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COMPLEX FORMATION
TITRATION
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Complexometry
Volumetric method involves reaction of metal with ligand
to form complex
M+ Ligand
Electron acceptor Coordinate bond Electron donor

Complex formation is a type of acid base reaction according to lewis

concept,
where metal ion is lewis acid (electron acceptor) and ligand is lewis
base electron donor

Ligand Buffer

Sample Metal Indicator

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Sample
Metal

 The tendency to form complex is inherent property in all metals

 Therefore Metals form with water Aqua complex

(solvated metal ion) as oxygen of water donate electrons to metal
ions

Complexation reaction is the replacement of solvent molecules by ligand

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Ligand
Ligand may be:

 Mono dentate
 Bi dentate
 Tri dentate
 Multi dentate
Sequestering Chelating agent that
agent form soluble chelates

Chelating Form complex Ring (sol. or

agent Insol complex)
Complexing
Form complex
agent
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The most common ligand used is ..

EDTA
Ethylene Diamine Tetra Acetic acid di sodium salt
Na2H2y. 2H2O

Na
Na

EDTA is a typical sequestering agent

EDTA is a Secondary Standard .. Why?
Due to the presence of impurities from industrial synthesis
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Advantages of EDTA Disadvantage of EDTA

 Cheap, commercially available  Its reaction is reversible,
 Versatile, reacts with most requires alkaline buffer
metals
 Form stable complexes with  It’s non selective
most metals (stable than metal reagent
indicator complex)
 Reacts in ratio 1:1 with metals

M2+ + H2Y2- MY2- + 2H+

M3+ + H2Y2- MY- + 2H+
M4+ + H2Y2- MY0 + 2H+

Mn+ + H2Y2- MY(n-4) + 2H+

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Metallochromic Indicators
Form colored complex with metals

Examples of metallochromic indicators:

1) EBT (Eriochrome black T or Solochrome Black) Solid powder

2) Murexide (ammonium salt of purpuric acid) Solid powder
3) Xylenol Orange Solution

 Each indicator has a color in the free state and another color
in combined ( metallized) state

Requirments for successful use of metal indicators

 M/EDTA complex is more stable than M/Ind complex
 Indicator Free color should be distinguished from M/Ind color
 Most metal indicators are acid-base indicators so, their color
change due to pH
 Indicator is not necessary to be specific but at least selective
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Alkaline buffer is used in complexometric

titrations .. Why
1. Shift reaction between EDTA and metal forward, to prevent
the reversibility of the reaction
2. Make color change at end point due to change in metal
concn. not due to pH as most metal indicators are also acid
base indicators

ComplexOmetry Compleximetry
Titration against EDTA Titration against any
other complexating
EDTA = Complexon III = agent
Sequesterene
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Metal aqua complex Sample

(M.H2Ox)2+
Indicator

Metal aqua M-Ind

complex complex
EDTA M/EDTA complex is more
stable than M/Ind complex

Metal- EDTA M-Ind

complex complex
EDTA
Free
Metal- EDTA complex + Indicator
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Precautions during complexometric titration

Gentle shaking during first 5 mls of titrant

After the first 5 mls, VIGEROUS SHAKING
with Rapid titration

 Indicator can be increased any time during titration

Once end point is reached (free form of

indicator), color do NOT change with
addition of excess titrant
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DETERMINATION
OF
NICKEL SAMPLE
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1- Principle
Direct Complexometry
Ni2+ e.g. NiSO4
Directly titrated against EDTA in presence of NH3 buffer
(pH=10) using Murexide as indicator

End point: Yellow (Metallized form) Purple (free form)

NH3
Buffer
+

Yellow Purple
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Ni/EDTA complex is more stable than

EDTA Ni/Murexide complex

Ni2+ Murexide Before titration

During titration

Ni2+ Murexide + EDTA Ni2+

During titration

Ni2+ Murexide
+ EDTA Ni2+

At End
point Murexide + EDTA Ni2+
Free form
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2- Procedure
In Conical Flask

10 ml Sample
+ 2 ml NH3 buffer
+ few specks Murexide (yellow color)

Titrate against 0.01M EDTA

End point: Purple
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3-Calculation
F

1ml 0.01M EDTA

2
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DETERMINATION
OF
COPPER SAMPLE
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1- Principle
Direct Complexometry
Cu2+ e.g. CuSO4.5H2O
Directly titrated against EDTA in presence of dil. NH3
using Murexide as indicator

End point: Purple (free form)

+NH3
Cu2++NH3 Cu(OH)2 [Cu(NH3)4]2+
Copper Copper ammine complex
hydroxide ppt Soluble (blue color)

dil
NH3 +
Purple
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Cu/EDTA complex is more stable

EDTA than both Cu/amine complex and
Cu/Ind complex

[Cu(NH3)4]2+ Cu-Murexide
Blue + Yellow
EDTA reacts first with copper ammine
complex because it is the less stable than Cu-
Ind complex

During titration, color gets lighter

End point: purple

(free form of
indicator)
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2- Procedure
In Conical Flask
10 ml Sample
+ 2 ml dil NH3 drop wise
till the ppt formed dissolve to give Copper
ammine complex (Blue color)

+ few specks Murexide (Dark green color)

Titrate against 0.01M EDTA

End point: Purple
Role of dil NH3
 Auxillary complexing agent
 Give the suitable pH for formation of Cu/EDTA complex
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3-Calculation
Na2H2Y. 2H2O+ CuSO4.5H2O Na2CuY+ H2SO4+ 7H2O

2
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DETERMINATION
OF
LEAD SAMPLE
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1- Principle
Direct Complexometry
Pb2+ e.g. (CH3COO)2Pb
Directly titrated against EDTA in presence of Hexamine
(pH=5-6) using Xylenol orange as indicator
End point: violet red yellow
(metallized form) (free form)

pH =5-6 .. Why ?
For maximum stability of Pb/EDTA complex, to increase selectivity

Hexamine +
violet red yellow
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2- Procedure
In Conical Flask

10 ml Sample
+ 2 ml Hexamine
+ 2 dps Xylenol Orange (violet red color)

Titrate against 0.01M EDTA

End point: yellow
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3 Calculation

2
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DETERMINATION
OF
ZINC SAMPLE
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1- Principle
zinc is determined by direct complexometric titration
against EDTA using EBT as indicator in presence of
ammonia buffer (pH=10)
End point: Violet Full Blue
(metallized form) (free form)

EDTA
Zn-EBT Zn-EDTA+ free EBT
Violet Full Blue
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2- Procedure

10 ml Sample
+ 2 ml NH3 buffer
+ few speaks of EBT (Violet)

Titrate against 0.01M EDTA

End point: full blue
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3-Calculation

1 ml 0.01M EDTA = Mwt.of ZnSO4.7H2O = 0.002874g

100Χ1000

+2
Conc.of Zn = mlsΧ fΧFΧ1000 = g/l
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Thank You
T.A. Aya Ahmed
Analytical chemistry department