AC 101

Unit 1
Titrimetric analysis
Analysis:
Qualitative
Quantitative
Gravimetric
Volumetric/ Titrimetric

Definition

It is the quantitative analysis carried out for determining

the concentration of any unknown solution whose fixed
volume will react with the definite volume of known/
standard solution. Concentration can be determined by
applying law of normality.
N1 V 1 = N 2 V 2
 Pre-requirements for the Titration

• Chemical reaction must be quick, quantitative and take

place according to the reaction equation
• Standard solution must have a defined concentration that
can be determined exactly (titer)
• It must be possible to determine a clear endpoint of the
titration
• The endpoint of the titration should agree with the
equivalence point or be very close to it.

OH- + CO32- == H2O + HCO3- === H2CO3==H2O + CO2

Some terms used in volumetric titrimetry
•Titriation: A process in which a standard reagent is added to a
solution of an analyte until the reaction between the analyte and
reagent is judged to be complete.
• Equivalent point: the point in a titration when the amount of
added standard reagent is exactly equivalent to the amount of
analyte.
• End point: the point in a titration when a physical change
occurs that is associated with the condition of the chemical
equivalence.
• Indicators are often added to the analyte solution to produce an
observable physical change at or near the equivalence point.
• Titration error (Et) : the difference in volume or mass between
the equivalence point and the end point Et = Vep – Veq

Vep: the actual volume of reagent required to reach the end

point

Veq: the theoretical volume to reach the equivalence point

Indicators • Physical change: the appearance or disappearance

of a color, the change in color, the appearance or

disappearance of turbidity).

Standard solution: A reagent of exactly known concentration

that used in a titrimetric analysis
Primary Standards
◎Primary Standard: A highly purified compound that serves
as a reference material in volumetric and mass titrimetric
method
1. High purity
2. Atmospheric stability
3. Absence of hydrate water
4. Modest cost
5. Reasonable solubility in the titration medium 6.
Reasonably large molar mass

Secondary standard:
Standard Solution
1. Be sufficiently stable
2. React rapidly
3. React more or less complete
4. Undergo a selective reaction
Different ways of expressing the concentration of the
solution
The amount of the substance present in the definite
quantity of the solution is called concentration of the
solutions.
The concentration of the solution can be expressed in any
of the following ways.

Molarity (M) = moles/litre or mmoles/mL

Normality(N) = equivalence/litre or meq/mL

Formality(F) = is identical to molarity

Molality(m) = moles/1000g solvent

• Percentage strength means number of parts of solute in 100
parts of solution which is expressed in three different ways:
a. % in weight by weight (w/W):
b. % in weight by volume (w/V):
c. % in volume by volume (v/V):
Type of Titrations
Classified into four types based on type of reaction involved;
1. Acid-base titrations, in which an acidic or basic titrant
reacts with an analyte that is a base or an acid
2. Complexometric titrations, involving a metal-ligand
complexation reaction.
3. Redox titrations, where the titrant is an oxidizing or
reducing agent.
4. Precipitation titrations, in which the analyte and titrant
react to form a precipitate.
•Neutralization reaction is when an acid and a base react
to form water and a salt.
It involves the combination of H+ ions and OH- ions to
generate water.
When a strong acid neutralizes a strong base, the pH of
the salt solution will always be 7.
When a strong acid neutralizes a weak base, the resulting
solution's pH will be less than 7.
When a strong base neutralizes a weak acid, the resulting
solution's pH will be greater than 7
 THEORY OF INDICATORS:

 An indicator is a substance which is used to determine the

end point in a titration.

 In acid-base titrations, organic substances (weak acids or

weak bases) are generally used as indicators.

They change their color within a certain pH range.

 The colour change and the pH range of some common
indicators are tabulated below:

Indicator pH range Colour change

Methyl orange 3.2-4.5 Pink to yellow

Methyl red 4.4-6.5 Red to yellow

Litmus 5.5-7.5 Red to blue

Phenol red 6.8-8.4 Yellow to red

Phenolphthalein 8.3-10.5 Colourless to pink

 Theory of acid-base indicators:

Two theories have been proposed to explain the change of

colour of acid-base indicators with change in pH.

1. Ostwald's theory: According to this theory:

(a) The colour change is due to ionisation of the acid-base

indicator. The unionised form has different colour than the
ionised form.

