ELECTRO ANALYTICAL METHODS

OF ANALYSIS
Analytical chemistry spans nearly all areas of chemistry but
involves the development of tools and methods to measure
physical properties of substances and apply those techniques to
the identification of their presence (qualitative analysis) and
quantify the amount present (quantitative analysis) of species.

Electroanalytical methods are a class of techniques in analytical

chemistry which study an analyte by measuring the potential
(volts) and/or current (amperes) in an electrochemical cell
containing the analyte
 A number of important analytical methods are based on the
electrochemical properties of solutions. Eg: Functioning of a
galvanic cell and electrolytic cell.

 In general such electrical effects will depend on the

composition of the solution and on the nature of the
electrodes, and hence can have analytical importance.

 The distinction between the various electroanalytical

methods are determined largely by the nature of the
electrodes and by the external instrumentation.
 Some of the principal analytical methods that depend on electrochemistry
are:

 Conductometry: In this analytical method, two identical inert

electrodes which constitutes a conductivity cell is used. The
conductance of the solution between the electrodes is measured.

 Potentiometry: Potentiometric methods are concerned with the

measurement of potential as a function of analyte activity or
concentration.

 This is the direct analytical application of the Nernst equation

through the measurement of the potentials of non polarized
electrodes with no current flowing.
 Voltametry and polarography: These are the methods of
studying the composition of electrolytic solutions by
plotting current-voltage curves.
 Current is measured as function of applied potential
 Polarography is a subclass of voltammetry where the
working electrode is a dropping mercury electrode (DME)
 Voltammetry is the general name for the method, the
term polarography is usually restricted to applications of
the dropping mercury electrode
 Conductometric analysis

 Conductometric analysis is based on the measurement of the

electrical conductivity of the solution

 The electrical conductivity is entirely due to the movement of

ions. The ability of any ion to transport charge depends on
the mobility of the ion

 The mobility of an ion is essentially its rate of movement
through the solution under the influence of the imposed force
which could be an electrical field or a concentration gradient

 The mobility of an ion is affected by factors such as the
charge, size and the extent of solvation.
 TERMS AND TERMINOLOGIES:
 Conductance: In case of electrolytes, the term
conductance implies the ease with which the current
flows through a conductor. It is the reciprocal of
resistance
C = 1/R
Units: ohm-1 or mhos or Siemens.

Specific Resistance:
R ά l/a
R =ρ l/a
ρ = R x a/l
Where, ρ is constant called specific resistance or resistivity.
 Thus, specific resistance is defined as the resistance of a
uniform column of the material of the conductor having
a length of 1cm and area of cross section of 1cm2
 Units: ohm. cm
Specific Conductance: The specific conductance of any
conductor is the reciprocal of the specific resistance. It can
be considered to be the conductance of 1cm. cube of
material. It is denoted by κ (Greek, small kappa)
R =ρ l/a
R = 1/κ x l/a
κ = 1/R x l/a
Units: mho cm-1 or S m-1
If l=1cm and a= 1sq.cm. then
κ = 1/R = ρ
 Equivalent Conductance: This may be defined as the conductance of
a solution containing 1gm equivalent of an electrolyte when placed
between two sufficiently large electrodes which are 1cm apart. It is
denoted by λv where, v is the volume in c.c. containing 1gm
equivalent of electrolyte dissolved in it and is measured in reciprocal
ohms or mhos.
 λv = κ x V where,
 V= volume in c.c. containing 1gm equivalent of electrolyte
dissolved in it.
 Units: mho.cm2 or S. m2

 Molar Conductance: This may be defined as the conductance of a

solution containing 1gm mole of the electrolyte when placed
between two sufficiently large electrodes placed 1cm apart. It is
denoted by μv where V is the volume in c.c containg 1 gm
molecular weight of electrolyte,
 μv = κ x V where,
 V = volume in c.c containg 1 gm molecular weight of
electrolyte dissolved in it.
 Units: mho.cm2 or S. m2
 EFFECT OF DILUTION
On the Conductance: Conductance of a solution is due to the presence of
ions. The degree of dissociation of electrolyte increases with dilution,
which means more ions are produced in solution. The conductance of a
solution therefore increases with dilution
On the Specific Conductance: Specific conductance depends on the number
of ions present per c.c. of the solution. Even though the degree of
dissociation of electrolyte increases with dilution, the number of ions per
c.c. decreases. Therefore, the specific conductance decreases with dilution
On the Equivalent and Molecular Conductance: The equivalent
conductance increases on dilution. This increase is because of the fact that
equivalent conductance is the product of specific conductance and the
volume V of the solution containing 1gm equivalent of the electrolyte. The
decrease value of specific conductance is more than compensated by the
increasing value of V, therefore, the equivalent conductance will increase
on dilution.
Similarly molecular conductance increases with increase of dilution.`1`1
The equivalent conductance tends to become
maximum as the concentration decreases or
dilution increases.
 The maximum value of equivalent conductance
of as electrolyte obtained at very high dilution is
called the equivalent conductance at infinite
dilution.
It is denoted by the symbol λά .By infinite
dilution it means that the solution is already so
dilute that further dilution will not produce any
change in the equivalent conductance.
 EFFECT OF OTHER FACTORS ON DILUTION.
 Temperature: The conductance of all electrolytes increases
with temperature.
 Similar behavior is exhibited by the equivalent
conductance of strong electrolytes in finite
concentrations. However, with weak electrolytes the
variation of λ is not so regular, for in these not only
velocities of the ions and the inter ionic forces change,
but also the degree of dissociation.

