➢ Analytical Applications of Complex Equilibria BY J.

INCZEDY
➢ Complexation in Analytical Chemistry (Chemical Analysis) BY Anders Ringbom
Complexation/complex forming reaction

Complex formation equilibria

 Complex formation Equilibria of mononuclear complexes

The complexes are usuaaly formed in a step-wise manner,

: (1)
: :
: : :

: (2)
:
(3)
 CONDITIONAL EQUILIBRIUM CONSTANTS:

➢ The dependence of the stability constants of the complexes on the ionic strength is already known.

➢ It is very rare that the metal ions and the ligands which are involved in the complexation reaction are the only species
present in the system.
➢ The constituents of the complex may also take part in equilibrium reactions with other species present in the system. This
may also include the ions which are produced by the solvent.
➢ The ligand may be protonated and it may also be competed for by other metal ions present in the solution, if any.
Therefore, the real concentration of the free ligand may differ in solutions of the same total ligand concentration.
➢ Similarly, the real concentration of the free metal ion may differ in solutions of the same total metal concentration. This is
because the metal ion may interact with other complexing ligands present, including hydroxide ions.
➢ Therefore, comes into picture, the name Conditional constant. It expresses the notion of the term which can be assumed as
constant only under given conditions of concentration and pH.
 where [M’] is the apparent free metal ion concn., which means the concn. of metal ion that has not reacted with complexant L
and similarly, [L’] is the apparent ligand concn. i.e., the concn. of the ligand not bound to the central ion M. This may include
the concn. of the ligand whether L is in protonated or non-protonated form, or in the form of complexes with other metal ions.

Relationship between the apparent and free metal ion concentration:

If M and L are involved in more than one side reaction, the  values are summed to give an
overall value:
M = M(Y) + M(X) +………. - (i-1) (7)
L = L(B) + L(H) +………. - (i-1) (8)
Where i is the number of side-reactions. The correction -(i -1) is necessary since all  functions involve 1, representing free
M or free L. In practice one or two  terms predominate, therefore, -(i-1) can often be neglected including the other  terms.
The complex itself may undergo side-reactions, for eg,
(i) Formation of protonated complexes
(ii) Formation of mixed ligand complexes

If no side reactions are involved, the value of the -function is 1. In such cases, [𝑀′]/[𝑀] = 1, therefore, [M′] = [M] and
similarly, [𝐿′]/[𝐿] = 1, Hence, [L′] = [L].
The importance of conditional constants is that they can be applied in calculations like true constants, to yield answers that
refer to particular conditions.
 Role of hydrogen ion concn in complex formation:
The hydrogen ion concn plays an important part in complex formation. This is because ligands are usually strong Bronsted
Bases and hence are easily protonated, and hence the free ligand concn depends on pH.

In the presence of metal ion which forms mononuclear complexes, the total ligand concn is given by the following equation :

If CL >> CM (practically if CL>>20CM), the first term on the right hand side of eq. (1) may be neglected, Hence CL = [L]L(H).
log [L] = log CL – log L(H) (3)
The pH above which the ligand is less than 1% protonated, depends on the value of first protonation constant and is given by:

L(H) = 1 + K1[H+] + …..

to be smaller than 1.01, the second term must be smaller than 10 −2. Therefore,
log K1 + log [H+] ≤ − 2
log K1 + log [H+] ≤ − 2
log β1 − pH ≤ − 2
pH ≥ 2 + log K1
In the eq. (1) the amount of ligand bound to the metal in the complex is given by the first term on the right hand side. Dividing
this by the total metal ion concentrations gives the average number of ligands bound by one metal ion:
Another example
Another pH dependent phenomenon to be considered when dealing with aqueous solutions is the formation of hydroxo-
complexes, which is another side reaction of the metal ion, and has to be taken into account when calculating conditional
equilibrium constants. Hydroxo complexes are formed by dissociation of protons from the corresponding aquo-complexes.

In cases where only the formation of mononuclear complexes is to be considered, the hydroxo-complex formation can be
taken into account simply by using the − function in equilibrium calculations.

The pH below which practically no hydroxo-complexes are formed (less than 1%) depends on the stability constant of
the hydroxo-complex first formed, since the first stability constant is usually the greatest.

For the function,

M(OH) = 1 + β1[OH] + …..
to be smaller than 1.01, the second term must be smaller than 10 −2. Therefore,
log β1 + log [OH−] ≤ − 2
log β1 + log [H+] + log [OH−] ≤ − 2 + log [H+]
log β1 − 14 ≤ − 2 − pH
pH ≤ 14 − 2 − log β1
Direct Methods:
If only one complex species is formed, i.e., MLn,
M + nL ⇄ [MLn]
n is the stability constant for this reaction.

as [MLn] = CM − [M] and [L] = CL – n[MLn]

The calculation is more complicated if more complex species are formed. Leden and Froneous have made use of another
function called degree of overall complexation, which is the ratio of total and free metal ion concentration,

The function AM(L) obtained is the reciprocal of the function,  (mole fraction) for the free metal ion.

If the potential of a reversible MZ+/M electrode is measured in a solution of concentration CM in the absence and also in the
presence of complexant, the value of the function A can be calculated directly from the difference between the two potentials
measured. In the first case [M] = CM, whereas in the second [M] = CM/AM(L). The electrode potentials are
This can be done by using the above equation in graphical method of calculation : (as shown by Leden). Also known as
elimination method.
(B). Determination of free ligand concn :
A series of solutions is prepared in which the total concn of the central metal ion is the same but
the concn of the ligand is varied within wide limits.
The concn of the free ligand is determined potentiometrically in each solution by using ion-specific
electrode.
The average ligand number is calculated for each solution using the following equation :
𝐶𝐿 −[𝐿]
𝑛=
𝐶𝑀

From the calculated 𝑛 , and related [L] data, the overall stability constants are determined by using
the following equation :
𝑁 𝑖
𝑖=1 𝑖𝛽𝑖 [𝐿]
𝑛 = = 𝑁 𝑖
{1 + 𝑖=1 𝛽𝑖 𝐿 }
Ion-specific electrodes used are silver-silver halide electrodes, Calomel is the reference electrode.
When only one complex species is formed of the composition (1:1), the calculation or graphical evaluation can be done as
follows,

The calculation is more complicated if more complex species are formed. If two complex are formed, the formation function
can be written as:

Accurate evaluation can be done by the application of the method of least squares.
Curve-fitting method

This method is given by Sillen and is introduced as Curve-fitting method. The principle says, if the basic function containing
several constants parameters y = f(x, p1,p2….), a normalized function Y = F(X) is to be considered.
Or
Curve-fitting is simply about adopting the trend in the data by assigning a single function across the entire range

Interpolation Curve-fitting

The goal of the curve fitting is to identify the value of ‘a’ and ‘b’ such that the function fits the data well.
Case-I Average ligand number associated with metal ion ( = 1), Formation function can be written as

log X
Case-II Average ligand number associated with metal ion ( = 2), Formation function can be written as

In a similar way, a suitable modified equations can be used to calculate the overall stability constant if the values of pairs of
[L] and 1 or 2 are known. For example, the mole-fraction of the ML2 complex is known at different free ligand
concentrations

one coordinate of both the original and the normalized functions is logarithmic, the condition of normalization refers to the
variables log[L] and logX,
 If x > xmax ; then
If x < xmax ; then
If x = xmax ; then
If the stability of the complex is greater, peak is sharper, hence, tangents can be drawn easily and if the stability of the complex
is less, drawing of the tangents becomes uncertain.
If the free metal ion or ligand also absorbs at the same wavelength chosen, then the absorbance due to the metal or ligand has to
be subtracted from the absorbance measured, and the difference in absorbances is plotted as the ordinate.
 (B). Mole - Ratio Method :
The principle of the method is that a series of solutions is prepared in which the concn of one complex (usually CM) is kept
constant and that of the other varied. The absorbances of solutions is measured at a suitable wavelength and plotted versus the
ratio of the variable and constant concns, i.e., the ratio of the concn of 𝐶𝐿/𝐶𝑀 = a.

If only one stable complex is formed, which has selective light absorption, then the absorbance increases approximately linearly
with the mole-ratio and then becomes constant. The abscissa of the point of intersection of the two tangents gives the number of
ligands in the complex, if it was the ligand concn that was varied.

The stability constant can be calculated from the coordinates of the

points of the straight lines and the curve in a similar way as in the case
of the method of continuous variation.

For the formation of ML complex,

∅ML = [𝑀𝐿]/𝐶𝑀 = [𝑀𝐿]/𝐶𝑥 = 𝐴/𝐴𝑒𝑥

Before, the intersection, Cx = CL and after that Cx = CM.

Conditions : similar to those in the case of method of continuous variation.
 Bjerrum’s Method : Graphical method
This method can be used in the case of successive complex formation, if the ligands tend to protonate (and the protonation
constants are known) and the complex with maximum number of ligands has selective light absorption at the wavelength
chosen. When determining stability constants, it is necessary to know the composition of the complex species formed.

A series of solutions is prepared in which both CM and CL are constant, CL >> CM but the pH is varied. The absorbances of the
solutions are measured and plotted vs the logarithm of the free ligand concn.

If the overall stability constant of the light absorbing complex with maximum coordination
number is high enough, then the absorbance will reach a limiting value in the pH range
investigated (as presented in figure).
Plotting the left hand side of the above equation against log[L] gives a straight line, the intercept of which is logβ1.
A great advantage of studies made by changing the pH is that the free ligand concn can be changed sensitively over a wide range
without changing the ionic strength [Link] drawback of this method is that above pH 7, the results may be falsified by
competing formation of metal-hydroxo complexes.

The conditions for the applicability of the method are:

The maximum ligand number should not be greater than 2 (or 3) and only the complex species with maximum coordination number
should have appreciable absorption at the wavelength chosen.
If N = 1, another light – absorbing constituent is permissible.
➢ The value of 𝛽𝑁 has to be high enough for Emax to be reached in the pH range investigated but not so high that the metal ion is
present in the form of MLN even in acid solution (pH < 3).
➢ The first protonation constant should be large and the metal ion should not be involved in any side reaction in the pH range studied.

