Chapter

Stability Constants of Metal

Complexes in Solution
Jagvir Singh, Abhay Nanda Srivastav, Netrapal Singh
and Anuradha Singh

Abstract

In the formation of metal complexes in an aqueous medium, equilibrium con-

stant or stability constant is used to determine the strength of interaction between
reagents that make the final product after the formation of bonds. In general
stability means that a complex may be stored for a long time under suitable condi-
tions or this compound may be existing under suitable conditions. Regarding how
much is the concentration of complexes in solution, stability constant provides this
information via calculations. These calculations are very much important in many
areas of science like chemistry, biology, and medicine. During the complex forma-
tion in aqueous medium, two types of stabilities are considered: one is the thermo-
dynamic stability, and the other is kinetic stability. Stability of metal complexes
may be affected by various factors like nature of central metal ion and ligand,
chelating effect, etc., and some parameters like distribution coefficients, conduc-
tance, refractive index, etc. are useful for the determination of stability constants.
Various modern techniques are used to determine the stability constant of simple as
well as mixed ligand compounds.

Keywords: thermodynamic stability, kinetic stability, chelate effect, distribution

method, ion exchange method, Bjerrum’s method

1. Introduction

Stability constant of the formation of metal complexes is used to measure inter-

action strength of reagents. From this process, metal ion and ligand interaction
formed the two types of metal complexes; one is supramolecular complexes known
as host-guest complexes [1] and the other is anion-containing complexes. In the
solution it provides and calculates the required information about the concentration
of metal complexes.
Solubility, light, absorption conductance, partitioning behavior, conductance,
and chemical reactivity are the complex characteristics which are different from
their components. It is determined by various numerical and graphical methods
which calculate the equilibrium constants. This is based on or related to a quantity,
and this is called the complex formation function.
During the displacement process at the time of metal complex formation, some
ions disappear and form a bonding between metal ions and ligands. It may be
considered due to displacement of a proton from a ligand species or ions or mole-
cules causing a drop in the pH values of the solution [2]. Irving and Rossotti

1
Stability and Applications of Coordination Compounds

developed a technique for the calculation of stability constant, and it is called

potentiometric technique.
To determine the stability constant, Bjerrum has used a very simple method, and
that is metal salt solubility method. For the studies of a larger different variety of
polycarboxylic acid-, oxime-, phenol-containing metal complexes, Martel and Cal-
vin used the potentiometric technique for calculating the stability constant. Those
ligands [3, 4] which are uncharged are also examined, and their stability constant
calculations are determined by the limitations inherent in the ligand solubility
method. The limitations of the metal salt solubility method and the result of solu-
bility methods are compared with this. M-L, MLM, and (M3) L are some types of
examples of metal-ligand bonding. One thing is common, and that is these entire
types metal complexes all have one ligand.
The solubility method can only usefully be applied to studies of such complexes,
and it is best applied for ML; in such types of system, only ML is formed. Jacqueline
Gonzalez and his co-worker propose to explore the coordination chemistry of calcium
complexes. Jacqueline and et al. followed this technique for evaluate the as partial
model of the manganese-calcium cluster and spectrophotometric studies of metal
complexes, i.e., they were carried calcium(II)-1,4-butanediamine in acetonitrile and
calcium(II)-1,2-ethylendiamine, calcium(II)-1,3-propanediamine by them.
Spectrophotometric programming of HypSpec and received data allows the
determination of the formation of solubility constants. The logarithmic values, log
β110 = 5.25 for calcium(II)-1,3-propanediamine, log β110 = 4.072 for calcium(II)-
1,4-butanediamine, and log β110 = 4.69 for calcium(II)-1,2-ethylendiamine, are
obtained for the formation constants [5]. The structure of Cimetidine and histamine
H2-receptor is a chelating agent. Syed Ahmad Tirmizi has examined Ni(II) cimeti-
dine complex spectrophotometrically and found an absorption peak maximum of
622 nm with respect to different temperatures.
Syed Ahmad Tirmizi have been used to taken 1:2 ratio of metal and cimetidine
compound for the formation of metal complex and this satisfied by molar ratio data.
The data, 1.40–2.4
108, was calculated using the continuous variation method and
stability constant at room temperature, and by using the mole ratio method, this
value at 40°C was 1.24–2.4
108. In the formation of lead(II) metal complexes with
1-(aminomethyl) cyclohexene, Thanavelan et al. found the formation of their
binary and ternary complexes. Glycine, L-proline, L-alanine, L-isoleucine, L-valine,
and L-leucine are α-amino acids, and these are important biologically [6]. These
α-amino acids are also investigated by potentiometric technique at 32°C. The mixed
ligands were also studied using these methods. 50% (v/v) DMSO-water medium
used for the determination of acidity constants and their stability constants these
type ligands. In a stepwise manner, the ternary complexes were synthesized.
Using the stability constant method, these ternary complexes were found out,
and using the parameters such as Δ log K and log X, these ternary complex data were
compared with binary complex. The potentiometric technique at room temperature
(25°C) was used in the investigation of some binary complex formations by
Abdelatty Mohamed Radalla. These binary complexes are formed with 3D transition
metal ions like Cu2+, Ni2+, Co2+, and Zn2+ and gallic acid’s importance as a ligand and
0.10 mol dm3 of NaNO3. Such types of aliphatic dicarboxylic acids are very
important biologically. Many acid-base characters and the nature of using metal
complexes have been investigated and discussed time to time by researchers [7].
The above acids (gallic and aliphatic dicarboxylic acid) were taken to determine
the acidity constants. For the purpose of determining the stability constant, binary
and ternary complexes were carried in the aqueous medium using the experimental
conditions as stated above. The potentiometric pH-metric titration curves are
inferred for the binary complexes and ternary complexes at different ratios, and

