Name: Dr. Pramod B.

Thakur
Class: T.Y.B.Sc
Subject: Analytical Chemistry
Title of Topic: Complexometric
Titrations
 T.Y.B.Sc.
Paper IV- USCH504
Analytical Chemistry-Unit-II
COMPLEXOMETRIC TITRATIONS
By Dr. P. B. Thakur
 COMPLEXOMETRIC TITRATIONS
General introduction
EDTA titrations
Advantages and limitations of EDTA as the titrant
Absolute and conditional formation constants of
Metal-EDTA complex
 Construction of Titration curve
Types of EDTA Titrations
Methods of increasing the selectivity of EDTA as a titrant
 Metallachromic indicators
 Theory Metallachromic indicators
Applications of Metallachromic indicators
 What is complex????
Complex consists of an metal ion surrounded
by molecules or anions.
How Complex forms????
Complex is formed by the combination of metal ion
with electron donating group or nucleophile.
Complexometric Titrations:
 A complexometric titration is technique of volumetric
analysis in which a soluble, undissociated, stiochimetric
complex is formed during the addition of titrant to the sample
solution.
 In Complexometric titration the formation of a colored
complex is used to indicate the end point of a titration.
 Complexometric titrations are particularly useful for the
determination of a mixture of different metal ions in solution.
 An indicator capable of producing an definite color
change is usually used to detect the end-point of the titration.
Which complexation reaction can be used as
a volumetric technique????
 The reaction which reaches equilibrium rapidly
after each portion of titrant is added.
 The reactions in which interfering situations do
not arise. e.g. The formation of several different
complexes of the metal ion with the titrant, during
the titration process.
 The reaction in which a indicator is capable of
locating equivalence point with fair accuracy is
available.
Complexation titrations are particularly useful for
the determination of a large number of metal ions in
solution. In practice, the use of EDTA as a titrant is
well established in such complexometric reactions.
EDTA Titrations:
What is EDTA???
 EDTA is Ethylene Diamine Tetra Acetic acid.
It has four carboxyl groups and two amine groups.
 Commonly EDTA is represented
in the acid form as H4Y.

EDTA = H4Y

Due to low solubility of acid form of EDTA in water,

its disodium dihydrate EDTA salt i.e. Na2H2Y.2H2O is used

disodium dihydrate EDTA

= Na2H2Y.2H2O
Different Forms of EDTA

EDTA =
H4Y
EDTA has four carboxyl groups and two amine groups.
EDTA is polydenated ligand as it donate its six lone pairs of
electrons for the formation of coordinate covalent bonds with
metal cations to form Metal-EDTA complex.

Metal-EDTA complex Metal-EDTA complex

 Role of pH in EDTA titrations
 EDTA titrations are carried out in buffered solution of

the metal ions to be estimated.

 The use of proper pH is important and is related to
the stability constant of a metal-EDTA complex.
E.g. Alkaline pH is required for the metals having
low stability constant.
Low Alkaline to mild acidic pH is required for
the metals having high stability constant.
 The dissociation reactions of acid form EDTA, H 4Y
are also pH dependant.
 pH is also an important criteria for the proper
functioning
Thus of important
it is very the indicator
to substance.
maintain the pH during
the EDTA titrations
 Advantages of EDTA as titrant:

1.ETDA form stable complex with various metal ions.

2.The complexation occurs in a single step and hence the
titration of the metal produce 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
all charge on the metal ions. The stoichiometry is hence same for
all metal ions. The reaction can be represented as:

Mn+ + H2Y-2 + H2O MY(n-4) + 2H3O+

 Limitations of EDTA as titrant:

1.Formation of insoluble hydroxides:

Many ETDA titrations are carried out under alkaline pH which
may lead to formation of insoluble hydroxieds or basic salts
that may compete with the complexation process .

