CHE 401 : ANALYTICAL CHEMISTRY

MODULE
7
COMPLEXATION REACTIONS AND TITRATIONS

INTRODUCTION
This module discuss complexation reactions and titrations. It is important to learn to balance the
reactions concerning cations and the principle of the process. At the end of the module, the students
are expected to understand the calculations involved and be familiar with the analysis of metals
using this methods

INTENDED LEARNING OUTCOMES

At the end of the module, the following learning outcomes are expected to be acquired by the
students:
1. Understand the concepts and principles of complexation reactions.
2. Execute calculation techniques used in complexation reactions.
3. Acquire skills in laboratory technique required to perform and plan chemical analysis and
systematically collect and interpret data obtained in quantitative analytical process.

CONTENT OVERVIEW
Indicative contents included the following topics:
1. Complexation reactions
2. Complexomatric titrations
3. Complexes of EDTA and metal ions
4. Indicators for EDTA Titrations
5. Titrations method employing EDTA
6. Analysis of sample
7. Sources of error
8. Complexometry
9. Pharmaceutical analysis

END OF THE MODULE TEST

The following are the assessment provided to evaluate students level of understanding after the
discussion of the modules:

Coursework (100 points )

Solving problems involving oxidation reduction reactions.

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Table of Contents

MODULE 7. COMPLEXATION REACTIONS AND TITRATIONS ........................................ 3

7.1 COMPLEXATION REACTIONS ...................................................................................... 3

7.2 COMPLEXOMETRIC TITRATIONS ............................................................................ 4

7.2.1 Organic Complexing Agents ........................................................................................ 5

7.3 COMPLEXES OF EDTA AND METAL IONS ................................................................ 7

7.3.1 Titration Curve ............................................................................................................. 8

7.4 INDICATORS FOR EDTA TITRATIONS ..................................................................... 9

7.5 TITRATION METHODS EMPLOYING EDTA .......................................................... 11

7.5.1 Direct Titration ........................................................................................................... 11

7.5.2 Back-titration Methods ............................................................................................... 12

7.6 ANALYSIS OF A SAMPLE ......................................................................................... 12

7.7 SOURCES OF ERROR ................................................................................................. 13

7.8 COMPLEXOMETRY - Determination of cations ......................................................... 13

7.8.1 TITRATION FOR EDTA .......................................................................................... 14

7.9 PHARMACEUTICAL ANALYSIS ................................................................................. 16

7.10 END OF MODULE TEST ............................................................................................. 36

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MODULE 7. COMPLEXATION REACTIONS AND TITRATIONS

A complexation reaction can be described as a reaction that forms a "complex". Complex-forming

reactions involving many metal ions can serve as a basis for accurate and convenient titrations for
such metal ions. These kinds of complex ion titration procedures referred to as complexometric
titrations, have high accuracies and offer the possibility of determinations of metal ions at the
millimole levels. They have their applications in many chemical and biological processes. The
processes involved in the formation of complex ions are basically acid-base type reactions in which
the metal ion acts as an acid and the anions or molecules as the base.

7.1 COMPLEXATION REACTIONS

In the broadest sense, complexation is the association of two or more chemical species that are
capable of independent existence by sharing one or more pairs of electrons. Although this type of
a chemical reaction can be classified as a Lewis acid-base reaction, it is more commonly known
as a complexation reaction. As applied to chemical analysis, this definition is generally taken to
mean the bonding of a central metal ion, capable of accepting an unshared pair of electrons with
a ligand that can donate a pair of unshared electrons.

In a complexation reaction, the product of the reaction is termed a complex. The species which
donates the electron pairs by acting as a Lewis base is known as a complexing agent or ligand,
and the ion which accepts the donated electrons, theLewis acid, is called the central ion or central
atom. Central ions are generally metallic cations. The ligand can be either a neutral molecule such
as water orammonia; or an ion such as chloride, cyanide, or hydroxide. The complex can have
either a positive or a negative charge, or it can be neutral. Complexation titration can also be called
EDTA Titration.

Fig. 7.1 EDTA Titration

Complexation equilibria can be complicated by side reactions involving the metal or the ligand.
Such side reactions make it possible to exert some additional control over the complexes that form.

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Metals can form complexes with ligands other than the one of interest. If these complexes are
strong, we can effectively prevent complexation with the ligands of interest. Ligands can also
undergo side reactions. One of the most common side reactions is a ligand that can protonate, that
is, the ligand is a weak acid.

7.2 COMPLEXOMETRIC TITRATIONS

- Classical application of complexation reactions

Figure 7.2 Titration curves for complexometric titrations. Titration of 60.0 mL of a solution that
is 0.020 M in metal M with (A) a 0.020 M solution of the tetradentate ligand D to give MD as
the product: (B) a 0.040 M solution of the bidentate ligand B to give MB2 : and (C) a 0.080 M
solution of the unidentate ligand A to give MA. The overall formation constant for each product
is 1020.

A metal ion reacts with a suitable ligand to form a complex, and an indicator or an appropriate
instrumental method determines the equivalence point. Tetradentate or hexadentate ligands are
more satisfactory as titrants than ligands with a lesser number of donor groups because their
reaction with cations are more complete and because they tend to form 1:1 complexes.

TABLE 7.1. Typical Inorganic Complex-Forming Titrations

Titrant Analyte Remarks
Products are neutral
Hg(NO3)2 Br-, Cl-, SCN-, CN-, thiourea Hg(II)complexes: various
indicator used.
Products is Ag(CN)2: indicator is I
AgNO3 CN-
: titrate first turbidity of AgI
Product is Ni(CN)4-2 ; indicator is
NiSO4 CN-
I-, titrate to first turbidity of AgI.
Products are Cu(CN)4-2, Hg(CN)2,
KCN CU2+, Hg2+, Ni2+ and Ni(CN)4-2 ; various indicators
used.

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7.2.1 Organic Complexing Agents

- Important in analytical chemistry because of their inherent sensitivity and potential
selectivity in reacting with metal ions.

1. EDTA
 Ethylenediaminetetraacetic acid
 Also called (ethylenedinitilo) tetraacetic acid
 Most commonly used complexometric titrant
 Has six potential sites for bonding a metal ion: the four carboxyl group and the two
amino group

Standard EDTA solutions are ordinarily prepared by dissolving weighed quantities of

Na2H2Y-2H2O and diluting to the mark in a volumetric flask.

Fig 7.3 Composition of EDTA solutions as a function of pH. Note that the fully protonated
form, H4 Y is only a major component in very acidic solutions (pH<3). Throughout the pH range
of 3 to 10, the species Hz2 and Hy3- are predominant. The fully unprotonated form y4- is a
significant component only in a very basic solutions (pH>10).

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2. Nitrilotriacetic Acid (NTA)

 is the second most common aminopolycarboxylic acid for titrations.
 When EDTA is added to foods, it so tightly binds most metal ions that they are unable to
catalyze the air oxidation reaction. EDTA and other similar chelating agents are often
called SEQUESTERING AGENTS because of their ability to remove or inactive metal
ions.

