Complexometric Titration

1
 Introduction
What is complex?
• A complex cpd is formed by the combination of a molecule that is capable of

donating electrons to form covalent bond with metal ion.

• Cu2+ form complexes with lone pair of electrons present in the neutral molecule

ammonia

The technique involves titrating metal ions with a complexing agent or chelating

agent (Ligand) and is commonly referred to as Complexometric titration.

In this method, a simple ion is transformed into a complex ion and the

equivalence point is determined by using metal indicators or electrometrically.

2
 Introduction…

 Any complexation reaction can in theory be applied as a volumetric

technique provided that :

 The reaction reaches equilibrium rapidly following each addition of titrant.

 Interfering situations do not arise (such as stepwise formation of

various complexes resulting in the presence of more than one complex

in solution in significant concentration during the titration process).

 A complexometric indicator capable of locating equivalence point with

fair accuracy should available

3
 Structure of complex
A complex is a form of compound which consists
 Central ion (complex former)

 Is a +ve ion positioned at the center of the complex

 Ligands (coordinating agents)

 Are -ve ions or neutral molecules residing in the immediate vicinity of

the central ion

 Anionic ligands include: halides, SCN-, CN-, OH-, RCOO-, S2-, C2O42-
etc.

 Molecular ligands include: water, ammonia, RNH 2 (amines), C5H5N

(pyridine) , H2NCH2CH2NH2 (ethylenediamine), etc.

 The central ion and ligands constitute the inner sphere in the compound.
 Apart from the inner sphere , in most cases there is also an outer coordination
sphere that consists of a -ve or +ve ion.
4
 Structure of complex…
 The ions of the outer sphere are attached to the complex ion ionogenically
where as the central ion and the ligands are in nonionogenically i.e. either with
dative bond or covalent bond.

 Examples of complex compounds

 [Ag(NH3)2]NO3

 K4[Fe(CN)6]

 [Co(NH3)6]Cl3

 Na2[ZnCl4]

In K4[Fe(CN)6]

Fe2+……………the central ion

CN………………the ligand
K+………………the outer sphere

Fe(CN)64-……...the inner sphere 5

 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.

The negative charge on the complex ion is equal to the total number of the

negative groups minus the valency of the metal ion, e.g. [Fe(CN)6]4-

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+

6
 Classification of Ligands

A ligand (complexing agent) is any electron donating ion or molecule

which attaches itself (by covalent or dative bond) to the central ion to

form a complex.

– Most of the time electron donating atoms are N, S,O and the halogens

and, possibly, carbon in such groups such as CO and (CN) -.

1. unidentate : Ligands that are bound to the central ion at only one point.

E.g. NH3, F-, H2O, Halide ions, cyanide ions…

7
 Classification of Ligands…
The formation of complex [Cu(NH3)4]2+ proceeds in the following
steps:

8
 Classification of Ligands…
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 is an example of bidentate ligand.

H2N-CH2-CH2-NH2

Ethylene diamine tetra acetic acid (EDTA) is an example of hexa

dentate ligand.

9
 Classification of Ligands…

The important difference b/n the unidentate and the

multidentate ligand is
• Multidentates

– Form complex in single-step

• Unidentates

– Form complex in multi-step

10
 Chelate Compound or Chelate
Complexes involving simple ligands, i.e., those forming only one bond are described

as co-ordination compound. E.g. [Cu(NH3)4]2+

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 influences 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

11
 Chelate…

The hexacyanoferrate iron (III) ion

Ligands having more than one electron donating groups are called
chelating agents.

12
 Chelate…
The most effective complexing groups in a ligand are :

 Amine (-NH2), Phenolic groups

 Alcholic groups (-OH)

 Carboxylate(-COOH) groups.

Solubility of metal chelates in water depends up on the presence of hydrophilic

groups like 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 solubility of both the chelating agent

and the metal chelate will be low, but they will be soluble in organic solvents.

13
 Chelate…
The term sequestering agent is generally applied to chelating agents

that form water-soluble complexes with bi- or poly-valent metal ions.