 Dielectric Constant: The conductance behavior observed

in non aqueous solvents depends much on the dielectric
constant of the medium. The dielectric constant of water
is very high, 78.6 at 25oC, whereas that of most other
solvents is considerably lower. As the dielectric constant
of a solvent is lowered the conductance of an electrolyte
in the medium decreases.
H2O and NaCl(reduces the attraction between the ions)
“The greater the dielectric constant of the solvent, the greater
is its dissociating power.”
 Conductance Measurements:
 Requirements:
 Source of A.C.: Direct current can not be used in
the conductance measurements. This is because of
the fact that direct current results in the electrolysis
of electrolyte and bring about change in the
concentration of the electrolyte. This results in
polarization . To avoid these problems source of
A.C is used.

 Because if DC is used, solution undergoes

electrolysis and the products of electrolysis set up a
back emf which opposes the flow of current
 Polarization set ups and causes the variation in the
resistance
 Concentration of the solution varies
Conductivity cell: Conductivity cells are used to
measure the conductance of electrolyte. Different types
of conductivity cells are used for different purposes. Off
these simple dipping form of conductivity cell is
commonly used for conductometric titrations.

The fundamental requirement of conductivity cell is

that it should have a pair of electrodes that are firmly
located in a constant geometry with respect to one
another.
 The cells are usually made up of Pyrex
glass or quartz and are fitted with
platinum electrodes. The electrodes
are platinum plates coated with finely
divided platinum to reduce the
polarization effect and to achieve the
sharp end point. These are welded to
platinum wires which are sealed
through two glass tubes.
 These tubes are firmly fixed in an
ebonite cover so that the distance
between the electrodes is not altered
during the experiment. The electrodes
of the conductivity cell is connected to
the circuit.
The platinization is carried out by taking 2-3%
solution of chloroplatinic acid and 0.02to 0.03g
of lead acetate in the cell. The amount of the
solution should be enough to dip the electrodes.
The current is passed for 10-15min.The
electrolysis of chloroplatinic acid takes place and
the electrodes are blackened because of the
coating of finely divided platinum. The electrodes
are then washed repeatedly with distilled water
and these should be kept in conductivity water
when not in use.
 3.Conductivity Water: The conductivity of solution of
any electrolyte is very sensitive to the presence of
impurities. It is essential that water used in the
measurements of conductance should be of high degree
of purity. Hence ordinary water can not be used for the
preparation of solutions. Water for the conductance
measurements purpose can be prepared by distilling
distilled water.
 The presence of small amount of impurities such as
ammonia, CO2 and other traces of impurities in the water
influences the ionization of electrolyte there by altering
the conductance
Thermostat: The conductance of a solution is affected by
changes in temperature. Temperature coefficient for
conductance measurements is about 2% per degree of
Celsius. It is therefore, desirable to carry out measurements
at constant temperature. This is done by using a proper
thermostat, which can maintain the required temperature.
Measurement of conductance

Re sis tan ce of the solution Length Bd


Re sis tan ce R Length Ad

Thus, knowing R, Ad and Bd the resistance of the solution can be

calculated.

Conductivity of the solution = 1/Resistance of the solution

CONDUCTOMETRIC TITRATIONS:-

“The determination of the end point of a titration by

means of conductivity measurement is termed as
conductometric titration.”
 The titrant is added from the burette and the
conductivity readings corresponding to various
increments of titrant are plotted against the volume of
titrant.

Two curves will be obtained which will intersect each

other at a point, called “end point” or “equivalence
point.”
In order to get straight line graphs, it is essential that
the total volume of the solutions remains constant
during the titration. The concentration of the titrant
must be 10 times as the solution being titrated. This is
done to keep the volume change small.
Whenever necessary, a correction to the reading can
also be applied.
Thus, Actual conductivity = { v+V/V} x observed conductivity

Where, v= Volume of the titrant or reagent added.

V= Initial volume.
v + V = Final volume.
This correction presupposes that conductivity is a
linear function of dilution. In the interest of keeping v
small, the reagent for a conductometric titration is
ordinarily several times more concentrated than the
solution being titrated.
•It is possible to perform any titration conduct
metrically, if the conductance of the titrating solution
varies with one slope before the end-point and with
another slope after the end-point.
•The point of intersection of the two line marks the
end-point.
Reason for variation of conductance:-
(i) Dilution
(ii) Replacement of molecular species by ionic species or one
ionic species by another.
(iii) Conductance of an electrolyte is directly proportional to
mobility of ions and number of ions present in unit volume.
(iv) Mobility of H3O+ ions is about 5 to 7 times that of other
cations and that of OH- ions is about 3 to 5 times that of
other anions.
Advantages of conductometric titrations:-
(i) They are particularly useful in the case of coloured or turbid
liquids, where ordinary indicators cannot function.
(ii) They can be employed for the analysis of dilute solutions and
also for weak acids.
(iii) No special precautions are necessary as the titration
approaches the equivalence point, since the latter is found
graphically.
(iv) Mixture of acids can be titrated accurately.
(v) Very weak acids such as boric acid and phenol also can be
titrated by conductometric titrations.
 Questions related to the topic:

What is meant by conductometric method of analysis of the

solution?
Define: Conductuctance, specific conductance, molar conductance
and equivalence conductance. Write their S.I.unit.
Explain the effect of dilution on specific and equivalence
conductance.
Explain the effect of temperature and dielectric of the medium on
conductance.
What are the requirements of conductometric measurements?
Describe the construction of conductivity cell.
Define cell constant. What is its unit?
Explain in detail the basic principles of conductometric titration.
Give reason: In a conductometric titration strength of the burette
solution must be at least 10 times higher than the solution to be
titrated.
Applications of conductometric titrations:
Acid –base titration
Strong acid vs strong base

 When HCl acid is titrated with NaOH (approx. 10 times

more concentrated than HCl), more mobile H3O+ ions
are replaced by Na+ ions due to the neutralization of
H3O+ by OH - of NaOH added.

 HCl + NaOH  2H2O + NaCl

 Therefore conductance of the solution is maximum before

any NaOH is added. It goes on decreasing due to the
replacement of H3O+ ions by less mobile Na+ ions of
NaOH.
 This continues until the end-point. NaOH added
remains in solution after the end-point, as the
solution does not contain HCl to neutralize NaOH.