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Stability Constants of Metal Complexes in Solution
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formation of ternary metal complex formation was in a stepwise manner that

provided an easy way to calculate stability constants for the formation of metal
complexes.
The values of Δ log K, percentage of relative stabilization (% R. S.), and log X
were evaluated and discussed. Now it provides the outline about the various com-
plex species for the formation of different solvents, and using the concentration
distribution, these complexes were evaluated and discussed. The conductivity mea-
surements have ascertained for the mode of ternary chelating complexes.
A study by Kathrina and Pekar suggests that pH plays an important role in the
formation of metal complexes. When epigallocatechin gallate and gallic acid com-
bine with copper(II) to form metal complexes, the pH changes its speculation. We
have been able to determine its pH in frozen and fluid state with the help of
multifrequency EPR spectroscopy [8]. With the help of this spectroscopy, it is able
to detect that each polyphenol exhibits the formation of three different mononu-
clear species. If the pH ranges 4–8 for di- or polymeric complex of Cu(II), then it
conjectures such metal complexes. It is only at alkaline pH values.
The line width in fluid solutions by molecular motion exhibits an incomplete
average of the parameters of anisotropy spin Hamilton. If the complexes are differ-
ent, then their rotational correlation times for this also vary. The analysis of the
LyCEP anisotropy of the fluid solution spectra is performed using the parameters
determined by the simulation of the rigid boundary spectra. Its result suggests that
pH increases its value by affecting its molecular mass. It is a polyphenol ligand
complex with copper, showing the coordination of an increasing number of its
molecules or increasing participation of polyphenol dimers used as ligands in the
copper coordination region.
The study by Vishenkova and his co-worker [8] provides the investigation of
electrochemical properties of triphenylmethane dyes using a voltammetric method
with constant-current potential sweep. Malachite green (MG) and basic fuchsin
(BF) have been chosen as representatives of the triphenylmethane dyes [9]. The
electrochemical behavior of MG and BF on the surface of a mercury film electrode
depending on pH, the nature of background electrolyte, and scan rate of potential
sweep has been investigated.
Using a voltammetric method with a constant-current potential sweep examines
the electrical properties of triphenylmethane dye. In order to find out the solution of
MG and BF, certain registration conditions have been prescribed for it, which have
proved to be quite useful. The reduction peak for the currents of MG and BF has
demonstrated that it increases linearly with respect to their concentration as
9.0
105–7.0
103 mol/dm3 for MG and 6.0
105–8.0
103 mol/dm3 for BF
and correlation coefficients of these values are 0.9987 for MG and 0.9961 for BF [10].
5.0
105 and 2.0
105 mol/dm3 are the values used as the detection limit of
MG and BF, respectively. Stability constants are a very useful technique whose size is
huge. Due to its usefulness, it has acquired an umbrella right in the fields of chemis-
try, biology, and medicine. No science subject is untouched by this. Stability con-
stants of metal complexes are widely used in the various areas like pharmaceuticals as
well as biological processes, separation techniques, analytical processes, etc. In the
presented chapter, we have tried to explain this in detail by focusing our attention on
the applications and solutions of stability of metal complexes in solution.

