Chapter 26

Conditional Stability Constants

The introduction of conditional stability constants permits us, from a theoretical

standpoint, to treat a complexation equilibrium to which are superimposed other
equilibria of any nature as if it were alone, at least in some conditions. Conditional
stability constants were introduced by G. Schwarzenbach 1957 to take into account
acido-basic phenomena occurring simultaneously with complexation phenomena.
The first case for which conditional stability constants were introduced concerned the
titration of some metallic ions with EDTA tetraanion. The scope of their application
scope was extended to other parasitic phenomena by A. Ringbom 1959.

26.1 Species Existing in Solution When a Metallic

Ion Is Titrated with EDTA

In a typical titration of a metal cation with EDTA tetraanion, the solution in the reac-
tion vessel, among other species, contains the formed complex [MEDTA](n4)+ , free
remaining metallic ions Mn+ , hydroxo complexes resulting from their hydrolysis,
and some complexes formed with a possibly present buffer. Usually, the latter are
those formed with ammonia and with acids-alcohols (see Chap. 28).
We have become aware of the complexity of the titrand solutions composition and
of the difficulty in calculating the different species concentrations after all the reac-
tions in the reaction vessel have taken place. It indeed appears to be a true challenge.
Fortunately, the formation of polynuclear complexes, which would complicate the
calculations even further, may be neglected since the concentrations of these deriva-
tives are usually very weak close to the equivalence point. This is due to the strong
complexing power of EDTA. But the titrand solution also contains other species,
which this time come from the addition of the titrant. They are the protonated forms
of EDTA: HEDTA3 , H2 EDTA2 , H3 EDTA , and H4 EDTA. The complex under
study, [MEDTA](n4)+ , may possibly capture a proton or a hydroxide ion, therein ex-
hibiting a basic or acidic character. Finally, we shall see that a secondary complexing
agent may be added (see Chap. 28). This once more complicates our calculations.

J.-L. Burgot, Ionic Equilibria in Analytical Chemistry, 485

DOI 10.1007/978-1-4419-8382-4_26, Springer Science+Business Media, LLC 2012
486 26 Conditional Stability Constants

grading : EDTA4, HEDTA3, H2EDTA2, H3EDTA, H4EDTA

M, [M(OH)], [M(OH)2], etc.

[M(NH3)], [M(NH3)2], etc.
NH4+/NH3 [MEDTA], [M(H)EDTA], [M(OH),EDTA]

Fig. 26.1 Various species that may be present in the titration of a metallic ion M with EDTA or
with its anions (the possible presence of a secondary complexing agent is not mentioned)

26.2 Conditional Constants, Parasitic Reaction Coefficients,

and Apparent Concentrations

Using conditional constants permits us easily and rapidly to quantitatively predict

the course of complexes formation reactions that would occur in the experimental
conditions depicted in the previous section. However, the prediction can be performed
only at the cost of some approximations, which can be legitimized.
The underlying principle of the conditional constant concept is that in analysis,
the concentration of utmost importance is that of the anticipated complex, and not
necessarily that of any other species in the reaction vessel.
Lets consider the classical titration of a metallic ion1 M with H4 EDTA or with
one of its anions in a medium buffered with the couple NH4 +/NH3 . Suppose that
the metallic ion also gives hydroxo and ammine complexes. Both behaviors are
normal. Well also suppose that the complex under study, [MEDTA], exhibits an
acidic character by capturing a hydroxide anion to give [MEDTA(OH)] or a basic
character by capturing a proton to give [MEDTAH], or even exhibits both characters.
(The latter two behaviors are less typical than the previous one.) These possibilities
are summarized in Fig. 26.1.
Let [M] be the total concentration of the metallic ion for whatever species it is
engaged in except for the exact complex in which we want to engage it and also the
hydroxylated or protonated forms of this complex; that is,
[M] = [M] + [M(NH3 )] + [M(NH3 )2 ] + + [M(OH)] + [M(OH)2 ] + .
Lets call [EDTA] the total H4 EDTA concentration (tetraacid and its anions) except
for the concentration of the complex under study:
[EDTA] = [EDTA]4 + [HEDTA]3 + [H2 EDTA]2 + [H3 EDTA] + [H4 EDTA]
and let [MEDTA] be the total concentration of the mononuclear complex under
study:
[MEDTA] = [MEDTA] + [MHEDTA] + [M(OH)EDTA].

