1.

HISTORICAL DEVELOPMENT:

All the important electroanalytical methods make use, in one

form or another of electrolysis, in other words, of redox in a
processes in a solution in the immediate neighborhood, and under
the influence of an electrode. Some of the electrochemical methods
will briefly reviewed at elementary level.

Chemical transformation resulting from the flow of current

through the electrolytic cells were studied in the early stages of the
development of electrochemistry and electrochemical phenomena;
but a little attention was paid towards the study of electrode
process owing to the easiness of observing a chemical
transformation rather interpreting it. It was Cruickshank1 (1801),
who perhaps, for the first time made use of electrochemistry to
analytical applications. Quantitative application of this
electrogravimetric method was developed by Wolcott Gibbs2 and
subsequently by Luckow3. After words the progress was of the
significant contributions of Sand4, Fischer5 and Haber6. The
quantitative study of electrode reactions and establishment of
Faraday's Law were followed by the classical work of Hittorf on
transference processes and the investigations of on conductance
measurements electrolytes. Probably Grower7 (1917) was first to
bring about the application of the Faraday's Laws to chemical

1
analysis. As a result, the measurement of the quantity of
consumed electricity in an electrode reaction can be utilized for
analytical determinations under generic term of Coulometry;
which came of age only in the last fifty years thanks to the work of
Szebelledy and Somogi8, Lingane9, Swift10, Furman11, Evan and
Bannister and others . On the other hand, the conductance of
electrolyte depends on the total salt concentration, resulting in a
limited application of direct conductometric measurements in
chemical analysis. Dutroit14 elucidated and elaborated the
usefulness of conductometry by developed for the determination
of many substances owing to the marathon endeavours of
Kolthoff, Britton, Jander, Pfundt and many other investigators.
Interest of analytical chemists in conductometric analysis has been
revived by the development of high frequency methods. The
possibility of carrying out high-frequency conduotometric titration
was first pointed out by Blake15. A modified form of this method
was put forward by Jensen and Parrack16 in 1946; and then
developed with success for several titrations " . The attractive
and salient feature of this method is that the electrodes may be
placed outside the titration cell avoiding their contaminations.
Recent work on the oscillometric methods has led to realization of
the potential use of dielectric constant measurements in chemical
analysis.

2
 The researches of Faraday (1834), Hittorf (1853) and
Kohlrausch (1877) contributed much to advance the
electrochemistry, but only with the development or
thermodynamics in the second half of the nineteenth century, the
electrochemical equilibria has been made use of in the quantitative
analysis. Nernst26 in 1889 derived his well-known equation for
equilibrium electrode potential and laid down the foundation of
potentiometry and its application to analytical chemistry followed
soon. Behrend was, perhaps, the first to devise the
potentiometric titration in 1893. Owing to the ease of
measurement of the voltage exhibited by electro-chemical cells,
the technique of potentiometric titrations is quite simple and
versatile. Many titration reactions have been studied by the
schools of Bottger, Muller, Kolthoff, Furman, Willard and
numerous other investigators who have also contributed much to
the advancement in this field. The emphasis during the last decade
has been placed on titration in non-aqueous solvents and on the
development of instrumentation for automatic titrations ' .

Salomon53 (1897) originated the idea of using the charge in

the current between the two identical electrodes across which a
constant voltage of the order of few millivolts is applied to detect
the titration end point. The technique was further developed by
Foulk and Bawden who coined the term "dead-stop and point" for
their new method.

3
 In 1919 Hostetter and Roberts54 noticed that in the ferrous
dichromate titrations, palladium electrode does not respond much
readily to change in potential as compared to platinum electrode.
They found that the potential difference between a platinum and
palladium electrode in a solution of ferrous ion that is being
titrated with dichromate is very small until the end point is
approached and at the equivalence point it increases sharply.
Hence, the usual combination of platinum and reference
electrodes can be replaced by the platinum and palladium
electrodes to indicate the end point during such titrimetric
determinations. The phenomenon is purely a time effect and
depends on the fact that the palladium electrode requires a much
longer time to reach equilibrium than platinum electrode. Quick

titration gives the best results. According to Kolthoff64 the

functional mechanism of the Pt-W couple seems to differ from the
Pt-Pd pair; the tungsten undergoes the anodic oxidation and thus
functions as a kind of "attackable reference electrode". The use of
such bimetallic combinations is empirical and the optimum
conditions must be established by trial. Many combinations of

other metals with platinum have been studied55'64. The polarized

indicator electrodes are usually used in the potentiometric
titrations of slow reactions.

