POLAROGRAPHY

Polarography is the study of the electrolysis of solutions of electrooxidizable and

or electroreducible substances between a dropping mercury electrode (DME) and some
reference electrode (RE) . The potential between these electrodes is varied and the
consequent changes in the flow of current is measured Fig. 1. On plotting the changes in
current flow versus the potential variation, one obtains an i - E curve known as
polarogram. The first scientist who discovered the use of the DME in electrolysis is
Jaroslave Heyrovsky in 1922 and received the Nobel Prize in Chemistry in 1959.
+
_

A node

Ca t hode

Fig. 1 The Polarographic Circuit

From the measurements of the current - potential curves resulting from electron
transfer processes at the surface of a DME, the identity and concentration of the reactant
substance can be determined. One of the vertues of polarography is that solutions as
dilute as 10-8 M can be analyzed and sample volumes as small as 0.05 ml can be
manipulated. Thus, the position of a wave in a polarogram along the potential axis gives
the identity of the substance while the magnitude of the limiting current gives picture of
the concentration variation of this material.
A very pure mercury patch can be obtained through distillation under vacuum (
99.99 % pure ) . Each drop represents a fresh electrode with a new exposed surface. The

reproducibility of geometry of each drop with the laps of time is another advantage of the
DME over other electrodes. The large activation overpotential for hydrogen gas
evolution makes this electrode valuable for the study of cathodic processes. One of the
most important drawbacks of the Hg as electrode is its ease of oxidation. Thus, Hg
undergoes anodic dissolution at +0.25 V vs. SCE and is oxidized to insoluble Hg2Cl2 in
presence of chloride ions at zero V vs. SCE so it cannot be used for anodic oxidation
above +0.25 V vs. SCE. Also it is important to mention that Mercury vapors are very
poisonous besides Hg itself is considered to be one of the major pollutants of the
environment.
A polarogram or better a polarographic wave has the S shape illustrated in Fig. 1
.

Diffusion current id
Wall of the wave

Half-Wave potential E1/2

Residual current

Applied e.m.f. (E)

Fig.2 The i - E Curve ( Polarogram )

The slowly increasing current at the foot of the wave is known as the residual current.
This current is non faradaic in nature. The diffusion current id is, as shown, the distance
between the limiting diffusion plateau and the residual current. The potential at the midpoint of the wave, where the current is exactly half its limiting value, is known as the
half-wave potential E1/2and its quantity is characteristic of a particular species under
fixed experimental conditions. Thus E1/2 value serves as finger-print for the species

undergoing redox. Furthermore, the limiting current is usually proportional to

concentration of the species being reduced or oxidized and thus serves for quantitative
analyses. Over the diffusion current plateau region the DME is behaving as a completely
polarized electrode since it adopts any applied potential to it with no change in current
flow. It is interesting to notify that polarization always results from slow stage in the
overall electrode process. The slow stage here is the diffusion process which occurs very
much slower than the electron transfer. This type of polarization is known as
concentration polarization and the DME is said to be concentration polarized. At
potentials corresponding to the rising part of the wave the electrode is depolarized since
here the current flow is strongly dependent on the applied potential. At this stage it is
important to emphasize that in any electrolysis two types of processes are encountered.
i- Mass transfer process which brings the electroactive material to the electrode surface
ii- Electrochemical process which involves the act of electron transfer between the
surface of electrode and the electroactive species.
The mass transfer is usually achieved through a- migration, b- diffusion and dconvection. Migration is an electric field effect and depends upon the charge on the
species, concentration and mobility in a field of force. Diffusion depends upon
differences in concentration between species at the surface of the electrode and in the
bulk of solution. Finally convection arises from any mechanical or thermal disturbance
in the solution. For a redox process to occur it is essential that electrons pass between the
electrode and the species in solution . However, by no means electron transfer in its
crude definition acts alone, thus adsorption, rearrangement of electronic configuration
within the species to give a suitable form for the electron exchange is a normal
observable sequence. After the electron exchange a primary product is formed which reundergoes an electronic rearrangement, desorption and may suffer further side reactions
to form the final product. These electrolytic processes may be reversible or irreversible
in nature depending on the activation energy values.
Diffusion Current
According to Ficks first law of diffusion, the rate of diffusion is proportional to the
concentration gradient. Since diffusion in polarography is the rate controlling (
determining ) step, consequently the rate of diffusion is thus equal to the rate of electrode
reaction and therefore the rate of the electrode reaction is proportional to the
concentration gradient.
Rate of Diffusion (dC/dx)x=0

i / n F A ( dC / d x ) x=0

For a plane electrode

i / n FA = D ( dC / dx )x=0

i = n F A D ( dC / dx ) x=0

[ Plane electrode of surface area A across which a current i passes due to the impressed
emf , n is the number of electrons, F is the faraday, D is the diffusion coefficient in cm2 /
sec., C is the concentration , x = 0 means at the electrode surface ].
We can picture the situation near to the electrode by the model illustrated in Fig. 3.
Cb

Bulk of solution
Ce

Distance from electrode (x)

Fig. 3 Schematic Representation of the Concentration Gradient
Cb is the concentration in the bulk of solution and Ce is the concentration at the surface
of the electrode. Thus, the value ( Cb - Ce ) represents the fall across the diffusion layer
which is known as the Nernst diffusion layer ( 10-2 -10-3 ).
[ Cb - Ce ] / = ( dC / dx ) x=0

i = n F A D( Cb-Ce / )

Cb >>> Ce

& Ce at a certain time tends to zero

id = [ n F A D Cb ] /

5
4

where id is the maximum limiting current. Ficks first law is limited only for the cases
where the diffusion layer is of constant thickness and where the conditions are stationary.
In other cases when the diffusion layer thickness alters with time and concentration is
varying with both time and distance, Ficks second law must be introduced .
dC / dt = D [d2C / dx2]