2. Lack of selectivity:
Since EDTA forms stable complexes with most of the metal
ions, it lacks selectivity if it is used to estimate a single metal
cations from a solution of mixture of metal ions.
 Absolute formation constant
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.
If fully uprotonated form of EDTA (Y-4) is react with metal ion as follows:

M+n + Y-4 MY(n-4)+

Then absolute formation constant KMY is given as,

[MY(n-4)+]
KMY = ................................eq 1

[M+n] [Y-4]
KMY is also referred as absolute stability constant. Higher
the value of K , higher is the stability of complex formed.
Metal Cation KMY Log KMY
Mg2+ 4.9 X 108 8.69
Ca 2+
5.0 X 10 10
10.70
Group I
Sr2+ 4.3 X 108 8.63
Titrated in
Ba2+ 5.8 X 107 7.76 pH 8-11
Mn2+ 6.2 X 1013 13.79
Fe2+ 2.1 X 1014 14.33
Co2+ 2.0 X 1016 16.31 Group II
Ni2+ 4.2 X 1018 18.62 Titrated in
Cu2+ 6.3 X 1018 18.80 pH 4-8
Zn2+ 3.2 X 1016 16.50
Cd2+ 2.9 X 1016 16.46
Al3+ 1.3 X 1016 16.13
Pb2+ 1.1 X 1018 18.04
Hg3+ 6.3 X 1021 21.80
Group III
Fe 3+
1.3 X 10 25
25.1
V3+ 7.9 X 1025 25.9
Titrated in
Th4+ 1.6 X 1023 23.2
pH 1-4
 Conditional formation constant
In absolute formation constant only fully uprotonated form of EDTA (Y -4) is taken
consideration. EDTA is tetra protonic acid. It is represented as H 4Y. The four different
stages of dissociation of this tetra protonic acid can be represented as follows:
[H+] [H3Y-]
H4Y H+ + H3Y- Ka1 = = 1.0 X 10-2
[H4Y]
[H+] [H2Y-2]
H3Y- H+ + H2Y-2 Ka2 = = 2.2 X 10-3
[H3Y-]
[H+] [HY-3]
H2Y-2 H+ + HY-3 Ka3 = = 6.9 X 10-7
[H2Y-2]
[H+] [Y-4]
HY-3 H + + Y- 4 Ka4 = = 5.5 X 10-11
[HY-3]
Each of the equilibrium is pH dependent and Y-4 will predominates only in
solution of very high pH.
At lower pH value, the forms of EDTA HY-3 , H2Y-2 ,H3Y-1 , H4Y may also be
present. Then the total concentration of uncomplexed EDTA (C Y) is given by
sum of the all forms of EDTA

CY = [Y-4] + [HY-3] + [H2Y-2] + [H3Y-] + [H4Y]

[H+] [H3Y-] [H+] [H2Y-2]
[H4Y] = [H3Y-] =
Ka1 Ka2

[H+] [HY-3] [H+] [Y-4]

[H2Y-2] = [HY-3] =
Ka3 Ka4

Substituting the concentrations of the various species in terms of Ka1, Ka2, Ka3, Ka4 in
above equation and solving the equation for the fraction Y-4 form, we get

[Y-4] Ka1Ka2Ka3Ka4
=
CY [H+]4 + [H+]3 Ka1 + [H+]2 Ka1 Ka2 + [H+] Ka1 Ka2Ka3 + Ka1 Ka2Ka3Ka4
 We may now define α4 as the fraction of EDTA in Y-4 form
[Y-4]
i.e. α4 = or α4 . CY = [Y-4] ...........eq 2
CY
Substituting equation 1 in equation 2
[MY(n-4)+]
KMY =
[M+n] . α4 . CY

[MY(n-4)+]
KMY . α4 = = K’MY
[M+n] . CY
K’MY is known as conditional formational constant, or
conditional stability constant or effective stability constant
 Conditional formation constant (K’MY) is product of absolute
formation constant (KMY) and α4 .

K’MY = KMY . α4
 The Conditional formation constant (K’MY) is easily calculated
by knowing the absolute formation constant (KMY) and α4
value at the pH of solution.

 The Conditional formation constant (K’MY) is greater practical

use because it represents the actual tendency of EDTA to
form the complex with metal at the pH value of the solution.