4
2. VOLTAMMETRY AND POLAROGRAPHY
Electroanalysis, classical potentiometry and conductometry
were rather common subjects of research in electrochemistry
during the first quarter of the twentieth century, but
electrochemical methods whose application requires the
interpretation of mass transfer processes by diffusion or
convection were in general overlooked. Heyrovsky65 in 1920 by his
polarographic investigations, paved the excellent way to novel
modes of approach in electroanalytical chemistry. The
polarographic method is outlined on the interpretation of the
current-potential characteristics exhibited by the dropping
mercury or other metallic electrode(s). The first paper dealing with
polarography65 appeared in 1922 and the pertaining literature,
thereafter expanded and now accumulated to several thousand
papers. This method was rather empirical at the beginning but its
quantitative interpretation was developed by Heyrovsky and his
school at the Charles University, Prague. Ilkovic and Heyrovsky
(1934) derived an equation, which is the foundation for the
quantitative treatment of polarographic analysis66'67. The
fundamentals of polarography were well understood by 1935
and, by this time the method beoame well known outside
Czechoslovakia. Semerano68, writing a monograph, as early
as in 1933, promoted the growth of polarographic method

5
in Italy; Von Stacklberg and others did likewise in Germany.
Kolthoff, Lingane, Laitinen, Stook, Meites and other have
contributed a lot to the diffusion of polarography in the United
States and elsewhere. In the determination of current potential
curves, rotated solid electrodes, rotated solutions have also been
utilized. Laitinen and Kolthoff66 in 1941 demonstrated the
application and usefulness to the chemical analysis of the
voltammetric initiating a rapid progress.

In conventional voltammetry and polarography the applied

voltage of the cell is kept essentially constant during the
measurement of the current. In 1938, Matheson and Nichols70 have
shown that current voltage curve for stationary electrodes can also
be recorded by varying continuously the applied voltage of the
electrochemical cell. The fundamentals of voltammetry with
continuously varying potential were established by Sevcik and
Randles for reversible processes and by Delahay for
irreversible processes. A useful voltammetric method has been
developed in which the voltage applied to the cell is a sinusoidal
function of time. Randless , Gerischer , Ershler , Grahame and
others have shown that their method of electrolysis with
superimposed alternating voltage is a powerful tool in
electrochemical kinetics. In this method electrolysis current is the
measured quantity and the voltage applied is the variable being

6
controlled. The opposite method has also been devised in which
the current is controlled and the voltage across the cell is
measured. Webber78 (1879) was the pioneer worker who made use
of constant current electrolysis in the verification of Fick's Second
Law of diffusion. But the potentialities of this method in analytical
and physical chemistry were recognized by Gierst and Juliard79,,
and theory was developed by Sand80 and Karaoglanoff81. Further
theoretical advances were recently made by Delahay and
coworkers82'83. The first use of polarography with the dropping
mercury electrode was made by Heyrovsky and Berezicky84 in the
titration of barium ion with sulphate. Majer85, discussing the
titration of lead with sulphate and some general characteristics of
the method, introduced the term "Polarometric Titrations" for this
(type of titration), but the expression amperometric titration which
was suggested by Kolthoff and Laitinen is generally used at
present86. Kolthoff and his students especially Laitinen, Lingane
and Stock have been very active in this field and various types of
amperometric titrations are now performed on a routine basis in
analytical laboratories. Several voltammetric titrations, which
differ in principles from that of Majer's amperometric titration
have been put forward in recent years by the group of Gauguin
and Chariot at Paris, Furman at Princeton, Stock at Storrs in
U.S.A., Duyckaerts and Kies at Delft in the Netherland, and Singh
and collaborators in India.