2. Stability constant of metal complexes

Stability or formation or binding constant is the type of equilibrium constant

used for the formation of metal complexes in the solution. Acutely, stability

3
Stability and Applications of Coordination Compounds

constant is applicable to measure the strength of interactions between the ligands

and metal ions that are involved in complex formation in the solution [11]. A
generally these 1-4 equations are expressed as the following ways:
ðMLÞ
Metal þ Ligand ⇆ Metal  Ligand K1 ¼
½M½L
(1)
ðML2 Þ
Metal þ Ligands ⇆ Metal þ Ligand2 K2 ¼
½ML½L
(2)
ðML3 Þ
Metal þ Ligand3 ⇆ Metal þ Ligand3 K3 ¼
½ML2 ½L
(3)

Thus
ðMLn Þ
Metal þ Ligandn1 þ L ⇆ Metal þ Ligandn Kn ¼
½MLn1 ½L
(4)

K1, K2, K3, … Kn are the equilibrium constants and these are also called stepwise
stability constants. The formation of the metal-ligand-n complex may also be
expressed as equilibrium constants by the following steps:
B1 ðMLÞ
Metal þ Ligand



! Metal  Ligand, β ¼
½M½L
(5)
B2 ðML2 Þ
Metal þ 2Ligand



! Metal  Ligand2 , β2 ¼ (6)
½M½L2
Bn ðMLnÞ
Thus Metal þ nLigand



! Metal  ligandLn, βn ¼
½M½Ln
(7)

β1, β2, β3, … βn are the equilibrium constants, and these equilibrium constants
are known as overall stability constants or overall formation. βn is called as the nth
cumulative or overall formation constant [12]. Any metal complexes will be of
greater stability if its stability constant has the higher value. Sometimes the 1/k
values are alternative values of stability constant, and now this is called as instability
constant. Log10K1, log10K2 … log10Kn, and log10βn are the ways that expressed the
stepwise and cumulative stability constants.

3. Relationship or interaction between βn and K1, K2, K3, … Kn

The parameters K and β are related together, and these are expressed in the
following example:

ðML3 Þ
β3 ¼ (8)
½M½L3

Now the numerator and denominator are multiplied together with the use of [metal-
ligand] [metal-ligand2], and after the rearranging we get the following equation:

½ML3  ½ML½ML2 
β3 ¼

½M½L 3 ½ML½ML2 
(9)
½ML1  ½ML2  ½ML3 
¼

¼ K1 x K2 x K3
½M½L ½ML½L ½ML2 ½L
½ML1  ½ML2  ½MLn 
Thus βn ¼
…: ¼ K1 x K2 … Kn (10)
½M½L ½ML½L ½MLn1 ½L

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Now we expressed it as the following:

X
n¼n
βn ¼ Kn (11)
n¼1

From the above relation, it is clear that the overall stability constant βn is equal to
the product of the successive (i.e., stepwise) stability constants, K1, K2, K3, … Kn.
This in other words means that the value of stability constants for a given complex
is actually made up of a number of stepwise stability constants. The term stability is
used without qualification to mean that the complex exists under a suitable condi-
tion and that it is possible to store the complex for an appreciable amount of time.
The term stability is commonly used because coordination compounds are stable in
one reagent but dissociate or dissolve in the presence of another regent. It is also
possible that the term stability can be referred as an action of heat or light or
compound. The stability of complex [13] is expressed qualitatively in terms of
thermodynamic stability and kinetic stability.

3.1 Thermodynamic stability

In a chemical reaction, chemical equilibrium is a state in which the concentra-

tion of reactants and products does not change over time. Often this condition
occurs when the speed of forward reaction becomes the same as the speed of reverse
reaction. It is worth noting that the velocities of the forward and backward reaction
are not zero at this stage but are equal.
If hydrogen and iodine are kept together in molecular proportions in a closed
process vessel at high temperature (500°C), the following action begins:

H2 þ I2 ! 2HI (12)

In this activity, hydrogen iodide is formed by combining hydrogen and iodine,

and the amount of hydrogen iodide increases with time. In contrast to this action, if
the pure hydrogen iodide gas is heated to 500°C in the reaction, the compound is
dissolved by reverse action, which causes hydrogen iodide to dissolve into hydrogen
and iodine, and the ratio of these products increases over time. This is expressed in
the following reaction:

2HI ! H2 þ I2 (13)

For the formation of metal chelates, the thermodynamic technique provides a

very significant information. Thermodynamics is a very useful technique in
distinguishing between enthalpic effects and entropic effects. The bond strengths
are totally effected by enthalpic effect, and this does not make any difference in the
whole solution in order/disorder. Based on thermodynamics the chelate effect
below can be best explained. The change of standard Gibbs free energy for equilib-
rium constant is response:

ΔG ¼ 2:303 RT log 10 β: (14)

Where:
R = gas constant
T = absolute temperature
At 25°C,

5
Stability and Applications of Coordination Compounds

ΔG = ( 5.708 kJ mol1)  log β.