 The values of Conditional formation constant (K’MY) varies with

pH because α4 vary with pH.
 Values of α4 for EDTA at different pH
pH α4
2.0 3.7 X 10-14
2.5 1.4X 10-12
3.0 2.5X 10-11
4.0 3.3X 10-9
5.0 3.5X 10-7
6.0 2.2X 10-5
7.0 4.8X 10-4
9.0 5.1X 10-2
10.0 3.5 X 10-1
11.0 8.5X 10-1
12.0 9.8X 10-1

As pH increases, α4 values also increases and Conditional

formation constant (K’MY) is also increases
 Due to such important role of pH in complex
formation with EDTA , normally the solution of metal
ions are buffered so that the pH will remain constant.

 In this way the Conditional formation constant (K’MY)

can be estimated and it is possible to calculate and
construct the titration curve from which it is possible
to judge the feasibility of the complexometric titration.

 The pH is often adjusted to as low a value as is

consistent with feasibility.

 The construction of the titration curve for metal-EDTA

titration can be given as below.
Titration curve for metal-EDTA titrations

In the Case of metal-EDTA titration, the EDTA is added to the

buffered solution of metal and pM is calculated by using
pM = -log10 [Mn+] during the titration. The obtained pM values
is plotted on Y-axis against the volume of EDTA solution
added on x axis. This curve give the point of inflexion at the
equivalence point. The curve of pM agaist volume of EDTA
added is known as Titration curve of metal-EDTA
titrations.
Example: Titration curve of Ca+2 with EDTA
 Example: Titration curve of Ca+2 with EDTA

Absolute formation constant (KMY) for CaY-2 is 5.0 X 1010 and

α4 at pH 10 is 0.35.

K’MY = KMY . α4 = 5.0 X 1010 X 0.35 = 1.8 X 1010

Solution:

 Take 10 cm3 of 0.01 M ca+2 solution buffered at pH 10 and

titrate with 0.01 M EDTA solution.

 Calculate the pCa at different stages of titration such as,

1. At the start of the titration

2. After addition of 1.0 cm3 of titrant EDTA
3. At the equivalence point
4. After addition of 11.0 cm3 of titrant.
1. At start of Titration:

At start of Titration when no titrant EDTA is added to the

solution, only Ca+2 , will be present in the solution.
The concentration of Ca+2 can be given as,

[Ca+2] = 0.01
pCa = -log10 [Ca+2] = -log10 [0.01] = 2.0

pCa = 2.0
2.09
2. At the addition of 1.0 cm3 of titrant:

When 1.0 cm3 of titrant EDTA is added to the solution, 1.0 cm3
Ca+2 will react with EDTA and it will form complex. The 9.0
cm3 of Ca+2 will remained unreacted in the solution and total
volume of solution will become 11 cm3.
The concentration of Ca+2 present in the solution can be given
as,
= 0.0082 M
[Ca ] = 0.01 X 9
+2

11

pCa = -log10 [Ca+2] = -log10 [0.0082] = 2.09

pCa = 2.09
3. At the equivalence point: (when 10 Cm3 of EDTA is added)
When 10.0 cm3 of titrant EDTA is added to the solution, 10.0
cm3 Ca+2 will react with EDTA and it will form complex and
total volume of solution will become 20 cm3.
The concentration of Complex [CaY-2] present in the solution
can be given as,
[CaY-2] = 0.01 X 10
= 0.005 M
20
At equivalence point, concentration of Ca+2 will be equal to the
concentration of EDTA . As EDTA is present in its all form.
So the concentration of EDTA is given by CY

[Ca+2] = CY
Conditional formation constant (K’MY) for CaY-2 is 108 X 1010,
Now Conditional formation constant (K’MY) is
[CaY-2]
K’MY = = 1.8 X 1010
[Ca2+]. CY

Since [Ca+2] = CY
[CaY-2]
K’MY = = 1.8 X 1010
[Ca2+]. [Ca+2]
By substituting,
K’MY = 1.8 X 1010
[CaY-2] = 0.005
In the above equation and we can calculate the concentration
of [Ca2+]
 0.005
1.8 X 1010 =
[Ca2+]2

0.005
[Ca2+] = 1.8 X 1010

[Ca2+] = 5.2 X 10-7

pCa = -log10 [Ca+2] = -log10 [5.2 X 10-7] = 6.28

pCa = 6.28
4. After the addition of 11 Cm3 of EDTA:
When 11.0 cm3 of titrant EDTA is added to the solution, 10.0
cm3 Ca+2 will react with EDTA and it will form complex and
1.0 cm3 of EDTA will remain excess in the solution. Total
volume of solution will become 21 cm3.

