Dr.

Puspendra Kumar

Complexometric Titrations

By
Dr. Puspendra Kumar
M. Pharm., Ph.D.

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 Dr. Puspendra Kumar

COMPLEXOMETRIC TITRATIONS
 Complexometric titration (som
metimes chelatometry) is a form of volumetric analysis
anal in which
the formation of a colored complex
mplex is used to indicate the end point of a titration.
 Complexometric titrations
ns are pparticularly useful for the determination
ination of a mixture of
different metal
tal ions in solution.
 An indicator
tor capable of producing an una
unambiguous color change is usually used to detect the
end-point of the titration.
PRINCIPLE OF COMPLEXOMETRIC TITRATION
In theory, any complexation
plexation reaction can be used as a volu
volumetric technique
echnique provided that:
 The reaction reaches equilibrium rapidly after each portion of titrant is added..
 Interfering situations do not aarise. For instance, the stepwise formation of several different
di
complexes of the metal ion with the titrant, resulting in the presence
esence of more than one
complex in solution during thee tit
titration process.
 A complexometric
etric indicator capa
capable of locating equivalence point with fair accuracy is
available.
 In practice, the use of EDTA as a titrant is well esta
established

Ca+2/Mg+2 + Eriochrome Black T/Mordant Black T (Indicator)

(Wine Red Color)

(Titrant: E
Ethylene diamine tetra acetic acid/ EDTA)

Ca-EDTA
EDTA Complex / Mg
Mg-EDTA Complex + Free Eriochrome Black T Indicator
(Colorless) + (Blue Color)
(Final Color at the end point Blue)

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 Dr. Puspendra Kumar

Complexing Agents
1. EDTA (ethylene diamine tetra acetic acid)

 It has four carboxyl groups and two amine groups that can act as electron pair donors,
or Lewis bases.
 The ability of EDTA to potentially donate its six lone pairs of electrons for the
t
formation of coordinate
oordinate covalent bonds to metal cations makes EDTA a hexadentate
ligand.
 However, in practice EDTA is usually only partially ionized, and thus forms fewer
than six coordinate covalent bonds with metal cations.
 Disodium EDTA is commonly used to standardize aqueous solutions of transition
metal cations.
 Disodium EDTA (often
ten written as Na2H2Y) only forms 4 coordinate
oordinate covalent bonds
to metal cations at pH values ≤12. In this pH, the amine groups remain
ain protonated and
unable to donate electrons to the formation of coordinate covalent bonds.
2. DTPA (Diethylene triamine penta acetic acid
acid)

 Pentetic acid or Diethylene triamine penta acetic acid (DTPA

DTPA) is an
aminopolycarboxylic acid consisting of a diethylenetriamine backbone with five
carboxymethyl groups.
 The molecule can be viewed as an expanded version of EDTA and is used similarly.
 It is a white, water-soluble
soluble solid.
 The conjugate base of DTPA has a high affinity for metal cations. Thus, the penta-
penta
anion DTPA5− is potentially an octadentate ligand assuming that each nitrogen centre
and each COO−-group
group counts as a centre for coordination.

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 Dr. Puspendra Kumar

3. EGTA (Ethyleneglycol-bis [amino ethyl ether] tetra acetic acid.

 EGTA (ethylene glycol tetraacetic acid) is an aminopolycarboxylic acid, a chelating

agent.
 Compared to EDTA, it has a lower affinity for magnesium, making it more selective
for calcium ions.
 It is useful in buffer solutions that resemble the environment in living cells where
calcium ions are usually at least a thousand fold less concentrated than magnesium.
MASKING AND DEMASKING AGENTS
Masking agents
Masking agents act either by precipitation or by formation of complexes more stable than the
interfering ion-EDTA complex.
Masking by Precipitation
 Many heavy metals e.g.- Co, Cu and Pb, can be separated either in the form of insoluble
sulphides using Sodium sulphide, or as insoluble complexes using thioacetamide.
 These are filtered, decomposed and titrated with disodium EDTA.
 Other common precipitating agents are sulphate for Pb and Ba, oxalate for Ca and Pb,
fluoride for Ca, Mg and Pb, ferrocyanide for Zn and Cu, and 8-hydroxy quinoline for
many heavy metals.
 Thioglycerol (CH2SH.CHOH.CH2OH) is used to mask Cu by precipitation in the assay
of lotions containing Cu and Zn.
Masking by Complex formation:
 Masking agents form more stable complexes with the interfering metal ions.
 The most important aspect is that the masking agent must not form complexes with the
metal ion under analysis.
 The different masking agents used are enlisted below:

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 Dr. Puspendra Kumar

1. Ammonium fluoride will mask Al, Fe..

2 . Ascorbic acid is a convenient reducing agent for Fe+3 which is then masked by
complexing as the very stable hexacyanoferrate(II) complex.
3. Dimercaprol (2,3-Dimercaptopropanol); (CH 2SH.CHSH.CH2OH). Cations of mercury,
cadmium, zinc, arsenic, tin, lead and bismuth react with dimercaprol in weakly acidic
solution to form precipitates which are soluble in alkaline solution.
4. Potassium cyanide reacts with silver, copper, mercury, iron, zinc, cadmium, cobalt
and nickel ions to form complexes in alkaline solution which are more stable than the
corresponding edetate complexe.