7
3. VOLTAMMETRIC TITRATIONS
Voltammetric methods can be applied to the determination
of the equivalence point of many titrations. Either the voltage
across the electrochemical cell or the current through the cell is
measured during the titrimetric process. The method based on the
measurement of electrode potential is assigned as "Potentiometric
titrations"; and the intensity of the current through the cell is
either equal to zero or has a constant value of low order.
Amperometric titrations involve current measurements and the
voltage applied to the electrolytic cell has a constant values equal
to or different from zero. The variations of the electrical quantity
being measured depend on the nature of the electrodes; which
form the basis of the following classifications :
(i) Potentiometric titrations at electrode zero current.
(ii) Potentiometric titrations at constant non-zero current-
(a) with one indicator electrodes.
(b) with two indicator electrodes.
(iii) Amperometric titrations -
(a) with one indicator electrodes.
(b) with two indicator ' electrodes, at constant
applied voltage not involving diffusion current.
Potentiometric titrations at zero current and amperometric
titrations with one indicator electrode involving diffusion current
have become classical and their development in last decade has

8
been mainly oriented towards the search for new applications and
improvements in instrumentation87. The end point of an
electrotitration is determined by following, during titration, the
variations of some electrochemical property of the titrated solution
or titrant. Such a relationship is often represented graphically
under the form of titration curve, which is obtained by plotting the
electrical variable being measured, against the volume of titrant
added. The various reviews by Furman88, Kolthoff89, Laitinen90
and Stock , Lingane and others provide additional
informations on the subject.

3.1 Potentiometrie Titrations at Constant Current with

one Indicator Electrode:
Recently Gauguin, Chariot and coworkers94 developed this
new potentiometrie method for ascertaining the equivalence point:
an indicator electrode and an unpolarised electrode e.g., calomel
electrode, comprise the titration cell. The substance to be titrated
my be reduced or oxidized, but not the titrant, in the same range
of potentials. The current of the order of 2x10 pA is kept constant
during the titration and therefore conditions of mass transfer at
the indicator electrode are well defined. During the titration, with
the decrease of the concentration of the titrate the corresponding
limiting current also decreases accordingly, when the constant
current of intensity, ic is much smaller than the limiting current, id

9
for the substance to be titrated. Under these conditions the
potential corresponding to current, ic/ is shifted towards more
cathodic values as the titration proceeds. When V exceeds the
limiting current 'id' for the substance, the potential of the polarized
indicator electrode becomes so cathodic that either the supporting
electrolyte or water is reduced resulting in a rapid variation in
potential. If the current ic, is small enough, the variations of
potential occur in the immediate vicinity of the equivalence point.
The potential after the end point is virtually constant on account of
the reduction of the solvent or the supporting electrolyte.

The potential of the polarized electrode neglecting the

residual current can be readily evaluated from the equation of
current potential. For the dropping mercury or metallic micro­
electrode and reversible process. We have,
RT id - ic
E = E1/2 +----- In----------- ------- (1)
nF ic

Where,
id = P (l-X)Co ------- (2)
P is proportionality constant embodied in the Ilkovic
equation> Co the bulk initial concentration of the substance to be
titrated before titration and 1 the degree of completion of titration.
On combining (1) and (2) we get,

10
 RT P (l-A,)Co
E = Ei/z + In------------------1 ------- (3)
nF ic

The vertical asymptote to the curve of equation (3) intersects

the abscissa axis at the point corresponding to
ic
X = 1 ------- ------- (4)
PC0

where PCo represents the diffusion current before titration

and thus the titration error is negligible, since ic is small and the
ratio ic/PCo is of the order of 10'3. On transposing this reasoning to
electrodes with stirred solution and the irreversible processes
similar equations will be obtained. In such cases the end point is
indicated by the rapid variation of the potential of the polarized
electrode and the method has the marked advantages over the
conventional potentiometric titrations in most of the cases.

