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Complexes, Ligands and Chelates:

Metal ions in solution are always solvated i.e., a definite number of solvent molecules (usually
two, four or six) firmly bound to the metal ion. This metal ion is called central cation. These
bound molecules are replaced by other molecules or ions to form a metal complex. Molecules
or ions which displace the solvent molecules are called ligands. The ligand must have a lone
pair of electrons.
That means, the ion or molecule that can donate a lone pair of electrons to the central metal ion
is called ligand and the central metal ion surrounded by ligands is called metal complex.
Example:

In this reaction, [Cu(NH3 )4 ]2+ is a metal complex and NH3 molecule is a ligand.

Classification of Ligands
 Unidentate Ligand: When a ligand can donate one lone pair of electrons i.e., is involved
in the formation of the complex, the ligand is called unidentate ligand. Even although
water has two lone pairs of electrons, it can only donate one pair of electrons.
 Bidentate Ligand: A ligand that can donate two lone pairs of electrons is a bidentate
ligand.
 Multidentate Ligand: A ligand that can donate more than two lone pairs of electrons is
a multidentate ligand. Such ligands can also be classified more specifically according to
the actual number of donor groups in the molecule, such as bidentate (two donor atoms),
tridentate (three donor group), quadridentate (four donor group) etc.

Chelates: When multidentate ligand attaches to a central metal ion at more than one site, an
organic ring structure is formed. These ring compounds are called chelates.

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Types Lewis Structure Ligand

Unidentate Ammonia

Bidentate Oxalate ion (ox)

Multidentate Diethylenetriamine (dien)

Types Chelates Ligand

Bidentate Ethylenediamine

Tridentate Diethylenetriamine

Quadridentate Nitrilotriacetic acid

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COMPLEXATION & COMPLEX IONS

Complexation:
The process of complex ion formation is called complexation. A complexation reaction with
metal ion involves the replacement of one or more of the coordinated solvent molecules by
another nucleophilic group called ligand. In aqueous solution, the reaction can be represented
by the equation:
M(H2 O)n + L = M(H2 O)n−1 L + H2 O
Here, the ligand (L) can be either a neutral molecule or a charged ion, and successive
replacement of water molecules can occur by other ligand groups until the complex MLn is
formed; n is the co-ordination number of the metal ion and represents the maximum number
of monodentate ligands that can be bound to it.

Complex Ion
A complex ion can be defined as an electrically charged radical which is obtained by the
combination of a metal cation with one or more neutral molecules or simple anions.
A complex ion is formed by the union of a simple ion with either other ions of opposite charge or with
neutral molecules. For example -

 When KCN solution is added to a solution of AgNO3 , a white precipitate of silver cyanide is
formed at first.
AgNO3 + KCN ⟶ AgCN ↓ +KNO3
This precipitate dissolves upon the addition of excess of potassium cyanide, the complexion ion
[Ag(CN)2 ]− being produced.

AgCN + KCN ⟶ [Ag(CN)2 ]− + K+

(Complex ion)
 When NH3 is added to AgCl solution, the complex ion [Ag(NH3 )2 ]+ is produced.

AgCl + 2NH3 ⟶ [Ag(NH3 )2 ]+ + Cl−

Dissociation Constant and Formation Constant (or Stability) of Complex

Formation Constant of A Complex: The formation constant (K f ), describes the formation of a

complex ion from its central ion and attached ligands. This constant may be called a stability
constant or association constant. The thermodynamic stability of a species is a measure of the
extent to which the species will be formed from other species, when the system has reached
equilibrium. Complexation is an equilibrium process which can be defined by the law of mass
action. A complex MLn is formed by the reaction:

M + nL ⟶ MLn

Where, ‘M’ is the metal ion, ‘L’ is the ligand and ‘n’ is the number of ligand molecules reacting
with the metal ion.

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The concentration in mole per liter of these various species at equilibrium are defined by the
equation.
[MLn ]
K s or K f = … … … … … … … … (1)
[M][L]n

Recently it has been recognized that metal complexes form in a stepwise fashion by the
following general equations.