The concentration of Complex [CaY-2] present in the solution can

be given as,

[CaY-2] = 0.01 X 10
= 4.76 X 10-3 M
21
The 1.0 cm3 of EDTA is excess,
concentration of excess of EDTA present in the solution can be
given as,

[Excess of EDTA] = 0.01 X 1

= 4.76 X 10-4 M
21

The concentration of EDTA in the solution given by CY

CY = 4.76 X 10-4 M
 Conditional formation constant (K’MY) for CaY-2 is 1.8 X 1010,
Now Conditional formation constant (K’MY) is
[CaY-2]
K’MY = = 1.8 X 1010
[Ca2+]. CY
By substituting,
K’MY = 1.8 X 1010
[CaY-2] = 4.76 X 10-3
[CY] = 4.76 X 10-4 M

In the above equation and we can calculate the concentration

of [Ca2+]
 4.76 X 10-3
1.8 X 1010 =
[Ca2+] X 4.76 X10-4

4.76 X 10-3
[Ca2+] = 1.8 X 1010 X 4.76 X10-4

[Ca2+] = 5.55 X 10-10

pCa = -log10 [Ca+2] = -log10 [5.55 X 10-10] = 9.26

pCa = 9.26
 Table of pCa Value
Volume in Cm3 of 0.01 M
EDTA added pCa
0.0 2.0
1.0 2.09
5.0 2.48
10.0 6.28
11.0 9.26
12.0 9.56

When the pCa is plotted against volume of titrant added, it gives

the Familiar S shaped titration curve with sharp increse in the
curve in the value of pCa in the vicinity of the equivalence point.
Titration curve for Ca+2 - EDTA titrations

pCa

Volume of 0.01 M EDTA added

 Types of EDTA Titrations:

EDTA Titrations

Replacement/ Indirect
Direct Back Displacement/ Alkalimetric Titrations
Titrations Titrations Substitution Titrations
Titrations
 Direct Titrations:
 This is a direct determination of a metal ion by adding
standard EDTA titrant 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 prevent the precipitation of the hydroxide
of metal ion.
 Cu+2, Zn+2, and Ni+2 can be determine by using direct
titration method.
 Back Titrations:

 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 indicator.

ZnCl2, ZnSO4, MgCl2, MgSO4 is used as standard metal ion

solution.
 Back Titration Process

+ +
Sample Excess of Metal-EDTA Unreacted
Metal standard EDTA Complex standard EDTA
ion M1 M1-EDTA

Metal-EDTA Standard
Complex Metal ion M2
M2-EDTA
Replacement, Displacement or Substitutions Titrations:

 This is method, weak EDTA complex of another metal ion (M2)

is added to the solution of metal ion (M1) to be determined.

 Mg-EDTA & Zn-EDTA are frequently used weak EDTA

complex

 The weaker metal EDTA complex is replaced with strong

metal

EDTA complex.
 Replacement, Displacement or
Substitutions Titrations Process

+ +
Weak Strong Replaced
Sample Free metal
Metal-EDTA Metal-EDTA
Metal ion M2
Complex Complex
ion M1
M2-EDTA M1-EDTA

Standard
Metal-EDTA
EDTA solution
Complex
M2-EDTA
 Alkalimetric Titrations:

 This method, use the principle of liberation of free H+ ions

during the complexation.

 The reaction between metal ion and EDTA H2Y-2 produce H+.

