IMA- ELECTROMETRIC METHODS

I.POTENTIOMETRIC TITRATION

 Potentiometric methods are based on the difference in potential between 2 electrodes in an

electrochemical cell. 
 One of these electrodes is the indicator electrode and the other a reference.
 The indicator electrode is one whose response is proportional to some variable (i.e.
concentration or activity of a species) in the solution. 
 The reference electrode is one whose potential is constant throughout the experiment.
 The potential developed in a cell in which no current flows is given by:
 
Ecell = Eind - Eref + Ej
 
Where
Ecell is the potential of the cell,
Eref is the potential of the reference electrode,
Eind is the potential of the indicator electrode, and
Ej is the liquid junctionpotential. 

The liquid junction potential is a potential generated at the interface between dissimilar
solutions due to migrational differences between ions. 
 In a properly designed system both the reference potential and the liquid junction potential
are constant so the indicator potential gives information on the activity of the species in the
solution.
INSTRUMENTATION:-

1. Non – electronic instruments

2. Electronic instruments
3. Automatic instruments

Non – electronic instruments:-

1. A potentiometer for titration can be made from simple components as shown in fig.
2. In this apparatus B is a battery which supplies working current and consists of two dry cells
in the series. R is a variable resistor and V is a voltmeter A galvanometer G, of intermediate
sensitivity is critically damped by the resistor Rd.
3. A reversing switch Sa helps in connecting the reference and indicator electrodes in either
polarity.
4. The instrument can be operated by dipping the electrodes in the sample solution, closing S1
and adjusting R until there is no deflection in the galvanometer.
5. Finally the voltmeter reading is recorded. If balance point is not obtained, then S2 is reversed
and the process is repeated after each addition of reagent.

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Electronic instruments:-

1. These instruments have many advantages over non-electronic instruments. Due to high
resistance of the glass electrode, it cannot be used with a simple potentiometer.
2. An electronic amplifier for use with glass electrode is called a PH meter. These PH meters with
glass electrode and electronic voltmeters for PH measurements and Potentiometric titration are
commercially and available. A schematic diagram of a circuit for vacuum triode null point
detector is shown in Fig.
3. The vacuum tube consists of a cathode F, a plate P and a grid G.
4. When the cathode F is heated by a source of low voltage, the electrons are thrown out. These
electrons are attracted towards plate P by virtue of positive charge on P produced by its being
connected to the positive pole of the battery B.
5. The small current passing through the external plate is indicated by the millimeter. The flow
of electrons is repelled back from the cathode to the plate by impressing a negative charge on
the grid G.
6. This reduces the plate current indicated by millimeter. The negative terminal of the cell X is
joined to the grid, so that any unbalance between the meters. The balance is then restored by
adjusting the potentiometer.
7. The extent of adjustment necessary to restore the millimeter to the position corresponding to
no charge on the grid gives the potential drop in X.

Automatic instruments:-

1. When used manually so as to give a detailed titration curve. A potentiometer titration is a

time consuming and tedious job. Automatic instrument for performing and recording the
titration curve provides a logical solution to the problem.
2. The basic features of commercial titration are alike. In the delivery unit a short length of the
flexible tubing is shut in some way, with no current passing through the solenoid.
3. After setting the instrument and reading the burette level, a switch is pressed to start the
titration.
4. The solenoid is energized , the pressure on the tubing is released. And then the titrant is
allowed to flow through the delivery tip. The titration proceeds at a fast rate until a
predetermine distance from the end point,
5. When the anticipation control automatically shows the delivery of the titrant. At the end
point the delivery is stopped. A schematic circuit diagram of an automatic titrator is shown in
Fig.
6. The control units has a calibrated potentiometer, a null-sensing amplifier, and an anticipator
circuit. To operate the potentiometer is set at the potential expected at the end point, the
electrode assembly immersed in the sample solution and the operating switch is pressed.
7. The difference signal arising between the cell, E.M.F. and the present voltage on the
potentiometer is amplified. As the end point is approached, the difference signal diminishes.
When the two signals are matched, the delivery of the titrant is stopped.

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 8. The final category of automatic titrators are known as differential titrators. These instruments
and titrants at a constant rate the derivative of differential titrators is that equivalence point
potential need not be known to employ these devices.
9. Finally it should be kept in mind that automatic titrators are no more accurate than manually
performed titrations. Thus, they are most useful in those solution where speed is the
predominant factor.

