CHE-158

Topic:-

DOA :
DOR : 20/10/2010
DOS : 10/11/2010
Submitted to-
Submitted by-
Dr. Lobo Bhini Rani
Chandan Malagar
Department of Chemistry Roll No.-
RA4006A38

Reg No.-11001457
This project is result of collective effort of
many persons.
Firstly I would like to thank our Chemistry
teacher Dr. Lobo , who has provided us with
his full support.

Then, I would like to thank authors of some

book-

Engineering Chemistry of O.G.Palanna,

which proved to be a very helpful in clearing
concepts. It is also our textbook.
Other books were-

- Quantitative chemical analysis by

D.C.Harris .
- Analytical chemistry

Some sites were also very helpful which are

as follows-
- www.titration.info
- www.facultystaff.richmond.edu
- www.tau.ac.il

Last but not the least I would like thank my

parents, who encouraged me every time
regarding studies and other activities.
I wholeheartedly acknowledge all those
people who have contributed to make this
project.

Topics
page no.

-- Introduction 1-3
-Equivalence points & end points 2
-- Descriptive part
*Acid-base titration 4
* Precipitation titration
-- REDOX TITRATION 5
-- Summary & appilicattion 6-7
Of Redox reaction
-- Potemtiometry 8-9

-- Electrochemical analysis 10-11

-- Potentiometric titration 12

-- Ion selective electrode 13

--Summary 14
--A step farward 15-16

Introduction:-
Analytical chemistry is the study of the chemical
composition of natural and artificial materials. Unlike other
major sub disciplines of chemistry such as inorganic
chemistry and organic chemistry, analytical chemistry is not
restricted to any particular type of chemical compound
or reaction. Properties studied in analytical chemistry
include geometric features such as molecular morphologies
and distributions of species, as well as features such as
composition and species identity. The contributions made by
analytical chemists have played critical roles in the sciences
ranging from the development of concepts and theories (pure
science) to a variety of practical applications ,such
as biomedical applications ,environmental monitoring, quality
control of industrial manufacturing and forensic
science(applied science).
Titration is a common laboratory method of quantitative
chemical analysis that is used to determine the unknown
concentration of a known reactant.

Because volume measurements play a key role in titration, it

is also known as volumetric analysis.

A reagent called the titrant or titrator of a known

concentration (standard solution) and volume is used to react
with a solution of analyte or titrand whose concentration is not
known.
Titrimetric Methods of Analysis consist in determining the
number of moles of reagent (titrant), required to react
quantitatively with substance being determined.
(1)
In Titrimetry we add a reagent, called the titrant, to a
solution containing another reagent, called the titrand, and
allow to react. Titrant can be added-
• Volumetrically.
• Electrochemical method.

The type of reaction provides us with a simple way to divide

titrimetry into the following four categories :
Acid–base titrations, in which an acidic or basic titrant
reacts with a titrand that is a base or an acid.
Complexometric titrations based on metal – ligand
complexation.
Redox titrations, in which the
titrant is an oxidizing or reducing agent.
Precipitation titrations, in
which the titrand and titrant form a precipitate.
Various methods are available for end point determination
like:
Spectrophotometry
Potentiometry
Amperometry
Conductometry

Equivalence Points and End

points
If a titration is to be accurate we must combine
stoichiometrically equivalent
amount of titrant and titrand. We call this stoichiometric
mixture the two compounds as
equivalence point.
(2)

At equivalence point –
Number of equivalence of titrand = number of equivalence of
titrant.ie.
N1*V1 = N2*V2.

Where N & V are the normality and volume of both

compounds.
If we know the stoichiometry of the titration reaction, then we
can calculate
the moles of titrand.
We stop adding titrant when at an end point of our choosing.
Often this end point is a change in the colour of a
substance, called an indicator that we add to the titrand’s
solution.

THIS IS A TITRATION CURVE-

(Volume of NaOH -VS- Ph of solution )

(3)
The difference between the end point volume and the
equivalence point volume is a determinate titration error. If
the end point and the equivalence point volumes coincide
closely, then the titration error is insignificant and
it is safely ignored. Clearly, selecting an appropriate end point
is critically important.