1
Henceforth, for the sakes of generality and simplicity, we will omit electrical charges except in
some particular cases.
26.2 Conditional Constants, Parasitic Reaction Coefficients . . . 487

(Polynuclear complexes are of little interest in analysis. However, they can also be
taken into account in analysis through conditional constants. This will not be the
case here.) [M] , [EDTA] , and [MEDTA] are called the apparent concentrations of
the metallic ion, of EDTA, and of the complex, respectively.
We shall demonstrate that apparent concentrations are given by the following
expressions:

[M] = M [M],
[EDTA] = EDTA [EDTA4 ],
[MEDTA] = MEDTA [MEDTA],

where M , EDTA , and MEDTA are coefficients that depend on the nature of the
species and on the experimental conditions. According to the IUPAC, they must be
called parasitic reaction constants. Taking the stability constants of the different
complexes into account, it is easy to check, after the expressions that define [M] ,
[EDTA] , and [MEDTA] , that, for example,

M = 1 + 1 NH3 [NH3 ] + 2 NH3 [NH3 ]2 + + 1 OH [OH ] + 2 OH [OH ] + ,

2

where 1 NH3 = [M(NH3 )]/[M][NH3 ], 2 NH3 = [M(NH3 )2 ]/[M][NH3 ]2 ,

1 OH = [M(OH)]/[M][OH ], etc.,

and Y = 1 + 1 Y [H+ ] + 2 Y [H+ ]2 + . (with Y EDTA for the sake of

brevity), MY = 1 + KMHY [H+ ], where 1 NH3 , 2 NH3 , 1 OH , etc. are the overall
stability constants of the ammine and hydroxo complexes. 1 Y is the inverse of the
ionization constant Ka4 of EDTA:

1Y = 1/Ka4 ,
1Y = [HEDTA3 ]/[H+ ][EDTA4 ].

2 Y and so on are defined in the same manner.

The interest in conditional constants lies in the fact that they can be easily calcu-
lated. Indeed, for Y and MY it is sufficient to know the solutions pH, the constants
1 Y , . . . , and KMHY being determined once and for all. The calculation of M appears
to be more complicated since the unknown concentration of free ammonia [NH3 ]
intervenes in its expression. We only know its analytical concentration, which is
given by the expression

CNH3 = [NH3 ] + [M(NH3 )] + 2[M(NH3 )2 ] . . . .

However, if a great excess of ammonia compared to the metallic ion concentration

is added, the ammine complexes concentrations remain negligible with respect to
the free ammonia concentration. Therefore, we can write

[NH3 ] CNH3 .
488 26 Conditional Stability Constants

In these conditions, the calculation of M is immediate since the stability constants

intervening in its expression are known. (Lets recall incidentally that the strategy
consisting of adding a great excess of reagent to simplify calculations is a method
frequently used in analytical chemistry. The closer we are located to the equivalence
point, the better the condition [NH3 ] CNH3 is since, by the definition of a satisfac-
tory titration, the cation and ammine complexes concentrations must be very weak
at this point.)
The conditional constant K  prevailing in the above experimental conditions is
calculated from the thermodynamic constant K as follows. The expression of the
thermodynamic constant K is

K = [MY]/[M][Y].

It does not take into account phenomena other than that of the complexation under
study. In the framework of the introduction of conditional constants, K  governing
the equilibrium under study is defined by the relation

K  = [MY] /[M] [Y] .

This is the constant of prime interest to the analyst. It indeed governs the stability of
the complex as a function of the ligand and metallic ion concentrations regardless of
their form in the experimental conditions. By comparing the expressions K and K  ,
we find

K  = KMY /M Y .

Hence, K  is easily calculable since K is known definitively, and the coefficients

are calculated as explained above.
The first point to underline is the fact that the conditional constant is really a con-
stant in the given experimental conditions. The second point to stress is that the
coefficients must be greater than 1 due to their polynomial structure containing
unity. If the complex under study exhibits no acidic or basic character, MY = 1 and

K  = K/Y M .