M+n + H2Y-2 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 instrumental method.
 Alkalimetric Titrations Process

+ + 2H+
Sample standard EDTA Metal-EDTA Liberated H+
Metal H2Y-2 Complex ions
ion M+n MY(n-4)+

NaOH
Standard
Acid-Base Alkali solution
Titration product
 Indirect Titration:

 This method is used to determine the ions such as Halides,

phospates, and sulphates that do not form complex with EDTA .

 In the determination of sulphate ion, SO4-2 ion solution is

treated with excess of standard solution of Barium ion.

 The formed precipitate of BaSO4 is filtered off and unreacted

Barium ions present in filtrate is titrated with EDTA.

 In this way, we are able to indirectly determine the amount of

sulphate ion present in the sample solution.

 Indirect Titrations Process

+ + Ba+2
Anions Excess of BaSO4 Unreacted Ba+
like standard Barium Precipitate ions
SO4-2 solution

Standard
Ba-EDTA EDTA solution
Complex
 Methods of increasing the
selectivity of EDTA as Titrations

Methods

Chemical pH Masking Unmasking Kinetic

Separation Control Masking
 Chemical Separation
 In this technique, the selectivity is increases by
separating the species from other components from the
sample solution.

 The separated species is then dissolved in suitable

solvents and then titrated against EDTA using indicator.

 Eg: Ca+2, Mg+2, Ni+2 and Cu+2 ions can be first separated as
Ca-oxalate, Ni-DMG, Mg-ammonium phosphate and
Cu-thiocyanide.

 These precipitate are then dissolved in separate suitable

solvents and then titrate against EDTA using indicator.
 Chemical Separation

Ca+2 Mg+2

Ni+2 Cu+2

Ammonium
Oxalate DMG phosphate thiocyanide

Ca-oxalate Ni-DMG Mg-ammonium Cu-thiocyanide

precipitate precipitate Phosphate precipitate
Precipitate
Ca-oxalate Ni-DMG Mg-ammonium Cu-thiocyanide
phosphate

solvent solvent solvent

solvent
Ca+2 Ni+2 Cu+2
Mg+2

EDTA EDTA EDTA EDTA

Ca-EDTA Ni-EDTA Mg-EDTA Cu-EDTA

 Control of acidity of pH of the solution
 In this technique, the selectivity is increases by
controlling the pH of the solution.

 The conditional formation constant for metal-EDTA

complex 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.: Ca+2 can be determined in the presence of Mg+2 in

strongly alkaline solution (pH < 10).

 Trivalent ions loke Bi+3, Fe+3 can be selectively

determined from the solution of bivalent metal ions in
strongly acidic solution (pH ~ 2.
 Selectivity by pH Control

A+2 B+2 A+2 B+2

Ca+2
Mg +2

Bi+3 Fe+3

EDTA EDTA EDTA

At Alkaline At Alkaline
At Alkaline
pH < 10 pH ~2
pH ~2

Metal-EDTA Metal-EDTA Metal-EDTA

Complex Complex Complex
Ca-EDTA Bi-EDTA Fe-EDTA
 Use of Masking agent

 Masking is a process in which substance is prevented to

take part in the reaction without physical separation of it.
The reagent used in masking is known as masking agent.

 Cyanide ion is an effective masking agent for EDTA

titrations. It forms stable cyanide complex with the metal
cation like Cd, Zn, Hg, Cu, Co, Ni, Ag, Pt but does not
form
complex with alkaline earth metals like Mg, Ca etc as well
as Mn and Pb.

 Thus it is possible to determine Ca, Mg, Pb, Mn in the

presence of other metal cations by masking agents like
CN- ion
 Masking

Ca+2 Zn+2

Hg+2 Ni+2

CN-

Ca+2 Zn-CN Hg-CN Ni-CN

ions complex complex complex
 Masking CN-

Ca+2 Zn-CN Hg-CN Ni-CN

ions complex complex complex

EDTA
Masked complexes
Metal-EDTA Prevented to take part in
Complex reaction
Ca-EDTA
 Use of Demasking
 In this technique, the one of the cation is first masked
and remaining free cation is titrated with standard EDTA.

 Then previously masked cation is demasked by using

suitable reagent to get free cation.