➢ The practical directions given for determination of protonation constants and application of the method of continuous variation
apply.
➢ The complete series of measurements can be made on one solution of known composition by adding to it small portions of standard
alkali solution from a burette, and measuring the pH and absorbance of the solution simultaneously. It is important that the dilution
of the solution during the measurements is negligible or can be corrected for (without causing further other errors).
POLAROGRAPHIC METHODS :
Complexation reaction:
If a metal ion can be reversibly reduced to the metallic state at a dropping mercury electrode, the metal ion may behave in the
presence of a complexing agent in either of the following two ways:
1. If the complex-formation reaction is fast compared with the reduction of the metal ion, then one polarographic wave
occurs, with a half-wave potential more negative than that of the uncomplexed metal ion. From the shift in the half-wave
potential with concentration of the complexant the composition and stability constant of the complex can be determined
According to the Ilkovic equation, the intensity of the limiting diffusion current (id) is proportional to the concentration (c) of
the reduced component under given experimental conditions
id  c or id = dc {where ‘d’ is diffusion constant and ‘c’ is conc. of reduced metal}
d = 6.3nFD1/2m2/3t1/6
where D = diffusion coefficient of the ion; m = drop rate of Hg; t = drop time

CM
(7)
At 25C, (8)
(2) If the complex-formation reaction is slow compared with the reduction of the metal ion, which occurs less frequently, then
two polarographic waves are obtained,
(i) Due to the reduction of the free metal ion, idA → Mn+
(ii) Due to the complexed metal ion. idB → MLn
The amount of free metal ion can be determined directly from the height of the
first wave. From the dependence of the height of the waves on the ligand
concentration, the composition and the stability constant of the complex formed
can be calculated.

idB vs [L], from this composition of the complex stability constant can be computed. If a series of solution is prepared with
constant CM, but with CL increasing from zero (CM=constant and CL = 0 to [L]), then the free metal concentration (i.e, Mn+),
determined from height of first wave, are plotted against CL/CM. (Plot of id[M] vs CL/CM)

The intersection of the abscissa with the tangent to the initial section of the curve
gives information about the composition of the complex. From the related CM, CL
and [M] values, the stability constant of the complex can be calculated. This
method can be used only if one complex species is formed. From the
conditional stability constant determined under the given experimental conditions
the stability constant can be calculated by using the - functions for the side-
reactions.
 (Inczedy : Pages 155-165)
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orthe
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(𝐴)𝑜
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[𝐴]𝑜𝑜 ==d dAA (P, (P, T,T,II==constant),
constant), (𝐴)
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(𝐴)𝑜 𝑜
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(P, distribution
T, I = constant
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[𝐴]
Where d
Where dAA isis the
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𝐴
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than in 𝐶
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The distribution coefficient is given by :𝐶 𝐴 = D AA 𝐴
Where, D is 𝐴
𝐶𝐴
the ratio of the total or analytical concns of the substance in the two phases.
Where, D is the ratio of the total or analytical 𝐺concns
𝐴 of the substance in the two phases. GtheA is the
The
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D is the ratiocoefficient
of the
Where, D is the ratio of the total ortotal total is given
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𝐶𝐴
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the caseof of
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or analytical and concns
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different even in case of same substance
different even in the case of same substance and solvents. and solvents.
total
Let concn in
s denote thethe organic
ligand phaseofand
number theCneutral
A is that in the aqueous
complex phase. dby
to be extracted A and DA mayAssume
a solvent. be completely that
different
only evencomplex
the final in the case ofthe
with same substance and
composition, MLssolvents.
soluble in the organic pahse and that the free
ligand remains in the aqueous phase, the distribution coefficient of the metal ion, M will be :
(𝑀𝐿 𝑠 )
DM =
𝐶𝑀
 𝐶𝑀
(𝑀𝐿 𝑠) 𝑠)
(𝑀𝐿
DM =
The = 𝐶𝑀
DM distribution constant of the
(𝑀𝐿 𝑠 )
neutral complex is given as :
𝐶𝑀 D M =
𝐶𝑀
The (𝑀𝐿 𝑠 ) constant of the neutral complex is given as :
distribution
𝑑The
𝑀𝐿 𝑠 =distribution constant
or (𝑀𝐿
of the
The ) = 𝑑𝑀𝐿
neutral [𝑀𝐿𝑠 ]is given
complex
𝑠 distribution𝑠 constant of theas :
neutral complex is given as :
[𝑀𝐿
(𝑀𝐿 𝑠 ]
(𝑀𝐿𝑠) )
𝑑𝑀𝐿
𝑑 𝑠
= = 𝑠 or or (𝑀𝐿(𝑀𝐿
𝑑 𝑠
) = =) (𝑀𝐿
𝑑=𝑀𝐿
𝑑𝑠 )[𝑀𝐿𝑠 ]
[𝑀𝐿
𝑠in the or 𝑠 ] (𝑀𝐿 ) = 𝑑𝑀𝐿rewritten
[𝑀𝐿𝑠 ] as :
The 𝑠 [𝑀𝐿 𝑠
𝑀𝐿concn ] the
of
[𝑀𝐿 𝑠 ] different species present
𝑀𝐿 𝑠 𝑠
[𝑀𝐿 𝑀𝐿] 𝑠
𝑠
aqueous pahse
𝑠 can be 𝑠

𝑑𝑀𝐿𝑠species
The concn of the different [𝑀𝐿𝑠 ] present in the aqueous pahse can be rewritten as :
The
DM =concn of the different The concn
species of the
present in different
the aqueousspecies present
pahse can in
bethe aqueousas
rewritten pahse
: can be rewritten as :
𝑀 + 𝑀𝐿 +𝑑 𝑀𝐿 2 + …….+ [𝑀𝐿 𝑁 ]
𝑀𝐿𝑠 [𝑀𝐿𝑠 ] 𝑑𝑀𝐿𝑠 [𝑀𝐿𝑠 ]
DM = 𝑑 [𝑀𝐿 ]
DM =𝑀 + 𝑀𝐿 + 𝑀𝐿2 + …….+
𝑀𝐿 𝑠 DM = [𝑀𝐿 ]
𝑠
𝑀 +𝑁 𝑀𝐿 + 𝑀𝐿2 + …….+ [𝑀𝐿𝑁 ]
𝑀 + 𝑀𝐿 + 𝑀𝐿2 + …….+ [𝑀𝐿𝑁 ]
𝑀𝐿 𝑠
Also , M + sL ⇄ MLs Hence, βs =
𝑀 [𝐿]𝑠
𝑀𝐿 𝑀𝐿 𝑠
𝑠
Also , M + sL ⇄ MLs Hence, Also βs, =M + 𝑀𝐿 sL𝑠 𝑠
⇄ ML s Hence, β s =
Also
𝑀𝐿𝑠 , =Mβs[M]
+ sL[L]⇄s MLs Hence, βs 𝑀
= [𝐿][ML]
Similarly, = β [M] [L] 𝑀 [𝐿]𝑠
𝑀 [𝐿]𝑠 1
s
𝑀𝐿𝑠 = βs[M] [L]s s 𝑀𝐿 𝑠β 𝑠= β]s[L]
Similarly,
𝑑 𝑀𝐿 [M 𝑠 [L] = β1 [M] [L]Similarly, [ML] = β1 [M] [L]
[ML]
[M]
𝑠
𝑀𝐿𝑠 = DβMs[M]
Therefore, = [L] Similarly, [ML] = β1 [M] [L]
𝑀 + 𝛽1 𝑑 𝑀 𝐿β + [M …….+
] [L] 𝑠 𝛽 𝑁 𝑀 𝐿 𝑁 𝑑 𝑀𝐿 𝑠 β 𝑠 [M ] [L]𝑠
𝑀𝐿 𝑠 𝑠
Therefore, DM = 𝑠
Therefore, DM = 𝑑 𝑀𝐿 𝑠 β 𝑠 [M ] [L] 𝐿 + …….+ 𝛽 𝑁 𝑀 𝐿 𝑁
Therefore, DM =𝑀 + 𝛽 1 𝑀 𝑑 𝑀𝐿 …….+ 𝛽 𝑁 𝑀
𝐿 𝑠 β+𝑠 [L] 𝑠 𝑀 +𝐿 𝛽𝑁1 𝑀 𝑑 𝑀𝐿 𝑠 β 𝑠 [L]𝑠
DM = 𝑀 + 𝛽 1 𝑀 𝐿 + …….+ 𝛽 𝑁 𝑁 𝑀 = 𝐿𝑑 𝑀𝐿 𝑁
𝑁β𝛽 [L] 𝑠𝑖 𝑑 𝑀𝐿 𝑠 β 𝑠 [L]𝑠
1 + 𝛽 1𝑑 𝑀𝐿
𝐿 +β 𝑠…….+ 𝑠
[L] DM = 𝛽 𝑁 𝐿 𝑠 𝑠
𝑑 𝑀𝐿 𝑠0β 𝑠 [L]
𝑖 𝐿 𝑠
DM =
𝑠 𝑠 = 𝑠𝐿 𝑁
= 𝑁 𝛽 𝐿 𝑖
𝑑 𝑀𝐿 β 𝑠 [L] 𝑁 1 + 𝛽 1 𝐿 𝑁+
𝑑 …….+
𝑀𝐿 β
𝑖 𝑠 𝛽
[L]
𝑁 0 𝑖
where N is the =1 + 𝛽 1 ligand
DMmaximum 𝐿 + …….+
number𝛽 𝑁 𝐿
𝑠
𝑁 = 0 𝛽𝑖 𝐿 𝑠
𝑁 𝛽 𝐿 𝑖
1 + 𝛽 1 𝐿where+ …….+N is the𝛽maximum
𝑁𝑖 𝐿 ligand number
0 𝑖
where N is the maximum ligand number β𝑖 [L]
D M = N
where 𝑑𝑀𝐿 ∅𝑠 maximum
is 𝑠the ∅𝑖 =number𝑁 𝑖
{ as ligand 𝑖
} β𝑖 [L]
𝑖
DM = 𝑑β 1+ 𝛽 𝐿
∅𝑠 𝑖 { as ∅𝑖 = }
𝑀𝐿𝑖 [L]
𝑖=1
𝑠 1+ 𝑁 𝛽𝑖 𝐿 𝑖
DM = 𝑑𝑀𝐿 𝑠 ∅𝑠 { as ∅𝑖 = 𝑁 β 𝛽[L] 𝑖𝑖
} 𝑖=1
∅D𝑠M==mole fraction of complex with 1+ 𝑖=1
composition 𝑖 𝑖 𝐿 MLs. This means that the distribution coefficient
𝑑𝑀𝐿 𝑠 ∅𝑠 { as ∅ ∅𝑖𝑠 ==mole 𝑁 𝛽of𝐿complex𝑖
}
1+fraction
𝑖=1 𝑖
with composition MLs. This means that the distribution c
∅is𝑠 proportional
= mole fraction of complex
to the with composition
mole fraction of the extractable MLs. Thiscomplexmeans that the distribution coefficient
species.
is proportional to the mole fraction of the extractable complex species.
s = N, and a series of solutions are prepared in which the total metal concn is constant and the
ligand concn is varied, then if a constant phase-volume ratio is used, the distribution coefficient of
If the metal
ligand concnion M forms
is varied, complexes
then with phase-volume
if a constant other ligands in addition
ratio to L.
is used, theFor example, coefficient
distribution with of
the metal ion is determined on the basis of extraction experiments. A plot of
If theside
D
numberM vs log [L] gives
of ligands
hydroxide ion to form hydroxo complexes, and the complexes formed in the reaction areinnot
the extractable complex is equal to the m
the metal ion is determined on the basis of extraction [Link] plot of D M vs log [L] gives
a saturation – type curve, that is, the distribution coefficient approaches = a N,
limiting value
and a series at higher
of solutions are prepared in which the total me
extractable, then the denominator on the right hand side of the above equation will contain the
a saturation
ligand concns. – type curve, that is, the distribution coefficient approaches a limiting
ligand concn value
is varied, then if at higher
a constant phase-volume ratio is used,
terms corresponding to the formation of these species, therefore, the metal ion is determined on the basis of extraction experiments.
ligand concns.
𝑑 𝑀𝐿 𝑠 β 𝑠 [L]𝑠 a saturation – type curve, that is, the distribution coefficient approac
DM =
1 + 𝛽 1 𝐿 + 𝛽 2 𝐿 2 ……. + 𝛽 𝑁 𝐿 𝑁 + 𝛾1 𝑂𝐻 + ……… ligand concns.

