Unit 5 Electrogravimetry and Coulometry
Unit 5 Electrogravimetry and Coulometry
Unit 5 Electrogravimetry and Coulometry
COULOMETRY
Structure
5.1 Introduction
Objectives
5.2 Electrogravimetric Analysis
5.3 Polarisation
5.4 Types of Electrogravimetric Methods
Constant Current Electrolysis
Constant Potential Electrolysis
5.5 Coulometry
5.6 What is a Coulometer?
5.7 Types of Coulometric Methods
Controlled Potential Coulometry (Potential Coulometry)
Constant Current Coulometry (Amperostatic Coulometry)
5.8 Summary
5.9 Terminal Questions
5.10 Answers
5.1 INTRODUCTION
In Units 3 and 4, we have discussed potentiometry and conductometric methods. You
have seen in potentiometry measurements are performed under conditions of
essentially zero current. In this unit, we describe two important related
electroanalytical methods – electrogravimetry and coulometry. In the two techniques
which we are going to deal, electrolysis is carried out long enough to make sure that
the analyte is completely oxidised or reduced to a single product. In
electrogravimetry, the product is weighed as a deposit on one of the electrodes. In
coulometry, the quantity of electricity needed to complete the electrolysis is measured
as coulombs. Both the methods are quite sensitive, rapid and accurate.
Both these techniques differ from potentiometry in the sense that they require a
significant current (a required amount of current to initiate the electrode reaction)
throughout the process. However, in potentiometry measurements are performed
under conditions of essentially zero current. When there is a current in an
electrochemical cell, the cell potential is no longer the difference between the
electrode potentials of the cathode and the anode. The applied potential in an
electrolytical cell is usually greater than the theoretical potential and the phenomenon
of ohmic potential (IR drop) and polarisation will come into effect.
We shall describe the principle and instrumentation of electrogravimetry and later the
principle, methodology and applications of coulometry. The importance of these two
analytical techniques in quantitative analysis will be discussed.
Objectives
After going through this unit, you should be able to
• explain ohmic potential (IR drop) and polarisation and their significance in
electrodeposition,
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Electroanalytical • calculate the potential of a given cell to initiate deposition of a metal ion and
Methods-II
calculate the residual concentration of the ion in solution before the
commencement of the deposition of the next ion,
Before learning the principle of this analysis, let us understand some important terms
used. From potentiometric studies, now we know what is a cell? Normally a cell
consists of two electrodes immersed in an electrolyte. There are two types of cells – a
galvanic cell and an electrolytic cell. A galvanic or voltaic cell is a device which
converts chemical energy into electrical energy. The galvanic cell usually consists of
two electrolytic solutions in which two electrodes of different materials are dipped in
it. A Daniel cell is an example of a galvanic cell.
When the energy is supplied from an external source, the cell through which it flows is
known as electrolytic cell. Irrespective of whether the cell is galvanic or electrolytic,
we call the electrode where oxidation takes place as anode of the electrode, where
reduction takes place as cathode. In potentiometry, we have already learnt that a
cathode is assigned a positive sign and an anode a negative sign in a galvanic cell.
However, in an electrolytic cell, these electrodes acquire charges opposite to the
above. The capacity to do electrical work by a cell is called the cell potential and is
expressed in volt.
Consider a cell of the type where copper is deposited at the cathode and oxygen is
evolved at the anode.
Cu | Cu2+ || 2H+ , ½ O2 | Pt
2+
Cu + H2O ⇌ Cu + ½ O2 (g) + 2H+
Cathode Cu++ + 2e ⇌ Cu°
Anode HgO ⇌ 2H+ + ½ O2 + Cu°
Cu++ + HgO ⇌ 2H+ + ½ O2 + Cu°
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The potential of the electrochemical cell, (Ecell ), is the difference between the electrode Electrogravimetry and
potential of the cathode and the electrode potential of the anode. That is Coulometry
Consider the electrolytic cell shown in Fig. 5.1. A voltage Eapplied is applied to the cell
in such a way that a current flows through the cell. When Eapplied > Ecell , there will be
a flow of current in the circuit. When there is a current, the potential of the cell is less
than the thermodynamic potential because one or one of the following phenomena are
operating: IR drop, concentration polarisation and kinetic(chemical) polarisation.
We know that when applied potention, Eapplied = Ecell, no current flows through the
cell. When you gradually increase the applied potential, a small current appears in the
circuit. This current through the cell encounters resistance R resulting in a potential
drop of –IR volts. In other words, the applied potential must be greater than the
theoretical cell potential by –IR volts. Thus, in the presence of a current, a cell
potential must be modified by the addition of the term –IR.