5. Potassium iodide is used to mask the mercury(II) ion as (HgI4)2- and is specific for
mercury. It can be used in the assay of mercury(II) chloride.
6. Triethanolamine [N(CH2.CH2.OH)3] forms a colorless complex with aluminium, a
yellow complex with iron(III).
Demasking.
 The use of masking and selective demasking agents permits the successive titration of many
metals.
 Masked substance regains its ability to enter into a particular reaction.
 It is used to determine a series of metal ions in one solution.
 Eg: Using masking & demasking agents in complexometry is the analysis of 3 metals:
o Cu, Ca and Cd.
o Direct titration with EDTA: It will give the amount of 3 metals (Cu, Ca, Cd)
Cu + EDTA  Ca-EDTA
Ca + EDTA  Ca-EDTA
Cd + EDTA  Ca-EDTA
o Cu & Cd masked by Cyanide: Only Ca can be determined.
Cu+ Cyanide ion  Cu-Cyanide complex
Cd+ Cyanide ion  Cd-Cyanide complex
Ca+ Cyanide ion  No reaction (Free Ca) + EDTA  Ca-EDTA
o Formaldehyde/Chloral hydrate is added to damask the Cd and titrate the
solution to determine the Ca and Cd.

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 Dr. Puspendra Kumar

Cu-Cyanide complex + HCHO  Cu (Free)

Cd-Cyanide complex + HCHO  No reaction
Then titration reaction will be
Ca + EDTA  Ca-EDTA
Cd + EDTA  Ca-EDTA
o So we can determine the values of Cu, Ca & Cd separately.
o Ca is directly determined after masking Cu & Cd.
o Cd= (Ca+Cd) - Ca
o Cu= (Cu+Ca+Cd) - (Ca+Cd)
TYPES OF COMPLEXOMETRIC TITRATION
Complexometric titrations are of 4 types:
1. Direct Titration: It is the simplest and the most convenient method used in chelometry.
In this method, the standard chelon solution is added to the metal ion solution until the
end point is detected. E.g.-calcium gluconate injection, calcium lactate tablets and
compound sodium lactate injection for the assay of calcium chloride (CaCl 2.6H2O).
Limitations -slow complexation reaction
-Interference due to presence of other ions
2. Back Titration: In this method, excess of a standard EDTA solution is added to the
metal solution, which is to be analyzed, and the excess is back titrated with a standard
solution of a second metal ion. E.g. Determination of Mn. This metal cannot be directly
titrated with EDTA because of precipitation of Mn(OH)2. An excess of known volume of
EDTA is added to an acidic solution of Mn salt and then ammonia buffer is used to adjust
the pH to 10 and the excess EDTA remaining after chelation, is back titrated with a
standard Zn solution kept in burette using Eriochrome blackT as indicator. This method is
analogous to back titration method in acidimetry. e.g.- ZnO
3. Replacement Titration: In this method the metal, which is to be analyzed, displaces
quantitatively the metal from the complex. When direct or back titrations do not give sharp
end points, the metal may be determined by the displacement of an equivalent amount of
Mg or Zn from a less stable EDTA complex.

Mn+2+ Mg EDTA-  Mg+2 + Mn EDTA-2

Mn displaces Mg from Mn EDTA solution. The freed Mg metal is then directly titrated

