrality in the a!ueous

phase0( E!uation /4(990 has been teste', an' the results agree' &ith >2900
eperi"ents un'er varying con'itions, see Fig( 4(>( The ea"ple illustrates the
rather co"plicate' situation that "ay occur even in such 2si"ple3 syste"s as
the etraction o$ KH6
9
by T4,(
4.) EXTRACTION OF COORDINATIVEY
SATURATED META CHEATE TYPE
COMPEXES !TYPE III"'#
Heutral, coor'inatively saturate' "etal co"ple MA
#
in organic phase
<etal ion M
#+
is co"plee' by # A

ligan's to M
#+
+
#A

MA
#
$or" neutral MA
#
Fig. 4.* Test o$ the e!uations in Ea"ple 2 $or etraction o$ 0(0=L0(J < nitric aci'
&ith 90I T4, in -erosene at te"peratures 20L;0
o
C( /Fro" :e$( =9(0
e
Section 9(2 'escribes an i"portant class o$ organic ligan's that are able
to co"ple a "etal ion through t&o or "ore bin'ing sites o$ 2basic3 ato"s, li-e
6, H, or S, to $or" metal chelates( Table 4(> presents the various types, their
nu"ber o$ aci'ic groups, the chelate ring si7e, an' the coor'inating ato"s( Heu5
tral chelate co"poun's are illustrate' in )ppen'i AM Jh, =4b an' =4'( 8n )p5
pen'i AMJh the ring si7e is ; $or the co"ple bet&een Cu
2
+

an' each o$ the
t&o acetylacetonate anions, )a
, &hile $or the 'i"eric KAEK, ligan' in the

$igures in )ppen'i AM=4b an' =4c the ring si7e beco"es P $or the <
9
+

an'
2+
#6
2
co"plees /see the structures in )ppen'i A0( )s 'iscusse' in Chapter 9,
Table 4.* So"e 6rganic Co"poun's Functioning as ,oly'entate )nions
in <etal Etraction
Chelate
ring si7e
)ci'ic
groups
Coor'inating
ato"s Co"poun' group an' ea"ples
4 = 6, 6 Carboylic aci', :C66K1 e(g(, per$luorobutyric
/C
9
F
P
C66K0, salicylic C
;
K
4
/6K0C66K, cin5
4 = 6, 6
a
na"ic /C;KJ/CK0
2
C66K0 aci's
Ai/al-yl or aryl0phosphoric an' phosphinic
aci's, ::,6/6K01 e(g(, KAEK,
b
1 correspon'5
ing thioaci's
a
4 = S, S Aithiocarba"ate, ::HC/S0SK, anthate,
:6C/S0SK1 e(g(, HaAAC
c
4 2 6, 6
a
<ono/al-yl or aryl0phosphoric an' phosphinic
aci', :,6/6K0 1 e(g(, K <EK,
'
2 2
J = 6, 6 Hitrosohy'royla"ine, :H/H606K1 e(g(, cup$er5
ron /: C
;
K
J
01 hy'roa"ic aci', :C/60HK6K
J = 6, H F5Ky'roy!uinoline /oine0, C
>
HK
;
6K
J or ; = S, H, or H, H Aiphenylthiocarba7one /'ithi7one0, C
;
K
J
HKHC
/SK0HHC
;
K
J
; = 6, 6 5Ai-etone, :C/60CKC/6K0:1 e(g(, acetylace5
tone /' ' CK
9
0, KTT)
CF
9
0
/' C
4
SK
9
, '
; = 6, 6 l5Hitroso525naphthol, C
=0
K
;
/H606K
; 2 6, 6 Ai/al-yl or aryl0pyrophosphate, :,/60/6K0
>J or 2 4 2 6, 6
6,/60/6K0'1 e(g(, 'ioctylpyrophosphate /'
' C
F
K
=P
60
Aicarboylic aci's, :/C66K02
a
6, S, or S, S $or the correspon'ing thioaci's(
b
Ai/25ethylheyl0phosphoric aci'(
c
So'iu" 'iethyl'ithiocarba"ate(
'
<ono/25ethylheyl0phosphoric aci'(
e
Thenoyltri$luoroacetone(
&ourceM :e$( =2(
n n
#
chelation provi'es etra stability to the "etal co"ple( The $or"ation an'
etrac5 tion o$ "etal chelates are 'iscusse' etensively also in re$erences B=4L
=;C(
8n Chapter 9 &e 'escribe' ho& an uncharge' "etal co"ple <)
7
is
$or"e' $ro" a "etal ion <
7
+

/central atom0 through a step&ise reaction &ith
the anion )

/ligand 0 o$ a "onobasic organic aci', K), 'e$ining a stepwise
formation constant 0
n
, an' an o"erall formation constant
n
, &here
B<)
#
n
C NB<
# Q
CB)

C
n
/4(940
The <)
7
co"ple is lipophilic an' 'issolves in organic solvents an' the distri!
bution constant K
AC
is 'e$ine' /in'e C $or co"ple0M
K
AC
B<)
7
C
org
NB<)
7
C /4(9J0
Ta-ing all "etal species in the a!ueous phase into account, the 'istribution
o$ the "etal can be &ritten /o"itting the in'e a! $or &ater0
D
<
B<)
7
C
org
#
K
AC

7
B ) C
#
/4(9;0
B<)
n
C
7
B) C
The 'istribution ratio 'epen's only on the $ree ligan' concentration, &hich
"ay be calculate' by E!( /4(200( <ost coor'inatively saturate' neutral "etal
co"plees behave Dust li-e stable organic solutes, because their outer "olecular
structure is al"ost entirely o$ the hy'rocarbon type, an' can there$ore be e5
tracte' by all solvent classes 2LJ o$ Chapter 2( The rules $or the si7e o$ the
'istribution constants o$ these coor'inatively saturate' neutral "etal co"plees
are then in principle the sa"e as $or the inert organic solutes o$ section 4(4(
Ko&ever, such co"plees "ay still be a"philic 'ue to the presence o$ electro5
negative 'onor oygen ato"s /o$ the chelating ligan'0 in the chelate "olecule(
8n a!ueous solution such co"plees then behave li-e polyethers rather than
hy'rocarbons( Harbutt B=PC has stu'ie' such outer5sphere hy'rate' co"plees
an' sho&n that the 'ehy'ration in the trans$er o$ the co"ple $ro" &ater to the
organic solvent 'eter"ines the 'istribution constant o$ the co"ple( This is
$urther elaborate' in Chapter =;(
Ea"ple 9M Etraction o$ Cu/880 by acetylacetone(
Si"ple 5'i-etones, li-e acetylacetone /)ppen'i AM J'0 can coor'inate
in t&o &ays to a "etal ato", either in the uncharge' -eto $or" /through t&o
-eto oygens0, or in 'issociate' anionic enol $or" /through the sa"e oygens0
as sho&n in )ppen'i AM Jc, Jh( 8t acts as an aci' only in the enolic $or"(
Figure 4(=0 sho&s the etraction o$ Cu/880 $ro" = < HaCl6
4
into ben7ene at
various concentrations o$ the etractant acetylacetone /K)0 B=FC( )cetylace5
tone reacts &ith Cu/880 in a!ueous solutions to $or" the co"plees Cu)
+

an'
Cu)
2
( 4ecause acetylacetone bin's through t&o oygens, the neutral co"ple
Cu)
2
contains t&o si5"e"bere' chelate rings1 thus $our coor'ination posi5
tions are ta-en up, $or"ing a planar co"ple /)ppen'i AM J$0( This co"ple
is usually consi'ere' to be coor'inatively saturate', but t&o a''itional very
D
2
+
Fig. 4.1+ Etraction o$ Cu/880 $ro" = < HaCl6
4
into ben7ene as a $unction o$ pK
/large $igure0 an' o$ $ree acetylacetonate ion concentration /insert0 at seven 'i$$erent
total concentrations o$ acetylacetone /BK)C
a!
0(0JL0(000> <0( /Fro" :e$( =F(0
&ea- bon's can be $or"e' perpen'icular to the plane1 &e can neglect the"
here(
The 'istribution o$ copper, D
Cu
, bet&een the organic phase an' &ater is
then 'escribe' by
BCu) C

2org
Cu
BCu
2Q
C + BCu)
Q
C + BCu)
C
/4(9P0
6ne then 'erives
2 2
K B) C K B ) C
D
AC 2

AC 2
/4(9F0
Cu
= + B)

C + B)

C
2
B)

C
n
= 2 n
&here K
AC
re$ers to the 'istribution constant o$ the uncharge' co"ple Cu)
2
(
8n E!( /4(9P0, log D is a $unction o$ B)
C, the free ligand concentration,

only, an' so"e constants( 8n Fig( 4(=0, log D
cu
is plotte' vs( log BK C / pK0(
Through E!s( /4(=P0 an' /4(=F0 it can be sho&n that log D
Cu
is a $unction o$
pK only at constant BK)C
org
/or BK)C
a!
0, &hile at constant pK the log D
Cu
'e5
pen's only on BK)C
org
/or BK)C
a!
0(
7
n
M e org
2
8n the insert o$ Fig( 4(=0, log D is plotte' as a $unction o$ log B)
C,
&here B)
C has been calculate' $ro" pK, BK)C

0
, phase volu"es, an' K an'
org a
K
A:
/sa"e as K
D,K)
0 $or K) by "eans o$ E!( /4(2001 it is $oun' that all curves
coinci'e into one at high pK /high B)
C0, as epecte' $ro" E!( /4(9F0( The

'istribution curve approaches t&o asy"ptotes, one &ith a slope o$ 2 an' one
hori7ontal /7ero slope0( Fro" E!( /4(9F0 it $ollo&s that, at the lo&est B)
C
concentration /lo&est pK0, the concentration o$ Cu)
+
an' Cu)
phase beco"es very s"all1 E!( /4(9F0 is then re'uce' to
in the a!ueous
li" D
BCu) C NBCu
2Q
C K B)

C
2
/4(9>0
B )

C0
Cu 2 org AC 2
)t the highest )

concentrations a hori7ontal asy"ptote is approache'M
li" D
BCu) C NBCu) C K
/4(400
B )

C
Cu 2 org 2 AC
The hori7ontal asy"ptote e!uals the 'istribution constant o$ Cu)
2
, i(e(, K
AC
(
Fro" the curvature bet&een the t&o asy"ptotes, the stability constants
=
an'
2
can be calculate'(
This ea"ple in'icates that in solvent etraction o$ "etal co"plees &ith
aci'ic ligan's, it can be "ore a'vantageous to plot log D vs( logB)
C, rather
than against pK, &hich is the "ore co""on /an' easy0 techni!ue(
8n or'er to calculate D
<
$ro" E!( /4(9;0, several e!uilibriu" constants as
&ell as the concentration o$ $ree )

are nee'e'( Though "any re$erence &or-s
report stability constants B=>, 20C an' 'istribution constants B4, 2=C, $or practical
purposes it is si"pler to use the etraction constant K
e
$or the reaction
<
7Q
/a!0 + 7K)/org0 <) /org0 + 7K
Q
/a!0
/4(4=a0
in &hich case the <)
75n
co"plees in the a!ueous phase are neglecte'( The
relevant etraction e!uations are
B<) C BK
Q
C
7
B<
7Q
C
=
BK)C
7
/4(4=b0
an'
K
e 7 org
D K BK)C
7
BK
Q
C
#
org
/4(4=c0
Thus only one constant, K
e
, is nee'e' to pre'ict the "etal etraction $or given
concentrations BK
+
C an' BK)C
/see re$erences given0(
org
( Tables o$ K
e
values are $oun' in the literature
7n
E!uation /4(4=0 is vali' only &hen the co"plees <)
n
can be neglecte'
in the a!ueous phase( Co"paring E!s( /4(9Pb0 an' /4(4=c0, it is seen that no
hori7ontal asy"ptote is obtaine' even at high concentrations o$ )
, or K) an'
K( Thus, $or very large 'istribution constant o$ the uncharge' co"ple /i(e(,
=0000 a straight line &ith slope # is eperi"entally observe', as in the case
$or the Cu/8805thenoyltri$luoroacetone /KTT)0 syste" /)ppen'i AM Jg0(
2
2
org
+
Ea"ple 4M Etraction o$ Cu/880 by Thenoyltri$luoroacetone(
Figure 4(==a sho&s the 'istribution o$ Cu/880 bet&een three organic sol5
vents an' &ater in the presence o$ isopropyltropolone /K8T,0 or thenoyltri$lu5
oroacetone /KTT)0 as a $unction o$ pK B22C( The straight line o$ slope 2 in
the pK5plot $its E!( /4(4=c01 thus # 2( 8t in'icates that the a!ueous phase 'oes
not contain any signi$icant concentrations o$ the co"plees Cu)
+
or Cu) , yet
Cu)
2
"ust be $or"e' in consi'erable concentrations, other&ise there &oul' be
no etraction o$ Cu/880( The line also correspon's to the asy"ptote E!( /4(9>0,
or /i(e(, B)
C BK
+
C
=
0( Thus the conclusion is that the a!ueous phase is co"5
pletely 'o"inate' by Cu
2
+
, &hile the organic phase contains only Cu) ( This
lea's to the copper 'istribution ratio
D BCu) C NBCu
2Q
C /4(420
Cu 2 org
&hich is vali' $or the reaction
Fig. 4.11 Aistribution o$ Cu/880 bet&een heone /0, carbon tetrachlori'e /0, or chlo5
ro$or" / 0 an' 0(= < HaCl6
4
in the presence o$ isopropyltropolone /8,T0 or thenoyl5
tri$luoroacetone /TT)01 /a0 as a $unction o$ logBK
+
C at constant BTT)C 0(= <1 /b0
as a $unction o$ BTT)C
org
at constant BK C 0(=<( /Fro" :e$( 22(0

org
Cu
2Q
+ 2K)/org0

Cu) /org0 + 2
K
Q
/4(49a0
The etraction constant is
K
e
BCu)
2
C
org
BK
Q
C
2
NBCu
2Q
C BK)C
2
/4(49b0
an' co"bining &ith E!( /4(420
D K BK)C
2
BK
Q
C
2
/4(440
Cu e org
Fro" E!( /4(440 a plot o$ log D against logBK
+
C shoul' yiel' a
straight line &ith slope +2, as in Fig( 4(==a, an' a plot against log BK)C
org
as in
Fig( 4(==b shoul' also yiel' a straight line &ith slope +2( Continue' in
Ea"ple =4(
This ea"ple illustrates a case o$ consi'erable analytical i"portance, es5
pecially $or the 'eter"ination o$ co"ple $or"ation constants $or hy'rophilic
co"plees, as 'iscusse' in section 4(=2, &hen the e!uilibriu" constants $or
the step&ise "etal5organic co"plees are o$ secon'ary interest( K
e
values are
tabulate' in several re$erence &or-s( K
e
is a con'itional constant an' only vali'
provi'e' no other species are $or"e' besi'es the etracte' one(
The 'istribution constant o$ the neutral co"ple <)
7
, K
AC
, has been re5
$erre' to several ti"es( 8n $avorable cases, &hen both the organic an' the a!ue5
ous phases are 'o"inate' by the sa"e uncharge' co"ple over a larger concen5
tration region, K
AC
can be 'irectly "easure', as is the case $or "ost o$ the 'ata
in Table 4(=0 B22L29bC( 6ther&ise K
AC
can be esti"ate' or calculate' $ro" K
ex
'ata co"bine' &ith
n
, K
a
, an' K
A:
Bsee E!s( /4(F0 an' /4(4;0C(
4.* EXTRACTION OF META COMPEXES
AS ADDUCTS !TYPE III"C#
Coor'inatively saturate' "etal a''uct MA
#
b
co"ple in organic phase /an' 0 /0
For"ation neutral co"ple cor'inatively M
#+
+
#A

+
b

MA
# b
saturate' by a''uct $or"er
8$ the neutral "etal co"ple is coor'inatively unsaturate', it $or"s <)
7
/K
2
60
x
in the a!ueous phase, &here 2# + x /) being bi'entate0 e!uals the "ai5
"u" coor'ination nu"ber( 8n the absence o$ solvating organic solvents, this
co"5 ple has a very lo& 'istribution constant( 6bviously, i$ &ater o$ hy'ration
can be replace' by organic "olecules 4, the result is a "ore lipophilic a''uct
co"ple <)
7
4
b
1 "any a''uct $or"ers are liste' in )ppen'i A an' several
tables( Ae5 pen'ing on the ligan', several types o$ such a''ucts eistM /i0 type
<)
7
4
b
, &here ) an' 4 are 'i$$erent organic structures1 /ii0 type <V
7
4
b
, &here
<V
7
is a neutral inorganic co"poun' /salt01 an' /iii0 type <)
7
/K)0
b
, &here )
an' K) are the basic an' neutral variant o$ the sa"e "olecule /so5calle' self5
adducts0(

7
7 b org
B4C
org
B4C
2
Table 4.1+ Aistribution Constants $or )cetylacetone /K)0 an' So"e <etal
)cetylacetonates 4et&een Oarious 6rganic Solvents an' = < HaCl6
4
at 2JC
log K
AC
log K
A:
6rganic solvent
a
Solvent %A Yn) Cu)
2
Hp)
4
n5Keane /=0 =(FF 0(022 =(JP E 0(J
Cycloheane /90 2(02 0(0=9 =(=; 0(04 0(F
Carbon tetrachlori'e /40 2(24 0(J2 0(9> 0(FJ 2(P
<esitylene
b
/;0 2(2F 0(44 E 0(49 E
Vylene /P0 2(2P 0(JP 0(4P 0(F0 E
Toluene /F0 2(9F 0(;; 0(9P 0(FJ E
4en7ene />0 2(2F 0(PP 0(2= =(04 9(9
Aibutylether /20 9(0; E =(0J E E
<ethylisobutyl-etone /J0 =9(= 0(PP 0(=J 0(;= E
Chloro$or" /=00 4(> =(9F 0(F9 2(J4 E
4en7onitrile /==0 2J(2 0(2= E E
a
Hu"bers in parentheses re$er to Figs( 4(29 an' 4(2;(
b
=,9,J5tri"ethylben7ene(
&ourceM :e$s( 22L29(
4.4.1 (eta"51rganic Com6"exes with 1rganic $%%uct
&ormers3 T!6e ($
+
7
b
The etraction o$ the "etal co"ple a''uct can be &ritten
<
7Q
/a!0 + 7K)/org0 + b4/org0

<) 4 /org0 + 7K
Q
/a!0
/4(4Ja0
The etraction constant is 'e$ine' by
B<) 4 C BK
Q
C
#
K
e

