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Chemistry Notes

Unit – II, Electroanalytical Techniques

Chemical Analysis is of two types:

A) Qualitative analysis: Study of composition / content present in material.

B) Quantitative analysis: Study of amount / quantity of various components present.

Electroanalytical Technique: Analytical Techniques based on Electrochemical principle make use of

basic electrical measurements of current, resistance or voltage alone or in combination.

In this chapter we have to study four Electroanalytical Techniques.

1) Conductometry 2) pH metry 3) Potentiometry 4) UV- Visible spectroscopy

But before these concepts some basic terms must be clear.

Introduction:

REPRESENTATION OF A DANIEL CELL:-

i) Zn(s) | ZnSO4 (sol) || CuSO4 (sol) |Cu (s)

ii) Zn-| ZnSO4 (aq.) || CuSO4 (aq.) | Cu+
iii) Zn|Zn2+||Cu2+|Cu
iv) Zn|Zn2+ (1M) ||Cu2+|Cu (1M)

The Nernst Equation:- E cell = E0cell - (RT/nF) lnK

Ecell = cell potential under nonstandard conditions (V)

E0cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical reaction (mol)
F = Faraday's constant, 96500 coulombs/mol
K = reaction quotient / constant

Sometimes it is helpful to express the Nernst equation differently:

Ecell = E0cell - (2.303 x RT/nF) log K

at 298K, Ecell = E0cell - (0.0591 /n) log K

Application of Nernst equation in electrochemistry:-

1. The potential of an electrode and EMF of a cell can be calculated at any temperature and concentration.
2. If potential of an electrode is known, the concentration of the reactant can be calculated.
3. The concentration of a solution in the galvanic cell can be determined.
4. The pH of a solution can be calculated by measuring the EMF.

Types of Electrodes:- Reference electrodes & Indicator electrode

Reference electrodes are those electrodes whose standard potential is known or strength is known.
Ideal reference electrodes are:
1) It is reversible and obeys the Nernst’s equation.
2) Which exhibits a potential that is constant with time.
3) Which returns to its original potential after being subjected to small currents.
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In general, there are two types of reference electrodes,

A) Primary reference electrode - e.g., Hydrogen electrode

B) Secondary reference electrode – e.g. Calomel electrode, silver-silver chloride electrode.

Difficulties in using standard hydrogen electrode -

1) Platinum used in it, gets poisoned by absorption of impurities from the solution and the gas, hence it
does not behave reversible for longer period.
2) Because of presence of oxidizing agent, unsaturated organic compounds, alkaloids etc. in solution alters
the potential.
3) It cannot be used in presence of Cu, Ag, Au etc.
4) It is difficult to prepare and maintain pure H2 gas at 1atm pressure and concentration of electrolyte 1 M.
So, we use secondary reference electrode which is convenient to handle.

Secondary Reference Electrode: Calomel Electrode

Construction:
Calomel electrode consists of a narrow glass tube at the
bottom of which is liquid mercury, above it is a paste of Hg –
Hg2Cl2 (calomel) and remaining portion of glass tube is filled
with 1 N or 0.1 N or saturated solution of KCl. The potential of
the calomel electrode depends upon the concentration of KCl
solution.

Pt. wire dipping into the mercury layer, is used to make

electrical contact.
Calomel electrode is represented as: Hg | Hg2Cl2(s) | KCl sat.
Reaction:-

Hg2Cl2 + 2e- 2 Hg + 2 Cl-

Advantages of Calomel electrode:-
1) The construction is very simple.
2) The cell potential is reproducible
3) Potential does not vary for much long time.

Disadvantages of Calomel electrode:-

1) It should not be used above 800C, because calomel
disproportionate at very high temp. into mercury and mercuric
chloride.
2) It involves handling of poisonous Hg and Hg2Cl2

Indicator Electrode (Glass Electrode):-

1. Principle
When two solutions of different [H+] are separated by a
thin glass membrane, a potential difference is developed at the two
surfaces of membrane. The potential difference developed is
proportional to the difference in [H+] of the two solutions.

The glass membrane acts as ion exchanger i.e. exchange of Na+ of

glass with H+ of solution.