M + L ⇌ ML K1 = [ML] / [M][L]
ML + L ⇌ ML2 K 2 = [ML2 ] / [ML][L]
ML2 + L ⇌ ML3 K 2 = [ML3 ] / [ML2 ][L]
………………… … … … … … … … … … ….
………………… … … … … … … … … … ….
ML(n−1) + L ⇌ MLn K 2 = [MLn ] / [ML(n−1) ][L]

The equilibrium constants K1, K2, K3 ...... Kn are referred to as stepwise stability constant.

The overall stability constant KS or Kf can be expressed by the following general formula.

K f = K1 , K 2 , K 3 … … … … … K n --------------------- (2)

If the value of K f increases, the stability of the complex is greater and the concentration of the
unbound metal ions and ligand is decreased.

Dissociation Constant: The complex ion dissociates to give metal ion according to following
equation:
[MLn ]+m ⇌ M+m + nL

At equilibrium, the dissociation constant is given by:

[M+m ][L]n
KD = … … … … … … … … (3)
[MLn ]+m

The dissociation is the reciprocal of stability constant i.e.,

1
KD = … … … … … … … … … (4)
K f or K S

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Metal Ion Buffers:

The equation for complex formation,
M + L ⇌ ML

The equilibrium constant for formation constant:

[ML]
𝑜𝑟, Kf =
[M][L]
[ML]
𝑜𝑟, [M] =
K f [L]
𝑜𝑟, log[M] = log[ML] − logK f − log [L]

𝑜𝑟, − log[M] = logK f + log[L] − log[ML]

[ML]
∴ pM = logK f − log
[L]

This shows that the pM value of the solution is fixed by the value of ‘K’ and the ratio of complex
ion concentration to that of the free ligand. If more M is added to the solution, more complex
will be formed and the value of pM will not change of appreciably. Again, if M is removed from
the solution, some of the complex dissociate to restore the value of pM. This recalls the behavior
of buffer solutions and the complex-ligand system is called metal-ion buffer.

COMPLEXONES:
The formation of a single complex species rather than the stepwise production of such species
will clearly simplify complexometric titration and facilitate the detection of end points.

The complexing agents that form complexes with metal directly rather than stepwise
production and thus facilitate the detection of end point of the titration, are called Complexones.
Example:

 The most widely used complexones is ethylenediamine tetra-acetic acid (EDTA) and its
sodium salt, mainly disodium salt.

 Other complexones are Nitrilotriacetic acid (NTA); trans-1,2-diamimocyclohexane-N, N, N’,

N’- tetra acetic acid (DCTA); ethylene glycol bis-N, N, N’, N’-tetra acetic acid (EGTA) and
triethylene tetra amine-N, N, N, N’, N’, N'-hexa acetic acid (TTHA).

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EDTA COMPLEXONES:
EDTA has the widest general application in analysis because of its powerful complexing action
and commercial availability. The spatial structure of its action which enables it to satisfy the
coordination number of six frequently encountered among the metal ions and to form stainless
five membered rings on chelation.

Figure: Representation of the three-dimensional structure of an EDTA complex with a metal ion of co-ordination
number six.

EDTA is tetrabasic acid and is often represented by the symbol H4 Y. The four-dissociation
equilibrium then may be written:
K1
H4 Y ⇌ H+ + H3 Y −
K2
H3 Y − ⇌ H + + H2 Y −2
K3
H2 Y −2 ⇌ H + + HY −3
K4
HY −3 ⇌ H+ + Y −4

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The acid dissociation constants have the values pK1 = 2, pK2 = 2.67, pK3 = 6.16, pK4 = 10.26.
Since, Y −4 is the usual ligand species, evenly the complex formation equilibrium will be affected
by the pH of the medium.

Stability Constant or Formation Constant of EDTA Complex:

The dissociation salt of EDTA (N2H2Y) affords the complex forming ion H2 Y −1 in aqueous
solution. It reacts with all metals in 1: 1 ratio. The reactions with cations, e.g., M+2 may be
written as:
M+2 + H2 Y −2 ⇌ MY −2 + 2H + -------------------(1)
For other cation, the reaction may be expressed as:
M +3 + H2 Y −2 ⇌ MY − + 2H +
M +4 + H2 Y −2 ⇌ MY + 2H +
or, M +n + H2 Y −2 ⇌ MY n−4 + 2H +

The equilibrium constant is expressed as,

[MY n−4 ][H + ]2
Kf =
[M +n ][H2 Y −2 ]
where, K f = formation constant or stability constant.