7Q 7
B< C BK)C
org
or
b
org
/4(4Jb0
K
e
D
<
BK
Q
C
7
BK)C
7
b
org
/4(4Jc0
Thus the 'istribution o$ the "etal, D
<
, is sho&n to 'epen' on the concentrations
o$ K
+

an' K)
org
to the po&er 7 o$ the charge o$ the "etal ion, an' on the
concentration o$ 4 to the po&er o$ b /i(e(, nu"ber o$ a''uct $or"ers in the
etracte' co"ple0(
8t can be sho&n that
7 7
K
e
K
a
7
K
A:
K
AC
K
a',b4
/4(4;0
K B<) 4 C NB<) C
o 4
&here /o"itting ionic charges0 K
a
BKCB)CNBK)C is the aci' 'issociation con5
stant Bsee E!( /4(=F0C, K
A:
BK)C
org
NBK)C is the 'istribution constant $or the
un'issociate' aci' K) Bsee E!( /4(=P0C, an'
b
a',b4 7 b org 7 org
/4(4P0
is the $or"ation constant $or the a''uct <)
7
4
b
in the organic phase Bsee E!s(
/4(=J0, /4(=;0, an' /4(2;0C( The $ive para"eters K
a
,
n
, K
A:
, K
AC
, an' K
a',b4
are
in principle unrelate', even though it "ay not al&ays be possible to change one
&ithout a$$ecting the others, as each "olecular species "ay ta-e part in several
e!uilibria( Githout consi'ering the in'epen'ent para"eters, it is o$ten 'i$$icult
to un'erstan' &hy K
e
varies in the $ashion observe', an' it "ay be i"possible
to pre'ict i"prove"ents o$ the syste"( ) goo' ea"ple is the etraction o$
Yn/880 by 5'i-etones an' T4,M
Ea"ple JM The etraction o$ Yn/880 by 5'i-etones an' phosphoryl a''uct
$or"ers(
Figure 4(=2 illustrates the etraction o$ Yn/880 $ro" = < HaCl6
4
into
carbon tetrachlori'e by 5'i-etones /K)0 in the presence o$ the a''uct $or"ers
Fig. 4.12 Enhance"ent o$ Yn/880 etraction, D D
=
, $ro" = < HaCl6
into carbon
tetrachlori'e containing the co"pleing etractants acetylacetone / 0, tri$luoroacetone
/0, or hea$luoroacetone / 0 as a $unction o$ the concentration o$ the a''uct $or"er
trioctyl phosphine oi'e /40( The curves are $itte' &ith E!( /4(J00 using the constants
log K
a'=
9(0P /))0, ;(P0 /TF)0, P(0 /TF)0, an' K
a'2
4(;; /))0, nil /TF)0, ==(;
/KF)0( /Fro" :e$( 24(0
D
Zn o
Yn
n
T4, an' T6,6 /40 B=2C( The etracte' neutral co"ple is Yn)
2
4
b(
The 'istri5
bution ratio beco"es
BYn) C + BYn) 4C + BYn) 4 C + L

2 org 2 org 2 2 org
BYnC + BYn)C + BYn)
2
C +
L
/4(4Fa0
To analy7e these syste"s, the overall etraction reaction "ust be bro-en into
its partial reactions, or by intro'ucing E!( /4(4P0, to obtain
K B)C
2
/= + K
B4C + K B4C
2
+ L0
D
AC 2 a',= org a',2 org
/4(4Fb0
Yn
B)C
n
&here the a''uct $or"ation constant is 'e$ine' by
K BYn) 4 C BYn) C
=
B4C
b
/4(4>0
a',b 2 b org 2 org org
8n the absence o$ any a''uct $or"er, D
Yn
is given as a $unction o$ the $ree
ligan' concentration by E!( /4(9;0, i(e(,0 the parentheses in E!( /4(4Fb0 e!uals
=1 'enoting this D
Yn
5value as D
o
, an' intro'ucing it into E!( /4(4F0 gives
/= B4C B4C
2
L0 /4(J00
D D + K
ad ,= org
+ K
a',2 org
+
D
Yn
/instea' o$ D
Y
n
0 in'icates that this epression is vali' only at constant
B)
C, or, better, constant BK

+
C an' BK)C
=
org
Bsee E!s( /4(9;0 an' /4(4=c0C( 8n Fig(
4(=2, log D
Y
n
D
o
is plotte' as a $unction o$ log B4C
org
( The 'istribution ratio
procee's $ro" al"ost 7ero, &hen al"ost no a''uct is $or"e', to&ar's a li"it5
ing slope o$ 2, in'icating that the etracte' co"ple has a''e' t&o "olecules
o$ 4 to $or" Yn)
2
4
2
( Fro" the curvature an' slope the K
a',b
5values &ere 'eter5
"ine' /see section 4(=00( The calculation o$ the e!uilibriu" constants is $urther
'iscusse' un'er Ea"ple =9(
Tables 4(==L4(=9 presents a''uct $or"ation constants accor'ing to E!(
/4(4P0( For the al-aline earths TT) co"plees in carbon tetrachlori'e in Table
4(==, the T4, "olecules bon' perpen'icular to the s!uare plane o$ the t&o TT)
rings, pro'ucing an octahe'ral co"ple( The higher the charge 'ensity o$ the
Table 4.11 )''uct For"ation Constants
$or the :eaction </TT)0
2
+ bT4, V
</TT)0
2
/T4,0
b
in CCl
4
Sho&ing E$$ect
o$ Charge Aensity
<
#+
/r p"0 log Ka'=
log K
a'2
Ca
2+
/=000
4(== F(22
Sr
2+
/==F0 9(P; P(J2
4a
2
+

/=9J0 2(;2 J(F4
&ourceM :e$( 4(
)''uct $or"ing
ligan' /0 log K
a'=
log K
a'2
log K
a'=
log K
a'2
TT)/sel$5a''uct0 0(J; E >0(J E
Keone =(=; =(J2 =(P= 2(94
[uinoline 9(2> E 9(4F J(=;
T4, 9(;9 J(40 J(9; F(>;
T6,6 J(40 P(;0 P(4> =2(2;
&ourceM :e$( 4(
Table 4.12 )''uct For"ation Constants $or the :eaction Eu)
9
/org0 +
bT4,/org0 V Eu)
9
/T4,0
b
/org0, E!( /4(2;a0, Ghere org CKCl
9
,
an' %A Substitute' )cetylacetone Ligan's
Ligan' /A0 Log K
a
Log K
a'=
Log K
a'2
)cetylacetone, )) F(P; =(>0 E
4en7oylacetone, 4Y) F(P4 =(;0 E
Tri$luoroacetone, TF) E 9(92 4(;4
4en7oyltri$luoroacetone, 4T) E 9(;4 J(2F
25Furoyltri$luoroacetone, FT) E 9(J0 J(00
Thenoyltri$luoroacetone, TT) ;(9 9(94 J(2F
&ourceM :e$( 4(
central ato", the stronger is the a''uct co"ple &ith T4,( HoteM $harge
density re$ers to the electrostatic interaction bet&een ions o$ opposite charge
accor'ing to the 4orn e!uation Bsee /2(=90, an' /9(=90C /base' on the Coulo"b
interac5 tion0( 8t is "ostly given as the ratio bet&een the ionic charge, #
+
/or
#
+
#
0 an' the ionic ra'ius r

+
/or r
+
r
0( Table 4(=2 co"pares the a''uct $or"ation

o$ the europiu" 5'i-etone co"plees &ith T4, in chloro$or"( 8n
Eu/TT)0
9
the TT)s only occupy si o$ the eight coor'ination positions
available1 the t&o e"pty positions have been sho&n to be occupie' by &ater(
Though the ten'ency is not strong, the stronger the aci' /i(e(, the larger its
electronegativity0, the larger is the a''uct $or"ation constant( Table 4(=9
co"pares the a''uct $or"a5 tion ten'ency o$ the Eu/TT)0
9
co"ple &ith
various a''uctants( The basicity o$ the 'onor oygen ato" increases in the
or'er as sho&n in Table 4(=9, as 'oes the a''uct $or"ation constant1 this is in
agree"ent &ith the or'er o$ basicity in Table 4(F an' the 'onor nu"bers o$
Table 9(91 see also section 4(2(
Table 4.13 Constants $or For"ation o$ Eu/TT)0
9
4
b
)''ucts
)ccor'ing to E!( /4(2;a0
Chloro$or" Carbon tetrachlori'e
4
9
4
The 'i$$erence bet&een the t&o solvent syste"s is li-ely a result o$ CKCl
9
solvating the Eu co"ple to so"e etent, &hile CCl
4
is inert( This has t&o
e$$ectsM the K
AC
value increases 'ue to the solvation by CKCl
9
/not sho&n in the
table0, &hile the a''uct $or"ation constant K
a'
'ecreases as the solvation hin'ers
the a''uct $or"ation1 the "ore inert solvent CCl
4
causes an opposite e$$ect, a
lo&er K
AC
an' a larger K
a'
(
4.4.2 (eta" Inorganic Com6"exes with 1rganic
$%%uct &ormers3 T!6e (8
+
7
b
The etraction o$ "ineral salts is generally less co"plicate' than the etraction
o$ "ineral aci's( <etal salts &ith "ono'entate univalent anions li-e Cl
, Cl6
,
SCH
, an' H6

are strongly hy'rate' in the a!ueous phase an' have !uite s"all,
i$ any, solubility in inert solvents( 8n or'er to etract these aci's, they "ust
either $or" an a''uct &ith a strongly basic etractant li-e T4, or T6,6, or be
in solvating solvents such as ethers, -etones, alcohols, or esters( Ea"ples o$
etracte' "etal salt a''ucts areM 4r
9
/Et60
b
, ,aCl
9
/<84S0, #6
2
/H6
9
0
2
/T4,0
2
,
Co/Cl6
4
0
2
/octanol0
b
, etc( /b is uncertain0( Tables o$ the etraction o$ a large
nu"ber o$ "etal salts by solvating solvents or co""ercial a''uct $or"ers 'is5
solve' in -erosene are given /see :e$( BJC0(
8t has been sho&n B2JC that "ono"eric "etal hy'roi'es can be etracte'
by strong 'onor "olecules1 e(g(, in the $or" o$ the a''ucts Ln/6K0
9
/T6,60
b
into CKCl
9
, &here b is 2L9( #n'er $avorable con'itions, the D
Ln
value "ay
ecee' =, though the $raction o$ hy'roi'e is !uite lo&(
Ghen the solvent is a goo' solvater, the 'eter"ination o$ the solvation
nu"ber b is 'i$$icult, unless the 'epen'ence o$ the etractant concentration on
the solvent can be obtaine'( Solvation nu"bers can be obtaine' in "itures o$
a solvating etractant an' an inert 'iluent li-e heane( Further, in these syste"s
the etraction o$ the "etal co""only re!uires high concentrations o$ salt or
aci' in the a!ueous phase, so the activity coe$$icients o$ the solutes "ust be
ta-en into account(
Ea"ple ;M Etraction o$ Yn/880 thiocyanate co"plees by T6,6(
Figure 4(=9 sho&s the etraction o$ Yn/880 $ro" a!ueous thiocyanate
/L
0 solutions into 0(00= < T6,6 /40 in heane1 the a!ueous phase is =(0 <
Ha/SCH
, Cl6
0 at a pK aroun' J B2;C( Yn/880 is -no&n to $or" a nu"ber o$

n2
&ea- Yn/SCH0
n
co"plees in the a!ueous phase( The uncharge' one is as5
su"e' to accept T6,6 to $or" the a''ucts Yn/SCH0
2
/T6,60
b
, &here b =
or 2(
)ssu"e that the reaction bet&een the neutral co"ple an' the solvating
"olecule ta-es place at the inter$ace /to assu"e the reaction to ta-e place in
the organic phase &oul' be unrealistic, as the 7inc thiocyanate is insoluble in
heane01 thus the etraction reaction is
4
D
D
n
Yn
Fig. 4.13 Aistribution ratio o$ Yn/880 &hen etracte' $ro" = < Ha/SCH
,Cl6
0 into
0(00= < T6,6 in heane, as a $unction o$ a!ueous SCH

concentration( The $ollo&ing
P
e!uilibriu" constants &ere obtaine' &ith E!( /4(J90M
=
9(P,
2
2=,
9
=J, K
e
2(J =0
b 2( /Fro" :e$( 2;(0
$or
YnL
+ b 4/org0

YnL 4
/org0
/4(J=0
2 2 b
$or &hich &e "ay 'e$ine an e!uilibriu" constant K
e,b4
(
4ecause "ore than one solvate' species "ay be etracte', the 'istribution ratio
beco"es
BYnL 4C + BYnL 4 C + L

2 org 2 2 org
BYnC + BYnLC + BYnL
2
C + BYnL
9
C +
L
/4 J20
8nserting the partial e!uilibriu" constants Bsee E!( /4(4;0C,
BLC K B4C
b

2 2 e ,b4 o rg
Yn
= + BLC
n
/4(J90
&here both su""ations are ta-en $ro" =( The solvation nu"ber b can be 'eter5
"ine' $ro" the 'epen'ence o$ D on B4C
org
&hile BLC is -ept constant( Fro" the
slope o$ the line in Fig( 4(=9 at lo& SCH

concentrations, it $ollo&s that b
21 thus only one a''uct co"ple is i'enti$ie'M Yn/SCH0
2
/T6,60
2
( The authors
&ere able to calculate the $or"ation constants
n
$ro" the 'eviation o$ the
curve $ro" the straight the line at constant B4C
org
, assu"ing b constant( Gith
4
4
org
D
,"
these e!uilibriu" constants, the line through the points &as calculate' &ith E!(
/4(J90(
4.4.3 'e"f5$%%ucts3 T!6e ($
+
0,$2
b
Ky'ration only occurs in neutral co"plees that are coor'inatively unsaturate'
by the organic ligan'( The hy'rate &ater re'uces the etractability o$ the co"5
ple( 8n the absence o$ strong 'onor "olecules, &hich can replace this hy'rate
&ater, there is still a chance $or the un'issociate' aci' to replace the &ater,
lea'ing to a self5adduct accor'ing to the reaction
<)
7
/K
2
60
&
+ bK)

<)
7
/K)0
b
+
&K
2
6
/4(J4a0
This co"petition bet&een the $or"ation o$ an a''uct &ith K) or &ith K
2
6 is
observe' as an increase' etraction &ith increasing K) concentration( Ko&ever,
stoichio"etrically the co"plees <)
Y
/K)0
b
an' K
b
<)
Y+b
are e!uivalent( For5
"ally the $or"er is a sel$5a''uct an' the latter is an ion pair( Thus E!( /4(J4a0
coul' be &ritten

b
Q
<)
7
/K
2
60
w
+ bK) </K
2
60
w2
)
7Qb
+ b
K
+ w 2b K
2
6 /4(J4b0
assu"ing the K) can replace 2 K
2
6 through its bi'entate structure( )ll o$ the
hy'rate &ater can be 'isplace' by the organic ligan', &ith $or"ation o$ nega5
tively charge' chelate co"plees(
Che"ical e!uilibriu" eperi"ents, e(g(, 'istribution ratio "easure"ents,
cannot 'istinguish bet&een these t&o types o$ co"plees1 ho&ever, they "ay
be i'enti$ie' by $ingerprinting techni!ues li-e H<:, 8:, or 5ray structure 'e5
ter"inations( Eistence o$ si"ilar a''ucts li-e <)
7
4
b
support the eistence o$
sel$5a''ucts( The case o$ pro"ethiu"/8880 acetylacetone is an interesting illus5
tration o$ this proble"(
Ea"ple PM Etraction o$ ,"/8880 by acetylacetone(
Figure 4(=4 sho&s the 'istribution ratio log D
,"
$or pro"ethiu" in the
syste" acetylacetone /K)0, ben7eneN= < HaCl6 as a $unction o$ logB)
C
p) at various starting concentrations, BK)C
o
, o$ K) in the organic phase( The
coor'ination nu"ber o$ ,"/8880 &ith respect to oygen is reporte' to be F or
>( 8n the a!ueous phase all step&ise co"plees up to ,")

can there$ore be
epecte' to be $or"e'( The vacant coor'ination sites "ay be $ille' &ith &ater
/$or"ing a hy'rate0 or un'issociate' acetylacetone /$or"ing a sel$5a''uct0(
The last assu"ption is suppporte' by the $act that a large nu"ber o$ a''ucts
o$ type Ln)
9
4
b
are -no&n(
6"itting &ater o$ hy'ration, the 'istribution ratio beco"es
B,") C + B,") K)C + B,") /K)0 C + L

9 org 9 org 9 2 org
B,"C + B,")C + B,")
2
C + L +
B,")
4
C
/4(JJa0
&hich is abbreviate', using the earlier relations, to
D
3
Fig. 4.14 Etraction o$ ,"/8880 by acetylacetone /K)a0 $ro" = < HaCl6
4
into ben5
7ene at three 'i$$erent original concentrations o$ K)a in the organic phase( p)
logB)a
C is calculate' accor'ing to E!( /4(200( The analysis o$ the syste" yiel'e' the
constants log
=
J(9J, log
2
>(20, log
9
=9(22, log
4
=4(0;, K
a'=
P, K
a'2
9, an' K
AC
0(00F, sho&n $or Pm in Fig( 4(=J( /Fro" :e$s( 2Pa,b(0
K B)C
9
/= + K
BK)C + K BK)C
2
+ L0

AC 9 a '= o rg a '2 o rg
,"
B)C
n
/4(JJb0
&here K
AC
re$ers to the 'istribution o$ uncharge' ,")
9
bet&een the ben7ene
an' the a!ueous phase
K
AC
B,")
9
C
org
NB,")
9
C /4(J;0
K
a',b
is the e!uilibriu" constant $or the sel$5a''uct $or"ation in the organic
phase, i(e(,
,") 4/org0
+
b K)/org0

,") /K)0
/org0
/4(JPa0
9

9 b
K B,") /K)0 C
B,") C
=
BK)C
b
/4(JPb0
a',b 9 b org 9 org org
For pe'agogic reasons &e re&rite E!( /4(JJb0
D
4
n
K /= + K
BK)C + K BK)C
2
+ L0

AC a ',= org a ',2 org
,"
/ B)C
9
0
=
B)C
n
/4(JF0
3 n
Hote that the 'eno"inator only re$ers to species in the a!ueous phase(
Thus at constant BK)C
org
, the curvature o$ the etraction curve an' its position
along the B)
C aes is only cause' by varying B)
C, i(e(, the a!ueous phase

co"pleation( The nu"erator re$ers to the organic phase species only, an' is
responsible $or the position o$ the etraction curve along the D5ais1 thus at
three 'i$$erent constants BK)C
org
, three curves are epecte' to be obtaine', &ith
eactly the sa"e curvatures, but higher up along the D5scale &ith higher
BK)C
org
concentration1 see Fig( 4(=4(
The asy"ptote &ith the slope o$ 9 at high p) /i(e(, lo& B)
C0, $its E!(