This second order equation can only be solved mathematically by Laplace integral
transform resulting in the famous Cottrell equation. This equation shows that it
decreases with time due to a broadening of the diffusion layer and a decrease in the
diffusion rate. Noteworthy that this equation is the backbone of the Ilkovic equation.
it = n F A (D)Cb ( t)

To convert 7 into Ilkovic equation one assumes both that the drop is spherical and that
the mercury flow rate is uniform, that is , that the drop volume increases linearly with
time.
A = 4 r2

V = 4 / 3 r3

d=W/V

10

V = W / d = 10-3m t / d

11

Combining 9, 11 equation 12 is obtained

r = [(3 X 10-3m t) / 4d]1/3

12

Replacing r value in 8 by 12 and by combining the terms one obtains 13

13
A = { [ 6 X 10-3 X m t ] / d } 2/3
Substituting A value in 7

14

it = {(n F Cb D1/2 t1/6 )/ 1/6 } {(6 X1 0-3m) / d} 2/3 ( 7 / 3 )1/2

id = 708 n D1/2 t1/6 m2/3 Cb

15

Where V is the volume in cm3, W is the weight of the drop in g, m is the rate of Hg flow
in mg/sec. , d is the density g / cm3, ( 7 /3 )2/3 is introduced to account for the fact that
the drop is continually expanding. Solving 14 and defining the diffusion current as the
current at the end of the drop life t, one obtains 15 the Ilkovic equation where id is
expressed in A, Cb in mM per liter and t in seconds. Equation 15 is a linear equation of
the form
id = KCb . This linear relation is the basis of quantitative analyses ( calibration curve ) in
polarography
The Polarographic Wave Equation
The shape of voltammetric curves are directly related to the rates of electron transfer.
Two classes of electrode processes are well established the fast electron transfer known
as reversible process and the slow one known as the irreversible process.
Reversible Process
Consider the following electrode process:
An+ +
ne=
B
16
o form
r form
When the rate of forward and backward reactions are relatively fast, the Nernst aquation
is satisfied over the entire length of the voltammetric curve
E = Eo - R T / n F ln [Cr / Co ]e

17

For convenience consider a solution containing only the oxidized form of a redox couple
and potentials are scanned at cathodically increasing values.
i ( Cob - Coe )

18

i = ko ( Cob - Coe )

19

At i = id, Coe tends to zero

id = ko Cob

20

i = ko Cob - ko Coe

21

Coe = (ko Cob - i) / ko = (id -i) / ko

22

Where ko = 708 n Do1/2 m2/3 t1/6

For the anodic process occuring at the electrode surface
i = - kr (Crb - Cre)

23

Where kr = 708 n Dr1/2 m2/3 t1/6

i = kr Cre

since Crb is equal to zero

E = Eo - RT / nF ln [ i / kr ] / [ id - i / ko ] = Eo - RT / nF ln [ i / id - i . ko / kr ]
E = Eo - [ RT / nF ln i / id - i + RT / nF ln ko / kr ]
E = Eo - RT / nF ln Do / Dr - RT / nF ln i / id - i

24
25

When i = 1/2 id
E = E1/2 = Eo - RT / nF ln Do / Dr
and hence E = E1/2 - RT / nF ln i / id - i

26

at 25 oC
E = E1/2 - .0592 / n log i / id - i

27

From equation 27 the number of electrons can be obtained by plotting the what so called
logarithmic plots or well known practically as test of reversibility.
Equation 28 describes the irreversible process where is the transfer coefficient 0 < <1
E = E1/2 - .0592 / n log i / id-i

28

Determination of the Number of Electrons in Voltammetry

The actual number of transferred electrons in a reversible electrode process can be
determined from the logarithmic plots which simply consist of plotting log id - i / i versus
E as illustrated in Fig. 4. The slope of the obtained straight line is equal to n F / 2.303 RT
7

from which n is determined. These calculations are valid for low electron transfer
reaction i.e. one to two electron process. If the obtained n number is a meaningless
fraction , the reaction should be irreversible and n is obtained through Faradays law, the
basics of coulometry

+
iog id-i/i

Slope = nF/2.303 RT
0
E

E= E1/2

_
Fig. 4 Logarithmic Analysis
Q = it X t

29

The total quantity of electricity Q in coulombs passed in an electrolysis is given

by
Q = it dt

30

Current decays in accordance with

it = io e -kt

31

Solving 30
Q = io e -ktdt

32

Q = io e

-kt

dt

33

Q = io | e- kt / -k | limits of i from 0 to

34

Q = io [ e-k / -k - e-k0/-k ]

35

Q =io / k

36

Taking the natural logarithm of equation 31 one obtains

log i
log io

t
Fig. 5 The i - t relation
ln it = ln io - kt

37

2.303 log it = 2.303 log io - kt

38

log it = log io - [ k / 2.303 ] t

39

Ounce Q is measured, the weight W in grams be determined n can be calculated from

Faradays law of electrolysis
W=QM/nF

40
9

CYCLIC VOLTAMMETRY
Cyclic voltammetry is a variant of a technique called stationary electrode voltammetry.
This technique is also known as cyclic triangular wave voltammetry. Typical stationary
electrode voltammograms are illustrated in Fig. 6. Notice that the potential may be swept
either anodically or cathodically, and that, unlike polarography, the curves are peaked.
As the potential moves into the region where the substrate is reduced or oxidized, the
region adjacent to the electrode becomes depleted of material and the current decreases.
The relation relating the peak current ip to the experiment parameters of a stationary
electrode is given by equation 41
2/3
ip = 2.687 X 105 n A D1/2 C 1/2

41

n, A, D, and C have their usual significance. is the potential sweep rate expressed in
volt per second. Equation 41 ( the Randles- Cevcik equation) is based on the
assumptions that the electrode process is reversible and linear diffusion, when these
conditions are fulfilled the ratio ip / 1/2 is constant.
0