A highly mobile OH- ion of NaOH added increases

the conductance of the solution after the end-
point.

Thus a V-shaped graph is produced when

conductance of the solution is plotted with volume
of NaOH. The point of inter-section marks the
end-point of the titration.
Titration of weak acid against strong base:

 CH3COOH + NaOH  CH3COONa + H2O

 When CH3COOH is titrated with NaOH, the

conductivity decreases initially. Since the concentration of
H+ ions in CH3COOH is small.

 The conductance increases with the further addition of

NaOH due to the formation of Na+ and CH3COO- ions.
 When the neutralization of acid is complete, further
addition of NaOH produces excess of OH- ions and the
conductance of the solution increases more rapidly.
 Strong acid with a weak base:

Eg: HCl Vs NH4OH

HCl + NH4OH → NH4Cl + H2O

 Initially conductance decreases, due the replacement

of highly mobile H+ ions with less mobile NH4+ ions
due to the formation of NH4Cl.

 After the end point conductance will remain almost

constant, due the feeble dissociation of the weak
electrolyte, NH4OH.
 Weak acid with a weak base:
 v
Eg: H3C COOH Vs NH4OH
H3C COOH + NH4OH → H3C COONH4 + H2O
 In this case, the conductivity is governed by the extent of
ionization and concentration before the end point.
 The conductance decreases first, because of the replacement of
highly mobile H+ ions by less mobile NH4 ions. Then upto the
end point conductivity increases due to the dissociation of
fairly strong electrolyte, H3C COOH.
 After the end point excess of addition of NH4OH decreases the
conductivity due to very low degree of dissociation of
NH4OH.
conductance

Volume of NH4OH
 Related questions on the topic:

 Explain the procedure for a typical conductometric

titration.
 What precautions should be taken before doing
conductometric titration?
 Explain the nature of the graph for the conductometric
titration of strong acid against strong base with an
example.
 How can you explain the variation observed in the
conductometric titration of weak acid against strong base.
 Compare and give a proper explanation for the observed
trend in the conductometric titration of strong acid Vs
weak bas and weak acid Vs weak base.
Mixture of strong and weak acid against weak base.

HCl + NaOH  NaCl + H2O

CH3COOH + NaOH  CH3COONa + H2O

In the titration of a mixture of hydrochloric acid (strong acid)

and acetic acid (weak acid) with sodium hydroxide (strong
base), initially the conductance falls due to replacement of
highly mobile H3O+ ions by less mobile Na+ ions until all
the strong acid is neutralized.
Then the conductivity rises as the weak acid (feebly ionized) is
converted into its salt (highly ionized) and finally it rises
more steeply as excess of strong alkali (highly ionized giving
highly mobile OH- ions) is introduced.
This results in two break points on the Conductometric
titration curve, corresponding to two equivalent points;
neutralization of hydrochloric acid and neutralization of
acetic acid.

conductance
Precipitation titrations:-
 In precipitation titrations, one pair of ions is substituted for
another and based on choice of reagents, results in sparingly
soluble precipitate
K+ + Cl- + Ag+ NO3- K+ + NO3- + AgCl

(i) The addition of AgNO3, the conductance does not change

very much because the Cl- ions are replaced by NO3- ions; both
have almost same ionic conductance.
(ii) After the end point is passed, the excess of the added salt
causes a sharp increase in conductance.
Precipitation Titration

When Li2SO4 (or K2SO4) is

titrated with BaCl2, a white
ppt. of BaSO4 is formed by
the replacement of SO42-
ions with Cl- ions having
almost same conductance.
So, conductance remains
constant during titration.
After equivalence point
excess of BaCl2 added
increases the conductance
due to excess of Cl- ions
having higher conductance
than Ba2+ ions,

When conductance is plotted against volume of BaCl2 added, two st.

lines are obtained. The intersection point between two lines is the
volume of BaCl2 required to precipitate completely Li2SO4 (or
K2SO4) as BaSO4. Knowing the strength of BaCl2, strength of Li2SO4
can be calculated.
Conductometry titration
*Merits:
*Can be used in coloured solutions.
*Prior knowledge of pH of the solution is not necessary.
*Can be used for very dilute solutions and very weak
acids.
*Result obtained are more accurate since end point
obtained by graphical method.

*Limitations:
*Less accurate and less satisfactory in case of concentrated
solutions.
*Applications in redox titration is limited.
*Do not give good results for precipitation titrations.
 Questions related to the topic:

 With a neat diagram explain the variation of

conductance in case of mixture of strong and weak acid
against strong base.
 In what way conductometric titration is better than
volumetric estimation for the titration of mixture of
acids?
 What is a precipitation titration? How is it done by
conductometric method?
 What are the advantages of conductometric titrations?
 List the demerits of conductometric titrations?
POTENTIOMETRY

Potentiometry is an electro analytical technique in

which the amount of a substance in solution is
determined, from measurement of emf between two
electrodes that are dipped into the solution.

Nernst equation is the basis for the relationship between

the voltage generated by an electrochemical cells a
result of the two half cell reactions and the relevant
concentration at each electrode.
E = Eoox,red + (RT/2F) ln (aox/ared)
E can be measured by combining the electrode with a
reference electrode and measuring the emf of the cell.
The procedure of using single measurement of electrode
potential to determine the concentration of an ionic
species in solution is referred to as direct potentiometry.

The electrode, whose potential is dependent upon the

concentration of the ion to be determined, is termed as the
indicator electrode.

The indicator electrode responds to the change in

concentration of the analyte species present in the
solution, in which it is in contact with.
Measurement of pH and measurement of ion
concentrations using ion selective electrodes are the
example for direct potentiometry.
Classification of Electrodes.

 Gas electrode ( Hydrogen electrode).

 Metal-metal insoluble salt (Calomel

electrode).