The enthalpy term creates free energy, i.e.,

ΔG ¼ ΔH–TΔS (15)

For metal complexes, thermodynamic stability and kinetic stability are two
interpretations of the stability constant in the solution. If reaction moves from
reactants to products, it refers to a change in its energy as shown in the above
equation. But for the reactivity, kinetic stability is responsible for this system, and
this refers to ligand species [14].
Stable and unstable are thermodynamic terms, while labile and inert are kinetic
terms. As a rule of thumb, those complexes which react completely within about
1 minute at 25°C are considered labile, and those complexes which take longer time
than this to react are considered inert. [Ni(CN)4]2 is thermodynamically stable but
kinetically inert because it rapidly exchanges ligands.
The metal complexes [Co(NH3)6]3+ and such types of other complexes are
kinetically inert, but these are thermodynamically unstable. We may expect the
complex to decompose in the presence of acid immediately because the complex
is thermodynamically unstable. The rate is of the order of 1025 for the decomposi-
tion in acidic solution. Hence, it is thermodynamically unstable. However,
nothing happens to the complex when it is kept in acidic solution for several days.
While considering the stability of a complex, always the condition must be
specified. Under what condition, the complex which is stable or unstable must be
specified such as acidic and also basic condition, temperature, reactant, etc.
A complex may be stable with respect to a particular condition but with respect
to another. In brief, a stable complex need not be inert and similarly, and an
unstable complex need not be labile. It is the measure of extent of formation or
transformation of complex under a given set of conditions at equilibrium [15].
Thermodynamic stability has an important role in determining the bond
strength between metal ligands. Some complexes are stable, but as soon as they are
introduced into aqueous solution, it is seen that these complexes have an effect on
stability and fall apart. For an example, we take the [Co (SCN)4]2+ complex. The ion
bond of this complex is very weak and breaks down quickly to form other com-
pounds. But when [Fe(CN)6]3 is dissolved in water, it does not test Fe3+ by any
sensitive reagent, which shows that this complex is more stable in aqueous solution.
So it is indicated that thermodynamic stability deals with metal-ligand bond energy,
stability constant, and other thermodynamic parameters.
This example also suggests that thermodynamic stability refers to the stability
and instability of complexes. The measurement of the extent to which one type of
species is converted to another species can be determined by thermodynamic sta-
bility until equilibrium is achieved. For example, tetracyanonickelate is a thermo-
dynamically stable and kinetic labile complex. But the example of hexa-amine
cobalt(III) cation is just the opposite:
 3þ  3þ
CoðNH3 Þ6 þ 6H3 Oþ ! CoðH2 OÞ6 þ 6NH4 þ (16)

Thermodynamics is used to express the difference between stability and inertia.

For the stable complex, large positive free energies have been obtained from ΔG0
reaction. The ΔH0, standard enthalpy change for this reaction, is related to the
equilibrium constant, βn, by the well thermodynamic equation:

ΔG0 ¼ RT ln β (17)

ΔG0 ¼ ΔH0  TΔS0 (18)

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For similar complexes of various ions of the same charge of a particular transi-
tion series and particular ligand, ΔS0 values would not differ substantially, and
hence a change in ΔH0 value would be related to change in βn values. So the order of
values of ΔH0 is also the order of the βn value.

3.2 Kinetic stability

Kinetic stability is referred to the rate of reaction between the metal ions and
ligand proceeds at equilibrium or used for the formation of metal complexes. To
take a decision for kinetic stability of any complexes, time is a factor which plays an
important role for this. It deals between the rate of reaction and what is the mech-
anism of this metal complex reaction.
As we discuss above in thermodynamic stability, kinetic stability is referred for
the complexes at which complex is inert or labile. The term “inert” was used by
Tube for the thermally stable complex and for reactive complexes the term ‘labile’
used [16]. The naturally occurring chlorophyll is the example of polydentate ligand.
This complex is extremely inert due to exchange of Mg2+ ion in the aqueous media.

4. Factors affecting the stability of complexes

The nature of central atom of metal complexes, dimension, its degree of oxida-
tion, electronic structure of these complexes, and so many other properties of
complexes are affected by the stability constant. Some of the following factors
described are as follows.

4.1 Nature of central metal ion

In the coordination chemistry, metal complexes are formed by the interaction

between metal ions and ligands. For these type of compounds, metal ions are the
coordination center, and the ligand or complexing agents are oriented surrounding
it. These metal ions mostly are the transition elements. For the determination of
stability constant, some important characteristics of these metal complexes may be
as given below.

4.2 Ionic size

Ligands are oriented around the central metal ions in the metal complexes. The
sizes of these metal ions determine the number of ligand species that will be attached
or ordinated (dative covalent) in the bond formation. If the sizes of these metal ions
are increased, the stability of coordination compound defiantly decreased. Zn(II)
metal ions are the central atoms in their complexes, and due to their lower size
(0.74A°) as compared to Cd(II) size (0.97A°), metal ions are formed more stable.
Hence, Al3+ ion has the greatest nuclear charge, but its size is the smallest, and
the ion N3 has the smallest nuclear charge, and its size is the largest [17]. Inert
atoms like neon do not participate in the formation of the covalent or ionic com-
pound, and these atoms are not included in isoelectronic series; hence, it is not easy
to measure the radius of this type of atoms.