3.2 Potentiometric Titrations at Constant Non-zero

Current with Two Indicator Electrodes :
This type of titration was used empirically by Van Name
and Fenwick56, but the credit for the development of this method
in a rational way should go to Reilly, Cooke and Furman95. The
latter authors call this method as "derivative polarographic
titrations" but the term "potentiometric titrations at constant

11
current" is in better agreement with classification of the
electrochemical method. Two similar' or dissimilar polarized
electrodes are connected to a source of battery and the voltage on
the terminals of the electrodes is measured during titration.
Equivalence points are obtained by usual plots of potential against
volume of the titrant added. The titration curves, obtained are
purely qualitative and have been quantitatively analysed94"96
giving rise to expression.
RT ic
V=2 ------- --------------- ------- (5)
nF P(1-a) XCo

where Co is the initial concentration of the titrated substance

and P is constant X, the degree of completion of titration and V is
the voltage across the cell, measured during titration. The voltage
reaches a minimum Vmin for A=0.5, and the V/Vmin is
V 0.25

Vmin (1-X) X

A plot of V/Vmin versus X shows the rapid variation of the

voltage before the end point, corresponding to a sharp peak in the
titration curve. This method has, thus, several advantages over the
conventional potentiometric titrations.

12
3.3 Amperometric Titration With One Indicator
Electrode:
Amperometry, is a generic term for techniques, whereby, the
concentrations of an electroactive substance is measured by the
current resulting from its reaction at an electrode. Amperometric
titrations are those in which amperometry is used to follow
concentration changes and thus, to detect equivalence point. The
classical amperometric titrations are based on the measurement of
the diffusion current (limiting current-residual current) of the
substance being titrated or that of the reagent or of the both during
the titration. The change in concentration of any substance giving
a diffusion current may be followed during a titration by its
diffusion current. The potential of a suitable microelectrode is
maintained at the proper value and measurements are made after
the addition of successive amounts of the titration reagent.
Equivalence point is established by taking a few readings well
before and sufficiently beyond equivalence point to be on the
linear branches of the curve, and the interaction of the linearly
extrapolated branches is accepted as the equivalence point.

13
3.4 AMPEROMETRIC TITRATIONS AT CONSTANT
VOLTAGE WITH TWO INDICATOR ELECTRODES:
The fundamental principle of amperometry with two
indicator electrodes is that, the potential adopted by the electrodes
when subjected to a constant applied electromotive force is such
that the anodic and cathodic currents are equal. One of the
electrodes functions as a reference electrode while other as an
indicator electrode, because of the general unequal polarisability
of the electrodes. The most polarized electrode behave as an
indicator electrode, and the two electrodes may change their roles
after the equivalence point is passed. Before the end point the
indicator current may be controlled by the rate of supply of
electroactive material to the anode where as beyond the end point,
the rate of supply to the cathode becomes current controlling. The
potential of the electrode acting as indicator electrode may not
correspond to the limiting current, thereby even minor variations
in the applied voltage or rate of stirring usually produce large
changes in the indicator current.

In this method two electrode, subjected to a constant

potential difference, are directly put into the solution. Variations
in current during the titration can be predicted from the titration
curves. Willard and Fenwick55 suggested the polarization as the
most effective method for obtaining the satisfactory behaviour of

14
electrodes. And ultimately they observed that a polarized
bimetallic system consisting of two protons cut from very pure
platinum wire save the best equivalence point indications. The
two identical electrodes were polarized anodicallv and
eathodically with a very small applied potential. A rapid decrease
in the current is observed in the vicinity of the end point during
the determination of iodine with thiosulphate, which led Foulk
and Bawden97 to coin the term "dead stop end point"' for their
method. The fundamental condition for the production of dead
stop end point is the use of so low a potential (10 to 15 milli volts)
between the electrodes in the solution to be titrated that the back
electromotive force of polarization balances it and consequently
no current flows, the galvanometer registering almost zero. It is
assumed that the polarization is due to oxygen absorbed on the
anode and hydrogen on the cathode and that the anode can,
therefore, be depolarized by a suitable reducing agent and cathode
by a suitable oxidizing agent. This method, as originally
introduced, was considered to be applicable only to titrations with
iodine. Recent work, however, has shown it to be closely allied to
other amperometrie titrations, though not involving diffusion
current.