If the number of ligands in the extractable complex is equal to the maximum ligand number, i. e.,
s = N, and a series of solutions are prepared in which the total metal concn is constant and the
ligand concn is varied, then if a constant phase-volume ratio is used, the distribution coefficient of
the metal ion is determined on the basis of extraction experiments. A plot of DM vs log [L] gives
a saturation – type curve, that is, the distribution coefficient approaches a limiting value at higher
DM is proportional to the mole fraction of the complex extracted, therefore, at the ligand concn
ligand concns. D is proportional to the mole fraction
M of the complex extracted,
DM isthe
when proportional to the
curve reaches mole fraction
the limiting value, of
thethe complex
mole fraction, ∅𝑠 of thewhen
extracted, therefore,
species ML
the curveat the
s is ligand
unity,
reaches and concn
the limiting value, the mole fraction, ∅𝑠 of

∅𝑠 values for different free ligand concn values can be obtained grap
∅ 𝑠 values
when thefor different
curve freethe
reaches ligand concnvalue,
limiting valuesthe
can be obtained
mole ∅𝑠 of the
graphically
fraction, as shownML
species in the
s is graph
unity, and
above.
above.
∅𝑠 values for different free ligand concn values can be obtained graphically as shown in the graph
When limiting value is reached then, ∅𝑠 = ∅𝑁 = 1.
above.
When limiting value is reached then, ∅𝑠 = ∅𝑁 = 1. As DM = 𝑑𝑀𝐿 𝑠 ∅𝑠 therefore, DM = 𝑑𝑀𝐿 𝑠
Hence, the distribution coefficient is equal to the distribution cons
As DM =
When 𝑑𝑀𝐿 𝑠 value
limiting ∅𝑠 therefore,
is reached then, ∅𝑠 = ∅𝑁 D =M1.= 𝑑𝑀𝐿 𝑠 (s = N)
Actually, the metal ion can be considered as being wholly in the for
DM is proportional to the mole fraction of the complex extracted, therefore, at the ligand concn
Hence,
As D the= 𝑑distribution
∅ coefficient is equal to the distribution
therefore, D = 𝑑 constant(sof= the N) species extracted.
amount of the metal ion in other forms does not exceed 1 % of the t
𝑀𝐿reaches
whenMthe curve 𝑠 𝑠 M
the limiting value, the mole fraction, 𝑀𝐿the
∅𝑠 of 𝑠 species MLs is unity, and
Actually, the metal ion can be considered as being wholly in the form of the complex, MLN, if the
Hence, the
∅𝑠 values fordistribution
different freecoefficient isvalues
ligand concn equalcan
to be
theobtained
distribution constant
graphically of the
as shown in species extracted.
the graph
amount of the metal ion in other forms does not exceed 1 % of the total.
above.
The procedure is similar in the case when S < N, but the extractable complex is stable and is
predominant in a fairly wide range of ligand concns. In such cases, D M vs log [L] plot exhibits a
plateau corresponding to ∅𝑠 = 1.
As we
As
As
As we know
weknow
we that
that::::
knowthat
know that
𝑑𝑑𝑑 𝑠𝑠 𝑠𝑠 𝑠𝑠
𝑑𝑀𝐿
𝑀𝐿𝑀𝐿𝑠ββ𝑠
β
[L]
𝑠[L]
β 𝑠 [L]
[L] 𝑑𝑑
𝑀𝐿𝑀𝐿
𝑑
𝑑 𝑠β
β
𝑀𝐿𝑠
[L]
𝑠[L]
β
β 𝑠 [L]𝑠𝑠
[L]
DM
D
D =
M=
=
M=
𝑠
𝑀𝐿 𝑠𝑠 𝑠 =
= = = 𝑁
𝑠𝑀𝐿 𝑠
𝑁 𝛽 𝑠 𝐿𝑖 𝑖 𝑠
D 1 +
1 +𝛽𝛽11 𝐿𝐿 + …….+ 𝛽𝛽𝑁𝑁 𝐿𝐿𝑁𝑁 𝑁
+ …….+ 𝑁
𝑁 0 0𝛽 𝑖𝑁𝑖𝐿𝛽 𝐿 𝑖𝑖
M
11++𝛽𝛽11 𝐿 𝐿 ++ …….+
…….+ 𝛽 𝛽𝑁 𝐿
𝑁 𝐿 0 𝛽 𝑖𝑖 𝐿
0
Taking log on both sides :
Taking
Takinglog
Taking logon
log onboth
on both
both
sides : :
sides
sides :
+ ss log
log[L]
[L] ++ log
logββ 𝑁 𝑁 𝛽 [𝐿] 𝑖 𝑖
log D
log DM = log
M= 𝑑𝑀𝐿
log 𝑑 𝑀𝐿𝑠𝑠 + s s −−log
log 0𝛽𝑖 [𝐿]
𝑖𝑁
𝑁
log D
log DM = log
M= 𝑑𝑀𝐿
log 𝑑 + ss log
𝑀𝐿𝑠𝑠 + log [L]
[L] + log
+ log β
βss −
− log 0
log 0
0
𝛽 [𝐿]𝑖𝑖
𝛽𝑖𝑖 [𝐿]
Differentiating this
Differentiating thisequation,
equation,w.r.t.
[Link]
log[L]
[L]: :
Differentiating this
Differentiating this equation,
equation, w.r.t.
w.r.t. log
log [L]
[L] ::
𝑑 (log
(log 𝐷𝐷𝑀𝑀))
𝑑
𝑑𝑑 (log 𝐷 = ss −
𝑀)) = − 𝑛𝑛where,
where,𝑛 𝑛==average
averageligand
ligandnumber
number
𝑑(log
(log 𝐷
(log [𝐿])
[𝐿])
𝑀 = ss −
−𝑛 𝑛 where, 𝑛 == average
𝑑 (log [𝐿]) = where, 𝑛 average ligand
ligand number
number
𝑑 (log [𝐿])
Accordingto
According tothis
thisequation,
equation,the
therelated
related[L] and𝑛𝑛values
[L]and valuescan
canbebe obtained
obtained byby graphical
graphical differentiation
differentiation
According
According to
to this equation, the related [L] and
and 𝑛 values
𝑛 values can be
be obtained
obtained by graphical
graphical differentiation
of
of the
the log
log DDMMthis
vs equation,
vs log
log [L]plot,
[L] the
plot,ififrelated
‘s’ [L]
‘s’isisknown.
known. From
From can
a asufficiently
sufficientlylarge
large by
number
number ofof differentiation
values taken
values taken
of
of theaalog
the
from
from log
wideDrange
D
wide M vs log
M vs
range log
of [L]
of ligand
ligandplot,
[L] plot,
concns
concnsif ‘s’
if ‘s’
the
theis
is known.
known.
overall Fromconstants
From
stability
overall stability aaconstants
sufficiently
sufficiently
can
can large
belarge
be number
number
calculated of eqn
of
using
calculated usingvalues
values
eqn taken
: : taken
from
from𝑁
𝑁aa wide
wide 𝑖range
𝑖
[𝐿]range
of ligand
of ligand concns
concns the
the overall
overall stability
stability constants
constants can
can be
be calculated
calculated using
using eqn
eqn ::
𝑖=1 𝑖𝛽
𝑖=1 𝑖𝛽𝑖𝑖[𝐿]
discussed
𝑁𝑁 discussedearlier.
earlier.
{1+
{1+𝑁 𝑁 𝛽 𝐿𝐿𝑖𝑖𝑖𝑖}}
𝑖𝛽𝛽𝑖𝑖[𝐿]
𝑖=1 𝑖[𝐿]
𝑖=1
𝑖=1 𝑖𝛽
𝑖=1 𝑖
𝑁 𝑖 discussed earlier.
discussed earlier.
{1+ 𝑁
{1+ 𝛽𝑖
𝑖=1 𝛽 𝐿𝐿 𝑖 }}
𝑖=1 𝑖
Assuming that the overall stability
Assuming that constant increases
the overall stability with increasing
constant increasesligand number, and
with increasing thenu
ligand
concns of the species with ligand
concns of thenumbers, N−2,
species with N – numbers,
ligand 3, etc canN−2, N – 3, etccompared
be neglected with that
can be neglected com
of the
of the species with ligand speciesN
number, – 1,ligand
with number,
the ligand N –above
concn 1, the ligand
whichconcn above
the metal which
ion the metal io
is completely
present in the form of present
species in
MLthe
N form of deduced
can be species ML
: N can be deduced :
[MLN] > [ML ]
100 N[MLN−1]
> 100 [MLN−1]

[M] [L]N βN > [M] [M] β[L]

100 [L]
N
>β
N N−1 100 [M] [L]N−1 βN−1
N−1
1
[L] 𝛽 𝑁 −1 > 1 100 𝛽 𝑁 −1 = 100 ( )
[L] > 100 = 100 ( ) 𝛽𝑁 𝐾 𝑁
𝛽𝑁 𝐾𝑁
log [L] > log 100 – log KN
log [L] > log 100 – log KN
log [L] > 2 – log KN
log [L] > 2 – log KN

The procedure is similar in the case when S < N, but the extractable complex
The procedure is similar in the case when S < N, but the extractable complex is stable and is
predominant in a fairly wide range of ligand concns. In such cases, D M vs log [L]
predominant in a fairly wide range
plateau of ligand
corresponding to concns.
∅ = 1. In such cases, D M vs log [L] plot exhibits a
𝑠
plateau corresponding to ∅𝑠 = 1.
 s log L evaluation
log DM = log 𝑑𝑀𝐿 𝑠 + Graphical + log β𝑠 − DM vs.𝑁
oflog 0 log 𝐿 𝑖 (Dyrssen
𝛽𝑖 [L] and1Sillen)
------------ Graphical Evaluation of log DM vs log [L] plot –