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 Dr. Puspendra Kumar

with a standard EDTA solution. In this method, excess quantity of Mg EDTA chelate is
added to Mn solution. Mn quantitatively displaces Mg from Mg EDTA chelate. This
displacement takes place because Mn forms a more stable complex with EDTA. By this
method Ca, Pb, Hg may be determined using Eriochrome blackT indicator.
4. Indirect Titration: This is also known as Alkalimetric titration. It is used for the
determination of ions such as anions, which do not react with EDTA chelate. Protons from
disodium EDTA are displaced by a heavy metal and titrated with sodium alkali.
e.g. - Barbiturates do not react with EDTA but are quantitatively precipitated from alkaline
solution by mercuric ions as 1:1 complex.
Barbiturate + EDTA  No reaction
Barbiturate-Hg + EDTA (In Excess) Gives reaction and remaining EDTA are titrated.
INDICATORS
To carry out metal cation titrations using EDTA, it is almost always necessary to use a
complexometric indicator to determine when the end point has been reached. Common
indicators are organic dyes such as Fast Sulphon Black, Eriochrome Black T. Color change
shows that the indicator has been displaced (usually by EDTA) from the metal cations in
solution when the endpoint has been reached. Thus, the free indicator (rather than the metal
complex) serves as the endpoint indicator.
Table: Indicators used in complexometric titrations
S.No. Name of the Indicator Colour pH Metals detected
change range
1. Mordant black II Red to Blue 6-7 Ca, Ba, Mg, Zn, Cd, Mn,
Eriochrome black T Pb, Hg
Solochrome black T
2. Murexide or Ammonium Violet to Blue 12 Ca, Cu, Co
purpurate
3. Catechol-violet Violet to Red 8-10 Mn, Mg, Fe, Co, Pb
4. Methyl Blue Blue to 4-5 Pb, Zn, Cd, Hg
Yellow
Thymol Blue Blue to Grey 10-12
5. Alizarin Red to Yellow 4.3 Pb, Zn, Co, Mg, Cu
6. Sodium Alizarin sulphonate Blue to Red 4 Al, Thorium
7. Xylenol range Lemon to 1-3 Bi, Thorium
Yellow 4-5 Pb, Zn
5-6 Cd, Hg

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Instrumental methods of end point detection:

Spectrophotometric detection: The change in absorption spectrum when a metal ion of a
complexing agent is converted to the metal complex, or when one complex is converted to
another can usually be detected more accurately and in more dilute solution by
spectrophotometric than by visual methods
Amperometric titration: The effect of complex formation on the half-wave potential of an
ion is to render it more negative.
Potentiometric titration: Since disodium EDTA reacts preferentially with the higher valency
state of an ion.
High Frequency Titrator: This method is particularly suitable for dilute solutions, in some
cases with concentrations as low as 0.0002M. The ions may be titrated directly in buffered
solution or excess reagent can be added to the un-buffered solution and the liberated protons
titrated with standard alkali. Since buffer solution and other extraneous electrolytes reduce the
sensitivity of the titration, their concentration must be kept to a minimum.

ASSAY OF ALUM BY COMPLEXOMETRIC TITRATION

Preparation of 0.05 M Disodium EDTA Solution (Disodium Edetate 0.05 M)
Materials Required: Disodium ethylenediaminetetracetate : 18.6 g.
Procedure: Weigh accurately 18.6 g of disodium ethylenediaminetetracetae, dissolve in sufficient
DW in a 1 litre volumetric flask and make up the volume upto the mark.
Calculations:

Standardization of 0.05 M Disodium Edetate Solution

 Weigh accurately about 0.8 g of granulated zinc dissolve by gentle warming in 12 ml of dilute
hydrochloric acid and 5 drops of bromine water.
 Boil to remove excess bromine, cool and add sufficient DW to produce 200 ml in a
volumetric flask.

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 Pipette 20 ml of the resulting solution into a flask and neutralize carefully with 2N sodium
hydroxide.
 Dilute to about 150 ml with DW, add to it sufficient ammonia buffer (pH 10.0) to dissolve the
precipitate and add a further 5 ml quantity in excess.
 Finally add 50 mg of Mordant Black II mixture (mixture of 0.2 part Mordant Black II with
100 parts of NaCl)
 Titrate with the disodium edetate solution until the solution turns green.
 Each 0.003269 g of granulated zinc is equivalent to 1 ml of 0.05 M disodium ethylene
diamine tetra acetate.
Calculations:

Determination of Aluminium in Alum By Complexometric Titration

 Transfer alum solution (containing 40-50 mg Al) to conical flask.
 Dilute to about 100ml with distilled water.
 Add exactly 50mL of 0.05 M disodium EDTA solution.
 If solution is acidic add ammonia to bring pH to about pH 3-4 (check with indicator paper).
 Add 20 ml of acetate buffer.
 Heat the solution to boil and keep it boiling for 2-3 minutes. Wait till it cools down.
 Add 0.5 ml of ferrocyanide/ferricyanide solution and 3-4 drops of 3, 3'-dimethylnaphthidine
solution.
 Titrate with zinc solution till the color changes to pink. Titrate slowly and stir vigorously,
especially close to the end point.
 Reactions taking place during titration are - at first
Al3+ + EDTA4- → Al-EDTA-
(This is the slow part), then
Zn2+ + EDTA4- → Zn-EDTA2-
Which is fast enough for use in direct titration.

