Chapter Six

Electroanalytical Methods

1 Sisay K.
 Outline
2

 INTRODUCTION TO ELECTROCHEMISTRY
 POTENTIOMETRY
 POLAROGRAPHY
 CONDUCTOMETRY
 COULOMETRY

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 Objectives
3

 To introduce to the students

 What electrochemistry is in general
 The principle of potentiometry and its application
 The principle of Polarography and its application
 The principle of conductometry and its application
 The principle of coulometry and its application

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 Learning outcomes
4

At the end of this session students will be able to :

 define electrochemical methods

 describe the basic principles of the different

electrochemical methods

 describe the different applications of these methods

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 INTRODUCTION
5

Definition:

 Electroanalytical methods are methods in which a measurement

of potential, current, or charge in an electrochemical cell
serves as the analytical signal.

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 INTRODUCTION…
6

Classification:
 The simplest division is between

 Bulk methods- property of the whole solution

 Interfacial methods- the signal is a function of
phenomena occurring at the interface between an
electrode and the solution in contact with the electrode.

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INTRODUCTION…

7 Sisay K.
 INTRODUCTION…
8

Terminology:
 Electrolyte: A substance present in solution which is at least
partly in the form of charged species (ions).
 Cations:
 Anions:

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 INTRODUCTION…
9

 Electrode: electron transfer occurs; it can be an anode or a

cathode.
 Anode: oxidation
 Cathode: reduction
 Electrochemical cell: electrochemical measurements
 Contains Cathode and Anode compartments

The anode is the source of electrons, making it the

negative part of the electrochemical cell
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 INTRODUCTION…
10

The cathode is the positive post of the electrochemical cell as it

consumes electrons

Red Cat
An ox

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 INTRODUCTION…
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Terminology…
 Half-cell:
 the anode or the cathode compartment and
 all reactions that occur at that particular electrode.
 Half-reaction: the redox reaction that occurs in one half-cell
 Interface (Junction):
 the location where two distinct phases come in contact with each other: Salt
Bridge
 Reduction and oxidation
 Oxidizing Agent and reducing agent Sisay K.
 INTRODUCTION…
12

Electro neutrality:
Suppose, that we immerse a piece of zinc metal in pure water.

- As this process goes on – charge buildup in the solution Very

soon, therefore, the process stops.
 For the oxidation of the metal to continue__couple it with some
other process that restores electroneutrality to the two phases.

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 INTRODUCTION…
13

 A simple way to accomplish this would be

 To immerse the zinc in a solution of copper sulfate
instead of water.

 The solution remains electrically neutral

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 INTRODUCTION…
14

 There is always potential difference developed at the interface

between the metal immersed and the solution.

 However, Single electrode potential differences are not

directly observable.
 We can easily measure a potential difference between two such
electrodes immersed.

“electrochemistry with a single electrode is like the

sound of one hand clapping”

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 INTRODUCTION…
15

 The arrangement of such cell is known as electrochemical cell.

 The following figure shows an electrochemical cell for the

redox reaction between Zn and Cu.

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 INTRODUCTION…
16

 The simplest electrochemical cell uses two electrodes.

 Indicator electrode and reference electrode

 Indicator electrodes- selectively responds to changes in the

activity of the analyte being measured
 Reference electrodes- its composition is fixed and its
response is stable over time. Eg standard hydrogen
electrode (SHE)

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 INTRODUCTION…
17

Types of Electrochemical Cells

Two types
voltaic/galvanic/ and electrolytic.
a. Voltaic or galvanic cells
• Spontaneous chemical rxn that produes current

 Chemical energy is converted to electrical energy

e.g. batteries
b. Electrolytic cells
• Electrolysis is used to drive an oxidation-reduction and
therefore is non-spontaneous.
Electrical enrgy to chemical energy….eg electroplating
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 INTRODUCTION…
18

Similarities b/n Electrolytic cells and voltaic (galvanic) cells in

the sense that both
 Require a salt bridge,

 Have a cathode and anode side, and

 Have a consistent flow of electrons from the anode to the

cathode

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 INTRODUCTION…
Differences
19

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20

POTENTIOMETRY

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 Potentiometry
21

o In potentiometery, the potential of an electrochemical cell is

measured under static conditions.

o Because no current flows while measuring a solution’s

potential
• Its composition remains unchanged
• For this reason, potentiometry is a useful quantitative
method

o Potentiometric measurements are made using a potentiometer

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 Potentiometry…
22

Figure 2: Example of potentiometric electrochemical cell

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 Potentiometry…
23

 Note that the electrochemical cell is divided into two half-cells

o Each containing an electrode immersed in a solution
containing ions whose concentrations determine the
electrode’s potential.
 This separation of electrodes is necessary to prevent the redox
reaction
o From occurring spontaneously on the surface of one of the
electrodes
o This makes the measurement Sisay
of cell
K. potential impossible.
 Potentiometry…
24
Short hand notation for electrochemical cells