– Ethylenediamine-tetra-acetic acid is a typical sequestering agent,

– whereas, dimethylglyoxime and salicylaldoxime are chelating agents, forming

insoluble complexes.

14
 Chelate…
 Example of commonly used Chelating Agents

15
 Stability of complexes

 The complex ion behaves as a weak electrolyte and

dissociates to a small extent.

 E.g. the complex [Ag(NH3)2]NO3 first undergoes ionization

as a strong electrolyte, that is almost completely ionizes.

[Ag(NH3)2]NO3 [Ag(NH3)2]+ + NO3-

complex ion

16
 Stability of complexes…

 Then the complex ion ionizes through steps (not at ones)

k1
[Ag(NH3)2]+ [Ag(NH3)]+ + NH3
[NH3][Ag(NH3)]+
k1=[Ag(NH ) ] +
3 2

k2
[Ag(NH3)]+ Ag+ + NH3

17
 Stability of complexes…

[Ag+][NH3]
k2 =
[Ag(NH3)]+

kins= k1 x k2
[NH3][Ag(NH3)]+ [Ag+][NH3]
x
= [Ag(NH3)2] +
[Ag(NH3)]+

[Ag+] [NH3]2
=
[Ag(NH3)2]+

18
 Stability of complexes…

 NB. The greater the value of the constant (K ins), the more

extensive is the dissociation of the complex and less stable it is.

– This constant is therefore, called the instability constant,

kins, of the complex.

The reciprocal of kins is known as the formation/stability

constant.

Kstab = 1
kins
19
 Factors affecting the stability of complexes
1. Nature of the central metal ion
 The greater the charge and the smaller the size of a central metal
ion, the greater is the stability of its complexes.

2. Nature of the ligand

 The greater the ease of electron donation

- Increase kstab :S, N, O, Br-, Cl-, I-, F-

 For –ve ligands

Increase kstab
- the greater the charge, and

- the smaller the size

3. Presence of ring structure

 The larger the number of chelating rings in a complex, the greater

is the stability of the complex.

20
 Ethylenediaminetetraacetic Acid (EDTA)
 EDTA is the most widely used complexometric titrant.

NaOOC.H2C CH2COOH
N CH2.CH2 N
HOOC.H2C CH2COONa

 EDTA is:

 A hexadentate ligand

 Represented by the symbol H4Y

 In commerce, it is mostly found as a form of disodium EDTA, but

also in the form of Zn, Fe, and Ca is marketed.

 Disodium EDTA (Na2H2Y) is very soluble in water

21
 The Nature of EDTA Complexes with Metal Ions
 Solution of EDTA are valuable as titrant because the reagent combines with

metal ions in a 1:1 ratio regardless of the charge on the cation.

Ag+ + Y4- AgY3-

Ca2+ + Y4- CaY2-

Al3+ + Y4- AlY-

 EDTA is a remarkable reagent not only because it forms chelates with all

cations 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 is

effectively surrounded and isolated from solvent molecules.

22
 General principles involved in disodium edetate
titrations
 There are 5 methods of titration with EDTA based on the
nature of the analyte to be analyzed. These are:
 Direct titration

 Back titration

 Replacement of one complex by another

 Alkalimetric titration of metals

 Indirect titration with EDTA

23
 1. Direct titration

 In this method, a suitable buffer solution and indicator are

added to the metal ion solution and the solution is titrated with

standard disodium edetate until the indicator just changes color.

 A blank titration may be performed.

24
 2. Back titration
 In a back titration

– A known excess amount of EDTA is added to the analyte

– The excess EDTA is then titrated with a standard solution of a 2 nd

metal ion (Zn or Mg chloride)

 Back titration is necessary

– If the analyte precipitates as hydroxide at a pH required for titration

– If the sub reacts too slowly with EDTA under titration conditions

– For insoluble sub like lead as sulphate, calcium as oxalate

25
 Back titration cont’d

 The 2nd metal ion used in the back titration must not displace the

analyte metal ion from its EDTA complex.