Sta

i
Start
0

Cathodic Sweep

Anodic Sweep

Fig. 6 Stationary Electrode Voltammogram

The experimental feature of interest in cyclic voltammetry is the variation of the
potential of the working electrode as a triangular wave ( Fig. 7 ) i. e. after the stationary

10

electrode voltammogram of a substance has been measured by sweeping past the

potential Ep the direction of voltage scan is reversed. Either a single cycle [ from E1 to
E2 and back to E1 ] or many cycles may be carried out. Typical CV are shown in Fig. 8
where it is obvious that cyclic volammetric behavior can exhibit a variety of forms. The
shape of the CV curve is highly dependent on the relative rates of electron transfer, mass
transport, and any chemical reactions occurring at the electrode surface. Scan rates can
be varied over a wide range .
Cyclic voltammetry serves nicely as a tool for the test of reversibility. Consider the
reversible reduction of a species O to R.

O
+
n e=
R
the CV showing this behavior is illustrated in Fig.8 and expanded in Fig. 9

E2

E1

Time

Fig. 7 The Triangular Wave Form

Reversible

Irreversible
E

11

EC process

Fig. 8 Representative CV Curves

Reduction of O takes place at a certain potential Epc when the voltage scan direction is
reversed an anodic peak due to the oxidation of R is observed . Now if Epa and Epc are
the potential corresponding to the anodic and cathodic peak currents and Epa/2 and Epc/2
are the potentials corresponding to the half peak currents it may be shown that Epa - Epc
and Epc/2 - Epa/2 will be each equal to 0.056 / n for a reversible process. Also the
following expressions are valid within experimental error ( Fig 9 ).
Epc/2 = Epa = Eo + 0.028 / n
Epa/2 = Epc = Eo - 0.028 / n
Suppose that the electrode process of interest is totally irreversible

O
+
n e-
R
The CV curve as illustrated in Fig. 8 will have no anodic peak upon scan reversal past the
peak potential. This is consistent with a very low rate of reoxidation of R and is a
conclusive evidence of irreversibility.

12

Epc

ipc

ipc/2

Epa - Epc = Epc / 2 - Epa /2 = 56 mV

Epa

- E

Fig. 9 CV Curve of a One Electron Reverible Process

These simple electron transfers are known as the E mechanisms and as previously
pointed out the CV shapes are determined both by the heterogeneous charge transfer and
the diffusional mass transfer. The heterogeneous charge transfer is described by the
Butler - Volmer equation[ the basic equation in electrokinetics ].
Je(0, t) = i/nFA = Ce(0,t) ko e[ -nF( E-Eo)/RT]-Cb(0, t)ko e[ 1- ]nF (E - Eo) / RT
ko is the heterogeneous standard rate constant, Eo the standard electrode potential A the
surface area of the electrode and J is the flux at the electrode interface. If ko > 10-1 cm s1
ko is considered to be very high and a dynamic equilibrium is established at the electrode
interface and the Butler - Volmer equation is reduced to Nernst equation and Ce and Cb
will depend only on the actual applied electrode potential and are no longer influenced by

13

heterogeneous kinetic effects and a thermodynamic equilibrium exists at the phase

boundary. The current is thus influenced solely by the mass transport which is the
slowest step ( diffusion ). If ko < 10-5 cm s-1 the reaction is very slow and the term i /
nfAko cannot be neglected and depending on the potential only one of the cathodic or
the anodic heterogeneous reactions has a measurable rate, the current is thus largely
controlled by the rate of charge transfer reaction. In this case Nernst equation as is does
not apply and one speaks of an irreversible process.
The third frequently encountered type of behaviour is the EC process shown in Fig. 8 .
An anodic peak is observed in the reversal scanning but this peak is diminished
considerably in height relative to the cathodic peak. Furthermore, A faster scan rate will
increase the relative height of this anodic peak and could reach at any instant the height
of the cathodic peak. on the other hand at very low scan rates the anodic peak can
completely disappear. This behaviour is usually associated with a chemical reaction
subsequent to electron transfer such that a fraction of the R reacts chemically and is not
available for reoxidation upon scan reversal. If the scan rate is very high relative to kf
little R will be lost to the
O
+
n e= R
kf
R
Product
succeeding chemical reaction, and the the CV curve will resemble the reversible case.
Conversaly if the scan rate is low relative to kf the chemical reaction will be completed
before reversal of scan and the electrode process will be totally irreversible. This
mechanism is known as the EC mechanism. Fig. 10 illustrates the profile of an EC

14

kf1

kf2

kf3

A
P

P
X

Fig. 10 Concentration Profile of an EC Mechanism

kf1 << kf2 << kf3
mechanism. In the follow - up reaction the initially formed anion R decays and a new
product is formed P, only a small amount of R is available for oxidation in the reverse
sweep depending on the rate of the following up reaction and the scan rate . Accordingly
the anodic current in the cyclic voltammogram decreases until it disappears at high rate
constants and low scan rates. The rate of the follow - up reaction can be determined from
the ratio of ip and ic of the CV curves at an appropriate scan rate .

APPLICATION OF VOLTAMMETRY IN ORGANIC ELECTRODE

PROCESSES
The Square Diagram
Let us undertake a detailed examination of a relatively simple system in which two
electrons and two protons are gained or lost during an elctrochemical process. This type
of reaction is very common in electroorganic mechanism. It is obvious to chemists

15

accustomed with reaction mechanisms that this process can occur only in stages . In
principle there could be seven intermadiates involved in such process . In the scheme
diagrammed below all electron transfers are given by horizontal lines and all chemical
changes are given by vertical lines
The computer analysis of such diagram leads to the following conclusions.