 Uses symbols to identify different phases and that lists the composition of each phase.
 Vertical slash(|)--- to identify a boundary between two phases

 A comma (,)--- to separate species in the same phase

 Shorthand cell notations begin with the anode and continue to the cathode

Example: for figure 2

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25

 Potentiometric electrochemical cells are defined such that the

indicator electrode is the cathode (right half-cell) and the
reference electrode is the anode (left half-cell).

 Current flows from positive to negative, which is opposite to

the direction of the electron flow.

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26

Example
 Write the reactions occurring at the anode and the cathode for
the poten-tiometric electrochemical cell with the following
shorthand notation.

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 Potentiometry…
27

Potential and Concentration-the Nernst Equation

 The potential of a Potentiometric electrochemical cell is given as

 These reduction potentials are a function of the

concentrations

E ͦ = Standard electrode potential (SEP)

R = Gas constant (8.314 JK–1 mol–1),
T = Absolute temperature (K),
F = Faraday (96500 C/mole of electrons)
n = Number of electrons involved in the electrode
reaction.
Q = reaction quotient
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 Potentiometry…
28
 Under typical laboratory conditions (temperature of 25 °C or
298 K) the Nernst equation becomes

 Q (the activity quotient) is the ratio of products over

reactants as in equilibrium calculations
Example: for

Q is given by

 NB. If there is a pure liquid, pure solid, or the solvent, it is

not included in the equation due to the fact that its
concentration is constant. Sisay K.
 Potentiometry…
29

Example: write the nernst equation for the ff.

1.

2.

3.

4.

5.
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 Potentiometry…
30

Given the ff. reduction potentials, Calculate Ecell

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 Potentiometry…
31

Exercise
The Cu2+ ion concentration in a copper-silver electrochemical
cell is 0.1M. If Eo(Ag+/Ag) = 0.8V, Eo(Cu2+/Cu) = 0.34V, and
Cell potential (at 25oC) = 0.422V, find the silver ion
concentration.

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 Potentiometry…
32

Types of Electrodes
1. Reference electrodes:
o Electrode with known constant potential
o Potentiometric electrochemical cells are constructed such that
one of the half-cells provides a known reference potential
 The potential of the other half-cell indicates the analyte’s
concentration.
o By convention

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 Potentiometry…
33

Properties of an ideal RE
 It must provide a stable potential so that any change in E
cell
 is attributed to the indicator electrode, and, therefore, to a
change in the analyte’s concentration.

 Ideally, if a small current is passed through the electrode,

the potential change is negligible
 and in any case, returns to the initial value when the current

ceases.

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 Potentiometry…
34

Properties of an ideal RE….

 In addition, the ideal reference electrode should be easy to
make and to use.
 Should be reproducible from electrode to electrode.

 The three common reference electrodes are discussed as follows.

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 Potentiometry…
35

A. Standard Hydrogen electrode (SHE):

 Used to establish standard-state potentials for other half-

reactions.

 The SHE consists of a Pt electrode immersed in a solution in

which
 The hydrogen ion activity is 1.00 and in which H2 gas is
bubbled at a pressure of 1 atm.

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 Potentiometry…
36

is, by definition, 0.00 V for all

temperatures.
The SHE is rarely used because it is
difficult to prepare and inconvenient to
use
But is important because it is the
reference electrode used to establish
standard-state potentials for other
half-reactions.

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 Potentiometry…
37

 Reduction potential: the magnitude of the half cell’s tendency

to acquire electrons and proceed as a reduction.
 If done under standard conditions, then it is referred to as the
standard reduction potential
Table 1: Standard reduction potentials

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 Potentiometry…
38

B. Saturated calomel electrode (SCE):

SCE consists of two concentric glass tubes
 A saturated solution of KCl is in the outer tube
Within the inner tube is a paste - like material
known as calomel
Calomel is the common name for the compound
Hg2Cl2.
When in use, the following half-cell reaction
occurs:

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 Has a potential of +0.2444 V at 25 °C .

39 Sisay K.
40

Shorthand notation of the cell is

The potential of a calomel electrode, therefore, is determined

by the activity of Cl–in equilibrium with Hg and Hg2Cl2

Because the concentration of Cl– is fixed by the solubility of

KCl, the potential of an SCE remains constant

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 Potentiometry…
41

C. Silver-Silver chloride electrode

 based on the redox couple between AgCl and Ag.