 This free cation is then titrated by using standard EDTA.

 eg. Formaldehyde is used to demasked Zn-CN complex

[Zn(CN)4] + 4HCHO + 4H Zn+2 + 4HOCH2CN

 This free Zn+2 ion is then titrated by using standard EDTA.

 Thus it is possible to determine Zn in the presence of Ca.
 Demasking

Ca+2 Zn+2

Masking CN-

Ca+2 Zn-CN
ions complex
 Ca+2 Zn-CN
ions complex

Demasking
EDTA
Zn+2 ion
EDTA
Metal-EDTA
Complex
Ca-EDTA Metal-EDTA
Complex
Zn-EDTA
 Kinetic masking

 Some of the metal undergoes fast complexation some of

undergoes slow complexation with EDTA .

 Hence it is possible to titrate the metal ions which

undergoes fast complexation with EDTA in the presence
of those metal ions which undergoes slow complexation
with EDTA .

 eg. Fe+3 can be easily estimated in the presence of Cr+3 ,

because Cr+3 reacts slowly with EDTA to form complex as
compared to Fe+3.
 Kinetic masking

Fe+3 Cr+3

EDTA- EDTA-

FAST- SLOW

Metal-EDTA Metal-EDTA
Complex Complex
Fe-EDTA Cr-EDTA
Metallochromic
indicator

Theory and
Applications
 Metallochromic indicator
 The metallochromic indicators are organic compounds
which are capable of forming intensely coloured
complex with EDTA.
 This metal –indicator complex is weaker than the
Metal-EDTA complex and it has different colour than
uncomplexed indicator.
 During the course of titration, the metal ion from
metal –indicator complex is replaced to form
Metal-EDTA complex.
 Metallochromic Indicator

+
Sample Indicator Metal-Indicator
Metal Organic Weak Complex
ion Compound Colour 2
Colour 1

EDTA

Metal-EDTA
Strong Complex
Colour 3
Requirement for Metal ion indicator
1. The colour must be sufficiently intense, so that a
minimum 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.
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.
Theory of metal ion
indicators
The reaction corresponding to use of a metal ion indicator
in an EDTA titration can be represented as

M-In + EDTA M-EDTA + In

This reaction will take place only if the M-EDTA complex is
more stable than the M-In complex.

M + In M-In
Stability of the Metal-Indicator complex KIn, is given by the
equation [M-In]
KIn =
[M] [In]
Since, the indicator colour change also affected by the
hydrogen ion concentration, so it is convenient to
define the conditional indicator constant K’In which
varies with pH.

For small the error, K’In > 104 and the ratio of
conditional formation constant of the metal-EDTA
complex K’MY to K’In should be of the order 104 to
provide a good end point.
use of metal ion
indicators
Examples Of metal
ion indicators
 Eriochrome Black T

1.Chemically it is sodium salt of 1-(1-hydroxy-2

naphthylazo)-6 nitro-2-naphthol-4-sulphonic acid.

2. It is dark powder with a slight metallic luster

3. Eriochrome Black T (EBT) is abbreviated as H3D in
strongly acidic medium.
4. In basic pH it is present in dissociated form and
abbreviated as H2D-, HD-2 and D-3.
5. Different form and colour of EBT can be summarised as
follows:
EBT Acidic pH H3D Black

EBT pH- 6 H2D- Red

EBT pH- 7-11 HD-2 Blue

EBT pH > 12 D-3 Orange

In EDTA titrations, BDT forms red colour Metal-EDTA weak
red colour complex complex . As titration begins, EDTA will
replace indicator ion and it will form strong
Metal-EDTA blue colour complex.

Metal – Metal –
Indicator EDTA
EDTA
Metal + Indicator Weak Strong
Red colour Blue colour
Complex Complex

So, end point with EBT indicator is Red to blue.

 EBT Indicator

+
Sample EBT Indicator Metal-Indicator
Metal Weak Complex
ion Red Colour

EDTA

Metal-EDTA
Strong Complex
Blue Colour
 EBT is used to estimate Ca, Mg, Zn,
Mn, Cd, Hg, Pb, Cu, Al, Fe, Ti, Co, Ni and
Pt metal ions in Back and replacement
EDTA titrations.