AH

.
A

.
AH

AH

e-

2-

H
2+
AH
2

+.
AH
2

He e H

AH

HHe e
He He

+
+ 2 e- + 2 H

AH 2

i- The reaction path which is followed depends on the acid-base equilibrium constants
which are involved in the scheme and on the kinetics of electron transfers and chemical
reactions.
ii- For a given electrode potential, several pathways may be simultaneously followed.
The relative importance of each depends on the applied potential.
iii- Reaction paths may be different in oxidation and in reduction.
Protons in Organic Electroreduction Processes
In electrode processes involving Organic species the E1/2 is usually dependent on the
variation of H+ concentration and thus is shifted towards negative values. The variation
of E1/2 with pH is usually linear . The slope of this linear dependence is given by
16

d E1/2 / d pH = -0.0592 / n X P
where P is the number of protons in the rate determining step in a reversible reaction
according to Mairanovskii. On the other hand for an irreversible reation the shift can be
described by

d E1/2 / d pH = -0.0592 / n X P
ELECTROLYSIS
Controlled Electrolysis and Selectivity
The practical quantities to be controlled in an electrolysis is the current measured
in amperes or the potential of the working electrode expressed in volts. The differences in
these two ways are illustrated in Fig. 11 . In this figure curve I depicts schematically the

Fig. 11 Schematic Illustration of the Deformation of Waves During Electrolysis

connection between the current through the cell and the potential of the working
electrode. Consider a solution containing two reducible species or one molecule with two
electroactive sites (waves 1 and 2). When the potential at the cathode is varied between 0
17

and EA, no electron transfer across the electrical double layer can take place and thus no
current runs through the cell. If the cathode potential is made more negative, the electron
transfer becomes possible; that is, the reduction of the most easily reducible compound or
group starts. Between EA and EB the current rises in dependence on the potential, but
when the value EB has been reached, all the molecules that arrive at the electrode and
which can undergo the first reduction are reduced as soon as they reach the electrode. In
the potential interval EB to EC the current is limited by the transport of the reducible
compound to the cathode. This current is called the limiting current il1,2 and under fixed
conditions it is proportional to the concentration of the electroactive compound and
known as the diffusion current id.
A further change of the electrode potential in the negative direction results in the
occurrence of the second electrode reaction and the current rises; a similar S-shaped
curve results from this reduction. At more negative potentials (>ED) a third reaction the
reduction of the medium takes place ( Wall of the electrolyte ).
If a suitable current i1 [i1 < id1] is sent through the cell, the cathode potential
assumes the value E1 between EA and EB, and when i1 < id1 is well below the potential
(EC) at which the second electrode reaction starts; a selective reduction thus occurs at the
beginning of the electrolysis. During the electrolysis the concentration of the reducible
compound, and thus its limiting current, diminishes and after a while (curve II) the
limiting current becomes smaller than the applied current [i1 > id1]. The cathode
potential has then, by necessity, reached the value E in between EC ED and at this
potential the second electrode reaction also takes place; the electrolysis is no longer
selective. When the electrode potential is the factor controlled and is kept at a suitable
value, eg. on the limiting current plateau of the first wave, the second electrode process
cannot take place, and the reduction remains selective to the end of electrolysis. The
current through the cell is never higher than the limiting current corresponding to the first
electrode reaction. This means that the current decreases during the reduction and
becomes very small toward the end of the reaction, as the limiting current is proportional
to the concentration of the electroactive material .

Controled Current Electrolysis ( CCE ) Manipulation

This electrolysis preparation is usually carried out in a simple two electrode cell.
The cell and circuit are illustrated in Fig.1 2 . The basic components for the circuit are :
The
constant current supply with a stable current output of maximum 10 A ( for a laboratory
scale electrolysis ), the voltage and current measuring devices, and the cell, which can be
18

Fig. 12 Control Current Electrolysis Cell

simply a pyrex beaker with a working (WE) and a counter (CE) electrode. To minimize
the IR dropin the cell the distance between the electrodes should be very small. The
choice of the WE material depends mainly on the actual type of electrolysis and medium.
In classical electrooxidation processes the Platinum and Carbon electrodes are widely
used, In indirect electrooxidation large scale electrolytic preparations the Nickel oxide
hydroxide anode is used. Mercury and Lead electrodes are the commonly used cathodes
in electroreduction processes. The reduction of Oxygen leading to the superoxide ion in
aprotic media using Hg, Au, Pt and C cathodes with the proper supporting electrolyte is
another powerful indirect electrolysis technique.
Controlled Potential Electrolysis ( CPE ) Manipulation
A circuit as the one illustrated in Fig. 13 is fairly sufficient for performing such
CPE experiments together with the help of a classical DC polarograph a must for finding
out the optimum experimental conditions through routine analyses of the compound
to

19

Fig. 13 Circuit Used in Controlled Potential Electrolysis

be electrolyzed. The circuit consists in its simple form of a potentiostat (used for
controlling the applied potential), galvanometer (used as current measurement device)
and a valve voltmeter to check the accuracy of the applied potential and to detect any
resistance in the cell during the course of electrolysis. A 250 ml conical or flat bottom
flask (Fig. 14)

20

Fig.14 Controlled Potential Electrolysis Cell

in which the reference (RE) and auxiliary (AE) electrodes have been inserted by means
of a cork or Teflon stopper, is a practical cell for this purpose. The working electrode
(WE) in electroreduction processes is usually mercury which has been previously
purified by classical methods. Finally, a magnetic stirrer is used for agitation of mercury
with the help of a stream of purified N2 or H2 gas which is continuously bubbled through
the mixture. This stream repels and prevents contamination of the solution with
atmospheric O2. The number of electrons consumed in the electrochemical reaction is
usually calculated either directly by inserting an electronic integrator into the circuit or
simply by recording the decay in current with time using Lingane's method of analysis
emphasized further on.
For this purpose a complete detailed study of the half-wave potential (E1/2) and
limiting current (i1) versus pH dependence of the compound to be electrolyzed must be
undertaken using different solvent compositions. A plot of i1 versus time t curve, from
which a knowledge about the stability of a certain species towards a certain medium, is
also of great value. In the following are summarized some important hints for carrying
out large scale laboratory preparative electrolysis:
(1) The choice of electrolysis potential must be taken in the medium where i1 is
practically pH and time independent (Fig.15).