4.3 Ionic charge

The properties of stability depend on the size of the metal ion used in the com-
plexes and the total charge thereon. If the size of these metal ions is small and the total

7
Stability and Applications of Coordination Compounds

charge is high, then their complexes will be more stable. That is, their ratio will depend
on the charge/radius. This can be demonstrated through the following reaction:
 3
Fe3þ þ 6CN ⇆ FeðCNÞ6 logβ ¼ 31 ðMore StableÞ (19)
 4
Fe2þ þ 6CN ⇆ FeðCNÞ6 logβ ¼ 8:3 ðLess StableÞ (20)

An ionic charge is the electric charge of an ion which is formed by the gain
(negative charge) or loss (positive charge) of one or more electrons from an atom or
group of atoms. If we talk about the stability of the coordination compounds, we
find that the total charge of their central metal ions affects their stability, so when
we change their charge, their stability in a range of constant can be determined by
propagating of error [18]. If the charge of the central metal ion is high and the size is
small, the stability of the compound is high:

Liþ >Naþ >Kþ >Rbþ >Csþ (21)

Th4þ >Y3þ >Ca2þ >Naþ and La3þ >Sr2þ >Kþ (22)

In general, the most stable coordination bonds can cause smaller and highly
charged rations to form more stable coordination compounds.

4.4 Electronegativity

When an electron pair attracts a central ion toward itself, a strong stability complex is
formed, and this is due to electron donation from ligand ! metal ion. This donation
process is increasing the bond stability of metal complexes exerted the polarizing effect
on certain metal ions. Li+, Na+, Mg2+, Ca2+, Al3+, etc. are such type of metal cation which
is not able to attract so strongly from a highly electronegative containing stable com-
plexes, and these atoms are O, N, F, Au, Hg, Ag, Pd, Pt, and Pb. Such type of ligands that
contains P, S, As, Br and I atom are formed stable complex because these accepts electron
from M ! π-bonding. Hg2+, Pb2+, Cd2+, and Bi3+ metal ions are also electronegative ions
which form insoluble salts of metal sulfide which are insoluble in aqueous medium.

4.5 Temperature and pressure

Volatile ligands may be lost at higher temperature. This is exemplified by the

loss of water by hydrates and ammonia:
   
CoðNH3 Þ6 Cl3 ðΔ175  180°CÞ ! CoðNH3 Þ5 Cl Cl2 þ NH3 (23)

The transformation of certain coordination compounds from one to another is

shown as follows:
    
AgHg AgI4 ðredÞð45°CÞ ⇆ Ag2 HgI4 yellow (24)

4.6 Ligand nature

A ligand is an ion or small molecule that binds to a metal atom (in chemistry) or
to a biomolecule (in biochemistry) to form a complex, such as the iron-cyanide
coordination complex Prussian blue or the iron-containing blood-protein hemoglo-
bin. The ligands are arranged in spectrochemical series which are based on the order
of their field strength. It is not possible to form the entire series by studying

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complexes with a single metal ion; the series has been developed by overlapping
different sequences obtained from spectroscopic studies [19]. The order of common
ligands according to their increasing ligand field strength is

O2 2 < I < Br < S2 < SCN ðS–bondedÞ < Cl < N3  < F < NCO < OH < C2 O4 2
   
 < H2 O < NCS ðN–bondedÞ < CH3 CN < gly glycine < py pyridine
    (25)
< NH3 < en ethylenediamine < bipy 2, 2’  bipyridine
< phen ð1, 10  phenanthrolineÞ < NO2  < PPh3 < CN < CO < CH2

The above spectrochemical series help us to for determination of strength of

ligands. The left last ligand is as weaker ligand. These weaker ligand cannot forcible
binding the 3d electron and resultant outer octahedral complexes formed. It is as-
Mn2þ < Ni2þ < Co2þ < Fe2þ < V2þ < Fe3þ < Cr3þ < V3þ < Co3þ . For the given ligand,
it is not possible to say about the exerted strong or weaker field on the central metal
ion. The values of Δ are observed as:

1. Increasing the oxidation number the value of Δ increased.

2. Δ increases from top to bottom.

However, when we consider the metal ion, the following two useful trends are
observed:

1. Δ increases with increasing oxidation number.

2. Δ increases down a group. For the determination of stability constant, the

nature of the ligand plays an important role.

The following factors described the nature of ligands.