 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

1.Chemically it is ammonium salt of purpuric acid. It’s

single charged ions has the following structure.

2. It is pinkish brown powder

Different form and colour of EBT can be summarised as
follows:

Indicator pH Colour

Murexide Up to pH 9 Reddish violet

Murexide pH- 9-11 Violet

Murexide pH > 11 Blue Violet

 Murexide Indicator
+
Sample Murexide Indicator Metal-Indicator
Metal Weak Complex
ion Red Colour

EDTA
Metal-EDTA
Strong Complex
Blue violet Colour

So end point of the titration using Murexide indicator is

Red to Blue violet
 Murexide is used to estimate Ca, Ni,
Co, Zn, Cd, Cu metal ions in EDTA
titrations.

 The indicator is prepared by dissolving

Merexide powder in water. Aqueous
solution of murexide is unstable hence it
must be prepared freshly.
 Pyrocatechol violet
OH

SO3H

OH

OH

Pyrocatechol violet is used to estimate

Al, Bi, Cd, Co, Cu, Ga, Fe, Pb, Mg, Mn, Ni,
Th, Ti, Zn metal ions in EDTA titrations.
 Xylenol orange
HOOC HOOC

HOOC N HOOC N

HO O

HO

CH3 SO3H

Xylenol orange is used to estimate Bi, Cd,

Pb, Sc,Th, Zn metal ions in EDTA
titrations.
 Pyridylazonaphthol (PAN)

N
N N

HO

Pyridylazonaphthol (PAN) is used to

estimate Cd, Cu, In, Sc, Zn, metal ions in
Back and replacement EDTA titrations.
Fast Sulphon Black F is
a complexometric
indicator used
with EDTA, almost
exclusively used
in copper complexatio
n determination IUPAC name: 1-hydroxy-8-(2-hydroxy-1-
naphthylazo)-2-(4-sulfo-1-naphthylazo)-
naphthalene-3,6-disulfonic acid

Fast Sulphon Black is purple when complexed with

copper, and turns green
when titrated against EDTA as the EDTA displaces it,
being the better complexing agent due to the chelate
effect.
Determination of Calcium:
Direct estimation of calcium is not possible because a
sharp endpoint is not obtained with the indicator,
Solochrome Black (Eriochrome Black T). Therefore, the
estimation is carried out by substitution titration.
The solution of Ca2+ ions is first treated with Mg-EDTA
complex and the liberated Mg+ ions are titrated with
standard EDTA solution using Solochrome Black as the
indicator During the titration, the following reactions take
place.

Ca2+ + H2Y2- ---------CaY2- + 2H+

Mg2+ + H2Y2- ---------→ MgY2- + 2H+
MgIn- + H2Y2- --------→ MgY2- + HIn2- + H+
(wine red) (blue)
The MgIn- complex is more stable than the
Ca-ln- complex but is less stable than the
Mg-EDTA complex.
As a result, the EDTA reacts first with Ca2+
ions, then with Mg2+ ions and lastly with
Mg-In complex.
This complex is wine red in colour and the
free indicator is blue in colour at a pH = 7 to
11.
The colour change at the endpoint is thus
wine red to pure blue.
Estimation of Copper:
Copper can be directly estimated by titration with
standard EDTA solution using Fast Sulphon Black F as
the indicator.
This indicator forms a red coloured complex with
copper in ammonical solutions.
To 25 cm3 of the copper ion solution in a conical flask
about 100 cm3 of de-ionised water is added followed by
5 cm3 concentrated ammonia solution and 5 drops of
the indicator solution.
This is then titrated against standard EDTA solution.
The endpoint is reached when the colour changes
from purple to dark green.
(1 mole EDTA = 1 mole Cu2+)
Example :
Titrating a 50.0 cm3 of a well water sample for total hardness
requires 4.0 cm3 of 0.01 M EDTA. Calculate the hardness of
the water as parts per million calcium carbonate