Example 7.1
Calculate the equilibrium concentration of Ni 2+ in a solution with an analytical Niy2- concentration
of 0.0150 M at pH (a) 3.0 and (b) 8.0.

TABLE 10-2. FORMATION CONSTANTS FOR EDTA COMPLEXES

Cation KMY* Log KMY Cation KMY Log KMY
+ 7 2+ 18
Ag 2.1×10 7.32 Cu 6.3×10 18.80
2+ 8 2+ 16
Mg 4.9×10 8.69 Zn 3.2×10 16.30
2+ 10 2+ 16
Ca 5.0×10 10.70 Cd 2.9×10 16.46
2+ 8 2+ 21
Sr 4.3×10 8.63 Hg 6.3×10 21.80
2+ 7 2+ 18
Ba 5.8×10 7.76 Pb 1.1×10 18.04
2+ 13 3+ 16
Mn 6.2×10 13.79 Al 1.3×10 16.13
2+ 14 3+ 25
Fe 2.1×10 14.33 Fe 1.3×10 25.1
2+ 16 3+ 25
Co 2.0×10 16.31 V 7.9×10 25.9
2+ 18 4+ 23
Ni 4.2×10 18.62 Th 1.6×10 23.2

Ni2+ + Y4- NiY2- KNIY = [NiY2-]/[Ni2+][Y4-] = 4.2x1018

The equilibrium concentration of NiY2- is equal to the analytical concentration of the

complex minus the concentration lost by dissociation. The latter is identical to the equilibrium Ni 2+
concentration. Thus,
[NiY2+] = 0.0150 – [Ni2+]

If we assume that [Ni2+]<<0.0150, an assumption that is almost certainly valid in light of

the large formation constant of the complex, this equation simplifies to
[NiY2-] ≈ 0.0150

Since the complex is the only source of both Ni2+ and the EDTA species,
[Ni2+] = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y] = CT

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Substitution of this equality gives

[𝑁𝑖𝑌 2− ]
𝐾 ′𝑁𝑖𝑌 = = 𝛼4 𝐾𝑁𝑖𝑌
[𝑁𝑖 2+]𝐶𝑇

(a) It is indicated that α4 is 2.5 x 10-11 at pH 3.0. If we substitute this value and the concentration
of NiY2- into the equation for K’MY, we get
0.0150
= 2.5𝑥10−11 𝑥 4.2𝑥1016 = 1.05 𝑥 108
[𝑁𝑖𝑌 2+]2
[𝑁𝑖 2+] = (1.43𝑥10−10 )1/2 = 1.2𝑥10−5 𝑀

(b) At pH 8.0, the the conditional constant is much larger. Thus,

𝐾′𝑁𝑖𝑌 = 5.4 𝑥 10−3 𝑥 4.2 𝑥 1018 = 2.27 𝑥 1016
And after we substitute this into the equation for K’NiY, we get

[Ni2+]={(0.0150)(2.27x1016)}1/2= 8.1 x 10-10M

7.3 COMPLEXES OF EDTA AND METAL IONS

Solutions of EDTA are particularly valuable as titrants because the reagent combines with
metal ions in a 1:1 ratio regardless of the charge on the cation. For example, the silver and
aluminum complexes are formed by the reactions;

𝐴𝑔+ + 𝑌 4− ⇌ 𝐴𝑔𝑌 3−
𝐴𝑙 3+ + 𝑌 4− ⇌ 𝐴𝑙𝑌 −

EDTA is remarkable reagent not only because it forms chelates with all cation except alkali
metals but also because most of these chelates are sufficiently stable for titrations. This great
stability undoubtedly results from the several complexing sites within the molecule that give rise
to a cage-like structure, in which the cation i8s effectively surrounded by and isolated from solvent
molecules. One of the common structures for metal/EDTA complexes is shown in Figure 14-3.
The ability of EDTA to complex metals is responsible for its widespread use as a preservative in
foods and in biological samples.

Table 10-2 lists formation constants KMY for common EDTA complexes. Note that the
constant refers to the equilibrium involving the fully unprotonated species Y4- with the metal ion:

𝑛+ 4− (𝑛−4)+ [𝑀𝑌 (𝑛−4)+]

𝑀 + 𝑌 ⇌ 𝑀𝑌 𝐾𝑀𝑌 =
[𝑀𝑛+][𝑌4− ]

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7.3.1 Titration Curve

Fig 7.4 EDTA titration curves for 50.00mL of 0.00500 M Ca2 + (K CaY = 1.75 x 1010) and
Mg2+ (K’MgY = 1.72 x 108) at pH 10.00.

Note that because of the larger formation constant, the reaction of calcium ion with EDTA is
more complete and a larger change occurs in the equivalence point region. The shaded areas
show the transition range for the indicator Eriochrome Black T .

Fig 7.5 Influence of pH on the titration of 0.0100 M Ca2+ with 0.0100M EDTA.

Note that the end point becomes less sharp as the pH decreases because the complex formation
reaction is less complete under these circumstances.

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Fig 7.6 Titration curves for 50.00mL of 0.0100M solutions of various cations at pH 6.0.

Fig 7.7 Minimum pH needed for satisfactory titrations of various cations with EDTA.

7.4 INDICATORS FOR EDTA TITRATIONS

Nearly 200 organic compounds have been investigated as indicators for metal ions in
EDTA titrations. The most common indicators are given by Dean. In general, these indicators are
organic dyes that form colored chelates with metal ions in a pM range that is characteristic of the
particular cation and dye. The complexes are often intensely colored and are discernible to the eye
at concentrations in the range of 10-6 to 10-7 M.

Figure 10-7 Structure and molecular model of Eriochrome Black T.

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The compound contains a sulfonic acid group that completely dissociates in water and two
phenolic groups that only partially dissociate. Eriochrome Black T is a typical metal ion indicator
that is used in the titration of several common cations. The structural formula of Eriochrome Black
T is shown in the figure 10-7. Its behavior as a weak acid is described by the equations:

𝐻2 𝑂 + 𝐻2 𝐼𝑛− ↔ 𝐻𝐼𝑛−2 + 𝐻3 𝑂 𝐾1 = 5𝑥10−7

𝐻2 𝑂 + 𝐻𝐼𝑛2− ↔ 𝐼𝑛3− + 𝐻3 𝑂 𝐾2 = 2.8𝑥10−12

Note that the acid and their conjugate bases have different colors. Thus, Eriochrome Black
T behaves as an acid/base indicator as well as a metal ion indicator. The metal complexes of
Eriochrome Black T are generally red, as is H2In-. Thus, for metal ion detection, it is necessary to
adjust the pH to 7 or above so that the blue form of the species, HIn 2-, predominates in the absence
of a metal ion. Until the equivalence point in a titration, the indicator complexes the excess metal
ion so that the solution is red. With the first slight excess of EDTA, the solution turns blue as a
consequence of the reaction
𝑀𝐼𝑛− + 𝐻𝑌 3− ↔ 𝐻𝐼𝑛2− + 𝑀𝑌 2−

Eriochrome Black T forms red complexes with more than two dozen metal ions, but the
formation constants of only a few are appropriate for end point detection.

