INTRODUCTION TO CHEMICAL AND LIFE SCIENCES

UNIT-IV

PRINCIPLES OF TITRAMETRIC
ANALYSIS
• The methods employed in quantitative
chemial analysis are generally divided into
two classes, viz. volumetric and
gravimetric.
• As its name implies, volumetric analysis
titrimetry relies on methods involving
accurate measurement of volume of
liquids.
TERMS USED IN VOLUMETRIC ANALYSIS
• Various terms used in volumetric analysis
are
• 1. Titration 2. Titrant 3. Titrate 4.
Equivanence point 5. Indicator 6. End
point 7. Titration Error 8. Standard
solution 9. Normality 10. Molarity 11.
Normality Equation
1. Titration : Titration is the process of
adding one solution from the burette to
another in the conical flask, in order to
complete the chemical reaction. Out of
the two solutions one must be standard
2. Titrant: The reagent of known
concentration is called the titrant.
3. Titrate: The substance being titrated is
termed as the titrate.
4. Equivalence point: It is the point at which
the amounts of reagent and uOStance
being determined are chemically
equivalent or it is the exact stage at which
the chemical reaction involved in the
titration is just complete.
5. Indicator: The substance which helps in
the visual detection of the completion of
the titration is known as indicator
6. End point: The point at which the colour
change of the indicator becomes apparent
to the eye is called the end point
7. Titration error: Ideally, the visible end
point and the equivalence end point
should coincide but in ce there is always a
difference between the two, this
difference is called the titration error.
• This errors because an indicator changes
its colour little before or after the
equivalence point.
8. Standard solution : A solution of known
strength is known as standard solution, e.
g, N/10 sodium hydroxide is a standard
solution.
CLASSIFICATION OF TITRIMETRIC
REACTIONS or TITRATIONS
1. Acid base reactions or neutralization
reactions
2. Oxidation-reduction or Redox reactions
3. Precipitations reactions
4. Complexometric reactions
OXIDATION-REDUCTION(REDOX) TITRATIONS:
• Several substances in solution can be
estimated by oxidation-reduction reactions
• In such methode Oxidation and reduction
reactions occur together, i.e., one substance
is oxidised and another is reduced
Oxidation and reduction:
• The loss of one or more electrons by a
substance is called oxidation, while the gain
of one or more electrons by a substance is
called reduction
 Fe2+ → Fe3+ + e- (Oxidation)
Ce4+ + e- → Ce3+ (Reduction)
Redox reactions:
• The reactions which proceed with
simultaneous loss and gain of electrons
among the reacting substances are called
redox reactions or oxidation-reduction
reactions.
• For example, in the following case Fe2+ ion
is oxidised to Fe3+ while Ce4+ on is reduced
to Ce3+ ion.
Fe2+ + Ce4+ → Fe3+ + Ce3+
• Oxidising agent (Oxidant) and Reducing
agent (Reductant): The substance which
gains electrons, ( ie, undergoes reduction)
in a redox reaction ís called oxidising agent,
while the substance which loses electrons
(i.e, undergoes oxidation) in a redox
reaction is called a reducing agent. COOH
(Oxidation)
• Thus in the above reaction, Ce4+ gains the
electron lost by Fe2+ and hence Ce4+ ion acts
as an oxidising agent while Fe2+ ion acts as a
reducing agent
• Potassium permanganate (KMnO4) and
potassium dichromate (K2Cr207) are the
common oxidsing agents, while ferrous
ammonium sulphate
[FeSO4(NH4)2(SO4 )2.6H20] (Mohr’s salt) and
oxalic acid (COOH. COOH. 2H20) are the
common reducing agents used in redox
titrations
Titration Involving Potassium Permanganate:
Introduction:
• Potassium permanganate KMnO4 is one of
the useful and versatile oxidants
• It is readily available in a moderate cost and
acts as a self indicator in most titrations
• It was first introduced in volumetric analysis
by F. Marguerette in 1840 for the titration
for ferrous iron
• Titrations are usually carried out in the
acid medium with consequent reduction
of permanganate ion to manganous
ion(Mn2+)
• Among the three mineral acids available,
only sulphuric acid is most suitable for
use with potassium permanganate
because it does not act on permanganate
ion in dilute solutions
• Hydrochloric acid sometimes causes
difficulties because of its rducing action
• Nitric acid cannot be used because it is an
oxidising agent itself
Equivalent weight of KMNO4:
• In acid solution, the permanganate is most
widely used. This reaction may be
represented as
• 2KMNO4 + 3H2SO4 → K2SO4 + 2MnSO4
+ 3H2O + 5[O]
• In the ionic reaction, manganese
undergoes a change in oxidation numbr
from +7 to +2 by accepting 5 electrons.
