COMPLEXOMETRIC

TITRATION

By- Ms. Priyanka Wanjul

Asst. Professor
 COMPLEXOMETRIC
General introduction TITRATIONS
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
 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.
Complexes are compounds formed from
combination metal with ligands
of
(complexing ions
agents). A metal ionis an electron
deficient species while a ligand is an electron
rich, and thus, electron donating species. A
metal ion will thus accept electrons from a
ligand where coordination bonds are
formed. Electrons forming coordination
bonds come solely from ligands.
A ligand is called a monodentate if it donates a
single pair of electrons (like :NH3) while a bidentate
ligand (like ethylenediamine, :NH2CH2CH2H2N:)
donates two pairs of electrons.
Ethylenediaminetetraacetic acid (EDTA) is a
hexadentate ligand. The ligand can be as simple 2+
as
ammonia which forms a complex with
Cu2+, for example, giving the complex Cu(NH3)4 .
When the ligand is a large organic molecule having two
or more of the complexing groups, like EDTA,
the ligand is called a chelating agent and the
formed complex, in this case, is called a chelate.
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.

EDT = H4Y
A

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
Stability Constant
 Stability of Metal-Ligand Complexes
The stability of complexes is influenced by a number of
factors related to the ligand and metal ions.
1.Nature of the metal ion: Small ions with high charges
lead to stronger complexes.

2.Nature of the ligand: The ligands forming chelates

impart extra stability (chelon effect). For example the
complex of nickel with a multidentate ligand is more
stable than the one formed with ammonia.

3.Basicity of the ligand: Greater basicity of the

ligand results in greater stability of the complex.

14
4.Size of chelate ring: The formation of five- or
six - membered rings provides the
maximum stability.

5.Number of metal chelate rings: The stability of

the complex is directly related to the
number of chelate rings formed between the
ligand and metal ion. Greater the number of
such rings, greater is the stability.

7. Steric effects: These also play an

important role in the stability of the
complexes.
 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, H4Y are also pH
dependant. pH is also an important criteria for the proper functioning
of the indicator substance.

Thus it is very important to 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.
1. The Metal-EDTA complexes are all water soluble and hence
all studies can be performed in aqueous media.
1. 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:

+ H2Y-2 + H2O + 2H3O+

Mn+ MY(n-4)
 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 hydroxides 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 unprotonated form of EDTA (Y -4) is
react with metal ion as follows:
+n
+ -4 (n-4)+
M Y MY
Then absolute formation constant KMY is given as,

KMY = [MY(n-4)+]

[M+n] [Y-4]

KMY is also referred as absolute stability constant. Higher the

value of KMY, higher is the stability of complex formed.
Metal Cation KMY Log KMY
4.9 X 108 8.69
Mg2+
5.0 X 1010 10.70
Group I
Ca2+
4.3 X 108 8.63 Titrated in
Sr2+
5.8 X 107 7.76 pH 8-11
Ba2+
6.2 X 1013 13.79
Mn2+
2.1 X 1014 14.33
Fe2+
2.0 X 1016 16.31 Group II
Co2+
4.2 X 1018 18.62 Titrated in
Ni2+
Cu2+
6.3 X 1018 18.80 pH 4-8
3.2 X 1016 16.50
Zn2+
2.9 X 1016 16.46
Cd2+
1.3 X 1016 16.13
Al3+
1.1 X 1018 18.04
Pb2+
6.3 X 1021 21.80
Hg3+ Group III
1.3 X 1025 25.1
Fe3+
7.9 X 1025 25.9
Titrated in
V3+
1.6 X 1023 23.2
pH 1-4
 Conditional formation constant
In absolute formation constant only fully unprotonated 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
follows:
represented as [H+] [H3Y-]
Ka1 =
H 4Y +
+ H 3Y
-
[H4Y]
H

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

[H+] [HY-
+ HY-3 Ka3 = 3]
H2Y-2 H+
[H2Y-2]

Ka4 [H+] [Y-4]

=
HY-3 H + + Y- 4 [HY-3]
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.