As with the saturated calomel electrode,

the potential of the Ag/AgCl electrode is
determined by the concentration of Cl– used
in its preparation.
When prepared using a saturated solution of
KCl, the Ag/AgCl electrode has a potential of
+0.197 V at 25 °C.
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 Potentiometry…
42

Types of Electrodes…
2. Indicator electrodes
 The reference electrode represents half of the complete system
for Potentiometric measurements.

 The potential of the indicator electrode in a potentiometric

electrochemical cell is proportional to the concentration of
analyte
 They are either specific (for one ion) or selective (for several

ions).
 Can be either Metallic or membrane electrodes

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 Potentiometry…
43

(A) Metal Indicator Electrodes

 The potential of a metallic electrode is determined by the
position of a redox reaction at the electrode–solution
interface.

 Three types of metallic electrodes

i. Electrodes of the First Kind
ii. Electrodes of the second kind
iii. Electrodes of the third kind

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 Potentiometry…
44

Electrodes of the First Kind

 An electrode of the first kind is a pure metal electrode that
is in direct equilibrium with its cation in solution

 For example, the equilibrium between a metal M and its

cation Mn+ is

Mn+ (aq) + ne- = M(s)

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 Potentiometry…
45

In general, for a metal M, in a solution of Mn+, the cell potential

is given as

Where K is a constant that includes the standard-state potential

for the Mn+/M redox couple and the potential of the reference
electrode.

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 Potentiometry…
46

ii. Electrodes of the second Kind

 Metals not only serve as indicator electrodes for their own

cations but also respond to the activities of anions.

 For example, the potential of a silver electrode in a solution of

Ag+ is given by

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 Potentiometry…
47

ii. Electrodes of the second Kind…

 If the solution is saturated with AgI, then the solubility
reaction

 Determines the concentration of Ag+; thus

 Where Ksp, AgI is the solubility product for AgI. substitution

gives us the following equation.

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 Potentiometry…
48
 When the potential of an electrode of the first kind responds to
the potential of another ion
 that is in equilibrium with Mn+, it is called an electrode of
the second kind.

 When this electrode is incorporated into a Potentiometric

electrochemical cell

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 Potentiometry…
49

iii. Electrodes of the third Kind (redox electrodes)

 Electrodes of the first and second kind develop a potential

 as the result of a redox reaction in which the metallic

electrode undergoes a change in its oxidation state.

 Metallic electrodes also can serve simply as a source of, or a

sink for, electrons in other redox reactions.
 Such electrodes are called redox electrodes.

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 Potentiometry…
50

 An inert conductor, such as platinum, gold, palladinium or

carbon responds to the potential of a redox system with which
it is in contact.

 For example the potential of platinum electrode immersed in a

solution of Fe2+ and Fe3+ is determined by the ratio of
concentration of both ions.

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 Potentiometry…
51

(B) Membrane /ion-selective/ electrode

 ion-selective electrode: an electrode in which the membrane

potential is a function of the concentration of a particular ion
in solution

 Two reference electrodes are used; one positioned within the

internal solution, and one in the sample solution

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 Potentiometry…
52

 Interaction of the analyte with the membrane results in a

membrane potential if there is a difference in the analyte’s
concentration on opposite sides of the membrane

 One side of the membrane is in contact with an internal solution

containing a fixed concentration of analyte, while the other side
of the membrane is in contact with the sample

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53 Sisay K.
 Potentiometry…
54

The glass electrode

o The glass electrode is the most widely used hydrogen ion
responsive electrode

o Its use is dependent upon the fact that when a glass membrane is
immersed in a solution,
o a potential is developed which is a linear function of
hydrogen ion concentration of the solution.

 The basic arrangement of a glass electrode is shown in the

figure below.
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 Potentiometry…
55

o The bulb is immersed in the solution whose hydrogen ion

concentration is to be measured

o The electrical circuit is completed by filling the bulb with a

solution of hydrochloric acid and inserting a silver-silver
chloride electrode

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 Potentiometry…
56

The overall potential of the electrode is governed by

the hydrogen ion concentration of the test solution

E = E0 - 0.0592 log [H+]ext/[H+]int

E= E* - 0.0592 pH

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 Potentiometry…
57

 Glass electrodes are manufactured using a glass, with a

composition of approximately 22% Na2O, 6% CaO, and
72% SiO2.

 When immersed in an aqueous solution, the outer

approximately 10 nm of the membrane becomes hydrated
over the course of several hours.

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 Potentiometry…
58

 Hydration of the glass membrane results in the formation of

negatively charged sites, G–, that are part of the glass
membrane’s silica framework.