Three cases may arise from the stand point of the conditions
of electrode(s) during the titration :

15
(a) One electrode is polarized - The titrant must then depolarize
this electrode. This actually happens in the titration of
thiosulphate or of arsenite with iodine. The reducing agents
present keep the anode depolarized throughout the titration
while at the equivalence point the first trace of excess iodine
depolarizes the cathode.

(b) Both electrodes are polarized - The titrating solution must

then be capable of depolarizing both the electrodes. This is
possible because of the use of a mixture of reagents as
titrant, and as a rule this case be transferred into ease (a) by
the addition of a suitable reagent, the additional depolarizer.

(c) Both electrodes are depolarized - This presupposes the

presence of both, an oxidizing and a reducing agent, which
do not react with each other, or at any rate not in an
irreversible way. This happens in the titration of iodine with
thiosulpnate or arsenite.

The qualitative interpretation of titration curves was advanced

by Delahay98 many years after publication of Foulk and Bawden.

Delahay reported that the "dead-stop end point" depends on the
change from the reversible redox couple to an irreversible redox couple
or vice versa at the equivalence point. These observations suggest
that the dead-stop phenomenon is not a polarization effect based

16
on gas adsorption on the electrode surface, but at least in part an
electrochemical phenomenon based on oxidation at the anode and
reduction at the cathode. If this is so, then by applying suitable
potentials and using appropriate electrodes any redox titration
may be followed using the dead stop method. Quantitative
treatments have been developed by several authors95,96,99'100.
The current through the cell is
i = 1/2 (di/dE) i=0 x Vc ------- (7)

where Vc is the constant voltage applied to the cell and is so low

that the current-potential curve can be identified with its tangent
at zero current. If the titrated substance forms a reversible couple
with its reaction product,
ii,c - 0 ii,a
0 (8)
1+0

where ii/C and ii,a are the cathodic and anodic limiting currents,
and 0 is given by
r nF
0 = exp. (E-E°) (9)
v RT J

assuming the activity coefficient of substances involved in the

titration are equal from the relationship
r dE ^ dE d0
------ = — x ------ ------- (10)
^ di J d0 di

17
it is obvious,
r dE"i RT il,a+il,c
— (ii)
1
i
^ di nF . il,aXil,c
oTi'
^ di ^ i=0 nF ii,axii,c
--------- (12)
RT il,a+il,c

The limiting currents ii,a and ii/C in equation can be replaced

by
ii,a = P(l-A,) Co --------(13)
ii,c « P' X Co ......... (14)

where Co is the initial concentration of the titrated substance, P

and P' are the proportionality constants depending on the mass
transfer, and X is the fraction titrated. Assuming P=P' for the sake
of simplification
nF
i= ---- P(l- X) X CoVc ----- -(15)
RT

The current, i exhibits a maximum imax when the degree of

the titration is 0.5; The ratio i/imax is
i/ imax = 4 (1-A,) X ------- (16)

Theoretical curves for the titration of ferrocyanide with ceric

ions101, ferrous ammonium sulphate with vanadate ions102,
cobaltous sulphate with ceric ions103 and chloramine-T104 in

18
presence of EDTA, correspond to the above equation and
exemplify that the current is maximum at mid point of titration.

During the titration of a irreversible system with a reversible

couple, the current is very low and practically constant before the
equivalence point and a very rapid increase in the current
indicates the end point. Titration of thallium(I)105, arsenic and
antimony106 with ceric ions are few typical examples. Titration of
an irreversible system by another irreversible couple may yield
satisfactory results by judiciously selecting the voltage applied to
the cell. The suitable voltage can be determined by determining
the current potential curve for each of the redox couple involved
under the experimental conditions of the actual titration. The
magnitude of the voltage to be applied to the cell varies greatly
from one case to another. Stone and Scholten succeeded, in the
titration involving two irreversible systems: hydrogen peroxide by
permanganate ions101.