4.7 Size and charge

The size and charge are two factors that affect the production of metal com-
plexes. The less charges and small sizes of ligands are more favorable for less stable
bond formation with metal and ligand. But if this condition just opposite the prod-
uct of metal and ligand will be a more stable compound. So, less nuclear charge and
more size= less stable complex whereas if more nuclear charge and small in size=
less stable complex. We take fluoride as an example because due to their smaller
size than other halide and their highest electro negativity than the other halides
formed more stable complexes. So, fluoride ion complexes are more stable than the
other halides:

FeF2 þ log β ¼ 6:0 (26)

þ
FeCl2 log β ¼ 1:3 (27)

As compared to S2 ion, O22 ions formed more stable complexes.

4.8 Basic character

It is suggested by Calvin and Wilson that the metal complexes will be more
stable if the basic character or strength of ligands is higher. It means that the
donating power of ligands to central metal ions is high [20].

9
Stability and Applications of Coordination Compounds

It means that the donating power of ligands to central metal ions is high. In the
case of complex formation of aliphatic diamines and aromatic diamines, the stable
complex is formed by aliphatic diamines, while an unstable coordination complex is
formed with aromatic diamines. So, from the above discussion, we find that the
stability will be grater if the e-donation power is greater.
Thus it is clear that greater basic power of electron-donating species will form
always a stable complex. NH3, CN, and F behaved as ligands and formed stable
complexes; on the other hand, these are more basic in nature.

4.9 Ligand concentration

We know that if the concentration of coordination group is higher, these coor-

dination compounds will exist in the water as solution. It is noted that greater
coordinating tendency show the water molecules than the coordinating group
which is originally present. SCN (thiocynate) ions are present in higher concen-
tration; with the Co2+ metal ion, it formed a blue-colored complex which is stable in
state, but on dilution of water medium, a pink color is generated in place of blue, or
blue color complex is destroyed by [Co(H2O)6]2+, and now if we added further
SCN, the pink color will not appear:
 2  2þ
CoðSCNÞ4  þH2 O ⇆ CoðH2 OÞ6 þ 4SCN
(28)
Blue Pink

Now it is clear that H2O and SCN are in competition for the formation of Co(II)
metal-containing complex compound. In the case of tetra-amine cupric sulfate
metal complex, ammonia acts as a donor atom or ligand. If the concentration of NH3
is lower in the reaction, copper hydroxide is formed but at higher concentration
formed tetra-amine cupric sulfate as in the following reaction:
 
CuSO4 þ NH4 OH ! CuðOHÞ2 Small quantity of ligand (29)
CuSO4 þ NH4 OH ! CuðOHÞ2 ½CuðNH4 Þ2SO4 :H2 O ðHigh concentration of ligandÞ
(30)

4.10 Chelating effect

For a metal ion, chelating ligand is enhanced and affinity it and this is known as
chelate effect and compared it with non-chelating and monodentate ligand or the
multidentate ligand is acts as chelating agent. Ethylenediamine is a simple chelating
agent (Figure 1).
Due to the bidentate nature of ethylenediamine, it forms two bonds with metal
ion or central atom. Water forms a complex with Ni(II) metal ion, but due to its
monodentate nature, it is not a chelating ligand (Figures 2 and 3).
The dentate cheater of ligand provides bonding strength to the metal ion or
central atom, and as the number of dentate increased, the tightness also increased.
This phenomenon is known as chelating effect, whereas the formation of metal
complexes with these chelating ligands is called chelation:

Figure 1.
Structure of ethylenediamine.

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Figure 2.
Structure of chelating configuration of ethylenediamine ligand.

Figure 3.
Structure of chelate with three ethylenediamine ligands.

ðML2Þ
Metal þ 2 Ligand $ MetalLigand2 K ¼ (31)
½M½L2
Metal þ Ligand–Ligand $ MetalLigand  Ligand (32)

or (33)

Some factors are of much importance for chelation as follows.

4.11 Ring size

The sizes of the chelating ring are increased as well as the stability of metal
complex decreased. According to Schwarzenbach, connecting bridges form the
chelating rings. The elongated ring predominates when long bridges connect to the
ligand to form a long ring. It is usually observed that an increased a chelate ring size
leads to a decrease in complex stability.
He interpreted this statement. The entropy of complex will be change if the size
of chelating ring is increased, i.e., second donor atom is allowed by the chelating
ring. As the size of chelating ring increased, the stability should be increased
with entropy effect. Four-membered ring compounds are unstable, whereas
five-membered are more stable. So the chelating ring increased its size and the
stability of the formed metal complexes.

4.12 Number of rings

The number of chelating rings also decides the stability of complexes. Non-
chelating metal compounds are less stable than chelating compounds. These num-
bers increase the thermodynamic volume, and this is also known as an entropy
term. In recent years ligands capable of occupying as many as six coordination
positions on a single metal ion have been described. The studies on the formation
constants of coordination compounds with these ligands have been reported.