EXAMPLE 7.2

Determine the transition ranges for Eriochrome Black T in titrations of Mg2+ and Ca2+ at pH 10.0,
given that (a) the second acid dissociation constant for the indicator is

2− 3− +
[𝐻3 𝑂+ ][𝐼𝑛3−]
𝐻𝐼𝑛 + 𝐻2 𝑂 ⇌ 𝐼𝑛 + 𝐻3 𝑂 𝐾2 = = 2.8 × 10−12
[𝐻𝐼𝑛2−]

(c) the formation constant for MgIn- is

[𝑀𝑔𝐼𝑛−]
𝑀𝑔2+ + 𝐼𝑛3− ⇌ 𝑀𝑔𝐼𝑛− 𝐾1 = = 1.0 × 107
[𝑀𝑔2+][𝐼𝑛3−]

And (c) the analogous constant for Ca2+ is 2.5 × 105 ,

We assume, as we did earlier (see section 14A-1), that a detectable color change requires
a 10-fold excess of one or the other of the colored species; that is, a detectable color change is
observed when the ratio [𝑀𝑔𝐼𝑛−|/[𝐻𝐼𝑛2−] changes from 10 to 0.10. Multiplication of K2 for the
indicator by K1 for MgIn- gives an expression that contains this ratio;
[𝑀𝑔𝐼𝑛−][𝐻3 𝑂+]
= 2.8 × 10−12 × 1.0 × 107 = 2.8 × 10−5
[𝐻𝐼𝑛2−][𝑀𝑔2+]

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which rearranges to
[𝑀𝑔𝐼𝑛−] [𝐻3 𝑂+]
[𝑀𝑔2+] = ×
[𝐻𝐼𝑛2−] 2.8 × 10−5

Substitution of 1.0 × 10-10 for [H3O4] and 10 and 0.10 for the ratio yields the range of
[Mg2+] over which the color change occurs:
[𝑀𝑔2+] = 3.6 × 10−5 𝑀 𝑡𝑜 3.6 × 10−7 𝑀
𝑝𝑀𝑔 = 5.4 ± 1.0

Proceeding in the same way, we find the range for pCa to be 3.8± 1.0.

7.5 TITRATION METHODS EMPLOYING EDTA

Several different types of titration methods can be used with EDTA:

7.5.1 Direct Titration

Methods that use an added metal ion are also widely employed. Many of the metals in the periodic
table can be determined by titration with standard EDTA solutions. Some methods based on
indicators that respond to the analyte itself, while others are based on an added metal ion. An
excess standard solution is added and the excess is determined by the addition of another solution.

Methods Based on Indicators for the Analyte

Indicators that respond to the metal directly cannot be used in all cases, either because no indicator
with an appropriate transition range is available or because the reaction between metal ion and
EDTA is so slow as to make titration impractical.

Methods Based on Indicators for an Added Metal Ion

When a good, direct indicator for the analyte is unavailable, a small amount of a metal ion for
which a good indicator is available can be added. The metal ion must form a complex that is less
stable than the analyte complex.

Potentiometric Methods
Potential measurements can be used for end point detection in the EDTA titration of those metal
ions for which specific ions electrodes are available electrodes of this type are described in Section
21D-1. In addition, a mercury electrode can be sensitive to EDTA ions and used in titration with
this reagent.

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Spectrophotometric Methods
Measurement of UV/visible absorption can be used to determine the end points of titrations. In
these cases, an instrument responds to the color change in the titration rather than relying on a
visual determination of the end point.

7.5.2 Back-titration Methods

Back-titration is useful for the determination of cations that form stable EDTA complexes and for
which a satisfactory indicator is not available. The method is also useful for cation such as Cr(III)
and Co(III) that react only slowly with EDTA. A measured excess of standard EDTA solution is
added to the analyte solution. After the reaction is judged complete, the excess EDTA is back-
titrated with a standard magnesium or zinc ion solution to an eriochrome blackT or Calmagite end
point. For this procedure to be successful, it is less stable than the corresponding analyte complex.
Back-titration is useful for analyzing samples that contain anions that would otherwise
form sparingly soluble precipitates with the analyte under the analytical conditions. Here, the
excess EDTA prevents precipitate formation.
An excess standard solution is added and the excess is determined by the addition of
another solution.

Displacement Methods
In displacement titrations, an unmeasured excess of a solution containing the magnesium or zinc
complex of EDTA is introduced into the analyte solution. If the analyte forms a more stable
complex than that of magnesium or zinc, the following displacement reaction occurs:
MgY 2− + M 2+ → MY 2− + Mg 2+
where M2+, represents the analyte cation. The liberated Mg2+, or, in some cases Zn2+, is then titrated
with a standard.

7.6 ANALYSIS OF A SAMPLE

1. Preparation of the sample solution.

2. Titration of the sample solution.
-solution is titrated with a standard solution of the reagent. The titration maybe either:
a. Dead stop end point
b. Past the end point followed by back titration with a sample solution or
another standard solution
3. Computation can be expressed in
a. M or N of the solution
b. Weight of the given substance present
c. % of the given constituent of the sample

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7.7 SOURCES OF ERROR

1. Loss of sample or solution by spilling in weighing, spilling solution in transfer, leaking
burets, faulty piping
2. Contamination in dilution of solution by failure to properly rinse burets, pipets, and
bottles
3. Faulty mixing of solution after they had been diluted
4. Impurities in the primary standard in which the concentration values are based
5. Errors in weighing
6. Errors in reading buret
7. Use of wrong indicator in titration
8. Poor drainage from buret to pipet

Masking Agent
- is a complexing agent that reacts selectively with a component in a solution to prevent
that component from interfering in a determination

Hard Water
- contains calcium, magnesium, and heavy-metal ions that form precipitates with soap (but
not detergent)

7.8 COMPLEXOMETRY - Determination of cations

1. Determination of cyanide using Liebig method

2CN − + Ag + → Ag(Cn)2 −
Ag(Cn)2 − + Ag → Ag(Ag(CN)2 )s
Self-indicating; ep. Formation of permanent faint turbidity.

2. Determination of Nickel
Addition of excess Cyanide
Ni(NH3 )6 +3 + 4CN − + 6H2 O → Ni(CN)4− + 6NH4
Back Titration
2CN − + Ag + → Ag(CN)2 −
Endpoint
Ag(CN)2 − + Ag → Ag(Ag(CN)2 )s

3. Titration with EDTA (Ethylene Diamine Tetra Acetic Acid)

MIn− + HY −3 → HIn− + MY −2
Red Blue

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4. Direct Titration with added metal ions

-determination of Ca+2
-small amount of MgCl2 is added to EDTA
-Ca+2 replaces Mg+2 then bind with EBT to form red complexes

EXAMPLE 7.3

A 500 mg sample containing sodium cyanide read 23.5 ml of 0.1255 M AgNO3 to obtain
a permanent faint turbidity. Express the result of this analysis to % cyanide.
1 Ag 2 CN
(23.5ml)(0.1255)AgNO3 ( )( ) ⎸CN⎹
1 AgNO3 1 Ag
× 100% = 30.69%
500