/4(JF0, &hen ,"
9+
'o"inates the 'eno"inator /i(e(, the a!ueous phase0, &hile
the asy"ptote &ith slope o$ += $its the sa"e e!uation &hen the a!ueous phase
is 'o"inate' by ,")
( 4et&een these t&o li"iting slopes, the other three

,")
n
co"plees are $or"e' in varying concentrations( ) 'etaile' analysis o$
the curves yiel'e' all e!uilibriu" constants K
e
, K
n
, K
a',b
an' K
AC
/see section
4(=4(90, &hich are plotte' in Fig( 4(=J( The curves in Fig( 4(=4 have been
calculate' &ith these constants( K
n
is 'e$ine' by
n
K
n
accor'ing to E!( /9(J0(
/4(J>0
The "ai"u" 'istribution ratio $or the ,"5K) syste" /D
,"
about 0(=0
is reache' in the pK range ;LP( 8t is &ell -no&n that the lanthani'es hy'roly7e
in this pK region, but it can be sho&n that the concentration o$ hy'roly7e'
species is <=I o$ the concentration o$ ,")
n
species $or the con'itions o$ Fig(
4(=4, an' can thus be neglecte'(
Sel$5a''ucts are rather co""on, an' have been i'enti$ie' $or co"plees o$ Ca,
Sr, 4a, Hi, Co, Yn, C', Sc, Ln, an' #/O80 &ith acetylacetone, thenoyltri$luoro5
acetone, tropolone, an' oine( Table 4(=4 lists so"e sel$5a''uct constants( The
$act that the constants vary &ith the organic solvent in'icates that the sel$5a''uct

Fig. 4.1$ The syste" La/8880 acetylacetone /K)0 =< HaCl6
4
Nben7ene at 2JC as a
$unction o$ lanthani'e ato"ic nu"ber Z1 /a0 The 'istribution ratio D
Ln
/stars, right ais0
at B)
C =0
9
an' BK)C
org
0(= <, an' etraction constants K
e
/crosses, le$t ais0 $or
the reaction Ln
9+
+
4K)/org0 V Ln) K)/org0
+
9K
+
( /b0 The $or"ation constants, K ,
9
$or $or"ation o$ Ln)
9n
lanthani'e acetylacetonate co"plees /a brea- at
n
;4
G' is in'i5
cate'01 circles n =1 crosses n 21 triangles n 91 s!uares n 4( /c0 The sel$5a''uct
$or"ation constants, K
a'
, $or the reaction o$ Ln)
9
/org0 + K)/org0 V Ln)
9
K)/org0 $or
org ben7ene( /) secon' a''uct, Ln)
9
/K)0
2
, also see"s to $or" $or the lightest Ln
ions(0 /'0 The 'istribution constant K
AC
$or hy'rate' lanthanu" triacetylacetonates, Ln)
9
/K
2
60
29
, bet&een ben7ene an' =< HaCl6
4
( /Fro" :e$( 2F(0
Table 4.14 Constants $or the For"ation o$ So"e <etal Sel$5)''ucts
)ccor'ing to MA
#
/org0 + b %A/org0 V <)
7
/K)0
b
<etal ion M
#+
Ligan' an' a''uct $or"er K) 6rganic solvent Log K
a'
Yn/880 8sopropyltropolone, 8,T CKCl
9
=(P2
Yn/880 8sopropyltropolone, 8,T CCl
4
=(>
La/8880 )cetylacetone, )) C
;
K
;
2(;
Eu/8880 Thenoyltri$luoroacetone, TT) CKCl
9
0(J;
Eu/8880 Thenoyltri$luoroacetone, TT) CCl
4
0(J
Eu/8880 8sopropyltropolone, 8,T CKCl
9
2(=
Eu/8880 8sopropyltropolone, 8,T CCl
4
2(0
#/O80 )cetylacetone, )) CKCl
9
=(=;
#/O80 Thenoyltri$luoroacetone, TT) C
;
K
;
0(J0
&ourceM :e$( 4(
reaction probably occurs in the organic phase( Table 4(=4 contains both very
inert /e(g(, CCl
4
0, polar /CKCl
9
0, an' pi5bon'ing solvents /C
;
K
;
0(
4.1+ META EXTRACTION 'Y I,UID ANION
EXCHAN&ERS !TYPE III"D#
6rganic phase &ith anion :HK
+
*

/:HK
+
0 M*
p
p n
echanger an' "etal co"ple
)!ueous phaseM "etal &ith M
#+
+
nL

+
p:HK
+
*

/:HK
+
0
<L
p
p n
co"pleing anions L
an' a"ine
<etals that react &ith inorganic ligan's to $or" negatively charge' co"5
plees as 'escribe' in Chapter 9 can be etracte' into organic solvents &ith
large organic cations in a process re$erre' to as li+uid anion exchange(
4.19.1 Two In%ustria""! Im6ortant Cases
Etraction o$ "etals $ro" chlori'e solutions into -erosene containing trioctyl
a"ine /T6)0, as illustrate' by Fig( =(9, has $oun' application in the pro'uction
o$ pure Co an' Hi "etals $ro" their ores, as 'iscusse' in Chapter ==( The
a!ueous phase contains the Co an' Hi in a''ition to other "etals in chlori'e
solution, &here the chlori'e concentration goes to 900 gNL /i(e(, about F(J <0(
)t this high a!ueous ionic strength, a rigorous "athe"atical treat"ent o$ the
syste" &oul' re!uire the use o$ activities in or'er to eplain the etraction
n
4
4 9
'iagra"1 ho&ever, here it su$$ices to use concentrations( )n interesting $eature
in Fig( =(9 is the 'i$$erences bet&een "etals in various oi'ation state, notably
Fe/880 an' Fe/8880, the latter being "uch "ore easily etracte' than the $or"er
because Fe/8880 $or"s "uch stronger co"plees &ith Cl

ions( The re!uire"ent
$or etraction o$ "etals by an a"ineli-e T6), or by its a"ine salt, T6)K
+
Cl
,
is the $or"ation o$ negatively charge' "etal chlori'e co"plees in the a!ueous
phase( The co"ple $or"ation $ro" <
7
+

to <Cl
7
n
, &here 7 n =, procee's
in the step&ise "anner 'escribe' in Chapter 9( For ea"ple, Fe/8880 $or"s the
co"ple FeCl
, &hile cobalt $or"s CoCl

2
( The etraction reaction $or Co can

4
be &ritten
2
4
Q
CoCl
4
+ 2 :HK Cl /org0

/:HK0
2
CoCl
4
/org0 + 2
Cl
/4(;0a 0
)"ine etraction is use' also in another i"portant in'ustrial process, the
etraction o$ uraniu" $ro" sulphuric aci' leache' ores, &hich uses trilauryl
a"ine /TL)0( 8n that case, the etraction reaction is
2 Q 2
#6
2
/S6
4
0
4
+ 2 /:HK 0
2
S6
4
/org0

/:HK0
4
#6
2
/S6
4
0
9
/org0 +
S6
4
/4(;0b0
These processes are re$erre' to as li!ui' anion echange, because the
a!ueous anionic "etal co"ple replaces the anions Cl

or S6
2

o$ the large
organic a"ine co"ple( The a"ine co"ple is an ion pair, or salt, :HK
+

L
,
&here : is a large hy'rocarbon group( The a"ine salt is highly soluble in the
organic /e(g(, -erosene0 phase, an' al"ost insoluble in the a!ueous phase( The
reaction is presu"e' to occur either at the inter$ace or in the a!ueous phase &ith
a lo& concentration o$ 'issolve' :HK
+

L
( 4e$ore 'iscussing these reactions in

ter"s o$ "olecular species, it is necessary to consi'er "ore speci$ic aspects o$
li!ui' anion echangers(
4.19.2 *ro6erties of Li:ui% $nion Exchangers
)s "entione' earlier, hy'rogen ions can be solvate' by strong 'onor "olecules
li-e T4,, so"eti"es lea'ing to the etraction o$ a solvate' hy'rogen salt,
K4
+
L
1 in Ea"ple 2, T4, etracts nitric aci', KH6 , in the $or" o$ the a''uct
b 9
+
co"ple T4, KH6
9
, &hich coul' be consi'ere' as the co"ple KT4, H6
9
ion pair( The a"ines $or" stronger a''ucts &ith hy'rogen ions1 in $act, they are
so strong that they re"ain protonate' &hile echanging the anion( ) classical
reaction is the $or"ation o$ the a""oniu" ion HK
+

&hen HK is 'issolve' in
&ater(
The organic a"ines /the amine base :H0 have a nitrogen ato" H attache'
to a large organic "olecule : usually containing >P aliphatic or aro"atic carbon
ato"s( They are highly soluble in organic solvents /'iluents0 an' al"ost insolu5
ble in &ater( 8n contact &ith an a!ueous phase containing KL, the a"ine base
:H reacts &ith the aci' KL to $or" :HK
+

L
, but etracts &ith an ecess

a"ount o$ aci' KL /over the =M= KLM:H ratio0 into the organic solvent, an'
also &ith a''itional &ater( The practical concentration o$ a"ine in the organic
solvent is usually less than 20I1 at higher concentrations the a"ine salt solu5
tions beco"e rather viscous( The a"ine salts 'issociate in highly polar solvents,
&hile in "ore inert 'iluents they easily poly"eri7e to $or" "icelles, an' at
higher concentrations a thir' phase( For ea"ple, in ylene /TL) K4r0
n
aggre5
gates &ith n 2, 9, an' 90 have been i'enti$ie', an' in other syste"s aggrega5
tion nu"bers above =00 have been reporte'( TL) KH6
9
is "ainly tri"eric in
"5ylene at concentrations 0(002L0(2 <, but larger aggregates are $or"e' at
higher a"ine concentrations( These aggregates see" to behave li-e "ono$unc5
tional species, each etracting only one anionic "etal co"ple( The aggregation
can be re'uce', an' the thir' phase $or"ation avoi'e', by using aro"atic
'iluents an'Nor by a''ing a modifier, usually another strong Le&is base /e(g(,
octanol or T4,0( Such a''itions o$ten lea' to consi'erable re'uction in the K
e
value(
Four types o$ organic a"ines eist, as sho&n in Table 4(FM pri"ary a"ines
:HK
+
, secon'ary : HK
+
, tertiary : HK
+
, an' !uaternary : H
+
/)ppen'i
A0(
9 2 2 9 4
The hy'rocarbon chain : is usually o$ length C
F
RC
=2
, co""only a straight
aliphatic chain, but branche' chains an' aro"atic parts also occur( 8n general
the a"ines etract "etal co"plees in the or'er tertiary > secon'ary > pri"ary(
6nly long5chain tertiary an'Eto a s"aller etentE!uarternary a"ines are use'
in in'ustrial etraction, because o$ their suitable physical properties1 trioctyla"5
ine /T6), F carbons per chain0 an' trilauryl a"ine /TL), =2 carbons per chain0
are the "ost $re!uently use'( For si"plicity &e abbreviate all a"ines by :H,
an' their salts by :HK
+

L
(
The tertiary an' !uaternary a"ine bases are viscous li!ui's at roo" te"5
perature an' in$initely soluble in nonpolar solvents, but only slightly soluble in
&ater( The solubility o$ the ion5pair :HK
+

L

in organic solvents 'epen's on
the chain length an' on the counterion, L
M the solubility o$ TL) KCl in &et

ben7ene is 0(P <, in cycloheane 0(0F <, in CKCl
9
=(2 <, an' in CCl
4
0(P <(
Hitrate an' perchlorate salts are less soluble, as are lo&er "olecular &eight
a"ines(
The $or"ation o$ the ion pair salt can be &ritten
:H/org0 + K
Q
+ L

:HK
Q
L

/org0
K
e,a"
/4(;=0
Table 4(=J gives the e!uilibriu" constants K
e,a"
/$or extraction, amine0 $or this
reaction &ith trioctyla"ine in various solvents( )lthough the ion pairs are only
slightly soluble in &ater, they can echange the anion L

&ith other anions, V
,
in the a!ueous phase( /Hote that &e use L

to in'icate any anion, &hile V

is
use' $or /an alternative0 inorganic anion(0

:HK
Q
*

/org0 + 2

HK
Q
2

/org0 +
*
K
e,ch
/4(;20
4
Table 4.1$ E!uilibriu" Constants K
e,a"
$or For"ation
o$ Trioctyl )"ine Salts BE!( /4(;=0C
)nion Solvent Log K
e,a"
F
Toluene 9(0
Cl
Toluene J(>
Cl
Carbontetrachlori'e 4(0
Cl
4en7ene 4(=
4r
Toluene F(0
H6
9
Toluene ;(;
H6
9
Carbontetrachlori'e J(0
S6
2 a
4
Carbontetrachlori'e ;(P
S6
2 a
4
4en7ene F(9
a
The e!uilibriu" constant re$ers to the $or"ation o$ /: HK0 S6 (
&ourceM :e$( J(
9 2 4
The e!uilibriu" constant /K
e,ch
$or extraction, echange0 $or this reaction in5
creases in the or'er Cl6

< H6

< Cl

< KS6

< F
( Fro" Chapter 9 it $ollo&s

4 9 4
7n
that the $or"ation constants $or the "etal co"ple <L
n
usually increases in
the sa"e or'er( There$ore, in or'er to etract a "etal perchlorate co"ple, very
high Cl6

concentrations are re!uire'1 the perchlorate co"ple is easily re5
place' by anions higher in the se!uence(
)ll negatively charge' "etal co"plees can be etracte' by li!ui' anion
echangers, in'epen'ent o$ the nature o$ the "etal an' the co"pleing ligan'(
Li!ui' anion echange has etensive in'ustrial application, an' "any ea"ples
are given in later chapters( Lists o$ etraction values are $oun' in other &or-s
Be(g(, J, 2=C(
4.19.3 E:uations for Li:ui% $nion
Exchange Extractions
The 'iscussion on the properties o$ the a"ine salts serves to eplain &hy, in
"etal a"ine etractions, it is 'i$$icult to obtain si"ple "athe"atical relations
that agree &ell &ith the eperi"ental 'ata( Ghile there is no 'i$$iculty, in princi5
ple, in obtaining reasonably goo' values $or the $or"ation o$ the negatively
charge' "etal co"plees in the a!ueous phase, there is a "aDor proble" in
'e$ining the organic phase species, &hich "ay consist o$ $ree a"ine B:HC,
"ono5 "eric B:HKLC, an' poly"eric B:HKLC
n
a"ine salt, an' several etracte'
"etal co"plees B/:HK
+
0 /<L
p
0C( ) contributing 'i$$iculty in practice is the

nee' to
p n
use high ligan' concentrations, BL
C, in the a!ueous phase in or'er to obtain the

negatively charge' co"plees /see Fig( =(90(
n
n
n
<
n <
8n general the "etal <
7
+

reactions &ith a "onobasic anion L

can be
&ritten
#
+

7n 7n 7Q n
< + n L
<L
n
n
B<L
n
C NB< C BL C /9(J, 4(940
Ghen 7 n p is negative, a negatively charge' "etal co"ple has been
$or"e', &hich can be etracte'
p Q
Q pQ p
<L
n
+ p :HK L /org0

/:HK 0
p
<L
n
/org0 + p L /4(;9a0
Ge 'e$ine the etraction constant by
B/:HK0
Qp
<L
p
C BL

C
p
p n org
K
e
B<L
p
C B:HKLC
p
/4(;9b0
n org
) priori, it "ust be assu"e' that the a!ueous phase contains all the step&ise
co"plees <L
7
n
( Thus the 'istribution ratio is
B/:HK0
Qp
<L
p
C
BL

C
p
B:HKLC
p
p n org p org
D
<
B<L
7
n
C
K
e
= +
p
BL

C
p
/4(;40
The 'istribution o$ < 'epen's on both the $ree a"ine salt in the organic phase
an' the concentration o$ $ree L

in the a!ueous phase until all "etal in the
a!ueous phase is boun' in the <L
p
co"ple( )t constant a"ine concentration,
E!( /4(;40 in'icates that a plot o$ D vs( BL
C &oul' have a linear slope p i$ the

'eno"inator o$ E!( /4(;40 is =1 i(e(, the "etal species in the a!ueous phase
are 'o"inate' by the unco"plee' "etal ion <
7
+
( )t higher BL
C concentrations,
&here the <L
p
co"ple begins to 'o"inate in the a!ueous phase, the D
p
value
beco"es e!ual to K
e
B:HKLC
org
( E!uations /4(;40 an' /4(40 sho& that &5shape'
curves result $or "etals &ith large K
e
values( 8n a plot o$ D
<
vs( B:HKLC
org
a
straight line o$ slope p is obtaine' only at constant BL
C( Fro" such "easure5