 Ion selective electrode.(Glass electrode).

Gas electrode.

Construction.
 It consists of gas bubbling
over an inert metal wire
or foil immersed in a
solution containing ions of
the gas.

 Standard hydrogen
electrode is the primary
reference electrode, whose
electrode potential at all
temperature is taken as
zero arbitrarily.
 Representation: Pt,H2(g)/ H+

 Electrode reaction: H+ + e- 1/2 H2(g)

The electrode reaction is reversible as it can undergo
either oxidation or reduction depending on the other half
cell.

 If the concentration of the H+ ions is 1M, pressure of H2 is

1atm at 298K it is called as standard hydrogen electrode
(SHE).
Application
 To determine electrode potential of other unknown electrodes.
 To determine the pH of a solution.
E=Eo- 2.303 RT/nF log [H2]1/2/[H+]
= 0 -0.0591 log 1/[H+]
= -0.0591pH.
Cell Scheme: Pt,H2,H+(x)// SHE
 The emf of the cell is determined.
 E (cell) = E (c) – E(A)

= 0 – (- 0.0592 pH)
E (cell) = 0.0592 pH
pH = E(cell)/ 0.0592
Limitations.

 Construction and working is difficult.

 Pt is susceptible for poisoning.

 Cannot be used in the presence of oxidising agents.

 Difficult to maintain the pressure as 1 atmosphere,

and concentration of electrolyte as 1 M.
 Metal –metal salt ion electrode.

These electrodes consist of a metal and a

sparingly soluble salt of the same metal
dipping in a solution of a soluble salt having
the same anion.

Eg: Calomel electrode.

Ag/AgCl electrode.
Construction.

 Representation: Hg; Hg2Cl2 / KCl

It can act as anode or cathode

depending on the nature of the other
electrode.

As anode: 2Hg + 2Cl- → Hg2Cl2 + 2e-

As Cathode: Hg2Cl2 + 2e- → 2Hg + 2 Cl-

E = Eo – 2.303 RT/2F log [Cl-)2

= Eo -0.0591 log [Cl-] at 298 K

Its electrode potential depends on the concentration of

KCl.
Conc. of Cl- Electrode potential
0.1M 0.3335 V
1.0 M 0.2810 V
Saturated 0.2422 V
 Applications.

 Since the electrode potential is a constant it can be

used as a secondary reference electrode.

 To determine electrode potential of other unknown

electrodes.

 To determine the pH of a solution.

Pt,H2/H+(X) // KCl,Hg2Cl2,Hg
pH = E(cell) – 0.2422/ 0.0592
 Ion Selective Electrode

It is sensitive to a specific ion present in an

electrolyte.

The potential of this depends upon the

activity of this ion in the electrolyte.

Magnitude of potential of this electrode is an

indicator of the activity of the specific ion in
the electrolyte.

*This type of electrode is called indicator

electrode.
 Glass Electrode:`
Scheme of typical pH glass electrode

1. a sensing part of electrode,

2. a bulb made from a specific glass
sometimes electrode contain small
amount of AgCl precipitate inside the
glass electrode
3 internal solution, usually 0.1M HCl for
pH electrodes
4. internal electrode, usually silver chloride
electrode or calomel electrode
5. body of electrode, made from non-
conductive glass or plastics.
6. reference electrode, usually the same
type as 4
7. junction with studied solution, usually
made from ceramics or capillary with
asbestos or quartz fiber.
 Development of Glass Electrode Potential.
 The hydration of a pH sensitive glass membrane involves
an ion-exchange reaction between singly charged cations in
the interstices of the glass lattice and protons from the
solution.
H+ + Na+ Na+ + H+
Soln. glass soln. glass
 The overall potential of the glass electrode has three
components:

 The boundary potential Eb,

 Internal reference electrode potential Eref.

 Asymetric potential Easy.- due to the difference in response of

the inner and outer surface of the glass bulb to changes in [H+].

Eg = Eb + Eref. + Easy.
Derive an expression for glass electrode.

Eb = E1 ~ E2
= RT/nF ln C1 – RT/nF ln C2
= L + RT/nF ln C1

Eb depends upon [H+]

Eg = Eb + EAg/AgCl + Easy.
= L + RT/nF ln C1 + EAg/AgCl + Easy.
= Eog + RT/nF ln C1
= Eog + 0.0592 log [H+]
Eg = Eog – 0.0592 pH.
Applications.

Determination of pH:

Cell: SCE ║Test solution / GE

E cell = Eg – Ecal.
E cell = Eog – 0.0592 pH – 0.2422

pH = Eog -Ecell – Ecal. / 0.0592

 Advantages:
*It can be used without interference in solutions
containing strong oxidants, strong reductants,
proteins, viscos fluids and gases as the glass is
chemically robust.
*It can be used for solutions having pH values 2 to 10.
With some special glass (by incorporation of Al2O3
or B2O3) measurements can be extended to pH
values up to 12.
*It is immune to poisoning and is simple to operate
*The equilibrium is reached quickly & the response is
rapid
It can be used for very small quantities of the solutions.
Small electrodes can be used for pH measurement in
one drop of solution in a tooth cavity or in the
sweat of the skin (micro determinations using
microelectrodes)
6. If recently calibrated, the glass electrode gives an
accurate response.
7. The glass electrode is much more convenient to
handle than the inconvenient hydrogen gas
electrode.
Disadvantages:
* The bulb of this electrode is very fragile and has to
be used with great care.

* The alkaline error arises when a glass electrode is

employed to measure the pH of solutions having
pH values in the 10-12 range or greater. In the
presence of alkali ions, the glass surface becomes
responsive to both hydrogen and alkali ions. Low
pH values arise as a consequence and thus the glass
pH electrode gives erroneous results in highly
alkaline solutions.
* The acid error results in highly acidic solutions
(pH less than zero)Measured pH values are high.