According to this method the equations of the asymptotes drawn to the initial and final part of the
experimental curve possessing a maximum are :
If L → 0
log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 + s log L
log L0 log L
For this equation it is assumed that at small ligand concns, the metal ion is present practically
log L0 log L
entirely as the aqueous-complex in the aqueous phase. 𝑑 𝑀𝐿 𝑠 β 𝑠 [L]𝑠
DM = 𝑁 𝑑 𝑀𝐿 𝑠 β 𝑠 [L]𝑠
0 𝛽𝑖 𝐿 𝑖 DM = 𝑁 𝛽𝑖 𝐿 𝑖
If L →  0
log DM = log 𝑑𝑀𝐿 𝑠 + s log L −D
+ log β𝑠log log 𝑁
0 𝛽𝑖 𝐿+
M = log 𝑑
𝑖
------------
s log L
1
+ log β
𝑀𝐿 𝑠 𝑠
log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 − log β𝑁 − (N − s) log L
According to this method the equations of the asymptotes drawn
According to to the
this method theinitial andoffinal
equations the as
Similarly, this equation indicates that in the high ligand concn range
experimental curvepractically
possessingonly the species
a maximum are : experimental curve possessing a maximum are :
MLN with maximum ligand number is present in the If aqueous
L → 0phase. The staright line in the graph If L → 0
represents the two extremes of Eqn 1. log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 + s log L
log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 + s log L For this equation it is assumed that at small lig
At intersection of two asymptotes ,
entirely
For this equation it is assumed that at small ligand as the aqueous-complex
concns, the metal ioninis
thepresent
aqueous p
log DM = log DM
entirely as the aqueous-complex in the aqueous phase.
If L → 
 log β𝑁 = − N log L0 log L0 is the abscissa of the intersection.
log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 − log β𝑁 −
Intercepts are : A = log 𝑑𝑀𝐿 𝑠 + log β𝑠 If L → 
Similarly, this equation indicates that in the hig
log DM = log 𝑑𝑀𝐿 𝑠 + log β𝑠 − log β𝑁 −ML
(N − s) log L
B = log 𝑑𝑀𝐿 𝑠 + log β𝑠 − log β𝑁
N with maximum ligand number is present in
represents the two extremes of Eqn 1.
Similarly, this equation indicates that in the high ligand concn range practically only t
At intersection of two asymptotes ,
MLN with maximum ligand number is present in log
theD
aqueous phase. The staright line in
= log D
 A – B (difference between A and B) will give log N and slopes are ‘s’ and − (N − s) M M
represents the two extremes of Eqn 1.  log β𝑁 = − N log L0 log L0
At intersection of two asymptotes ,
Another case :

The investigation of extraction equilibria can be used also as an indirect method for studying
complexes which are not soluble in organic solvents, and for the determination of their overall
stability constants.

Let Y be a complexing agent which forms practically only one complex of the composition MY s
with a metal ion, and this complex is extractable from the aqueous phase with an organic solvent.
The distribution coefficient of the metal ion is given as :
𝑑 𝑀𝑌 𝑠 [M Y 𝑠 ]
DM =
𝑀 + 𝑀𝑌𝑠
Supposing a complexing agent, L, is also present and it forms complexes which cannot be extracted
by the organic solvent, then the distribution coefficient will be given as follows :
𝑑 𝑀𝑌 𝑠 [M Y 𝑠 ]
DM(Y, L) =
𝑀 + 𝑀𝑌𝑠 + 𝑀𝐿 + 𝑀𝐿 2 + ……….
If the complex formation equilibrium constants are introduced and the overall stability constant of

the complex MYs is denoted by γ𝑠 and the constants for ML1, ML2…… by β1, β2 ……., the eqns
can be written as :
𝑑 𝑀𝑌 𝑠 γ 𝑠 [Y ]𝑠
DM(Y) = ---------------------- 2
1 + γ 𝑠 [Y ]𝑠

𝑑 𝑀𝑌 𝑠 γ 𝑠 M [Y ]𝑠
DM(Y, L) =
𝑀 + γ 𝑠 M [Y ]𝑠 + 𝛽1 𝑀 𝐿 + 𝛽2 𝑀 [𝐿]2 + ……..

𝑑 𝑀𝑌 𝑠 γ 𝑠 [Y ]𝑠
= -=-------------- 3
1 + γ 𝑠 [Y ]𝑠 + 𝛽 1 𝐿 + 𝛽 2 [𝐿]2 + ……..

Dividing eqn 2 by eqn 3,

𝐷 𝑀 (𝑌 ) 1 + γ 𝑠 [Y ]𝑠 + 𝛽1 𝐿 + 𝛽 2 [𝐿]2 + ……..
=
𝐷 𝑀 (𝑌 ,𝐿 ) 1 + γ 𝑠 [Y ]𝑠
In this, a series of solutions is prepared in which the concns of the complex-forming agent Y and
the metal ion M are constant (and for protonating ligands also the pH is constant), whereas that of
the ligand L is varied starting from zero.
The distribution coefficients of the metal ion and hence the values of the function A M(L) are
determined for each member of the series for each ligand concn [L].
It is very important that the concn of the ligand Y, the pH and the concn of the additives remain
the same in the solutions which do and do not contain the ligand.
From the related [L] and AM(L) values the overall stability constants can be calculated by Leden’s
successive extrapolation method.
E = , when Vw = Vo
𝐷 +1
Techniques of extraction : The three basic techniques in liquid-liquid extraction are :
1. Batch extraction
2. Continuous extraction
3. Counter current extraction
Batch extraction is the simplest one which consists of extracting solute from one immiscible layer
by shaking two layers until an equilibrium is attained. After this the layers are allowed to settle
and separate.
Completeness of extraction depends upon the number of extractions carried out. The best results
are obtained with a large number of extractions with a small volume of solvent.
If V mL of an aqueous solution containing x0 g of a solute be extracted n times with v mL portions
of a given solvent, then the weight of solute xn remaining in the water layer is given by the
𝐷𝑉
expression : xn = x0 ( )𝑛
𝐷𝑉 +𝑣
where D = distribution ratio between water and the given solvent. Extraction is never 100 %.
Batch extraction : Batch extractions can be used when distribution ratio is large.

Continuous extraction is used when distribution ratio is relatively small, so that a large number
of batch extractions would be required to give effective quantitative separation. So high efficiency
depends on the viscosity of the phases and other factors affecting the rate of attaining equilibrium,
the values of D, the relative volumes of the two phases and any other factors. Efficiency can
improved by employing a large area of contact. The half extraction volume is the volume of
extracting solvent necessary to decrease the amount of extracted constituent to one half the former
value. This volume can be used to get the distribution factor, K, from
0.693 𝑊
K= , K = concn of solute in the extracting solvent divided by the concn of original soln.
𝑉
Half extraction volume = V mL and W = volume of original soln.

Continuous counter current extraction

It involves a process whereby the two liquid phases are allowed to flow counter to each other. It is
used for separating materials for isolation or purification purposes. This is applicable to the
fractionation of organic compounds and less applicable to inorganic compounds.

The choice of solvent extraction method depends on the value of the distribution ratio of the
solute of interest, and the separation factor of interfering materials.
Precautions to be taken in the laboratory in the extraction experiments :
1. Care should be taken that the total metal ion concn is low (< 10−3 M) and concn of bound
ligand is negligible compared to the total ligand concn.
2. Also ligand is usually a weak base and so it tends to become protonated and the metal ion
may form hydroxo-complexes at higher pH values, therefore, pH of the solutions must be
measured and the protonation and the hydroxo-complex constants must be known. One
should keep either the pH or the total ligand concn constant (and vary the other). If concn
of bound ligand is negligible compared to the total concn, [L] can be obtained using eqn,
[L] = CL / L(H).
3. A suitable inert electrolyte is used to ensure constant ionic strength of the solutions.
4. A suitable organic solvent should be selected on the basis of experiments. The solvent
should not give an interfering chemical reaction with the components of the aqueous
solution and that the miscibility with water is as low as possible. The ratio of the volume
of the organic phase to that of the aqueous phase should be kept constant throughout the
whole series of experiments.
5. Distribution and chemical equilibria should be completely attained during the period of
shaking. As the rate of chemical reactions is generally higher than that of material transport
between the two phases, the extraction should be done in a well-stoppered separating
funnel by vigorous shaking for a long enough period.
The minimum time of shaking is determined by performing the extraction on samples of
the same composition by shaking for different times and subsequently analyzing the
phases.
For calculating the distribution coefficient it is sufficient to determine the concn in one of
the phases after extraction if the total amount of metal present and the ratio of the volumes
of the phases are known.
 the phases after extraction if the total amount of metal present and the ratio of the volumes
of the phases are known.
6. Good phase separation is very important from the point of view of the reliability of the
result of chemical analysis; the phases should not be turbid. An inert additive (cetyl
alcohol)alcohol)
may bemay
usedbetoused
reduce foaming.
to reduce The separation
foaming. of theofphases
The separation may may
the phases be accelerated by
be accelerated
centrifuging.
by centrifuging.
7. The concn of the metal ion distributed can be determined in either phase or in both by
𝐺𝐴
spectrophotometry, polarography, radioactive tracer technique, etc. Eqn = DA is used
𝐶𝐴
to calculate distribution coefficient.
8. The basic requirement for calculations is that the concns used are truly equilibrium data.
9. The free ligand concn calculation and possible side recations should be delt with in the
same way as in pH and spectrophotometric methods.

Batch extraction : Batch extractions can be used when distribution ratio is large.

Continuous extraction is used when distribution ratio is relatively small, so that a large number
of batch extractions would be required to give effective quantitative separation. So high efficiency
ION EXCHANGE METHODS
(Inczedy : Pages 165 - 174) Ion-Exchange Methods

The ion exchange resins have been broadly classified as cation exchange resins, i.e., those of the H H
C CH2 CH CH2 C
resins are capable of exchanging cations and anion exchange resins, which are the ones capable of
(A) C CH2
exchanging anions. These resins have been further classified depending upon the structure and H

presence of functional groups as strongly basic or strongly acidic resins, respectively.