Eapplied = Ecell – IR … (5.1)
Eapplied = Ecathode – Eanode – IR … (5.2)
where Ecathode and Eanode = Ecell are electrode potentials computed with the Nernst
equation.
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Electroanalytical − E applied
Methods-II
1
I = + ( E cathode − E anode )
R R
… (5.3)
E cell − E applied
I =
R
For small currents and brief periods of time, Ecathode and Eanode remain relatively
constant during electrolysis. The cell behaviour can be represented by the reaction.
- E applied
I= +k … (5.4)
R
where, k is a constant.
Fig. 5.3: Current/voltage curves for (a) an electrolytic and (b) a galvanic cell
Cells that exhibit non-linear relationship are said to be polarised and the degree of
polarisation is given by overvoltage or overpotential. Polarisation requires the
application of a potential greater than the theoretical value to give a current of the
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expected magnitude. Thus an overpotential of – 0.04 V is required to obtain a current Electrogravimetry and
of 0.06 A in the electrolytic cell as illustrated in Fig. 5.3a. In a galvanic cell, the Coulometry
output cell potential decreases by about 0.03 V i.e. the overvoltage is 0.03 V as
illustrated in Fig. 5.3b. Note that in each case the overvoltage is negative.
Hence, for an electrolytic cell affected by overvoltage, Eq. (5.1) then becomes,
Eapplied = Ecell – IR – overvoltage … (5.5)
In simple terms, the overvoltage is the potential difference between the theoretical cell
potential determined by Eq. (5.1) and the actual cell potential at a given level of
current. It can be calculated by Eq. (5.1). On the other hand polarization is the
departure of the electrode potential from its theoretical value on passage of current.
We will take up these phenomena in more detail in next section, but before that try the
following SAQs.
SAQ 1
What is Ohmic potential? Determine it Units. How it is related to cell potential and
applied potential.
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SAQ 2
Following cell is used for the determination of Cd in the presence of Cl − ions in an
electrogravimetric method.
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5.3 POLARISATION
Consider again the situation illustrated in Fig. 5.3a. If we further increase the Eapplied,
the current becomes independent of Eapplied. This give rise to limiting current as
illustrated in Fig. 5.4. At this situation, the electrode is said to be completely polarized,
since its potential can be changed widely without affecting the current. Polarisation
can be conveniently divided into two categories: concentration polarisation and kinetic
(chemical) polarisation. Polarisation is an electrode phenomenon that may affect
either or both of the electrodes in a cell.
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Electroanalytical
Methods-II
Fig. 5.4: Current potential curve for electrolyte illustrating ohmic region (linear portion
of the curve) and limiting current situation
Concentration polarisation
When ions are discharged and deposited on an electrode as a result of passage of
current, the area in the immediate vicinity of the electrode is depleted of ions and the
layer offers resistance to the passage of current. This type of resistance due to
changes in concentration of the electrolyte around the electrode is known as
concentration polarisation. Concentration polarisation occurs when the ions do not
arrive at the cathode or the product species do not leave the anode fast enough to
maintain the desired current.
We have already seen that reactants are transported to an electrode surface by three
mechanisms. (1) Diffusion, (2) migration and (3) convection. Concentration
polarisation arises when the effects of diffusion, migration and convection are
insufficient to transport the ions at a rate that produce a current of desired magnitude.
If the depleted area in the vicinity of the electrode is not supplied with ions from the
bulk of the solution by increased diffusion or by convection – agitation (stirring), the
cathode will assume more and more negative potential as the applied potential is
increased. As a result, a back emf is set up and if the current has to flow, the applied
emf must be sufficiently above the equilibrium potential to overcome the polarisation.
Hence, concentration polarisation requires applied potentials that are larger than the
theoretical i.e., calculated from Eq. (5.1), to maintain a given current in an electrolytic
cell.
For this reason, vigorous stirring and heating are important in electrodeposition to
minimize the concentration polarisation.
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formation of films on the electrode. For example, an aluminium anode is liable to be Electrogravimetry and
passivated by a coat of alumina on it Coulometry
Complex ions yield smoother deposits. For example, silver when deposited from a
[Ag(CN)2] – complex yields a satisfactory deposit.
Importance of overvoltage
• The existence of overvoltage explains numerous phenomena. In a lead
accumulator, during charging, the metal is deposited on the cathode instead of
hydrogen being evolved, due to the high overvoltage of lead.