 Hydrogen ions from solution diffuse into the membrane and

displace the sodium ions

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 Potentiometry…
59

 In a pH meter, the meter read out is typically calibrated in both

pH units and volts, making the pH meter a rather versatile device

 Above a pH of 9–10, the glass membrane may become more

responsive to other cations, such as Na+ and K+ (Alkaline error)

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 Potentiometry…
60

o Glass Electrodes for Other Ions- If the preference for hydrogen

ion exchange shown by glasses is reduced

Table 2: composition of glasses for cation-sensitive glass electrodes

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 Potentiometry…
61

Other types of ion selective electrodes

ii. Crystalline Solid-State Ion-Selective Electrodes
iii. Liquid-Based Ion-Selective Electrodes
(read)

C) Molecule selective electrodes: gas sensing probes and

biocatlytic membranes

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 Potentiometry…
62

Applications of Potentiometry

 pH determination
 Potentiometric titrations

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63

Polarography

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 Polarography…
64

 Techniques which utilize the electrolytic cell concept, rather

than the galvanic cell
 utilize an external power source

 Ccurrent is measured instead of potential, as a function of the

concentration of the analyte.

 Include
 Polarography

 Coulometry and

 Voltammetry
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 Polarography…
65

 Electrolytic cells can involve large currents than galvanic cells.

 The two electrode system and the solution composition

discussed for Potentiometry usually must be modified in order to
obtain desirable results

 A reference electrode, such as SCE or silver-silver chloride

electrode, can not handle larger currents

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 Polarography…
66

 In addition, the solution into which the electrodes are dipped

must be able to sustain such a current

 Thus,
 a three electrode system and

 a supporting electrolyte

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 Polarography…
Instrumentation – Three electrodes
in solution containing analyte
Working electrode
Reference electrode
Auxiliary or counter
electrode
Working electrode:
microelectrode whose potential is
varied with time

Reference electrode: potential

remains constant (Ag/AgCl
electrode or calomel)
67 Sisay K.
 Polarography…
Counter electrode: Hg or Pt that completes circuit, conducts e-
from signal source through solution to the working electrode

Supporting electrolyte: excess of nonreactive electrolyte

(alkali metal) to conduct current

68 Sisay K.
 Polarography…
69

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 Polarography…
70

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 Polarography…
71

 The process occurring at the auxiliary electrode is unimportant

analytically.

 Real world sample solutions and standards which have very low
analyte concentrations often do not have sufficient electrolyte
content- supporting electrolyte

 An electrolyte species which is difficult to oxidize or reduce

compared to the analyte should be chosen to minimize
interferences.

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 Polarography…
72

Polarography
 Is a technique which utilizes a special non-stationary electrode

for the working electrode.

 Dropping mercury electrode (DME) is used

 The DME consists of liquid mercury flowing through a very
narrow-bore capillary tube.

 The mercury flows through the capillary tube by gravity from a

reservoir of mercury

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73 Sisay K.
 Polarography…
74

 The drop forming at the capillary tip grows, and it tears away
when at a time after the start of formation it has attained a certain
mass

 After its detachment a new drop starts to form and grow, and the
cycle is repeated

 The growing drop, while suspended, is used as the cathode for

reduction of various substances

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 Polarography…
75

Advantages

Its fluid nature eliminates two problems

I. Contamination of the electrode surface resulting from
electrode reactions
• The mercury surface is continuously renewed in the case of
the DME.

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 Polarography…
76

II. The decay of the current to small values with time due to the
diffusion – limited transportation of analyte to the electrode
surface when the solution is not stirred
• The solution is stirred in the case of the DME each time the
drop fall

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 Polarography…
77

Disadvantages
 It is usually used as a cathode

 The capillary is very small in size so easy to block and so all

process stopped.

 The presence of impurities in the sample or in mercury cause

blockage of the capillary results in malfunction of the
electrode
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 Polarography…
78

 Current is measured in polarography

 A plot of Current vs voltage - polarogram

 Parameters associated with the polarogram are:

 Diffusioncurrent (id),
 Half-wave potential (E1/2),
 Back ground (Residual) current, the limiting current
and
 Decomposition potential

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79 Sisay K.
 Polarography…
80

1-Residual current(Id): at small applied potential only a residual

current flow in the cell which is caused by:
 The presence of impurities in the supporting electrolyte or
sample

2-Limiting current: is the region on the polarogram in which the

current after increased sharply , becomes essentially
independent on the applied potential

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 Polarography…
81

3-Diffusion current: it is the difference between limiting and residual

currents .
 It is directly proportional to the concentration of the reactive

substance.
 Ilkovic examined the various factors which govern the diffusion

current

Where . Id- diffusion current (micro-Amper),

 C-concentration (M)
 D- diffusion coefficient (cm2/seconds),
 m-rate of flow of the mercury and
 t- drop time (seconds)
 n-number of electrons transfered
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 Polarography…
82

4- Half wave potential (E1/2) : is the potential at which the current

is equal to one half the diffusion current.