SO3 H+ SO3 H +
H
Both the cation and anion exchange resins are mostly organic in nature. The inorganic ion- H2C C C CH2 (C)
H H2C C CH2
(B) H
exchangers are the zeolites and heteropolyacids of the metals. H2C CH HC CH2

Theory of ion-exchange
SO3 H + SO3 H +

Donnan membrane theory : It deals with the unequal distribution of ions on two sides of a Anion exchange resin (D) is prepared by co-polymerisation of styrene and divinylbenzene
membrane. One side contains an electrolyte whose ions cannot penetrate through the membrane. followed by chloromethylation and interaction with a base such as trimethylamine.
In ion-exchange equilibria, the interface between solid and liquid phases may be considered as a H H
C CH2 CH CH2 C
membrane.
Mz+ + z RNa ⇄ zNa+ + RzM R = Resin
+
CH2NMe3 Cl +
CH CH2NMe3 Cl
Synthesis of Ion-exchange resins : (D)
H2C CH2

Cation Exchange resin is defined as a high molecular weight, cross-linked polymer containing H2C CH HC CH2

sulphonic, carboxylic, phenolic groups as an integral part of the resin and an equivalent number of
cations.
An anion exchange resin is a polymer containing amine (or quarternary ammonium) groups as + +
CH2NMe3 Cl CHNMe3 Cl

