Complexometric Titration

CHM 222

Dr Etchie, A. T.

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Introduction
• A titration is a technique where a solution of known
concentration is used to determine the concentration
of an unknown solution.
• Typically, the titrant (the know solution) is added from
a biuret to a known quantity of the analyte (the
unknown solution) until the reaction is complete.
• Knowing the volume of titrant added allows the
determination of the concentration of the unknown.
• Often, an indicator is used to usually signal the end of
the reaction, the endpoint.
•

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Types of titrations
• Neutralization titration
• Complex formation titration
• Precipitation titration
• Oxidation-Reduction Titration

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Complexometric titration
• Complex consists of a metal ion surrounded by
molecules or anions.
• Complex is formed by the combination of metal
ion with electron donating group or nucleophile

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Formation of complexes
• Complexes are compounds formed from combination
of metal ions with ligands (complexing agents).
• A metal ion is an electron deficient specie while a
ligand is electron rich (an electron donating specie).
• A metal ion will thus accept electrons from a ligand
where coordination bonds are formed.
• Electrons forming coordination bonds come solely
from ligands.

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Examples of complexes

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 Types of complexing agents
Ligands can be classified according to the number of
sites of attachment to the metal ion

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 Complexometric Titrations
• A complexometric titration is a technique of volumetric
analysis in which a soluble, undissociated stoichio-
metric complex is formed during the addition of titrant
to the sample solution.
• Complexometric titrations are particularly useful for
the determination of a mixture of different metal ions
in solution.
• An indicator capable of producing a definite colour
change is usually used to detect the end-point of the
titration.

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Classification of Complexometric Titrations

1) Direct Titration
2) Back titration
3) Replacement Titration
4) Alkalimetric titration of metals

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Direct Titration
• This is a direct determination of a metal ion by adding
a small quantity of indicator and standard EDTA titrant
from burette to the sample solution.
• Metal ion + EDTA →[ Metal-EDTA ] complex
• The solution containing the metal ion is buffered to the
desired pH and titrated directly with standard EDTA
solution.
• Some auxiliary complexing agent such as tartarate can
be added to prevent the precipitation of the hydroxide
of metal ion.
• Cu²⁺, Zn²⁺, and Ni²⁺ can be determined by using direct
titration method.

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An example of direct complexometric titration is direct
determination of water hardness
• Water hardness is due to the presence of Ca²⁺, & Mg²⁺
salts. EDTA forms complex with Ca²⁺ & Mg²⁺.
• Ca-EDTA complex is more stable than Mg-EDTA
complex.
Determination of total Ca²⁺ & Mg²⁺
• Total Ca²⁺ and Mg²⁺ is determined by titration with EDTA
at pH 10 using ammonia buffer and Eriochrome Black
T (EBT) as indicator.
• Upon titration with EDTA, Ca²⁺ will be chelated first,
then Mg²⁺.
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Determination of Ca²⁺ only:
• Direct titration with EDTA at pH 12 using 8% NaOH
and Murexide. At pH 12 EDTA forms complex with
Ca²⁺ only. Mg²⁺ is precipitated as Mg(OH)₂ leaving
Ca²⁺ which is titrated with EDTA.

Determination of Mg²⁺:
• Total – Ca²⁺ = Mg²⁺

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Back Titrations:
• In this is method, an excess of standard EDTA is added
to the sample solution of metal ion.
• The resulting solution will contain unreacted EDTA which
is then back titrated with standard metal ion solution in
the presence of an indicator.
• ZnCl₂, ZnSO₄, MgCl₂, MgSO₄ is used as standard metal
ion solution.
• Al³⁺, Co²⁺, Pb²⁺, Mn²⁺, Hg²⁺, and Ni²⁺ can be determine by
using Back titration method

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Example of back titration is determination of Aluminium
salts:
• Sample containing Al³⁺ is heated with known excess of
standard EDTA at pH 7-8.
• The solution is then adjusted to pH 10 using ammonia
buffer.
• The residual EDTA is titrated against standard Zn²⁺
using EBT indicator.
• The colour changes from blue to wine red.

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Replacement, Displacement or Substitutions
Titrations:
• When both back titration and direct titration is not
possible due to the end point not being sharp
enough. Then the replacement titration is a method
of choice.
• In this method of titration, determination of metal ion is
done by displacing magnesium or zinc ions from EDTA
complex with an equivalent amount of metal ion and
liberated Mg or Zn ions are then titrated with standard
EDTA solution.
• Mordant black used as indicator.