As a result, the conditional constant must be weaker than the thermodynamic one:

K  < K.

The complex yield we are seeking is less important than that expected according
to the thermodynamic constant. The ratio K  /K may even be very weak. When the
complex exhibits a basic or acidic character, MY , which is also superior to unity,
tends to increase the value of the conditional constant. However, experience shows
that conditional constants are always lower than the corresponding thermodynamic
ones.
The change of K  with MY , Y , and M is difficult to predict, especially the
change with M . This parasitic reaction coefficient is indeed composed of two poly-
nomials, one taking the complexation with the buffer into account, the other the
26.3 Examples of Conditional Constants Calculations 489

formation of hydroxo complexes. Changes in both polynomial values occur simul-

taneously and independently. This is the reason why the M coefficient changes and,
consequently, why K  is difficult to predict.

26.3 Examples of Conditional Constants Calculations

Exercise 1 Calculate the conditional constant of the nickelEDTA complex in

a solution buffered with a mixture of ammonia (0.1 mol/L) and ammonium ions
(0.1 mol/L). The measured pH is 9.24 (pK a value of ammonium ion). The stability
constants are 1 NH3 = 102.80 , 2 NH3 = 105.04 , 3 NH3 = 106.77 , 4 NH3 = 107.96 ,
5 NH3 = 108.71 , 6 NH3 = 108.74 , 1 OH = 103.4 , 2 OH = 1010.2 , and 3 OH = 1013 ;
MY = 1, and K(Ni-EDTA2 ) = 1018.56 .
[NH3 ] 0.1 mol/L (pH = pK a ). Using the expression

M = 1 + 1 NH3 [NH3 ] + + 1 OH [OH ] +

gives M = 1.5104 . Through this calculation, we find that hydrolysis (formation of

hydroxo complexes) has a very weak influence on the formation of the nickelEDTA
complex. It is the formation of amminenickel that exerts a strong such influence.
From another standpoint,

Y = 1 + 1.82 1010 [H+ ] + 2.62 1016 [H+ ]

2

+ 1.23 1019 [H+ ] + 1.20 1021 [H+ ] ;

3 4

Y = 11.5. Since MY = 1,

K  = 1018.56 /(1.51 104 11.5), K  = 2.1 1013 .

K  is considerably smaller than K (about five orders).

Exercise 2 Calculate the conditional constant of the CuII EDTA complex at
pH = 13 in the absence of any buffer and of any other complexant. (We shall
not take the acidic character of the complex or the formation of a binuclear complex
into account.) We give K = 1018.8 and 1 OH = 106 .

Y = 1,
M = 1 + 106 1014 /1013 ,
K  = 1013.8 .

Exercise 3 Express the conditional constant of the EDTAmagnesium complex as

a function of pH in the presence of the buffer ammonia at a 101 mol/L concen-
tration. We give 1 OH = 102.58 , K(MHY) = 103.85 , pK a (NH4 +/NH3 ) = 9.24, n
490 26 Conditional Stability Constants

Fig. 26.2 The coefficient Mg buffer

as a function of pH with and 0,3
without the buffer NH3 added
M
0,2

log M
0,1

0
8 9 10 11
pH

(Mg(NH3 )n ) with 1 < n < 6: 1.70, 1.20, 0.457, 0.091, 0.01, 5.0 104 (n going
from 16). In order to solve the problem, we suppose that in the presence of EDTA,
the metallic ion concentration is very weak (otherwise, complexation would present
no interest!). The ammonia concentration obeys the following relations:

[NH3 ] + [NH4 + ] = 0.10,

[NH4 + ] = 1.78 109 [H+ ][NH3 ],

[NH3 ] = 0.10/(1 + 1.78 109 [H+ ]).

(We must note that this expression is legitimate only if the ammine complexes
concentrations are negligible in the mass balance relation on the buffer.) Developing
the stability constants expressions as a function of the concentration of magnesium
ions gives

M = 1 + 1.70[NH3 ] + 1.20[NH3 ]2 + + 3.98 1012 /[H+ ].