(b) The ionisation of the indicator is largely affected in acids

and bases as it is either a weak acid or a weak base.
Considering two important indicators phenolphthalein (a weak
acid) and methyl orange (a weak base), Ostwald theory can be
illustrated as follows:

Phenolphthalein: It can be represented as HPh. It ionises in

solution to a small extent as:

HPh ↔ H+ + Ph-
Colourless Pink
The undissociated molecules of phenolphthalein are
colourless while Ph- ions are pink in colour.
• In presence of an acid the ionisation of HPh is practically
negligible as the equilibrium shifts to left hand side due to
high concentration of H+ ions. Thus, the solution would
remain colourless.
• On addition of alkali, hydrogen ions are removed by OH -
ions in the form of water molecules and the equilibrium
shifts to right hand side.
• Thus, the concentration of Ph- ions increases in solution
and they impart pink colour to the solution.
Methyl orange: It is a very weak base and can be
represented as MeOH. It is ionized in solution to give Me +
and OH- ions.
MeOH ↔ Me+ + OH-
Yellow Red
• In presence of an acid, OH- ions are removed in the form of
water molecules and the above equilibrium shifts to right
hand side.
• Thus, sufficient Me+ ions are produced which impart red
colour to the solution. On addition of alkali, the
concentration of OH- ions increases in the solution and the
equilibrium shifts to left hand side, i.e., the ionisation of
MeOH is practically negligible. Thus, the solution acquires
the colour of unionised methyl orange molecules, i.e.,
yellow.
This theory also explains the reason why phenolphthalein is
not a suitable indicator for titrating a weak base against
strong acid.
• The OH- ions furnished by a weak base are not sufficient to
shift the equilibrium towards right hand side considerably,
i.e., pH is not reached to 8.3.
• Thus, the solution does not attain pink colour.
Similarly, it can be explained why methyl orange is not a
suitable indicator for the titration of weak acid with strong
base.
Quinonoid theory: According to this theory:
(a) The acid-base indicators exist in two tautomeric forms
having different structures. Two forms are in equilibrium. One
form is termed benzenoid form and the other quinonoid form.

Benzenoid form Quinonoid form

(b) The two forms have different colors. The color change in
due to the interconversation of one tautomeric form into
other.
(c) One form mainly exists in acidic medium and the other in
alkaline medium.
Phenolphthalein

C14H20O4
Phenolphthalein has benzenoid form in acidic medium and
thus, it is colourless while it has quinonoid form in alkaline
medium which has pink colour.

OH-

H+

Benzenoid form Quinonoid form

Acidic medium Alkaline medium
Colourless Pink
H2In In2-
Functional groups present in Phenolphthalein and methyl
orange and its solubility in water
Methyl orange has quinonoid form in acidic solution and
benzenoid form in alkaline solution. The color of benzenoid
form is yellow while that of quinoniod form is red.

+
Selection of suitable indicator or choice
of indicator
The neutralisation reactions are of the following four types:
(i) A strong acid versus a strong base.
(ii) A weak acid versus a strong base.
(iii) A strong acid versus a weak base
(iv) A weak acid versus a weak base
In order to choose a suitable indicator, it is necessary to
understand the pH changes in the above four types of
titrations. The change in pH in the vicinity of the
equivalence point is most important for this purpose The
curve obtained by plotting pH as ordinate against the
volume of alkali added as abscissa is known as
neutralisation or titration curve.
In each case 25 mL of the acid (N/10) has been titrated
against a standard solution of a base (N/10). Each titration
curve becomes almost vertical for some distance and then
bends away again. This region of abrupt change in pH
indicates the equivalence point. For a particular titration,
the indicator should be so selected that it changes its
colour within vertical distance of the curve.
• Strong acids and bases dissociate 100% in solution
• All [H+] can react with all [OH-] to make water and
neutralize at pH =7
• No side reactions occurring here
pH curve of strong acid (say
HCI) and strong base (say
NaOH) is vertical over almost
the pH range 4-10. So the
indicators phenolphthalein
(pH range 8.3 to 10.5), methyl
red (pH range 4.4-6.5) and
methyl orange (pH range 3.2-
4.5) are suitable for such a
titration.
pH curve of weak acid (say
CH3COOH of oxalic acid) and
strong base (say NaOH) is
vertical over the
approximate pH range 7 to
11. So phenolphthalein is
the suitable indicator for
such a titration.
 pH curve of strong acid (say
HCl or H2SO4 or HNO3) with a

weak base (say NH4OH) is

vertical over the pH range of 4
to 7. So the indicators methyl
red and methyl orange are
suitable for such a titration.

pH curve of weak acid and weak

base indicates that there is no
vertical part and hence, no
suitable indicator can be used
for such a titration. Titration of
soluble carbonate with strong
acid.
pH curve of sodium carbonate with HCI shows two inflection
points. First inflection point (pH 8.5) indicates conversion of
carbonate into bicarbonate.
Na2CO3 + HCI → NaHCO3 + NaCl
As the inflection point lies in the pH range 8 to 10,
phenolphthalein can be used to indicate the above
conversion.
The second inflection point (pH 4.3) indicates the following
reaction:
NaHCO3 + HCI → NaCl + CO2 + H2O
As the point lies between 3 to 5, methyl orange can be used.
 Alkalimetry
Alkalinity is primarily a way of measuring the acid
neutralizing capacity of water.