 E.g. Ni2+ can be analyzed by back titration using standard Zn 2+ at pH

5.5 with xylenol orange indicator (yellow[free] to red[complex])

BACK TITRATION

Excess Na edetate, Mg or Zn
buffer solution chloride
cooled M-EDTA
Metal- Ind
Ind Na edetate not
required by the
sample
Heat source
26
 3. Replacement of one complex by another
 When direct or back titration do not give sharp end point, the metal may be

determined by the displacement of an equivalent amount of Mg or Zn from a

less stable edetate complex according to the equation;

M2+ + MgX2- MX2- + Mg2+

 e.g. Ca, Pb, & Hg with mordant black II indicator can be determined by this

method.

 Example: the direct titration of Ca2+ with EDTA is not possible with

Eriochrome Black T indicator b/c the Ca2+-Ind complex is very weak; the color

change at the end point is vague.

27
 Replacement cont’d
 However, the Mg2+-Ind complex is strong, and the end point for the

titration of Mg2+ with EDTA is good, moreover, the Ca2+-EDTA complex

is stronger than the Mg2+-EDTA complex

 The determination is carried out by adding some Mg-EDTA complex to

the Ca2+ solution in the presence of Ind. This mixture is titrated with

EDTA. The Ca-EDTA complex is formed, where as the Mg-Ind complex

maintains the typical red color. After all of the Ca2+ has been titrated,

the EDTA displaces the indicator from the Mg-Ind complex, the color

changes to blue.

28
 Replacement cont’d

Ca-Ind weak Mg-Ind strong

Ca-EDTA strong Mg-EDTA not
strong
Ca-EDTA
Mg-EDTA EDTA +
Ca-EDTA Mg-EDTA
Ca2+, Ind- Ca +
+
Ind-
Ca-Ind, Mg-Ind
Ca2+,

29
 4. Alkalimetric titration of metals

 In this method, protons from disodium edetate are displaced by

heavy metals, and titrated with standard alkali according to the

equation:

Mn+ + [H2X]2- [MX]n-4 +2H+

– The titration is carried out in unbuffered solution.

– A visual pH indicator may be used, but a potentiometric method

of detecting the end point is also suitable, specially when the

color of the complex would mask that the pH indicator.

30
 5. Indirect Titration with EDTA

• Anions that precipitate with certain metal ions can be analyzed with

EDTA by indirect titration.

– The principle is that the anion is precipitated with known amount

of excess metal ion.

– The precipitated is filtered and washed, and the excess metal

ion in the filtrate is titrated with EDTA.

– Anions such as CO32-, CrO42-, S2-, & SO42- can be determined by

indirect titration with EDTA.

31
 Titration of Mixtures: Selectivity, Masking and
Demasking Agents

 EDTA is a very unselective reagent because it complexes with numerous

doubly, triply and quadruply charged cations
 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

32
 Use of masking and demasking agents:
 Masking agents act either by precipitation or by formation of complexes more stable

than the interfering ion-EDTA complex.

 Colour developed by either precipitates or auxiliary complexes should not obscure the end-point.

a) Masking by 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.

33
• Example of using masking and demasking agents in complexometry is the
analysis of three metals: Cu, Cd & Ca

34
• Note:

1. Direct titration of the mixture with the EDTA gives the sum
of the 3 metals.

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,

– Only Cd is demasked and the EDTA titrates the sum of Ca and Cd.
– In this manner, the conc of 3 ions are determined by 3 individual
titrations.

35
 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, Fe3+ 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 & the chelating agent.
36
 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.

Indicators & end point detection

 There are two ways of detecting end point in complexometric
titration.

a. Chemical indicators

b. Instrumental methods
37
 Chemical indicators
 The indicator is a dye w/c is capable of acting as a chelating agent to give a

dye-metal complex.

 The dye-metal complex is

 different in color from the dye itself

 has a lower stability constant than metal-EDTA/other chelating agent/complex.

 The color of the solution, therefore,

 remains that of the dye-M complex until the end point

 As soon as there is a slight excess of edetate, the metal-dye complex

decomposes to produce free dye;

 this is accomplished by a change in color.