Replacing [NH3 ] by its above expression as a function of [H+ ] permits us to draw

M as a function of pH (Fig. 26.2). The figure also mentions the change in M with
pH when no ammonia is added. In this case, at high pH values, M increases only
because of the formation of the hydroxo complex [Mg(OH)+ ]. The coefficient Y
is given by the expression given in Exercise 1. In the pH range where the buffer is
efficient,

MY = 1;

i.e., [MY ] = [MY].

As a result, we obtain

K  = K/M Y .

Evidently, K is a complicated function of pH. At pH = 9, for example, the

conditional constant is about 200 times weaker than the thermodynamic one.
26.4 Quantitative Changes in Coefficients 491

Fig. 26.3 Diagram Y /pH log Y

(Y EDTA) 12

pH
14 12 7 2 0

26.4 Quantitative Changes in Coefficients

The important point to notice is that the coefficients may change considerably
with experimental conditions. This proves, in some manner, the vanity of the pre-
diction of the extent of complexation reactions according to the only consideration
of thermodynamic constants.
Concerning the L coefficients (devoted to the ligands), they usually are intro-
duced to take their basic character into account. Hence, they vary with the pH value.
EDTA is perhaps the most important example of this kind of behavior. The expression
that permits the calculation of its Y coefficient is given in Exercise 1.The diagram
Y /pH is calculated and drawn once and for all (Fig. 26.3).
Through this example, we see that the Y coefficients may considerably change
with the pH value. For example, at pH = 2.3, log Y = 12, and at pH = 12,
log Y = 0. Diagrams of this sort, but fitting some other basic ligands such as oxalate,
acetate, fluoride, etc., have been drawn definitively. A particularly important case of
such ligands for chemical analysis is that of metal ion indicators (see Sect. 26.7).
Concerning the metal cations, their coefficients, M , are usually introduced to
take into account the formation of complexes with the buffer, in particular ammonia,
and also to take their hydrolysis into account. In Fig. 26.4, we give log M values
for some metallic ions that form ammine complexes. Log M is plotted as a function
of the analytical concentration of ammonia, the ammine complexes concentrations
being negligible compared to [NH3 ].
Again, we notice that changes in M may be considerable. Numerous tables giving
M values for some metal cations and for several amines are published. Of course,
when M coefficients are introduced to take into account the formation of hydroxo
complexes, they depend on the pH value only.
We give M values as a function of pH for some metallic ions in Fig. 26.5.
Again, the changes in M values may be considerable.
Parasitic reactions such as those of the formation of ammine complexes and those
of the formation of hydroxo complexes may occur simultaneously. In this case,
a global parasitic reaction coefficient is introduced. It takes both phenomena into
account. Actually, this was already done in Exercise 1, in which M was expressed
492 26 Conditional Stability Constants

Fig. 26.4 Log M as

a function of log(NH3 ) for 10
some metallic ions

8
Zn
Cu

Log M(NH3)
Ni
Co
Ag Cd
4

0
3 2 1 0
Log [NH3]

Fig. 26.5 Log M values 18

concerning the formation of
some hydroxo mononuclear
complexes 16
Al
14
Zn
12
FeIII
Log M(OH)

10

Bi Co
6

2
Ni
0
2 4 6 8 10 12 14
pH
26.5 Conditional Constants, Masking, and Selective Complexations . . . 493

by the relation

M = 1 + 1 NH3 [NH3 ]+ 6 NH3 [NH3 ]6 + + 1 OH [OH ]+ + 3 OH [OH ] .

3

We can, of course, define two M coefficients, one relative to the ammine complexes
and the other to hydroxo complexes; that is,
M NH3 = 1 + 1 NH3 [NH3 ] + + 6 NH3 [NH3 ]6 ,

M OH = 1 + 1 OH [OH ] + + 3 OH [OH ] .
3

To be rigorous from a mathematical standpoint, the global coefficient M is not equal

to the sum of partial coefficients:
M global = M OH + M NH3
because of the fact that the number 1 occurs twice in the global coefficient. To be
rigorous, we must write
M global = M NH3 + M OH 1,
and after generalization,
M global = M L1 + M L2 + + (1 p),
where p is the number of types of parasitic reactions (in Exercise 2; formations of
ammine and hydroxo complexes) and where L1 and L2 are the ligands giving rise to
parasitic reactions. Actually, the difference (1 p) is often very weak compared to
the terms M L1 and M L2 and is negligible. Thus, we can write
M global M L1 + M L2 + .
In brief, we must bear in mind that conditional constants may differ considerably
from thermodynamic ones. Moreover, they can also exhibit values that may differ
considerably among experiments depending on the experimental conditions.