It is
 a characteristic of the nature of the reactive material
 independent on concentration
 depend on pH of the medium, type of supporting
electrolyte and type of electrode
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 Polarography…
83

5- Decomposition potential:

is the potential at which the substance begin to oxidize or

reduce.

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 Polarography…
84

Polarographic maxima
 Inhibit the accurate measurement of the diffusion current.
 Are distortions of the current manifested by large peak of
current immediately beyond the half-wave potential.

 The cause is not well understood

 Usually solved by the addition of small amounts of gelatin or
surfactant to the solution.

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 Polarography…
85

Example:
۩ Curve A is that for copper ions in 0.1M potassium hydrogen

citrate solution
۩ Curve B is the same polarogram in the presence of 0.005

percent acid fuchsine solution.

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 Polarography…
86

Oxygen waves
 Dissolved oxygen is readily reduced at various electrodes; an
aqueous solution saturated with air exhibits two distinct waves
attributable to this element.
 The first results from the reduction of oxygen to peroxide.

O2(g)+2H++2e= H2O2

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 Polarography…
87

Oxygen waves…
 The second corresponds to the further reduction of the
hydrogen peroxide.

H2O2+2H++2e = 2H2O

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 Polarography…
88

Oxygen waves…
 As a result, during an experiment, a suitable solution of the
electroactive substance under examination is freed-from
oxygen by:-
 bubbling oxygen free nitrogen through for several minutes
and
 blanketing the solution with nitrogen.

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 Polarography…
89

Applications

Some functional groups reducible in polarography include

 Diazo compounds Aldehydes

 Nitrocompounds  - Diazonium salts
 Ketones  Aromatic carboxyl groups
 Sulphones
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90

COULOMETRY

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 Coulometry…
91

 Analog of titration where the substance being examined is

quantitatively converted to a reaction product not by the addition of
titrant, but by a certain amount of electric charge Q.
 The analyte is quantitatively oxidized or reduced at the
working electrode or reacts quantitatively with a reagent
generated at the working electrode.
 Measures the amount of charge Q consumed for the complete
conversion (oxidation or reduction) of the substance being
examined.
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 Coulometry …
92

 The total charge, Q, in coulombs, passed during an electrolysis

is related to the absolute amount of analyte by Faraday’s law.
Faraday’s Law
-The current or charge passed in a
redox reaction is proportional to
where the moles of analyte.

 n is the number of electrons transferred per mole of analyte,

 F is Faraday’s constant (96487 C mol–1), and
 N is the moles of analyte.

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 Coulometry …
93

 A coulomb is also equivalent to an A.s; thus, for a constant

current, i, the charge is given as

 where te is the electrolysis time. If current varies with time, as it

does in controlled potential Coulometry, then the total charge is
given by

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 Coulometry …
94

 To obtain an accurate value for N, therefore, all the current must

result in the analyte’s oxidation or reduction
 There are two forms of coulometry:

a. Controlled-potential coulometry- in which a constant potential

is applied to the electrochemical cell

b. Controlled-current coulometry- in which a constant current is

passed through the electrochemical cell

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 Coulometry …
95

A. Controlled-Potential Coulometry
 The potential is selected so that the desired oxidation or
reduction reaction goes to completion
 The current is proportional to the analyte’s concentration.
 As electrolysis progresses the analyte’s concentration
decreases, as does the current.

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 Coulometry …
96

A. Controlled-Potential…
 The resulting current-versus-time profile for controlled-
potential coulometry, which also is known as potentiostatic
coulometry, is shown in Figure below

 Integrating the area under the curve from t = 0 until t = te,

gives the total charge

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 Figure: Current versus time for a controlled-potential
coulometric analysis
The measured current is shown by the red curve. The
integrated area under the curve, shown in blue, is the total
charge(Q)
97 Sisay K.
 Coulometry …
98

A. Controlled-Potential…
 From the figure current decreases continuously throughout
electrolysis.

 The factors that determine the analysis time need to be

considered.