Fig. 15 Effect of Time on Limiting Current of a Polarographic Wave

21

(2) In molecules displaying well defined polarographic waves the potential of

electrolysis must be chosen in a way that it covers the beginning of the limiting current
i.e. -0.2 V > E1/2 value. On the other hand, if the wave is located at very negative
potential i.e. near hydrogen evolution in acid media or near the limiting wall of
supporting electrolyte, the potential must be fixed at value within the beginning of the
rising portion of the wave in question.
(3) Calculated amounts, not exceeding 100 mg, of starting material are practical
in CPE experiments to decrease as much as possible electrolysis time and in turn side
chemical (CR) and secondary electrochemical reactions (ECR). In addition, the use of
calculated amounts help controlling the efficiency of experiment.
(4) It is preferable to use a medium in which the compound to be electrolyzed is
completely soluble. However, if the products of electrolysis are soluble in the medium,
suspensions of the starting materials may be used. Preferable to use acid medium or
faintly acidified medium to minimize as much as possible conductance problems.
(5) pH-control (Cf,further ) is mandatory since, in some processes molecules of
basic character are obtained as main products of electrolysis and thus will change the pH
of solution in the course of electrolysis.
(6) Room temperature is suitable for most CPE experiments if not otherwise
specified for a certain reaction.
Finally, before carrying out a large scale electrolysis a researcher needs to
emphasize in a way or another to overall picture occurring inside his electrochemical cell
and thus it is wise to perform an experiment on a small scale say 10-4 mol dm-3
depolarizer, in which the electrochemical reactions are closely monitored through
periodic plotting of i-E curves using classical DC-voltammetric techniques using a DME,
HMDE or a RDE. This will help to shed light on the mechanism and kinetics of the
electrode processes. At the end of electrolysis products are identified via spot tests or an
other convenient analytical technique. The purpose of this low concentration CPE is to
improve the experimental conditions, to get information as much as possible on the
stability of the resulting products, the intermediates (if any) and to estimate the average
total time that will be consumed in a large scale preparative electrolysis.

Best Cell Geometry

Potential Distribution
Potential gradient should be the same all over the electrode surface so as to obtain
a uniform density distribution. The design of electrodes help to improve the potential
distribution in a certain cell thus a good distribution is obtained in concentric electrodes
22

such as Swiss-roll (Cf. further) and cylindrical electrodes followed by the plane parallel
electrodes. (Fig.16).

Fig. 16 Common Electrodes a-Plane Parallel b- Cylindrical C-Swiss-Roll

Position of a Reference Electrode
Electrochemists generally approved the position concept which states that "In the
general case the best approach is to place the reference electrode as near as possible to
the working electrode surface on the line of minimum distance between the counter and
working electrode" (cf. Fig. 17).

Fig. 7 Location of the Reference Electrode in an Electrolysis Cell

a- Best Position b- Not Advisable Position b- Error Caused by IR Drop
d- Minimal IR Drop Position
Ohmic Resistance
The diagram in Fig. 18 illustrates schematically the potential distribution in an
electrochemical cell. If one wishes to diminish the ohmic resistance the first approach is
to minimize the distance between the working and counter electrodes [in some cases one
may reach a value of 0.1 to 0.2 mm (Swiss-roll electrodes)]. Secondly is to increase the
surface of the electrodes and finally diaphragms should be used only when unavoidable.

23

Fig. 18 Potential Distribution in an Electrolytic Cell

Diaphragms
These should be used only when the products of the auxiliary electrode may
interfere with the desired electrode reaction occurring on the working electrode.
Mass Transfer
An efficient mass transfer must be acting all the time through electrolysis by
either stirring (mechanically or magnetically), recycling pumping or heating.
Heat Transfer
Excess heating resulting from electrochemical processes in resisting solutions
should be avoided by proper cooling procedures or the use of flow cells.
Closed System
In electrolytic reduction processes closed systems should be used to avoid
contamination with atmospheric oxygen which is reduced at the surface of the electrode
causing an indefinite number of problems. Also, when dealing with non-aqueous media,
contamination with H2O vapors is also avoided by the use of closed systems.
Difference between Micro and Macro Scales Electrolyses
Shifting from micro to macro scale preparative electrolysis requires some skills
due to the interference of few newly borned factors such as .

24

(a)

Prolonged time of electrolysis

Usually macro scale electrolysis consumes longer time ranging from several hours to 7
days a time which is long enough to allow consecutive chemical reactions to occur
between solvent and products or between reagent and starting molecules or the
interference of known common chemical reactions such as hydrolysis or hydration.

(b)

Enlarged surface area of electrode

Increasing the concentration of the substrate requires the immediate increase of the
available surface area of the electrode and this by turn causes the following.
Adsorption phenomena resulting in the blocking of the electrode surface.
Increase of the rate of chemical surface reactions of species adsorbed on the surface of
the electrode.

i)
ii)

(c)

Higher concentrations
The high concentration of electrolysable material causes higher order reactions such as
dimerization, oligomerization and polymerization. This can clearly be observed in some
cases from the variation of the uptake number of electrons by the same species at higher
and lower concentrations.

(d)

pH-control
The pH in macro scale electrolysis vary in the vicinity of the electrode according to the
obtained electrolysis products and hence is difficult to be controlled with high degree of
accuracy. Thus in the CPR of hydrazones amines are produced as main products of
electrolysis and hence the pH will increases drastically and the solution becomes highly
alkaline.
Difference in E1/2 measured by a micro electrode and a large surface electrode

(e)

(macro electrode)
For an irreversible reaction at a stirred pool.The half-wave potential of a Hg pool
electrode as compared to that of a DME is given by the following relation.
Dt /
E1/2 (Hg pool) = E (DME) + RT / nF ln 1.349
D is the diffusion coefficient, t is the drop time, is the diffusion layer
thickness. (D is ~ 6x10-6 cm/s for a t of 4 sd-1 for a medium sized molecule
and is ~ 3x10-3 cm)
For a reversible system
E1/2 (Hg pool) = E1/2 (DME) - RT/nF ln R/ O
and hence the two are nearly equal.