• By definition, the equivalent weight of any
oxidising agent is =
Mol. Wt. of oxidising agent / Number of
electrons accepted by one molecule of
oxidising agent
= Mol. Wt. of KMnO4/5e-
= 158/5
= 31.6
Indicator:
• In the presence of dilute sulphuric acid,
potassium permanganate reacts with reducing
agents according to the equation:
• 2KMNO4 + 3H2SO4 → K2SO4 + 2MnSO4 +
3H2O + 5[O]
• Reducing agent + [O] → Products
• As the titration proceeds potassium sulphate
and manganese sulphate accumaulate, but at
the dilution used, gives colourless solution
because K2SO4 and MnSO4 are colourless
solution.
• As soon as the oxidation is complete and
potassium permanganate is in excess, the
solution becomes known as a self-indicator.
• Thus in potassium permanganate titrations
the use of external indicator is unnecessary
as it itself is a self-indicator
• Potassium permanganate is not a primary
standard because
i) It cannot be obtained in pure state
Ii) It udergoes decomposition, in the
presence of impurities to MnO2, on
standing.
• Hence it is required for a solution of
KMnO4 to be standardised with the
solution of a suitable primary standard
such as oxalic acid, sodium oxalate, etc.
• KMnO4 solution is stored in amberlight
coloured bottle inorder to avoid
reduction of the solution
Titration Involving Potassium Dichromate:
Introduction:
• Potassium dichromate is not so strong
oxidant but has many useful applications
and certain advantages over the other
oxidants like potassium permanganate,
ceric sulphate, the.
• Some of these advantages are
(i) Potassium dichromate can be obtained
in very high purity and, therefore, serves
as an excellent primary standard.
• (ii) Its solutions are stable indefinitely if they
are properly protected from evaporation
• (iii) Its solution are stable towards light and
are little affcted by dust, organic matter in
general, or by autocatalytic reaction
• (iv) It can be used as an oxidising agent in
presence of HCl or chloride. Its solutions do
not oxidise chlorides at room temperature
even in 1-2N acid.
• There are certain disadvantages of
potassium dichromate over potassium
permanganate
• (i) Since dichromate is reduced to a highly
coloured chromaic ion, it is impossible to
observe the end point of these titrations
visually without an added indicator.
• In fact, the colour of the reduced ion even
with an added indicator makes the
detection of the end point difficult for some
people
• (ii) The oxidant has limited applications and
its titrations are comparatively tedious
Equivalent weight:
• Potassium dichromate like the
permanganate is employed as an oxidant in
acid solution
• K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 +
4H2O + 3(O) or ionically,
• Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
• During reduction of Cr2O72- to Cr3+, a
molecule of K2Cr2O7 acccepts 6 electrons.
• Hence, according to the definition of
equivalent weight of oxidising agents, we
get
• Eq. wt. of K2Cr2O7 = Molecular wt. of
K2Cr2O7 /6
= 294/6
= 49
pH of solution:
• The equation for the half reaction
illustrating the reduction of dichromate is
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
• This equation reveals that the oxidation
potential of the dichromate chromic
couple must be strongly influence by the
concentration of acid.
• The most useful application of
dichromate as an oxidant in volumetric
determinations are those that are carried
out in 1-2N acid. It is of no value in
neutral or alkaline solution
Indicator:
• Potassium dichromate is of particular
importance for the estimation of ferrous
ion in the presence of hydrochloric acid
or sulphuric acid.