1 Ag 2 CN
(23.5ml)(0.1255)AgNO3 ( )( ) ⎸NaCN⎹
1 AgNO3 1 Ag
% impurity = × 100% = 57.81%
500

7.8.1 TITRATION FOR EDTA

An EDTA solution prepared from its disodium salt was standardized using 506.3 mg of
primary standard CaCO3 and consumed 28.50 ml of solution. The standard solution was used to
determine the hardness of a 2.0 L sample of mineral water which required 35.57 ml of EDTA
solution. Express the analysis in terms of ppm CaCO3.
506.3 mg = 28.5 ml EDTA

506.3 mg
mg CaCO3 × 35. 57 ml
ppmCaCO3 = = 28.5 ml = 315.95 ppm CaCO3
L solution 2.0 L

Pb, Mg and Zn can be determined on a single sample by two titrations of EDTA and one
titration with Mg+2. The sample is first treated with an excess NaCN which masks Zn and prevent
H+ from reacting with EDTA. Zn2+ + 4CN ⇌ Zn(CN)4 2 The Pb2+ and Mg2+ are then titrated with
EDTA. After the equivalence point has been reached, a solution of the BAL (2, 3-dimercury-2, 1-
propanol) which will formulate R (SH) 2 is added to a solution. This reacts selectively with Pb 2+
that is much more stable than PbY2-. The liberated Y4- is then titrated with Mg2+. Finally, Zn2+ is
demasked by formaldehyde. The liberated Zn2+ is then titrated with EDTA. Supposed the initial
titration of Mg2+ and Pb2+ required 42.22ml of 0.02064 M EDTA, titration of the Y4- liberated by
the BAL consumed 19.35ml of 0.007657 M Mg2+. Finally, after addition, the liberated Zn 2+ was
titrated with 28.63 ml EDTA. Calculate the percent of the three elements in a 0.4085 g sample.

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mmol Zn mg
28.63 ml × (0.002064 )( ) (65.41 )
%Zn = ml EDTA EDTA mmol = 9.46%
1000 mg
0.4085 g × 1g

mmol PbY 2− Pb
19.35 ml × (0.007657 )( )( ) (207.2)
ml MgY 2− PbY 2−
%Pb = = 7.52%
1000 mg
0.4085 g × 1g

mmol EDTA = mmol PbY 2− + mmol MgY 2−

2−
1 mol PbY 2−
mmol PbY = 19.35 × 0.007657 ( ) = 0.1482 mmol
Mg +2

mmol EDTA = 42.22 ml × 0.02064 = 0.8714 mmol

mmol MgY 2− = 0.8714 − 0.1482 = 0.7234 mmol

Mg
0.7234 MgY 2− ( ) (24.31)
MgY 2−
% Mg = = 4.3%
1000 mg
0.4085 g × 1g

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7.9 PHARMACEUTICAL ANALYSIS

Theoretical Basis of Analysis: Complexometric Titrations

Introduction

The technique involves titrating metal ions with a complexing agent (ligand) and is
commonly referred to as complexometric titration. This method represents the analytical
application of a complexation reaction. In this method, a simple ion is transformed into a complex
ion and the equivalence point is determined by using metal indicators or electrometrically. Various
other names such as chilometric titrations, chilometry, chilatometric titrations and EDTA
titrations have been used to describe this method. All these terms refer to same analytical method
and they have resulted from the use of EDTA (Ethylene diamine tetra acetic acid) and other
chilons. These chilons react with metal ions to form a special type of complex known as chelate.

Chilon Chelate

Metal ion + Complexing agent Metal-ion Indicators Complex ion

(analyte; Chelating agent Metal co-ordination compound

pM Indicators
Cation) Ligand Metal complex
Sequestering agent Chelate compound

Metal ions in solution are always solvated, i.e. a definite number of solvent molecules (usually 2,
4 or 6) are firmly bound to the metal ion. However, these bound solvent molecules are replaced by
other solvent molecules or ions during the formation of a metal complex or metal co-ordination
compound.
The molecules or ions which displace the solvent molecules are called Ligands. Ligands or
complexing agents or chelating agents can be any electron donating entity, which has the ability
to bind to the metal ion and produce a complex ion. An example of a complexation reaction
between Cu (III) ion and four ammonium molecules in an aqueous solution may be expressed by
the following equation:
2+ 2+
OH2
OH2 4 NH3 NH3 NH3

Cu Cu

OH2 OH2 NH3 NH3

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Bonding in Complexes
The bonds are either ordinary covalent bonds in which the metal and the ligand contribute
one electron each, or co-ordinate bonds in which both electrons are contributed by the ligand.
Thus, the hexacyanoferrate ion may be considered to consist of three ordinary covalent bonds and
three co-ordinate bonds, although in the complex the bonds are identical hybrid bonds which have
been shown to be directed towards the species of a regular octahedron.
The negative charge on the complex ion is equal to the total number of the negative groups
minus the valency of the metal ion. When neutral groups only are involved, the charge on the
complex is positive and is equal to the metal ion, e.g. (Cu (NH3)4)2+.

Werner’s Co-ordination Number

Werner (1891) first noticed that for each atom there were an observed maximum number
of small groups which can be accommodated around it. This number, which is called Werner’s co-
ordination number, depends purely upon steric factors and is in no way related to the valency of
the ion. Thus, although the valency shell of the elements of the third period is theoretically capable
of expanding up to 18 electrons, and that of the fourth to 32 electrons, there is, in practice, a limit
to the number of small groups which can be accommodated owing to limitations of space around
the ion. For example, in the [BF4]- ion, the octet is completed and the maximum co-ordination
number is reached, but in the [AIF6]- ion the outer shell contains 12 electrons and cannot expand
to the maximum number of 18 electrons since the maximum co-ordination number has been
reached.

Within the limits imposed by Werner’s co-ordination number, there is a tendency for the
metal to attain or approach inert gas structure, and this is probably the driving force for complex
formation.

Classification of Ligands

1. Unidentate Ligands: Ligands that are bound to metal ion only at one place are called
unidentate ligands (one toothed). NH3, for example, is a unidentate ligand capable of
complexing with cupric ions. Halide ions, cyanide ions and NH3 are common examples of
unidentate ligands. The formation of complex Cu (NH3)42+ proceeds in the following steps:

Cu
Step 1 Cu 2+
+ NH3 (NH3)2+
Cu Cu
Step 2 (NH3)2+ + NH3 (NH3)22+
Cu 2 Cu 2
Step 3 (NH3)2 + + NH3 (NH3)3 +

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CHE 401 : ANALYTICAL CHEMISTRY

Cu 2 Cu 2
Step 4 (NH3)3 + + NH3 (NH3)4 +

Considering the overall reaction:

Cu
Cu2+ + 4NH3 (NH3)42+

2. Bidentate and Multidentate Ligands: Many ligands are known that contain more than
one group, capable of binding with metal ions. Such ligands are known as multidentate
ligands or chelating agents. They include bidentate ligands (2 donar atoms), tridentate
ligands (3 donar atoms), quadridentate ligands, etc.

Thus, ethylene diamine tetra acetic acid (EDTA) is an example of bidentate ligand.
H2N-CH2- CH2-NH2. Ethylene diamine tetra acetic acid (EDTA) is an example of
mutidentate ligand.