Efficiency of an Electrochemical Process

25

According to the first Faraday law of electricity "For any electrode process the
amount of material converted by electrolysis is proportional to the product of current and
time of its passage, that is, the total electric charge". On the other hand the Second
Faraday's law describes the effect of nature of ions. Accordingly this law states that "the
amounts of different substances produced by the passage of the same electric charge are
proportional to their equivalent masses". The electric charge required to liberate 1
equivalent of any substance by electrolysis is 96500 coulombs or 26.8 Ah. In practice the
amount of substance liberated by electrolysis is always smaller than the theoretical
amount calculated from Faraday's laws.
The efficiency of a certain electrochemical process is basically defined by its
current yield (in percentage) and by the coefficient of energy. The current yield or
efficiency (CE) is the ratio of the actual amount wa of matter obtained by electrolysis to
the theocratical amount wth which should be obtained with the same energy consumption
according to Faraday's Law.
(CE) = wa / wth

or Actual Ah / Theoretical Ah.

but
wth = ( I x t x wo ) / 1000
where I is the current in amperes, t is the duration of electrolysis in hours and wo is the
amount of material liberated at the working electrode with the passage of 1Ah charge.
The coefficient of energy is equal to the ratio of the theoretical amount of
energy th to the actual consumed amount of energy in the electrolysis process a.
= th / a
the theoretical consumed amount of energy in an electrolysis (kW/Kg of product) is given
by
th = Eth x I x t / wth
where Eth is the theoretical applied voltage which is the difference between the
equilibrium potentials of the anodic ea and ec potentials in volts.
Eth= ea - ec
The equilibrium electrode potentials are given by Nernst equation as follows.
ec = eo + RT/nF ln a1
ea = eo + RT/nF ln a2
where eo is the standard electrode potential, R is the gas constant, n is the number of
electrons, F the Faraday, T the absolute temperature. On the other hand the actual
operating voltage Ea is higher than Eth owing to polarization and overvoltage, as well as
to the losses due to the ohmic resistances of electrolyte and current leads. The actual
operating voltage equation will take the following form.
26

Ea = (ea - ec) + ea + ec + IR
where ea and ec are the voltage compensating terms for both electrochemical
polarizations at the anode and cathode respectively and IR is the voltage drop
compensation. The actual consumption of energy (Energy efficiency) in an electrolysis
process is given by
a = Ea x I x t / wa
and will be equal to Eth / Ea .
To summarize one can conclude that the energy efficiency of an electrochemical process
can be developed from observation of the cell operating voltage and the efficiency of the
current in converting the substrate to the desired product . It should be always
remembered that the cell current efficiency is increased usually by decreasing resistance
losses, selection of electrode material and avoiding as much as possible secondary
reactions.

Recent Trends in Electrolysis

Mediated Electrochemical Reactions
Two types of mediated or what so called regenerative electrochemical reactions have
been thoroughly investigated in this decade. The first type is known as the internal
mediation which consists of an electrochimically generated reactive species which reacts
with the substrate to form a product and this mediator is electroregenerated ( reformed ).
The second type involves the electrochemical generation of an oxidizing or reducing
reagent within the cell , reaction of the reagent with the substrate externally to the cell ,
and return of the reduced or oxidized reagent to the electrolysis cell for regenerattion.

Internally mediated reactions

Figure19 illustrates the principle of the internally mediated reaction. The radical ion
formed at the anode reacts with the substrate, transforming the latter to the radical anion .
The deactivated mediator is recycled at the anode , and the substrate radical anion is
transformed into the reaction product. The mediator thus acts as a catalyst for the
electrochemical transformation. Four cases in which mediated reactions may be
attractive alternatives to classical electrochemical reactions.
i- To obtain products of an electrochemical rection that are not obtainable during direct
electrolysis.

27

ii- To conduct electrochemical rections at potentials lower than those required for direct
electrolysis.
iii- To conduct electrochemical reactions of substrates who are not obtainable under
classical electrolysis conditions.

Med

.+
Substr.

A
n
o
d
e

Substr.

Med

.+

Prod.

Fig.19 Principle of Mediated Electrolysis with Internal Mediators

iv- To conduct reactions using catalytic amounts of metallic redox reagents with
reduction of the required inventory of the redox agent required for the direct reaction.

Case i example
An example of this case is the reaction of benzene with electrochemically generated
hydroxyl ion via the Fenton reaction. Classically this reaction gives very poor yiels but
electrochemically the yield reaches 64% It is important to draw attention that ferrous
ions are both chemically and electrochemically regenerated during the electrolysis.
Fe+3 + e- = Fe+2
Fe+2 + H2O2 = OH- + OH. + Fe+3
OH. + C6H6 [ C6H6OH ].
[ C6H6OH ]. + Fe+3 = C6H5OH + H+ +

Fe+2

Case ii example
The use of an elctrochemically generated intermadiate to reduce the voltage required to
drive electrochemical reaction has been illustrated in a modification of the Kolbe reaction
RCOO- RCOO.

e-

28

The observed potential of this initial step of the Kolbe synthesis is 2 .46 V vs Hydrogen
reference electrode . By the use of mediator the formation of the alkyl radical can occur
at 1.3 V. This has been accomplisned by using tris-( p-brmophenyl ) amine ( TBA ) and
lead to the following mechanism requiring only 1.3 V.
TBA TBA.+ + eTBA.+ + RCOO- TBA + RCOO .
RCOO. R. + CO2