• It is possible to deposit electrolytically the metals, which have a more negative
potential than hydrogen such as zinc, cadmium, tin, etc. from an acid solution
because of high overvoltage of hydrogen on such metals.
• Overvoltage plays an important role in the industrial production of chlorine and
sodium hydroxide by the electrolysis of brine – sodium chloride solution.
• When electrodes of high overvoltage are used in electrolytic reduction, it would
mean to increase the reducing power. Electrodes with high overvoltage like
lead instead of platinum are used in organic electrolytic reductions to get the
desired products.
SAQ 3
Distinguish between concentration polarization and kinetic polarization.
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SAQ 4
List the importance of overvoltage.
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Electroanalytical
Methods-II 5.4 TYPES OF ELECTROGRAVIMETRIC METHODS
Electrolytic precipitation or electrodeposition has been widely used for the
determination of metals. In most applications, the metal is deposited on a weighed
platinum cathode and the increase in mass is determined. There are two types of
electrogravimetric methods (i) Constant current electrolysis and (ii) Constant
potential electrolysis.
As shown in Fig. 5.5, the apparatus for constant current electrolysis consists of a
suitable cell and a direct current source. A 6 V storage battery can be used for DC
power source. An ammeter and voltmeter are used to indicate the current and applied
voltage respectively. The voltage applied to the cell is controlled by a resistor. The
cathode is usually a cylindrical platinum gauze.
As mentioned earlier the principal factors that influence the physical characteristics of
deposits are current density, temperature and the presence of complexing agents.
Ordinarily the best deposits are formed at current densities that are less than 0.lA /cm2.
Stirring generally improves the quality of a deposit. The time of deposition is reduced
when the solution is stirred vigorously or if the electrode is rotated at a uniform speed.
This type of stirring lowers the concentration overpotential and enables a higher
current density without any adverse effect.
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Simultaneous evolution of gas at an electrode, during deposition is not a desirable Electrogravimetry and
factor, since continuous evolution of bubbles on the electrode surface disturbs the Coulometry
orderly growth of the crystal structure of a metal deposit. Porous and spongy deposits
are obtained if there is continuous evolution of gases.
The chemical nature of the ion in solution has an important influence on the physical
form of the deposit. For example, a pure bright and adherent deposit of copper can be
obtained by electrolysing a nitric acid solution of cupric ions. In contrast, a coarse
tree-like deposit of silver is got under similar conditions. The electrolysis from a
solution of Ag [CN] −2 complex produces a suitable deposit. Complex ions exhibit a
property known as ‘throwing power’ - the property of a solution by virtue of which a
relatively uniform deposit of metal is obtained on irregular surfaces – cyanide and
ammonia complexes often provide the best deposits.
Fig. 5.6: (a) current, (b) IR drop, and cathode-potential change during the electrolytic
deposition of copper at a constant applied cell potential.
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Electroanalytical Consider a case in which a solution contains Cu2+ and Pb2+ ions. Lead (II) begins to
Methods-II deposit at point A on the cathode potential curve (Fig. 5.6b). Hence lead (II) ion
would co-deposit well before copper deposition was complete and would interfere.
Co-deposition of hydrogen during electrolysis often leads to spongy and flaky deposits
that do not adhere to the electrode. Such a situation is unsatisfactory for analytical
purposes. The use of depolarisers often improves the efficiency of the process. A
depolariser is a substance which gets reduced at the cathode without gasification or
gets oxidised at the anode before oxygen evolution and stabilises the potential of the
working electrode by minimising concentration polarisation. Thus copper deposited
from a nitric acid solution is smoother and more adherent because nitrate ions act as
cathodic depolarisers and prevent evolution of hydrogen. Generally reducing agents
like hydrazine hydrochloride will act as anodic depolarisers.
The cathodic depolariser, nitrate ion gets reduced at a potential less negative than at
point C (Fig. 5.6b) as
SAQ 5
What are depolorisers? Name the few commonly used depolarizers.
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of the other species begins before the analyte is completely deposited. A large Electrogravimetry and
negative drift in the cathode potential can be avoided by using a three electrode system Coulometry
as shown in Fig.5.7.
The purpose of the reference circuit is to monitor continuously the potential between
the working electrode and the reference electrode. When this potential reaches a point
at which codeposition of an interfering species is about to begin, the potential across
the working and counter electrode is decreased by moving contact C to the left (Fig.
5.7). Since the potential of the counter electrode remains constant during the change,
the cathode potential becomes smaller, thus preventing codeposition.
Fig.5.8: Change in cell potential (a), and current (b), during a controlled cathode-
potential deposition of copper. The cathode is maintained at – 0.36 V versus
SCE throughout the experiment.