* Dehydration of the working surface may cause

erratic electrode performance. It is crucial that
the pH electrode be sufficiently hydrated before
being used. When not in use, the electrode
should be stored in an aqueous solution because
once it is dehydrated, several hours are required
to rehydrate it fully.
* As the glass membrane has a very high
electrical resistance (50 to 500 mΩ), the
ordinary potentiometer cannot be used for
measurement of the potential of the glass
electrode.
* Thus special electronic potentiometers are
used which require practically no current for
their operation.
* Standardization has to be carried out frequently because
asymmetry potential changes gradually with time.
Because of an asymmetry potential, not all glass
electrodes in a particular assembly have the same value of
EoG . For this reason, it is best to determine EoG for each
electrode before use.
* The commercial version is moderately expensive
 Limitations.

* The bulb is very fragile and has to be used with

great care.
* In the presence of alkali ions, the glass surface
becomes responsive to both hydrogen and alkali
ions. Measured pH values are low.
* In highly acidic solutions (pH less than zero)
measured pH values are high.
* When not in use, the electrode should be stored
in an aqueous solution.
Principles of Potentiometric Titrations:
Potentiometric methods includes two major types of
measurements.
The direct measurement of an electrode potential from which
the concentration of an active ion may be found and the
changes in the EMF of an electrolyte cell brought about by the
addition of a titrant
The equivalence point of the reaction will be revealed by the
change in potential in the plot of e.m.f readings against the
volume of the titrating solution.
The change in the electrode potential upon the addition of the
titrant are noted against the volume of the titrant added. At the
end point the rate of change of potential is maximum. The end
point is determined by plotting a curve of potential versus the
volume of titrant and recording the inflexion point.
 Kinds of titration
(1) Acid-base
(2) Redox
(3) Complexometry
It is used when the end points are very difficult to determine, either when
(1) Very diluted solution
(2) Coloured and turbid solution
(3) Absence of a suitable indicator
It is a regular titration but instead of the indicator we
used the potentiometer.
Electrode will measure the pH of the media.

Instruments requirement:-
Combined glass electrode (double function electrode)
Potentiometer pH meter
Redox (mV)
Magnetic stirrer
Hot-plate (use the stirrer and make sure heat is off)
Magnet capsule
 Objectives
Titration of a weak acid (acetic acid) against a strong
base (NaOH)
Stock solution:-

(1) Unknown acetic acid solution

(2) 0.1N NaOH
Experiment

Fill the burette with the standard titrant.

Pipette 5 mls of acetic acid sample into 100 mls
beaker and dilute to 50 by distilled water.
Put a magnet stirrer and dip in the combined electrode
( make sure that the bulb of the electrode and the
junction bridge are dipped completely under the
water.
Switch on the stir and allow few second before
reading the pH of the solution.
 start the titration by adding 0.5 mls of the titrant,
stir well and then read the pH of the solution .
Continue titration as before until near the end point
( pH change is grater than 0.2 ) , add small portion
of the titrant ( 0.1mls), stir well then take the pH
reading.
Repeat until about 10 mls of the standard
titration has been added.

Plot the potentiometric curve ( pH value against

ml of the titrant ) , determine the end point from
the curve and calculate any required data.
Background

Consider the following graph:

13

12

11

10

9
pH

3
0 5 10 15 20 25 30 35
Volum e NaOH (m L)
 13

12

11

10

9
pH

3
0 5 10 15 20 25 30 35
Volum e NaOH (m L)

In this region H+ dominates, the small change in pH is the

result of relatively small changes in H+ concentration.
 13

12

11

10

9
pH

3
0 5 10 15 20 25 30 35
Volum e NaOH (m L)

In this region, relatively small changes in H+

concentration cause large changes in pH, The midpoint
of the vertical region is the equivalence point.
 13

12

11

10

9
pH

3
0 5 10 15 20 25 30 35
Volum e NaOH (m L)

In this region sodiumacetate (CH3COONa) dominates,

the small change in pH is the result of relatively small
changes in CH3COONa concentration.
The titration curve can also be obtained by plotting
emf readings obtained with the glass electrode.
Over most of the titration ranges, the cell emf varies
gradually, but near the end point, the cell emf changes
very abruptly as the logarithm of the concentration
changes rapidly.
The resulting titration curve will be a S-shaped curve
as shown in the figure.
 The end point can be located on the steeply rising portion of the
curve, at the point of inflection, the point which corresponds to
the maximum rate of change of cell emf per unit volume of the
titrant.

 The accuracy of the result obtained by the above procedures

will be dependent upon the skill with which the titration curve
has been drawn through the points plotted on graph from the
experimental observations.
 The first derivative curve gives a maximum at the point of
inflection of the titration curve, i.e., at the end point.
 Fig shows the second derivative for the data changes sign
at the point of inflection.
 This change is used as the analytical signal in some
automatic titrators.
 The point at which the second derivative crosses zero is
the inflection point, which is taken as the end point of the
titration; this point can be located quite precisely.
Vol.
Acid base titrations:-
For an acid base titrations, the indicator electrode has
to be a pH sensitive or H+ sensitive electrode as it has to
respond to the change in pH during the titration.
The accuracy of the method depends upon the
magnitude of the change in emf in the neighborhood of
the equivalence point, and this depends upon the
concentration and strength of the acid and alkali.
For eq (i) CH3COOH Vs. NaOH
(ii) Mixture of acids Vs. NaOH
 Principles of Potentiometric Titrations:

 Potentiometric methods includes two major types of

measurements.

 The direct measurement of an electrode potential from

which the concentration of an active ion may be found
and the changes in the EMF of an electrolyte cell brought
about by the addition of a titrant

 The equivalence point of the reaction will be revealed by

the change in potential in the plot of e.m.f readings
against the volume of the titrating solution.
One electrode must maintain a constant,
The other electrode must serve as an indicator of
the changes ion concentration and must respond
rapidly.

The solution must be stirred during the titration.