• The end point may be dtetcted by
diphenylamine (C6H5-NH-C6H5) indicator
Role of Phospharic Acid:
• Potassium dichromate oxidises ferrous
ions to ferric ions. After the reaction in a
certain titration mixture has proceeded to
a sufficient extent there would be present
in the solution(titration mixture) an excess
of ferric ions over ferrous ions, which will
naturally oxidise diphenylamine indicator
to give the bluish-violet or purple colour
before all ferrous ions are changd to ferric
ions.
• Therefore, the end point will be reached
much earlier than it acturally should have
been, therby causing error.
• It is known that phosphoric acid lowers
the oxidation potential of the ferric-
ferrous system by forming a complex
Fe(HPO4)+ with the ferric ions.
• Hence, phosphoric-sulphuric acid mixture
is used here to remove ferric ions in the
form of a complex as soon as they formed
Iodimetry and iodometry:
• Iodine acts as a mild oxidising agent in
solution and oxidises thiosulphate,
sulphite, arsenite, stannous and ferrous
ions quantitatively in neutral or moderately
acid solutions
• It is, therefore, employed for the estimation
of all these ions by titration
• The titrations involving the use of iodine
are termed as iodine titrations.
These are of two types:
(a) Iodimetry:
• All such titrations where a reducing agent is
directly titrated against standard iodine
solution are grouped under the head
iodimetry
• It includes determination of thiosulphate,
sulphite, arsenite, etc. The reaction may be
represented as follows:
I2 + 2S2O32- → S2O62- + 2I-
• I2 + SO32- + H2O → SO42- + 2H+ + 2I-
• I + AsO 3- + H O → AsO 2-+ 2H+ + 2I-
(b) Iodometry:
• In such titrations, iodine is librated as a
result of chemical reactions involving
oxidation of an iodide ion (usually
potassium iodide) by a strong oxidising
agent in neutral or more usually acid
solutition, iodine is evolved in equivalent
amount and is titrated with a standard
solution of a reducing agent, which is
generally sodium thiosulphate
• Examples of such titrations are:
 2MnO4- + 10I- + 16H+ → 2Mn2+ + 5I2 +
8H2O
Cr2O72- + 6I- + 14H+ → 2Cr3+ + 3I2 + 7H2O
ClO- + 2I- + 2H+ → Cl- + I2 + H2O
Br2 + 2I- → 2Br- + I2
Cl2 + 2I- → 2Cl- + I2
• Indicator and End Point: In iodometry
starch solution is used as an indicator since
it gives an intense blue colour with iodine.
Hence disappearance of blue colour in
Starch is said to form an adsorption
compound of intense blue colour with
iodine at room temperature. The complex
is not stable at higher temperature.
PRECIPITATION TITRATIONS:
Introduction:
• Argentometry is that branch of volumetric
analysis in which a solution of silver
nitrate is titrated against a halide or
thiocyanate resulting in the precipitation
of silver halide or silver thiocyanate
• The reaction is instantaneous and
quantitive
Ag+ + Cl- → AgCl ↓
Ag+ + CNS → AgCNS ↓
• As this method involves precipitation, it is
also termed as precipitimetry or a
precipitation titration
• The exact completion of the titration is
determined by using an indicator as we do
in other titrations
Types of Silver Nitrate Titrations
• There are three types of silver nitrate
titrations depending upon the types of
indicators used they are i) Mohr’s method
ii) Volhard’s method and iii) Fajan’s
Mohr’s Method:
• The method was developed by Mohr in 1856
using potassium chromate as an indicator.
• This method involves the titration of silver
nitrate against halides in neural solution
using 2% solution of potassium chromate as
an indicator.
• The end point is marked by the appearance
of a brick red precipitate or colouration due
to the formation of silver chromate with an
excess of silver nitrate
 Ag+ + Cl- → AgCl↓
(White)
2Ag+ + CrO42- → Ag2CrO4↓
(Brick red)
• This method is based on the fact that
silver halide is more insoluble than silver
chromate. Hence so long as there is any
chloride or bromide left in the solution,
no silver chromate is formed
• In fact silver chromate even if formed, will
immediately change to silver chloride or
bromide by interaction with chloride or
bromide e.g.
Ag2CrO4 + 2Cl- → 2AgCl + CrO42-
• When the whole of chloride has been
used up silver chromate will be formed
and brick red colouration of precipitate
will appear