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• Calcium salt is determined in this way. In this, add
standard volume of Mg-EDTA solution to Ca salt in
the presence of buffer.
• Calcium displaces Mg ion and forms a stable complex
with EDTA as Ca-EDTA complex.
• The displaced and liberated Mg ions are then titrated
Standard EDTA solution using Mordant black as
indicator.

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Alkalimetric titration of metals
• This method use the principle of liberation of free H⁺
ions during the complexation.
• The reaction between metal ion and EDTA (H₂Y²⁻)
produce H⁺.
• Mⁿ⁺ + H₂Y²⁻ → MY⁽ⁿ⁻⁴⁾⁺ + 2H⁺
• The free H⁺ ions is titrated with standard solution of
alkali like NaOH by using suitable acid-base indicator.
• The H+ ions can also be determined by potentiometric
method.

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Methods of increasing selectivity in complexometric
titrations

• Chemical separation
pH control
Use of masking and
• pH control
demasking agents
Classical separation
• Use ofKinetic
masking and demasking
masking agents
• Kinetic masking

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Chemical Separation
• In this technique, the selectivity is increased by separa-
ting the analyte species from other components of the
sample solution.
• The separated species is then dissolved in suitable
solvents and then titrated against EDTA using indicator.
• Ca²⁺, Mg²⁺, Ni²⁺ and Cu²⁺ ions can be first separated as
Ca-oxalate, Ni-DMG (Nickel bis(dimethylglyoximate)),
Mg-ammonium phosphate and Cu-thiocyanide.
• These precipitate are then dissolved in separate suitable
solvents and then titrate against EDTA using indicator.

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pH control
• In this technique, the selectivity is increased by
controlling the pH of the solution. That 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.
• E.g.: Ca²⁺ can be determined in the presence of Mg²⁺ in
strongly alkaline solution (pH < 10).
• Trivalent ions like Bi³⁺ and Fe³⁺ can be selectively
determined from the solution of bivalent metal ions in
strongly acidic solution (pH ~ 2).

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Masking agents:
• Masking agents: are reagents which prevent interfering
ion from reaction without physical separation.
• These reagents form complexes with interfering ions and
the complexes formed are more stable than complexes
formed with indicator & EDTA

• Examples of masking agents include: fluorides, cyanides

etc.

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Demasking
• The previously masked cation is damasked by using
suitable reagent to get free cation. This free cation is
then titrated by using standard EDTA.
• Formaldehyde, chloral hydrate and methanol acetic acid
mixture (3:1) is used to demask cyanide complexes
(CN-) of cadmium and zinc. The liberated metal ions are
then titrated with standard EDTA.

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 Stability of Metal-Ligand Complexes
• The stability of metal-ligand complexes formed in
complexometric titrations is influenced by a number of
factors related to the ligand and metal ions. These
factors include:
1. Nature of the metal ion: Small ions with high charges
lead to stronger complexes.
2. Nature of the ligand: The ligands forming chelates
impart extra stability (chelon effect), depending on the
number of binding sites. For example, the complex of
nickel with a multidentate ligand is more stable than
the one formed with ammonia.
3. Basicity of ligand: Greater basicity of the ligand results
in greater stability of complex formed.
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4. Size of chelate ring: The formation of five- or six -
membered rings provides the maximum stability.
5. Number of metal chelate rings: The stability of the
complex is directly related to the number of chelate
rings formed between the ligand and metal ion.
Greater the number of such rings, greater is the
stability.
6. Steric effects: These also play an important role in
the stability of the complexes.

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Advantages of EDTA as ligand:
1. ETDA form stable complex with various metal ions.
2. The complexation occurs in a single step and hence
titration with a metal produces a sharp change in the
metal ion concentration at the equivalence point.
3. The metal-EDTA complexes are all water soluble and
hence all studies can be performed in aqueous
media.
4. EDTA forms 1:1 complex with all metal ions
irrespective of the charge on the metal ions. The
stoichiometry is hence same for all metal ions.

