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COMPLEXOMETRIC
TITRATIONS
SHILPA JOY
ASSISTANT PROFESSOR
DEPARTMENT OF CHEMISTRY
KURIAKOSE ELIAS COLLEGE
MANNANAM
Complexometric titrations or
Chelatometry
Volumetric analysis in which the formation
of colored complex is used to indicate the end
point of a titration.
Estimation of metal ion in solution
Stability of the complex formed is the
determining factor
Indicator- unambiguous color change.
1. Reaction reaches equilibrium rapidly after each
portion of titrant is added
2. Interfering situations do not arise
3. Complexometric indicator capable of locating
equivalence point with fair accuracy is available
4. the technique involves titrating metal ions with a
complexing agent or chelating agent(ligand)
Metal ion + complexing agent complex ion
EDTA – Ethylene diamine tetraacetic acid- titrant
Erio-chrome black-T --- indicator
o 4- hydroxyl groups and two amine groups- act as
electron pair donor
oThe ability of EDTA to donate 6 lone pairs of electrons for
the formation of coordinate covalent bonds to metal
cations makes EDTA a hexadentate ligand.
o EDTA is usually only partially ionized form, thus forms
fewer than 6 coordinate covalent bonds with the metal.
Disodium EDTA is commonly used to standardise
aqueous solutions of metal cations.
Na2H2Y forms 4 coordinate covalent bond at a Ph <12 .
EDTA forms an octahedral complex with most M+2 ions
in aqueous solution
• EDTA is extensively used in the standardisation of
metal cation solutions since the formation constant for
the most metal cation –EDTA complexes are very high.
M2+ + H4
Y MH2
Y + 2H+
equilibrium lies far to the right.
carrying out the reaction in basic buffer solution
removes H+ as it is formed , which also favours the
formation of the complex product.
Formation of metal cation –EDTA complex goes on
completion- advantage
Magnesium
Calcium
Cadmium
Lead
Copper
Nickel
cobalt
Iron
Bismuth
Thorium
Zironium
Direct
determination
Analyte is titrated with standard EDTA solution buffered at a pH
where kf is large.
Back titration
4 dozen of elements- direct titration with EDTA
with a suitable metal ion indicator
non availability of suitable indicator– direct
titration is not possible
In back titration , excess standard solution of
EDTA is added to the analyte and excess EDTA
or unreacted EDTA is back titrated against a
standard solution of Mg+2 or Zn+2 using
eriochrome black T
MASKING OF IONS
Mg+2 or Ca+2 ions can be titrated in the
presence of interfering Cd+2,Cu+2,or Ni+2 by
adding cyanide ion reaction mixture
Cyanide act as masking agent
It can form complexes with Cd+2,Cu+2,or Ni+2
thereby eliminating interference
Advantages
Estimates hardness of water –calcium and
magnesium ions.
EDTA is a convenient reagent, it always react
with metals 1:1 basis, making calculation easy.
Selection of solution Ph allows to determine
one metal in the presence of other
Cations with high charges (Fe+3, Bi+3) have large
stability constant,so they can be titrated at low
pH , in the presence of divalent cations which will
not interfere in this condition.
Indicators
Eriochrome Black T
Eriochrome Red B
Murexide
Fast Sulphon Black
.
Triethanolamine – comlpexant to
mask
Aluminium ions- before performing
titration
Multiple metal ins can be subsequently
titrated by careful control of the pH
These dyes binds metal cations in the solution to form
colored complexes.
Since EDTA binds to the metal cations more strongly
than does the dye used as an indicator, the EDTA will
displace the dye from the metal cations as it is added
to the solution of analyte
MgEbT(red) + EDTA(colourless)
Mg Edta (colourless)+ EbT(blue)
Titration curve

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Complexometry

  • 1. COMPLEXOMETRIC TITRATIONS SHILPA JOY ASSISTANT PROFESSOR DEPARTMENT OF CHEMISTRY KURIAKOSE ELIAS COLLEGE MANNANAM
  • 2. Complexometric titrations or Chelatometry Volumetric analysis in which the formation of colored complex is used to indicate the end point of a titration. Estimation of metal ion in solution Stability of the complex formed is the determining factor Indicator- unambiguous color change.
  • 3. 1. Reaction reaches equilibrium rapidly after each portion of titrant is added 2. Interfering situations do not arise 3. Complexometric indicator capable of locating equivalence point with fair accuracy is available 4. the technique involves titrating metal ions with a complexing agent or chelating agent(ligand) Metal ion + complexing agent complex ion
  • 4. EDTA – Ethylene diamine tetraacetic acid- titrant Erio-chrome black-T --- indicator
  • 5. o 4- hydroxyl groups and two amine groups- act as electron pair donor oThe ability of EDTA to donate 6 lone pairs of electrons for the formation of coordinate covalent bonds to metal cations makes EDTA a hexadentate ligand. o EDTA is usually only partially ionized form, thus forms fewer than 6 coordinate covalent bonds with the metal.
  • 6. Disodium EDTA is commonly used to standardise aqueous solutions of metal cations. Na2H2Y forms 4 coordinate covalent bond at a Ph <12 . EDTA forms an octahedral complex with most M+2 ions in aqueous solution
  • 7. • EDTA is extensively used in the standardisation of metal cation solutions since the formation constant for the most metal cation –EDTA complexes are very high. M2+ + H4 Y MH2 Y + 2H+ equilibrium lies far to the right. carrying out the reaction in basic buffer solution removes H+ as it is formed , which also favours the formation of the complex product. Formation of metal cation –EDTA complex goes on completion- advantage
  • 9. Back titration 4 dozen of elements- direct titration with EDTA with a suitable metal ion indicator non availability of suitable indicator– direct titration is not possible In back titration , excess standard solution of EDTA is added to the analyte and excess EDTA or unreacted EDTA is back titrated against a standard solution of Mg+2 or Zn+2 using eriochrome black T
  • 10. MASKING OF IONS Mg+2 or Ca+2 ions can be titrated in the presence of interfering Cd+2,Cu+2,or Ni+2 by adding cyanide ion reaction mixture Cyanide act as masking agent It can form complexes with Cd+2,Cu+2,or Ni+2 thereby eliminating interference
  • 11. Advantages Estimates hardness of water –calcium and magnesium ions. EDTA is a convenient reagent, it always react with metals 1:1 basis, making calculation easy. Selection of solution Ph allows to determine one metal in the presence of other Cations with high charges (Fe+3, Bi+3) have large stability constant,so they can be titrated at low pH , in the presence of divalent cations which will not interfere in this condition.
  • 12. Indicators Eriochrome Black T Eriochrome Red B Murexide Fast Sulphon Black .
  • 13. Triethanolamine – comlpexant to mask Aluminium ions- before performing titration Multiple metal ins can be subsequently titrated by careful control of the pH
  • 14. These dyes binds metal cations in the solution to form colored complexes. Since EDTA binds to the metal cations more strongly than does the dye used as an indicator, the EDTA will displace the dye from the metal cations as it is added to the solution of analyte MgEbT(red) + EDTA(colourless) Mg Edta (colourless)+ EbT(blue)