Potentiometric titrations types:

The titration in which the equivalent or end point of a reaction is determined with the help of
measurement of the potentials of the reaction mixture is known as potentiometric titration.
Types :
1. Acid-Base Titrations:
2. Redox titrations:
3. Precipitation reactions:

1. Acid-Base Titrations:
1.1. The acid solution whose strength has to be determined is taken in a beaker and the
hydrogen electrode and calomel electrode were dipped in the solution.
1.2. The electrodes are connected to the potentiometer and the EMF is measured.
1.3. A known volume of standard alkali solution is added from a burette, stirred
thoroughly and the EMF of the cell is recorded. Like this 10-15 readings are recorded by
repeating the procedure of the addition of alkali.
1.4. The volume of alkali added is plotted against EMF observed. The steepest portion of
the curve indicates the equivalent point of the titration.

NaOH + HCl NaCl + H2

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2. Redox titrations:
2.1. The EMF of the
electrode is determined by the activity of ratio of the substance being oxidized or reduced.
For example Fe+2 titrated against K2Cr2O7
2.2. . Ferrous iron
solution is taken in the beaker and treated with dil. H2SO4.
2.3. Platinum
electrode and calomel electrode are dipped into the solution and they are connected to the
potentiometer.
2.4. The EMF of the
solution after the addition of K2Cr2O7 from burette is recorded.
2.5. A graph is
plotted with EMF and volume of K2Cr2O7. The steep rise is the end point of the titration.
3. Precipitation reactions:
3.1. The EMF of the electrode is determined by the precipitation of product.
3.2. For example, titration of AgNO3 with AgCl where the later precipitates out. AgCl is
used along with calomel electrode.
3.3. AgNO3 is taken in the burette and AgCl is taken in the beaker containing electrodes.
3.4. The EMF of the cell is measured and plotted against volume of silver nitrate added.
The steep rise in the curve shows the end point of the titration.

-
AgNO3 + Cl AgCl (ppt) + NO3-

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II.Conductometric Titration :
The determination of the end point of a titration by means of conductance measurements is
known as conductometric titration.
Conductometeric titration based on the following
i) Size of ions
ii) Mobility of ions
iii) Charge of ions.
Instrumentation :
1. The two essential tools used in the conductometric titration theory include an apparatus for
measuring and studying conductivity changes and a conductivity cell that has dipping
electrodes.
2. But carrying out simple titration using this theory, need a dipping electrode, a mechanical
stirrer and a beaker of a suitable size. also require measuring circuits that will assist in
preventing concentration changes as a result of reactions at the electrodes.
Conductometric Titration types
Acid-base titrations:
a) Strong acid vs strong base

1) Consider the reaction in which a strong alkali, e.i., 0.1 N NaOH is added to a solution of
strong acid e.g., 0.01N HCl.
2) The reaction can be symbolized as follows:
a. (H⁺ + Cl⁻ )+ (Na⁺ + OH⁻ )  Na⁺ + Cl⁻ +H₂ O

3) The highly conducting hydrogen ions present initially in the solution are replaced by sodium
ions having a much smaller conductance whereas the concentration of chloride ions remains
constant.
4) After the equivalence point, the future addition of sodium hydroxide results in an increase of
conductance .
5) Since the hydroxyl ions are no longer consumed in the chemical reaction.

Shows the graph produced in the above case. It consists of two straight lines intersecting at the
equivalence point. .
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(b) Strong acid vs weak base:

1) When a strong acid is titrated against a week base e.g NH₄ OH,The first part of the curve is
decrease rapidly,
2) But after the equivalence point , the conductance does not vary so much, as the free base
behaves like weak electrolyte and its conductance is very small’.
3) The shape of curves is as shown

(c) Weak acid vs strong base:

When a weak acid e.g., acetic acid is titrated with a solution of strong alkali e.g., NaOH, the
reaction proceeds as:
(CH₃ COO⁻ + H⁺ )+(Na⁺ + OH⁻ )  CH₃COONa +H₂ O

1) The curve obtained in this titration is shown in fig .

2) In this case, the concentration of any ion does not remain constant throughout.
3) Intially the solution of a moderately weak acid has low conductance which is further
decreased by adding the alkali solution.
4) Through sodium acetate formed here has high conducting power yet there is a fall in
conductance.
5) This is due to the repressing nature of the acetate ion i.e., due to common ion effect,
dissociation of acetic acid is checked.
6) On further addition of alkali, the amount of acetate ion increases regularly as it is released
from the acetic acid, until the equivalence point is reached.
7) After the equivalence point, the conductance increases more because of the excess of
OH⁻ ion and the curve .
(d) Weak acid vs weak base:
1) The complete titration-curve is shown in fig.(d).
2) Intially the solution of a moderately weak acid has low conductance which is further
decreased by adding the alkali solution.