integral parts of the polymer lattice and an equivalent number of anions, such as chloride, hydroxyl,
or sulphate ions.
Cation exchange resin is obtained by co-polymerisation of styrene (A) and divinylbenzene (B),
followed by sulphonation, represented by C :
Techniques
Techniques in in Ion-Exchange
Ion-Exchange methods methods
Techniques
Techniques in Ion-Exchange
in Ion-Exchange methods
methods
1.
1. When
When solution
solution is is passed
passed on on resin,
resin, wewe call
call itit sorption.
sorption. In In sorption,
sorption, we we take
take small
small aliquot
aliquot of of
1. When solution
1. When solution isions is passed
passedthe on resin,
on resin, we we call it sorption.
call it passed In
sorption. column sorption,
In sorption, we take small
we take rate. aliquot
small aliquot of of
solution
solution containing
containing ions of of the mixture
mixture which
which is is passed on on column at at some
some flowflow rate.
solution
solution containing
containing ions
ions of
of the
the mixture
mixture which
which is
is passed
passed on
on column
column at
at some
some flow
flow rate.
rate.
2.
2. All
All ions
ions capable
capable of of exchanging
exchanging on on resin
resin are
are retained
retained by by it
it and
and the
the molecular
molecular species
species are
are released
released
2.
2. All
All ions
ions capable
capable of
of exchanging
exchanging on
on resin
resin are
are retained
retained by
by it
it and
and the
the molecular
molecular species
species are
are released
released
in
in the
the outgoing
outgoing solution
solution called
called Effluent.
Effluent.
in
in the
the outgoing
outgoing solution
solution called
called Effluent.
Effluent.
3.
3. After
After washing
washing column
column with with small
small quantity
quantity of of water,
water, we we start
start process
process of of desorption
desorption whichwhich is is
3.
3. After
After washing
washing column
column with
with small
small quantity
quantity of
of water,
water, we
we start
start process
process of
of desorption
desorption which
which is
is
called
called Elution
Elution withwith eluant.
eluant. The The eluant
eluant is
is a
a solution
solution which
which is is capable
capable of of removing
removing ions ions or
or resins
resins inin
called
called Elution
Elution with
with eluant.
eluant. The
The eluant
eluant is
is a
a solution
solution which
which is
is capable
capable of
of removing
removing ions
ions or
or resins
resins in
in
column.
column.
column.
column.
(i)
(i) if
if same
same eluant
eluant is is used
used with
with increasing
increasing concn
concn like like 1M1M and and 4M4M eluant,
eluant, this
this process
process is is called,
called,
(i) if same eluant
(i) if sameelution. is used with increasing concn like 1M and 4M
eluant is used with increasing concn like 1M and 4M eluant, this process is called, eluant, this process is called,
Gradient
Gradient elution.
Gradient
Gradient elution.
[Link] for one ion but not for second, we call this as the specific eluant.
(ii)
(ii) if
if an
an eluant
eluant is is specific for one ion but not for second, we call this as the specific eluant.
(ii)
(ii) if
if an
an eluant
eluant is specific
is specific forfor oneone ionion but
but not
not for
for second,
second, we we call
call this
this as
as the
the specific
specific eluant.
eluant.
(iii)
(iii) if
if an
an eluant
eluant is is eluting
eluting twotwo or or more
more ions
ions under
under different
different set set of
of conditions,
conditions, we we call
call this
this asas the
the
(iii) if
(iii) if anan eluant
eluant is eluting
is eluting two or more ions under different set of conditions,
two or more ions under different set of conditions, we call this as the we call this as the
process of selective
process of selective elution. elution.
process of
process of selective
selective elution.
elution.
4.
4. The
The process
process of of converting
converting resin resin into
into the
the original
original formform after
after work
work for for subsequent
subsequent use use isis called
called
4.
4. The
The process
process of
of converting
converting resin
resin into
into the
the original
original form
form after
after work
work for
for subsequent
subsequent use
use is
is called
called
regeneration.
regeneration.
regeneration.
regeneration.
5.
5. In
InIon
ionexchange,
exchange, several ions are
several ionsremoved successively
are removed
removed from the column
successively from by the
process of selective
column elution. Such
by process
process selectivity
of selective
selective
5. In ion exchange, several ions are successively from the column by of
5. In
5. In ion
depends ion exchange,
upon the (i) concn
exchange, several ions
of eluant,
several ions are
(ii) are
pH orremoved successively
molarity ofsuccessively
removed from the
eluant, (iii) temperature
from the column
of column byflow
elution, (iv)
by process of
rate of of
process selective
solvent through
selective
elution. Such selectivity depends upon the (i) concn of eluant, (ii)
elution. Such selectivity depends upon the (i) concn of eluant, (ii) pH or molarity of eluant, (iii)
column. pH or molarity of eluant, (iii)
elution. Such
elution. Such selectivity
selectivity depends
depends upon upon the
the (i)
(i) concn
concn of of eluant,
eluant, (ii)(ii) pH
pH oror molarity
molarity of of eluant,
eluant, (iii)
(iii)
temperature of
temperature of elution,
elution, (iv)(iv) flow
flow rate
rate of
of solvent
solvent through
through column.
column.
elution. Such selectivity depends upon the (i) concn of eluant, (ii) pH or molarity of eluant, (iii)
temperature of elution, (iv) flow rate of solvent through column.
6. After desorption or elution of a particular ion or charged complex from column, it is
quantitatively analysed preferably by instrumental methods like spectrophotometry,
conductometry, polarography, etc.
7. Since ion exchange is reversible process, an equilibrium state is reached and needs more amount
of resin if solution is highly concentrated.
8. The rate of exchange is controlled by particle diffusion process. Slow process ensures complete
sorption followed by elution process.
9. Regeneration is reverse process, and complete regeneration proceeds with large volume of
regenerating solution.
10. The total number of exchanging groups in the column is expressed as milli equivalents and is
called as total exchange capacity. Breakthrough capacity is lower than total exchange capacity and
is dependent on kind of resin, its affinities and concn, particle size, flow rate and several other
factors influencing elution.
EXCHANGE METHODS :
The principle is similar to that of extraction methods. The principle of ion-exchange method is that
there is a distribution of the metal ion between the ion-exchanger and a solution phase and from
the position of the distribution equilibrium, degree of the complex formation with a ligand in the
solution can be determined. Also the stability constants and overall stability constants can be
calculated on the basis of the distribution equilibria measured.
Usually a cation or anion exchange resin is used (or a liquid ion-exchanger). The method can be
used when the ligand is charged and complex formation involves a change in the charge.
A cation-exchange method is generally used when the ligand is a multivalent anion larger in size
than the metal ion. In such cases only the free metal ion present as an aquo complex is bound by
z+
M + z RNa
the cation-exchange zNa+
⇄resin. + RzM
Mz+ + z RNa ⇄ zNa+ + RzM
where R astands
Consider for in
situation the equivalent
which amount
a univalent of the
sodium ion-exchange
ion is resin.
exchanged for The equilibrium
a multivalent metal ionconcn
:
z+ +
M + z RNa ⇄ zNa M+ z+ RzMwhere R stands
+ z RNa ⇄ zNa+ for the equivalent amount of the ion-exchang
+ RzM
constant is :
constant is :
where R stands 𝑧 for the equivalent
where Ramount of the
stands for theequivalent
ion-exchange
amountresin.
of theThe equilibrium
ion-exchange [Link]
The eq
𝑀 [𝑁𝑎 ]
K x = constant is : 𝑀 [𝑁𝑎 ]𝑧
constant
𝑀 is
(𝑁𝑎: )𝑧 Kx =
𝑀 (𝑁𝑎 )𝑧
𝑀 [𝑁𝑎 ]𝑧
𝑀 [𝑁𝑎 ]𝑧 K =
The
Kx =symbols in𝑧 round brackets xdenote the)𝑧concn
𝑀 (𝑁𝑎
The symbolsinin
the ion-exchange
round resinthe
brackets denote and those
concn inin the
the square
ion-exchan
𝑀 (𝑁𝑎 )
brackets denote the concn in the
The solution.
brackets
symbols denote
in round thedenote
brackets concn the
in the solution.
concn in the ion-exchange resin and th
The symbols in round brackets denote the concn in the ion-exchange resin and those in the square
The distribution
brackets denotecoefficientthe concn of the in the metal ion, M, can be expressed as :
solution.
The distribution
𝑀
The distribution coefficient
brackets
(𝑁𝑎 )𝑧
coefficient denote
𝑧
The of the the
distribution
of the metalconcnmetal in
(𝑁𝑎 )ion, ion, M, can
the solution.
coefficient M, can
of the be expressed
be expressed
metal ion, M, as as:can: be expressed as :
z
DM = 𝑀 The
𝑀
=distribution
x[(𝑁𝑎
KThe (𝑁𝑎
)𝑧𝑧 ] = coefficient
coefficient
distribution
)
Kxof[(𝑁𝑎 the metal
(𝑁𝑎
)
)of]zzthe)ion, M, can be expressed as :
𝑧metal ion, M, can) be expressed as :
DM = 𝑀 = Kx[(𝑁𝑎 [𝑁𝑎 )]𝑧 ] =𝑧 Kx [(𝑁𝑎
𝑧 𝑀 [𝑁𝑎)] ]z (𝑁𝑎 (𝑁𝑎 z
D = 𝑀 = K𝑀 [ [𝑁𝑎 ] D ]
(𝑁𝑎 ==) K = [ [𝑁𝑎
K [ ]
(𝑁𝑎] ) ] = K [ ]
DM== KD x[= 𝑧] = 𝑀 [) K ] ]]𝑧 (𝑁𝑎 ) z [𝑁𝑎 ]
M
DM = 𝑀 x 𝑀 M K(𝑁𝑎 x 𝑧 x z x
𝑀 [𝑁𝑎
[𝑁𝑎 K ][
] 𝑧 ] =
x [𝑁𝑎
[𝑁𝑎 [ ][𝑁𝑎
]
M = metal
𝑀 the
x = ion K] x[is
𝑧 ] =smaller
x Kx] [ than ]
If the concn of 𝑀 [𝑁𝑎 [𝑁𝑎 much
]𝑧 [𝑁𝑎 [𝑁𝑎 ] that of the Na-ion, then concn of Na in ion-
If the concn of the metal If the ionconcn is much of the smaller
metal than ion isthat much of smaller
the Na-ion, than then that of concn of Na in
the Na-ion, then ion- con
If the
exchange concn
If the concn resin
If the
of
of the
the
is
concn
metal
metal
considered
of the
ion
ion
metal asis
is ion
much
much
constant
is much
smaller
smaller
and the
smaller
than
than value
than
that
that of
that
of
of Dof
the
the the
Na-ion,
Na-ion,
depends
Na-ion,
then
then
only
then
concn
concn
on
concnthe ofofNaNa
concn
of Na in
in
in
of ion-
ion-
Na-
ion-
M
exchange resinIfisthe concn of the
considered
exchange as metalconstant
resin
ion is
is and
considered
muchthe smaller
value
as
than
of
constant DM that of the Na-ion,
depends
and the valueonlyofon D
then
the concn
concn
depends
of of
NaNa-
only
in io
on
exchange
exchange
ion resin is
resin
exchange
in the solution. isresin
considered
considered
If is
this considered
is as constant
as
constant, constant
as constant
then and
andD the
the
andis value
value
the
also value of D
of
constant. DMM
of D M
depends
depends
depends only
only only onon
on the
M
the
the concnof
concn
concn ofofNa-Na-
Na-
exchange resin is considered as constant and the value of D M depends only on the concn of N
M
ion in the solution. If this ionIfis in constant,
theissolution. thenIfD M is
this isalso
constant,constant. then DM is also constant.
ion
ion in
in the
ion
the solution.
in the
solution.
In the presenceion of in If
solution.
If this
this
a negatively is
is constant,
this
constant,
the solution. charged constant, then
then DD
then
complexing
If this is constant, M
M D
isis M also
is
also
then D also constant.
constant.
constant.
ligand
M is also , L, because only the free metal ion is
constant.
In the presence of a negatively Inathe charged
presence complexing
of complexing
a negatively ligand
charged , L, because
complexing only
ligand the free
, L, metalonly
because ion is the
In the presence
In the
In the presence
transferred In
into ofof
presence
the a
thearesin,negatively
of
presence
negatively negatively
of charged
a charged
negatively
charged complexing
the distribution complexing
charged
coefficientligand ligand
complexing ligand
of the ,metal , L,, L,
ligandbecause
L, because because
,
ion willL, only
only
because
only be the the
the
onlyfree
free
the metal
metal
: free metal ionfree ionis
ion
metal isis
ion
transferred into the
transferred resin,
into the the distribution
transferred
resin, the into
distribution coefficient
the resin, of of
the distribution
coefficient thethe metal ion
coefficient
metal ion will
will of be
bethe:: metal ion will be :
transferred
transferred (𝑀)into
into the
the resin,
transferred
resin, the
into
(𝑀)
the distribution
the resin,
distribution the coefficient
distribution
coefficient of
of the
coefficient
(𝑀)
the metal
metal of the ion
ion metalwill
will ion
bebe : be :
will
:
DM(L) = (𝑀) = (𝑀) (𝑀) = (𝑀)
DM(L) = 𝐶 𝑀 = 𝑀
(𝑀)  + 𝑀𝐿 D M(L)
(𝑀) +
(𝑀) 𝑀𝐿 = (𝑀)
2 (𝑀)
+ ……… =
(𝑀)
(𝑀)= 𝑀  + 𝛽 1 𝑀 𝐿 + (𝑀) 𝛽(𝑀)
2 𝑀= 𝐿(𝑀)
2 + ………
(𝑀)
D DM(L)
= (𝑀)
𝐶𝑀 = =D𝑀 𝑀 += =𝑀𝐿 +(𝑀)
+= 𝑀𝐿 𝐶+ ……… + 𝑀𝐿
𝑀………= +𝑀 =
𝑀𝐿 +𝑀+𝛽 1 =
𝑀𝐿𝑀  𝐿 +(𝑀)
+………𝛽 𝛽𝑀 𝐿
𝑀 2
2
 𝛽+
++ ………
𝛽 𝐿
𝑀 𝐿+ ………
+ 𝛽 2 𝑀𝐿2 + ………
M(L)
DM(L) = 𝐶𝑀 = 𝑀 M(L)
𝐶  𝑀 
𝐶 𝑀𝐿  𝑀 +
2 + 
𝑀𝐿
𝑀 𝑀𝐿  +  
= 2𝑀 ++ 𝛽𝛽 1𝑀
+ ……… + 𝛽 
2𝑀 𝑀 
+𝐿 𝛽 + 
2 𝑀 
𝐿 
𝑀 
+ 𝐿 2
𝑀 
………
1  2
𝑀 + + 𝑀𝐿
𝑀𝐿𝑀+ + 𝑀𝐿 2  + ………
2
𝑀𝐿𝐿 +
1 1 𝑀 𝐿2
2
𝐿  +
2 ………
Assuming𝐶 that the
𝑀 concn of𝑀𝐿sodium
2  + ……… ion𝑀 in the1 solution + 𝛽𝛽
2 𝑀the
2is +
same
……… as in the absence of the
Assuming that
Assuming the concnAssuming
that thethat
Assuming of
concn sodium
the of that
concnsodium the
ion concn
in the
ion in ion
of sodium of sodium
solution
the in solution ion
is
the solution thein
is the is the
same
same solution
the as as
sameinin theis in
the
as the same
absence
absence
the as
ofofthe
absence in oftht
the
Assuming
Assuming that
complexing that
agent,the concn
the therefore,
concn of the of sodium
sodium distribution ion in the
ion in coefficients solution
the solutioncan is
is the the same
same astoin
be divided as in
get the
the the absence
absence
equation, of
of the the
complexing complexing agent,
complexing
agent, complexing
therefore, therefore,
agent, thetherefore,agent,
the distribution
distribution therefore,
the distribution
coefficients the
coefficientsdistribution can
coefficients
can bebe coefficients
divided
can
divided be divided
toto get can
get to be divided
equation,
theget to get th
the equation,
equation,
complexing
𝐷𝑀
complexing agent, therefore,
agent, therefore, the distribution distribution coefficients coefficientscan canbe bedivided
dividedto togetgetthe theequation,
equation,
1
𝐷 𝑀 + 𝛽𝐷 𝑀𝐿 +𝐷 𝑀𝛽 the  𝐿  2
+ … … …
𝐷𝑀
𝐷𝐷
=
(𝐿) =𝐷 𝑀1 + = 𝐷𝛽 11 + 𝐿 
=𝛽+ 1
1 𝐿+ 𝛽2+ 𝛽
=𝐿1 𝛽1
𝐿  +
22 𝐿++ …
2
𝛽𝛽1+ 𝐿…
2… …… 2
++ =
=…A A𝛽
… =
2 A
…𝐿…
M(L)  =+AM(L)
2
M(L) … … … = AM(L)
+ 𝛽1𝐿 𝐿 + 𝛽22𝐿 𝐿 +
𝐷𝑀𝑀 1 𝐷 2 2 M(L)
(𝐿) = 1 + 𝛽 +… …… …… … =
(𝐿) 𝑀 (𝐿) 𝑀 (𝐿) 2
𝐷 𝑀𝑀
𝐷 𝑀 (𝐿) = 1 + 𝛽1
=A AM(L)
M(L)
𝐷
The above eqn enables the A values forvalues different ligand
𝑀 (𝐿) The above The above
eqn eqn
enables
The above enables
the AM(L)
eqn the AM(L)
values
enables for for values
different ligandconcns
different ligand
concns to
to be
concns be calculated
to beconcns
calculated
calculated from
from fro
forthe A ligandfor different ligand to be
M(L) M(L)
The above eqn enables the AM(L) values different concns to be calculated from
The above
The above eqn
eqn enables
of enables thethethe of A A values
values for
for different
different ligand
ligand concns
concns totoabsence
bebe calculated from
ionincalculated andfrom
measurements the M(L)
distribution coefficient of the metal ion in question absence
measurements
measurements the of distribution distribution
measurements M(L)coefficient
ofcoefficient of the
the distribution of metal
the metal ion
coefficient ioninin question
ofquestion
the metalinin absence in andpresence
and
question inpresen
presence abse
measurements of the distribution coefficient of the metal ion in question in absence and presence
measurements
measurements
of of the
of
of the complexing
the complexing the
the distribution
complexing
distribution
agent, ofagent,
in
thesolutions in
complexing
coefficient
agent,
solutions in
ofsolutions
coefficient theof same
agent,
ofin
of
the the
same ionicmetal
ofsolutions
the the
metal same
ionic ion
ionionic
strength.
strength.
of
instrength.
in
the
question
question
From
same From From instrength.
in
related
related
ionic
absence
related
absence
AAM(L) A and
and
M(L) and
and
From
presence
and [L] valu
presence
[L]
M(L)
[L] values
values
related AM
of the complexing agent, in solutions of the same ionic strength. From related AM(L) and [L] values
of the
of the complexing
the overall
complexing the complex
overall
agent,
agent, complex
in solutions
stability stability ofcan
constants constants
the same
can can
ionic
beionic bestrength.
computed. computed.
strength. From relatedA AM(L) and[L] [L]values
values
the overall complex thein
stability solutions
overallconstants complex of the same
stability
be [Link] can Frombe related
computed. M(L)and
the overall complex stability constants can be computed.
complex stability
the overall complex stability constantsconstants can can be be computed.
computed.
positively charged
If the metal complexes
ion is in are also
an oxidation stateformed whichgreater
numerically are absorbed bynegative
than the the cation exchanger.
charge on the In such
ligand,
cases the method
positively chargeddeveloped
complexesby
areFronaeus canwhich
also formed be used.
are The error by
absorbed of the
the cation
cation-exchange
exchanger. method
In such
increases
cases the with increasing
method ligand
developed number. Itcan
by Fronaeus canbe
beused.
used The
mainly forof
error N the
< [Link]-exchange method
increases with increasing ligand number. It can be used mainly for N < 4.
The use of anion-exchanger is advantageous in cases where the ligands are of small size, that is,
the
Thenegatively charged complexes
use of anion-exchanger formed can
is advantageous in be absorbed
cases where by
the the resinare
ligands without anysize,
of small significant
that is,
difficulty caused
the negatively by slow
charged diffusion,
complexes and where
formed can be the formation
absorbed of resin
by the complexes ofany
without higher ligand
significant
numbers
Suppose,isthere
difficulty being
causedis studied.
aby slow L,
ligand, diffusion,
bearing one and negative
where the Cl −, and
formation
charge, of of
complexes of higher
all the species formed ligand
with
−
Suppose, there is a ligand, L, bearing one negative charge, Cl , and of all the species formed with
numbers is beingz+studied. Suppose, there complex
is a ligand,species
L, bearing one negative −
charge,charge
Cl , andisofbound
all the spec
the metal ion M , only the mononuclear bearing p negative on
z+
the metal ion M , only the mononuclear complex species bearing p negative charge is bound on
the metal ion Mz+, only the mononuclear complex species bearing p negative cha
the resin. The equilibrium constant of the ion exchange reaction is given as 
the resin. Thepequilibrium constant of the ion exchange reaction is given as 
p The equilibrium constant of the ion exchange reaction is given as 
the resin.
MLn + (L) ⇄ (MLn) + L
MLn + (L)p ⇄ (MLn) + ML L
n
p + (L)p ⇄ (MLn) + Lp
𝑀𝐿𝑛 𝐿 𝑝
p = n − zK = 𝑀𝐿𝑛 𝐿 
𝑝
Kx = 𝑀𝐿𝑛 𝐿 𝑝𝑝 p= n−z
Kx = 𝑀𝐿𝑛 (𝐿)𝑝 p = n − z x 𝑀𝐿𝑛 (𝐿)𝑝
𝑀𝐿𝑛 (𝐿)
If the amount of metal ion isIfvery small compared
the amount of metal ion with the
is very capacity
small of the
compared withresin, i.e., (ML
the capacity 
n) resin
of the
If the amount of metal ion is very small compared with the capacity of the resin, i.e., (ML n) 
(L), and the ionic strength (L), and the ionicasstrength
is considered is considered
constant, then to as constant,
a first then to a firstKapprox
approximation, x is
(L), and the ionic strength independent
is considered of theas constant, then to a first approximation, K x is
concns.
independent of the concns.
independent of the concns. By multiplying both the numerator and denominator of the fraction by CM 
By=multiplying
MMLLnn •• CC both •the Lnumerator
p and denominator of the fraction by C M 
M • (L),L
M
K
Kxx = independent By multiplying
of the concns. both the as numerator
constant, and then denominator of the fraction by C M 
C • MM L   • L(L)pand p the ionic strength is considered to a first approximation,
 K x is
M  
K = M C LM C L Byn multiplying
(L) p By both the
multiplying numerator
both the and denominator
numerator and of
denominator the fraction
of the by C
fraction M by C
By multiplying
x Mn M both
M n  the (L) numerator
p
L p andboth denominator of the pfraction of bytheCfraction M
Kx = C
M ML n• L CnM• independent By multiplying
of the concns. M L the numeratorC and Ldenominator by C M 
Kx =
The C MfactorM
first •onL n  right
the right(L)
M •L
p
hand
n side side
p C MKM
of xL =
the
n
LCpM• is the
equation
M
L p
•distribution
ispdenominator
the coefficient of the metal ion
The first
The first M factor
L
Cfactor
M n
on
on
the
MCK
the ML
x = 
rightByhand L(L)•
multiplying
hand
n C Kx = M L CM K p
xM
side
of
= L the
both
of
n
n
theequation
the• •
numerator
C M
equation
M M
L
and• L
is n
distribution
the (L)pof coefficient
 p distribution the fraction byof
coefficient CM the
 metal ion
of the metal ion
K = • • • equation(L) MppL•n  (L)
Thex
M and first
and the factor
the secondon the
isistheright hand
thereciprocalM
reciprocal side of
valuenthe
C Mof of M the n  mole
L is the p distribution
(L)fraction coefficient
of complex
the complex of the
species metal
withion ligand
M and C
the M
second
second M isL n
the K
M L npvalue
(L)
reciprocal
x = •
C MThe
value
the
first
•
of
L mole
factor
the mole
fraction
on the
fraction
of the
right hand
of side
the of
complex
species
the equation with
species is ligand
the
withdistribution
ligand coefficient of
The
M and
number,
first
number, n. the factor
second
[Link]
Thatis,
on
is
is, The
thethe right
first
reciprocal CM
factor handThe
on
value
The first factor
Mside
first
the Lof
n
factor
 the
right of
on
the
on
(L)
hand
the
pthe
moleright
equation
rightof
side
fraction
hand
hand
the
side ofis
side the
equation
of the
the
distribution
of the equation
is
complex
equation the is
is thecoefficient
distribution
species
the
distribution
with
distribution coefficient
ligand
coefficient
of the
coefficient
of
of themetal
the
of
metal
metal
ion
the metal
ion i
ion
Mthe and the second is the reciprocal value of the mole of fraction of the species
complex species
The [Link]
number, That onM
is, the and
right
The hand
first M and
factor
thereciprocal
second
side
on the
issecond
the
ofrightthe
second hand
reciprocal
equation
isside
the of
valuethe is
reciprocal the
equation
of the
distribution
value
is the
mole
the molecoefficient
ofdistribution
fraction
fraction
coefficient the
of of
the the
complex
metal metal
ion ion with ligan
M and n.
number, the Thatsecond
11 is, L L is
p p the M and the
number,value is the
n. ofreciprocal
That the
is, mole valuefraction
of the mole the of
of fraction the
complex
of thecomplex species
complex species with
species with ligand
withligand
ligand
KMxx =and
= DDM •• second
Mthe 1 •• (L) L
is p M and
p pthe reciprocal
p
the number,
second
That is,n. value
is [Link] That is,
reciprocal
That is, of the mole
value of the mole fraction of the complex
fraction of the complex species with ligand species with ligand
DMM•• ∅1 L
number, [Link],
• • (L)
number,
Kxx == D n. ∅ 𝑛That
𝑛 (L)
is, 1 p L p
p L •
K number, n. That is, 1
∅∅ pp K x1 =•
p D M • L•
1 M •L
number, n. That
𝑛 is,
(L) K = D
  −p 𝑝 𝑝Kx1= D
𝑝𝑝 x M p
Kx𝐿 =D •
𝑛 − Lp∅ ∅(L)
𝑛 p (L)
D
DM M = Kxx ∅
= K ∅ (𝐿)
𝑛𝑛 1(𝐿)𝑝 𝑝 𝐿 L KM x =•DM • • • ∅𝑛p p 𝑛
(L) p
KMM
D
D x = ==D KK xx∅
M •
∅ 𝑛𝑛 1(𝐿)•𝐿
(𝐿)  
L
𝐿 p
−
p
−𝑝 𝑝 ∅ 𝑛 ∅𝑛 (L)
D
(L)
∅
= K (𝐿) ∅ 
𝑝 (𝐿)𝑝
𝐿  −𝑝
 𝐿  −𝑝
𝑛− 𝑝𝐿  is a function of the ligand concn and of the
− 𝑝
If
KK K= x and
DM(L) • are ∅ • (L)
𝑛 constant, the D
distribution
= Kx𝑝∅
M = K
M
𝑝𝑛coefficient
x
 (𝐿)
𝑝
x 𝑛
M = Kx ∅𝑛 (𝐿) 𝐿 
If x x and (L)
∅are constant,
(L) p
D Mthe=D KMdistribution
x ∅𝑛 (𝐿) 𝐿 −𝑝
coefficient is a function of the ligand concn and of the
If K
If Kxx andand(L) (L)are 𝑛
are D
constant,
constant, the the distribution
distribution
If [Link] coefficient
coefficient
(L) are(L) areis
constant, a is adistribution
function
the function
the of theof the isligand
ligand
coefficient concn concn
and
is a function a and
is of the
of theofligand
the concn andconc
of t
x If Kare and constant, distribution coefficient function of the ligand
 