"ents both p, K
e
an'
p
can be evaluate'( The $ollo&ing ea"ple illustrates
this(
Ea"ple FM Etraction o$ Trivalent )ctini'es by TL)(
8n an investigation o$ the etraction o$ trivalent actini'es, )n/8880 $ro"
0(0= < nitric aci' solutions o$ various LiH6
9
concentrations into o5ylene
containing the tertiary a"ine salt trilauryl"ethyla""oniu" nitrate, TL<)
KH6
9
, Oan 6oyen B2>C $oun' that the a"ine &as "ono"eric only at very lo&
concentrations /0(=< in the organic phase0 but at higher concentration $or"e'
both 'i"ers an' tri"ers(
#sing trace concentrations o$ Ce/8880 an' )n/8880 a log5log plot o$ D
<
=N2
against the nitrate ion activity, m
t
BLiH6
9
C , ha' a slope o$ approi"ately
9, Fig( 4(=;b( Fro" E!( /4(;40 this slope correspon's to the p5value o$ 9 &hen
the a!ueous phase is 'o"inate' by the $ree "etal ion, &hich is not an unrea5
sonable assu"ption at lo& nitrate concentrations(
Fig. 4.1% Aistribution ratio o$ <
9Q
ions bet&een the trilauryl"ethyl a""oniu" nitrate
/TL<)0 in o5ylene an' a!ueous phases o$ varying LiH6
9
concentrations( /a0 )s a
$unction o$ TL<)H6
9
concentration at =LP <, 2LJ <, 9L9 < LiH6
9
( /b0 Etraction
o$ Eu/8880 an' tree actini'e/8880 ions at 0(= < TL<)H6
9
in o5ylene an' varying a!ue5
ous salt concentrations( /Fro" :e$( 2>(0
4
4 4
+
8n plots o$ log D
)"
against BTL<) H6
9
Corg at 'i$$erent nitrate concen5
trations, the curves in Fig( 4(=;a ha' straight slopes o$ =(JL=(F at lo& concen5
trations o$ TL<) H6
9
, but ben'ing at higher concentrations, &as eplaine'
by the $or"ation o$ poly"eric a"ine species( 8$ E!( /4(;40 is vali', these slopes
correspon' to the nu"ber o$ TL<) KH6
9
groups attache' to the etracte'
)" species( Thus Oan 6oyen 'escribe' his co"ple as \/TL<) H6
9
0
n
]
2
)"/H6
9
0
9
, $or &hich n = only at the very lo& a"ine concentrations( Thus
$or n = the co"ple coul' as &ell be &ritten /TL<)0
2
)"/H6
9
0
J
( The Ce
an' other )n co"plees &oul' have si"ilar con$igurations(
4.11 OTHER EXTRACTA'E META COMPEXES
!TYPE III"E#
8on pair /an' possibly 2counter species30 /$
+
2

an' 3
+
A
0 $
+
A

in organic phase
)!ueous cation $
+

an' anion A

associate' $
+

+ A

$
+
A
into ion pair $

+
A
There are a $e& types o$ co"plees that 'o not $it &ell into the previous
classi$icationsM "onovalent "etals that $or" etractable co"plees &ith large
organic "onobasic anions, an', conversely, "onovalent inorganic anions that
$or" etractable co"plees &ith large organic cations( Though the a"ine5type
li!ui' anion echangers coul' $it into the latter group, it is si"pler to treat the"
as a separate ho"ogenous group /class 8885A0( The large "onovalent ion
pair,
tetraphenylarsoniu" tetraphenylborate /,h
4
)s ,h 4
0, &hich has been suggeste'

as a re$erence in solvent etraction /see Chapter 20, also belongs to this class(
6$ so"e i"portrance is the etraction o$ al-ali ions by tetraphenylborate
an' by cro&n ethers /)ppen'i AM 2=0, o$ $luori'e by tetraphenylanti"oniu"
ions, an' o$ perrhenate by tetraphenylarsoniu" ions( 4ecause "ost o$ the vol5
u"e o$ these co"plees is ta-en up by organic groups, the co"plees are highly
lipophilic an', there$ore, etractable into organic solvents &ithout a''itional
solvation( Though these syste"s have li"ite' applications, the cro&n ethers
o$$er so"e interesting etraction syste"s( The ethers $or" cage co"poun's
/2clath5 rates301 i(e(, the "etal cation $its into a cage $or"e' by the cro&n
structure( 4e5 cause the cage can be 'esigne' to $it al"ost any ion o$ a
certain si7e, rather selective etractions are possible &ith this syste", as
'escribe' in Chapter =J(
Ea"ple >M Etraction o$ S
+
by tetraphenylborate(
Consi'er the etraction o$ S
+

$ro" a!ueous solution into the organic
solvent nitroben7ene by a''ition o$ Ha,h 4( )bbreviating ,h 4
by )
, the
etracte' co"ple is the ion pair S
+
)
( 8n an inert solvent this is a stable ion

pair, but in a highly polar solvent li-e nitroben7ene, the ion pair "ay 'issociate(
The organic phase "ay thus contain both solvate' S
+
an' S
+
)

species, &hile

the only potassiu" species in the a!ueous phase is $ree S
+
(
The etraction e!uilibria "ay be &ritten
S
Q
+ )

S
Q
)

/org0 E!uil( const( K /4(;J0
&hile $or the reaction in the organic phase
S
Q
)

/org0

S
Q
/org0 + )

/org0 E!uil( const( K /4(;;0
The 'istribution ratio o$ K
+
beco"es
D /BS
Q
)

C Q BS
Q
C
0 BS
Q
C
=

K
B)

C/= +
K
NB)

C 0 BSC
=
/4(;P0
S org org e ass org
Ghen )

is a''e' into the a!ueous phase as a Ha
+

salt in large ecess to S
+
,
the 'issociation in the organic phase beco"es negligible an' E!( /4(;P0 is re5
'uce' to
D K B)

C /4(;F0
S e
Figure 4(=P sho&s the 'istribution ratio o$ S
+

&hen a large ecess o$
Ha
+
)

is a''e' to the syste"( )lthough the etracte' co"ple shoul' be co"5
Fig. 4.1( Aistribution ratio o$ potassiu"/80 bet&een nitroben7ene an' &ater as a
$unction o$ initial a!ueous tetraphenylborate concentration in 0(=< HaCl6
4
( /Fro" :e$s(
90a,b(0
p <
D
7 org n
< <
D K BK)C
<
o
pletely 'issociate' in the nitroben7ene, the ionic concentration o$ the organic
phase is large enough to suppress 'issociation, an' the 'istribution ratio thus
beco"es proportional to the concentration o$ the etractant in the a!ueous
phase(
4.12 STUDIES OF HYDROPHIIC COMPEXATION
'Y SOVENT EXTRACTION !TYPE IV#
Coor'inatively saturate' "etal MA
#
co"ple in organic phase
For"ation o$ etractable an' M
#+
+
#A

+
n2

MA
+
M2
#n
# n
nonetractable co"plees
Solvent etraction has beco"e a co""on techni!ue $or the 'eter"ination o$
$or"ation constants,
n
, o$ a!ueous hy'rophilic "etal co"plees o$ type <V
n
,
particularly in the case &hen the "etal is only available in trace concentrations,
as the 'istribution can easily be "easure' &ith ra'ioactive techni!ues /see also
section 4(=J0( The "etho' re!uires the $or"ation o$ an etractable co"ple o$
the "etal ion, &hich, in the si"plest an' "ost co""only use' case, is an un5
charge' lipophilic co"ple o$ type <)
7
( The "etal5organic co"ple <)
7
serves as a probe $or the concentration o$ "etal <
7
+

ions in the a!ueous phase
through its e!uilibriu" &ith the $ree <
7
+
, section 4(F(2( This sa"e principle is
use' in the 'esign o$ "etal selective electro'es /see Chapter =J0( Etractants
typically use' $or this purpose are 5'i-etones li-e acetylacetone /K))0 or
thenoyltri$luoroacteone /TT)0, an' &ea- large organic aci's li-e 'inonyl naph5
talene sulphonic aci' /AHH)0(
The pertinent 'istribution e!uation is
D
B<)
7
C
org
/4(;>0
<
B<C\= + B)C
n
+ BVC
p
]
n p
/su""e' $ro" = to n or p0 &here the $or"ation constants $or <)
n
are
n
an'
those $or the <V
p
co"plees
p
an' su""ations are ta-en $ro" =( 8n the ab5
sence o$ <V co"plees, the 'istribution ratio o$ < is 'e$ine' by D
o
M
o
B<) C NB<C /= + B)C
n
0 /4(P00
8$ the con'itions are chosen so that the a!ueous co"plees o$ K) can be ne5
glecte' Bsee E!( /4(4=0 an' Ea"ple 4C, D
o
o$ E!( /4(P00 e!uals D o$ E!(
/4(4=c01 i(e(,
<
D
<
Bo$ E!( /4(4=c0C
7
e org
BK
Q
C
7
/4(4=c, 4(P=0
$or &hich linear correlations are obtaine' in plots o$ log D
<
against log BK)C
org
at constant pK, or against pK at constant BK)C
org
( Aivi'ing E!( /4(;>0 by E!(
/4(P00 gives
p
e org
n
4
D
o
ND = + BVC + BVC
2
+ BVC
9
+ L
/4(P20
= 2 9
Thus a plot o$ D
o
ND against BVC provi'es a polyno"ial $ro" &hich the s can
be calculate' /see section 4(=40(
Ea"ple =0M Aeter"ination o$ $or"ation constants $or 4e/880 oalate co"5
plees(
Figure 4(=F sho&s the etraction o$ berylliu" &ith KTT) into heone
as a $unction o$ the concentration o$ oalate ions, 6
2
, in the a!ueous phase(
Kere the con'itions have been chosen so that the a!ueous co"plees o$ TT)
can be neglecte' as has been 'escribe' earlier, an' thus E!( /4(P=0 is vali',
o 2 2
an' the relation D
<
K
e
BK)C
org
BKC so that
log D N D
o
log D K
=
BK)C
2
BKC
2
Z log /= + =0
9(JJ
B6
2
C + =0
J(40
B6
2
C0
2
/4(P90
The para"eter values on the right5han' si'e o$ the e!uation, are the
n
values,
an' &ere 'eter"ine' by a curve $itting techni!ue /section 4(=40( 8ntro'ucing
these values in E!( /4(P=0 gives the soli' line through the points in Fig( 4(=F(
The a'vantage o$ this 2strange3 or'inate is that the curvature only re$lects the
oalate co"pleation(
Ky'rolysis o$ so"e "etals begins at very lo& pK /e(g(, Yr at pK 0(4, Th/8O0
an' #/O80 at pK =L2, the lanthani'es at pK 9LJ, etc(0( Ko&ever, i$ co"ple
Fig. 4.1) Aecrease in 'istribution ratio o$ 4e/880 as a $unction o$ oalate ion /6
2
0
concentration 'ue to $or"ation o$ a!ueous 4e6
2
2n
co"plees( The etraction syste" is
0(09 < TT) in "ethylisobutyl-etone an' =(0 < Ha/0(J 6
2
, Cl6
0( See E!( /4(P20 $or

or'inate $unction( /Fro" :e$( 9=(0
$or"ation strongly 'o"inates over hy'rolysis, the latter can be neglecte'( 8n the
overvie& in section 4(9, it &as sho&n in Fig( 4(9 that the general shape o$ the
etraction curves in'icates the type o$ co"plees $or"e'( Thus, the etraction
o$ galliu"/8880 &ith acetylacetone, Fig( 4(=>, in'icates a behavior accor'ing to
Fig( 4(9c( in the plot o$ log D vs( $ree ligan' concentration, B)
C(
Ea"ple ==M For"ation o$ hy'roly7e' Ga/8880 acetylacetonates(
Figure 4(=> sho&s the etraction o$ Ga/8880 by acetylacetone into ben5
7ene at various concentrations o$ total acetylacetone, BK)C
t
, an' constant ionic
strength, using the )S#FOE techni!ue /see section 4(=J(90( 4y co"paring
&ith Fig( 4(9, one "ay guess that hy'roy co"plees are $or"e' /'iagra" c0(
8$ the general co"ple is 'esignate' Ga
"
)
n
/6K0
p
, a $irst investigation sho&e'
Fig. 4.1* The 'istribution o$ Ga/8880 bet&een ben7ene an' = < HaCl6
4
as a $unction
o$ p) logB)
C at ; 'i$$erent acetylacetone /K)0 concentrations /0(0;L0(000; <0(The

'i$$erent curves are 'ue to 'i$$erent etent o$ hy'rolysis in the a!ueous phase( The con5
centration o$ K) 'ecreases $ro" the upper le$t corner, &here BK)C
a!
is 0(0; < /0,
to&ar' the right lo&er corner, &here it is 0(000; < / 0( /Fro" :e$( 92(0
that no polynuclear co"plees &ere $or"e', i(e(, m =, as the etraction
curves &ere in'epen'ent o$ the Ga/8880 concentration( This &as also epecte'
as the total concentration o$ Ga/8880 range' $ro" =0
4
to =0
;
<( Het, using a
co"puter progra", the $or"ation constants $or the $ollo&ing co"plees &ere
'eter"ine'M Ga)
2+
, Ga)
+
, Ga) , Ga/6K0 an' Ga/6K0

B92C( 8t &as conclu'e'
2 9 9 4
that no "ie' co"plees &ith both )

an' 6K

&ere $or"e'( The organic
phase containe' only Ga)
9
/&hich &as hy'rate'0(
8n using this techni!ue accurately, it is necessary to consi'er possible
sources o$ errors( ) rather etensive su""ary o$ this techni!ue applie' to hy5
'rophilic actini'e co"pleation by practically all inorganic ligan's, as &ell as
a consi'erable nu"ber o$ &ea- organic aci's, has recently been presente'
B99a,99bC(
4.13 EFFECTS AND CORREATIONS
4ecause o$ the "any para"eters involve' in solvent etraction, che"ical as
&ell as physical, it is a 'i$$icult tas- to 'ra& reliable conclusions about the
reactions that are responsible $or the observe' 'istribution values( 8n the intro5
'uctory part o$ this chapter, section 4(2, the etraction reaction 'escribe' by K
e
&as sho&n to be a pro'uct o$ a nu"ber o$ para"eters relate' to the 'i$$erent
steps involve' in the $or"ation o$ the etracte' co"ple( Sections 4(4L4(==
have 'escribe' these various subreactions, &hich are 'escribe' by E!( /4(4;0M
K K
7
K
#
K K /4(4;, 4(P40
e a 7 A: AC a',b4
Ea"ples o$ ho& K
e
'ata "ay be interprete' in "ore $un'a"ental ter"s $ollo&(
8n the lac- o$ in$or"ation on the in'epen'ent para"eters o$ E!( /4(P40, tenable
conclusions can be 'ra&n about their si7e an' e$$ects $ro" -no&n correlations
bet&een the para"eters( This section eplores the e$$ect o$ such correlations(
4.13.1 Effects of the Dissociation Constant
of $ci%ic Ligan%s an% &ormation Constants
of the Corres6on%ing (eta" Com6"exes
4.13.1.1 The Lig!" #A$i"% Di&&'$i(i'! C'!&(!( K
a
)ccor'ing to E!( /4(P40 K
e
increases to the # po&er o$ the 'issociation constant,
K
a
, $or the etractant aci' K)( Thus it appears 'esirable to use stronger aci's
as etractants, i(e(, those &ith large K
a
/or s"all pK
a
0( Thus $actors that a$$ect
the 'issociaton constant o$ an aci' are o$ i"portance $or etraction behavior(
The aci'ity o$ organic aci's increases /i(e(, pK
a
'ecreases0 by electrophilic
substitution in the carbon chain( For ea"ple, replacing an K ato" in the CK
9
group o$ acetic aci' /pK
a
4(PJ0 by 8, 4r, Cl, an' F ato"s yiel's "onohali'e
acetic aci's &ith pK
a
o$ 9(0, 2(>, 2(F, an' 2(P, respectively( The "ono5, 'i5,
an' trichloroactic aci's have pK
a
2(F, =(4F, an' about =(=, respectively( 6ther
a
+
7
electrophilic groups &hich can increase aci'ity are K6R, HCR, H6
2
R, etc(
Conversely, nucleophilic substitution by aliphatic or aro"atic groups usually
has little e$$ect on the pK
a
, though it "ay a$$ect the 'istribution constant K
A:
/see section 4(=9(20M e(g(, the a''ition o$ a CK
9
R or C
;
K
J
R group in acetic aci'
changes the pK
a
to 4(> /propionic aci'0 an' 4(9 /phenyl acetic aci'0( The $urther
the substitution is $ro" the carboylic group, the less the e$$ectM e(g(, &hile pK
a
$or ben7oic aci' is 4(=>, a Cl in orthoposition yiel's pK
a
2(>2 an' in the parapos5
ition, 9(>F(
These general rules hol' rather &ell $or the aci'ic organic etractants an'
can be use' to etrapolate $ro" relate' co"poun's to ne& ones as &ell as to
'evelop ne& etractants( The e$$ect o$ various substituen's on pK
a
is etensively
'iscusse' in tetboo-s on organic che"istry Be(g(, =4, 94C(
4.13.1.) The C'*+,e- .'/*(i'! #'/ S(0i,i(1%
C'!&(!(
!
K
e
also increases &ith increasing $or"ation constant o$ the uncharge' "etal
co"ple,
7
( Ther"o'yna"ic $actors an' geo"etrical aspects that in$luence the
si7e o$
n
are 'iscusse' in Chapter 9( So"e $urther observations $ollo&(
To achieve the highest possible D value, the concentration o$ the etracte'
uncharge' co"ple /<)
7
, <)
7
4
b
or 4
b
<L
7+b
0 "ust be "ai"i7e'( ) large
value $or the $or"ation constant o$ the neutral co"ple $avors this goal( 8n
Chapter 9 it &as pointe' out that $or har' aci's the co"ple $or"ation constant
increases &ith the charge 'ensity o$ the "etal ion, provi'e' there is no steric
hin'rance( This is seen $or the "etal $luori'e co"plees in Fig( 9(4 /no steric
hin'rance0( For the lanthani'e acetylacetonates in Fig( 4(=Jb, the increase in
n
$ro"
JP
La to
;4
G' is 'ue to a re'uction in the ionic ra'ius an', accor'ingly, to
the increase' charge 'ensity( 8t shoul' be note' that the 'i"inishing lanthani'e
si7e lea's to a successive 'i"inution o$ the coor'ination nu"ber /$ro" > to F
$or K
2
60 $or La G'1 $or G' Lu the coor'ination nu"ber is probably
con5 stant, as is in$erre' $ro" Fig( 4(=Jc1 see also B9JC(
4.13.1.3 C'//e,(i'!& Be(2ee! K