There are three sources of alkalinity in water samples

Hydroxide Alkalinity OHˉ
Carbonate Alkalinity CO32-

Bicarbonate Alkalinity HCO3ˉ

Total Alkalinity is the sum of all

Equations
1. H+ + OH- H2O (neutral)

2. H+ + CO32- HCO3ˉ (slightly basic)

HCO3ˉ + H+ H2CO3 (acidic)

3. H+ + HCO3ˉ H2CO3 (acidic)

 COMPLEXOMETRIC TITRATION
It is the type of volumetric analysis involving the formation of
complexes which are slightly ionized in solution, like weak
electrolyte and sparingly soluble salt.
• Complex is formed by the reaction of metal ion (Mn+, an
acceptor, a central atom or a cation)) with Ligand (L)
The formation of a colored complex is used to indicate the
end point of a titration.
 M+ + L ML
Ag+ + 2 CN- [Ag(CN)2]-
Cu2+ + 4 CN- [Cu(CN)4]2-
Ag+ + 2 NH3 [Ag(NH3)2]+
• Central metal atom = acts as Lewis acid (electron acceptor)
• Ligand = acts as Lewis base (electron donor)
• Coordinate bond (dative) = The bond formed between
central metal atom (ion) (acceptor) and the Ligand (donor)
Dative bond is similar to covalent bond (formed of two
electrons) But in dative bond the electrons pair are
donated from one atom to the other. The atom gives
electron pair is known as donor, while the atom accept
electron pair is known as acceptor. The bond is
represented by an arrow ( ) from donor to acceptor.
 Types of complexing agents (Classification of ligands
according to the no. of sites of attachment to the metal ion)
• Unidentate (Monodentate) Ligand or "Simple Ligand" • The ligand
attached to metal at one site e.g. H2O , NH3 , CN - , Cl- , I - , Br - ,
(i.e. forming one coordinate bond, or capable of donating one
unshared pair of electrons)
• Bidentate Ligand The ligand attached to metal at two sites.

Tridentate Ligand: The Ligand attached to metal at 3 sites

 Chelation
• Chelate: It is a complex formed between the ligand
containing two or more donor groups and metal to form ring
structure. (heterocyclic rings or chelate rings).
• Chelating agents: organic molecules containing two or
more donor groups which combine with metal to form
complex having ring structure.
• Chelates are usually insoluble in water but soluble in
organic solvent.
• Sequestering agent : Ligands which form water soluble
chelates e.g. EDTA.
 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 H 4Y.

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 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.
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+

 Metallochromic indicator
 The metallochromic indicators are organic compounds which
are capable of forming intensely coloured complex with metal.
 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
+ Indicator in
free state (diff
 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]
 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 H3 D Black

EBT pH- 6 H2D- Red

EBT pH- 7-11 HD-2 Blue

EBT pH > 12 D-3 Orange

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

Metal – EDTA Metal –

Metal Indicator Indicator EDTA
+ Weak Complex
Red colour colorless
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
colorless
 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

N1V1=N2V2 N1xeq. Wt of CaCO3= Total hardness of water
Colour changes with EBT
Ethylene diamine tetraacetic acid (EDTA) is used as chelator (Hexadentate).
EDTA has six potential sites for bonding a metal ion; the four carbonyl groups and
two amino groups.
Acidic properties of EDTA: EDTA is a hexaprotic system. The relative amounts of
EDTA species H4Y, H3Y, H2Y2-, HY3- and Y4- vary as a function of pH.
Complexes of EDTA and Metal Ions:
Mn + + Y4- MY (n-4)+
 Redox Titrations

involves reaction between an oxidant and reductant

where both of them undergo a change in oxidation state

Eg.

KMnO4 + Fe2+ + H+  Mn2+ + Fe3+ + H2O

Here,
Mn gets reduced from +7 to +2 oxidation state and

Fe gets oxidized from +2 to +3 state.