mole fraction of the complex
𝑝 If Kxspecies −
If K𝑝 x and
x
are (L) constant, the distribution
coefficientcoefficient a the
function
ligandof the ligand concn and of the
mole = Kx ∅
fraction of (𝐿)
the complex 𝐿 − species
and (L) bound.
constant, the distribution is a function of concn and of the
 
DM fraction 𝑛the If 𝑝K x and species
(L) 𝑝 are constant, the distribution coefficient
bound. is a function of the ligand concn and of the
mole
mole
DM =fraction
Taking Kx ∅of
logarithms 𝑛
of (𝐿)
the
andcomplex 𝐿
complex
differentiating
mole
mole
species
mole
fraction w.
fraction
mole
bound.
fraction
of bound.
the [Link]
t. log
the
of
offraction
the
L
complex
species
complex
of
 the species
bound.
species
complex [Link] bound.
Taking logarithms and differentiating Taking
w. r. t. logand
logarithms
Ldifferentiating
 w. r. t. log L log L 
If log
Kx 𝐷
Taking
𝑑
Taking and (L) 𝑑are
logarithms
logarithms mole
and
log constant,
and fraction
∅differentiating
TakingTaking
differentiating of
logarithmsthew. [Link]
Taking
the distribution r. t.r.
logarithms
and log
[Link] L
species
logarithms
differentiating
log  w.
L
coefficient bound.
and
differentiating r. [Link]
logw. L
isr.a log L
t. function w. r. [Link] the ligand concn and of the
∅ 𝑑−logp 𝐷
𝑀
𝑑If log
Kx and 𝐷 𝑀 (L) = are 𝑑 log constant, the𝑑distribution assuming coefficient K and is
(L) a function
are constant of the ligand concn and of the
− log 𝐷log 𝑑 ∅ log 𝑑 ∅ log
L 
x
𝑑𝑑 log
log 𝐷[𝐿] = 𝑑 𝑑 log
logTaking
[𝐿]
∅ logarithms
𝑑p 𝑀log 𝐷 𝑀𝑑𝑑
and log =𝐷𝑀 assuming
𝑀 differentiating
∅𝑑 log
−𝑑 p= − K − w.K ∅
p r. t.
−
and log(L) are assuming
constant
−
𝑑
molelog 𝐷 𝑀
fraction 𝑑 log
of log
the[𝐿] ∅complex =
species = [𝐿]bound. xassumingpareassuming
Kx and (L) are K
Kxassuming andare
constant
andx(L) (L) are constant
𝐷−
𝑑 log [𝐿]𝑀 = 𝑑 p 𝑑 log [𝐿] assuming log [𝐿] p x and (L) constant Kconstant
x and (L) are constant
mole
𝑑 fraction = 𝑑oflog the 𝑑
complex log [𝐿]
𝑑p logspecies 𝑑 log
[𝐿] 𝑑 log bound.
𝑑[𝐿] log assuming
[𝐿] 𝑑 log [𝐿] Kx and (L) are constant
𝑑 log
The log
right[𝐿]
[𝐿]hand side 𝑑 log 𝑑[𝐿]
of log
[𝐿]The
the 𝑀
equation =
𝑑
gives logthe ∅
−
average charge number. That number.
assuming is,Kx and
Taking
The
Taking logarithms
rightlogarithms
hand side 𝑑 of and
and thedifferentiating
log [𝐿]equation The
differentiating
right hand
The right 𝑑
right
side
gives
loghand
The
ofhand
[𝐿]
thew.
the
sider.
right
w.
sidep
r.
equation
average
[Link]
hand
of
t.
log
the
log
gives
side L L
equation
the
charge
equation 
of the 
averagegives
number.
gives the
charge
the average
equation
average
Thatcharge
gives
That(L)
charge
is,average
the
is,are
number.
constant
[Link] That
charge is, is, That is,
number.
The
𝑑 logright𝐷 𝑀hand side of the 𝑑equation 𝐷 𝑀 𝑑 gives the average charge number. That is,
The right hand
= 𝑝 side of the log equation
𝑑 log = log
𝐷𝑝 𝐷 𝑀 the average charge number. That is,
gives
𝑀𝑑 log=𝐷𝑝
𝑑
𝑑 log
log 𝐷𝐷 𝑑The log 𝑑∅log 𝑝 equation
−
𝑀𝑀 right hand
[𝐿] 𝑑side = the
of 𝑀 gives the average charge number. That is,
𝑑𝑑 log
𝑑 log
log𝐷 [𝐿]
𝐷 = 𝑝 𝑑 log ∅ = 𝑝 assuming
−
log [𝐿]
𝑑𝑑 log
log 𝐷 𝑀𝑀
[𝐿]𝑀 = 𝑝
== 𝑑 log
p p [𝐿] 𝑑 log [𝐿] assuming K Kx and
x and (L) (L)
are are constant
constant
𝑑
The log
𝑑𝑑 log
log [𝐿][𝐿] = 𝑝
[𝐿]
following 𝑑
𝑑 𝑑log
relationshiploglog [𝐿]
𝐷exists
The
[𝐿] 𝑀 following
between
The
relationship
following the
exists
average
relationship
between
charge
the
exists
average
number
between
charge
and
number
the ligand
average
and
number
ligand number if the
charge if and
numberthe ligand
and ligand number
if theif t
𝑑 log [𝐿] =
The 𝑝 following
The
relationship
following
exists
relationship
between
exists
the
 the average charge number and ligand number if the
average
between
charge
the
number
average charge number
number
and ligand n
The following
followingrelationship 𝑑 logsign
relationship [𝐿] is also considered
exists between
The
The
sign right hand sideof ofthe exists
the between
sign
equation is also the
gives average
considered the 
 average charge
average number
charge and
[Link] number
That is, if the
Theis
The
also hand
right
following
consideredside
relationship 𝑝 =
sign
equation
𝑁
exists 𝑝
is also gives
∅between
sign
=
considered
z −
is the
also
𝑛
the average
considered
-------B charge
charge number.
number and That
ligand is, number if thenumber if the
 0 𝑖 𝑖
− z𝑛− 𝑛 -------B
sign is also considered 
considered The following relationship𝑁 exists between the average charge number and ligand
sign
𝑝
𝑑𝑑 =logis also
𝑁
𝐷
𝐷 𝑝 ∅ = z − 𝑛 =𝑝 =0 𝑝0𝑖 ∅𝑝𝑖 𝑖 =
𝑝 -------B 𝑁 ∅ 𝑖z= -------B
sign is also 0 𝑀
𝑀 𝑖
𝑁 considered
=
= 𝑖
𝑝𝑝 sign is also considered 𝑝 = 0 𝑝𝑖 ∅𝑖 = z − 𝑛
𝑁
-------B
𝑝
𝑝𝑑 =
𝑑=log 0
𝑁
[𝐿]
[𝐿]𝑝∅ =z−𝑛
𝑝 ∅ = z − 𝑛 -------B
-------B
0𝑁 𝑖𝑖 𝑖 𝑖
𝑝 = 0 𝑝𝑖 ∅𝑖 =𝑝z =− 𝑛0 𝑝𝑖 ∅𝑖-------B 𝑁
=z−𝑛 -------B
 If the distribution slopeof
coefficient ofathe curve
metal at on
ion anyan
point gives the average
anion-exchange charge
resin is number from
determined which
for the average ligand
solutions
If the distribution
complex ion is formed. coefficient of a metal ion on an anion-exchange resin is determined for solutions
number can be obtained from the above equation, B. The overall stability constant can be
in
If in which
thewhich the ligand
the ligand
distribution concn
of a is
concn
coefficient is different,
different,
metal and
and
ion on an the
the results
results are
anion-exchange resinplotted
are plotted in
in a
is determineda log
log D
D vs log L
vs log
for solutions L graph
graph the
the
At the maximum the slopecalculatedis zero, andfrom 𝑝 the=related 𝑛 the
0, i.e., and uncharged speciesearlier.
[L] values discussed predominates.
inslope
which of
thethe curve
ligand at
concn any
is point
different, gives
and thethe average
results are charge
plotted in
slope of the curve at any point gives the average charge number from which number
a log D vs from
log L
which
graphthe
the average
the average ligand
ligand
For a univalent ligand, The
the ligandlog D vs
numberlog L
is curve
equal has a maximum
to the and
oxidation a part
state of negative
of the slope
metal if aznegatively
ion,can n at charged
= be
number
slope of the can
curvebe
at obtained
any point
number can be obtainedcomplex from
gives the
the
from ion above
average
theisabove equation,
charge number B.
fromThe overall
which the stability
average ligandconstant
equation, B. The overall stability constant can be
formed.
the maximum.
number can be obtained from the above equation, B. The overall stability constant can be
calculated
calculated from
from the
the related
At 𝑛
related 𝑛 and [L]
the and [L] values
maximum values discussed
discussed
the slope
earlier.
𝑝 = 0, i.e., the uncharged species predominates.
earlier.
is zero, and
calculated from the related 𝑛 and [L] values discussed earlier.
The
The log D vs log L
L curve
For has a
a maximum
a univalent andligand
ligand, the a
a part of negative
number is equal slope if a
a negatively
to the oxidation charged
state of the metal ion, z = n at
The loglog D log
D vs vs L
log curvecurve has
has a maximummaximum
and a partand part
of negativeof negative
slope slope
if a negativelyifcharged
negatively charged
complex
complex ion isis formed.
formed. the maximum.
complex ion ion
is formed.