2. Construction: A glass electrode is made of a long glass tube with a

thin walled glass membrane bulb at the bottom. A Pt wire or AgCl
coated Ag wire is dipped in the 0.1 M HCl solution in the bulb.
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The half cell representation is: Pt | 0.1 M HCl | H+ (Test Solution)

and potential, EG = E0G + 0.0591 pH

Where E0G is the potential of glass electrode in a solution of known pH

Working: A glass electrode is coupled with calomel electrode, to determine the pH of a solution. The
electrodes are dipped into the solution of unknown pH.

EMF of the cell is measured, (Ecell)

E0G is the potential of electrode when electrode is in contact of solution of known pH.

Advantages of glass electrode:-

1) It is portable and compact gives accurate & quick results.
2) Equilibrium is easily attained.
3) It can be used in the presence of biological fluids.
4) It is used for determining pH of the solution and estimate H+ ions in presence of other type of ions.
5) It is not used in strongly acidic and alkaline solutions.

Ion Selective Electrodes:

A membrane of a half cell is sensitive to particular ion in

solution and ion exchange takes place between the membrane
electrode and the solution containing specific ions and develops
a potential which depends upon the concentration of that ion.

a) Glass membrane electrodes : These electrodes are formed

by doping molten SiO2 with various chemicals. The most
common such electrode is the H+ sensitive electrode or pH
electrode. The H+ from solution get exchanged with Li+ in the
glass.

Li+ Gl− + H+ ⇄ H+ Gl− + Li+

Thus different glass compositions can be made to measure Na+, Ag+, K+, +NH4. On immersing glass
electrode in a solution, a hydrated gel layer formed causes swelling of the membrane. The ion exchange
process takes place in the gel layer of the glass membrane, generates a phase boundary potential, given by,

Egl = E0gl. + 0.0591 log10 [M+ n]

E0gl. = Standard electrode potential

[M+ n] = Concentration of the ions of
interest (study) in solution

b) Solid-state electrodes :
In the non glass solid state sensors,
ionic conducting membranes are used.
e.g.

(i)Homogeneous electrode of finely divided crystalline material like LaF3 for determination of F– in water.
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ii)Heterogeneous electrode consisting solid crystalline material incorporated with polymer like PVC or
silicon.

c) Gas-sensing electrodes :

These electrodes are useful to

analyze gases such as NH3,
NO2, SO2, CO2 and H2S.
A nitrate ion responsive
electrode is for NO2 while a
sulphide-ion selective electrode
is for H2S.

The microporous membrane is

hydrophobic, made from polypropylene or any other fluorocarbon which allows only dissolved gases to
pass through.

The electrodes Ag/AgCl and glass pH-electrode are dipped in the inner solution. Area of membrane being
small and volume of liquid being less, it reaches equilibrium with the test solution rapidly.

d) Liquid-liquid membrane electrode :

Liquid ion exchange membranes have functional

groups to form co-ordination complexes.

The inner solution containing known concentration

of the ion is placed in a glass tube fitted with
Ag/AgCl electrodes selective to it. The outer
aqueous solution is separated from the inner
solution by liquid ion-exchange membrane.

The membrane seals the bottom of the electrode

vessel. The outer compartment contains the organic
liquid ion exchanger. The membrane is
replaceable.
The boundary potentials across the two solutions membrane interface is functionally dependent on the ion
activity and is fixed at a constant temperature.

A) CONDUCTOMETRY: INTRODUCTION

The ability of any ion to transport charge depends on the mobility of the ion, mobility of ion is
affected by factors like the charge on ion, size and mass of ion and extent of solvation.

Important laws, definitions and Relations used in conductometry

Ohm’s Law:- “The current flowing through a given solution is directly proportional to the voltage
(potential difference) between the two ends of the conductor through which the current is flowing”.

Mathematically it is written as, I α V or I α E

E=RI (Where I = current strength, E = V = potential difference)

R = Proportionality constant called resistance

i.e. R = E / I OR V / I
Unit of resistance (R) = Volts/ampere,
therefore its unit is Ω (ohm).
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Resistance (R): The tendency of a material to stop the flow of current is known as resistance. It is
measured in ohms (Ω).
According to Ohm's law, the resistance offered by a substance is directly proportional to
its length (l), but inversely proportional to its cross sectional area (A). cm2

ρ is the proportionality constant and is known as specific resistance or resistivity of solution of length 1
cm and area of cross section 1 cm2, then R = ρ. In other words, ρ is the resistance of 1 c.c. of solution.
𝐴𝐴 cm2
Its unit is ohm cm 𝜌𝜌 = 𝑅𝑅 = 𝑜𝑜ℎ . = ohm. cm
𝑙𝑙 cm

Specific conductance / Conductivity (k): Reciprocal of specific resistance ρ is called as specific

conductance and it is the conductance of one cm3 of solution, denoted by k (kappa).