Table: Stability constant (as logK) of metal EDTA complexes. These are applied to medium of
ionic strength, I = 0.1 at 20 °C.

Mg +2 8.7 Fe+3 25.1

Ca+2 10.7 Y +3 18.2
Sr +2 8.6 Cr +3 24
Ba+2 7.8 Ce+3 15.9
Mn+2 13.8 La+3 15.7
Fe+2 14.3 Lu+3 20
Co+2 16.3 Sc +3 23.1
Ni+2 18.6 Ga+3 20.5
Cu+2 18.8 In+3 24.9
Zn+2 16.7 Th+4 23.2
Cd+2 16.6 Ag + 7.3
Hg +2 21.9 Li+ 2.8
Pb+2 18 Na+ 1.7
Al+3 16.3

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PROPERTIES OF EDTA
1. EDTA Complex is easily soluble in water.
2. 1:1 complex is usually formed when, EDTA, reacts with metal ion and calculation is easy.
3. Due to presence of four or six available for co-ordination to à metal cation in such a way
that five membered rings are produced. This complex does not react with H2 S and do not
undergo precipitation.
4. Stability of complex is higher. Stability constant is greater than 8.
M +n + H2 Y −2 ⇌ MY n−4 + 2H+
From the above reaction it is understood that the reaction is depend on valency. Hence,
most of the metals form complexes.
5. EDTA forms complex rapidly with most of the metals. Although Cr (III), Al (III), Fe (III)
reacts slowly with EDTA at room temperature.
6. EDTA is a primary standard substance.
7. To detect the end point, it has instrumental method.
8. During titration, it gives colored and non-colored complex.
9. EDTA complexes are more stable than EDTA.
10. EDTA form complexes with bi-, tri- and tetravalent cations in the pH range 6-8, 2-4 and
0-1 respectively.

COMPLEXOMETRIC TITRATION:
Complexometric titration is the titration by which the quantity a any metal ion can be
determined with the formation of complex-compound in a solution. Metal ion solution is
titrated with a standard complex forming solution at a particular pH and suitable indicator.
When ЕDТА is used as a titrant, then the titration is called EDTA titration. End point is detected
by color change or indicator.

Criteria of Complexometric Titration:

1. Substances must be in pure form.
2. They should not change during preparation.
3. The reaction must be very fast with the metal ion.
4. Free energy change must be negative.
5. The product of the reaction must be soluble in the solvent used.
6. There must be a device to detect the end point of the reaction.
7. The stability of the metal-indicator complex must be less than that of metal-EDTA
complex.
8. The stepwise complex formation should be minimum.
9. The color of the indicator complex, must be clearly different from the indicator color.

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Criteria of a Titrant:
1. The titrant must be pure.
2. The titrant should react rapidly.
3. To detect the end point of the titration, there must have a method.
4. The titration must be soluble in the solvent.
5. The titration energy must be negative.
6. Las heat produce.

Advantage of Na-EDTA Use in Complexometric Titration:

EDTA is a very active compound, where disodium salt is used. Disodium salt of EDTA is
completely ionizable. EDTA is used as a titrant in complexometric titration due to the following
properties:
1. It is much more water soluble than pure EDTA.
2. It is non hygroscopic.
3. It is more stable.
4. The molecular weight of Na2H2Y (372.25) is higher than that of EDTA (292.25). Hence the
purity of titrant is increased when Na₂H2Y is used.
5. Pure EDTA is very weak. It cannot ionize completely in water. But disodium salt of EDTA
is completely ionized.
6. It forms chelate complex with polyvalent metals in the ratio of 1:1.
7. It obeys all the requirements of primary standard substances.

Storing of EDTA Solution:

EDTA solution is stored in polyethylene bags and pyrex vessels but not in glass vessels. Because
glass vessels are composed of Ca, Mg and Na compounds. EDTA can react with these metals and
form metal-EDTA complex which are soluble in aqueous solution. For this reason, glass vessels
are broken when EDTA is contained in it. But EDTA does not react with polyethylene and pyrex
compounds. So, EDTA is stored in and pyrex vessels.