Instrumental methods used for end point detection in

Complexometric titrations are : Spectrometric
analysis, Ampheromtric analysis, Potentiometric analysis
 Sequestering agent
It is a chelating agent that forms water soluble complexes
with bi- or poly-valent metal ions.
Thus although the metal remains in solution, they fail to give
normal ionic reactions.
They form molecule in which the ions are held so securely
(sequestered) that they can no longer react.
Eg. EDTA is a typical sequestering agent and versatile
sequestering agent and versatile complexing agent.

EDTA has following properties:

• It has low price
• Very stable sequestering agent
• Forms chelates with nearly all metal ions
• Complex formation is quantitative and instantaneous
• Complex is more stable and water soluble
 Metallochromic indicator (pM 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.
Requirement for Metal ion indicator
1. The colour must be sufficiently intense, so that minimum
a
amount of indicator can be used.
2. The color 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
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

KIn = [M-In]
[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.
Examples Of metal ion
indicators
Eriochrome Black T [(Mordant black II), Solochrome black , EBT]

Chemically it is sodium salt of 1-(1-hydroxy-2 naphthylazo)-5 nitro-

2-
naphthol-4-sulphonate.

It is dark powder with a slight metallic

luster

EBT Acidic pH H3D Black

EBT pH- 6 H2D- Red
EBT pH- 7-11 Blue
HD-2
EBT pH > 12 Orange
D-3
 It has blue color at pH 10 and complex has red color at
pH 10
 EBT is used to estimate Mg, Ca, Zn, Cd gives excellent
results.
Hg, Pb, Mn
Cu, Al, Ti, Co, Ni and Pt metal form pre-stable
complexes with the dye than with the edetate
 A mixture of 0.2% Mordant black-II with 100 parts of
sodium chloride is employed as indicator
Murexide (Ammonium purpurate)
Murexide is used to estimate Ca, Ni, Co, Zn, Cd, Cu
metal ions in EDTA titrations.
 Mixture of 0.2% dispersed in sodium chloride is used
for determination of calcium at pH 12
 Complex of calcium-Murexide gives blue violet color
while indicator solution has red violet color
 Gives better result upon incorporation with 0.5% of
naphthol green
 Xylenol orange
3,3′-Bis[N,N-bis(carboxymethyl)aminomethyl]-o-
cresolsulfonephthalein tetrasodium salt
HOOC HOOC

HOOC N HOOC N

HO O

•Yellow color- in absence of metal indicators

• Prepared by mixing 1 part of indicator in 99
HO
parts of potassium nitrate
CH3 SO3H
• Alternatively 0.1% solution in 50% alcohol
is used
• Gives red-violet color with Hg, Pb, Zn
metals in acidic solution

Xylenol orange is used to estimate Bi, Cd, Pb, La,Th, Zn

metal ions in EDTA titrations.
 Pyridylazonaphthol (PAN)

1-(2-Pyridylazo)-2-naphthol (PAN)

N •Gives red color in presence of

N N
copper ions and yellow color in
absence of copper ion
H • Generally 0.1% solution in alcohol
O
is used as an indicator

Pyridylazonaphthol (PAN) is used to estimate Cd, Cu,

In, Sc, Zn, metal ions in Back and replacement EDTA
titrations.
 Calmagite
1-(1-hydroxyl-4-mrthyl-2-phenylazo)-2-napthtol-4
sulphonic acid

• Stable in aqueous solutions

• Used in place of Eriochrome Black T
• Blue color of calmagite at pH 10 changed to red
by addition of Mg2+
• 0.05 g of the calmagite in 100 cm3 of water is
employed as indicator & it is stable for a year.