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Electroanalytical Fig.5.8 illustrates the changes in cell potential and current during a controlled cathode
Methods-II potential electrolysis of copper. The applied cell potential has to decrease
continuously throughout the electrolysis. This decrease, in turn, diminishes the
current. Completion of the electrolysis will be indicated by the approach of the
current to zero. This technique demands constant attention during operation. Usually
some provision is made for automatic control.
Electrodes
Usually platinum gauze electrodes are used since they have the advantage of being
relatively non-reactive and can be ignited to remove any organic matter or gases that
would have a harmful effect on the physical properties of the deposit. Certain metals
like bismuth and zinc cannot be deposited directly on to platinum, since they cause
permanent damage to the electrode. Hence, a protective coating of copper is always
deposited on a platinum electrode.
Mercury cathode
Mercury cathode is particularly useful for removing easily reducing metals as a
preliminary step in an analysis (Fig.5.9). For example, copper, nickel, cobalt, silver
and cadmium are readily separated at this electrode from ions, such as aluminium,
titanium, the alkali metals, sulphates and phosphates. The precipitated elements
dissolve in mercury with little hydrogen evolution because mercury has a high
hydrogen overvoltage and hence no hydrogen evolution even at high applied
potentials.
Fig. 5.9: A mercury cathode for the electrolytic removal of metal ions from solution
Advantages of mercury cathode
1. It forms an amalgam with a number of metals
2. It has a high hydrogen overvoltage and hence no hydrogen evolution even at
high potentials.
Applications
Controlled cathode potential is very useful in the separation of quantitative
determination of metallic species.
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All these three elements are deposited from a neutral solution containing tartarate ions, Electrogravimetry and
which forms complex with tin (IV) and prevent its deposition. When lead deposition Coulometry
is complete, the solution is made strongly ammoniacal and cadmium and zinc are
deposited successively at –l.2V and –l.5V respectively. Finally, the solution is
acidified to decompose the tin-tartarate complex and tin is deposited at a potential of –
0.65V using a fresh cathode.
Now let us solve some SAQs related to the potential required to initiate deposition of
metals. Separation of metals based on controlled cathode potential analysis can be
achieved. The following examples will illustrate these points.
SAQ 6
Calculate the potential required to initiate deposition of copper from a solution that is
0.0l M in CuSO4 and the pH of the solution is 2.0.
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SAQ 7
Electrogravimetric analysis involving control of cathode potential is used to separate
Bi3+ and Sn2+ in a solution that is 0.l0 M in each ion and buffered to pH l.50.
a) Calculate the theoretical cathode potential at the start of the deposition of the
more readily reduced ion.
b) Calculate the residual concentration of the more readily reduced species when
the less reduced cation begins to deposit.
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Electroanalytical
Methods-II 5.5 COULOMETRY
Coulometric methods of analysis are based on the measurement of quantity of
electrical charge that passes through a solution during an electrochemical reaction.
The principle of coulometric method of analysis is governed by Faraday’s laws of
electrolysis.
According to the first law, the mass of a substance liberated at the electrodes during
electrolysis is directly proportional to the quantity of electrical charge (Q) that passed
through the electrolyte.
Thus, the first law relates the quantity of current passed and the extent of chemical
change that took place.
If m1 and m2 are the mass of two different substances liberated by the passage of same
amount of electricity and M1 and M2 are their respective molar masses and n1 and n2
are their respective valence number of ions, then
m1n1/M1 = m2n2/M2 (5.9)
For example, let us consider the passage of electricity through solutions of CuSO4 and
AgNO3 connected in series, so that the same amount of electricity is passed through
them, then from the second law, we get
Mass of copper deposited × 2 Mass of silver deposited ×1
=
Molar mass of copper Molar mass of silver
The quantity of electricity or charge (Q) is equal to the product of current strength or
charge and time for which the current is passed.
Q = current × time … (5.10)
= I×t
The practical unit of electricity is coulomb.
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When a current of 2 ampere flows for ten seconds, the quantity of electricity (Q) in Electrogravimetry and
coulombs is, current in amperes (I) multiplied by the time in seconds (t). Coulometry
The quantity of electricity carried by one mole of electrons is called Faraday and is
given by the symbol, F. The charge of an electron is l.6022 × l0-19. Hence the charge
on one mole of electrons would be
1.6022 × l0-19 × 6.022 × l023 C or 96485C.
Hence one Faraday = 96485 C or approximately 96,500C.
