Unit 3: Complexometric Titration

Introduction & Principle:

• Complexometric titrations are based on formation of a complex b/w

analyte and titrant.
• These are also defined as the reactions in which simple metal ions
are converted into metal complex by addition of a reagent known as
ligand or complexing agent.
• The end point is based on formation of a stoichiometrically stable
complex.
• Ligand is an electron donating ion or molecule which form only
single bond with the metal ion
• When it form water soluble complex it is called sequestering agent
• Ethylene diamine tetra acetic acid (EDTA) is the most commonly
used titrant (complexing agent) of metal ions.
• The important features of EDTA are-

1. Complexes formed are stable

2. Complex formation is quantitative and instantaneous
3. Complexes formed are water soluble
4. Complex formation occurs with most metals of periodic table in 1:1
ratio

• Besides EDTA many other aminopolycarboxilic acids have been

used due to certain advantages but EDTA remain most popular
titrant.
• Symbolic representation of EDTA disodium salt is as Na 2H2Y.H2O
it ionizes in water as reactive species is H2Y2-. So the reaction with
metal ions of various valency are-

M2+ + H2Y2- → MY2- + 2H+

M3+ + H2Y2- → MY1- + 2H+

Mn+ + H2Y2- → MY(n-4) + 2H+

In these reactions acid is liberated so buffer are used to maintain pH

of the solution because pH has marked effect on solubility of
complex formed

• Stability of complex is governed by low of mass action

 M + nL ⇌ MLn

So the stability constant Ks is

MLn
Ks =
[M][L]n

As the magnitude of Ks increases; stability of complex is more concentration of

unbound metal ion [M] and ligand [L] is less.

Classification of Complexing agents

1. Based on their tendency to donate electrons to metals ions:

a. Unidentate (one site) → donates only one pair of electron. Eg- cyanide ion,
ammonia, chloride ions
b. Bidentate (two sites) → donates two pairs of electron. Eg.- oxalic acid, glycine
c. Multidentate (more than two sites) → donate several pairs of electron. Eg.-
ethylene diamine tetra acetic (EDTA)
2. Based on functional groups:
a. Complexing agents containing oxygen: mainly includes carboxylation and
polycarboxylates. Eg.- acyclic acid polymer, maleic anhydride, polyacrylic
acid, sodium polyacrylate, etc.
b. Complexing agents containing phosphorus:
i. Phosphates: eg.- sodium triphosphate, sodium tripolyphosphate, tetra
potassium pyrophosphates.
ii. Phosphonates or phosphons acids: Eg.- aminotrimethyl phosphonic acid,
dimethyl triamine pentamethylene phosphonic acid, ethylene diamine tetra
methylene phosphonic acid, hexa methylene diamine tetra methylene
phosphonic acid, 1-hydroxy ethylene diphosphonic acid
c. Complexing agents containing nitrogen: eg.- ammonia, cyanides, EDTA,
Diethylene triamine penta acetic acid, hydroxyethyl ethylene diamine triacetic
acid, trisodium nitridotriacetate
d. Zeolite: complexing agent containing aluminium silicate
e. Miscellaneous: disodium citrate, sodium citrate, trisodium citrate, gluconic
acid, oxalic acid, tartaric acid, etc.
Types of Complexometric titration

Direct Indirect Titration/ Alkalimetric Titration

Titration Replacement
Back titration/ Titration/
Residual Titration substitution of 1
complex by other

1. Direct titration: it is performed by titrating metal ion containing buffer and

few drops of indicator with standard disodium EDTA solution. End point of
such titration is detected by change in colour of the indicator. Similar titration
 is performed by taking only buffer and indicator (blank titration) to verify
impurities present in the reagent. Eg.- soluble salts of magnesium, calcium,
zinc and bismuth can be titrated by this method.
2. Indirect titration: insoluble substances are titrated by back titration or
residual titration. This titration is performed by adding excess of EDTA
(complexing agent) to metal ion solution. Solution is heated and cooled to
promote complex formation b/w metal ion and EDTA. During this pH of
solution is adjusted by adding a suitable buffer. Finally excess EDTA is back
titrated using magnesium or zinc, sulphates or chloride in presence of suitable
indicator. Eg.- insoluble salt of calcium oxalate or phosphate, lead sulphate,
aluminium, manganese, etc. can be titrated by this method.
3. Replacement Titration: This titration is performed when direct and indirect
titrations do not give satisfactory results or end point. It is done by substituting
equal amount of magnesium or zinc form less stable complex.