 Redox reactions
Oxidation and reduction always occur together/simultaneously.
-
Oxidation  release of electrons Red – z e  Ox
-
Reduction  acceptance of electrons Ox + z e  Red

Most redox reactions are pH-dependent. This is why titrations

are usually carried out in acidic solutions (participation of
protons)
 Types of Redox titrations

1. Permanganometry 1. Self indicator

2. Internal indicator
2. Dichromate Titrations 3. External indicator
4. Adsorption indicator
3. Iodine titrations

Iodimetry

Iodometry
 Permanganometry
KMnO4 is used as titrant. The redox property of KMnO 4 is pH
dependent

In strongly acidic condition:

KMnO4
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O K2Cr2O7
Iodine
In moderately alkaline condition:

MnO4- + 2H2O + 3e-  MnO2 + 4OH-

In strongly alkaline condition:

MnO4- + e-  MnO42-

Eg. Oxalate with permanganate

5 C2O42- + 2 MnO4- + 16 H3O+  2 Mn2+ + 10 CO2 + 24

H2 O
Some important points:

1. For acidification of KMnO4 solution only H2SO4 is used.

1. HCl can not be used as some of the KMnO4 will oxidize HCl to Cl2 gas.

2. HNO3 can nit be used as it itself is a strong oxidizing agent

2. KMnO4 is not a primary standard

3. It can be standardized using a suitable primary standard

such as oxalic acid or Mohr‘s salt(Ferrous ammonium
sulfate, FAS).

4. It is self indicator
Dichromate titrations
Potassium dichromate is used as titrant
Cr2O72- + 14H+ + 6e-  2Cr3+ + H2O

K2Cr2O7 is an excellent primary standard unlike KMnO4

Eg. Iron(II) with dichromate

6 Fe2+ + Cr2O72- + 14 H3O+  2 Cr3+ + 6 Fe3+ + 21 H2O

Some important points:
1. It is less powerful oxidizing agent than KMnO4.
2. It is excellent primary standard
3. For acidification of H2SO4 and HCl both can be used.

4. Indicator: A dilute solution of K2Cr2O7 has a faint orange

colour and its reduction product chromium (III) is light
green in colour. So it can not act as self indicator.
5. Internal indicator: eg diphenylamine
6. External indicator: Potassium ferricyanide, K3Fe(CN)6
Redox indicators are compounds which have different colours in the oxidized and
reduced forms.

Inox + n e = Inred
They change colour when the oxidation potential of the titrated solution reaches a
definite value:
E = E° /n log [InOX]/[Inred]

When [Inox] = [Inred] , E = E°

Indicator colours may be detected when: [Inox]/[Inred] = 1/10 or 10/1 hence,

Indicator range: E = E°In ± /n
 Iodometry
titrations where liberated iodine from sample is
titrated with a suitable reductant MnSO4 , KI + KOH+
NaN3 Mn(O)OH2=brown color H2SO4= [O] + KI=I2
Examples back-titration
- +
Hydrogen peroxide H2O2 + 2 I + 2 H  I2 + 2 H2O
- - +
Iodate IO3 + 5 I + 6 H  3 I2 + 3 H2O
- - +
Periodate IO4 + 7 I + 8 H  4 I2 + 4 H2O
Lead dioxide PbO2 + 4 HCl  PbCl2 + 2 H2O + Cl2
Cl 2 +2 KI  I2 + 2 KCl
Chlorate KClO3 + 6 HCl  KCl + 3 H2O + 3 Cl2
3 Cl 2 + 6 KI  3 I2 + 6 KCl
2+ - +
Copper 2 Cu + 2 I  2 Cu + I2
- + 3+
Dichromate K2Cr2O7 + 6 I + 14 H  2 Cr + 3 I2 + 7 H2O
- + 2+
Permanganate 2 KMnO4 + 10 I + 16 H  2 Mn + 5 I2 + 8 H2O
 Iodimetry
these are titrations which are performed with std
solution of iodine as titrant
Examples direct titration

2- -
Sulfides S + I2  S + 2 I
2- 2-
Sulfites SO3 + I2 + H2O  + 2 HI SO4
Hydrazine N2H4 + I2  N2 + 4 HI
2- -
Antimony(III) SbO + I2 + 4 H2O  Sb(OH)6 + 2 HI
2+ 4+ -
Tin(II) Sn + I2  Sn + 2I
 Precipitation reactions

Involves a precipitate formation due to the reaction

between the titrant and analyte
Eg.