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 Coulometry …
99

The change in current as a function of time in controlled-potential

coulometry is approximated by an exponential decay; thus, the
current at time t is

Where i0 is the initial current, and k is a constant that is directly

proportional to the
 area of the working electrode and
 the rate of stirring
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 Coulometry …
100

o For an exhaustive electrolysis in which 99.99% of the analyte is

oxidized or reduced, the current at the end of the analysis, t e,
may be approximated as

 From this equation we see that increasing k leads to a shorter

analysis time.
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 Coulometry …
101

A. Controlled-Potential…
o For this reason controlled-potential coulometry is carried out
o in small-volume electrochemical cells
o using electrodes with large surface areas and
o with high stirring rates
o A quantitative electrolysis typically requires approximately
30–60 min, although shorter or longer times are possible.

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 Coulometry …
102

Instrumentation: the potential in controlled-potential

coulometry is set using a three-electrode potentiostat.
 Two types of working electrodes are commonly used: a Pt
electrode and Hg electrode.
 A saturated calomel or Ag/AgCl electrode serves as the
reference electrode.

Sisay K.
 Coulometry …
103

A. Controlled-Potential…
 The other essential feature of instrumentation for controlled-
potential coulometry is a means of determining the total
charge passed during electrolysis.

 One method is to monitor the current as a function of time and

determine the area under the curve .

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 Coulometry …
104

 Modern instruments, however, use electronic integration

 The total charge at the end of the electrolysis then can be read
directly from a digital readout or from a plot of Current versus
time

Sisay K.
 Coulometry …
105

B. Controlled-current coulometry
 A second approach to coulometry is to use a constant current
in place of a constant potential
 Controlled-current coulometry, also known as amperostatic
coulometry or coulometric titrimetry
 Has two advantages over controlled-potential coulometry

Sisay K.
 Coulometry …
106

 First, using a constant current makes for a more rapid analysis

since the current does not decrease over time….less than 10
min.
 Second, with a constant current the total charge is simply the
product of current and time….. integrating the current–time
curve, therefore, is not necessary.

Sisay K.
 Coulometry …
107

B. Controlled-current coulometry…
 There is a need for a method of determining when the analyte
has been exhaustively electrolyzed
 In controlled-potential coulometry this is signaled by a decrease
in the current to a constant background or residual current

Sisay K.
 Coulometry …
108

B. Controlled-current coulometry…
 The same end points that are used in redox titrimetry such as
visual indicators, and potentiometric and conductometric
measurements, may be used to signal the end point of a
controlled-current coulometric analysis

Sisay K.
 Coulometry …
109

 Instrumentation:

 Controlled-current coulometry normally is carried out using a

galvanostat and an electrochemical cell consisting of a working
electrode and a counter electrode.

 The other necessary instrumental component for controlled-current

coulometry is
 an accurate clock for measuring the electrolysis time, t , and
e
 a switch for starting and stopping the electrolysis.

Sisay K.
 Coulometry …
110

B. Controlled-current coulometry…
 Digital clocks provide a more accurate measurement of time.

 A switch controls the flow of current and the clock, so that an

accurate determination of the electrolysis time is possible.

Sisay K.
111 Sisay K.
 Applications of coulometry
112

Coulometric titrtions
Quantitative calculations
Example 1
To determine the purity of a sample of Na2S2O3, a sample is titrated
coulometrically using I- as a mediator and I3– as the titrant. A
sample weighing 0.1342 g is transferred to a 100-mL volumetric
flask and diluted to volume with distilled water. A 10.00-mL portion
is transferred to an electrochemical cell along with 25 mL of 1 M
KI, 75 mL of a pH 7.0 phosphate buffer, and several drops of a
starch indicator solution. Electrolysis at a constant current of 36.45
mA requires 221.8 s to reach the starch indicator end-point.
Determine the sample’s purity. (Ans 98.73% w/w)
Sisay K.
 Applications of coulometry…
113

Practice Exercise 2
 To analyze a brass alloy, a 0.442-g sample is dissolved in acid and

diluted to volume in a 500-mL volumetric flask. Electrolysis of a

10.00-mL sample at –0.3 V versus a SCE reduces Cu2+ to Cu,
requiring a total charge of 16.11 C. Adjusting the potential to –0.6
V versus a SCE and completing the electrolysis requires 0.442 C to
reduce Pb2+ to Pb. Report the %w/w Cu and Pb in the alloy. (Ans.
60.0% w/w Cu & 5.12% w/w Pb)

Sisay K.
 CONDUCTOMETRY

114 Sisay K.
 Conductometry
115

General Considerations
 An electrolytic solution contains free ions.
 One of the most important characteristics of electrolyte
solution is their capability to carry electric current
 The electrolyte conductance is possible through movement of
positive and negative ions, which originate through dissociation
of the electrolyte.

Sisay K.
 Conductometry…
116

Electrolytic conduction
 exhibited principally by molten salts and by aqueous

solutions of electrolytes.