Ca++ + Mg.EDTA → Ca.EDTA +

Mg++

Eg.- calcium, mercury and lead can be determined by this

method

4. Alkalimetric titration: In alkalimetric titration, protons produced due to

formation of metal-EDTA complex are titrated against standard alkali in
unbuffered solution using visual indicators or potentiometric method.
Alternatively, mixture of iodine-iodate liberates iodine when EDTA solution is
added to it. Liberated iodine is titrated against sodium thiosulphate solution in
presence of starch as an indicator.

Masking and Demasking

• One of the important aspects of complexometric titration is estimation of two or
more metals in some solution.
• This can be done either by selection of suitable pH at which one metal forms a
complex without involvement of other metal ion by using a suitable masking
agent.

Masking Agents: a masking agent is called as auxiliary chelating agent or complexing

agent.
• It is a substance that will form complex more strongly with the metal than the
titrant
• Masking agent titrate selectively in two ways-
1. By Precipitation: Precipitants are added to mixture to ppt metals which can
create barrier during titration so that metal analyzed selectively.
Precipitants Metals precipitated
sulphate Barium(Ba), lead (Pb)
Thioacetamide, sodium sulphide lead (Pb), cobalt (Co), copper (Cu)
Fluoride Magnesium (Mg), Calcium (Ca),
lead (Pb)
Oxalate Calcium (Ca), lead (Pb)
Ferrocyanide copper (Cu), Zinc (Zn)
 8-hydroxy quinoline Heavy metals

2. By forming complex: A substance that can donate electrons to a metal ion and
forms a complex via a single covalent bond known as complexing agent. These
agents form more stable complex with the metals to be eliminated than with
metal to be analyzed. So enables us in the selective titration of specific metal.
3.
Ligand (Complexing agent) Metal ions (complexed ions)
Potassium iodide Mercury (Hg)
Ammonium fluoride Titanium (Ti), Iron (Fe), aluminium
(Al)
Ferrocyanide + ascorbic acid Ferric (Fe3+)
triethanolamine Iron (Fe), aluminium (Al)
Potassium cyanide Nickel (Ni), cobalt (Co), cadmium
(Cd), Iron (Fe), Zinc (Zn)
Tiron Titanium (Ti), aluminium (Al)

Demasking Agents:
• It is the substance which releases the masked metal ion
• By adding these agents masked metal ion regain its ability to enter in specific
reaction.
• The cyanide complexes of zinc and cadmium can be demasked by
formaldehyde-acetic acid solution.

It can be done by:

1. pH control method: pH plays an important role in complex formation at specific
pH only selected metal form complex. Eg.- alkaline earth metals form stable
complex at basic pH (above 7). Other metals such as iron, cobalt, tin, etc form
stable complex in acidic solution with EDTA.
2. Solvent extraction: eg.- ammonium thiocyanate is used to extract zinc from lead
and copper; extracted zinc thiocyanate is then titrated with EDTA.
3. Classical separation: it is done by adding precipitants to mixture of cations. The
precipitate are redissolved and cations from the solution analyzed by
complexometric titration. Eg.- CaC2O4, Mg(NH4)PO4, CuSCN.

Detection of End point by Complexometric titration

Visual indicators Instrumental methods

1. Visual indicators or metal indicators or metallochromic indicators
• These are dyes which shows one colour in presence of metal ion and no colour
or different colour in absence of metal ion.
• The indicators act by following mechanism: Suppose metal ion is M; Indicator
is In and titrant is EDTA. Initially, reaction takes place b/w metal and
indicator form metal-indicator complex (MIn)
• Solubility constant for this is-
 MIn
KIn =
[M][In]

• During titration when titrant (EDTA) is added , free metal ion and
EDTA react to form metal-EDTA complex. Solubility constant Ks
for this is-