AgNO3 + NaCl  AgCl  + NaNO3

Here AgCl, a sparingly soluble salt of Ag is formed as a

result of the titration
These reactions are limited to those involving AgNO 3 solution
and hence are known as Argentometric titrations.
Precipitation occurs only when ionic product exceeds
solubility product.
Precipitate formed must be practically insoluble
Precipitate formation should be rapid
Equivalence point should be easily detectable.
Three types of precipitation titration depending on indicators
used
 Mohr’s method
 Volhard’s method
 Fajan’s method
 Mohr’s method
In 1856 Mohr introduced it.
• Determination of halide – chloride with silver nitrate using
potassium chromate solution as indicator.
• It is especially useful for the determination of chloride.
• Precipitated silver chromate, through sparingly soluble in water
is more soluble than silver chloride and the red color due to silver
chromate does not appear until all the chloride has been
precipitate as silver chloride .
The sensitivity of indicator depends on concentration,
temperature H+ ion concentration, concentration of electrolyte
and manner of observing the red coloration
This method utilizes chromate as an indicator.
Chromate forms a precipitate with Ag+ but this precipitate
has a greater solubility than that of AgCl, for example.
Therefore, AgCl is formed first and after all Cl - is consumed,
the first drop of Ag+ in excess will react with the chromate
indicator giving a reddish precipitate.
2 Ag+ + CrO4 2-
Ag2CrO4

Precaution •
medium should be neutral
In alkaline solutions, silver will react with the hydroxide
ions forming AgOH.
In acidic solutions, chromate will be converted to
dichromate.
 Volhard Method
• The method of estimation of silver ions [AgNO 3] in dilute acid solutions
by titrating against a standard thiocyanate solution in the presence of
ferric salt [Ferric ammonium sulphate] as indicator.
•Ammonium or potassium thiocyanate solution is used in conjunction

with 0.1 M AgNO3 in the assay of substances which react with nitrate but
which cannot be determined by direct titrations with silver nitrate
solution.
• In this method to the halide solution, a known excess of silver nitrate is
titrated with 0.1M ammonia or potassium thiocyanate solution
• The precipitate of Silver chloride is filtered off and the filtrate is titrated
with standard thiocyanate solution using ferric ammonium sulphate
solution as indicator.
At the endpoint a permanent red colour is produced due to the formation
of ferric thio cyanate.
 NH4Cl + AgNO3 AgCl + NH4NO3

Excess AgNO3 + NH4SCN AgSCN + NH4NO3

Fe(NH4)SO4 + 3NH4SCN Fe(SCN)3 + 2 (NH4)2SO4

Indicator

This is an indirect method for chloride determination where an

excess amount of standard Ag+ is added to the chloride solution
containing Fe3+ as an indicator. The excess Ag+ is then titrated
with standard SCN- solution untill a red color is obtained which
results from the reaction:

Fe3+ + SCN- Fe(SCN)2+

•The indicator system is very sensitive and usually good results
are obtained. The medium should be acidic to avoid the
formation of Fe(OH)3
• However, the use of acidic medium together with added SCN -
titrant increase the solubility of the precipitate leading to
significant errors. This problem had been overcome by two main
procedures.
•Removal of precipitate of silver chloride
• The reason for removing the precipitate of silver chloride react
with thiocyanate SCN to form the change in Titre value .
• In determination of iodide and bromide is not needed because
the reaction is negligible.
 Fajan method
• Adsorption indicator is used
• The action of these indicators are based on the simple
fact that the endpoint the indicators get adsorbed by the
precipitate [AgCl] and during the process of adsorption, a
change in colour of the indicator will takes place which
may result in a substance of different colour
• Fluorescein and its derivatives are adsorbed to the
surface of colloidal AgCl. After all chloride is used, the first
drop of Ag+ will react with fluorescein (FI-) forming a
reddish color.
Ag+ + FI- AgF
The precipitation titration in which silver ions is titrated with
halide or thiocyanate ions in presence of adsorption indicator
is called fajan’s method
• Since the adsorption of indicator takes place at end point
the method is also called indicator adsorption method
• The indicator, which is a dye, exists in solution as the
ionized form, usually an anion.
The method is generally used for the quantitative analysis of
halide ions or thiocyanate ions .
• For eg :titration of Cl– ions with AgN03 in presence of

adsorption indicator . Here AgN03 is kept in burette and the

Cl– ion solution with indicator is taken in titration flask
a) Before the equivalence point colloidal particles of AgCL
are negatively charged due to the adsorption of Cl – from
the solution . The adsorbed Cl– from the primary layer
which attract the positively charged Na + ions from the
solution to form a more loosely held secondary layer.
b) After the eqv. point ,excess of silver ions Ag + displace
the Cl– ions and form the primary layer which attract the
negatively charged nitrate ions N03 – .
c) At the end point anion of indicator in (weak organic acid
or base ) replace the negatively charged ion N0 3 –
from the
second layer and give the intense color. - This intense
color gives the end point of titration