38
 Chemical indicators…

 The colors of dyes and the metal complexes vary with pH.

 This fact together with complex stability, must be considered when

deciding at which pH to carry out a titration.

 It is also essential to use a buffer solution to maintain a required pH.

39
 Chemical indicators…

 Metal indicators must comply with the following requirements:

 Cpd must be chemically stable throughout the titration.

 It should forms 1:1 complex which must be weaker than the metal chelate

complex.

 Colour of the indicator and the metal complexed indicator must be

sufficiently different.

 Colour reaction should be selective for the metal being titrated.

 The indicator should not compete with the EDTA.

40
 Chemical indicators…

Mechanism of action of indicator:

 Let the metal be denoted 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 being added during the course of the titration is

chelating the free metal ions in solution at the expense of the MI

complex.
41
 Chemical indicators…

 Finally, at the end point, EDTA removes the last traces of the metal from the indicator

and the indicator changes from its complexed colour to its metal free colour. The overall

reaction is given by:

 Structures of some important indicators used in many cpds have been used as indicators
(Tables), like:
 Triphenyl methane dyes

 Phthalein and Phthaleins substituted

 Azo dyes

 Phenolic compounds

42
43
44
 Instrumental method indicators
These indicators are

1. Spectrophotometric
• Detects change in absorption
• Used in more dilute solutions

2. Amperometric
• Measures the current change

3. Potentiometric
• Measures the potential

45
 Applications of Complexometric reactions:

1. Determination of Water Hardness by EDTA titrations:

a. Titration using eriochrome black-T indicator and ammonia buffer

at pH 10, gives total hardness (Ca2+ + Mg2+).

46
(2) Determination of Pharmaceutical compounds having
Chelating properties:
Examples:

Carbidopa
Apomorphine

R
N
OH
Adrenaline 8-Hydroxyquinolines

47
(3) Determination of Pharmaceutical compounds which containing
metal ions that undergo complexation reactions
Examples:
 Aluminum, Calcium, magnesium and zinc salts of pharmaceutical
importance:

(A) Inorganic salts:

 Aluminum potassium sulfate, Aluminum chloride hexa-hydrate, dried
Aluminum hydroxide, Aluminum acetate, dried Aluminum phosphate &
Aluminum magnesium silicate.
 Calcium sulfate, Calcium carbonate & Calcium Oxide
 Barium sulfate
 Magnesium sulfate, Magnesium oxide & Magnesium carbonate
 Zinc sulfate and Zinc Oxide

48
(B) Organic Salts :

Zinc undecenoate
Aluminium Glycinate

Zinc acexamate
Calcium folinate

49
Calcium levulinate dihydrate
Calcium gluconate

Calcium pantothenate

Calcium ascorbate

Calcium dobesilate

50
 Application……

4) Medical applications.
 Detoxification in heavy metal poisoning cases.

 Ca-EDTA is administered.

 Heavy metals (e.g. Pb) form more stable EDTA

complex than calcium, and will displace calcium
from EDTA.
 The chelated lead is excreted via the kidneys.

51
 Application……
5) Food Industry
 Used in products such as mayonnaise to extend the
shelf-life
 EDTA will complex with cations, preventing them
from acting as catalyst in oxidation process

52
• E.g. The conc of a sol of EDTA was determined by standardizing against a sol of
Ca2+ prepared from the primary standard CaCO3. A 0.4071-g sample of CaCO3 was
transferred to a 500-mL volumetric flask, dissolved using a minimum of 6 M HCl,
and diluted to volume. A 50.00-mL portion of this solution was transferred into a
250-mL Erlenmeyer flask and the pH adjusted by adding 5 mL of a pH 10 NH3–
NH4Cl buffer containing a small amount of Mg2+–EDTA. After adding calmagite as
a visual indicator, the sol was titrated with the EDTA, requiring 42.63 mL to reach
the end point. Calculate the molar conc of the titrant (FW CaCO3 : 100g/mol).

53
Redox Titration

54