Now consider a reaction,
Mn+ + ne M … (5.11)
The quantity of electricity required for the deposition of 1 mole of an element will be
equal to nF, where n is the number of moles of electrons required for the reaction. Let
Mr be the relative atomic mass of one mole atom of an element. Hence, for the
deposition of Mr g (or 1 mole) of the element, we require nF or n × 96,500 C of
electricity.
M rQ
m= g … (5.12)
96500 n
where m = mass of an element deposited by the passage of Q coulomb of current or
M r × I ×t
m = … (5.13)
95600 n
This equation is useful in calculating the mass of an element deposited by the passage
of known quantity of current.
SAQ 8
Calculate the time needed for a constant current of 0.96 A to deposit 0.5 g of Co(II) as
elemental cobalt on the surface of a cathode. Relative molar mass of cobalt = 58.93
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SAQ 9
A solution containing 0.25 g of copper as Cu2+ requires 20 minutes for complete
deposition of copper at l.25 A. Calculate the coulombs required and efficiency of the
process (Mr = 63.54).
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Electroanalytical quantity of electricity needed to complete the electrolysis serves as a measure of the
Methods-II amount of analyte present in the solution.
Each coulometer is a second electrolytic cell, in which anode and cathode may be in
the same compartment or in separate compartments, supposed to proceed at 100%
current efficiency. It is put in series with the electrolytic cell, so that the same quantity
of electricity passes through both the cells. Various types of coulometers viz.
Gasometric coulometers - Hydrogen-oxygen coulometer, Gravimetric coulometers –
silver coulometers – Titrimetric coulometers – Iodine coulometers, etc. are in use.
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Such coulometers show an accuracy of about –0.l % at a current density of 0.l A cm-2, Electrogravimetry and
falling to – 4 % at 0.0l A cm-2 and the loss of efficiency increases as the current Coulometry
density decreases. At low current strengths below 50 milliamperes, they cause
negative errors. The relationship between gas production and current density has been
examined.
It has been reported that the loss of efficiency is due to the formation of hydrogen
peroxide at the anode, which aggravates the situation by being reduced at the cathode,
so that the cathodic current efficiency also suffers. The other common gasometric
coulometer is the hydrogen-nitrogen coulometer, wherein 0.l M hydrazine sulphate is
used as the electrolyte. The electrode reactions are similar except nitrogen gas is
evolved at the anode.
Anode : N2H5+ → N2 + 5H+ + 4e
Cathode : 4H+ + 4e → 2H2
Overall reaction : N2H 5+ → N2 + 2H2 + H+
Three moles of gas are produced by consumption of 4 Faradays and the yield is
theoretically 0.l74l cm3 at NTP of mixed gas per coulomb. Lingane reported an
average yield of 0.l738 ml over the current density range 0.l – 0.007 A cm–2.
Silver coulometer
A silver coulometer is an example of a gravimetric coulometer in which the amount of
metal deposited at cathode or the amount of metal stripped from an anode is
determined.
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Electroanalytical silver deposited. From the mass of the silver deposited, the coulomb involved in the
Methods-II reaction can be calculated.
Iodine coulometer
Iodine coulometer is an example of a titration coulometer in which anodically
generated iodine is titrated with thiosulphate or arsenic (III) solution. This has been
used in the determination of the Faraday constant.
Colorimetric coulometers
They are based on the principle of developing a colored species with a reagent with a
metal ion which may be anodically stripped. For example, the formation of a colored
species for a cobalt ion with nitroso-R-salt and measurement of absorbance with a
spectrophotometer. A metal ion may be cathodically reduced and subsequent
absorbance may be measured. For example, Reduction of iron (III) at the cathode and
subsequent measurement of absorbance with l,10-phenanthroline reagent.
Radioactivity coulometers
A microcoulometer based on counting deposits of 110Ag has been described. The
unknown silver solution is spiked with a known amount of radioactive silver 110Ag
and then deposition is made on a platinum wire in a cell in series with one containing
only radioactive silver. Equal amounts of silver are plated on each cathode. The ratio
of the radioactivities gives the amounts of silver in the unknown solution. The cell
containing the radioactive silver is the radioactivity coulometer.
The method is useful for small quantities and plating need not be taken to quantitative
completion, as it involves the measurement of the ratio of the radioactivities in the
two cells.
The above types of coulometers can be put in series in an electrolytic reaction and can
be used as a current measuring device.
Coulometric methods
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Two general techniques are used for coulometric analysis, namely, constant current Electrogravimetry and
(amperostatic) and controlled potential (potentiostatic) coulometry. Coulometry
Fe2+ Fe3+ + e
In a constant current electrolysis, towards the completion of the reaction (as the
concentration of iron (II) decreases) there is an increase in the applied cell potential.