Descriptive Part –

Acid-base titration
Proton transfer reactions in aqueous solutions are quite fast.
Aqueous acid-base titrations are thus
suitable for the analysis of any Bronsted acid or base.
Practically, the pKa or pKb of the analyte should
be less than about 10 (i.e., pKa or pKb < 10) for a complete
reaction between analyte and titrant.

Instrumental Endpoint Detection in

Acid-Base Titrations
Potentiometric endpoint detection using a pH meter is the
universal instrumental method used for
acid-base titrations, both in aqueous and nonaqueous solvents.
Special care of the pH electrode is
necessary for nonaqueous titrations – in particular, the
electrode must not be allowed to become
dehydrated.

Precipitation Titrations
Precipitation reactions in aqueous solution range from rapid to
slow, depending on the identity of the
precipitant. Many precipitations are sufficiently rapid and

(4)
complete to form the basis of quantitation.
by titration. Precipitation titrimetry has several advantages
over precipitation gravimetry, including
speed, sensitivity, and convenience.

Endpoint Detection
A variety of chemical indicators are used to indicate the
endpoint of argentometric titrations: the
Fajans, Volhard, and Mohr methods are discussed in some
detail in the lab handout Titrimetric

Analysis of Chloride.
A silver wire or ring is a sufficient indicator electrode for
potentiometric titrations using AgNO3,
while a fluoride ISE is suitable for potentiometric endpoint
detection for fluoride analysis using La3+
or Pb2+ titrant solutions.

Redox Titrations
Redox reactions are the most diverse of the four main
classes of inorganic aqueous reactions
(acid-base, pptn, complexation and redox). In principle,
then, redox titrations can be used to analyze
for any oxidizing or reducing agent. However, many
redox reactions are either too slow or have
inconsistent stiochiometry. The stability of titrant and
analyte solutions can also be a problem.
Nevertheless, a wide variety of analytes can be
conveniently determined by redox titrations.
(5)
Endpoint Detection for Redox
Titrations
• it is probably worthwhile to mention that starch is an
excellent chemical indicator for titrations
involving iodine.
• potentiometric detection with an inert indicator electrode
(e.g., Pt) is a general method for following
redox titrations

• amperometric detection can also be used in many cases

• many redox titrants are colored (e.g., permanganate or
iodine) and so photometric detection can also
be used to follow the course of the titration

Summary of Applications of
Redox Reactions
• analytes that are oxidizing agents are most conveniently
analyzed by addition of excess reducing
agent and then back-titrating. There are two common ways of
doing this: (i) addition of a measured
excess of ferrous ammonium sulfate and back-titrating the
unreacted excess with dichromate titrant;
(ii) addition of an unmeasured excess of potassium iodide and
using thiosulfate to back-titrate the
iodine produced by reaction of iodide with analyte.
• analytes that are reducing agents may be analyzed by a
variety of oxidizing agents: potassium
permanganate and ceric sulfate are strong oxidants, potassium
dichromate is a moderately strong
oxidizing titrant (especially suitable for the analysis of ferrous
(6)
iron, or back-titrations with FAS) and
iodine is a milder, more selective oxidizing agent that may be
used for the direct analysis of number of reducing agents

(iodimetry), as well as the indirect analysis of reducing agents

(back-titration with thiosulfate in iodometry; see above)

• pre-treatment of the analyte with an oxidizing agent or a

reducing agent is often needed in redox
Titrations.

Many methods can be used to indicate the endpoint of a

reaction.
Titrations often use visual indicators (the reactant mixture
changes color). In simple acid-base titrations a pH indicator
may be used, such as phenolphthalein , which become s pink
when a certain pH (about 8.2) is reached or exceeded. Another
example is methyl orange , which is red in acids and yellow in
alkali solutions.
Not every titration requires an indicator. In some cases, either
the reactants or the products are strongly colored and can
serve as the "indicator". For example, a redox titration using
potassium permagnet (pink/purple) as the titrant does not
require an indicator. When the titrant is reduced, it turns
colorless. After the equivalence point, there is excess titrant
present. The equivalence point is identified from the first faint
persisting pink color (due to an excess of permanganate) in
the solution being titrated. Due to the logarithmic nature of
the pH curve, the transitions are, in general, extremely sharp,
(7)
And thus, a single drop of titrant just before the endpoint can
change the pH significantly—leading to an immediate colour
change in the indicator. There is a slight difference between
the change in indicator color and the actual equivalence point
of the titration. This error is referred to as an indicator error,
and it is indeterminate.