!"
!
4ecause the K
+

ion acts as a har' "etal ion, one shoul' epect a close correla5
tion bet&een the $or"ation constants $or K) an' $or <)
7
( Since K
a
is 'e$ine'
as the dissociation constant o$ K), &hile
7
is the formation constant o$ <)
7
,
a correlation is there$ore epecte' bet&een pK
a
/ logK
a
0 an' log
7
( The corre5
lations in Figs( 9(J an' 9(; sho& that large log
n
values are usually observe'
$or organic aci's &ith large logK
a
( Since K
e
is 'irectly proportional to both
7
an' K
7
Bsee E!( /4(P40C, an' a large value is li-ely to be acco"panie' by a
s"all K
a
value /large pK
a
01 in E!( /4(P40 the t&o para"eters counteract each
other( Thus in or'er to obtain high $ree ligan' concentrations, &hich $avors the
$or"ation o$ the <)
7
co"ple, BK C "ust be lo&, i(e(, pK "ust be high( Ko&5
ever, at high pK the "etal "ay be hy'roly7e'( ) care$ul balance "ust be struc-
bet&een
7
, K
a
, an' pK to achieve an opti"u" "ai"u" concentration o$ the
uncharge' co"ple(
4.13.2 Effects of (o"ecu"ar ;o"ume an% .ater
'tructure 6on <
D
Chapters 2 an' 9 $actors are 'iscusse' &hich a$$ect the 'istribution o$ uncharge'
species bet&een the organic an' a!ueous phases, the "ost i"portant being /=0
the interaction o$ the species /co"ple or etractant0 &ith the solvents /solva5
tion01 an' /20 energy release' or re!uire' &hen an uncharge' species leaves its
original phase /cavity closure0 an' that re!uire' &hen it enters the ne& phase
/cavity $or"ation0( Sections 4(4 an' 4(J 'iscuss the 'istribution o$ inert species,
inclu'ing un'issociate' aci' K), K
A:
( Fro" E!( /4(P40 it is seen that K
e
is
negatively in$luence' by a large 'istribution constant $or the etractant reagent,
but $avore' by a large K
AC
$or the etraction o$ the "etal co"ple(
4.13.).1 Me(, C'*+,e-e&3 K
DC
There are rather li"ite' 'ata on syste"atics $or the 'istribution constants K
AC
o$ "etal co"plees( Table 4(=0 gives 'istribution constants $or Yn/880, Cu/880,
an' Hp/8O0 acetylacetonates in various solvents( The 7inc co"ple has an octa5
he'ral coor'inationM $our oygen ato"s $ro" the ligan's an' t&o oygen ato"s
$ro" &ater "olecules can occupy si positions in an al"ost spherical geo"etry
aroun' the 7inc ato"( The copper co"ple has a s!uare planar con$iguration
&ith $our oygen ato"s $ro" the acetylacetones in the plane1 a $i$th /an' possi5
bly sith0 position perpen'icular to the plane an' at a longer 'istance $ro" the
copper ato" can be occupie' by an oygen $ro" a &ater "olecule( The 7inc
co"ple has a larger 'egree o$ hy'ration in the a!ueous phase an' conse!uently
a lo&er 'istribution constant( The Hp)
4
structure is li-ely a s!uare antipris"
&ith no hy'rate &ater( 8t has a larger "olecular volu"e than the t&o other
co"plees, an' its larger 'istribution constant is in agree"ent &ith this, re$lect5
ing the release o$ "ore &ater structuring energy &hen leaving the a!ueous
phase(
T&o $urther observations can be "a'e $ro" Table 4(=0M /=0 the 'istribu5
tion constant see"s to increase &ith increasing polarity o$ the solvent1 /20 &hen
the reagent acetylacetone has a large K
D'
, the "etal co"plees also sho& a large
K
D$
value(
The lanthani'e ions, Ln
9
+
, are -no&n to contract &ith increasing ato"ic
nu"ber /Y0, $ro" La
9
+

&ith a hy'rate' ra'ius o$ =09 p" to Lu
9
+

o$ F; p"
/lanthani'e contraction0( Thus one epects that the neutral Ln)
9
co"ple be5
co"es s"aller &ith increasing ato"ic nu"ber, an' conse!uently that
9
shoul'
increase an' K
AC
'ecrease &ith increasing Y( Figure 4(=J' sho&s that "easure'
A ,
,
K
AC
values $or the lanthani'e acetylacetonates are the reverse $ro" that epecte'
$or the si7e e$$ect( The eplanation is li-ely that the neutral co"ple &ith the
$or"ula Ln)
9
is coor'inatively unsaturate', &hich "eans that a hy'rate' co"5
ple eists in the a!ueous phase /possibly also in the organic phase0( The "ore
coor'inatively unsaturate' lanthani'e co"plees /o$ the larger ions0 can acco"5
"o'ate "ore &ater an' thus are "ore hy'rophilic( The result is a K
AC
several
or'ers o$ "agnitu'e lo&er $or the lightest, La, than $or the heaviest, Lu(
The tetravalent "etal acetylacetonates B9;C have all coor'ination nu"bers
/CH0 F or > in the neutral co"plees( For Th /ra'ius =0> p" at CH >0 there is
o$ten one "olecule o$ &ater in Th)
4
, &hereas $or the correspon'ing co"plees
o$ #/8O0 an' Hp/8O0 /ra'ius =00 an' >F p", respectively, CH F0, there see"s
to be none( The "easure' 'istribution constants /log K
AC
0 are $or Th 2(JJ an'
$or # an' Hp 9(J2 an' 9(4J, respectively, in = < HaCl6
4
Nben7ene( This agrees
&ith the greater hy'rophilic nature o$ the Th)
4
K
2
6 co"ple(
4.13.).) C'//e,(i'!& Be(2ee! K
DR
!" K
DC
[ualitatively, the 'istribution constants o$ the co"pleing reagent an' the corre5
spon'ing neutral "etal co"ple are relate' 'ue to their si"ilar outer sur$ace
to&ar' the solvents( Thus it is reasonable that there shoul' be goo' correlation
bet&een K
A:
an' K
AC
$or ho"ologous series o$ reagents or co"plees( This is
in'ee' the case, as is seen &hen K
A,:
is plotte' vs( K
A,C
, in Fig( 4(20 $or a
co"ple &ith a variation o$ the solvent, an' in Fig( 4(2= $or co"plees o$
relate' reagents &ith the sa"e solvent( This correlation can be relate' to the
solubility para"eter concept 'iscusse' later(
4.13.3 The 'o"ubi"it! *arameter
8n Chapter 2 &e learne' that the cohesive $orces that -eep "olecules together
in a solution can be 'escribe' by
2
/% RT 0 N
,
/2(=1 4(PJa0
&here
2
is the cohesi"e energy density, an' , the solubility parameter, ,, the
"olar volu"e an' %
,
, the "olar heat o$ vapori7ation( This hol's $or regular
solutions B9PC that sho& i'eal entropy e$$ects in "iing solute an' solvent, an'
no interactions occur besi'es the cohesive $orces bet&een the solute an' solvent
"olecules( BHoteM :egular solutions ehibit heat changes &hen "ie', &hile $or
i'eal solutions, the heat o$ "iing is 7ero /see section 2(4(=0(C There is no
change o$ state in association or in orientation( Thus the &or- re!uire' to pro5
'uce a cavity, G
cav
, by the solute in the solvent is given by
G
cav
2
cav 4
/2(=01 4(PJb0
&here A
cav
is a proportionality $actor an' ,
4
is the "olar volu"e o$ the solute 4(
+ +
Fig. 4.2+ Aistribution constants K
AC
$or uncharge' "etal co"plees <)
7
, vs( 'istribu5
tion constants K
A:
$or the correspon'ing un'issociate' reagent, the aci' ligan' K), $or
various organic solvents an' = < HaCl6
4
M open circles Cu/880, soli' circles Yn/880( Hu"5
bers re$er to solvents liste' in Table 4(=0( /Fro" :e$( 9;(0
,ioneering &or- on the application o$ this theory $or correlating an' pre5
'icting 'istribution ratios &as 'one in the =>;0s B9FaL40cC( Several revie&s on
the use o$ this theory $or t&o5phase 'istribution processes are also available
B4=,42C( :ecently this theory has been re$ine' by the use o$ %ansen solubility
parameters B;,49,44C, accor'ing to &hich
2 2 2 2
total 'ispersion polar hy'rogen
/4(PJc0
&here interactions bet&een the solute an' the solvent are 'escribe' by contribu5
tions $ro" the various types o$ cohesive $orces( 8n general, the 'ispersion /or
Lon'on0 $orces 'o"inate( 8n Fig( 4(22 the "easure' 'istribution ratios o$ an
a"ericiu" co"ple bet&een an a!ueous nitrate solution an' various organic
solvent co"binations are co"pare' &ith 'istribution ratios calculate' $ro" tabu5
late' Kansen para"eter values B4JC(
Fe& solubility para"eters are available $or the "etal5organic co"plees
'iscusse' in this chapter( )nother approach is then necessary( The 'istribution
constant $or the reagent /etractant0, R, can be epresse' asM
Fig. 4.21 Aistribution constants, K
AC
, $or uncharge' "etal co"plees <)
7
vs( 'istribu5
tion constants K
A:
$or the correspon'ing un'issociate' aci' ligan' K)1 soli' circles
Yn/880, soli' triangles Co/8880( Oariation &ith ligan' co"positionM KF) hea$luoroace5
tylacetone, TF) tri$luoroacetylacetone, )) acetylacetone, FT) 25$uroyltri$luoroacetone,
TT) 25thenoyltri$luoroacetone, ,T) pivaloyltri$luoroacetone, 4F) ben7oyltri$luoroace5
tone, 4Y) ben7oylacetone( /Fro" :e$( 9;(0
org : : org a!
Fig. 4.22 Co"parison o$ "easure' an' calculate' 'istribution ratios D
)"
o$ a"erici5
u"/88805terpyri'ine5'ecanoic aci' co"plees bet&een 0(0J < KH6
9
an' various organic
solvent co"binations( The calculate' values are obtaine' &ith the Kansen partial solubil5
ity para"eters( /Fro" :e$( 4J(0
RT ln K
A:
,
:
B/
a!

:
0
2
/ 0
2
C Q RT , /=N , =N , 0 /4(P;0
&here K
A:
is given in ter"s o$ "ole $ractions( The solubility para"eter o$ &ater
has to be e"pirically esti"ate'( The ther"o'yna"ic value is 4F, but, since the
syste" "ay be sensitive to the choice o$
a!
, it is better to select a 2re$erence
a!
3
in each set o$ eperi"ents, assu"ing constant values $or the a!ueous syste"s in
the t&o 'i$$erent t&o5phase syste"s( <olar volu"es an' solubility para"eter
values are liste' in Table 2(= an' :e$s( B;,44C(
The overall enthalpy an' entropy changes $or the 'istribution reaction
/i(e(, trans$er o$ the "etal co"ple $ro" the a!ueous to the organic phase0 can
be obtaine' $ro" the te"perature 'epen'ence o$ K
A:
accor'ing to
R T ln K
A:
% + T
&
/4(PP0
2 2
)n enthalpy ter" correspon'ing to ,
:
B/
a!

:
0 /
org

a!
0 C an' an entropy
ter" correspon'ing to R ,
:
/=4,
org
=N,
a!
0 can be obtaine' $or"ally $ro" E!(
/4(P;0( 8$ the 'istribution constant $or a stan'ar' syste" is use' as a re$erence,
changes in enthalpy an' entropy relative to this stan'ar' syste" can be assesse'
by replacing
a!
an' ,
a!
&ith the correspon'ing 'ata $or the organic 'iluent in
the re$erence syste",
re$
an' ,
re$
(
org org
Thus $ro" solubility para"eters, &hich are speci$ic $or the various solutes
an' solvents, an' "olar volu"es, values $or K
A:
can be esti"ate', or 'eviations
$ro" regularity can be assesse'( These 'eviations can be esti"ate' !uantita5
tively an', in in'ivi'ual syste"s, can be ascribe' to speci$ic reactions in either
o$ the phases, e(g(, hy'ration, solvation, a''uct $or"ation, etc(
Fro" E!( /4(P;0 the relation
log K
AC
/,
C
N ,
:
0 log K
A:
+
const(
/4(PF0
can be 'erive'1 the subscript $ re$ers to the neutral "etal co"ple( The "olar
volu"e ratio is close to or s"aller than #, &here # is the nu"ber o$ singly
charge' anionic species attache' to the central "etal ion <
7
+
( Fro" Fig( 4(29 a
ratio o$ ca( =(J /$or # 20 is obtaine'( This e!uation is use$ul $or esti"ating K
A:
values in etraction syste"s &here the correspon'ing K
AC
value is -no&n(
:earrange"ent o$ E!( /4(PJ0 sho&s that log K
A:
N/
a!

org
0 vs( , &here
RT / 0
=
/,
=
,
=
0 /4(P>0
org a! org org a!
shoul' yiel' a straight line &ith slope ,
:
N RT ln=0( ) plot o$ this relation in
Fig( 4(29 'e"onstrates a satis$actory correlation bet&een 'istribution constants
an' solvent para"eters, in'icating the use$ulness o$ the solubility para"eter
concept in pre'icting K
A:
as &ell as K
AC
values(
Fig. 4.23 )pplication o$ the regular solution theory $or correlation o$ 'istribution con5
stants $or Yn)
2
an' Cu)
2
&ith solvent properties /solubility para"eters01 the nu"bers
re$er to the solvents liste' in Table 4(=0( /Fro" :e$( 22(0
4.13.4 Effects of the 'o"=ent 0Di"uent2 Com6osition
The co"position o$ the organic phase solvent /'iluent0 in$luences the 'istribu5
tion o$ both the neutral "etal organic co"ple <)
7
an' the co"pleing reagent
K), through si"ilar interactions ranging $ro" that o$ cavity $or"ation $or very
inert 'iluents li-e heane, through 'ipole5'ipole interactions, pi electron interac5
tion, an' hy'rogen bon'ing $or the "ore reactive solvents( The epecte' 'egree
o$ interaction can be Du'ge' $ro" values o$ per"ittivity an' solubility para"e5
ters( ,revious tables have illustrate' so"e o$ these aspectsM Table 4(= on the
'istribution o$ inert solutes /hole $or"ation0, Table 4(P on 'istribution o$ organic
aci's /polarity0, an' especially Table 4(=0 on 'istribution o$ "etal acetylaceto5
nates /solvent per"ittivity0, 'iscusse' in section 4(=9(2(=( These cases involve
the a!ueous phase, so so"e pheno"ena "ay be attribute' to the interaction &ith
&ater "olecules(
Figure 4(24 sho&s a 'ecrease in K
A
$or acetylacetone &ith increasing nu"5
ber o$ "ethyl groups in the substitute' ben7ene solvent( Since acetylacetone is
"ore soluble in aro"atics than in aliphatics, as illustrate' by the K
A:
se!uenceM
Fig. 4.24 Aistribution constants K
A:
o$ acetylacetone bet&een "ethyl5substitute' ben5
7enes at 'i$$erent a!ueous ionic strengthsM /a0 0(00= <, /b0 0(= <, an' /c0 =(0 < HaCl6
4
at 2JC( The nu"ber o$ "ethyl groups, n, changes the aro"atic character at n 0 to
"ore aliphatic at n 9( /Fro" :e$( 4;(0
heane 0(>J, cycloheane =(09, ethylben7ene 9(9=, an' ben7ene J(>9 /a!ueous
phase = < HaCl6
4
0, the 'ecrease observe' in Fig( 4(24 "ay si"ply be an e$$ect
o$ the increasing aliphatic character o$ the solvents(
4.13.> Effects of the $:ueous (e%ium
The e$$ect o$ the &ater activity o$ the a!ueous phase, 'iscusse' in Chapters 2,
9, an' ;, is 'eter"ine' by the total concentration an' nature o$ the salts( Gener5
ally, the 'istribution constant $or a neutral "etal co"ple &oul' increase &ith
increasing ionic strength, as illustrate' in Fig( 4(2J( This salting5out effect is
o$ten ascribe' to a re'uction in $ree &ater available $or hy'ration( 6n the other
han', the salt also brea-s 'o&n the &ater structure, &hich coul' re'uce the
energy to $or" a hole in the phase(
4.13.) Effects of the Tem6erature
The intro'uction o$ a neutral co"ple into a solution phase involves a nu"ber
o$ processes that can be associate' &ith large changes in enthalpy /solvation
processes0 an' in entropy /solvent orientation an' restructuring0, lea'ing to con5
si'erable te"perature e$$ects1 see Chapter 2( 8n general, the 'istribution o$ a
neutral "etal co"ple increases &ith increasing te"perature $or co"plees &ith
signi$icant hy'rophobic character( The "etal acetylacetonate syste"s in Fig(
4(2; illustrate this e$$ect( 8n these particular syste"s, the $ree energy o$ 'istribu5
tion bet&een the organic an' a!ueous phases is 'o"inate' by the enthalpy ter"(
Fig. 4.2$ The 'istribution constant K
AC
$or 7inc 'iacetylacetonate, Yn)
2
, bet&een ben5
7ene an' various concentrations o$ HaCl6
4
in the a!ueous phase1 2JC( /Fro" :e$( 9;(0
Fig. 4.2% Aistribution constant K
AC
$or "etal 'iacetylacetonates, <)
2
, bet&een or5
ganic solvents an' = < HaCl6
4
as a $unction o$ te"peratureM Cu/880 /open circles0 an'
Yn/880 /soli' circles0 &ith various solvents /nu"bers re$er to the solvents given in Table
4(=00( /Fro" :e$( 9;(0
Fro" "easure"ents o$ the te"perature 'epen'ency o$ the e!uilibriu"
constant, ther"o'yna"ic para"eters "ay be 'e'uce' /section 9(40( Oery $e&
enthalpy an' entropy constants have been 'erive' $or the 'istribution reaction
<)
7
/a!0