It is measured in ohm-1.cm-1 = mho. cm-1 in (C.G.S system); or Siemens m-1 (S.I system)

Equivalent conductivity: Conductance of solution by solution containing one gm-equivalent of an

electrolyte, dissolved in volume V ml solution is known as Equivalent conductance and it is denoted by ∧.
As one c.c. or ml of solution has conductance equal to (k) specific conductance, therefore
equivalent conductance and specific conductance are related as,

∧ = kV (where V is ml of solution containing one gm-equivalent of electrolyte)

If C is the concentration of solution as gm-equivalent per litre (normality), then volume V of the solution
in ml containing 1 gm-equivalent will be 1000/C.

Unit of ∧ is ohm– 1 cm2 per equivalent.

Molar conductivity:
Conductance of solution by solution containing one gm-mole of electrolyte is known as molar conductance
and it is denoted by μ.

where M is concentration of solution in moles/litre. Unit of μ is ohm– 1 cm2 per mole.

Cell constant: - The ratio of the distance between the electrodes (l) to the cross sectional area (A) of the
electrodes is known as cell constant.
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As we know that,

Variation of Equivalent Conductance with Dilution / Effect of dilution on specific conductance and
equivalent conductance:

Effect of Dilution is as follows: (summary)

(i) The conductivity of solution increases on dilution.
(ii) The specific conductivity decreases on dilution (as no. of ions decreases w.r.t. to volume).
(iii) The equivalent and molar conductivities increase with dilution.
(iv) The equivalent and molar conductivities tend to acquire maximum value with increasing
dilution. [Maximum at infinite dilution]

Effect of Dilution: (description)

Specific conductance is conductance of no. of ions per ml of solution. The degree of dissociation of weak
electrolyte is increased on dilution but no. of ions per ml are decreased. Thus Specific conductance of
solution of an electrolyte decreases with dilution.

The equivalent & Molar conductance, increases with decreasing concentration, (i.e. with increase in
dilution) for both weak and strong electrolytes. This is due to the fact that degree of ionization increases
with dilution thereby increasing the total number of ions in solution.
The plots of ∧ versus show that for strong electrolytes, linear plot is obtained. The electrolytes which
seem to approach dilute solution limit almost tangentially are called as weak electrolytes (From this plot
weak and strong electrolytes can be distinguished).

Equivalent conductance of a solution depends upon

the number of ions and the speed with which the
ions move in solution during conductance. Since,
strong electrolytes are almost completely ionised,
the number of ions is same at all dilutions. At high
concentration the interactions between oppositely
charged ions of strong electrolyte are high
appreciably and with dilution although number of
ions is not increased but the interactions are
lowered so the mobility of ions is increased;
increasing the ∧. At infinite dilution the ions are far
apart, interionic attractions are almost absent and each ion moves freely. The equivalent conductance then
approaches a limiting maximum value at the infinite dilution and it is denoted by ∧o.

Effect of temperature on conductivity :- The conductance increases with increase in temperature due to
1. Increase in the velocity of ions. 2. Decrease in the viscosity of the medium.
3. Decrease in the interaction between the ions.

Determination of conductivity of the solution

We know that conductivity is the reciprocal of resistance and the resistance is more frequently
determined by means of some form of Wheatstone bridge circuit. But, when direct current is passed
through the solution following difficulties arise:
(i) The concentration of the charges,
(ii) The polarisation set is due to the substance liberated at electrodes. With the result, a back E.M.F. is
set up and the resistance of the electrolyte is altered. Kohlrausch avoided these difficulties as follows:
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(a) By using an alternating current: The polarising effect of the deposition of substances due to the current
in one direction is neutralized by the effect of current in the other direction.
(b) By increasing the surface of electrodes: Polarisation is decreased further if the surface of the electrodes
is increased. This is done by coating electrodes in the cell with finely divided platinum.
(c) By using headphone: Since, with the passage of an alternating current, the ordinary galvanometer in
Wheatstone bridge cannot be employed to determine the null point, it is replaced by a headphone.
(d) By using an oscillator: To obtain still better results the induction coil is replaced by an oscillator
having a frequency of 2000-4000 cycles per second.