Effect of pH:
EDTA forms complex with metals by the following way:
H2 O
Na2 H2 Y ⟶ 2Na+ + H2 Y −2
M +2 + H2 Y −2 ⇌ MY −2 + 2H+
M +4 + H2 Y −2 ⇌ MY − + 2H+
M+2 + H2 Y −2 ⇌ MY + 2H +
M +n + H2 Y −2 ⇌ MY n−4 + 2H+

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From the above reaction, it is shown that two equivalent hydrogen ions are liberated in each
time. Thus, the hydrogen ion concentration is gradually increased.

Hence pH of the solution is gradually decreased. The formation of complex depends upon the
pH of the solution with the increase of H+ ion. As a result, reaction proceeds to the left i.e., the
stability of M-EDTA complex decreases and vice versa, which is shown as follows-
[MY]n−4 [H + ]2
Ks = = Constant
[M +n ][H2 Y − ]

Again, when the value of pH is increased (above 8), metal ions are precipitated as metal
hydroxide which is shown by the following equation -
[MY]n−4 + n[OH− ] ⇌ M(OH)n + Y −4

Hence, it is shown that the production of M-EDTA complex is interfered with increase and
decrease of pH.

Every metal ion has a particular pH for the formation of M-EDTA complex. In this pH, the
formation EDTA complex is very good. In order to maintain the pH at a constant level metal ion
solution is to be buffered.

Why Iron (III) is Titrated with EDTA Solution in Acidic Media rather than in Basic
Media?

Fe (III) is titrated with EDTA solution in acid solution rather than in basic solution. Because if
we titrate Fe (III) in basic solution by process of pH controlling this precipitated out as metal
hydroxide, such as-

Fe − EDTA + 3OH− ⟶ Fe(OH)3 + EDTA

For this reason, Fe (III) is not titrated in basic solution.

The pH is controlled by the following way-

For divalent → (6 − 8)
For trivalent → (2 − 4)
For tetravalent → (0 − 1)

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Detection of End Point of Complexometric Titration:

Many metal ions can be titrated with EDTA under such condition such that a sudden large
change in metal ion concentration occurs near the equivalence point. Many substances function
as visual indicators. These indicators form complexes with metal ions, the complexed and
uncomplexed forms having different colors. The use of a metallochromic indicator to signal the
end point in an EDTA titration is based on the reaction,

MI + Y + M ⇌ MY + I
colored complex Free indicator (Different color)

At the onset of the titration, the reaction medium contains the metal indicator complex (MI)
that has formed excess metal ions. When EDTA, the titrant is added to the system, competitive
reaction takes place between the free metal ions and the EDTA. Since, the metal-indicator
complex is weaker than the metal-EDTA chelate, the EDTA which being added to the system
during the course of the titration is progressively chelating the free metal ions in solution at the
expense of the metal indicator complex. Finally, at the equivalence point, EDTA removes the
last traces of metal from the indicator and the indicator changes from its complexed color to its
metal free color.

A widely used metallochromic indicator is Eriochrome Black T.

Metal indicators and their requirements/ Metallochromic indicator:

Metal Indicators or metallochromic indicators are the substances, usually dyes, which produce
one color in the presence of free metal ion and different color (or no color) when they absent.
Many of these substances also have typical properties of acid-base indicators and color changes
are the result of the displacement of H+ ion by a metal ion.

The following requirements of a metal indicator must be met under the conditions which are
encountered during a titration.

1. They must be chelating agents.

2. They have a clear intense color of their own.
3. They form complexes with metals whose stability is fairly high.

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4. They compound must be chemically stable during storage and throughout the titration
procedure.
5. The colors of the complexes are fairly prevented from that of indicator.
6. The stability of the metal-EDTA complex must be very high in comparison with the metal
indicator complex.
7. This color change must occur at the pH of the buffer solution fixed for the titration.
8. The metal indicator must have sufficient stability to withstand dilution and still give an
adequate color change at the end point.