Chelate Compound or Chelate

Complexes involving simple ligands, i.e. those forming only one bond are described as co-
ordination compound. A complex of a metal ion with 2 or more groups on a multidentate ligand
is called a chelate or a chelate compound. There is no fundamental difference between co-
ordination compound and a chelate compound except that in a chelate compound, ring influence
the stability of compound. Thus, a chelate can be described as a heterocyclic ring structure in which
a metal atom is a member of ring. The stability of a chelate is usually much greater than that of
corresponding unidentate metal complex.

Chelating Agent

Ligands having more than one electron donating groups are called chelating agents. The
most effective complexing agents in ligands are amino and carboxylate ions. All the multidentate
ligands important in analytical chemistry contain the structure component as follows:

The solubility of metal chelates in water depends upon the presence of hydrophilic groups
such as COOH, SO3H, NH2 and OH. When both acidic and basic groups are present, the complex
will be soluble over a wide range of pH. When hydrophilic groups are absent, the solubilities of
both the chelating agents and the metal chelate will be low, but they will be soluble in organic
solvents. The term sequestering agent is generally applied to chelating agents that form water-

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soluble complexes with bi- or poly-valent metal ions. Thus, although the metals remain in solution,
they fail to give normal ionic reactions. Ethylenediaminetetra-acetic acid is a typical sequestering
agent, whereas, dimethylglyoxime and salicylaldoxime are chelating agents, forming insoluble
complexes.

As a sequestering agent, ethylenediaminetetra-acetic acid reacts with most polyvalent

metal ions to form water-soluble complexes which cannot be extracted from aqueous solutions
with organic solvents. Dimethylglyoxime and salycylaldoxime form complexes which are
insoluble in water, but soluble in organic solvents; for example, nickel dimethylglyoxime has a
sufficiently low solubility in water to be used as a basis for gravimetric assay.

EDTA forms chelates with nearly all metal ions and this reaction is the basis for general
analytical method for these ions by titration with a standard EDTA solution. Such titrations are
called complexometric or chilometric or EDTA titrations.

Reagent EDTA

Disodium salt of EDTA is a water soluble chelating agent and is always preferred. It is
non-hygroscopic and a very stable sequestering agent (Ligands which form water soluble chelates
are called sequestering agents.).
There are chelating agents that form water insoluble chelates with metal ions. E.g. –oxine
or 8-hydroxy quinoline.

OH

EDTA and 8-hydroxy quinoline are important reagents used in analytical chemistry.
Sequestering agents are used to liberate or solubilize metal ions. The agents which form water
insoluble chelates are used to remove the metal ions from solution by precipitation. EDTA has the
widest general application in analyses because of the following important properties:

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CHE 401 : ANALYTICAL CHEMISTRY

 It has low price.

 The special structure of its anion which has 6 ligand atoms.
 It forms strainless five-membered rings.

Disodium EDTA is used as M/20 solution.

Purification of Disodium EDTA

Commercial samples of disodium EDTA may be purified for use as a primary standard by
adding ethanol to a saturated aqueous solution until the first permanent precipitate appears; filter
and add an equal volume of ethanol; filter the precipitated disodium EDTA, wash with acetone
and ether, and dry to constant weight at 80°C, drying may require four days. The official material
contains not less than 98% of the dihydrate.

Preparation of M/20 Disodium EDTA

Dissolve 18.6 gm of disodium EDTA in water and make the volume up to 1000 ml and
standardize the prepared solution.

Standardization of Disodium EDTA: Weigh accurately about 200 mg of CaCO3 in a

titration flask. Add 50 ml of water and minimum quantity of dil. HCl to dissolve CaCO 3. Adjust
the pH of the solution to 12 by adding NaOH. Add 300 mg of hydroxyl naphthol blue indicator
and titrate with the prepared M/20 disodium EDTA solution, until the solution is deep blue in
color.

The HCl solubilizes the CaCO3 by converting it to CaCl2. The NaOH makes the solution
alkaline and maintains the pH at about 12 so that the Ca-EDTA complex would be stable and any
Mg, which might be present as a contaminant, would not react. The colored Ca-indicator complex
gives up Ca to EDTA, liberating the free uncomplexed indicator, which is blue.

Factors influencing EDTA reactions:

 The nature and activity of metal ion
 The pH at which the titration is carried out
 The presence of interfering ions such as CN-, Citrate, Tartrate, F- and other complex
forming agents
 Organic solvents also increase the stability of complex

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Nature and stability of metal complexes of Ethylenediaminetetra-acetic acid:

thylenediaminetetra-acetic acid forms complexes with most cations in a 1:1 ratio, irrespective of
the valency of the ion

[MX]2- +
M2+ + [H2X]2- 2H+

M3+ + [H2X]2- [MX]- +2H+

M4+ + [H2X]2- [MX] +2H+

Where M is a metal and [H2X]2- is the anion of the disodium salt (disodium EDTA) which is most
frequently used. The structures of these complexes with di-, tri-, and tetravalent metals contain
three, four and five rings respectively:

Ethylenediamine tetra-acetic acid ionizes in four stages (pK1 = 2.0, pK2 = 2.67, pK3 = 6.16
and pK4 = 10.26) and, since the actual complexing species is Y 4-, complexes will form more
efficiently and be more stable in alkaline solution. If, however, the solubility product of the metal
hydroxide is low, it may be precipitated if the hydroxyl ion concentration is increased too much.
On the other hand, at lower pH values when the concentration of Y4- is lower, the stability constant
of the complexes will not be so high. Complexes of most divalent metals are stable in ammonical
solution. Those of the alkaline earth metals, such as copper, lead and nickel are stable down to pH
3 and hence can be titrated selectively in the presence of alkaline earth metals. Trivalent metal
complexes are usually still more firmly bound and stable in concentrated hydrochloric acid.

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Although most complexes are stable over a fair range of pH, solutions are usually buffered at a pH
at which complex is stable and at which the color change of the indicator is most distinct.

Color of Complexes:
There is always a change in the absorption spectrum when complexes are formed and this
forms the basis of many colorimetric assays.

Stability of Complexes:
The general equation for the formation of a 1:1 chelate complex, MX, is
M + X ⇄ MX
where M is the metal ion and X is the chelating agent.
∴ Stability Constant (K) = [MX]/ [M] [X]
where [ ] represents activities. Increase in temperature causes a slight increase in the ionization of
the complex and a slight lowering of K. The presence of electrolytes having no ion in common
with the complex decreases K, whilst the presence of ethanol increases K, probably due to the
suppression of ionization.

Principle of Complexometric Titration

Many principles of acid-base titrations are used in complexometric titration. In
complexometric titration, the free metal ions disappear as they are changed into complex ions. In
acid-base titrations, the end point is marked by sudden change in pH. Similarly, in EDTA titration,
if we plot pM (negative log of metal ion concentration) v/s volume of titrant, we will find that at
the end point, the pM rapidly increases (Fig. 1). This sudden pM raise results from removal of
traces of metal ions from solution by EDTA.