Method: The solution of an electrolyte whose conductivity is to be determined is taken is special type
of cell known as conductivity cell. This is made of Pyrex glass and is fitted with platinum electrodes. The
electrodes usually consist of stout platinum plates sealed into glass tubes which pass through mercury
placed in the tubes. The relative positions of the electrodes are fixed by cementing the tubes to the ebonite
cover. The electrodes are coated with finely divided platinum. To maintain definite temperature it is placed
in a thermostat. Copper wires are dipped in mercury placed in glass tube to make connections.

Determination of specific conductivity:

The cell is connected to resistance box, R on one side and thin uniform wire AB of Meter Bridge
on the other secondary of induction coil is connected to the ends of the V bridge while the primary is
connected to a battery. The headphone, G is connected to a sliding key, P and the binding screw in between
the cell and resistance box.

The sliding key, P is placed near the

middle. When the circuit is complete, a
buzzing sound is heard in the
headphone. Plugs are taken out from the
resistance box. The sliding key is moved
along the wire until the sound in the
headphone is reduced to a minimum.
Thus point H is recorded. The observed
conductivity of solution is then
calculated by applying the following formula:

Thus AH and BH are measured on

graduated scale and R in ohms from
resistance box.

Determination of cell constant: To find out cell constant, the cell is filled with 0.1 N solution of pure
KC1. The specific conductivity of 0.1 N KCI solution as determined accurately by Kohlraush is
at and the resistance of the solution is determined experimentally.
Substituting the value of specific conductivity (0.002765) and offered by potassium chloride solution, the
value of cell constant, x is calculated as follows:
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Kohlrausch’s Law

Kohlrausch’s law is regarding independent movement of ions, at infinite dilution. The law states that at
infinite dilution, each ion migrates independently of its co-ion and contributes a definite share to the total
equivalent conductance of the electrolyte. Thus

where are the equivalent conductances of +ve and -ve ions respectively, at infinite dilution.

The independence of these contributions is seen from the difference between ∧o values of electrolytes
containing a common ion e.g. when salts of lithium and potassium with a common anion are taken, the
difference between is constant. Same is true for salts with a common cation i.e.

. Thus, the differences are independent of other ionic species present.

Applications of Kohlrausch’s Law :

1. Finding ∧o for weak electrolytes :

∧o for weak electrolytes cannot be obtained directly. Kohlrausch’s law is useful for calculating the
equivalent limiting value of ∧o for weak electrolytes e.g. ∧o for acetic acid can be calculated by
measurement of ∧o for three strong electrolytes HCl, NaCl, CH3COONa.

2. Calculation of ionic conductances (λo) : Ionic conductance at infinite dilution can be calculated by
combining Kohlrausch’s law and transport number for the ion. (Transport number of an ion is the fraction
of the total current carried by an ion, denoted by t). Hence,

By studying transport number of a cation at infinite dilution λ+o and equivalent conductance of electrolyte
at infinite dilution, containing the cation; we can find individual contribution of an ion towards equivalent
conductance at infinite dilution.

Conductometric Titrations

a) Strong Acid versus Strong Base Titration

In the titration of strong acid like HCl against strong base

NaOH from burette, the acid is taken in conductivity cell.
When base is added, H+ ions in solution are replaced by Na+.

H+ + Cl– + Na+ + OH– Na+ + Cl– + H2O

The number of H+ ions of higher mobility will be replaced by slower moving Na+. Hence, conductivity
goes on decreasing, until the end point. After end point, there will be net addition of Na + and OH in the
mixture and there will be increase in conductance. End point corresponds to the minimum conductance.