Different types of metal indicator:

Types Structure
 Eriochrome Black T /
Solochrome Black T /
Eriochromeschwarz T:

Below pH-6, it HIn− appears in red color.

At pH-(6.3-11), it HIn−2 appears blue color.
Above pH-11.6, it In−3 appears orange color.
 Napthyl anoxin:

 Napthyl anoxin sulphate:

 Calmagite:

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Theory of the visual use of metal-ion indicators:

The use of a metal ion indicator in an EDTA titration may be written as:
MIn + EDTA → M-EDTA + In

This reaction will proceed if the metal indicator complex M-In is less stable than the M-EDTA
complex. The stability of the metal-indicator complex (M-In) may be expressed as the formation
constant (or indicator constant), KIn. The equation expressed as,

M + + In− ⟶ MIn ------------(1)

[MIn]
∴ K In =
[M + ][In− ]

where,
[MIn] = Concentration of metal-indicator complex.
[M+ ] = Concentration of metallic ion
[In− ] = Concentration of indicator ion

Taking log on both sides of the equation-

[MIn]
log K In = log
[M + ][In− ]
[MIn]
or, log K In = log − log [M + ]
[In− ]
[MIn]
𝑜𝑟, log K In = log + pM
[In− ]
[MIn]
𝑜𝑟, pM = log K In − log … … … … … … … (2)
[In− ]

The color of indicator can be detected by eye when its concentration becomes one-tenth of the
concentration of metal-indicator complex and vice versa.

So, the range of pM:

10
from, pM1 = logK In − log = logK In − 1
1
1
to, pM2 = logK In − log = logK In + 1
10
i. e., The range, pM = logK In ± 1

For a small titration error, KIn should be large (>104), the ratio of the apparent stability constant
of the metal EDTA complex, Kmy to that of the metal- indicator complex KIn should be large
(>104) and the ratio of the indicator concentration to the metal ion concentration should be
small (<10-2).

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TYPES OF EDTA TITRATION:

 Direct Titration:
This is a direct determination of a metal ion by
adding standard ETDA titrant to the sample solution.

In this procedure, the metal ion solution is buffered to the desired pH and titrated directly with
the standard EDTA solution. Before adding EDTA solution a pM indicator is added. Some
auxiliary complexing agent such as tartarate or citrate or triethanol amine may be added to
prevent precipitation of the hydroxide of the metal. At the equivalence point, the magnitude of
the concentration of the metal ion being determined.

Calculation: The strength of the metal ion solution is calculated by the equation:
𝑽𝟏 𝑺𝟏 = 𝑽𝟐 𝑺𝟐
where,
V1 = volume of metal ion solution.
S1 = strength of metal ion solution.
V2 = volume of EDTA solution.
S2 = strength of EDTA solution.

 Back Titration:
Back titration is employed when-
1. Suitable indicator is not available.
2. Metal ion reacts with EDTA slowly.
3. Metal ion precipitates out while the required pH is adjusted.
4. Metal ion may combine with atmospheric CO2 or other species while adjusting the pH.

In this procedure, an excess of a standard

solution of EDTA is added to the sample
metal solution being determined so as to
complex all the metal ions present in the
solution. The excess of EDTA left after
the complex formation with the metal is
back titrated with a standard solution of
a second metal ion to suitable end point.
Usually, standard metal ion solution
used are ZnCl2, ZnSO4, MgCl2.

After addition of excess EDTA solution, the resulting solution must be buffered to the desired
pH. The end point is detected with the aid of the metal indicator which responses the metal ions
introduced in the back titration.

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For example, in the determination of Mn (II) an excess of EDTA solution is added to an acidic
solution of the manganese salt. An ammonia buffer is used to adjust the solution pH to 10 and
the excess EDTA remaining, after chelation is titrated with a standard Zn (II) solution using
Eriochromic Black T as the indicator.

Calculation: The strength of the metal ion solution is determined by the equation-
𝑽𝟏 𝑺𝟏 + 𝑽𝟐 𝑺𝟐 = 𝑽𝟑 𝑺𝟑
where,
V1 = volume of required metal ion solution (known).
V2 = volume of required metal ion solution in back titration (known).
V3 = volume of EDTA added (known).
S1 = strength or concentration of metal ion solution (unknown).
S2 = strength or concentration of metal ion solution in back titration (known)
S3 = strength of EDTA solution (known).