In potentiometric titrations the change in the electrode
potential upon the addition of the titrant are noted
against the volume of the titrant added. At the end point
the rate of the change of the potential is maximum. The
end point is determined by plotting a curve of potential
versus the volume of titrant and recording the inflexion
point.
Location of End Points:

The end points in the usual potentiometric

titrations are obtained by graphical method, by
carrying out the reactions under constant current.

 Under such situations, sharp change of potential

is obtained at the end point.

When the titration curve has been obtained, i.e

the plot of e.m.f readings obtained with the
normal reference electrode-indicator electrode
pair against the volume of the titrant is added, S
shaped curve is obtained.
From the central portion of the curve the end
point will be located on the sharply rising
portion of the curve.

It will in fact occur at the point of inflection

The second method for the location of the end

point is analytical ( Derivative) method. This
consists in plotting the first derivative curve or
the second derivative curve.
Kinds of titration
(1) Acid-base(neutralization)
(2) Redox
(3) Complexometry

It is used when the end points are very difficult to

determine, either when
(1) Very diluted solution
(2) Coloured and turbid solution
(3) Absence of a suitable indicator
 Types of Potentiometric Titrations

1.Neutralisation Reaction:

Neutralisation titration is always accompanied by the

changes in the concentration of H+ ions and OH- ions.

HCl + NaOH -------- NaCl + H2 O

Indicator Electorde: Hydrogen electrode, glass electrode or

antimony electrode.

Reference electrode: Saturated calomel electrode.

Procedure:
A known volume of the acid to be titrated is kept in a beaker
having an automatic stirrer. A standared hydrogen electrode
is placed inside the beaker. It is connected to the calomel
electrode through the salt bridge. Electrodes are connected to
a potentiometer which records the e.m.f of the solution.
After the addition of the base from the burrette, readings are
recorded.
The values of e.m.f. are then plotted against the ml
of the base added.

E = Eo - 0.0591 log[H+]
This method may be used to titrate a mixture of
acids which differ greatly in their strength.
Eg; mixture of acetic acid and hydrochloric acid.

The first break in the titration curve occurs when

the stronger of the two acids is neutralized and
the second when neutralization is complete.

Satisfactory results are obtained in all types of

neutralization reactions except when either acid
or the base is very weak and the solutions are
dilute.
Oxidation and Reduction (Redox ) Titration:
 Redox reactions can be followed by an inert electrode
like bright Pt foil. The oxidizing agent is usually taken in
the burette.
M → Mn+ + ne-
 Ered = E0 red — 0.0591/n log[red]/[oxe]
 Where, E0 red is standard reduction potential of the
system.
 The potential of the immersed electrode is thus controlled
by the ratio of these concentrations. During the redox
reaction, the potential changes more rapidly in the
vicinity of the end point of the reaction.
 Eg: Titration of ferrous and cerium salts.
Ce4+ + Fe2+ → Ce3+ + Fe3+

Ce4+ + e → Ce3+ E0 = 1.61V

Fe3+ + e → Fe2+ E0 = 0.76V

E = E0 — 0.0591/n logK

ECe4+/Ce3+ = E0Ce4+/Ce3+ — 0.0591/1 log [Ce3+/Ce4+]

EFe3+/Fe+2 = E0Fe3+/Fe+2 — 0.0591/1 log [Fe2+/Fe3+]

At the middle of the titration:

[Fe2+] = [Fe3+]
EFe3+/Fe+2 = E0Fe3+/Fe+2
 At the equilibrium point concentration of unchanged
[Fe2+] ions equal to concentration of unchanged [Ce4+]
ions.

K = [Fe3+] [Ce3+] / [Fe2+] [Ce4+]

 At the equivalence point,

[Fe3+]/ [Fe2+] = [Ce3+]/[Ce4+] =K1/2

 Eeq[Ce4+]/[Ce3+] = E0[Ce4+]/[Ce3+] — 0.0591logK1/2

 Eeq[Ce4+]/[Ce3+] = E0[Ce4+]/[Ce3+] — 0.0591/2 logK

Similarly,

Eeq[Fe3+]/[Fe2+] = E0[Fe3+]/[Fe2+] — 0.0591/2 logK

On adding:

Eeq = E0[Ce4+]/[Ce3+] + E0[Fe3+]/[Fe2+]

------------------------------------
2
Applications:

Redox titrations may be used in procedures such

as monitoring of cyanide wastes from metal
plating inindustries or chlorine compounds in
bleaching compounds manufacturing.

These bleach compounds are used in paper

manufacturing.

They are also extensively used in water pollution,

sewage disposal, agricultural and biochemical
studies.
Precipitation Titration:

The titration of chloride ions with a standard solution of

silver nitrate using silver metal indicator electrode.

Any precipitation titration that involve insoluble salts of

metals such as Hg, Ag, Pb and Cu may followed
potentiometrically.

The indicator electrode may be metal involved in the

reaction or may be an electrode whose potential is
governed by the concentration of the anion being
precipitated.
Precipitation Titration:

The titration of chloride ions with a standard solution of

silver nitrate using silver metal indicator electrode.

Any precipitation titration that involve insoluble salts of

metals such as Hg, Ag, Pb and Cu may followed
potentiometrically.

The indicator electrode may be metal involved in the

reaction or may be an electrode whose potential is
governed by the concentration of the anion being
precipitated.
 The titration of chloride ions with a standared
solution of silver nitrate using silver metal
indicator electrode is an example of a
precipitation titration.
The indicator electrode may be metal involved
and the reaction or may be an electrode whose
potential is governed by the concentration of the
anion being precipitated.
NaCl + AgNO3 → AgCl + NaNO3
The magnitude of the potential change at the end
point depends on the solubility of the substance
being precipitated as well as the concentration
involved.
Polarography

It is a method of analysis in which the solution to

be analysed is electrolysed in such a way that, the
graph of current Vs voltage shows what is in the
solution and how much it is present.