Case iii example

The technically important side-chain oxidation of three heterocyclic compounds, such as
4-Picoline,

4-methylimidazol

and

2-methyl-4,5-dihydromethylimidazol,

can

be

performed electrochemically at low potentials, in CH3CN / MeOH / LiCl04 system, using

catalytic amounts of electrogenerated and regenerated triarylamine cation radicals as
organic mediators. It is important to attract attention to the fact that

direct

electrochemical oxidation of Picolines, because of the electron-poor heteroaromatic

ring,can only occure under acidic conditions.
R

Br
CH3

Br

HOH2C

CH3

N
N
N

R
R

CH2OH

Br

NH

NH
CH3

The applicability of triarylamines (TAA) as redox catalyst was first demonstrated in the
oxidation of cyanide ions. The advantage of triarylamine as mediator is the possibilty to
adjust their oxidation potential by the selection of the ortho and para substituents. A large
spectrum of substituted triarylamine has been developed and applied as mild and
selective oxidizing agents . The electrogenerated and regenerated triarylamine cation
radicals are usually

used for the side-chain oxidation of alkyl-substituted aromatic

compounds and benzyl alcohol oxidations.The following scheme is postulated for the
indirect mediated electrooxidation.

29

Ar 3 N - e-

Ar 3N.+

Ar3N.+ + RCH 3
.+
RCH 3 + CH3OH
RCH .2

ArN .+

+
RCH 2

CH 3OH

Ar3N + RCH 3
.
RCH2 + CH3OH2+
+
RCH+
2.

Ar 3N.

RCH2OCH 3

H+

Modified electrodes
Modified electrodes are considered as the most ideal form of internal mediators , the
process consists mainly of coating the workimg electrode with a metal complex in which
the metal will act as the mediator . This technique is considered very attractive since it
protects the electrode , and helps in using various types of low cost material electrode and
improves the purity of the obtained product and the film can be easly regenerated.
Externally mediated reactions
The block diagram for carrying out an industrial scale electrochemical reaction is given
in Fig.20 . The reducing or oxidizing reagent, is regenerated in the electrolysis cell and
then transferred to the chemical reactor, where reaction with the desired compound
occurs. Following the reaction , the product is extracted from the reaction mixture . The
unreacted substrate can be recovered and returned back to the reactor. The reacted
oxidizing or reducing agent is returned to the electrolysis cell for regeneration. The
oxidation of toluene to benzaldehyde by an external mediator is well known. In 5 M
HClO4
in the presence of Ce(IV) benzaldehyde yields were around 98.8 % .
C6H5CH3

C6H5CHO

30

Ce I V
Tol uene

Reac t or
CeI I I

Separ at or
CeI I I

CeI I I

Benz al dehy de

Fig. 20 Diagram for an Externally mediated Process

Commercial and Pilot-Plant Synthesis
General
Electrochemical preparation of ingredients or precursors of certain pharmaceuticals
and perfumes has been of commercial interest for a number of years. However,
production of organic chemicals at multithousand- ton- per- year rates is only relatively
recent. One of the first large plants was that of Atlas Powder Company, which was built
in 1937 for the manufacture of 1400 tons / yr. of sorbitol and mannitol by cathodic
reduction of glucose. This early success was rather short-lived and the process was
replaced within a few years by a high-pressure catalytic hydrogenation route. It was not
until 1964 that a truly largescale electrooganic manufacturing facility was erected the
Nalco's tetraalkyllead plant in the USA. The capacity of the original installation was
15,000 tons / yr. tetramethyllead or 18,000 tons / yr. tetraethyllead. The following year
Monsanto began production of adiponitrile electrolytically
Electroorganic processes that have been investigated on a pilot-plant or
semicommercial scale cover a wide range of reaction types. In addition to the reductive
31

coupling of acrylonitrile and the preparation of sorbitol / mannitol, examples of other

cathodic processes considered for commercialization include the reduction of (1) salicylic
acid to salicylaldehyde (2) phthalic acids to the corresponding dihydrophthalic acids (3)
benzoic acid to benzyl alcohol. Anodic processes claimed to have favorable economics
are (1) the oxidation of propylene to propylene oxide, (2) the bromination of hydrogen
cyanide to give cyanogen bromide, and (3) the oxidation of starch to the dialdehyde.

B. Commercial Process for Adiponitrile

In excess of a billion pounds per year of adiponitrile is produced worldwide as a
precursor to hexamethylenediamine, one of the monomers used in the manufacture of
nylon 66 polymer. The importance of the production cost of adiponitrile on the
economics of making nylon is well recognized and has been responsible for considerable
research activity on the preparation of this intermediate. The possibility of
electroreductive coupling of acrylonitrile to adiponitrile was reported in the 1940s, but it
was not until the discovery in 1963 of the importance of the supporting electrolyte that
commercially attractive selectivities and current efficiencies were realized. It was found
that through the use of concentrated solutions of certain quaternary ammonium salts, such
as tetraethylamonium p-toluenesulfonate, nearly quantitative yields of adiponitrile could
be achieved at lead or mercury cathodes. Following an intensive process development
program, Monsanto designed and built a 15,000 ton / yr facility for production of
adiponitrile via this technology. This plant has been improved and expanded substantially
since startup in 1965 and a new electrolysis facility to produce 90,000 tons / yr of
adiponitrile was put into operation in 1978 in England, by Polyamide Intermediates Ltd.
In the Monsanto process a catholyte consisting of an aqueous solution of
acrylonitrile, quaternary ammonium salt (QAS). The QAS serves the joint function of
increasing the solubility of acrylonitrile in water and improving the electrical
conductivity of the solution. The anolyte, a dilute solution of sulfuric acid, is similarly
circulated through the opposing anolyte compartments. The cathode is lead; a lead alloy,
stable in sulfate electrolysis, is used as the anode material. The electrodes are mounted on
polypropylene plates with the anode of one cell joined electrically to the cathode of the
next via internal connectors, providing series flow of current through the bank of cells. A
cation permselective membrane separates the anode and cathode compartments.
32

Electrolyte is pumped through each cell in parallel and both anolyte and catholyte are
recirculated through external exchangers for removal of the heat generated in the cells. A
side stream is withdrawn from the circulating catholyte and sent to an extraction system
for removal of the product ADN.