Calmagite is used to estimate Mg, Ca, metal ions

 Catechol Violet (Pyrocatechol)

benzene-1-2-diol or 1,2-dihydroxybenzene
H
O
H • It forms highly colored complex with wide range
O
of metals
• Complexes with metals are blue in color in acidic
solution
• Thorium complex at pH 3 & Bismuth complex at
pH 1.5 are stable
• Mg, Mn, Co, Zn, Ca, Cd can be titrated at pH
range of 4-7.
•0.1% solution in water is employed as an indicator

Catechol violet is used to estimate Th, Bi,Mg, Mn, Co,

Zn, Ca, Cd metal ions
Calcon (Mordant Black 17, Solochrome dark blue)

Sodium 1-(2-hydroxy-1-naphthylazo)-2-napthol-4-sulphonate

•Gives purple red color with calcium ion in alkaline solution & in
absence of metal ion gives blue color

• Employed as calcon mixture which is one part of calcon & 99 parts

of sodium chloride
 Mordant Red 7
Sodium 2-hydroxy-1-(5 hydroxy-3-methyl-1-phenyl-4-
pyrazolylazo)-2-naphthalein-4-sulphonate.

•Gives bluish violet color with nickel & green in presence of excess
EDTA solution

• 0.1% solution is employed.

 Fast sulphon black F
Sodium salt of 1-hydroxy-8-(2-hydroxynaphthylazo)-2-
(sulphonaphthylazo)-3,6 disuphonic acid

• Cu2+ ions can be determined in ammoniacal solution or pyridine, the

reaction is specific and color change is from magenta(pinkish-red) or
pale blue (depend on conc. of Cu2+ ions) to bright green.

• Cd, Pb, Ni, Zn, Ca & Ba can be determined

• 0.5% aqueous solution is employed.

 Types of EDTA Titrations:

EDTA Titrations

Direct Back Replacement/ Alkalimetric Indirect

Titrations Titrations Displacement/ Titrations Titrations
Substitution
Titrations
 Direct Titrations:
 This is a direct determination of a metal ion by
adding
standard EDTA titrant to sample solution.
the

+ [ Metal-EDTA ]
Metal ion + EDTA
 The complex
solution containing the metal ion is buffered to the
desired
pHand 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
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.

Al+3, Co+2, Pb+2, Mn+2, Hg+2 and Ni+2 can be determine by

using Back titration method

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.
The equivalent amount of metal M2 freed from the weaker
complex can be titrated with standard EDTA solution.
This method is useful for the determination of Ca+2 ion.
 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+.
+ + 2H+
M+n H2Y-2 MY(n-4)+
 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.
 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.

 Methods of increasing the
selectivity of EDTA as Titrations

Methods

Solvent
Extraction
Masking Demasking pH control Classical Kinetic
separation Masking
Use of masking and demasking agents:

Masking agents act either by precipitation or by

formation of complexes more stable than the
interfering ion-EDTA complex. Masking is a process
in which substance is prevented to take part in
the reaction without physical separation of it. he
reagent used in masking is known as masking agent

a)Masking by Precipitation

b)Masking by Complex formation

a) 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,
-8-hydroxy quinoline for many heavy metals.
-Thioglycerol is used to mask Cu by precipitation in the
assay of lotions containing Cu and Zn.
 b) Masking by complex formation
1. Potassium cyanide reacts with silver, copper, mercury,
iron, zinc, cadmium, cobalt and nickel ions to form
complexes in alkaline solution
2. 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.
3. Tiron (disodium catechol-3,5-disulphonate) will mask
aluminium and titanium as colourless complexes.
Iron forms highly coloured complex
4. Triethanolamine [N(CH2.CH2.OH)3] forms a
colourless complex with aluminium, a yellow
complex with iron(III), the colour of which is almost
discharged by adding sodium hydroxide solution,
and a green manganese(III) complex oxidizes mordant
black-II.
5. Ammonium Fluoride: Used to mask aluminium, iron
and titanium by complex formation

6. Ascorbic Acid: is a convenient reducing agent for iron

(III) which is then masked by complexing as the very
stable hexacyanoferrate (II) complex. This latter is
more stable and less intensely coloured than the
hexacyanoferrate (III) complex.
 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 damasked by using
suitable reagent to get free cation. This free cation is then
titrated by using standard EDTA.