26.5 Conditional Constants, Masking, and Selective

Complexations in the Presence of Several Metallic Ions

A parasitic reaction occurs because in the experimental conditions, its conditional

stability constant value allows its development. The converse is very interesting in
analysis. Indeed, one can conceive that in some experimental conditions, the condi-
tional stability constant value is too weak for the reaction it governs to noticeably
occur. For example, in very alkaline medium, zinc ions give zincate ions, which in-
hibit their reaction with EDTA. Hence, there is a possibility here of masking ions to
their reagents. These ions are said to be masked. The selectivity that can be achieved in
a titration with EDTA is based on the same principle. These notions will be extended
in Chapters 2729, which are devoted to complexometry.
494 26 Conditional Stability Constants

26.6 Conditional Constants and Calculation of the

Concentrations of the Different Species in Solution

Knowledge of the conditional constants permits the calculation of the apparent con-
centrations of species in solution once equilibria are reached. With these constants,
the calculation is carried out as if only one reaction (that under study) were occur-
ring. Conditional constants indeed take all the parasitic phenomena into account. An
interesting point to notice is that once the apparent concentrations are known, it is
easy to accede to the actual concentrations.
Exercise 4 A solution containing 1.0 102 mol/L magnesium ions and 2.0
102 mol/L H4 EDTA is buffered at pH = 10 by ammonia buffer at the analytical
concentration 101 mol/L. Calculate the apparent concentration of uncomplexed
Mg2+ and then its actual concentration. The conditional constant Mg-EDTA is K  =
1.45 108 .
According to the definition of the conditional constants, we can write

[MY ]/[M ][Y ] = 1.45 108 ,

[Y ] + [MY ] = 2.0 102 ,
[M ] + [MY ] = 1.0 102 .

The last two relations are the mass balance ones. (It is interesting to note that here
we are faced with the simple scheme of concentration calculation with the system
already encountered of three equations with three unknowns. This is the scheme
encountered when the complexation under study is the only reaction occurring.)
Instead of solving the second-order equation resulting from the preceding system,
we can consider that

[MY ] 1.0 102

since the K value is high and since EDTA is in excess. For the same reasons, we can
consider that

[Y ] 1.0 102 .

Inserting both numerical values into the expression of K  gives [M ] = 6.9 109
mol/L. It is easy to check that M = 1.19 at pH = 10 (see Exercise 3). As a result,

[Mg2+ ] = [M ]/1.19,

[Mg2+ ] = 5.8 109 mol/L.

Exercise 5 The value of the conditional stability constant of the MgEDTA complex
is 2.4 107 at pH = 9 in a solution buffered with the couple NH4 +/NH3 . Calculate
the fraction of complexed magnesium with EDTA when we mix 100 ml of a buffered
solution of 102 mol/L magnesium ions with 100 ml of a 102 mol/L EDTA solution.
26.6 Conditional Constants and Calculation of the Concentrations . . . 495

The first point to notice is that after the mixing of both solutions, the pH value
has not changed since the pH of a buffered solution does not vary with the dilution
(except in particular conditions of concentrations). When the equilibria are reached,
we can write

[MY] + [M ] = 5 103 ,

[MY] + [Y ] = 5 103 ,
[MY]/[M ][Y ] = 2.40 107 ,
[M ] = [Y ].

As a result,

[MY] = 4.99 103 mol/L.

The fraction of magnesium complexed with EDTA is

(4.99 103 /5.00 103 ) 100 = 99.7 percent.

This result shows that the concentration of free magnesium is very low. Hence, it
is possible to make the concentration of a metallic ion not only constant but also
very weak by carrying out a mixture in judicious proportions of a metallic ion and
a ligand that complexes it strongly, such as EDTA4 . This is the origin of the concept
of a metal buffer.
Exercise 6 A solution contains 1.0 102 mol/L of Mg2+ and 2.0 102 mol/L of
H4 EDTA. It is buffered at pH = 10 by the buffer ammonia at the analytical concen-
tration 101 mol/L. Calculate the concentration of free magnesium at equilibrium.
In these conditions, K = 1.45 108 and M = 1.19; repeat the same problem with
a concentration of Mg2+ equal to 1.40 102 mol/L, all other parameters keeping
the previous values.
By using the same equations as in the preceding exercise, we calculate in the first
case

[MY ] = 1.0 102 , [Y ] = 1.0 102 , [M ] = 6.9 109 .