Because of concentration polarisation, the increase in potential causes the anode
potential to the point wherein decomposition of water takes place
Ce3+ → Ce4+ + e
a coulometric determination of iron (II) can be achieved as :
Coulometric titrations are more popular because of the in situ generation of titrimetric
reagents. For example, the halogens have been found to be the most satisfactory
coulometric intermediates in coulometric titrations. The reactions with electrolytically
generated bromine and iodine are useful for the estimation of substances like oxine
and ascorbic acid and proceed with 100% efficiency.
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Electroanalytical quantity of electricity is most commonly measured with an electronic integrator or
Methods-II from the reading of a coulometer in series with the cell.
2. These methods are suited for both routine as well as rare analyses which involve
electrolytic method of determination.
3. Coulometric titrations are more popular and have the special advantage in the
sense that the tedious steps of preparation, storage and handling of standard
titrants are avoided.
6. Constant current coulometry has widely been used than the controlled potential
coulometry since the former is faster and requires simpler instrumentation and
less expensive.
Instrumentation
The instrumentation for potentiostatic coulometry consists of a potentiostat (to
maintain a constant potential), an electrolysis cell, a chemical coulometer or an
integrating device for determining the number of coulombs and placed in series with
the working electrode. The chemical coulometer such as hydrogen-oxygen
coulometer/silver coulometer can be used to measure the number of coulombs
(quantity of electricity).
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Cell Assembly Electrogravimetry and
Coulometry
The cell assembly consists of a platinum gauze working electrode, a platinum wire
counter electrode and a saturated calomel electrode as the reference electrode. The
counter electrode is separated from the test solution by a porous tube containing the
same supporting electrolyte (Fig. 5.12a).
Potentiostat
A potentiostat is an electronic device which maintains the potential of the working
electrode at a constant level relative to a reference electrode. Fig. 5.13 is a schematic
diagram of a potentiostatic coulometry.
Consider the circuit (Fig.5.13 a) of the diagram: The two resistances in the diagram
correspond to resistances in two parts of the electrochemical cell. Here Rs is the cell
resistance between the counter electrode and the tip P of the reference electrode and Ru
is the so-called uncompensated cell resistance, which is the cell resistance between P
and the working electrode (Fig. 5.13b). Because of the very high resistance of the
inputs to the operational amplifier, there is no current in the feedback loop to the
inverting input. The operational amplifier works to keep E1 and E2 equal in the non-
inverting configuration and the cell current IC is supplied by the operational amplifier
to maintain this condition. If we consider the path between the inverting input and the
circuit common at the output, we see that
E2 = E1 = ESCE + ICRu = ESCE + EC
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Electroanalytical where EC is the cathode potential and is equal to the potential difference between P
Methods-II and the working electrode. Since E1 and ESCE are constant, ICRU must also be
constant. During electrolysis, if RU and RS changes, the operational amplifier output
voltage changes in such a way so as to maintain EC = ICRu at a constant level. If Ru
decreases, the operational amplifier output voltage increases to maintain EC constant.
If Ru increases as a result of an increase in the cell resistance or due to concentration
polarisation, the output voltage of the operational amplifier decreases, which leads to a
decrease in IC.
Fig. 5.13: Schematic of a system for potentiostatic coulometry (a) Equivalent circuit (b)
resistance within the cell (c) Practical circuit
Integrators
Most of the modern apparatus for potentiostatic coulometry employ integrators to
determine the number of coulombs required to complete an electrolysis.
Efficient stirring is important for controlled potential electrolysis, since all analyte
species must be swept up to the electrode surface, so that the electrochemical reaction
is completed. Besides stirring, the ratio of the electrode surface to solution volume is
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another requirement of the experiment. This ratio plays a role in determining the time Electrogravimetry and
needed for complete electrolysis, since the electrical current will be directly Coulometry
proportional to electrode area, A and also directly proportional to the concentration, c,
of the analyte.
I ∝ c×A
Q = I × t, where Q is the coulomb of electricity consumed
Q=I×t ∝c×A×t
Applications
i) Inorganic Analysis
Controlled potential coulometric methods have widespread use in the determination of
several metal ions. As many as 55 elements of the periodic table can be determined by
the cathodic reduction of metal ions to metallic state. Most of the metals (about two
dozen element) can form amalgams with mercury, and hence controlled potential
coulometry with mercury cathode is usually preferred.