<)
7
/org0 o$ neutral co"plees1 such investigations give
in$or"a5
tion about hy'ration an' organic phase solvation(
4.13.- &urther 'tructura" Consi%erations
8n Chapters 2 an' 9 several physicoche"ical $actors o$ i"portance to solvent
etraction have been 'escribe', an' "any o$ their e$$ects have been illustrate'
in this chapter( Kere, &e su""ari7e so"e observe' regularities( The e$$ect o$
various structures on the bon' strengths in "etal organic co"plees has been
etensively treate' in other publications B4PL4>C(
4.13.4.1 Che,(e Ri!g Si5e
For"ation o$ "etal5organic chelate co"plees results in stronger co"pleation
/i(e(, larger
n
values0 co"pare' to interaction &ith "ono'entate ligan's /Chap5
ter 90( The co""on types o$ bi'entate ligan's are presente' in Table 4(>1 the
che"istry o$ these co"plees has been etensively 'iscusse' in the literature
B=4,4PC( Chapter 9 presents the "ost i"portant $actors in the $or"ation o$ such
co"pleesM /=0 the type o$ bin'ing ato"1 /20 the chelate ring si7e /or 2bite301
T46) 0(00J J BJ0C
T4<) =0(; ; BJ0C
T4S) >(9 P BJ0,J=C
A<A6<) 0(4P ; BJ2C
A<A6S) <0(0002 P BJ2C
2
2
2
2
e
an' /90 the nu"ber o$ chelate rings $or"e' /"ono5 or poly'entate0( The $ollo&5
ing 'iagra" illustrates the general structure o$ #6
2
+

an' )"
9
+

'ia"i'e chelate
co"pleesM t&o oygen bin'ing ato"s1 ring si7e is J + n, 2L9 chelate rings per
co"ple1 the R6R<R6R part is co""only re$erre' to as the 2cla&(3
X X
H C
n
K
2n
H
N ^ N ^ N ^
CK CK
6 6
^ N
<
The etractants T46), T4<), an' T4S) are very si"ilar, but their structural
'i$$erences /see $or"ulas in Table 4(=;0 allo& the $or"ation o$ only one type
o$ "etal chelate co"pleM J5, ;5, an' P5"e"bere' rings, respectively( Si"ilar5
ily, the reactants A<A6<) an' A<A6S) $or" only ;5 an' P5"e"bere'
chelates( Table 4(=; sho&s that etraction /i(e(, largest S
e
value0 is $avore' by
;5"e"bere' rings( This is not unepecte' as the K
e
values in this case re$lect
the stability constants
n
acc( to E!( /4(P40(
The electron shells o$ the <
9
+

ele"ents &ith un$ille' or partially $ille' 9',
4', an' J$ orbitals contract as these shells are being $ille' &ith electrons, in5
creasing the charge 'ensity /#4r0 o$ the cation, lea'ing to increasing stability
constants $or the <)
9
co"plees &ith increasing ato"ic nu"ber( For bi'entate
ligan's the f5electron /lanthani'e0 <)
9
co"plees are coor'inatively unsatu5
rate', i(e(, only si o$ eight available coor'ination sites are $ille'( There$ore, the
t&o re"aining sites are occupie' by K
2
6 or K) or so"e other 'onor "olecules
=
4, lea'ing to the sel$5a''uct <)
9
K) or a''uct <)
9
4
=L2
( 8t has been sho&n
that the a''uct $or"ation constants $or the reaction <)
9
+ 4 <)
9
4
'ecrease
Table 4.1% Consultants $or Etraction o$ )ctini'e )"i'es
$ro" Hitrate Solutions into an 6rganic Solvent Sho&ing the E$$ect
o$ Chelate :ing Si7e
<etal ion Etractant
a
K
#6
2+
#6
2+
#6
2+
)"
9+
)"
9+
:ing
si7e :e$(
a
T46) /C K 0 HC6 1 T4<) B/C K 0 HC6C CK 1 T4S) B/C K 0 HC6C /CK 0 1 4 > 2 2 4 > 2 2 2 4 > 2 2 2 2
A<A6<) /CK
9
C
F
K
=P
HC60
2
CK
2
1 A<A6S) /CK
9
C
F
K
=P
HC60
2
/CK
2
0
2
(
a 7 a
in the sa"e or'er B2PaL2FC, see Fig( 4(=J1 i(e(, the stronger the co"ple, the
&ea-er the a''uct(
The increase, by a''uct $or"ation, in the coor'ination nu"ber o$ the cen5
tral ato" is possible not only $or &ea- but also $or strong chelates, provi'e'
their ligan' bites are relatively short( To "a-e roo" in the inner sphere o$ the
"etal ion $or another a''uct5$or"ing ligan', three chelating ligan's o$ s"all
bite angle can easily be shi$te' a&ay &ithout signi$icant energy5consu"ing 'is5
tortion o$ the chelate rings BJ9a,bC( The electronic structure o$ the central ato"
is also o$ -ey i"portance $or synergis", as illustrate' by the easy a''uct $or"a5
tion o$ "etal ions &ith un$ille' or partially $ille' ' or $ orbitals, contrary to,
e(g(, p5bloc- ele"ents( 8nner5 an' outer5sphere co"pleation is $urther 'iscusse'
in the net t&o paragraphs an' in Chapter =;(
4.13.4.) D'!'/ Lig!" E66e$(&
Table 4(=P sho&s etraction constants $or so"e "etal ions &ith three al-yl
phosphates substitute' by 0, =, an' 2 sul$ur ato"s, but &ith al"ost i'entical
aliphatic branchings( Section 9(9 'iscusses har' an' so$t aci's an' bases /KS)4
theory0( )ccor'ing to this theory, har' aci's $or" strong co"plees &ith har'
bases, &hile &ea- aci's $or" strong co"plees &ith &ea- bases( 8n Table 4(=P,
the "etals are or'ere' in increasing har'ness, the sub 88(b group being rather
so$t /Table 9(20( ,resu"ably the K
e
values re$lect this pattern, as they are pro5
portional to K
7
an' ( 8n Table 4(=P, the aci'ity o$ the aci's increases /i(e(, K
increases0 in or'er ' ,SSK < : ,6SK < : ,66K /consult Tables 4(F an'
4(>0, as sul$ur is less basic than oygen( 8n general, the K
e
increases $or $or the
'ial-yl phosporic aci' /har' 'onor ligan'0 &ith increasing "etal charge 'ensity
&ithin each group as pre'icte' in Chapter 9( For the so$t "etals, K
e
also in5
creases &ith increasing so$tness o$ the ligan', &hile the opposite e$$ect is seen
$or the har' Ln5"etal ions( The 'ivalent subgroup 88(b "etals pre$er to bin' to
sul$ur rather than to oygen because they have a rather so$t acceptor character,
&hile the har' "etals 888(b pre$er to bin' to the har' 65ato" o$ the ligan'(
Table 4.1( Co"parison o$ the Etraction Constants K
e
$or the 88b5Subgroup Aivalent
8ons, an' 888b Lanthani'e 8ons, &ith Sul$ur or 6ygen Aial-yl ,hosphoric )ci's
a
<etal ion Kg
2
+
C'
2+
Yn
2+
La
9+
Eu
9+
Lu
9+
JP ;9 P=
Charge 'ensity Z
2
Nr 9(; 4(= J(4 P(F9 F(P4 >(;F
log K
e
$or ' ,66K 2(20 =(F0 =(20 2(J2 0(44 2(>
log K
e
$or /C
4
K
>
60
2
,6SK J(40 9(P0 0(P0 4(PF 4(29 0(94
log K
e
$or /C
4
K
>
60
2
,SSK 4(40 9(4> 2(40 F(2F
a
Oalues esti"ate' $ro" :e$s( J, 20, J4, JJ, an' J;( : is /C K CK/C K 0CK 60 ( 4 > 2 J 2 2
2 2 ;
2 2 ; 9
4.13.4.3 I!!e/ !" O7(e/ S+he/e C''/"i!(i'!

The etractabilities o$ "etal5organic co"plees 'epen' on &hether inner or
outer sphere co"plees are $or"e'( Case 8, section 4(2(=, the etraction o$ ura5
nyl nitrate by T4,, is a goo' ea"ple( The $ree uranyl ion is surroun'e' by
&ater o$ hy'ration, $or"ing #6 /K 60
2
+
, &hich $ro" nitric aci' solutions can
2+ 2
be crystalli7e' out as the salt #6
2
/K
2
60
;
/H6
9
0
2
, though it co""only is &ritten
2+
#6
2
/H6
9
0
2
/K
2
60
;
( Thus, in solution as &ell as in the soli' salt, the #6
2
is
surroun'e' by ; K
2
6 in an inner coordination sphere( 8n the soli' nitrate salt,
the 'istance d
#56
/nitrate0 bet&een the closest oygen ato"s o$ the nitrate anions,
/O0
2
HO, an' the #5ato" is longer than the correspon'ing 'istance, d
#56
/&ater0,
to the &ater "olecules, OK
2
, i(e(, d
#56
/nitrate0 > d
#56
/&ater01 thus the nitrate
anions are in an outer coordination sphere(
Ghen the a''uct $or"er T4, is a''e', the O,/6C
4
K
>
0
9
groups are closer
to the #5ato"s than the OK
2
+s, d
#56
/T4,0 < d
#56
/&ater0, t&o &aters are e5
pelle', although the O,5 bon' only occupies one coor'ination site( The charge
'istribution aroun' the #6
2
5group allo&s the nitrate group to enter the inner
coor'ination sphere o$ the uranyl co"ple( The resulting con$iguration is sho&n
in Fig( 4(2P( Thus, the etraction reaction can "ore correctly be &ritten
#6 /K 60
2Q
+ 2 H6

+ 2 T4,/org0
#6
2
/T4,0
2
/H6
9
0
2
/org0 + ;
K
2
6
/4(Jb0
8n "any syste"s it is 'i$$icult to 'istinguish bet&een inner an' outer
sphere co"pleation( 8n that case, -no&le'ge about the ther"o'yna"ic para"e5
ters % an' & "ay be o$ help( For inner sphere co"plees, the hy'ration is
'isrupte' "ore etensively an' the net enthalpy an' entropy changes are posi5
tive( 8n E!( /4(Jb0 it is note' that the nu"ber o$ entities increases $ro" $ive to
seven, an entropy increase( This entropy e$$ect /i(e(, T& 0 is obviously larger
than the enthalphy e$$ect, as the overall energy change G is negative( 8n outer
sphere co"plees, the 'ehy'ration is less 'isrupte', an' the net enthalpies an'
entropies are negative o&ing to the co"pleation &ith its 'ecrease in ran'o"5
ness &ithout a co"pensary 'isruption o$ the hy'ration spheres(
<igration eperi"ents have sho&n that the hy'rate' cations not only
carry &ith the" the &ater in the inner coor'ination sphere, but also one or "ore
shells o$ a''itional &ater "olecules, $or typical total values o$ =0L=J( Ghen the
"etal ion leaves the a!ueous phase in the solvent etraction step, this or'ere'
coor'inate' &ater returns to the bul- &ater structure, contributing an a''itional
$actor to consi'er in evaluating the ther"o'yna"ics o$ etraction(
4.13.4.4 S(e/i$ Hi!"/!$e
The closer the reactive ligan' ato"s get to the central "etal ion, the stronger
the bon', an', conse!uently, the greater the $or"ation constant( This can be
Fig. 4.2( Structure o$ the #6
2
/H6
9
0
2
2/C
2
K
J
60
9
,6( The uranyl oygens are situate'
perpen'icular to the plane sho&n aroun' the central ato"( /Fro" :e$( =2(0
e 2
2
9 4
9 4
9 4
9 4
e
stu'ie' by "a-ing substitutions in the organic ligan', &hich structurally inter5
$eres &ith the $or"ation o$ the co"ple( For ea"ple, Ayrssen BFC substitute'
oines /F5hy'roy!uinolinols0, )ppen'i A(; in various positions, Table 4(J,
an' "easure' their 'istribution constants, K
AC
( )lthough the pK
a
an' K
A,K)
in
Table 4(J 'i' not vary "uch &ith the substitution, the K
AC
$or the Th)
4
co"ple
&ith unsubstitute' oine &as 42J, an' $or the J5"ethyl substitute' co"ple
aroun' =000, &hile the 25"ethyl substitute' co"ple &as not etractable( This
can be attribute' to the 25"ethyl group bloc-ing the co"ple $or"ation(
Table 4(=F lists K values $or #6
2
+
an' ,u
4
+
&ith $our organophosphorous
etractants, T4, an' A64), an' Ti4, an' A6i4), the iso5$or"s being "ore
branche'( The 'ata in the upper hal$ o$ the table sho&s little change in K
e
&hen
T4, is replace' by Ti4,( Thus the branching has little e$$ect 'ue to the $ree
rotation o$ the substituents aroun' the phosphorous ato"( 8n the lo&er group,
the a"i'e A64), an' its branche' iso"er A6i4), the nature o$ :, : an' :
in ::HC6: is i"portant 'ue to the "olecular rigi'ity o$ the a"i'e group( The
branche' substituent strongly 'epresses the etraction constant, &hich li-ely is
'ue to a "uch lo&er stability constant $or the branche' co"ple( This e$$ect is
"ore pronounce' $or ,u/8O0 than $or #6
2
+
( 8n a search $or selective syste"s
$or separating trivalent actini'es $or" $ission lanthani'es, SpDuth et al( BJ>C in5
vestigate' the etraction o$ trivalent ions $ro" a!ueous KH6
9
solutions contain5
ing 25bro"o'ecanoic aci' /K4A)0 by "eans o$ terphenyl an' tria7ine 'eriva5
tives 'issolve' in the organic 'iluent tert5butylben7ene /T440( Figure 4(2F
sho&s the 'istribution ratio o$ the syste" as a $unction K4A) in T44 &ith an'
&ithout the terpyri'ine /$or"ula in Fig( 4(2>0( This is an illustration o$ the
Table 4.1) Constants $or Etraction o$ )ctini'e Hitrate )''ucts &ith
,hosphoric )ci' Trial-ylesters /Free :otation o$ the P Substituents0 an'
&ith ),)5Aial-yla"i'es /:estricte' :otation )roun' the )"i'e <oiety0
Sho&ing the E$$ect o$ Steric Kin'rance
Co"ple in Etraction
<etal ion Etractant organic phase
a
constant K :e$(
#6
2+
T4, #6 /H6 0 /T4,0 2F(9 BJPC
2 2 9 2 2
#6
2+
Ti4, #6 /H6 0 /Ti4,0 2; BJPC
2 2 9 2 2
,u
4
+

T4, ,u/H6 0 /T4,0
2
==(P BJPC
,u
4+
Ti4, ,u/H6 0 /Ti4,0
2
F(> BJPC
#6
2+
A64) #6 /H6 0 /A64)0 J(PJ BJFC
2 2 9 2 2
#6
2+
A6i4) #6 /H6 0 /A6i4)0 0(JJ BJFC
2 2 9 2 2
,u
4
+

A64) ,u/H6 0
,u
4+
A6i4) ,u/H6 0
/A64)0
2
/A6i4)0
2
0(29J BJFC
0(009 BJFC
a
T4, /C K 0 ,61 Ti4, B/CK 0 CKCK 6C ,61 A64) BC K CK/C K 0CK C HC6C K 1 4 > 9 9 2 2 9 4 > 2 J 2 2 9 P
A6i4) BC
4
K
>
CK/C
2
K
J
0CK
2
C
2
HC6CK/CK
9
0
2
(
Fig. 4.2) Etraction o$ Eu/8880 an' )"/8880 $ro" S,KH6
9
&ith 0(02 < oligopyri'ine
or tria7ine an' = < 25bro"o'ecanoic aci' in tert5butylben7ene( /Fro" :e$( J>(0
necessity to achieve synergistic e$$ects by using a''uct $or"ers $or etraction
o$ "etal ions that other&ise are too strongly hy'rate' to be etractable( The
structures o$ the terphenyls /a''uct $or"ers0 teste' are liste' in Fig( 4(2> &ith
the 'istribution ratios achieve' $or )"/8880, D
)"
( For ea"ple, in the syste"
&ith A6A6V_, D
)"
is 4(2, &hile &ith T)A,TY it is 9J>( The tria7ine T)A5
,TY is "ore branche' /the terphenyl A6A6V_ "ore linear0 an' has a slightly
larger "olar volu"e, but the 'i$$erence "ay also be attribute' to the greater
basicity /i(e(, s"aller K
a
0 co"pare' to terphenyl( Ko&ever, the =00 ti"es larger
Fig. 4.2* Structure o$ various oligopyri'ine an' tria7ine a''ucts, an' 'istribution ra5
tios /inserts0 $or )"/8880 co"plees &ith these oligopyri'ines /0(02 <0 an' 25bro"o'e5
canoic aci' /0(0002J <0 in tert5butylben7ene an' 0(0= < KH6
9
( /Fro" :e$( J>(0
etraction by the tria7ine cannot be eplaine' by the KS)4 theory1 various
eplanations are suggeste' BJ>C( Steric hin'rance can be pre'icte' by "o'eling
the "olecular structures an' che"ical reactions( )'vance' progra"s re!uire
"ain$ra"e co"puters, but use$ul progra"s are available $or 'es-top co"puters
B4>C(
4.14 CACUATION OF E,UII'RIUM CONSTANTS
Earlier sections presente' che"ical "o'els $or the etraction o$ aci's an' "etals
into organic solvents, an' sho& that these "o'els, epresse' "athe"atically,
agree &ith eperi"ental 'ata at trace "etal concentrations an' at constant activ5
ity coe$$icients( These "o'els provi'e a rationale $or un'erstan'ing the che"i5
cal principles o$ solvent etraction(
Fro" plots o$ the 'istribution ratio against the variables o$ the syste"E
B<C, pK, BK)C
org
, B4C, etc(Ean in'ication o$ the species involve' in the solvent
etraction process can be obtaine' $ro" a co"parison &ith the etraction curves
presente' in this chapter1 see Fig( 4(9( So"eti"es this "ay not be su$$icient,
an' so"e a''itional "etho's are re!uire' $or i'enti$ying the species in solvent
etraction( These an' a su""ary o$ various "etho's $or calculating e!uilibriu"
constants $ro" the eperi"ental 'ata, using graphical as &ell as nu"erical tech5
ni!ues is 'iscusse' in the $ollo&ing sections( Calculation o$ e!uilibriu" con5
stants $ro" solvent etraction is 'escribe' in several "onographs B;0L;4C(
4.14.1 I%entification of '6ecies
)n initial step in 'ata analysis is to 'evelop an e!uation that represents the
eperi"ental 'ata reasonably( )lthough previous sections 'ealt &ith this issue,
the approach assu"e' that certain species are $or"e'( T&o alternatives to this
proce'ure are 'iscusse' here, both yiel'ing the approi"ate stoichio"etry o$
the co"plees $or"e' in the syste"( The "ost ele"entary is re$erre' to as 5ob6s
method, &hile the ligand number method, 'evelope' by .( 4Derru", is slightly
"ore a'vance'(
4.14.1.1 J'08& Me(h'"
Ghen a "etal < &ith a ligan' ) $or"s an etractable co"ple o$ the che"ical
$or" <
"
)
a
, the etraction is at "ai"u" &hen the "olar ratio o$ these t&o in
the syste" is "Ma( Si"ilarily, i$ the etracte' species is <)
a
4
b
, a plot o$ the
"ole ratios o$ ) an' 4 yiel's a "ai"u" at the ratio aMb( This is illustrate' in
Fig( 4(2 $or the etraction o$ #/O80 in the TT)5T4, /or T4,60 syste"( The
curves are al"ost sy""etrical aroun' the "ole $ractions 0(JM0(J, in'icating that
the etracte' species has a =M= ratio o$ TT) to T4,( 4ecause the co"ple "ust
contain 2 TT) /$or electroneutrality0, there shoul' also be 2 T4, /or T4,60
"olecules in the co"ple, i(e(, <)
2
4
2
(
2
This "etho' is use$ul &hen only one species is etracte', but it has little
value $or the stu'y o$ solvent etraction syste"s that contain several co"ple
species(
4.14.1.) Lig!" N7*0e/ Me(h'"
This "etho' B;JL;PC is use$ul $or i'enti$ying the average co"position o$ the
"etal species in the syste"( Consi'er E!( /4(9;a0 $or the etraction o$ <)
7
, an'
assu"eE$or the "o"entEthat only one species, <)
n
, eists in the a!ueous
phase( Ta-ing the 'erivative o$ the logarith" o$ E!( /4(9;0 yiel's
d log D N d log B)C #
n
/4(F00
8n =>4=, .( 4Derru" B;JC 'evelope' the use$ul concept o$ a"erage ligand num!
ber, n7 , 'e$ine' as the "ean nu"ber o$ ligan's per central ato"M
n n B<)
n
C NB<C
t
/4(F=0
8t can be sho&n B;;aL;PC that n7 e!uals n in E!( /4(P>0, &hich can be re&ritten
n # d log D N d log
B)C
/4(F20
For ea"ple, in Fig( 4(=0 /Ea"ple 90, the slope o$ the plot o$ log D
Cu
vs( log
B)
C can be use' to conclu'e &hat species 'o"inate the syste" at a given B)
C
value( The relation in E!( /4(F20 in'icates an asy"ptote o$ slope 2, so the a!ue5
ous phase is 'o"inate' by unco"plee' Cu
2
+