+
[Mg2 ] = [M ]/M ,
[Mg2+ ] = 5.8 109 mol/L.

The remaining magnesium at the concentration (102 5.8109 mol/L) is engaged

in complexes formed with EDTA and with ammonia. In the second case, we calculate

[Mg2+ ] = 1.3 1010 mol/L.

We see that the presence of an excess of EDTA makes the [Mg2+ ] concentration
become a weak value that doesnt change much. Hence, the concept of a solution
496 26 Conditional Stability Constants

buffered in a metallic ion appears here. This sort of buffering phenomenon is quite
comparable to that encountered in acidbase phenomena. Hendersons equation is
pH = pK a + log([A ]/[HA]).
In the case of complexes with EDTA, we can write
[M ][Y ]/[MY ] = 1/K 
or log [M ] = pK log([Y ]/[MY ]).
We see that for [Y ] and [MY ] concentrations of the same order, log(M ) differs
little from the pK  value.
The concept of a metal buffer is important from a practical standpoint. It is used,
in practice, to complex traces of Fe(II) in some solutions, Fe(II) being able to be the
initiator of undesirable redox phenomena. This is the reason why EDTA is added in
some buffers.
It is even possible to define a conditional solubility product by the expression
Ks = [M ][L ].
It can easily be generalized to the case in which the metallic ion and the ligand do
not bring the same electrical charge.
Exercise 7 Ni2+ gives a scarlet complex with dimethylglyoxime whose structure
may be symbolized by the formula NiA2 , where A represents the dimethylglyoximate
rest as its anionic form (see Chap. 30). The complex is precipitated from a solution
buffered with the couple NH4 +/NH3 . Express the conditional solubility product of
the complex as a function of the pH of the buffer solution.
By definition,
Ks = [Ni ][A ] ,
2

[Ni ] = [Ni2+ ] + [Ni(NH3 )2+ ]

+ [Ni(NH3 )6 2+ ] + [NiOH+ ] + + [Ni(OH)3 ] . . . ,
[A ] = [A ] + [HA].
HA is the conjugate acid of the dimethylglyoximate rest. By using the Ni coefficient,
which is a function of the pH through the varied stability constants (see Exercise 1),
and by introducing the coefficient L such that
L = 1 + [H+ ]/Ka or L = ([A ] + [HA])/[A ],
where Ka is the acid dissociation constant of dimethylglyoxime, it is easy to find the
expression
Ks = Ks M (L )2 ,
where Ks is the thermodynamic solubility product. Ks is a complicated function of
pH.
An interesting point developed in this exercise is the introduction of the partic-
ular coefficient L . This coefficient may be considered an extension of the other
coefficients already encountered (see Sect. 26.8).
26.7 Case of Metal Indicators 497

26.7 Case of Metal Indicators

Metal indicators are derivatives, more precisely dyestuffs, that exhibit a color change
when the concentration of the metal cation they indicate changes within a certain
concentration range. They form complexes with specific metal cations. In principle,
they exhibit two colors depending on whether they are free or engaged in the complex
with the metallic ion. They are used to detect endpoints in complexometric titrations.
Like numerous ligands, metal indicators can take up protons. The protons taken up
also produce a color change; therefore, these derivatives are equally pH indicators. Of
course, free metal indicators, once protonated, have lost a fraction of their complexing
properties compared to their basic forms.
For analytical purposes, metal indicators can be studied from two standpoints,
which, additionally, are interrelated. The first concerns their ability to complex
metallic ions as a function of pH. The second standpoint concerns the stability of
metalindicator complexes compared to that of metaltitrant complexes. The latter
standpoint will be studied in Chap. 29.
Using conditional stability constants is a good strategy to orient and control the
use of metal indicators as a function of pH. As an example, we now consider the
case of eriochrome black T in details. The structure of eriochrome black T in acidic
medium is