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Electroanalytical
Methods-II
Fig. 5.14: An instrument for continuously recording the oxygen content of a gas stream
A special feature of this set up is that a galvanic cell is formed and hence no external
power supply is needed. There is no need of a potentiostat to control the potential of
the working electrode. The current produced is passed through a standard resistor and
the potential drop is recorded. The oxygen concentration is proportional to this
potential and a digital display can indicate the oxygen concentration directly. The set
up can be used for the determination of oxygen in any gas stream and can detect
oxygen concentration from 1 ppm to l%.
NO2 NH2
48
proceeds with l00 % efficiency. It involves a single chemical change in the analyte. Electrogravimetry and
Coulometric titration has a special advantage in the sense that a standard solution is Coulometry
not required. This method is very useful for the estimation of micro and semi-micro
quantities of substances.
Cell Assembly
The cell assembly consists of a generator electrode at which the titrant/reagent is
generated and a counter electrode to complete the circuit as in Fig. 5.16. The generator
electrode is a platinum foil or gauze with a large surface area.
49
Electroanalytical External generation of titrant
Methods-II
Since internal generation of titrant sometimes interferes with the titration, it becomes
necessary to generate the titrant externally and deliver to the reaction/titration cell. An
assembly of the type shown in Fig. 5.17 is generally used. For example, hydrogen
and hydroxyl ions are produced by the electrolysis of sodium sulphate solution.
Fig. 5.17: A cell for the external coulometric generation of acid and base
The cell consists of two electrodes of platinum gauze separated by a sintered glass
disk. The anode compartment produces H+ ions, while the cathode compartment
produces OH − ions. The apparatus is so arranged that flow of electrolyte continues
even after the current is discontinued, thus flushing the residual reagent into the
titration vessel.
This type of external generation apparatus has also been used for the generation of
other reagents such as iodine by the oxidation of iodide at the anode, generation of
titanous ions etc. The external generation technique has been successfully applied to
titrations involving hydrogen, hydroxyl, iodine etc. and for the generation of reagents,
which are quite unstable, such as chlorine, bromine, titanium (III) ions, etc. Thus,
coulometric titrations are more advantageous than the conventional volumetric
titrations.
It should be noted that external generation of reagents is possible if only the titrant be
generated with 100% current efficiency.
50
titrations can be stopped exactly at the end point. Besides, the observed emf (change Electrogravimetry and
in potential) does not depend on factors like geometry of the cell, conditions of Coulometry
stirring, etc. Thus these methods of detection of endpoints are more advantageous.
Spectrophotometric endpoint detection has been developed and in recent years, this is
of great importance in the titration of olefins with electrolytically generated bromine.
Some of the special advantages of the method of detection of endpoints are:
ii) By proper choice of λmax and molar absorptivit, the sensitivity and selectivity of
the methods can be improved.
i) Neutralisation Titration
Titrations of strong acids or weak acids with hydroxide ions generated at a cathode
have been developed.
51
Electroanalytical the ammine mercury (II) EDTA chelate at a mercury cathode was used to generate
Methods-II
[HY3-] ions.
52
Electrogravimetry and
Mn3+ Mn2+ Mn3+ + e H2C2O4, Fe(II), As(III)
Coulometry
Ag2+ Ag+ Ag2+ + e Ce(III), V(IV), H2C2O4, As(III)
SAQ 10
In a coulometric titration of iodine with 20 cm3 of thiosulphate, 25 minutes were
required to oxidise thiosulphate and 200 mA of current were used. Calculate the
molarity of thiosulphate solution.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
53
Electroanalytical SAQ 11
Methods-II
A 0.l80 g of a purified organic acid sample was titrated coulometrically with
hydroxide ions produced in 5 mins by a constant current of 0.5l4 amps. Calculate the
molar mass of the acid if n is one.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
SAQ 12
A neutral solution containing 0.5 g of copper is electrolysed until all the copper is
plated and the electrolysis is continued 7 minutes longer. The current is maintained at
an average of l.20 amps. throughout the electrolysis. On the basis of 100% current
efficiency,
a) calculate the time required for complete deposition of copper.
b) what volume of gas evolved during the entire electrolysis?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
5.8 SUMMARY
We have learnt the principle of electrogravimetric analysis. Here the analyte was
deposited quantitatively by an electrolytic reaction and weighed instead of chemically
precipitated from a solution. Hence the name electrogravimetry. We have described
the significance of ohmic potential (IR drop) and polarisation in an electrolytic cell.
The degree of polarisation is given by overvoltage or overpotential. We have also
learnt about the two types of polarisation-concentration polarisation and kinetic
polarisation and their role in electrodeposition.