 Replacement or Substitution Titrations

In this method, weak EDTA complex of another metal ion (M2) is added to the solution of metal
ion (M2) to be determined.
Substitution titration may be used for metal ions that do not react with metal indicator, or for
metal ions which form EDTA complexes that are more stable than those of other metals such as
magnesium and calcium. The metal ion (M n+ ) to be determined may be treated with the
magnesium complex with EDTA when the following reaction occurs.

M n+ + MgY −2 ⇌ (MY)(n−4) + Mg 2+

The amount of magnesium ion set free is

equivalent to the cation present and can be
titrated with a standard solution of EDTA and a
suitable metal indicator.

For example, in the direct titration of C++ ions,

Solochrome black T gives a poor end point; if
Mg++ is present, it is displaced from its EDTA
complex by calcium and an improve end point
results, by the following equation:

Mg-EDTA +Ca(II) ⟶ Ca-EDTA + Mg (II)

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 Acidimetric-Alkalimetric Titration
This method uses the principle of liberation of free H+ ion during the complexation. Metal-EDTA
complex formation reaction explains that protons are liberated from disodium edetate leading
to formation of acid.
The acid that is formed can be titrated against a standard alkali but unbuffered solution. End
point detection can be done by using acid-base visual indicator or potentiometric method of
detecting end point. For example,

When a solution of disodiumethylene

diamine tetra-acetate, Na2H2Y, is added to a
solution containing metallic ions, complexes
are formed with the liberation of two
equivalents of hydrogen ion:

𝐌𝐧+ + 𝐇𝟐 𝐘 𝟐− ⇌ (𝐌𝐘)(𝐧−𝟒)+ + 𝟐𝐇+

The hydrogen ions thus set free can be titrated with a standard solution of sodium hydroxide
using an acid-base indicator or a potentiometric end point; alternatively.

DETERMINATION OF CALCIUM
Calcium ions may be determined by the following four types of titrimetric procedure:
 Direct titration:
An accurately weighted sample of the calcium salt, equivalent to 100 mg of calcium is
dissolved in 50 ml of water with the aid of a few drops of HCl if necessary. When solution is
completed, the sample is diluted with water to volume in a 100 ml volumetric flask and
mixed thoroughly.

50 ml of the sample solution is pipetted into titration vessel containing 50 ml of water. The
pH of the solution is adjusted to 12 with a freshly prepared 1 N sodium hydroxide solution,
300 mg of Hydroxy Naphthol Blue indicator is added and titrated rapidly with 0.1 M EDTA
until the color changes to a deep blue. Each milliliter of the titrant equivalent to 4.008 mg of
Calcium.

 The solution must be titrated rapidly because CO2 from-air from air reacts with calcium ion
forming calcium carbonate, which tends to precipitate from highly alkaline solution.

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 Direct titration in the presence of magnesium salt:

The sample solution is prepared by the same procedure as direct titration:
50 ml of the solution is pipetted into a titration vessel containing so ml of water, 2 ml of 0.1
M MgSO4 solution is added. 5 ml of ammonia buffer and a few drops of Eriochrome black T
indicator is added. This mixture is titrated with 0.1 M EDTA solution to a deep-blue color.

The volume of 0.1 M EDTA consumed by the by the is calculated by subtracting the volume
of 0.1 M magnesium sulfate in milliliters from the volume of 0.1 M EDTA required to obtain
the deep-blue color at end point. Each milliliter of titrant is equivalent to 4.008 mg of
calcium.

 Back titration:
The sample solution is prepared by the same procedure as direct et titration.

50 ml of the solution is pipetted into vessel, 50 ml of the of EDTA solution is added. To this
5 ml of 0.1 M ammonia buffer and a few drops of Eriochrome black T indicator is added. This
mixture is titrated with 0.1M magnesium sulphate solution until color changes from blue to
wine red.

The difference in volume between the 0.1 M EDTA solution and the magnesium solution is
the volume of EDTA solution consumed by the calcium. Each milliliter of this solution is
equivalent to 4.008 mg of calcium.