Any method, which can determine this disappearance of free metal ions, can be used to
detect end point in complexometric titrations. End point can be detected usually with an indicator
or instrumentally by potentiometric or conductometric (electrometric) method.

log [M]

End point
Volume of EDTA
Fig. 1

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There are three factors that are important in determining the magnitude of break in titration
curve at end point.

1. The stability of complex formed: The greater the stability constant for complex formed,
larger the charge in free metal concentration (pM) at equivalent point and more clear would
be the end point.
2. The number of steps involoved in complex formation: Fewer the number of steps
required in the formation of complex, greater would be the break in the titration curve at
equivalence point and clear would be the end point.
3. Effect of pH: During a complexometric titration, the pH must be constant by use of a
buffer solution. Control of pH is important since the H+ ion plays an important role in
chelation. Most ligands are basic and bind to H+ ions throughout a wide range of pH. Some
of these H+ions are frequently displaced from the ligands (chelating agents) by the metal
during chelate formation.

Equation below shows complexation between metal ion and H+ ion for ligand:
M2+ + H2-EDTA2- M-EDTA2- + 2H+

End point in complexometric titration can be detected by the following two methods:

1. Indicators: The end point in complexometric titration is shown by means of pM indicators.

The concept of pM arises as follows:

If K is the stability constant,

K = [MX]/[M][X]

then, [M] = [MX]/[X]K

Or log [M] = log [MX]/[X] - log [K]

And pM = log [X]/[MX] – pK

Therefore, if a solution is made such that [X] = [MX], pM = -pK (or pM = pK’,
where K’ = dissociation constant). This means that, in a solution containing equal activities
of metal complex and free chelating agent, the concentration of metal ions will remain
roughly constant and will be buffered in the same way as hydrogen ions in a pH buffer.
Since, however, chelating agents are also bases; equilibrium in a metal-buffer solution is
often greatly affected by a change in pH. In general, for chelating agents of the amino acid
type (e.g., edetic acid and ammonia triacetic acid), it may be said that when [X] = [MX],
pM increases with pH until about pH 10, when it attains a constant value. This pH is,

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therefore, usually chosen for carrying out titrations of metals with chelating agents in
buffered solutions. The pM indicator is a dye which is capable of acting as a chelating
agent to give a dye-metal complex. The latter is different in color from the dye itself and
also has a low stability constant than the chelate-metal complex. The color of the solution,
therefore, remains that of the dye complex until the end point, when an equivalent amount
of sodium EDTA has been added. As soon as there is the slightest excess of EDTA, the
metal-dye complex decomposes to produce free dye; this is accomplished by a change in
color.

Over 200 organic compounds form colored chelates with ions in a pM range that is
unique to the cation and the dye selected. To be useful, the dye-metal chelates usually will
be visible at 10-6 – 10-7 M concentration. Many of these indicators also have the typical
properties of acid-base indicators and the color changes are the result of the displacement
of the H+ by a metal ion. Metal indicators must comply with the following requirements

 Compound must be chemically stable throughout the titration.

 It should form 1:1 complex which must be weaker than the metal chelate complex.
 Color of the indicator and the metal complexed indicator must be sufficiently
different.
 Color reaction should be selective for the metal being titrated.
 The indicator should not compete with the EDTA.

Mechanism of action of Indicator:

Let the metal be directed by M, indicator by I and chelate by EDTA. At the onset of the
titration, the reaction medium contains the metal-indicator complex (MI) and excess of metal ion.
When EDTA titrant is added to the system, a competitive reaction takes place between the free
metal ions and EDTA. Since the metal-indicator complex (MI) is weaker than the metal-EDTA
chelate, the EDTA which is being added during the course of the titration is chelating the free
metal ions in solution at the expense of the MI complex. Finally, at the end point, EDTA removes
the last traces of the metal from the indicator and the indicator changes from its complexed color
to its metal free color.
Structures of some important indicators used in complexometric titrations are given in Fig.
2. Many compounds have been used as indicators like:
 Triphenyl methane dyes
 Phthalein and substituted phthaleins
 Azo dyes
 Phenolic compounds

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Table 7.2 : Indicators used in Complexometric Titrations

Name of the indicator Color Change pH Range Metals Detected
Ca, Ba, Mg, Zn,
Mordant black II
Cd, Mn,
1. Red to Blue 6-7
Erichrome black
Pb, Hg
Solochrome black
Murexide or Ammonium
2. Violet to Blue 12 Ca, Cu, Co
purpurate
Mn, Mg, Fe, Co,
3. Catechol-violet Violet to Red 8-10
Pb
Methyl Blue Blue to Yellow 4-5
4. Pb, Zn, Cd, Hg
Thymol Blue Blue to Grey 10-12
Pb, Zn, Co, Mg,
5. Alizarin Red to Yellow 4.3
Cu
6. Sodium Alizarin sulphonate Blue to Red 4 Al, Thorium
Lemon to 1-3 Bi, Thorium
7. Xylenol Orange 4-5 Pb, Zn
Yellow
5-6 Cd, Hg

Fig. 2: Structures of some pM indicators

1)
O OH

OH

CH2N(CH2COOH)2

O
Alizarin fluorine blue (alizarin complexone)

2)

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3)

OH
HO COOH
NaO2.O2S N
N

Calcon carboxylic acid

4)

5)

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6)

7)

8)

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9)

10)

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11)

2. Instrumental methods of end point detection:

a. Spectrophotometric detection: The change in absorption spectrum when a metal

ion of a complexing agent is converted to the metal complex, or when one complex
is converted to another can usually be detected more accurately and in more dilute
solution by spectrophotometric than by visual methods. Thus, in disodium EDTA
titrations an accurate end point can be obtained using 0.001M solutions. In practice
an indicator giving a color change in the visible region is generally employed, but
colored ions may be titrated without an indicator using spectrophotometric
methods. Also it is sometimes possible to use an end point in the ultraviolet region
for ions and complexes which are colorless in the visible region.

b. Amperometric titration: The effect of complex formation on the half-wave

potential of an ion is to render it more negative. If the electrode potential is adjusted
to a value between that of the half-wave potential of the free cation and that of the
complex, and disodium EDTA solution is added slowly, the diffusion current will
fall steadily until it equals the residual current, that is, until the last trace of free

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cation has been complexed. This is the end point and the amount of standard
disodium EDTA solution added is equivalent to the amount of metal present.

c. Potentiometric titration: Since disodium EDTA reacts preferentially with the

higher valency state of an ion, it will reduce the redox potential according to the
equation,

𝐄 = 𝐄𝟎 + 𝐥𝐨𝐠𝐞 [𝐎𝐱]/[𝐑𝐞𝐝]

Where, E= the potential of the electrode

E0= The standard electrode potential
[Ox]= activity of the ions in the oxidized state
[Red]= activity of the ions in the reduced state

This method is of limited application owing to the lack of suitable indicator

electrodes. Iron (III) and Copper (II), however can be titrated in this way. Back
titration of excess disodium EDTA with ferric chloride in acid solution is possible
for some ions.

d. High frequency titration: This method is particularly suitable for dilute solutions,
in some cases with concentrations as low as 0.002 M. The ions may be titrated
directly in buffered solution or excess reagent can be added to the unbuffered
solution and the liberated protons titrated with standard alkali. Since buffer solution
and other extraneous electrolytes reduce the sensitivity of the titration, their
concentration must be kept to a minimum.

