COMPLEXOMETRY

Complexometric titration (3 h)
Suitability of ligands as titrants with EDTA as an example, stoichiometry of the reaction
(single step or multistep reactions), Titration methods employing EDTA: direct, back,
displacement and indirect determinations (2 h)
Indicators for EDTA titrations - theory of metal ion indicators, Application in determination of
hardness of water (1 h)

References:
1. Fundamentals of Analytical Chemistry, Skoog & West
2. Advanced Practical Inorganic Chemistry, Gurdeep R. Chatwal & Harish C Mehra

Dr. Pramod KM
 Ligands and Chelation
Ligand is an ion or a molecule that forms a covalent bond with a cation or
a neutral metal atom by donating a pair of electrons, which are then
shared by the two.

Types of ligands based on donor atoms

One donor atom : Monodentate ligands

Two donor atoms : Bidentate ligands
Three donor atoms : Tridentate ligands
Four donor atoms : Tetradentate ligands
Five donor atoms : Pentadentate ligands
Six donor atoms : Hexadentate ligands
 Chelating Ligands
• When a bidentate or a polydentate ligand is attached through two or more donor
atoms to the same central metal ion forming a ring structure, the ligand is called
Chelating Ligand and the resulting complex is called a Chelate.
• Five or six membered rings are generally favoured for Chelates.
• Chelate effect: Greater affinity of chelating ligands for a metal ion than that of
similar nonchelating (monodentate) ligands for the same metal.
Ethylene diamine complexes Oxalate complexes

Ex: [Fe(C2O4)3]3-
Ex: [Cu(en)2]2+ 3-
 Ethylenediamine tetra acetic acid (EDTA)

• EDTA is a Hexadentate Chelating Ligand which contains 4 Carboxylic groups

and 2 amino Nitrogens that are readily available for coordinating with
Metal ion for complexation.
• EDTA-Metal ion complexes are Chelate type complexes.
 Structure of EDTA
Dissociation constants of the hydrogens of 4 carboxylic groups suggest that
two of them are strongly acidic and this leads to a Zwitter ion structure.
EDTA can be represented as H4Y

Disodium salt of EDTA is Na2H2Y

(Complex forming ion is H2Y2- in
aqueous solution)

Zwitter ion structure of EDTA

EDTA forms 1:1 complex with all metal ions:

For reaction with divalent metal ions, M2+
M2+ + H2Y2- ⇌ MY2- + 2H+
In general, for cations, Mn+
Mn+ + H2Y2- ⇌ [MY](n-4)+ + 2H+
Structure of metal-EDTA Complex
 Complexometric Titrations
• Many complex forming ions of molecules have a tendency to form stepwise
complex ions and these complex ions can be titrated with the help of suitable
metal ion indicators; this is called Complexometry.
• Complexometric titration curves are generally a plot of pM (-log[M]) as a
function of Volume of the titrant.
• Normally, Ligand is the titrant and metal ion is the analyte; but in many
precipitation titrations, metal ions will be the titrant.
• Most simple inorganic ligands are unidentate which can lead to low complex
stability and indistinct titration end points.
• Multidentate ligands (4 or 6 donor groups) have two advantages over unidentate
ligands:
i) They react more completely with cations and thus provide sharper end points.
ii) They ordinarily react with metal ions in a single step process where as complex
formation with unidentate ligands involves 2 or more intermediate species.
 Single step or Multistep reactions
Complexation reactions involve a metal-ion ‘M’ reacting with a ligand ‘L’ to
form a complex ‘ML’, as shown below:
M + L ⇌ ML
Complexation reactions occur in a stepwise fashion and the reaction is often
followed by additional reactions:
ML + L ⇌ ML2
ML2 + L ⇌ ML3
MLn-1 + L ⇌ MLn
Unidentate ligands react with metal ions stepwise.
Ex: Cu(II), with a maximum coordination number of 4, can form complexes with
ammonia that have the formulas [Cu(NH3)]2+, [Cu(NH3)2]2+ , [Cu(NH3)3]2+ & [Cu(NH3)4]2+
With multidentate ligands, the maximum coordination number of the cation may be
satisfied with only one or a few added ligands.
Ex: With bidentate ligand glycine (gly): Complexes formed are [Cu(gly)]2+ & [Cu(gly)2]2+
 Suitability of EDTA ligand as titrant
• Complex with metals: EDTA forms complexes with nearly every metal
ions carrying more than unit positive charge (di, tri and tetravalent ions)
and even with Na+ and Li+ ions
• Stoichiometry of complex formation: EDTA forms 1:1 complex with
metal ions Instantaneously and therefore direct complexometric
titrations are possible.
EDTA forms 1:1 complex regardless of the charge on the cation:
Ag+ + Y4- ⇌ [AgY]3-
Al3+ + Y4- ⇌ [AlY]-
• Complex stability and pH: Stability of complexes depends on pH.
Divalent metal-EDTA complexes are stable in ammoniacal pH but
decomposes in acidic medium.
Trivalent transition metal-EDTA complexes are stable even in strongly
acidic medium.
 Suitability of EDTA ligand as titrant

• Solubility of Metal-EDTA Complexes:

Most of the metal-EDTA complexes are soluble in water
• Colour of Metal-EDTA complexes:
Colourless metal ions form colourless EDTA complexes.
Coloured metal ions form deep coloured EDTA complexes
• Solubility of EDTA:
EDTA has Limited solubility in water and can be precipitated from acid
solution
• Stability of EDTA:
EDTA can be destroyed by moderately powerful oxidising agents such as
dichromate
 Suitability of EDTA ligand as titrant
• Masking Reactions:
EDTA is very unselective reagent because it forms complexes with numerous di-, tri- and
tetravalent cations.
By the use of masking agents some of the cations in a mixture can often be masked so that
they can no longer react with EDTA.
Masking agents: Complexing agents which selectively reacts and form complexes with
particular cations in a solution to prevent that cations from interfering in the determination of
other cation.
Ex: Cyanide used as masking agents in the titration of Mg2+ and Ca2+ in presence of other
cations of Cd, Co, Cu, Ni, Zn and Pd.
• EDTA as primary standard:
EDTA may be prepared sufficiently pure with remarkable stability and can be used as a
primary standard solution.
EDTA itself has limited solubility in water and must be dissolved in small amount of base for
complete dissolution.
Free acid H4Y and dihydrate of disodium salt of EDTA Na2H2Y.2H2O are commercially available
and can be used to make primary standard solutions.