 Replacement titration:
The sample solution prepared by the same procedure as direct titration.

50 ml of the sample solution is pipetted into a titration vessel containing 50 ml of water. 25

ml of Mg-EDTA solution. 5 ml of ammonia buffer and a few drops of Eriochrome Black T
indicator are added. This mixture is titrated with 0.1 M EDTA solution to deep blue. Each
milliliter of titrant is equivalent to 4.008 mg of calcium.

TITRATION OF MIXTURES (How to increase the selectivity of the EDTA titration)

EDTA is very unselective reagent because it complexes with numerous di, tri, and tetra cations.
The following procedures help to increase the selectivity of the EDTA titration.

 By controlling suitable pH of the solution:

This technique utilizes the different stabilities of EDTA complexes based on pH. The selectivity
is increased by controlling the pH of the solution.

The conditional formation constant for metal-EDTA complex is depend on the hydrogen ion
concentration. So, by adjusting the pH of the sample solution containing several metal ions, it is
possible to allow only a single species to react with EDTA.

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E.g.: Ca+2 can be determined in the presence of

Mg+2 in strongly alkaline solution (pH < 10).
Trivalent ions like Bi+3, Fe+3 can be selectively
determined from the solution of bivalent metal
ions in strongly acidic solution (pH ~ 2).

Thus, Bismuth and Thorium can be titrated in

acidic solution (pH-2) with xylenol orange or
methyl thymol blue as indicator and iron (III) in
acidic solution (pH-3) with Variamine Blue as
indicator, whereas Ni at pH=8 with Muracid.
a. Adjusting pH at 2-3, Fe(II) can be titrated in presence of divalent metal ions with Variamine
Blue as indicator.
b. Adjusting pH at 6-8, Zn(II) can be titrated in presence of trivalent or tetravalent metal ions
with Eriochrome Black T.
c. Adjusting pH at 12-13, Ca(II) can be titrated in presence of Mg(II) with xylenol blue as
indicator.

 Solvent extraction method:

Zinc can be separated from copper and lead by adding excess of ammonium thiocyanate
solution and extracting the resulting zinc thiocyanate with isobutyl methyl ketone. The extract
is diluted with water and the zinc content is determined with EDTA solution.

 Classical Method
These may be applied when they are not tedious. At first from a mixture of metal ions, any cation
of these precipitated out and separated by a filter. After being redissolved, the precipitation in
a solution, the metal ion can be determined complexometrically. Thus, all of the metal ions may
be determined.
Numerous separations have been successfully employed. Some of the more common agents are
oxalate for removal of calcium ions, Sulfide for the heavy metals, fluoride for aluminum and
hydroxide for some transition metals (iron and magnesium).

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 Masking Method:
Masking is the process in which a substance is
prevented to take part in the reaction without
physical separation of it. So, it is transformed that it
does not participate in a reaction.

The reagent used in masking is known as masking

agent. Masking agent is a compound capable of
entering a complexation reaction. It is used to
indicate the determination of a metal in the
presence of the other metal, cyanide, ascorbate,
triethanolamine is used as masking agent.

Cyanide ion is an effective masking agent for EDTA

titrations. It forms stable cyanide complex with the
metal cation like Cd, Zn, Hg, Cu, Co, Ni, Ag, Pt but
does not form complex with alkaline earth metals like Mg, Ca etc. as well as Mn and Pb. Thus, it
is possible to determine Ca, Mg, Pb, Mn in the presence of other metal cations by masking agents
like CN- ion.

Masking Agent Titration Metal Metals Masked

a. Cyanide Alkaline earth metals, Mn, Pb, Ca, Cd, Zn, Hg (II), Cu, Co, Ni, Ag,
Mg Pt
b. Triethanolamine Mg (II) Ti (IV), Al (III), Fe (III),
c. NH4F Zn (II) Ca (II), Mg (II), Al (III)

 Demasking Method
 Demasking is the process in which the masked substance regains its ability to enter into a
particular reaction.
 In this technique, the one of the cations is first masked and remaining free cation is titrated
with standard EDTA.
 Then previously masked cation is demasked by using suitable reagent to get free cation.
 This free cation is then titrated by using standard EDTA
 The cyanide complexes of Zn and Ca may be demasked with chloral hydrate, formaldehyde
(H-COH) solution. e.g., Formaldehyde is used to demasked Zn-CN complex.
[Zn(CN)4 ]2− + 4H+ + 4HCOH ⟶ Zn2+ + 4HOCH2 CN

 This free Zn+2 ion is then titrated by using standard EDTA. Thus, it is possible to
determine Zn in the presence of Ca.