This method of instrumental analysis consists of

measurement of potential difference as current
flows in the solution.
The basic idea is to pass the current between two
electrodes, one large in are and other very small.

Normally, both the electrodes are of Hg. The

anode is a pool of Hg at the bottom of the cell.

The cathode is a drop of Hg coming out of a

very fine capillary tube.
The electrolytic solution is a very dilute solution of
the material to be analysed in a suitable medium,
containing an excess of indifferent electrolyte called
base or supporting electrolyte.

The purpose of supporting electrolyte is to carry the

bulk of the current and raise the conductivity of the
electrolyte.

From the current-voltage curve which is known as

polarogram the information about the nature and
the concentration of the material may be obtained.
ADVANTAGES OF DROPPING MERCURY ELECTRODE.
* Its surface area is reproducible.

* Mercury forms amalgam with metals there by

lowering their reduction potential.

* The surface area can be calculate by drop weight

method.

* Overvoltage of hydrogen is high, hence metal

deposition can take place more easily on the mercury
drop.

*Diffusion current reaches steady value almost

instantaneously and is reproducible.
LIMITATIONS OF DROPPING MERCURY
ELECTRODE.

* The area of the electrode constantly changes

with change in the size of the mercury drop.

* Mercury may be easily oxidized and limits its

utility.

* The capillary may easily blocked due to the

presence of even trace of impurities.
Cell Assembly
Description of cell assembly:

 A working electrode, at which the electrolysis under investigation takes

place-dropping Hg electrode.

 A reference electrode, which is used to measure the potential of the working

electrode—SCE

 An anode together with working electrode to carry the electrolysis current—

Hg pool.
 Polarographic analysis of CdCl2

* If a steadily increasing voltage is applied to a cell

incorporating a relatively large anode and a minute
mercury cathode (composed of a succession of small Hg
drops falling slowly from a capillary tube) it is frequently
possible to construct a reproducible current voltage curve.

 The entire polarographic study is carried out by passing

nitrogen gas, in order to avoid the reduction of oxygen
gas and hence to eliminate the polarographic maxima in
the graph.
Polarogram
 Curve AB: From A to B a small current flows. This is
known as residual current and is carried by the
supporting electrolyte and impurities present in the
sample

* At point B, the potential of the electrode becomes equal

to the decomposition potential of the Cd+2 ion. Then the
current increases along the curve BC. At the point C,
current no longer increases linearly with applied voltage
but reaches a steady limiting current.

 The difference between the residual current and the

limiting current is known as diffusion current and is
denoted by id.
 FACTORS AFFECTING THE LIMITING CURRENT:

 The factors which affects the current- voltage curve

are as follows:

 Residual current.

 Migration current.

 Diffusion current.

 Kinetic current.
 Residual Current:

The current is not zero when no residual ions are present.

As the mercury drop grows, ions from supporting
electrolyte gather around it. If the drop is negatively
charged, these ions are positively charged. However they
are not reduced at the mercury drop, but remain close to
the mercury drop forming the electrical double layer. This
effect is equal to charging of the condenser.
When the mercury drop falls off, a new drop forms new
condenser is charged up. This caused continuous increase
in the current as the potential increases. Small amount of
current also flows due to impurities present in the
electrolyte.
 Residual current = Condensor current + Faradic current
 Migration Current:

The electroactive material reaches the electrode by two

processes:

 The first involves the migration of charged particles in the

electrical field caused by the potential difference existing
between the electrode surface and the solution.

 The second involves the diffusion of particles.

 The current required for the above two processes is called

migration current. However, migration current can be
almost eliminated if an indifferent electrolyte is added to
the solution in a concentration so large that its ions carry
almost all the current.
Diffusion Current:

The maximum current flowing in the system is called

diffusion current. It is directly proportional to the
concentration of the substance being reduced or oxidized
at the dropping mercury electrode. The current is given
by the Ilkovic equation:

Id = 607 nC D½ m2/3 t 1/6

 Id = the diffusion current in microamperes
averaged over the lifetime of the drop

n = number of the electrons transferred per ion

C = concentration in millimoles per litre.

D = diffusion coefficient of the reducible ion in cm2
sec-1

m = mass the mercury flowing per second in

milligrams,

t= drop time in seconds.

Kinetic Current:

The limited current may be affected by the rate of non

electrode reaction.

It will be proportional to size of the mercury drop but is

independent of velocity of the mercury from the
capillary.

This current results if the oxidized or reduced form of the

electroactive species involved in the process.

Since they are rate processes resulting current is known as

kinetic current.
 EVALUATION OF QUANTITATIVE RESULTS IN
POLAROGRAPHY

With a well defined polarographic wave, where the

limiting current is parallel to the current curve, the
measurement of diffusion current is relatively simple.

In exact procedure, the actual residual curve is determined

separately with the supporting electrolyte alone and
subtracting the residual current from the value of the
current at the diffusion current plateau.

The measured wave height is directly proportional to

diffusion current which in tern related to concentration of
the given electrolyte by Ilkovic equation
Following methods are usually adopted for the
determination of strength of the solution by measuring
the wave heights.

Wave height –concentration plots

Solutions of several different known concentrations of the

ion under investigations are prepared, the concentration
of the supporting electrolyte and the amount of the
maximum suppressor added being the same for the
comparison standards and for unknown.
The heights of the waves obtained are measured in any
convenient manner, and plotted as a function of the
concentrations.

The polarogram of the unknown is produced exactly as

the standards, and the concentration is read from the
graph.
 Internal standard method

The relative diffusion currents of ions in the same

supporting electrolyte are independent of the
characteristics of the capillary and temperature.

Hence upon determining the relative wave heights of the

unknown ion and with some standard ion or pilot ion
added to the solution in known amount, and comparing
the these with the ratio for known amounts of the same
two ions, previously determined, the concentration of the
unknown can be determined
HALF WAVE POTENIAL

Half wave potential in polarography is

characteristic property of the electroactive
materials.