 Conductometry means measuring the conductivity of an

electrolyte or molten salts

 a conductometer measures the electrical conductivity of ionic

solutions.

Sisay K.
 Conductometry…
117

Conductometry
 done by applying an electric field between two electrodes
 The principle of electrolytic conduction is best illustrated by
reference to an electrolytic cell such as that shown in below for
the electrolysis of molten NaCl b/n inert electrodes

Sisay K.
 Conductometry…
118

 Within the cell, current is carried by the movement of ions;

cations moves towards negative electrode called the cathode
and anions towards the positive electrode called anode.
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 Conductometry…
119

 This movement of ions give rise to what is known as the

electrolytic conduction.
 Thus, electrolytic conduction depends on the mobility of ions
 Anything that inhibits the motion of ions causes resistance to
current flow.

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 Conductometry…
120

 Factors that influence the electrical conductivity of solutions

of electrolytes

 interionic attraction,
 solvation of ions,
 temperature and
 viscosity of solvents

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 Conductometry…
121

 ↑Temp leads increase average kinetic energy of the solute ions

 and, therefore, the resistance of electrolytic conductors
generally decreases
 that is, conduction increases as the temperature is raised.
 Important to make measurements at a constant temperature or
compensation by temperature coefficient

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 Conductometry…
122

Electrolytes and non-electrolytes

 The ionic compounds, which furnish ions in solution and
conduct electric current, are electrolytes e.g. NaCl, KCl, etc.

 There are covalent compounds, which also conduct electric

current in solutions.

These include HCl, CH3COOH, etc.

Sisay K.
 Conductometry…
123

 All other substances which do not produce ions in

solutions are called non-electrolytes

e.g. cane sugar, benzene, carbon tetrachloride,

etc.

Sisay K.
 Conductometry…
124

Strong and weak electrolytes

 Electrolytes can be classified as strong or weak.
 related to their extent of ionization not on concentration.
 Strong electrolytes: completely ionized in aqueous solutions
e.g. NaCl, NH4Cl, KNO3, HCl, HBr, etc.

 Weak electrolytes: ionize only to a certain extent

e.g. CH3COOH, HCN, etc.

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 Conductometry…
125

Strong and weak electrolytes…

 The behavior of electrolytes also depends on the nature of
solvents,

e.g.
 NaCl behaves as strong electrolyte whereas acetic acid as a weak
electrolyte in water.
 On the other hand, when dissolved in ammonia both NaCl and
acetic acid show comparable behavior towards electricity.
Sisay K.
 Conductometry…
126

Conductance of solutions

 The ease of flow of electric current through a body is called

its conductance.
 In metallic conductors it is caused by the movement of
electrons,
 while in electrolytic solutions it is caused by ions of
electrolyte.

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 Conductometry…
127

 Ohm’s Law states that the current I (amperes) flowing in a

conductor is directly proportional to the applied electromotive
force E (volts) and inversely proportional to the resistance, R
(ohms) of the conductor:

Sisay K.
 Conductometry…
128

Conductance of solutions…

 The electrolytic conductance, G, of a medium is equal to the

reciprocal of its electrical resistance R in ohms:

Sisay K.
 Conductometry…
129

Conductance of solutions…
 Since a solution is a three-dimensional conductor, the exact
resistance will depend on the spacing (l) and area (A) of the
electrodes.
 The resistance of a solution in such situation is directly
proportional to the distance between the electrodes and
inversely proportional to the electrode surface area.

Sisay K.
(rho)-Resistivity(Specific resistance)
 Conductometry…
130

Conductance of solutions…
 The reciprocal of resistivity is the conductivity, k(Kappa)
(Specific conductance) which is the conductance of one meter
cube of substance and has the units Ω -1 m-1
 But if rho is measured in ohm cm, then k will be measured Ω -1
c m-1.
 Most of the data in the literature are expressed in terms of k
measured in units Ω -1 cm-1
Sisay K.
 Conductometry…
131

Conductance of solutions…
 The expression for the conductance is therefore

and , therefore

 Cell constant: for a given cell, l and A are constant, and the
quantity (L/A) is called the cell constant(K).

 Substituting this value in the above equation

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 Conductometry…
132

 To obtain the value of the cell constant, it is not necessary to

determine l and A directly.

 Instead, it is measured by a solution of known conductivity.

 Potassium chloride solutions are invariably used for this
purpose, since their conductance's have been measured with
sufficient accuracy in cells of known dimensions.