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The use of masking and selective demasking agents

permits the successive titration of many Metals.
This solution containing Mg, Zn and Cu can be
titrated as follows:

1. Excess standard EDTA solution is added and

back titrated with standard Mg solution using
solochrome Black T as indicator. This gives the
sum of the metals present.
2. An aliquot portion is treated with an excess of
CN and filtered as before. This gives Mg only
because cyanide forms complex with Zn.
Zn2+ + 4CN− ⟶ [Zn(CN)4 ]2−
3. An excess of chloral hydrate (or of
formaldehyde acetic acid solution) is added the
titrated solution in order to titrate Zn form the
cyanide complex and is titrated until the
indicator turns blue. This gives only the Zn.

 Redox Masking
Sometimes the metal may be transformed into a different valency state. Thus, copper may be
reduced in acid solution by hydroxyl amine or ascorbic acid, such as in a solution of Cu(II) and
Zn(II), ascorbic acid is added and titrated with EDTA. Then only Zn-EDTA complex is formed as
Cu(II) is transformed into Cu(I) which cannot react with EDTA.
Reduced
Zn(II) + Cu(II) → Zn(II) + Cu(I)
Ascorbic acid

Zn(II) + Cu(I) ⟶ Zn-EDTA + Cu(I)

As for example, in case of three metal mixture e.g., Cu, Cd and Ca, direct titration of the mixture
with EDTA gives the sum of the three metals. Cu(II) and Cd(II) may be masked with the addition
of cyanide to the solution leaving only the Ca++ titratable. When formaldehyde and chloral
hydrate is added to the cyanide containing mixture, Cd is demasked only and the EDTA titrates
the sum of the calcium and cadmium. In this manner, the concentration of all three ions is
determined by three individual titrations. The reaction steps are as follows:

 Step-1: All three metals are titrated with EDTA which gives sum of the tree metals EDTA.

Cu Cu-EDTA

Cd + EDTA = Cd-EDTA

Ca CA-EDTA

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 Step-2: Addition of cyanide to the solution masks Cu(II)and Cd(II) leaving only Ca++. Only
calcium is titrated.
Cu + CN− ⇌ Cu-cyanide complex
Cd + CN− ⇌ Cd-cyanide complex
Ca + CN− ⇌ No reaction
Ca + EDTA ⇌ Ca-EDTA complex

 Step-3: After the addition of formaldehyde, Cadmium is demasked, Copper is masked and
EDTA titrates the sum of the Ca and Cd.
O−
Cd-cyanide complex + H-CHO ⇌ Cd(II) + H – C – H
demasking agent CN
Cu-cyanide complex + H-CHO ⇌ No reaction

Cd Cd-EDTA
+ EDTA ⇌
Ca Ca-EDTA

 Kinetic Masking Method

 The formation of metal EDTA complex have
different speed with different metal. Some of the
metal undergoes fast complexation some of
undergoes slow complexation with EDTA.
 Hence, it is possible to titrate the metal ions
which undergoes fast complexation with EDTA in
the presence of those metal ions which
undergoes slow complexation with EDTA. In this
reaction, the metals having low speed of reaction
with EDTA do not interfere.
 E.g., Fe+3 can be easily estimated in the presence of Cr+3, because Cr+3 reacts slowly with
EDTA to form complex as compared to Fe+3. Thus, Fe(III) can be titrated in presence of
Cr(III) without interfering.

REMOVAL OF ANION Document Credit,

Anion such as orthophosphate which can
interfere in complexometric titrations, G.M. Masud Parvez
may be removed by ion-exchange resins. Lecturer,
Department of Pharmacy,
Pabna University of Science & Technology.

Re-write & Edit: MD. Rasul Islam Raza Roll: 181307 Department of Pharmacy, PUST