Fig. 20 Industrial Production of Adiponitrile

The withdrawn catholyte stream is cooled and countercurrently contacted with
excess acrylonitrile in a multistage extraction column. The acrylonitrile/ adiponitrile
extract stream is then back-extracted with water in a similar column of dissolved QAS.
The organic stream leaving the second extraction column is sent to a stripping column,
where the acrylonitrile is distilled overhead and recycled to the process, following
removal of by-product propionitrile. The bottoms from the acrylonitrile stripper are
further refined by distillation to produce a 99% pure product, suitable for hydrogenation
into hexamethylenediamine. (Fig, 20).
The principal cathode reaction is:
2 CH2 = CHCN + 2 H2O + 2 e- NC(CH2)4CN + 2 OHWater is decomposed at the anode as follows:
H2O 2 H + 1/2 O2 + 2 eThe Monsanto cells can be operated at current densities ranging from 25 to 100 A /
dm2 with cell voltages ranging from 6 to 15 V, corresponding to power consumptions of
3-8 kWh / kg adiponitrile produced.

C. Commercial Process for Tetraalkyllead

33

Production of lead alkyls exceeded 5000,000 tons per year in the early 1970s in the
USA and although the demand has slackened in the United States in more recent years
because of environment constraints, the International markets have continued to show
modest growth.
Prior to the introduction by Nalco Chemical in 1964 of its electrolytic process for
tetraalkyllead, this important gasoline additive was produced via a 40-year-old process
involving the reaction of methyl or ethyl halide with sodium-lead alloy. Nalco combined
the large-scale production of Grignard reagent with a novel electrolysis system to pioneer
this new process and installed facilities to produce tetramethyllead (TML) or
tetraethyllead (TEL)in the USA. A simplified flowsheet of the Nalco TML process is
shown in Fig. 2.1
The first step is the production of the Grignard reagent from magnesium metal turnings
and alkyl halide in a mixture of anhydrous ethers, such as tetrahydrofuran and the diethyl
ether of tetraethylene glycol. The reaction is carried out in several 30 m3 propane-cooled
reactors, operating at about 2 kg / cm2 pressure and 35 - 40. Yields above 98% are
realized. The reactor product, containing excess alkyl chloride, is fed to ten 30 m3
electrolysis vessels containing a bank of steel-tube cathodes filled with lead shot. The
lead constitutes a sacrificial anode and is replaced through a feed arrangement in the top
head of the vessel. The bed of shot is insulated from the retaining steel cathode tubes by
porous diaphragms of plastic or ceramic. An improved version of the Nalco cell has been
described in which the bed of lead shot fills virtually the entire vessel and a number of
rectangular steel bars, covered with fiberglass cloth, are immersed in the bed to serve as
cathodes. The electrolysis is conducted at 40-50, cooling being provided by an ethyl
chloride refrigeration system. Current densities are typically 1.5-3.0 A / dm2 at 15-30 V.
The electrode reactions may be written as follows, assuming dissociation of the Grignard
reagent into two ions, R- and MgCl+ :
Anode reaction
4 R- + Pb R4 Pb + 4 eCathode reaction
4 MgCl+ + 4 e- 2 Mg + 2 MgCl2
Although the theoretical cathode reaction shows formation of a mole of free
magnesium for each mole of magnesium chloride, the excess alkyl halide added to the
34

feed combines with the magnesium to reform Grignard reagent equivalent to half of the
consumed. Thus, the overall reaction is
2 RMgCl + 2 RCl + Pb R4Pb + 2 MgCl2
If the concentration of alkyl halide in the electrolyte is too high, there is a loss of
reactants through WurtzFittig-type side reactions such as
RCl + RMgCl RR + MgCl2
On the other hand, insufficient levels of alkyl halide allow magnesium to be plated out on
the cathode, ultimately bridging the cathode-anode and causing short circuits. By proper
control of concentrations, temperature, and flow rate, yields up to 96% on the Grignard
reagent can be achieved at conversion levels as high as 99%, with yield based on the
magnesium consumed of 95%.The effluent from the cells is stripped with natural gas to
remove unreacted methyl chloride, which is subsequently reabsorbed in ether for recycle
to the Grignard reactors. The liquid phase from the stripper is contacted with water in a
series of extraction stages for separation of the magnesium chloride, TML, and mixed
ethers. The ethers are purified by azeotropic distillation and gas drying for recycle to the
process. By using different alkyl groups on the Grignard reagent and the alkyl chloride
fed to the cells, the process may be employed to prepare mixtures of tetraalkylleads, such
as Me4 Pb,
Me3 Et Pb, Me2 Et2 Pb, and Et4 Pb.

35

Fig. 21 Industrial Production of TML in the USA.

BIBLIOGRAPHY
1. "Electrochemistry at Solid Electrodes", R.N. Adams, Marcel Dekker, Inc., NY,
1969.
2. "Synthetic Organic Electrochemistry", A.J. Fry, Harper and Row, NY, 1972 .
3. "Organic Electrochemistry", M.M. Baizer and H. Lund, Marcel Dekker, Inc., NY,
1983.
4. "Cyclic Voltammetry-Electrochemlcal Spectroscopy" J. Heinze, Angewandte Vol.
23, Number 11, p 831, 1984.
5. "Polarography", D.R. Grow and J.V. Westwood, Methuen and Co. LTD, London,
1968.
6. Principles and Applications of Electrochemistry, D. R. Crow, Blackie Academic
&
Professional, 4th. Ed., NY, 1994.

36