1 ml 1N NaOH ≡ 36.5 mg of HCl

From equivalence point from graph, normality of NaOH, the amount of HCl can be calculated.
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Curve AB represents variation of conductance of mixture of progressively decreasing HCl and increasing
NaCl. Portion BC indicates the conductance of NaCl formed on neutralization of HCl, along with excess
base added. At B there are neither H+ nor OH in excess and it is the equivalence point of titration.

b) Weak Acid versus Strong Base

Consider weak acid like acetic acid titration against a strong

base like NaOH. In the beginning conductance of acetic acid is
low and it further decreases due to depression in its
dissociation by the common ion formed during early stage of
neutralization.

CH3COOH + Na+ + OH CH3COO– + Na+ + H2 O

After that the conductance increases, slowly due to increasing

amount of completely dissociating, salt sodium acetate formed
progressively upto equivalence point. Conductance at
equivalence point is completely due to sodium acetate. After that, conductance increases faster due to
excess of Na+ and OH ions added (Refer the plot) from burette.

1 ml 1N NaOH ≡ 60 mg acetic acid

From the end point or equivalence point volume, normality of NaOH, we can calculate amount of acetic
acid in solution.

c) Weak Base Against Strong Acid

Consider strong acid (HCl) from burette, against weak base (NH4OH) in
flask. Reaction during titration is,

NH4OH + H+ + Cl– NH4+ + Cl– + H2 O

Initially there is low conductance by the weak electrolyte but during

titration, there is formation of strong electrolyte NH4Cl, therefore,
conductance goes on increasing, upto equivalence point.

After equivalence point, the conductance increases very rapidly because of fast conducting H+ Cl–
added remains unreacted in the titration mixture.

Calculation: Plot a graph of conductance Vs ml of acid added from burette. From the equivalence point
noted from graph, normality of HCl, we can calculate amount of base
titrated.

d) Weak Acid with a Weak Base:

Consider weak acid (CH3COOH) in flask is titrated, against weak

base (NH4OH) from burette. Reaction during titration is,

CH3COOH + NH4OH CH3COO– NH4 + + H2 O

The nature of curve before the equivalence point is similar to the curve
obtained by titrating weak acid against strong base. After the equivalence point, conductance virtually
remains same as the weak base which is being added is feebly ionized and, therefore, is not much
conducting.

Precipitation Titration : Precipitation titrations can be carried out conveniently by conductivity

measurements, e.g. KCl versus AgNO3 is added from burette and conductance of KCl solution observed at
various occasions.
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K+ + Cl– + Ag+ NO–3 K+ + NO–3 + AgCl↓

The conductance of KCl decreases slowly upto equivalence point

because greater mobility Cl are replaced by lower mobility NO3–
ions. Because conductance difference in them is not large therefore
conductance decreases slowly upto equivalence point. After that
conductance increases rapidly, due to addition of Ag+ and NO–3 ions
from burette.

Calculation : Plot a graph of conductance Vs ml of titrant.

1 ml 1N AgNO3 ≡ 35.5 mg Cl– or 74.5 mg KCl

Equivalence point of titration is known from graph. From the known normality of AgNO3, equivalent point
volume, we can calculate amount of Cl– or KCl in solution.

Advantage of conductometric titrations:-

1. This method can be used with very dilute solutions
2. This method can be used with coloured or turbid solutions in which end point cannot be visible.
3. This method can be used in which there is no suitable indicator is found to work satisfactorily can be
successfully titrated by this method.
4. It has many applications, i.e. it can be used for weak acid and weak bases, redox, precipitation, or
complex titrations
5. More accurate results are obtained because the end point is determined graphically.

B) pH-Metry: INTRODUCTION
The concept of pH was first introduced by Danish chemist Sorensen. pH is a measure of the hydrogen
ion concentration of a solution. Solutions with a high concentration of hydrogen ions have a low pH and
solutions with low concentrations of H+ ions have a high pH.
pH= -log[H+]

For example is the H+ concentration is very low, lets say about 0.0000001M, then the pH is
pH= -log[.0000001] which is the same as -log[1 X 10-7]
The term log [1 X 10-7] = -7 ; Thus - (-7) = 7
Solutions with a pH below 7.0 are termed acidic and solutions with a pH above 7.0 are termed basic. A
pH value is a number from 0 to 14, with 7 as the middle (neutral) point.
Values towards 1 indicate more acidity while values towards 14 being the most alkaline. It is a logarithmic
scale in which two adjacent values increase or decrease by a factor of 10.
For example, a pH of 3 is ten times more acidic than a pH of 4, and 100 times more acidic than a pH of 5.
Similarly, a pH of 9 is 10 times more alkaline than a pH of 8, and 100 more alkaline than a pH of 7. pH of
blood is 7.4 and pure water is 7.
A pH meter is an electronic device used for measuring the pH (acidity or alkalinity) of a liquid.