The titration curve of a system involving: both the reversible

couple shows a minimum because the current corresponding to
the titrated substance decreases to almost zero or a small value at
the equivalence point where as the current for the titrant and its
reaction product increases beyond equivalence point. If the
titrated substance, but not the titrant, establishes a reversible
couple, the maximum in the indicator current will appear, the

19
current will, thereafter, diminish to a extremely low value, and
remains practically constant beyond the equivalence point. The
titration of ceric ion with oxalic acid in about or more than 3.0 M
H2SO4 medium is one such example.

Several calculations have been published with the aim of

deriving an equation which may define the shape of the titration
curves obtained during amperometric titrations with two indicator
Electrodes100'107. But none of these calculations considered the
influence of the increase of volume due to the addition of reagent
and the resistance of the circuit thereby necessiating the use of
corrections to these measurements in order to verify the
theoretical deviations. The influence of the increase in volume is
small, but the decrease of the potential difference between the
electrodes due to voltage losses in the galvanometer and the
electrolyte is usually by no means negligible. Recently Kao and
Hsu108 modified the expression taking the resistance in the circuit
into consideration., The resulting relation between current
Intensity i and the degree of completion of tiration X has become
complicated, yet it is useful. Kies109 has supplemented the paper
remedying some deficiency as regards some points. Although it is
true that the slope of the titration curve increases with the
resistance, yet the gain does not appear to be very great. The
modified equation provides important information about the
shape of titration curve very close to the equivalence point.

20
3.4.1 Apparatus and Technique for Amperometry with
Two Polarized Electrodes:
The apparatus for voltammetry at constant applied potential
was as the "dead stop end point' titration arrangement of Foulk
and Bawden97. Various designs for the apparatus and
improvements in the technique have been91 made in this field.
Two identical platinum electrodes are immersed into the titration
cell and a constant polarizing voltage of the order of 50 to 500
milivolts is applied to these electrodes either from a potential
divider or- a polarograph. A system such as described by
Wernimont and Hopkinson110 is convenient and accurate for
applying the constant potential to the electrodes and measuring
the current, which flows through the cell. The current through the
cell has been measured by a sensitive galvanometer while the
solution is stirred uniformly during titration through a magnetic
stirrer.

In titrations with two polarized electrodes, the use of various

combinations: platinum-silver, silver-amalgamated gold, silver
amalgamated sliver and vibrating platinum electrodes have beer,
suggested. The area of the two electrodes and the constant applied
voltage are coselected in order to keep the indicator current in the
microampere range, so that the reactions at the, indicator
electrodes do not alter appreciably the solution composition.

21
3.4.2 Accuracy And Scope :
The accuracy and precision of the amperometric equivalence
point is governed by the chemical and thermodynamic properties
of the titration system. The field of its application is very wide.
The method is more general than conventional voltammetry
because the various slow systems can be electrolyzed, by applying
an over potential,, and their determinations may be accomplished.
If the substance to be determined can neither be oxidized nor
reduced electrolytically, it can be titrated with a reagent which can
itself be electrolyzed.

In microscopic system (e.g., 0.01N titrant) it is possible to

titrate with a small error of about 0.1% by the drop wise addition
of the titrant in the vicinity of the equivalence point and mere
observation of the change in indicator current. Rapid titrations can
be made because only a few points are needed to plot the linear
curves for the location of the equivalence point.

Highly dilute solutions may be titrated generally with the

better precision than is possible in polarography. The working
conditions are well controlled, and it is not essential to work at a
definite temperature, provided the alteration is small during
titrations. The variations in the supporting electrolyte are not
important so long as these conditions are constant during titration.
A comparative wide variation in the concentration of indifferent

22
electrolyte is permissible without appreciable effect on the
accuracy of the results. The results do not depend on the
characteristics of the apparatus so that prior calibration is
unnecessary.