OH HO

+NaO N N
3S

NO2
(II)

It can be symbolized by H2 In . The sulfonic acid group remains, at least partly,

ionized in acidic medium. The presence of two phenol functions in its structure
makes eriochrome black T diacidic. Its predominance areas as a function of pH are
given in Fig. 26.6. They are delimited by the pK a values pK a1 = 6.3 and pK a2 = 11.6.
Incidentally, we notice that one of the phenol functions is by far easier to ionize
than the other, as indicated by the pK a values. Eriochrome black T is an example
of a metal indicator that exhibits properties of both a neutralization indicator and
a metal cation indicator.

Drawing the diagrams log KMIn = pM as a function of the pH value of the solution

where KMIn is the conditional stability constant of the [MIn] complex permits us to
rationalize the use of metal indicators. The drawing of these diagrams directly follows
from the mathematical expressions K  /pH. Lets investigate the indication of Mg2+
ions with eriochrome black T. The formation equilibrium for a metal ion indicator is

Mg2+ + In3  [MgIn ].

498 26 Conditional Stability Constants

H2I HI2 I3
red blue orange

0 6,3 11,6 pH

Fig. 26.6 Predominance areas of the protonated forms of uncomplexed eriochrome black T as
a function of pH

The thermodynamic stability constant is defined by the expression

K = [MgIn ]/([Mg2+ ][In3 ]), K = 1.0 107 .

According to what we said earlier,

[In ] = [In3 ] + [HIn2 ] + [H2 In ].

or by using the expressions of Ka1 and Ka2 , we have

 
[In ] = [In3 ] 1 + 3.5 1011 [H+ ] + 7 1017 [H+ ] ,
2

L = 1 + 3.5 1011 [H+ ] + 7 1017 [H+ ] .

2

Concerning the magnesium ion, we know (see Exercise 3) that

[Mg ] = [Mg2+ ] + [Mg(OH)+ ],

M = 1 + 102.58 1014 /[H+ ].

M plays a part only at high pH values. In every case,


KMIn = K/(L M ).

The obtained diagram is mentioned in Fig. 26.7. It is interesting to notice that


log KMIn is equal tolog M = pM when [In ] = [MIn], a condition that is required
for the best detection of the equivalence point.
From the diagram, we deduce that the color change due to the complexation of the
cation with the indicator (blue to red change) or the inverse can only be seen within
the range 6.3 < pH < 11.6. At pH < 6.3, both forms in equilibrium are H2 In and
MgIn . They are both red. At pH > 11.6, magnesium hydroxide may precipitate.
The diagram also mentions the precipitation area of magnesium hydroxide. It is
delimitated by the straight line calculated from the solubility product expression
Ks = [Mg2+ ][OH ]2 with Ks = 1010.74 . We notice that in this pH range, the
K  value is located in the range 101.9 < K < 106.5 . We shall reconsider these values
in Chap. 28 when we study the complexation of metallic ions with EDTA in the
presence of metal indicators.
26.8 Extension of the Concept of Conditional Stability Constants 499

Fig. 26.7 Diagram log K  /pH 8

of the Mg2+ eriochrome I3
HI2 orange
black T complex (in
dotted-line diagram pMg/ pH) blue
([In ] = [InM]; see text) 6
H2I

log KMgI = pMg

)2
(OH
red

g
4

precipitation of M
MgI
red
2

0
4 6 8 10 12 14
pH

26.8 Extension of the Concept of Conditional Stability

Constants

The notion of conditional solubility product is already an extension of the concept of

conditional constants. Among other possible extensions, lets also mention the case
for which in the studied complex, the metal and the ligand are combined in different
ratios. For example, lets consider the case in which successive complexes ML and
ML2 are forming. Well consider that the complex under study is ML; that is, it is
considered the principal complex. After having adopted the same logic as that which
prevailed in the adoption of conditional constants, we can write

[L ] = [L] + [ML2 ].

[L ] is the ligand for any form except the principal complex. If K1 and K2 are the
successive formation constants of the complexes ML and ML2 , we can write

[L ] = [L] + K2 [L][ML],

[L ] = [L](1 + K2 [ML]).