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 3) Through sodium acetate formed here has high conducting power yet there is a fall in
conductance.
4) This is due to the repressing nature of the acetate ion i.e., due to common ion effect,
dissociation of acetic acid is checked.
5) After the equivalence point, the conductance remains almost constant.
6) As the free base is a weak electrolyte.
7) The end point in this case is sharp.
(e)Mixture of strong acid and weak acid vs base:
1) The important feature of conductometric titration is that a mixture of a strong and a weak
acid can be analysed in single titrations.
2) For this type of titration we get two equivalence points.
3) The first is due to the neutralization of strong acid(HCl Vs NaOH) and second one is due
to the neutralization of weak acid (CH3COOH Vs NaOH).
4) The first point gives the volume of alkali for strong acid and the difference between the
second and first gives the volume of alkali used for weak acid.

(f)Precipitation reaction:
1) The conductance method is also applied to determine the equivalence point in precipitation
titrations.
2) If KCl is titrated against AgNO₃, KCl is replaced by an equivalent amount of precipitate and
also decreases the absorption.
3) (K⁺ +Cl⁻) + (Ag⁺ + NO₃⁻) = AgCl + K⁺ + NO₃⁻

4)
5) So, the conductance in early stages remains almost constant. After the equivalence point,
there is a sharp increases in conductance .
6) Similarly titrations between Ag₂SO₄ and BaCl₂, MgSO₄ and AgNO₃, etc., are carried out.

Advantage
1) The method of conductometric titration is potentially useful in any reaction

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 2) . The accuracy is increased by controlling the temperature
3) Conductometric methods can be used for the analysis of very dilute or coloured solution

APPLICATIONS OF CONDUCTOMETRIC TITRATIONS:

Conductometric titration has many applications, i.e. it can be used for acid base, redox, precipitation,
or complex titrations

1) Determination of sulphur dioxide in air pollution studies

2) Determination of soap in oil
3) Determination of accelerators in rubber
4) Determination of total soap in latex
5) Specific conductance of water

III.AMPEROMETRIC TITRATIONS:
Introduction:

In Amperometric titration current passes through the titration cell between a polarisable electrode and non
polarisable electrode is measured as function of volume of titrant added.

Principle:

1) According to Ilkovic equation , the diffusion current ( = limiting current - residual current) is directly
proportional to the concentration of the electro-active material in the solution
2) If some of the electro-active material is removed by interaction with reagent, the diffusion current
will decrease.This is the fundamental principle of amperometric titrations.
3) The observed diffusion current at a suitable applied voltage is measured as a function of the volume
of the titrating solution: the end point is the point of intersection of two lines giving the change of
current before and after the equivalence point.

Instrumentation:

1. Amperometric titration can be carried out with a rotating platinum electrode (See Fig.) .It consist of
a glass tube of length 15 – 20 cm in length and 6 mm in diameter.
2. The platinum wire extends 5-10 mm from the wall of glass tubing.
3. The electrode is mounted on shaft of the motor and rotated at constant speed of 600 RPM .
Electrical connection is made to the electrode by copper wire passing through the tubing to the
mercury covering the platinum wire seal.

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Nature of Titration Curves:

Titrand + Titrant ---------------- Product.

A) Titrand is reducible but titrant and product not:

1. When solution containing Pb+2 ion is titrated against SO4-2 ion. A precipitate of PbSO4 is formed.
2. The titration can be performed at fixed potential -0.8 Volt v/s saturated calomel electrode.
3. As titration is proceeds concentration of Pb+2 ion decreases and diffusion current also decreases till
it becomes minimum at equivalence point.
4. The diffusion current remains constant beyond end point. The values of diffusion current is plotted
against the volume of titrant added .The resulting titration curves is straight line leveling off at end
point .
5. The intersection of two extra plotted portions of the curves gives the end point.

B) Titrant is reducible but titrand and product not :

When solution containing Mg+2 ion is titrated against with the reducible species such as 8- hydroxy
quinoline.

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At constant potential of -1.6 volt. In this titration the current is steady till the end point because Mg+2 ion
does not undergoes reduction. Beyond the end point the 8- hydroxy 4  quinoline undergoes reduction. As its
concentration increases diffusion current also increases.

C) Titrand and titrant both are reducible but product not :

1. When solution containing Pb+2 ion is titrated against K2Cr2O7.
2. The titration is performed at potential of -0.8 Volt v/s SCE .
3. Diffusion current is decreases due to removal of Pb+2 ion.
4. The current is minimum at the end point. On further addition of the titrant the current once again
increases. V shaped curve is obtained.