11
Stability and Applications of Coordination Compounds

The numbers of ligand or chelating agents are affecting the stability of metal
complexes so as these numbers go up and down, the stability will also vary with it.
For the Ni(II) complexes with ethylenediamine as chelating agent, its log K1
value is 7.9 and if chelating agents are trine and penten, then the log K1 values are
7.9 and 19.3, respectively. If the metal ion change Zn is used in place of Ni (II), then
the values of log K1 for ethylenediamine, trine, and penten are 6.0, 12.1, and 16.2,
respectively. The log βMY values of metal ions are given in Table 1.
Ni(NH3)62+ is an octahedral metal complex, and at 25 °C its log β6 value is 8.3, but
Ni(ethylenediamine)32+ complex is also octahedral in geometry, with 18.4 as the value
of log β6. The calculated stability value of Ni(ethylenediamine)32+ 1010 times is more
stable because three rings are formed as chelating rings by ethylenediamine as com-
pared to no such ring is formed. Ethylenediaminetetraacetate (EDTA) is a hexadentate
ligand that usually formed stable metal complexes due to its chelating power.

4.13 Steric effect

A special effect in molecules is when the atoms occupy space. This is called steric
effect. Energy is needed to bring these atoms closer to each other. These electrons
run away from near atoms. There can be many ways of generating it. We know the
repulsion between valence electrons as the steric effect which increases the energy
of the current system [21]. Favorable or unfavorable any response is created.
For example, if the static effect is greater than that of a product in a metal
complex formation process, then the static increase would favor this reaction. But if
the case is opposite, the skepticism will be toward retardation.
This effect will mainly depend on the conformational states, and the minimum
steric interaction theory can also be considered. The effect of secondary steric is
seen on receptor binding produced by an alternative such as:

1. Reduced access to a critical group.

2. Stick barrier.

3. Electronic resonance substitution bond by repulsion.

4. Population of a conformer changes due to active shielding effect.

4.14 Macrocyclic effect

The macrocyclic effect is exactly like the image of the chelate effect. It means the
principle of both is the same. But the macrocyclic effect suggests cyclic deformation
of the ligand. Macrocyclic ligands are more tainted than chelating agents. Rather,
their compounds are more stable due to their cyclically constrained constriction. It
requires some entropy in the body to react with the metal ion. For example, for a

Metal ion log βMY (25°C, I = 0.1 M)

2+
Ca 11.2
2+
Cu 19.8
3+
Fe 24.9

Table 1.
Metal ion vs. log βMY values.

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Stability Constants of Metal Complexes in Solution
DOI: http://dx.doi.org/10.5772/intechopen.90183

Figure 4.
Structure of hemoglobin is the biological complex compound which contains Fe(II) metal ion.

tetradentate cyclic ligand, we can use heme-B which forms a metal complex using
Fe+2 ions in biological systems (Figure 4).
The n-dentate chelating agents play an important role for the formation of more
stable metal complexes as compared to n-unidentate ligands. But the n-dentate
macrocyclic ligand gives more stable environment in the metal complexes as com-
pared to open-chain ligands. This change is very favorable for entropy (ΔS) and
enthalpy (ΔH) change.

5. Determination of stability constants of complexes in solution

There are so many parameters to determination of formation constants or sta-

bility constant in solution for all types of chelating agents. These numerous param-
eters or techniques are refractive index, conductance, temperature, distribution
coefficients, refractive index, nuclear magnetic resonance volume changes, and
optical activity.

5.1 Methods based on study of heterogeneous equilibrium

5.1.1 Solubility methods

Solubility products are helpful and used for the insoluble salt that metal ions
formed and complexes which are also formed by metal ions and are more soluble.
The formation constant is observed in presence of donor atoms by measuring
increased solubility.

13
Stability and Applications of Coordination Compounds

5.1.2 Distribution method

To determine the solubility constant, it involves the distribution of the ligands or

any complex species; metal ions are present in two immiscible solvents like water
and carbon tetrachloride, benzene, etc.

5.1.3 Ion exchange method

In this method metal ions or ligands are present in solution and on exchanger. A
solid polymers containing with positive and negative ions are ion exchange resins.
These are insoluble in nature. This technique is helpful to determine the metal ions
in resin phase, liquid phase, or even in radioactive metal. This method is also helpful
to determine the polarizing effect of metal ions on the stability of ligands like Cu(II)
and Zn(II) with amino acid complex formation.

5.1.4 Electrometric techniques

At the equilibrium free metal and ions are present in the solution, and using the
different electrometric techniques as described determines its stability constant.

5.1.5 Potentiometric methods

This method is based upon the titration method or follows its principle. A
stranded acid-base solution used as titrate and which is titrated, it may be strong
base or strong acid follows as potentiometrically. The concentration of solution
using 103 M does not decomposed during the reaction process, and this method is
useful for protonated and nonprotonated ligands.