Potentiometry:-
These titrations are based on redox reactions.
There are many redox reagents used in redox titrations. To list
a few –
Potassium permanganate is used for determination of Fe2+,
H2O2 and oxalic acid
Potassium dichromate for determination of Fe2+ and Cu in
CuCl.
Bromate is used for tin and phenol.
Iodides (titrated with sodium thiosulphate) for H2O2 and Cu2+.
Cerium (IV) can be used to determine ferrocyanides and
nitrites.
There are also many other methods.
Commonly used indicators are substances that can exist in
two forms –
Oxidized and reduced- that differ in color.
Potential at which the substance changes color must be such
(8)
that the change occurs close to the equivalence point.
Examples of such substances are ferroin, diphenylamine.
Sometimes indicators that are oxidized irreversibly are used.
However, in most popular redox titrations there is no need for
a special indicator - permanganate has strong color by itself,
iodine gives strong color when combined with starch, so their
presence or disappearance can be easily detected without
additional indicators.
Potentiometry is the field of electro analytical chemistry in
which potential is measured in a electrochemical cell.
Potential is measured under the condition of no current flow.
The measured potential is directly proportional to the
concentration of analyte.
The potential that develops in the electrochemical cell is the
result of free energy change that would occur until the
equilibrium condition is reached.
The measured potential may then be used to determine the
analytical quantity of interest.

Generally, saturated
Fig: Calomel electrode Calomel electrode is
(9)

coupled with inert platinum electrode of the cell during

titration. (SCE- 0.2422V)

The measured EMF of a cell is:

Ecell = Ecathode – Eanode .
Ecell = Eindi – Eref .
Eindi = Ecell + Eref .
= Ecell + 0.2422V .
When platinum electrode is used as the indicator electrode in
potentiometric studies and the temperature is maintained
constant , the potential of the indicator electrode depends on
rate of the redox ionic concentrations , to which electrode is
dipped.

The potential of electrode depends upon the concentration if

ions
Then, according to Nernst Equation-

E = E0+ (0.05916/N) log [M+n]

Electrochemical Analysis :-
Electro analytical methods measure the potential (volts)
and/or current (amps) in an electrochemical cell containing
the analyte.These methods can be categorized according to
which aspects of the cell are controlled and which are
measured. The three main categories are
potentiometry (the difference in electrode potentials is
measured),
coulometry (the cell's current is measured over time), and
(10)
voltammetry (the cell's current is measured while actively
altering the cell's potential).
Electrochemical analysis is the group of chemical analytical
methods in which a potential change is generated by an
electrochemical reaction and is used for the quantitative
determination of a substance.
These methods depend upon electrode reaction. Two of these
methods are:
 Potentiometry using a reference calomel electrode and an
indicator electrode.

 Potentiometric titrations using ion selective electrode as

sensors.
Potentiometric titration
It is a technique similar to direct titration of a redox reaction.
No indicator is used; instead the voltage across the analyte,
typically an electrolyte solution is measured. To do this, two
electrodes are used, a neutral electrode and a standard
reference electrode. The voltage is recorded at intervals as the
titrant is added. A graph of voltage against volume added can
be drawn and the end point of the reaction is half way
between the jumps in voltage.
Let’s have an example of potentiometric titrations of ferrous
ammonium sulphate against standard potassium dichromate in
the presence of mineral acid.
The electrode reaction of one of the half cell of an
electrochemical cell in which charge transfer takes place at
the interface between the electrodes and the electrolyte is
coupled with a calomel reference electrode. The reference
electrode
(11)
should have a known, or at least a constant potential value
under the prevailing experimental conditions.