Hence, L = 1 + K2 [ML].
The introduction of this sort of coefficient is less interesting than that of the pre-
ceding coefficients. Indeed, we immediately see that L depends on the concentration
[ML] of the complex under study, a concentration that is unknown. L cannot be
known, and at first sight, its value appears extremely uncertain, as is, consequently,
the value of K  . However, the order of the value [ML] may be sufficient, and it can
500 26 Conditional Stability Constants

be estimated as follows. Since we consider that the formation of the ML complex

constitutes the principal reaction, we can use the approximation

[ML] analytical concentration of the metallic ion.

It is very often legitimate in the case of complexometric titrations of metal cations.

Another extension is possible in the case of the formation of mixed complexes. We
know, for example, that mixed complexes such as [M(H)Y] and [M(OH)Y] in which
EDTA is engaged may be formed. The following constants have been introduced:

KMHY = [MHY]/([MY][H+ ]),

KM(OH)Y = [M(OH)Y]/([MY][OH ]).

The apparent concentration of the complex formed is

[MY ] = [MY] + [MHY]

or [MY ] = [MY] + [M(OH)Y].

We immediately find

[MY ] = [MY](1 + KMHY [H+ ]),

[MY ] = [MY](1 + KM(OH)Y [OH ]),

and the corresponding coefficients are

= 1 + KMHY [H+ ],
= 1 + KM(OH)Y [OH ].

Other types of mixed complexes also exist. For example, Hg(II) forms the mixed
complex [Hg(NH3 )Y]2 with EDTA. The following coefficient:

= 1 + KHg(NH3)Y [NH3 ]

is introduced.

26.9 About the Interest in the Concept

of Conditional Constants

In order to discuss the interest in the introduction of conditional constants, we shall

compare the calculations, performed to calculate species concentrations, carried out
with and without the help of conditional constants.
26.9 About the Interest in the Concept of Conditional Constants 501

Lets again consider the example of the nickelEDTA complex in a solution

buffered with the couple NH4 +/NH3 (Exercise 1). In the case in which conditional
constants are not used, the mass balance equations are

CNi = [NiY2 ] + [Ni2+ ] + [Ni(NH3 )2+ ] + + [Ni(OH)+ ] + ,

CY = [NiY2 ] + [Y4 ] + [HY3 ] + ,
CNH3 = [NH4 + ] + [NH3 ] + [Ni(NH3 )2+ ] + 2[Ni(NH3 )2 2+ ] + .

By introducing the expressions of the stability constants 1 NH3 , 2 NH3 , . . . , 1 OH ,

and so on, we find
 
CNi = [NiY2 ] + [Ni2+ ] 1 + 1 NH3 [NH3 ] + + 6 NH3 [NH3 ]6 ;

that is, CNi = [NiY2 ] + [Ni2+ ]M and CY = [NiY2 ] + [Y4 ]Y .

We observe that the parasitic reaction coefficients introduced themselves sponta-
neously in the previous calculations. Likewise, we again find the notion that when
there is a great excess of the buffer NH4 +/NH3 , the analytical concentration of
ammonia decreases to

CNH3 = [NH3 ](1 + Ka /[H+ ]),

the concentrations of the ammine complexes being negligible. The concentration

[NH3 ] is calculated immediately if we know the pH value of the solution (Ka being the
acid dissociation constant of the ammonium ion). Hence, it turns out that conditional
constants play the role of an intermediary variable and that the calculations carried
out with them are strictly identical to those carried out without them.
As a result of these considerations, we can conclude that the concept of condi-
tional stability constants brings nothing new from a theoretical standpoint. However,
the advantage of their introduction is that in cases in which several equilibria occur
simultaneously, we may follow reasoning quite analogous to that followed in the far
more simple case in which only a single equilibrium is occurring. Their introduction
focuses our attention on the reaction we want to study. Furthermore, they exhibit an
undeniable practical interest, since numerous tables of conditional stability constants
are published. Even if their values are, of course, legitimate only in particular ex-
perimental conditions, they let us appreciate the quantitative character of the studied
reaction, quickly indeed, immediately in some favorable conditions.
In brief, using conditional stability constants appears to be an elegant way to study
the formation of complexes and, moreover, is in accordance with chemical intuition.