Types of Complexometric Titrations

Complexometric titrations are of 4 types:

1. Direct Titration: It is the simplest and the most convenient method used in chelometry.
In this method, the standard chelon solution is added to the metal ion solution until the end
point is detected. This method is analogous to simple acid-base titrations. E.g.- calcium
gluconate injection, calcium lactate tablets and compound sodium lactate injection for the
assay of calcium chloride (CaCl2•6H2O).
Limitations:
o Slow complexation reaction
o Interference due to presence of other ions

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2. Back Titration: In this method, excess of a standard EDTA solution is added to the metal
solution, which is to be analyzed, and the excess is back titrated with a standard solution
of a second metal ion. E.g.- determination of Mn. This metal cannot be directly titrated
with EDTA because of precipitation of Mn(OH) 2. An excess of known volume of EDTA
is added to an acidic solution of Mn salt and then ammonia buffer is used to adjust the pH
to 10 and the excess EDTA remaining after chelation , is back titrated with a standard Zn
solution kept in burette using Eriochrome black T as indicator. This method is analogous
to back titration method in acidimetry. E.g.- ZnO

3. Replacement Titration: in this method, the metal, which is to be analyzed, displaces

quantitatively the metal from the complex. When direct or back titrations do not give sharp
end points, the metal may be determined by the displacement of an equivalent amount of
Mg or Zn from a less stable EDTA complex.

Mn+2 + Mg EDTA-2 Mg+2 + Mn EDTA-2

Mn displaces Mg from Mn EDTA solution. The freed Mg metal is then directly

titrated with a standard EDTA solution. In this method, excess quantity of Mg EDTA
chelate is added to Mn solution. Mn quantitatively displaces Mg from Mg EDTA chelate.
This displacement takes place because Mn forms a more stable complex with EDTA. By
this method Ca, Pb, Hg may be determined using Eriochrome black T indicator.

4. Indirect Titration: This is also known as Alkalimetric titration. It is used for the
determination of ions such as anions, which do not react with EDTA chelate. Protons from
disodium EDTA are displaced by a heavy metal and titrated with sodium alkali.

Mn+ + H2X-2 MX (n-4) + 2H+

solution by mercuric ions as 1:1 complex

Method: Barbiturate to be analyzed is taken in a flask and heated with excess of mercury in
alkaline solution. When precipitated Hg-barbiturate complex is formed, it is filtered and dissolved
in excess of standard EDTA solution. The unreacted EDTA solution is then back titrated with a
standard Zn solution.
Some important elements which could be determined by complexometric titration are as follows:
i. Direct Titration: Analysis of Cu, Mn, Ca, Ba, Br, Zn, Cd, Hg, Al, Thallium, Sn,
Pb, Bi, Vanadium, Cr, Mo, Gallium, Fe, Co, Ni, and Pd.
ii. Indirect Titration: Analysis of Na, K, Ag, Au, As, C, N, P, S, Cl, Br, I, and F.

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Titration Selectivity, masking and Demasking agents

EDTA is very unselective reagent because it complexes with numerous doubly, triply and
quadruply charged cations. When a solution containing two cations which complex with EDTA is
titrated without the addition of a complex-forming indicator, and if a titration error of 0.1% is
permissible, then the ratio of the stability constants of the EDTA complexes of the two metals M
and N must be such that KM/KN ≥ 106 if N is not to interfere with the titration of M. Strictly, of
course, the constants KM and KN considered in the above expression should be the apparent
stability constants of the complexes. If the complex-forming indicators are used, then for a similar
titration error KM/KN ≥ 108.
The following procedures will help to increase the selectivity:
Use of masking and demasking agents:
 pH control
 Use of selective metal indicators
 Classical separation
 Solvent extraction
 Removal of anions
 Kinetic masking
Use of masking and demasking agents:

Masking agents act either by precipitation or by formation of complexes mare stable than the
interfering ion-EDTA complex.

a) Masking Precipitation: Many heavy metals e.g.- Co, Cu and Pb, can be separated either
in the form of insoluble sulphides using sodium sulphide, or as insoluble complexes using
thioacetamide. These are filtered, decomposed and titrated with disodium EDTA. Other
common precipitating agents are sulphate for Pb and Ba, oxalate for Ca and Pb, fluoride
for Ca, Mg and Pb, ferrocyanide for Zn and Cu, and 8-hydroxy quinoline for many heavy
metals. Thioglycerol (CH2SH.CHOH.CH2OH) is used to mask Cu by precipitation in the
assay of lotions containing Cu and Zn.

b) Masking by Complex formation: Masking agents form more stable complexes with the
interfering metal ions. The most important aspect is that the masking agent must not form
complexes with the metal ion under analysis. The different masking agents used are
enlisted below:

 Ammonium fluoride will mask aluminum, iron and titanium by complex

formation.

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 Ascorbic acid is a convenient reducing agent for iron (III) which is then masked
by complexing as the very stable hexacyanoferrate (II) complex. This latter is more
stable and less intensely colored than the hexacyanoferrate (III) complex.
 Dimercaprol (2,3-Dimercaptopropanol); (CH2SH.CHSH.CH2OH)-Cations of
mercury, cadmium, zinc, arsenic, tin, lead and bismuth react with dimercaprol in
weakly acidic solution to form precipitates which are soluble in alkaline solution.

All these complexes are stronger than the corresponding edetate complexes and are almost
colorless. Cobalt, copper and nickel form intense yellowish-green complexes with the reagent
under the above conditions. Cobalt and copper, but not nickel, are displaced from their edetate
complexes by dimercaprol.
 Potassium cyanide reacts with silver, copper, mercury, iron, zinc, cadmium, cobalt and
nickel ions to form complexes in alkaline solution which are more stable than the
corresponding edetate complexes, so that other ions, such as lead, magnesium, manganese
and the alkaline earth metals can be determined in their presence. Of the metals in the first
group mentioned, zinc and cadmium can be demasked from their cyanide complexes by
aldehydes, such as formaldehyde or chloral hydrate (due to the preferential formation of a
cyanohydrin), and selectively titrated.
 Potassium iodide is used to mask the mercury (II) ion as (HgI 4)2- and is specific for
mercury. It can be used in the assay of mercury (II) chloride.
 Tiron (disodium catechol-3,5-disulphonate) will mask aluminium and titanium as
colorless complexes. Iron forms highly colored complexes and is best masked as its
hexacyanoferrate (II) complex.
 Triethanolamine [N(CH2.CH2.OH)3] forms a colorless complex with aluminium, a
yellow complex with iron (III), the color of which is almost discharged by adding sodium
hydroxide solution, and a green manganese (III) complex which oxidizes mordant black
(II). For these reasons, if murexide is used in the presence of iron and manganese, it is best
to mask them with triethanolamine; similarly, mordant black II can be used in the presence
of triethanolamine-aluminium complex.

Demasking is the process in which the masked substance regains its ability to enter into a
particular reaction. This enables to determine a series of metal ions in one solution containing
many cations.