This potential is found on the steeply rising

portion of the current voltage curve and is one
half of the distance between the residual and
the limiting current.
 EXPRESSION FOR HALF WAVE POTENTIAL

Consider the reversible and rapid half cell reaction at the

microelectrode
Ox + ne  Red
eg: Cd+2 + e- -- Cd

Where Ox is the substance being reduced and Red stands

for the product.

The electrode potential is given by Nerst equation.

E cathode = Eo--- 0.0591/n log [ Red]o/[Ox]o

O indicates the concentration of the species on the DME

Eapplied = Ecathode + E anode

However,anode potential is equal to potential of SCE

Eapplied = Eo--- 0.0591/nlog [Red]o/[Ox]o + E anode

E applied---E SCE = Eo --- 0.0591/n log [ Red]o/[Ox]o

When the applied voltage is sufficiently large to reduce

some of the oxidant, the oxidant concentration at the
electrode surface starts decreasing. Some ions move
towards the surface of the microelectrode from the bulk
of the solution building up a concentration gradient. Thus
at the applied voltage, the observed current is given by
i = K ([Ox] – [OX]o) –(1)
where K stands for the capillary characteristics and other
constants of the Ilkovic equation.
 At the diffusion current plateau, the
concentration of the oxidant at the electrode
surface is virtually zero so that the diffusion
current is given by
id = K[Ox] ---(2)
Subtracting (2) from (1) get
[OX]o = id --i/ K
Again the concentration of the product [Red] at
the electrode surface provided it is soluble, is also
given by
i = K’[ Red]o
where K’ is another constant analogous to K
or [Red]o = i/K’
Substituting the above values of the concentrations in the
Nenrst equation we obtain

Eapplied ----ESCE = Eo ---- 0.0591/n log [i * K / id –i * K’]

Rewriting

Eapplied =
ESCE + Eo --- 0.0591/nlog K/ K’ - 0.0591/n log i/id-i

By definition i = id/2
E applied = E1/2
Substituting we get:
E 1/2 = E SCE + Eo --- 0.0591/n log K/ K’
 Thus have wave potential is a constant which
depends on the standard potential of the redox
system and is independent of the concentration
of the electro active substance.

Thus
Eapplied = E1/2 --- 0.0592/n log i/ id – I

A plot of Eapplied Vs log i/ id – i gives a straight

line with the slop equal to 0.0592/n .From the
slope the value of n i.e the number of electrons
gained by the reductant can be calculated.
 In polarographic practice with DME, a surface effect is
observed in many cases in the form of enhancement
of limiting current to a high value at some potentials
near the top plateau before the normal plateau is
gained. This effect is known as polarographic
maximum.
 Polarographic maxima
 As the applied potential is raised, the current,
after increasing as an ion is discharged, fails
to level off, but decreases again, leaving a
maximum in the curve. Such a maximum may
only be a slight hump or it may be a very
sharp peak,exceeding the true wave height.
This phenomenon is not fully understood,
though it appears to be related to the
tangential streaming motion of solution past the
surface of the drop.
 For accurate work the maxima must be eliminated or
suppressed. This can be done by the addition of a very small
quantity of surface active substance like dyestuff,methyl red
dye,gelatin or other colloids.. Such maximum suppresor
probably form an adsorbed layer on the aq. Side of the
mercury solution interface which resist compression. This
prevents the streaming movement of diffusion layer at the
interphase.
 Peaks arise from convection around the expanding Hg drop.
 Generally the addition of small amounts of surfactants
(0.002% to 0.01%) will eliminate maxima.
 Care must be taken to avoid adding large amounts of these
maxima suppressors because they can change the solution
viscosity and reduce the magnitude of the diffusion current.
These limitations along with the toxicity of Hg have been
responsible for the incresing polularity of solid electrodes versus
DME in voltammetry.
Applications of Polarography: --Inorganic Chemistry.

 Polarography can be used for the estimations of cations

and anions in the presence of interfering ions.

 Polarography of aqueous solutions of cations may be

determined in the concentration range of 10-2 and 10-6 M.
Successful results can be obtained by the proper selection
of supporting electrolyte.

* Lithium having a negative wave potential can be

estimated in the presence of other alkali metals, but the
concentration of other alkali metals should not be very
high.
 This technique is useful for the separation of zinc and
nickel, which have nearly identical half wave potential in
neutral chloride solution. An alkali hydroxide can be used
as the supporting electrolyte.

 Zincate ions are reducible, whereas nickel is precipitated

as the hydroxide. In the nickel and zinc, the two waves
can be separated at -1.06V and -1.33V using 1N ammonia-
aqueous ammonia buffer.

 In the determination of lead, ammonia-ammonium

nitrate buffer can be used as supporting electrolyte. The
estimation should be carried out at 0oC.The half wave
potential of the system is -0.35V.
The mixtures of ions can be determined if the
half wave potentials of the ions are separated by
0.2V. This difference is essential in order to
distinguish the height of two waves; otherwise
the overlapping of the waves takes place. The
various ions present can be estimated in a single
run.
 Determination Of dissolved oxygen
In this method the dissolved oxygen is not swept out withnitogen gas as
with other samples. Instead the oxygen waves are measured and
dissolved oxygen determined.
Two waves of approximately equal height are obtained depending
upon pH. Usually the medium is kept acid and the following reaction is
taken into consideration.
O2 + 2 H+ + 2e- H2O2
Study of complexes

 Polarography is a tool used in the study of the

composition of complexes if the simple metal ion and
complex of that metal ion in the same oxidation state
give reversible electrode processes and involve the
same no. of electrons.
Pharmaceuticals

 Some of the local anesthetics are directly reduced at

the DME. Ex: Ketones. Propiocaine showing waves at
negative potential ,the wave height proportional to
the conc. Polarographic studies of the vitamins have
also been done.