Formaldehyde ,chloral hydrate and methanol acetic

acid mixture (3:1): use to demask cyanide complexes
of cadmium and zinc
eg. Formaldehyde is used to damasked Zn-CN
complex
[Zn(CN)4] + 4HCHO + 4H +2
+ 4HOCH2CN
Zn
(Hydroxy ACN)

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

Thus it is possible to determine Zn in the presence of Ca.
 Separation of Cu, Cd and Ca:
 Step-I :Direct titration of the mixture with EDTA gives the sum
of the tree metals
[Ca Cd Cu ]+ EDTA Ca-EDTA Cd-EDTA Cu-EDTA

 Step-II : Cu and Cd may be masked with the addition of cyanide to

the solution, leaving only Ca ion.
[Cu ] + Cyanide ion Cu-Cyanide Complex

[Cd ] + Cyanide ion Cd-Cyanide Complex

EDTA
[Ca ] + Cyanide ion No reaction Ca-EDTA
 Separation of Cu, Cd and Ca:
 Step-III :Formaldehyde or chloral hydrate is added to the
cyanide containing mixture only Cd is demasked and the EDTA
titrates the sum of Ca & Cd.
Cd-cyanide complex+ HCHO Cd+

Cu-Cyanide Complex + HCHO No reaction

[Ca Cd ] + EDTA Ca-EDTA Cd-EDTA

 Control of acidity of pH of the solution
In this technique, the selectivity is increases by controlling the pH
of the solution. That 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.: +2
can be determined in the presence in
Ca Mg+2
strongly alkaline
ofsolution (pH < 10).

Trivalent ions like Bi+3, Fe+3 can be selectively determined

from the solution of bivalent metal ions in strongly acidic solution
(pH ~ 2).
 Classical 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 (Nickel (dimethylglyoximate)), Mg-
ammonium phosphate and Cu-thiocyanide.

These precipitate are then dissolved in separate suitable

solvents and then titrate against EDTA using indicator.
 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.
 Solvent Extraction
Zinc can be separated from copper and lead by addition of
excess of ammonium thiocyanate solution and extracting
the resulting zinc thiocyanate with isobutyl methyl ketone.

 Extract is diluted with water and the zinc content is

estimated by EDTA titration
 Applications of Complexometric Titrations
Complexometric titrations have been employed with success for
determination of various metals like Ca, Mg, Pb, Zn, Al, Fe, Mn, Cr
etc. in different formulations that are official in I.P., and also for the
determination of Hardness of water.

Determination of Calcium in different formulations: Calcium

can be determined in almost every formulation by EDTA-titrations.
e.g.- Five membered heterocyclic rings are formed with EDTA,
which are stain-free, and thus highly stable.
Assay of CaCO3
Calcium Lactate tablets
Calcium Lactate injection
Calcium Gluconate
Calcium Gluconate injection
Calcium Gluconate tablet

Determination of Magnesium: for the assay of Mg stearate and Mg

sulphate

Determination of Hardness of Water: Water hardness is due to Ca

and Mg (Amount of Ca and Mg ions in ppm) .Actually, the hardness is
due to both Ca and Mg salts but the two are determined together in the
titration.
Direct titrations of official drugs with disodium Edetate (0.05M)
Back titrations of official compounds with disodium Edetate
Replacement titrations of the official compounds with
disodium Edetate
 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 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. 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,
[Ca+2] = 0.01 X 9 = 0.0082 M
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
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
K’MY = = 1.8 X 1010
[Ca 2+].-2[Ca+2]
[CaY ]
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
[Ca2+] = 1.8 X 1010
0.005

[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 pCa
EDTA added
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