5.1.6 Polarographic method

This is the graphic method used to determine the stability constant in producing
metal complex formation by plotting a polarograph between the absences of sub-
stances and the presence of substances. During the complex formation, the presence
of metal ions produced a shift in the half-wave potential in the solution.

5.2 Other methods

5.2.1 Rate method

If a complex is relatively slow to form and also decomposes at measurable rate, it

is possible, in favorable situations, to determine the equilibrium constant.

5.2.2 Freezing technique

This involves the study of the equilibrium constant of slow complex formation
reactions. The use of tracer technique is extremely useful for determining the
concentrations of dissociation products of the coordination compound.

5.2.3 Biological method

This method is based on the study of the effect of an equilibrium concentration

of some ions on the function at a definite organ of a living organism. The

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Stability Constants of Metal Complexes in Solution
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equilibrium concentration of the ion studied may be determined by the action of

this organ in systems with complex formation.

5.2.4 Spectrophotometric method

The solution of 25 ml is adopted by preparing at the 1.0
105 M ligand or

1.0
105 M concentration and 1.0
105 M for the metal ion:
The solutions containing the metal ions were considered both at a pH suffi-
ciently high to give almost complete complexation and at a pH value selected in
order to obtain an equilibrium system of ligand and complexes.
In order to avoid modification of the spectral behavior of the ligand due to pH
variations, it has been verified that the range of pH considered in all cases does not
affect absorbance values. Use the collected pH values adopted for the determina-
tions as well as selected wavelengths. The ionic strengths calculated from the com-
position of solutions allowed activity coefficient corrections. Absorbance values
were determined at wavelengths in the range 430–700 nm, every 2 nm.

5.2.5 Bjerrum’s method

For a successive metal complex formation, use this method. If ligand is proton-
ate and the produced complex has maximum number of donate atoms of ligands, a
selective light is absorbed by this complex, while for determination of stability
constant, it is just known about the composition of formed species.
Bjerrum (1941) used the method stepwise addition of the ligands to coordination
sphere for the formation of complex. So, complex metal–ligand-n forms as the
following steps [22]. The equilibrium constants, K1, K2, K3, … Kn are called step-
wise stability constants. The formation of the complex metal-ligandn may also be
expressed by the following steps and equilibrium constants.
Where:
M = central metal cation
L = monodentate ligand
N = maximum coordination number for the metal ion M for the ligand

ðMLÞ
Metal þ Ligand ⇆ Metal  Ligand K1 ¼ (34)
½M½L

ðML2 Þ
Metal  Ligand ⇆ Metal  Ligand2 K2 ¼ (35)
½ML½L

ðML3 Þ
Metal  Ligand2 ⇆ Metal  Ligand3 K3 ¼ (36)
½ML2 ½L

ðMLn Þ
Thus Metal  Ligandn1 þ Ligand ⇆ Metal  Ligandn Kn ¼ (37)
½MLn1 ½L

5.2.6 Isotopic dilution method

If a complex ion is slow to reach equilibrium, it is often possible to apply the

method of isotopic dilution to determine the equilibrium concentration of one or
more of the species. Most often radioactive isotopes are used.

15
Stability and Applications of Coordination Compounds

5.2.7 Conductance measurement method

This method was extensively used by Werner and others to study metal com-
plexes. In the case of a series of complexes of Co(III) and Pt(IV), Werner assigned
the correct formulae on the basis of their molar conductance values measured in
freshly prepared dilute solutions. In some cases, the conductance of the solution
increased with time due to a chemical change, e.g.,
 þ  3þ
CoðNH3 Þ4 Br2 þ 2H2 O CoðNH3 Þ4 ðH2 OÞ2 þ 2Br (38)

6. Conclusion

It is concluded that the information presented is very important to determine

the stability constant of the ligand metal complexes. Some methods like spectro-
photometric method, Bjerrum’s method, distribution method, ion exchange
method, electrometric techniques, and potentiometric method have a huge contri-
bution in quantitative analysis by easily finding the stability constants of metal
complexes in aqueous solutions.

Acknowledgements

All the authors thank the Library of University of Delhi for reference books,
journals, etc. which helped us a lot in reviewing the chapter.

Author details

Jagvir Singh1*, Abhay Nanda Srivastav2, Netrapal Singh3 and Anuradha Singh4

1 Department of Chemistry, ARSD College, University of Delhi, New Delhi, India

2 Department of Chemistry, Nitishwar Mahavidyalaya (BRABU), Muzaffarpur,

Bihar, India

3 Department of Chemistry, Deen Dayal Upadhyaya University, Gorakhpur, UP,

India

4 Department of Zoology, Raghuveer Singh Govt Degree College, Lalitpur, UP,

India

*Address all correspondence to: [email protected]

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

16
Stability Constants of Metal Complexes in Solution
DOI: http://dx.doi.org/10.5772/intechopen.90183

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