The potential of indicator electrode is sensitive to the

concentration of analyte in the solution and changes with
analyte concentration, and the reference electrode provides a
stable reference potential for measurement of potential of the
indicator electrode.
The simplest one is an inert metal such as platinum, which can
be used to measure the ratio of the concentrations of the
oxidized & reduced species.

Determining Equivalence point in potentiometry:-

Direct plot a graph of potential ‘E’ against volume of titrant .

The end point of titration is where there is an abrupt change in
the value of potential at indicator electrode.

The first derivative of potential and the volume of titrant is

plotted against the volume of titrant.

The value of second derivative for the potential and volume

gives best result.

The point at which the second derivative crosses zero is the

inflection point , which is taken as the end point of titration.

An Electrochemical cell With ion selective electrode:-

Two half cell coupled from an electrochemical cell , ie . One
solution in contact with ISE (combined glass electrode) & the
(12)
other and the other a reference electrode. The EMF of the cell
(E) can be measured across the two terminals of the
potentiometer / pH meter.

The pH observed through the ion selective electrode is

directly proportional to the concentration of H+ ions
concentration of the analyte solution.
Calomel electrode(SCE) // glass/H+(unknown)/Cl‾/AgCl/Ag
(Combined glass electrode)

summary
Traditional analytical techniques -
Although modern analytical chemistry is dominated by
sophisticated instrumentation, the roots of analytical
chemistry and some of the principles used
in modern instruments are from traditional techniques many
of which are still used today. These techniques also tend to
form the backbone of most undergraduate analytical
chemistry educational labs. Examples include:
Titration
Titration involves the addition of a reactant to a solution being
analyzed until some equivalence point is reached. Often the
amount of material in the solution being analyzed may be
determined. Most familiar to those who have
taken college chemistry is the acid-base titration involving a
color changing indicator. There are many other types of
titrations, for example potentiometric titrations.
(13)
Standard Curve
A standard method for analysis of concentration involves the
creation of a calibration curve.

This allows for determination of the amount of a chemical in a

material by comparing the results of unknown sample to those
of a series known standards.
If the concentration of element or compound in a sample is
too high for the detection range of the technique, it can simply
be diluted in a pure solvent.
If the amount in the sample is below an instrument's range of
measurement, the method of addition can be used. In this
method a known quantity of the element or compound under
study is added, and the difference between the concentration
added, and the concentration observed is the amount actually
in the sample.

A Step Further-
Analytical chemistry research is largely driven by
performance (sensitivity, selectivity, robustness, linear range,
accuracy, precision, and speed), and cost (purchase, operation,
training, time, and space).

Among the main branches of contemporary analytical atomic

spectrometry, the most widespread and universal are optical
and mass spectrometry, elemental analysis of solid samples,
(14)

The new leaders are laser-induced breakdown and laser

ablation mass spectrometry, and the related techniques with
transfer of the laser ablation products into inductively coupled
plasma.

Advances in design of diode lasers and optical parametric

oscillators promote developments in fluorescence and
ionization spectrometry and also in absorption techniques
where uses of optical cavities for increased effective
absorption path length are expected to expand.
Steady progress and growth in applications of plasma- and
laser-based methods are noticeable.
An interest towards the absolute analysis has revived,
particularly in the emission spectrometry. A lot of effort is put
in shrinking the analysis techniques to chip size. Although
there are few examples of such systems competitive with
traditional analysis techniques, potential advantages include
size/portability, speed, and cost.

Examples of rapidly expanding fields in this area are:

• Genomics - DNA sequencing and its related
research. Genetic fingerprinting and DNA microarray are
very popular tools and research fields.
• Proteomics - the analysis of protein concentrations and
modifications, especially in response to various stressors,
at various developmental stages, or in various parts of the
body.
• Metabolomics - similar to proteomics, but dealing with
metabolites.
• (15)

• Transcriptomics- mRNA and its associated field

• Lipidomics - lipids and its associated field
• Peptidomics - peptides and its associated field
• Metalomics - similar to proteomics and metabolomics,
but dealing with metal concentrations and especially with
their binding to proteins and other molecules.
(16)