Advantages of amperometric titrations:

1. The titration can usually be carried out rapidly, since the end point is found graphically; a few current
measurements at constant applied voltage before and after the end point suffice.

2. Titrations can be carried out in cases in which the solubility relations are such that potentiometric or
visual indicator methods are unsatisfactory; for example, when the reaction product is markedly soluble
(precipitation titration) or appreciably hydrolysed (acid-base titration). This is because the readings near the
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equivalence point have no special significance in amperometric titrations. Readings are recorded in regions
where there is excess of titrant, or of reagent, at which points the solubility or hydrolysis is suppressed by
the Mass Action effect; the point of intersection of these lines gives the equivalence point.

3. A number of amperometric titrations can be carried out at dilutions (ca 10-4M) at which many visual or
potentiometric titrations no longer yield accurate results.

4. 'Foreign' salts may frequently be present without interference and are, indeed, usually added as the
supporting electrolyte in order to eliminate the migration current. If the current-voltage curves of the
reagent and of the substance being titrated are not known, the polarograms must first be determined in the
supporting .

Applications:

1) Using amperometric titrations precipitation titration can be performed.

2) amperometric titrations method is used for redox titrations and to study complex formation.

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V. Ion selective electrodes :

1. An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is

a transducer (or sensor) that converts the activity of a specific ion dissolved in a solution into
an electrical potential, which can be measured by a voltmeter or pH meter.
2. The voltage is theoretically dependent on the logarithm of the ionic activity, according to
the Nernst equation. The sensing part of the electrode is usually made as an ion-
specific membrane, along with a reference electrode.
3. Ion-selective electrodes are used to measurements of ionic concentration in an aqueous
solution 

Principle of ion-selective electrode (I.S.E.):

1. An ideal I.S.E. consists of a thin membrane across which only the intended ion can be
transported.
2. The transport of ions from a high conc. to a low one through a selective binding with some
sites within the membrane creates a potential difference.

Types of I.S.E.

1. Glass membrane (i.e. H+ electrode)

2. Solid-state electrode (e.g. F- electrode uses a Eu2+-doped LaF3 crystal)
3. Liquid-based electrode (e.g. Ca2+ electrode uses a liquid chelator)
4. Compound electrode (e.g. CO2 gas sensing electrode)

Advantages and limitations of I.S.E:

Advantages:

1. Linear response: over 4 to 6 orders of magnitude of A.

2. Non-destructive: no consumption of analyte.

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 3. Non-contaminating.

4. Short response time: in sec. or min. useful in indust. applications.

5. Unaffected by color or turbidity.

Limitations:

1. Precision is rarely better than 1%.

2. Electrodes can be fouled by proteins or other organic solutes.

3. Interference by other ions.

4. Electrodes are fragile and have limited shelf life.

5. Electrodes respond to the activity of uncomplexed ion. So ligands must be absent or masked. m
must be kept constant.

Electrode setup:

1. Fig  shows the basic components of ISE setup. It has an ion selective electrode, which allows
measured ions to pass, but excludes the passage of the other ions.
2. Within this ion selective electrode, there is an internal reference electrode , which is made of
silver wire coated with solid silver chloride, embedded in concentrated potassium chloride
solution (filling solution) saturated with silver chloride.
3. This solution also contains the same ions as that to be measured.
4. There is also a reference electrode similar to ion selective electrode, but there is no to-be-
measured ion in the internal electrolyte and the selective membrane is replaced by porous
frit, which allows the slow passage of the internal filling solution and forms the liquid
junction with the external text solution.
5. The ion selective electrode and reference electrode are connected by a milli-voltmeter.
Measurement is accomplished simply by immersing the two electrodes in the same test
solution.

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VITS

Electrochemistry

4. Determination of pH: The EMF of a solution depends on the concentration of H + ions or pH of

the solution. A hydrogen electrode containing solution of unknown pH is paired with a standard
calomel electrode.

+
Pt, H2 (1 atm) / H (unknown) // KCl (saturated) / Hg2Cl2, Hg

The EMF of this cell is measured by potentiometer and the pH of the unknown solution can be
determined.

E cell = E right - E left or E cell = 0.2415 – (-0.0591 x pH)

E cell = 0.2415 + 0.0591 x pH

Advantages:

1. Colored solutions where the use of indicator is impossible are estimated by

potentiometric titrations.
2. Solutions more than one halide can be analyzed in a single titration against silver nitrate.

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