Buffer solution: Solution which resists change in pH even on addition of small aquantity of acid or base.
Buffer solutions are of three types:
a) Acidic buffer b) Basic buffer c) Neutral buffer
a) Acidic buffer: Acidic buffer solution contains equimolar quantities of a weak acid and its salt with
strong base. For example: acetic acid, CH3COOH and sodium acetate I.e. CH3COONa. A solution
containing equimolar quantities of acetic acid and sodium acetate maintains its pH value around 4.74.

b) Basic buffer: Basic buffer solution contains equimolar quantities of a weak base and its salt with
strong acid. For example: ammonium hydroxide i.e. NH4OH and ammonium chloride I.e. NH4Cl. A
solution containing equimolar quantities of ammonium hydroxide and ammonium chloride maintains its
pH value around 9.25.
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c) Neutral buffer/ single salt buffer: It is salt of weak acid and weak base. eg. CH3COONH4

How buffer solution is a prepared?

Buffer solution is the solution which resists change in pH even if small amount of an acid or a base
is added in it. Buffer solution can be prepared by calculating amounts of salt and weak acid (or base)
required for a specific value pH with the help of Henderson equation.

where pKa and pKb are the negative log10 of the dissociation constants weak acid Ka and weak base Kb.

pH Metric Titration : HCl vs. NaOH

Procedure

Part - I: Calibration (Standardization) of pH meter :

(i) Make the connections of electrode to pH meter and pH meter to

electricity.
(ii) Clean the electrode (which is activated by keeping the electrode
immersed in distilled water overnight).
(iii) Immerse the electrode in the solution of known pH.
(iv) Adjust temperature knob on instrument on 20°C and mode on pH.
(v) Adjust the pH reading on display with ‘standardize’ knob equal to pH of the solution.
Do not disturb the ‘standardize’ knob, throughout experiment.

Part - II : Titration of Acids (HCl) against strong base (NaOH) Principle / Theory:
That titration where the end point is measure by change in pH is known as pH metric titration. On
addition of NaOH in of HCl- following reactions will occur:

HCl + NaOH→H2O+NaCl HCl H+ + Cl-

Initially the pH is around 1-2 as HCl is strong acid. When NaOH is added pH is increases slowly.
on continuing addition of NaOH from burette.
At pH 7all aid get Neutralized with NaOH . we get equivalence point where Sudden increase in p
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Procedure:
1) Pipette out 20 ml of acid mixture in a beaker and dip clean electrodes in it.
2) Keep beaker on magnetic stirrer. Note initial pH value.
3) Add 0.5 ml NaOH from burette and note pH of titration mixture displayed on digital screen of pH
meter.
• Similarly note the pH values for each subsequent addition of 0.5 ml burette solution.
Continue the titration till 3 times sudden rise in pH is observed.
Titration Curve
1. Plot pH against volume of titrant added. See the regions of rapidly changing pH. (fig.1)

2. Also plot curves of ∆ pH/∆V as a function of volume of titrant added; the equivalence point is the point
on the curve where ∆pH/∆V has its maximum value

Uses / Applications of pH metry:

1. a swimming pool must be constantly maintained by checking its pH. If the water becomes too acidic or
too basic, must be balanced

2. pH also is important when it comes to the body. Whenever someone gets heartburn, stomach acid builds
up and causes deep pain near the opening of the stomach. When one takes antacid tablets (a base), the
build up of acid is neutralized in the stomach, causing relief to the sufferer.

3. The blood is also important when dealing with pH. Usually, the pH of blood should only be slightly
basic. A fluctuation in the pH of the blood may result in serious injury to vital organs in the body.

4. The pH test is an important preliminary test analysis of water.

5. Also use in analysis of soil. Most plants can tolerate a wide pH range in solution culture, but they cannot
tolerate a wide range of acidity in the soil.

6. pH measurent also use in medical fiel

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