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Finally, we should mention reaction that is responsible for the end point detection - that is,
precipitation of the zinc ferrocyanide:
Zn2+ + Fe(CN)64- → Zn2Fe(CN)6
ASSAY OF CALCIUM GLUCONATE INJECTION BY COMPLEXOMETRIC
TITRATION
Preparation of 0.05 M Disodium EDTA Solution (Disodium Edetate 0.05 M)
Materials Required: Disodium ethylenediaminetetracetate : 18.6 g.
Procedure: Weigh accurately 18.6 g of disodium ethylenediaminetetracetae, dissolve in sufficient
DW in a 1 litre volumetric flask and make up the volume upto the mark.
Calculations:

Standardization of 0.05 M Disodium Edetate Solution

 Weigh accurately about 0.8 g of granulated zinc dissolve by gentle warming in 12 ml of dilute
hydrochloric acid and 5 drops of bromine water.
 Boil to remove excess bromine, cool and add sufficient DW to produce 200 ml in a
volumetric flask.
 Pipette 20 ml of the resulting solution into a flask and neutralize carefully with 2N sodium
hydroxide.
 Dilute to about 150 ml with DW, add to it sufficient ammonia buffer (pH 10.0) to dissolve the
precipitate and add a further 5 ml quantity in excess.
 Finally add 50 mg of Mordant Black II mixture (mixture of 0.2 part Mordant Black II with
100 parts of NaCl)
 Titrate with the disodium edetate solution until the solution turns green.
 Each 0.003269 g of granulated zinc is equivalent to 1 ml of 0.05 M disodium ethylene
diamine tetra acetate.
Calculations:

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 Dr. Puspendra Kumar

Determination of Calcium in Calcium gluconate injection By Complexometric Titration

 An accurately measured volume of the injection, equivalent to 0.8gm of Calcium
gluconate is taken in a titration flask and dissolved in water (150ml) and contains dil HCl
(5ml).
 To the acidified solution; NaOH (15ml) is added with murexide indicator (4mg), solution of
naphthol green (3ml).
 The reaction mixture is titrated with M/20 disod. EDTA until the solution is deep blue in
colour.
 1ml of M/20 disod. EDTA ≡ 0.02242gm of Ca gluconate

DETERMINATION OF HARDNESS OF WATER

Preparation of 0.05 M Disodium EDTA Solution (Disodium Edetate 0.05 M)
Materials Required: Disodium ethylenediaminetetracetate : 18.6 g.
Procedure: Weigh accurately 18.6 g of disodium ethylenediaminetetracetae, dissolve in sufficient
DW in a 1 litre volumetric flask and make up the volume upto the mark.
Calculations:

Standardization of 0.05 M Disodium Edetate Solution

 Weigh accurately about 0.8 g of granulated zinc dissolve by gentle warming in 12 ml of dilute
hydrochloric acid and 5 drops of bromine water.
 Boil to remove excess bromine, cool and add sufficient DW to produce 200 ml in a
volumetric flask.
 Pipette 20 ml of the resulting solution into a flask and neutralize carefully with 2N sodium
hydroxide.

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 Dr. Puspendra Kumar

 Dilute to about 150 ml with DW, add to it sufficient ammonia buffer (pH 10.0) to dissolve the
precipitate and add a further 5 ml quantity in excess.
 Finally add 50 mg of Mordant Black II mixture (mixture of 0.2 part Mordant Black II with
100 parts of NaCl)
 Titrate with the disodium edetate solution until the solution turns green.
 Each 0.003269 g of granulated zinc is equivalent to 1 ml of 0.05 M disodium ethylene
diamine tetra acetate.
Calculations:

Determination of Calcium and Magnesium ion to determine the hardness of water

 Water hardness due to Ca and Mg is expressed as the amount of Ca and Mg ions in ppm.
 Actually, the hardness is due to both Ca and Mg salts but these two are determined together
in the titration.
 The total Ca and Mg is titrated with standard EDTA solution using eriochrome blackT as
indicator.
Method:
 Disodium salt of EDTA has the general formula: Na2H2Y2.H2O, where Y is the
tetravalent anion of EDTA.
 When Ca is titrated with H2Y2-, a very stable complex is formed.

Ca2+ + H2Y2- CaY2- + 2H+

 Mg2+ forms a similar complex which is far less stable than the Ca complex.

 When a sample containing Ca and Mg ions is titrated with a solution of EDTA, the Ca 2+
are first complexed as CaY2-.

 As more reagent is added, all the Ca2+ is combined as complex. Mg ion forms MgY2-.
 The desired end point if the titration is the point at which all the Ca and Mg ions of the
solution have combined with the complexing agent.

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