AtAt
Atthethe maximum
maximum
the the
the slope
the slope
maximum is
is zero,
slope zero,
isand 𝑝 =and
zero, 𝑝
𝑝=
0, i.e.,
and the0,
= i.e.,
i.e., the
the uncharged
0,uncharged species
species predominates.
species predominates.
uncharged predominates.
For
For a univalent
univalent
a univalent
For a ligand,
ligand, the ligand
the ligand
ligand, the ligand number
numbernumber is the
is equal to
is equal to the
thestate
oxidation
equal to oxidation stateion,
of the metal
oxidation state of the
of the
z=n metal
at
metal ion, z
ion, z==n
n at
at
the maximum.
the maximum.
the maximum.

When complexes of low stability are being studied, high ligand concns should be used. But in such
cases, the ionic strength cannot be maintained
When complexes constant.
of low stability Perchlorate
are being which
studied, high ligand is inertshould
concns in complex
be used. But in such
cases,bound
formation reactions is strongly the ionic strength cannot be resins
in anion-exchange maintained
andconstant.
so cannotPerchlorate
be used which is inert in complex
for adjusting
constant ionic strength information reactions is strongly bound in anion-exchange resins and so cannot be used for adjusting
solutions with lower ligand concns. If displacement of ligand by
constant ionic strength in solutions with lower ligand concns. If displacement of ligand by
When complexes of low stability are being studied, high ligand concns should be𝑀𝐿 𝑛 But
used. 𝐿 in such
𝑝
perchlorate occurs, the following eqns are no longer valid : Kx = 𝑀𝐿𝑛 𝐿 𝑝
and
perchlorate
cases, the ionic strength cannot occurs,
be maintained the following
constant. eqns are
Perchlorate which 𝑀𝐿
no longer
is 𝑛
inert in
(𝐿)
valid : 𝑝Kx =
complex 𝑀𝐿𝑛 But
and
(𝐿)𝑝in such
When complexes of low stability are being studied, high ligand concns should be used.
When complexes of low stability are being studied, high ligand concns should be used. But in such
∅ (𝐿) 𝐿 
formation reactions is𝑝strongly− 𝑝 in anion-exchange
bound resins and so cannot be used for adjusting
DMcases,
= Kxthe
cases, the 𝑛ionic strengthDcannot
M = Kxbe∅ (𝐿) 𝑝
𝐿
maintained
be𝑛lower
 −𝑝
constant. Perchlorate which is inert in complex
constant ionicionic strength
strength cannot
in solutions with maintained constant.
ligand concns. Perchlorate which
If displacement of ligand is by
inert in complex
formation reactions is strongly bound in anion-exchange resins and
𝑝 so cannot be used for adjusting
Above a certain ligand concn limit, (L) cannot be constant, and on differentiation of the eqn,
DM = Kx ∅𝑛 (𝐿)𝑝 𝐿
−𝑝
another term remains in addition to the average ligand number. Marcus
and Coriell calculated the dependence of (L) on [L] by taking the Donnan equilibrium into account
and corrected the distribution coefficient.
The absorption of negatively charged ligands (anions of acids) on an anion-exchange resin can be
influenced by complex-forming metal ions. The distribution equilibria can be calculated by taking
into account the ion-exchange equilibrium constants of the complexes formed. The relationships
can be used for calculating stability constants, if the experimental relationship between the
distribution coefficient and the concn of the complex-forming metal ion is known.

Precautions
1. Strongly acidic cation exchanger or strongly basic anion exchanger should be used in the
experiments as the ion-exchanger is a strong electrolyte.
2. A medium cross-linked resin is suitable for metal ions or anions- Cl, CN of usual size. A
microporous or mesoporous (particle size- 50-100 mesh) resin should be used depending upon the
size of the metal ions or complex to be absorbed.
3. Low metal ion concn should be used in preparing solutions provided it can be determined with
Precautions
Precautions
1. Strongly
1. Strongly acidic
acidic cation
cation exchanger
exchanger or
or strongly
strongly basic
basic anion
anion exchanger
exchanger should
should be
be used
used in
in the
the
experiments as the ion-exchanger is a strong electrolyte.
2. A
2. A medium
medium cross-linked
cross-linked resin
resin is
is suitable
suitable for
for metal
metal ions
ions or
or anions-
anions- Cl,
Cl, CN
CN of
of usual
usual size.
size. A
A
microporous or
microporous or mesoporous
mesoporous (particle
(particle size-
size- 50-100
50-100 mesh)
mesh) resin
resin should
should be
be used
used depending
depending upon
upon the
the
size of
size of the
the metal
metal ions
ions or
or complex
complex to
to be
be absorbed.
absorbed.
3. Low
3. Low metal
metal ion
ion concn
concn should
should be
be used
used in
in preparing
preparing solutions
solutions provided
provided it
it can
can be
be determined
determined with
with
sufficient accuracy. In using the cation exchange method, it is very important to use the same
counter-ion in
counter-ion in the
the same
same concn.
concn. This
This ion
ion which
which does
does not
not take
take part
part in
in the
the complex
complex formation,
formation, is
is
responsible for
responsible for maintaining
maintaining the
the position
position of
of the
the ion-exchange
ion-exchange equilibrium
equilibrium in
in each
each experiment.
experiment.
4. pH should be kept constant if the ligand taking part in the complex formation tends to protonate.
If using
If using liquid
liquid ion-exchangers
ion-exchangers instead
instead of
of ion-exchange
ion-exchange resin,
resin, pH
pH should
should be
be kept
kept constant
constant
throughout the
throughout the series
series of
of experiments
experiments as
as liquid
liquid ion-exchangers
ion-exchangers are
are weakly
weakly acidic
acidic or
or weakly
weakly basic
basic
and
and their
their capacity
capacity depends
depends on
on the
the pH
pH of
of the
the solution
solution in
in contact
contact with
with them.
them.
5.
5. It
It is
is advisable
advisable to
to use
use static
static batch
batch method
method in
in determining
determining distribution
distribution coefficients.
coefficients. The
The time
time
required to attain equilibrium is determined by the rate of diffusion and thus the two phases should
be
be stirred
stirred for
for an
an appropriate
appropriate length
length of
of time,
time, i.e.,
i.e., for
for several
several hours.
hours. After
After equilibrium
equilibrium has
has been
been
reached,
reached, the
the concn
concn of
of the
the distributed
distributed component
component can
can be
be determined
determined in
in the
the two
two phases
phases by
by
radioactive tracer technique or by instrumental methods like spectrophotometry.
6.
6. The
The ions
ions absorbed
absorbed on
on the
the ion-exchanger
ion-exchanger can
can be
be determined
determined after
after elution
elution with
with a
a solution
solution of
of
appropriate
appropriate composition.
composition.