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Limitations of EDTA as a ligand:
1. Formation of insoluble hydroxides:
Many ETDA titrations are carried out in alkaline pH which
may lead to formation of insoluble hydroxides or basic salts
that may compete with complexation process.
2. Lack of selectivity:
Since EDTA forms stable complexes with most of the metal
ions, it lacks selectivity if it is intended to be used to
estimate a single metal cations from a solution of mixture of
metal ions.
Combating EDTA limitation
1. Auxiliary complexing agents such as tartarate,
ethanolamine, ammonia or citrate can be added to keep
the metals in solution, thus preventing formation of
hydroxides.
2. pH control to improve selectivity. 29
Absolute formation constant of metal-EDTA complex
• EDTA forms 1:1 complex with all metal ions irrespective
of all charge on the metal ions. The stoichiometry is
hence same for all metal ions.
• Unprotonated form of EDTA (Y-4) reacts with metal ion
as follows: 𝑀𝑛+ + 𝑌 4− 𝑀𝑌 𝑛−4 +
• Then absolute formation constant K MY is given as:
[𝑀𝑌 𝑛−4 + ]
𝐾𝑀𝑌 =
𝑀 𝑛+ [𝑌 4− ]
𝐾𝑀𝑌 is also referred to as absolute stability constant.
• The higher the value of K MY , higher is the stability of
complex formed.
• The equilibrium constant for the reaction between a metal ion and a
chelating agent is known as a formation constant or stability
constant.
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 Indicators for complexometric titrations
Metallochromic indicator
• The metallochromic (metal ion) indicators are organic
compounds which are capable of forming intensely
coloured complex with metals in sample solution.
• This metal–indicator complex is weaker than the
Metal-EDTA complex and it has different colour from
the uncomplexed indicator.
• Close to the end of titration, the metal ion from metal–
indicator complex is displaced and then forms metal-
EDTA complex with the EDTA.

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Note:
• At the start of the titration, the metal and the indicator
form a colour complex.
• The titration proceeds until all the free metal is
complexed with EDTA and only the small amount
complexed with the indicator is left.
• Then, with one more drop of EDTA, the EDTA must
remove the metal from the indicator complex which
afterwards changes back to its free form and you can
see the endpoint as the colour of uncomplexed indicator.
• If a metal and the indicator complex is too strong, the
metal is said to block the indicator and end point may not
be visible
• The colour of indicators is frequently a function of pH, so
you have to be careful of its pH as well as the EDTA.
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Requirement for Metal ion indicator
1. The colour must be sufficiently intense, so that a mini-
mum amount of indicator can be used.
2. The colour contrast between the indicator and metal-
indicator complex should be readily observable.
3. The metal-indicator complex should possess sufficient
stability to ensure a sharp colour change, however it
should be less stable than metal-EDTA complex.
4. The change in equilibrium from metal-indicator complex
to the metal-EDTA complex should be sharp and rapid.
5. The colour reaction of the indicator should be selective.

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6. The indicator must be very sensitive to metal ions so
that the colour change occurs at near the equivalence
point.
7. The indicator must be stable in the titration medium.
8. The indicator must be stable on storage also.
9. All the above requirements must be fulfilled in the pH
range in which the proposed titration is to carried out.
10. It should be commercially available in adequate purity

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• EBT is used to estimate Mg, Zn, Mn, Cd, Hg, Pb, Cu,
Al, Fe, Ti, Co, Ni and Pt metal ions .
• The indicator is prepared by dissolving 0.2 gm of the
EBT powder in 15 ml of triethanolamine followed by the
addition of 5 ml of absolute alcohol

• Murexide is used to estimate Ca, Ni, Co, Zn, Cd, Cu

metal ions in EDTA titrations.
• The indicator is prepared by dissolving Murexide
powder in water. Aqueous solution of Murexide is
unstable hence it must be prepared freshly.

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• Xylenol orange: 3,3′-Bis[N,N-
bis(carboxymethyl)aminomethyl]-ocresolsulfonephthalein
tetrasodium salt.
• Xylenol orange is used to estimate Bi, Cd, Pb, Sc,Th, Zn
metal ions in EDTA titrations.

• Pyridylazonaphthol: 1-(2-Pyridylazo)-2-naphthol (PAN).

• Pyridylazonaphthol (PAN) is used to estimate Cd, Cu, In,
Sc, Zn, metal ions in back and replacement EDTA
titrations.

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