Sisay K.
 Conductometry…
133

 A given solution of potassium chloride of conductivity k’ is

placed in the cell and its resistance R' is measured.
 The cell constant is then equal to k’ R'. Therefore

Sisay K.
 Conductometry…
134

Example: The resistance of a conductivity cell containing 0.01

mol cm−3 KCl is 150 Ω . The same conductivity cell gives the
resistance of 0.01 mol cm−3 HCl 51.4 Ω . The conductivity of
the KCl solution is 1.41 × 10–3 Ω-1 cm-1.

Calculate the following values:

i) Cell constant, and

ii) Conductivity of the HCl solution.

Sisay K.
 Conductometry…
135

 Conductance has an additive property, e.g. in an aqueous

solution containing several electrolytes, the total conductance
is

 where the summation is to be carried over all the electrolytes

present in the solution and G (water) is the conductance of
water, which is utilized for making the solution.

Sisay K.
 Conductometry…
136

 G (water) is often negligible in comparison to summation of Gi

as repeatedly distilled water (known as conductivity water) of
very low conductance is employed for making the solutions.

Sisay K.
 Conductometry…
137

Molar Conductivity
 The conductance of an electrolytic solution depends mainly on
 the type of ions present,
 speed with which the ions move in the solution and
 their concentration.

Sisay K.
 Conductometry…
138

Molar Conductivity…
 When a solution of elctrolyte is diluted, the conductance will
decrease.

 But, if all the solution be placed b/n two electrodes 1 cm apart

and large enough to contain the whole solution, the
conductance will increase as the solution is diluted.

Sisay K.
 Conductometry…
139

Molar Conductivity…

 This is due to
 a decrease in inter-ionic effects for strong electrolytes
and
 an increase in the degree of dissociation for weak
electrolytes.

Sisay K.
 Conductometry…
140

Molar Conductivity…
 The molar conductivity (Л) (Lambda) of an electrolyte is defined

as the conductivity due to one mole of the substance and is given

by:

Л = 1000k/C = k. 1000 V

Where C is the concentration of the solution in mol/lt, and V is the

dilution in liters (number of liters containing one mole)

Sisay K.
 Conductometry…
141

Molar Conductivity…
 At infinite dilution, the ions are quite far apart, the inter-ionic
attractions are almost absent and each ion moves completely
independent of co-ions.
 The molar conductivity then approaches a limiting value at
infinite dilution and represents the conducting power of one
mole of the electrolyte when it is completely slit up into ions.

It is denoted by Л
8

.
Sisay K.
 Conductometry…
142

Molar Conductivity…

Conclusion
 in case of weak electrolytes, the increase in molar conductivity
with dilution is mainly due to

(a) an increase in the number of ions in the solution (degree

of ionization increases with dilution), and

(b) smaller inter-ionic attractions at higher dilutions (mostly

useful for strong electrolytes).
Sisay K.
 Conductometry…
143

Measurement of conductance
 The conductance of a solution can be determined by
measuring the resistance
 For measuring resistance, the Wheatstone bridge principle is
used.
 It works on the principle of obtaining balance between two
arms with the help of a balance indicator (e.g. a
galvanometer) at the condition of potential being equal.
Sisay K.
 Conductometry…
144

 Let Rx be an unknown resistor, R1 and R2 two standard

resistors, R3 an adjustable resistor and G galvanometer.

A DC Wheatstone bridge
circuit

Sisay K.
 Conductometry…
145

 The bridge is connected to a source of power S, a battery, and

a tapping key K is placed in the path to control the
connections.

 To measure the resistance Rx, the tapping key K is held down

momentarily and the bridge is balanced by adjusting R3 to get
no deflection in galvanometer under these conditions.

Sisay K.
 Conductometry…
146

 In the bridge the total current is divided into two paths: i1

through R1 and R3, and i2 through R2 and Rx.

 Under the balancing conditions, the potential at points B and D

must be the same, i.e. the ohmic voltage drop through the
resistors R1 and R2 must be the same.

Sisay K.
 Conductometry…
147

 Hence, the potential at B must be equal to potential at D.

EB = ED or i1R1 = i2R2

Similarly, i1R3 = i2RX

Division of the first to the second gives

Sisay K.
 Conductometry…
148

 Thus , we can calculate Rx, as R1,R2 and R3 are all known.

Conductance, G, being the reciprocal of resistance will be

 Conductance can be read directly on commercially available

instruments.

Sisay K.
 Conductometry…
149

Applications
- conductimetric titrations (Reading A.)

Sisay K.
150

The End

Sisay K.
 QUIZ
151

1. What is conductometry?
Conductometry means measuring the conductivity of an
electrolyte or molten salts

2 Write factors that influence the electrical

conductivity of solutions of electrolytes
1. interionic attraction,
2. solvation of ions,
3. temperature and
4. viscosity of solvents

Sisay K.