Example of using masking and demasking agents in complexometry is the analysis of 3

metals, Cu, Cd and Ca. The following method of analysis is followed:
1. Direct titration of the mixture with the EDTA gives the sum of the 3 metals.

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2. Cu and Cd may be masked with the addition of cyanide to the solution, leaving only Ca
ion.
3. When formaldehyde or chloral hydrate is added to the cyanide containing mixture, Cd is
demasked and the EDTA titrates the sum of Ca and Cd. In this manner, the concentration
of three ions is determined by 3 individual titrations.
 pH Control Method: The formation of a metal chelate is dependent on the pH of the
reaction medium. In weakly acid solution, the chelates of many metals are completely
dissociated such as alkaline earth metals, whereas chelates of Bi, Fe 3+ or Cr are readily
formed at this pH. Thus, in acidic solution, Bi, can be effectively titrated with a
chelating agent in the presence of alkaline earth metals. This method is based upon the
differences in stability of the chelates formed between the metal ions and the chelating
agent.
 Use of selective metal indicators: These indicators are the metal complexing agents
which react with different metal ions under various conditions. Several selective metal
indicators have been used and they are specific for a particular ion.
 Classical separation: These may be applied if they are not tedious; thus the following
precipitates may not be used for separations in which, after being re-dissolved, the
cations can be determined complexometrically: CaC 2O4, nickel dimethylglyoximate,
Mg(NH4)PO4, 6H2O, and CuSCN.
 Solvent extraction: This is occasionally of value. Thus, Zinc can be separated from
copper and lead by adding excess of ammonium thiocyanate solution and extracting
the resulting zinc thiocyanate with 4-methylpentan-2-one (isobutyl methyl ketone); the
extract is diluted with water and the zinc content determined with EDTA solution.
 Removal of Anions: Anions, such as orthophosphate, which can interfere in
complexometric titrations, may be removed using ion exchange resins.
 Kinetic masking: This is a special case in which a metal ion does not effectively enter
into the complexation reaction because of its kinetic inertness. Thus the slow reaction
of chromium (III) with EDTA makes it possible to titrate other metal ions which react
rapidly, without interference from Cr (III); this is illustrated by the determination of
iron (III) and chromium (III) in a mixture.

Applications of Complexometric Titrations

Complexometric titrations have been employed with success for determination of various
metals like Ca, Mg, Pb, Zn, Al, Fe, Mn, Cr etc. In different formulations that are official in I.P.,
and also for the determination of hardness of water.

Determination of Calcium in different formulations:

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CHE 401 : ANALYTICAL CHEMISTRY

Calcium can be determined in almost every formulation by EDTA-titrations. E.g.- Five

membered heterocyclic rings are formed with EDTA, which are stain-free, and thus highly stable.

 Assay of CaCO3: Accurately weighed amount of CaCO3 is dissolved in water and then
acidified with HCl. A mixture of naphthol green and murexide is then added and titrated
with EDTA, kept in burette. 1ml of M/20 disodium EDTA □0.005005 gm of CaCO3
 Calcium Lactate tablets: 20 tablets are finely powdered and an accurately weighed
amount of the powder, representing about 0.5 g or calcium lactate, is transferred to a
crucible, ignited until free from carbon and then cooled. 10ml water is added and the
residue is dissolved by adding dropwise dil. HCl solution. This solution is then transferred
to a container, diluted to 150 ml with water and the assay is completed as is given under
general procedure.
1ml of M/20 disodium EDTA □ 0.01542 g of Ca lactate
 Calcium Lactate injection: Measure out a suitable volume of the injection, equivalent to
about 0.5 g of Ca lactate. Transfer to the titration flask and proceed as given under general
procedure.
 Calcium Gluconate: An accurately weighed quantity (0.8 g) is dissolved in water (150
ml) containing diluted HCl (5ml) to the acidified solution is added, solution of NaOH (15
ml), murexide indicator (4 mg), solution of naphthol green (3ml). The reaction mixture is
titrated with M/20 disodium EDTA until the solution is deep blue in color.
1ml of M/20 disodium EDTA □ 0.02242 g of Ca gluconate
 Calcium Gluconate injection: An accurately measured volume of the injection,
equivalent to 0.8 gm of calcium gluconate is taken in a titration flask and proceeded as
above.
 Calcium Gluconate tablet: 20 tablets are finely powdered. An accurately weighed amount
of the powder, equivalent to 0.8 gm of Calcium gluconate is transferred to a crucible and
proceeded as described under calcium lactate tablets.

Determination of Magnesium:
Dissolve an accurately weighed sample (75 mg) of Mg in sufficient water to make 100 ml.
Pipette out 50 ml of this solution in a titration flask, add 50 ml water, 5 ml of NH3 buffer solution
and a few drops of eriochrome blackT as indicator. Titrate it to a deep blue color.

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CHE 401 : ANALYTICAL CHEMISTRY

Each ml of M/20 disodium EDTA □ 0.02432 gm of Mg

This method could be used for the assay of Mg stearate and Mg sulphate.

Determination of Hardness of Water:

Water hardness due to Ca and Mg is expresses as the amount of Ca and Mg ions in ppm.
Actually, the hardness is due to both Ca and Mg salts but the two are determined together in the
titration. The total Ca and Mg is titrated with standard EDTA solution using eriochrome blackT as
indicator.

Method:
Disodium salt of EDTA has the general formula: Na 2H2Y2•H2O, where Y is the tetravalent
anion of EDTA. When Ca is titrated with H2Y2-, a very stable complex is formed.

Ca2+ + H2Y2- CaY2- + 2H+

Mg2+ forms a similar complex which is far less stable than the Ca complex. When a sample
containing Ca and Mg ions is titrated with a solution of EDTA, the Ca 2+ are first complexed as
CaY2-. As more reagent is added, all the Ca 2+ is combined as complex. Mg ion forms MgY2-. The
desired end point if the titration is the point at which all the Ca and Mg ions of the solution have
combined with the complexing agent.

7.10 END OF MODULE TEST

1. The Tl in a 9.76-g sample of rodenticide was oxidized to the trivalent state and treated with
an unmeasured excess of Mg/EDTA solution. The reaction is

Tl3+ + MgY 2− → TlY − + Mg 2+

Titration of the liberated Mg required 13.34 mL of 0.03560 M EDTA. Calculate

the percentage of Tl2SO4 (504.8 g/mol) in the sample.

2. A 50.00mL aliquot of a solution containing iron(II) and iron (III) required 13.73 mL of
0.01200 M EDTA when titrated at pH 2.0 and 29.62 mL when titrated at pH 6.0. Express
the concentration of the solution in terms of the parts per million of each solute.

3. A 1.509-g samle of a Pb/Cd alloy was dissolved in acid and diluted to exactly 250.0 mL in
a volumetric flask. A 50.00-mL aliquot of the diluted solution was brought to a pH of 10.0
with an HCN/NaCN buffer, which also served to mask the Cd 2+; 11.56mL of the EDTA

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CHE 401 : ANALYTICAL CHEMISTRY

solution were needed to titrate the Pb 2+. Calculate the percentage of Pb and Cd in the
sample.

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