M − EDTA
Ks =
[M][EDTA]

• The solubility constant of metal-EDTA is greater than metal-

indicator complex Ks>Kin
• Finally at end point, metal-indicator complex (MIn) breaks indicator
changes its colour from its complex form to its free form.
• This shows sharp break in a graph b/w

-log[M]= pM and conc of EDTA

Ideal properties of Metal Indicators:

• Metal ion indicator should be sufficiently stable. It should not

disclose, otherwise colour change not observed.
• It should produce sharp end point
• It should form complex weaker than metal-chelate complex.
• There should be difference in colour b/w free indicator and metal-
indicator complex
• Metal indicator used in titration should be sensitive and specific for
the metal being titrated
• Metal indicator should produce colour reaction within pH range
favourable for titration.

Indicators commonly used and official in IP:

Calcon: (mordant black 17, solochrome dark blue). It is 2-hydroxy-1-(2-hydroxy-1-
naphthylazo); naphthalene-4-sulphonic acid sodium salt.

• It gives purple-red colour with calcium ions in alkaline solution

In absence of metal ion that gives blue colour.

Catechol violet: it forms highly coloured complexes with wide range of metals.
Complexes with metals are blue in colour in acidic solutions.
• Thorium (Th4+) complex at pH 3
• Bismuth at pH 1.5
• Magnesium, manganese, cobalt, zinc, calcium, cadmium can be titrated in pH
range 4-7.
• A 0.1% solution in water is used as indicator.

Eriochrome black T (Mordant Black II):

• Chemically it is Sodium-1-(1-hydroxy-2-naphthylazo)-5-nitro-2-naphthol-4-
sulphonate
• A mixture of 0.2% mordant black II with 100 parts of sodium chloride is used
as indicator
• It has blue colour at pH 10 and complex has red colour at pH 10

Mordant blue 3: (solochrome cyanne R)

• Specific for aluminium
• In presence of aluminium it gives purple colour, pink colour when EDTA is in
excess

Mordant Red-7: (0.1% solution is used)

• Gives bluish violet colour with nickel, green in presence of excess EDTA

Murexide: (Ammonium purpurate)

• A mixture of 0.2% dispersed in NaCl used for determination of calcium at pH
12
• Complex gives blue violet colour while indicator solution has red violet
colour.

Xylenol Orange:
• One part of indicator in 99% of potassium nitrate for use
 • Gives red-violet colour with mercury, lead, zinc in acidic solution in absence
of metal ion gives yellow colour.

pH indicators:

Mn+ + H4Y → MY(n-4) + 4H+

Liberation of acid, then quantitatively produced acid is titrated with

standard alkali using acid-base indicator. Methyl red, methyl
orange can be used as indicator

Advantages of Visual methods

1. Instrumental methods includes titrations

2. Apparatus used for titrations is inexpensive, readily available and
also give accurate result.
3. Detection of end point is easy.

2. Instrumental methods for detecting end

point:Type equation here.

i. Potentiometric titration- In this method platinum electrode is

commonly used with standard reference electrode. It measures redox
potential with metal EDTA complex. Platinum electrode measures
redox potential with metal EDTA complex.

[Oxi]
𝐸 = 𝐸0 log
[Red]

Where, E= the potential of electrode

𝐸0 = the standard of electrode potential

[Oxi]= conc. Of ions in the oxidized state

[Red]= conc. Of ions in the reduced state

• Another indicator electrode is mercury electrode; it measures potential

changes occur when replacement reaction b/w metal ion M n+ and Hg ion
present in Hg-EDTA complex

M2+ + Hg-EDTA → Hg2+ + M-EDTA

ii. Photometric titrations:

• There is always a change in absorbance spectrum when complex is formed it is
basis of photometric titrations.
• Change in absorbance occurs more prominently in dilute solution (0.001-0.005)
• Some metal form complexes which are colorless; so these can be estimated in
UV region
• Metals like Fe(III), Cu(II) etc. for coloured complex; colorimetric analysis is
carried out.

iii. Amperometric titrations: Metal ions give diffusion current during

titration with EDTA metal ion conc. Decreases and so also the diffusion
current. This is the basis of amperometric titrations.