/n 00, &hile $or slope 0 the
neutral co"ple Cu)
2
'o"inates the syste" /n 20( E!uation /4(F20 sho&s that
any tangent slope o$ the curve /i(e(, d log D N d log B)C0 yiel's the 'i$$erence
# n7 in these si"ple syste"s(
Ea"ple =2M Etraction o$ Th/8O0 by acetylacetone(
Figure 4(90 sho&s a s"oothe' curve o$ "easure"ents o$ the 'istribution
o$ Th/8O0 $ro" 0(= < HaCl6
4
into chloro$or" containing the etractant acetyl5
acetone /K)0 B;;a,bC( Ta-ing the 'erivative o$ this curve accor'ing to E!(
/4(P>0 the average ligan' nu"ber is 'erive' as sho&n in the lo&er insert(
Th/8O0 is successively co"plee' by )

$or"ing Th)
9
+
, Th)
2
+
, Th)
+

an' un5
2 9
charge' Th)
4
, &hich is etracte'( )t p) > F(J the n7 5value is 7ero, i(e(, Th
is unco"plee', &hile at p) < 9(J the average ligan' nu"ber o$ 4 is
reache',
i(e(, Th is $ully co"plee' as Th)
4
( See also Ea"ple =J(
The average ligan' nu"ber can be use' to obtain approi"ate e!uilibriu" con5
stants, as 'escribe' by B;JC, assu"ing that at hal$ integer n7 5values the t&o
a'Da5 cent co"plees 'o"inateM e(g(, at n7 0(J the species <
7
+

an' <)
7
=
'o"inate, &hile at n7
=(J <)
7
=
an' <)
7
2
'o"inate, etc(( The $ollo&ing
epression $or the step&ise $or"ation constant is approi"ately vali' at
n n 0(J, log K
n
log B)C
n
/4(F90
This "etho' o$ obtaining an esti"ate o$ the $or"ation constants &as 'one as a
$irst step in the Th/8O05acetylacetone syste" in Fig 4(90, &here in the lo&er
n
Fig. 4.3+ #pper curveM the 'istribution o$ Th/8O0 bet&een ben7ene an' 0(= < HaCl6
4
as a $unction o$ a!ueous acetylacetonate ion concentration1 p) logB)
C1 the asy"p5
totes have slopes 0 an' 4( Lo&er curveM The average nu"ber o$ ligan's per central
ato", n7 , in sa"e syste", as obtaine' $ro" a 'erivation o$ the log D/p)0 curve(
#sing the ligan' nu"ber "etho', the $ollo&ing e!uilibriu" constants &ere esti"ate'
/&ith values $ro" graphical slope analysis &ithin parenthesis0M logK
=
F(0 /P(FJ0,
logK
2
P(; /P(P0, logK
9
;(4 /;(90, an' logK
4
J(= /J(00( Log K
A4
2(J0 is obtaine' $ro" the
hori7ontal asy"ptote( /Fro" :e$s( ;;a,b(0
$igure, n7 is plotte' against log B)
C, yiel'ing the preli"inary log

K
values
given in Fig( 4(9( 8n a si"ilar "anner, the a''uct $or"ation constants can be
'eter"ine'M
Ea"ple =9M The etraction o$ Yn/880 by 5'i-etones an' phosphoryl a''uct
$or"ers /cont( o$ Ea"ple J0(
Consi'er the $or"ation o$ a''ucts o$ the type <)
7
4
b
, as 'escribe' in
Ea"ple J /Fig( 4(=20( The 'erivative o$ E!( /4(4Fb0 &ith respect to B4C at
constant B)C yiel's
d log D N d log B4C
b
/4(F40
&here b is the average nu"ber o$ a''uct $or"ing "olecules in the "olecule
at given BC value( 8n Fig( 4(=2 the asy"ptote has a slope o$ 2, in'icating that
a "ai"u" o$ t&o "olecules o$ T4, /or T6,60 bin' to the neutral "etal
co"ple( Fro" the lo&er slopes o$ the curve, the average nu"ber, b, can be
esti"ate' accor'ing to E!( /4(F90(
2
4.14.2 ?ra6hic '"o6e $na"!sis
For a rational application o$ slope analysis it is i"portant to "easure the varia5
tion o$ the 'istribution ratio D &ith one co"ponent x at a ti"e &hile the others,
$, are -ept constant( The solvent etraction e!uation can then be epresse' in
the $or" o$ a si"ple polyno"ial o$ type
y a
0
+ a
=
x + a
2
x
+ L /4(FJ0
&here y is a $unction o$ the 'istribution ratio D
const(C
an' x a $unction o$ the
variable /e(g(, pK, the $ree ligan' ion concentration B)
C, the concentration o$
$ree etractant K) or a''uct $or"er 4 in the organic phase, etc(0(
4.14.).1 Li!e/ P,'(&
Ghen the 'istribution e!uation can be epresse' in the $or" y a
0
+ a
=
x, $ro"
a plot o$ y vs( x the intercept on the y ais yiel's the a
0
para"eter an' the slope
the a
=
para"eter( This treat"ent is re$erre' to as the limiting "alue method(
Ea"ple =4M The etraction o$ Cu/880 by KTT) /cont( $ro" Ea"ple 40(
Ea"ple 4 /Fig( 4(==a0, is represente' by E!( /4(440, &hich in logarith5
"ic $or" is &ritten
log D
log K + 2 log BK)C + 2 pK
/4(F;0
Cu e org
For constant BK)C
org
/Fig( 4(==a0, a plot o$ log D
Cu
vs( pK yiel's a line o$ slope
2, &hich intercepts pK 0 at log D
Cu
log K
e
+ 2log BK)C
org
( )nother plot o$
log D
Cu
against log BK)C
org
at constant pK yiel's a line that intercepts BK)C
org
0 at log D
Cu
log K
e
+ 2pK /Fig( 4(==b0( 8n either case, the KTT) syste"
yiel's log K
e
=(2J $or the CKCl
9
, an' =(0F $or the CCl
4
syste"( The corre5
spon'ing values $or the 8,T syste" are =(;0 an' 0(>J, respectively(
Ea"ple =JM Etraction o$ Th/8O0 by acetylacetone /cont( $ro" Ea"ple =20(
8n Ea"ple =2, it &as conclu'e' $ro" Fig( 4(90 that the a!ueous phase
containe' all Th)
n
5co"plees &ith 0 < n < 4, an' the organic phase only the
uncharge' Th)
4
co"ple( Ge can there$ore &rite the 'istribution o$ Th/8O0
bet&een chloro$or" an' &ater
D BTh) C N BTh) C
K
B)C
4
N B)C
n
/4(FP0
Th 4 org n AC 4 n
This is rearrange' to yiel'
D
=
/ /= + a x
=
+ a x
2
+ a
x 9
+ a x
4
0 N K /4(FFa0
Th 0 = 2 9 4 AC
&here K
AC
is the 'istribution constant o$ Th)
4
, x e!uals B)C, an' a
4n

n
N
4
(
= =
8n a plot o$ /
0
against x , the intercept beco"es K
AC
an' the slope is a
=
NK
AC
(
8n the net step the $unction /
=
is calculate'
/ /K D
=
=0 x a + a x
=
+ a x
2
+
L
/4(FFb0
= AC = 2 9
2 = = 2 9 4
H
<
n
=
9
) plot o$ /
=
vs( x yiel's a
=
at the intercept an' a
2
as the slope( 8n thir' step,
/ // a 0 x a + a x
=
+ a x
2
is calculate', yiel'ing a
2
an' a
9
, etc( #sing
this techni!ue all $our a
n
values are obtaine', $ro" &hich one can 'e'uce the
n
values Bactually the K
n
values in E!( /9(J0C an' the K
AC
value(
Ayrssen an' Sille`n B;FC pointe' out that 'istribution ratios obtaine' by
conventional batch&ise techni!ues are o$ten too scattere' to allo& the 'eter"i5
nation o$ as "any para"eters as use' in Ea"ples =J an' =;( They suggeste'
a si"pli$ie' graphic treat"ent o$ the 'ata, base' on the assu"ption that there is
2b
a constant ratio bet&een successive stability constants, i(e(, K
n
NK
n+=
=0 , an'
that all 'istribution curves can be nor"ali7e' so that )
=
log a, &here ) is
the nu"ber o$ ligan's )

in the etracte' co"ple( Thus, the 'istribution curve
log D vs( logB)
C is 'escribe' by the t&o para"eters a an' b, an' the 'istribu5

tion constant o$ the co"ple, K
AC
( The principle can be use$ul $or esti"ations
&hen there is insu$$icient reliable eperi"ental 'ata(
4.14.).) N'!,i!e/ P,'(&
8t is not possible to obtain si"ple linear relations bet&een D an' the variables
&hen both the a!ueous or organic phase contain several "etal species( 8nstea'
a 'ouble polyno"ial such as
2 9 i
D 3
b
0
+ b
=
+ b
2
y + b
9
y +
L
b
i
y

2
a
0
+ a
=
x + a
2
x

+ a
9
x + L a x
n
/4(F>0
is obtaine' $or &hich there is no si"ple solution(
Ea"ple =;M Etraction o$ #/O80 by acetylacetone(
Fig( 4(9= sho&s the etraction o$ #/O80 by acetylacetone /%A0 $ro"
nitric aci' solutions, D
#
, as a $unction o$ p) log B) C at si 'i$$erent total
concentrations o$ K)( ) co"parison &ith Fig( 4(9 in'icates that &e can epect
co"plees o$ the type <)
n
/6K0
p
/K)0
r
, &hich $or"ally is e!uivalent to
K
r+p
<)
n+r
( The etraction reaction is o$ the type E!( /4(F;0, as one epects a
series o$ sel$5a''uct co"plees <)
n
/K)0
r
in the organic phase, an' one or
t&o series o$ step&ise co"plees <)
n
an' </6K0
p
in the a!ueous phase( Thus
the etraction reaction is o$ the type E!( /4(F>0 &ith a ratio o$ several polyno5
"ials( Even in this case, a graphic etrapolation techni!ue &as use$ul by 'eter5
"ining a set o$ inter"e'iary constants $or each constant BK)C
org
$ro" logD
#
vs( p)( ,lotting these inter"e'iate constants vs( BK)C
org
, a ne& set o$ constants
&ere obtaine', $ro" &hich both the step&ise $or"ation constants
n,p
an' the
a''uct $or"ation constants K
a', =
an' K
a',2
$or the reaction #6
2
)
2
/K
2
60
2L9
+
nK)

#6
2
)
2
/K)0
=L2
in the organic phase( ) "ore 'etaile' analysis
also al5
lo&e' the 'eter"ination o$ $or"ation constants $or #6
2
/6K0
p
/ p = an' 20(
There "ay be other eplanations to the etraction results( Ko&ever, &ith the
"o'el use' an' the constants calculate', log D
#
coul' be correctly pre'icte'
over the &hole syste" range B#C
tot
0(00=L0(9 <, pK 2LP, an' BK)C
org
0(0=L=(0
<( See also Ea"ple =P(
Fig. 4.31 Etraction o$ #/O80 by acetylacetone /K)0 $ro" 0(= < HaCl6
4
into chloro5
$or" as a $unction o$ pK at 'i$$erent total concentrations o$ K)( /Fro" :e$( ;>(0
x
i 2
4.14.3 #umerica" (etho%s
The "ost co"plicate' e!uations presente' in this chapter are o$ the types sho&n
by E!( /4(F>0, &here a series o$ co"plees are $or"e' in the organic phase an',
at the sa"e ti"e, one or a series o$ co"plees in the a!ueous phase( <ore
co"plicate' e!uations &oul' be obtaine' i$ "ie' co"plees an'Nor polynu5
clear co"plees are present, an' i$ varying activity $actors are intro'uce', but
these cases are not 'iscusse' here( Thus the solvent etraction e!uations can be
epresse' by E!( /4(F>0, &here x an' y are in'epen'ent variables an' a
n
an' b
n
are un-no&n in'epen'ent para"eters( The polyno"ial in the 'eno"inator re$ers
to the $or"ation o$ a!ueous phase co"plees1 in the case that the "etal $or"s
several series o$ co"plees &ith 'i$$erent ligan's )
, L
, etc(, the 'eno"inator

contains several polyno"ialsM c
0
+ c
=
# +
( ( (
, etc( The polyno"ial in the nu"era5
tor al&ays re$ers to the $or"ation o$ organic phase co"plees(
There is no eact nu"erical solution to E!( /4(F>0 &hen both x an' y > 0(
8n practice, there$ore, one variable "ust be -ept constant /or 7ero0, &hile the
value o$ the other changes( This &as 'escribe' $or Ea"ple =;( Thus, i$ x is
-ept constant, the 'ouble polyno"ial is re'uce' to a si"ple one
y $
x
i
y
/$
=
a
0
+ a
=
x + a
2
x
+ L0 /4(>00
&here $

is a constant at constant x( The proble" is there$ore re'uce' to the
'eter"ination o$ the para"eters o$ a si"ple polyno"ial, to &hich "any nu"eri5
cal "etho's have been applie' &ith varying 'egrees o$ success( The "ain re5
!uire"ent is that all co"pute' para"eters shoul' be positive nu"bers /or 7ero0(
8n or'er to solve an algebraic syste" o$ n para"eters, only n e!uations
are nee'e' /a "ini"u" &ith no error esti"ates0( Ghen the solvent etraction
reaction can be 'escribe' by E!( /4(>00, there are as "any e!uations as there
are eperi"ental points( Co""only, in solvent etraction =0LJ0 points are
nee'e' to cover the &hole concentration range o$ interest, &hile the nu"ber o$
un-no&n para"eters in si"ple cases is <J( 8n evaluating the para"eters, it is
i"portant to use the co"plete suite o$ eperi"ental 'ata, as that gives greater
signi$icance to the a
n
or b
n
values(
There are several &ays to solve a large nu"ber o$ polyno"ials li-e E!(
/4(>00 $or the a
n
para"eters, e(g(, by "ini"i7ing the su" o$ the resi'uals, the
least s!uare "etho' /LS[0 being the stan'ar' proce'ure( 8t is an obDective re5
gression analysis "etho', &hich yiel's the sa"e results $or a given che"ical
syste", in'epen'ent o$ "etho' o$ investigation, provi'e' there are no errors in
the techni!ue or $un'a"ental che"ical assu"ptions( 4ecause the "etho' "ay
be applie' in so"e&hat 'i$$erent &ays, it "ay so"eti"es give slightly 'i$$erent
results( There$ore, in Du'ging a set o$ e!uilibriu" constants, it is use$ul to learn
ho& an author has applie' the "ini"i7ation techni!ue(
8n E!( /4(>=0 x is usually the $ree ligan' concentration B)
C, or concentra5
tion B4C o$ the a''uct $or"er, &hile y is a si"ple $unction o$ the 'istribution
i n i i i
2
ratio D( The least s!uare "etho' re!uires that & /the weighted s+uared residu!
als0 in epression E!( /4(>=0 is "ini"i7e'
*

)
n _
&

w
i

/a
n
x
i
0 y
i
/4(>=0
i=
n0 ,
&here ) + = is the nu"ber o$ para"eters, an' * the nu"ber o$ eperi"entals
points1 ) + * = is re$erre' to as the nu"ber o$ 'egrees o$ $ree'o" o$ the
syste"1 each point has a value x
i
N y
i
( 4ecause eperi"ents are carrie' out over
a large range o$ D, B)
C an'Nor B4C values, the points carry 'i$$erent algebraic