Amperometric' titrations can be performed for precipitation

actions, where, because of the solubility relations, the
potentiometric or visual indicator methods are unsatisfactory, as
the equivalence point have no special significance in
amperometric titration. Rapid titrations are possible because only
a few points are needed to plot the linear curves necessary to
locate the equivalence point.

Although very useful as end point detection technique, two

electrode amperometry is not reliable as amperometry with a
single indicator electrode for the precise concentration
measurements. In two electrode amperometry, the electrode
which functions as an indicator usually is not working at a
potential corresponding to a real limiting current, but rather on
the steep reaction of the current-potential curve. Consequently, the
indicator current is quite sensitive to minor accidental changes in
the applied voltage and even to small-variations in the iR drop
between the solution composition. An accuracy equal to, or
greater than, that attained in conventional titrimetry can be
achieved, and the determinations can be made at very low

23
concentrations often as low 10'5N. The sensitivity frequently
exceeds that of other methods, such as colorimetry and
conductometry, the advantage of this method is primarily the
simplification in technique and improved accuracy, rather than in
the possibility of devising new titrations. It is an excellent method
for the accurate determinations of traces.

3.4.3 Applications:
The dead-stop end points method has been applied to
various iodometric determinations in which iodine is liberated by
the oxidant to be titrated110®'113 and also to the determination of the
end point in the Karl Fischer titration of water110b'114'115. This
method has also been extended to various acid base titrations116.
There has been revived interest in the amperometric titrations at
constant voltage with two polarized electrodes117. Several new
applications of this method have been reported: titration of
stannous ion with Iodine118, various titrations with ceric,
permanganate, ferrous, and titanous ions101-119, determination of
Iodine120, and bromometric titrations121'123.

A useful modification has been proposed by Clippinger and

Foulk116 who, by introducing an additional "depolarizer" in the
titration vessel were able to titrate halides by silver nitrate; this
method is applicable for the titration of cyanide ion by silver
ion116. An interesting application of the method is that if neither

24
the substance to be determined, nor the reagent can be oxidized or
reduced electrolytieally, a small quantity of a substance can be
added which enables the equivalence point to be determined
electrolytieally. Calcium ion and other such ions have been
estimated by fluoride in presence of ferric ion as indicator124. More
recent applications of the bi-amperometric method have been
reviewed by Stock91 and Laitinen90.

The foregoing amperometric titrations with two polarized

electrodes may be of special interest in routine work, since they
are, in some cases simpler to apply than the conventional
amperometric method. The interest in this field and the related
technique has been sustained for some time. A notable publication
is the dissertation of Kies125, which includes a bibliography of 272
references. Additional information's are available in a paper by
Kolthoff and Nightingale126, and in the reviews by Stock127,
Hume128 and Laitinen129 for the history, theory and
interrelationship of the various methods130. Such techniques are
often sensitive at low concentrations and their values in micro­
chemical field are shown to be considerable as a result of pains
taking experiments in this laboratory131.

In the present investigations, the method has been extended

for the determinations of various elements in their pure salts
namely iron, antimony, tin, zinc and also various organic acids.

25
 The procedures suggested, demonstrate the' greater
possibilities of this amperometric titration method.

A review of literature shows that the examples of redox

amperometric titration of binary mixtures are scarce and
inadequate. Successive amperometric determination of end points
in the titration of mixtures of substances, or in redox titration of a
substance which undergoes stepwise oxidation or reduction,
possible, if certain conditions are established. The successive
equivalent determination is primarily dependent on the degree of
separation of the formal potentials of the substances involved in
the reaction. It demands more judicious choice of applied voltage
than monotitrations. The idealized curves have been anticipated
by Lingane132 on the assumption, that the applied voltage must be
smaller than the smallest difference between the formal potentials
of the several couples reacting during the titration. If this
condition is not fulfilled, the second substance will participate in
one or another of the indicator electrode reactions before the first
end-point or no indication of it will be observed. Theoretically
many types of titrations are expected. Many successful attempts
have been made in the successive ruinations of cerium and iron,
cerium and vanadium, vanadium and iron, molybdenum and a
number of other elements, gold and various other elements,
trivalent iron and other combinations133.

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