&eight /e(g(, the value =000 obscures a value o$ 0(00=0( There$ore, in or'er to
use the LS[ techni!ue properly, each point must be correctly weighted, w
i
( This
can be 'one in several &ays, the "ost co""on being to &eight it by y
i
, or by
2
, or by a percentage value o$ y 1 is the stan'ar' 'eviation in the "easure5
i i i
n
"ent o$ y
i
( The 'i$$erence a
n
x
i
y
i
/the residual0 is not 7ero, because the 'i$$er5
ence is to be ta-en bet&een a "easure' value, y
i
/"eas(0, an' the correspon'ing
calculate' value, y /calc(0, by the a x
n
$unction Bi(e(, y /calc(0 y /"eas(0C, using
the actual a
n
values at the ti"e o$ the operation(
The principle o$ the LS[ techni!ue is to co"pute the set o$ positive a
n
values that give the s"allest su" o$ the resi'uals1 E!( /4(>=0 reaches the &
"in
value( 8$ the resi'uals e!ual 7ero /&hich rarely occurs in practice0, &
"in
&oul'
be 7ero, an' there &oul' be a per$ect $it bet&een the eperi"ental points an'
the calculate' curve(
There are several "athe"atically 'i$$erent &ays to con'uct the "ini"i7a5
tion o$ & Bsee :e$s( P0LPJC( <any progra"s yiel' errors o$ internal consistency
/i(e(, the stan'ar' 'eviations in the calculate' para"eters are 'ue to the 'evia5
tions o$ the "easure' points $ro" the calculate' $unction0, an' 'o not consi'er
eternal errors /i(e(, the uncertainty o$ the "easure' points0( The latter can be
acco""o'ate' by &eighting the points by this uncertainty( The overall reliabil5
ity o$ the operation can be chec-e' by the
2
/chi s+uare0 test BP=C, i(e(, &
"in
N/*
+ ) =0 shoul' be in the range 0(JL=(J $or a reasonable consistency bet&een
the "easure' points an' the calculate' para"eters(
Ea"ple =PM Etraction o$ ,"/8880 by acetylacetone(
8n Ea"ple P, it &as conclu'e' that a nu"ber o$ sel$5a''ucts ,")
9
/K)0
b
&ere $or"e' in the organic phase /0 < b < 20 in a''ition to the ,")
n
co"plees in the a!ueous phase /0 < n < 401 so"e etraction curves are given
in Fig( 4(=4( E!uation /4(JJ0 is o$ the sa"e $or" as E!( /4(F>01 re&riting E!(
/4(JJb0
3 D
B)C
n
N B)C
9
K /= +
K
BK)C
+ L0 /4(>20
," n 9
&hich can be sub'ivi'e' into
AC a'= org
3 $ K /= +
K
BK)C
+ L0 /4(>9a0
B)C = AC a'= org
an'
3
$ D B)C
n
N B)C
9
/4(>9b0
BK)Corg 2 ," n 9
3
BK)Corg
contains the "easure' D
,"
, the B)C values, an' the
n
values( 8t can thus
in principle be treate' as an Ea"ple =; to yiel' the
n
values an' the $
2
values
/one $or each BK)C
org
0, re"e"bering that a
0
=( 4ecause 3
B)C
N$
=
3
BK)Corg
N$
2
3 , a secon' plot o$ 3 against BK)C
org
yiel's the K
A9
an' K
a'b
values( The
analysis o$ the syste" yiel'e' K
AC
0(00F, K
a',=
P an' K
a',2
9( 8n these cal5
culations, a S8<,LEV progra" &as use' BPJC(
8n co"parisons o$ e!uilibriu" constants collecte' $ro" the literature /e(g(,
Fig( 4(22 or B4PC0, or correlations o$ 'ata $or a large nu"ber o$ syste"s /e(g(,
Figs( 4(20L4(290, it is 'esirable to present both the statistical uncertainty o$ each
2point,3 &hich is o$ten given by the stan'ar' 'eviation /one or several +s0 o$
the point, an' the general reliability /statistical signi$icance0 o$ the &hole corre5
lation BP;C, $or &hich the chi5s!uare test o$$ers a 'eeper insight into the reliabil5
ity o$ the eperi"ental results BPPC( <ore a'vance' statistical tests $or syste"s
o$ our -in' have been 'escribe' by E-berg BPFC(
4.1$ EXPERIMENTA DETERMINATION
OF DISTRI'UTION RATIOS
The stu'ies 'escribe' above have the purpose o$ i'enti$ying the reacting species
in a solvent etraction process an' 'eveloping a !uantitative "o'el $or their
interactions( The $un'a"ental para"eter "easure' is the 'istribution ratio, $ro"
&hich etraction curves are 'erive'( Solvent etraction &or- can still be carrie'
out &ith si"ple batch&ise /or point5by5point0 techni!ue, but continuous on5line
"easure"ents give $aster an' "ore accurate results(
4.1>.1 'tirre% Ce"" 'emicontinuous Techni:ues
Each point5by5point eperi"ent re!uires a co"plete set o$ "iing, separation,
sa"pling, an' analysis( This usually lea's to scattere' results, though it "ay
not be critical, i$ the D values cover a li"ite' range $ro" 0(=L=0( Ko&ever, the
"ore the D values 'eviate $ro" =, the "ore accurate "ust be the "easure"ents1
also the nu"ber o$ points re!uire' $or a reliable etraction curve usually in5
creases( To re'uce the uncertainty an' labor involve' &ith the batch techni!ue,
the stirre' cell techni!ue has beco"e popular(
Figure 4(92 sho&s a typical ther"ostate' stirre' cell( The li!ui' volu"es
are co""only J0 + J0 "L( The stirrer "ay consist o$ a single pa''le at the
inter$ace, or a 'ouble pa''le, one in the center o$ each phase( The cell "ay
contain ba$$les, etc(, to i"prove the "iing( Stirring "ay be violent, co"pletely
'estroying the inter$ace an' pro'ucing very s"all / = ""0 'roplets, or slo&
Fig. 4.32 ) ther"ostate' 'ouble Dac-et /=0 cell $or solvent etraction stu'ies /heavier
phase F, lighter phase >0 un'er nonoi'i7ing con'itions, using a hy'rogen gas inlet /;0
to a ,'5blac- catalyst /==0, pK glass electro'e /90, "agnetic stirrer /=00, connections $or
a''itions /J0( )lternative constructions contain rotating pa''les an' $ie' pipings con5
necte' to the t&o phases $or $re!uent sa"ple &ith'ra&als(
in or'er not to 'estroy the inter$ace( The stirring rate is opti"i7e' to the ti"e
$or reaching e!uilibriu" an' co"plete phase separation( The eperi"ents are
either carrie' out &ith inter"ittent violent stirring, in &hich case sa"ples are
&ith'ra&n a$ter each co"plete phase separation, or &ith "il' stirring 'uring
&hich it is possible to continously &ithra& sa"ples( E!ual volu"es are sa"ple'
each ti"e, co""only <= "L( The si"ple stirre' cell has been i"prove' by
intro'ucing phase 'iscri"inating "e"branes in the sa"pling outlet BP>C( This
is particulary a'vantageous $or -inetic eperi"ents an' is $urther 'escribe' in
Chapter J( The sa"pling o$ the stirre' cell can be auto"ate', so that at regular
intervals pK an' te"perature are recor'e', an' sa"ples &ith'ra&n $or auto"atic
analysis o$ concentration o$ interesting species in "ore or less stan'ar' $ashion(
8t is also possible to use ion5sensitive probes in one o$ the phases instea' o$
sa"pling(
4.1>.2 Centrifuga" Extraction5'e6aration '!stems
) 'i$$erent approach to solvent etraction eperi"entation, re$erre' to as the
)S#FOE principle, &as 'evelope' in the =>;0s BF0aL'C( The )S#FOE is
illustrate' in Fig( 4(99( E$$icient "iing o$ the t&o phases an' their a''itions is
achieve' in the "iing vessel an' at the in$lo& into the phase separator, &hich
consists o$ a continuous flow centrifuge, &hich in a special separation cha"ber
an' at very high rotational velocity /J,000LJ0,000 rotations per "inute0 sepa5
rates the "iture into t&o very pure phases, containing <0(0=I o$ entrain"ent
o$ one phase in the other phase( The K5centri$uge "ay be "a'e o$ ,'5stabili7e'
Fig. 4.33 The )S#FOE solvent etraction apparatusM E$$icient "iing is achieve' in
the separate "iing vessel, $ro" &hich the "iture $lo&s 'o&n into the continuous
li!ui' $lo& centri$ugal separator /the K5centri$uge, hol'5up ti"e <= s0( /Fro" :e$s(
F9a,b(0 The out$lo& $ro" the centri$uge consists o$ t&o pure phases, &hich pass on5line
'etectors, )<Vs, $or on5line 'etectors or continuous sa"pling( /Fro" :e$s( F0aLF0',
F=(0
Ti, or ,EES /polyether ether -etone0 to allo& "easure"ents un'er very corro5
sive con'itions( The separate' phases pass )<V ga'gets $or on5line 'etection
/ra'io"etric, spectrophoto"etric, etc(0 or phase sa"pling $or eternal "easure5
"ents /ato"ic absorption, spectro"etric, etc(0, 'epen'ing on the syste" stu'ie'(
The a!ueous phase is also provi'e' &ith cells $or pK "easure"ent, re'o con5
trol /e(g(, by re'uction cells using platinu" blac- an' hy'rogen, "etal ion 'eter5
"ination, etc(0 an' te"perature control /ther"ocouples0(
The )S#FOE techni!ue allo&s a large nu"ber o$ points /J0L=000 to be
'eter"ine' in a one5'ay eperi"ent over a D5range o$ better than =0
9
to =0
9
,
not counting ti"e o$ preparation( 8n a special version o$ this techni!ue /L8S6L
$or L8!ui' Scintillation 6n Line0 BF2C, the D range =0
J
to =0
4
has been accu5
rately covere', as $or the ,"5acetylacetone syste", Ea"ple P an' Fig( 4(=4(
The centri$ugal separator o$ the )S#FOE syste" is also use' $or phase
separation in the S8S)S techni!ue BF4C( S8S)S is a "ultistage solvent etrac5
tion syste" that is use' $or stu'ies o$ properties o$ short5live' ra'ionucli'es,
e(g(, the che"ical properties o$ the heaviest ele"ents, an' solvent etraction
behavior o$ co"poun's &ith eotic che"ical states( 8n a typical S8S)S eperi5
"ent, Fig( 4(94, ra'ionucli'es are continuously transporte' $ro" a pro'uction
Fig. 4.34 ) typical S8S)S setup use' $or stu'ies o$ 5'ecaying nucli'es, e(g(, trans5
actini'es( /Fro" :e$( F4(0
site in an accelerator or a research reactor to the S8S)S e!uip"ent via a gas5
Det transport syste"( The nucli'es are 'issolve' in an a!ueous phase that is $e'
into a centri$uge battery co"prising =L4 solvent etraction steps( The pro'uct
solution leaving the last step is pu"pe', e(g(, to a nuclear ra'iation 'etection
syste"( The transport ti"e $ro" the target site to the 'etection syste" 'epen's
on the centri$uge si7e, nu"ber o$ centri$uge steps, an' $lo& rate( For a one5step
che"istry, i(e(, 'issolution step an' a single centri$uge etraction, an' "ai"u"
$lo& rates, the overall transport ti"e is aroun' 2(J s( This $ast transport has
allo&e' 'etaile' 5spectroscopic stu'ies o$ ra'ionucli'es &ith hal$5lives aroun'
= s( :ecently the S8S)S e!uip"ent &as succes$ully applie' to stu'ies o$ the
heaviest ele"ents, an' solvent etraction 'ata &ere obtaine' $or ele"ent =04 :$
BFJC( Fast che"ical separation syste"s have been 'evelope' $or !uite a large
nu"ber o$ ele"ents BF;C(
Centri$ugal etractors have been 'esigne' $or a nu"ber o$ in'ustrial uses
/see succee'ing chapters0( 8n so"e cases they have been scale' 'o&n to labora5
tory si7e but "ainly been use' $or 'eveloping in'ustrial "ultistage processes(
4.1>.3 Li:ui% *artition Chromatogra6h!
8n li!ui' partition chro"atography a solute 'istributes itsel$ bet&een a "obile
li!ui' phase an' an i""obile solvent attache' to a soli' "atri /in the earliest
eperi"ents a clayli-e 0ieselguhr0( 8t is outsi'e the scope o$ this chapter to
'iscuss this techni!ue, &hich, ho&ever, is brie$ly 'escribe' in Chapter =J(
4.1% CONCUSION AND FINA COMMENTS
The solvent etraction process is usually 'escribe' by a single net reaction,
'e$ine' by the etraction constant K
e
( Oariations in K
e
cause' by "o'i$ications
o$ the solvent syste", such as changes in the te"perature or a!ueous ionic
strength, or by replacing one solvent by another, or "a-ing substitutions in the
etractant "olecule, "ay be eplaine' by care$ul consi'eration o$ the para"e5
ters o$ the syste"( Ko&ever, such stu'ies are 'i$$icult an' not al&ays su$$icient
$or pre'icting ne& syste"s( ) better $oun'ation $or un'erstan'ing the etraction
process is to consi'er the steps in the process contributing to the net etraction
reaction, particularily &hen these steps are governe' by regularities( Sno&le'ge
o$ these regularities helps in interpreting syste"s as &ell as in pre'icting ne&
ones( Etension o$ these 'istribution 'ata to ther"o'yna"ic constants is li-ely
to give bene$its in increase' che"ical -no&le'ge o$ the behavior o$ solutes in
'i$$erent solvent syste"s( )'vance' !uantu" che"istry calculations an' co"5
puter "o'eling o$ etraction processes can help us in 'esigning ne&, selective
solvent etraction syste"s, as &ell as in interpreting etraction pheno"ena /see
Chapter =;0(
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9b( :y'berg, .( 'ec( Tra"( $him( 1956, ;<MP9P(
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?A, =>PP(
24( Se-ine, T(1 8hara, H( ull( $hem( &oc( 5ap( 1971, @@M2>42(
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/=>FF0(
2>( Oan 6oyen, .(1 Ayrssen, A(1 LilDen7in, .( 6(1 :y'berg, .( /E's(0 &ol"ent Extraction
$hemistry /(&E$ AC880, Horth5Kollan' ,ubl( Co(, )"ster'a", =>;P(
90a( Se-ine( T(1 Ayrssen, A( Anal( $him( Acta 1969, @<M499(
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9=( Se-ine, T(1 Sa-airi, <( ull( $hem( &oc( 5ap( 1967, @9M2;=(
92( LilDen7in, .( 6(1 Oa'as'i, S(1 :y'berg, .( $oordination $hemistry in &olution Ko%
g5 $el't, E( S&e'ish Hat( :es( Council1 Trans(:oy( 8nst(Techn(, 2F0, Stoc-hol",
=>P2(
99a( :y'berg, .( 'e"( (norg( $hem( 1999, ACM24J(
99b( :y'berg, .( Min( Pro( Ext( Met( 'e"( 2000, ?AM=;P(
94( Carey, F( )(1 Sun'berg, :( .( Ad"anced =rganic $hemistry, Thir' E'ition, ,lenu"
,ress, He& _or-, =>>0(
9J( Fu-s, L(1 <aD'an, <( Min( Pro( Ext( Met( 'e"( 2000, ?AM2J(
9;( )llar', 4( The $oordination of Tetra"alent Actnide $helate $omplexes with 5
Di0etones, Aiss( Chal"ers #niv( Techn( Gothenburg, =>PJ(
9P( Kil'ebran', .( K(1 Scott, :( C( &olubilities of )onelectrolytes, Aover ,ublishers,
=>;4(
9Fa( Sie-iers-i, S( 5( (norg( )ucl( $hem( 1962, ?@M20J(
9Fb( Sie-iers-i, S(1 6ls7er, :( 5( (norg( )ucl( $hem( 1963, ?@M=9J=(
9>( 4ucho&s-i, K( )ature 1962, AC@M;P4(
40a( Ga-ahayashi, T(1 6-i, S(1 6"ori, T(1 Su7u-i, H( 5( (norg( )ucl( $hem( 1964, ?8M
22JJ(
40b( 6"ori, T(1 Ga-ahayashi, T(1 6-i, S(1 Su7u-i, H( 5( (norg( )ucl( $hem( 1964, ?8M
22;J(
40c( 6-i, S(1 6"ori, T(1 Ga-ahayashi, T(1 Su7u-i, H( 5( (norg( )ucl( $hem( 1965, ?;M
==4=(
4=( 8rving, K( <( H( K( (on Exchange and &ol"ent Extraction, ,ol( 8, /<arins-y, .(1
<arcus, _( E's(0 <arcel Ae--er, He& _or-, =>P9(
42( Sie-iers-i, S( 5 'adioanal( $hem( 1976, ;>M99J(
49( Kansen, C(1 S-aaup, S( Dans0 Kemi 1967, @:MF=(
44( Kansen, C( %ansen &olubility ParametersM A Bsers %andboo0, C:C ,ress, 2000(
4J( Hilsson, <( (nfluence of =rganic Phase $omposition on the Extraction of Tri"alent
Actinides, Aipl( &or-, Aept( Hucl( Che"(, Chal"ers #niv( o$ Techn(, Gothenburg,
2000(
4;( .ohansson, K(1 :y'berg, .( Acta $hem( &cand( 1969, ?>M2P>P(
4P( Kancoc-, :( A(1 <artell, )( $hem( 'e"(, 1989, :CM=FPJL=>=9(
4F( Kancoc-, :( A( Prog((norg($hem( 1989, >8M=FPL2>0(
4>( Ca"bri'geSo$t Corp(, =00 Ca"bri'ge ,ar- Arive, Ca"bri'ge, <ass( /=>>>0(
J0( Si''all, T( K(, 8881 Goo', <( L( 5( (norg( )ucl( $hem( 1967, ?CM=4>(
J=( Charbonnel, <( C(1 <usi-as, C( &ol"( Extr( (on Exch( 1989, ;M=00P(
J2( <usi-as, C(1 Kubert, K( &ol"( Extr( (on Exch( 1987, <MFPP(
J9a( Harbutt, .(1 SreD7ler, .( (norg( $him( Acta 1999, ?:8M=PJ(
J9b( Harbutt, .(1 C7er&ins-i, <(1 SreD7ler, .( Eur( 5( (norg( $hem( 2001, 9=FP pp(
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2>J(
J;( Kan'ley, T( K( Anal( $hem( 1963, ><M>>=(
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< in organic phase

C0, salt concentration in the a!ueous phase, etc( The

C0, a!ueous salt concentration, etc( /b0 Sa"e syste"s

0(02 <0 in cycloheane( /Fro" :e$( 2(0

, only1 an' the #/O80 co"ple is poorly etracte', log

C, so that at the right vertical aes o$

Type (((5$ Adduct extraction of unsaturated metal complex

<etal &ith co"pleing anions L

, an' by 4 /$or adduct0(

, &here the neutral co"ple <) or <L is coor'inatively

C at various pK an' total concentrations o$ BK)C sho& three types o$

Table 4.% Aissociation K

a'= org org org

, in agree"ent &ith E!(

C, is an i"portant para"eter in the $or5

C is calculate' $ro" the "aterial balanceM

a''uct in a!ueous phase

, as long as pK > pK( The aci' "ay then act as a''uct5

, &here 4 re$ers to the a''uct $or"er or the solvating solvent1 b

C /electroneutrality in the a!ueous

, &hile $or the 'i"eric KAEK, ligan' in the

C, the free ligand concentration,

C has been calculate' $ro" pK, BK)C

C0, as epecte' $ro" E!( /4(9F0( The

C, or, better, constant BK

0 an' the ionic ra'ius r

0( Table 4(=2 co"pares the a''uct $or"ation

0 at a pK aroun' J B2;C( Yn/880 is -no&n to $or" a nu"ber o$

C aes is only cause' by varying B)

C, i(e(, the a!ueous phase

C0, $its E!(

( 4et&een these t&o li"iting slopes, the other three

, &hile cobalt $or"s CoCl

( The etraction reaction $or Co can

( 4e$ore 'iscussing these reactions in

, but etracts &ith an ecess

M the solubility o$ TL) KCl in &et

Copyright 2004 by Taylor & Francis Group, LLC

( Fro" Chapter 9 it $ollo&s

0C( ) contributing 'i$$iculty in practice is the

C, in the a!ueous phase in or'er to obtain the

C &oul' have a linear slope p i$ the

C( Fro" such "easure5

into ion pair $

0, &hich has been suggeste'

( 8n an inert solvent this is a stable ion

0( See E!( /4(P20 $or

C at ; 'i$$erent acetylacetone /K)0 concentrations /0(0;L0(000; <0(The

4.13.4.3 I!!e/ !" O7(e/ S+he/e C''/"i!(i'!

C can be use' to conclu'e &hat species 'o"inate the syste" at a given B)

C, yiel'ing the preli"inary log

C is 'escribe' by the t&o para"eters a an' b, an' the 'istribu5

, etc(, the 'eno"inator

C an'Nor B4C values, the points carry 'i$$erent algebraic

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