We began our study on coulometric analysis with the simple Faraday’s laws of
electrolysis. By making use of these laws, we solved some problems to calculate the
mass of an element deposited by the passage of known quantity of current. A current
measuring device called coulometer was explained. We discussed about the different
types of coulometers.
54
known as coulometric titrations was dealt in detail. We learnt about the cell assembly Electrogravimetry and
– external and internal generation of titrants and detection of end points in coulometric Coulometry
titrations. We finally discussed some of the applications of coulometric titrations in
various types of analysis and their advantages.
d) the applied potential, needed when [Ni2+] is l × l0-4 M assuming that all
other variables remain unchanged.
5.10 ANSWERS
Self Assessment Questions
1. The product of the resistance R of an electrolytic cell in Ohms ( Ω ) and the
current I is called the Ohmic potential or the IR. Unit of I is ampere and
resistance is Ohm’s ( Ω ), according to Ohm’s law
E = IR
E Volt
R = =
I Ampere
55
Electroanalytical Ampere × Volt
Methods-II IR =
Ampere
= Volt = V
IR can be related to cell potential and applied potential as IR = Ecell – Eapplied
56
Eanode = 1.23 – 0.0592/4 log 1/(l.00)(l.00 × l0-2)4 Electrogravimetry and
Coulometry
= l.23 – 0.ll8
= l.ll2 V
Ecell = Ecathode – Eanode
= 0.278 – l.ll2
= – 0.834 V
The potential required to initiate deposition of copper is – 0.834 V
a) Comparing the Eo values of the two system, bismuth will deposit first
Ecathode = Eo – 0.0592/3 log 1/[BiO+]
= + 0.320 –0.0592/3 log l/0.l
= + 0.320 – 0.0l97
= + 0.300 V
Theoretical cathode potential to start the deposition of Bi3+ = + 0.300 V.
X = 2.13 × 10 − 25 M
The concentration of bismuth when tin begins to deposit is
2.l3 × l0 − 25 M.
M r It
m=
96500 n
8.
58.93× 0.96 t
0.5 =
2 × 96500
0.5 × 2 × 96500
t =
58.93 × 0.96
= 1705.76 s
= 28.4 min s
Time needed to deposit 0. 5 gm of cobalt = 28.4 mins.
M rQ
9. m=
96500 n
57
Electroanalytical Coulombs to be required to deposit 0.25 g of copper
Methods-II
63.54 × Q
0.25 = or Q = 0.25 × 2 × 96500/63.54
96500 × 2
= 759.36 coulombs
coulombs expended = l.25 × 20 × 60 = l500 coulombs.
current efficiency = 759.36/l500 × l00 = 50.62%
10. Q = I ×t
= 25 × 60 × 0. 2 = 300 coulombs
96,500 × n coulombs = l gram molar mass
300 coulombs = 300/96,500 = 0.003l moles in 20 cm3 of solution.
Write the chemical equation involved:
2S2O 22− (aq) + I2(aq) → 2I–(aq) + S4O 26− (aq)
Hence, millimoles of idodine = 2 × millimoles of thiosulphate
0.003l moles × 20 cm3 = 2 × 0.003l moles × 20 cm3
Molarity of the thiosulphate solution = 2 × 0.003l × l000 / 20 = 0.31 M.
M rQ
m=
96500 n
M r × 0.514 × 5 × 60
0.18 =
11. 96500n
Mr 0.18 × 96500
=
n 0.514 × 5 × 60
= 112.6
Equivalent weight of acid, since n is 1, Mr = 112.6.
58
Terminal Questions Electrogravimetry and
Coulometry
1. m = Mr / n × It / 96500
The current applied is 0.50 amps. but current efficiency is 80%
Hence, I = 0.5 × 80/100 = 0.4
0.5 = l07.9/1 × 0.4t/96500
t = 96500 × 0.5/l07.9 × 0.4 = lll7.9 sec = l8.6 mins
Time required to deposit 0.5 g of silver = l8.6 mins.
2. a) Depositon of Ni2+
Ecell = Ecathode - Eanode
Ecathode = EoNi2+ - 0.0592/2 log 1/[Ni2+]
= -0.25 – 0.0592/2 log l/0.l
= -0.25 –0.0296 = -0.2796V approximately – 0.28V
Eanode = 1.23 – 0.0592/4 log l/(l.00)(l.00 × l0−2)4
pH = 2.00 or l0−2 M
= 1.23 – 0.0592/4 log 1/l0−8
= l.23 – 0.118 = 1.112V
Ecell = Ecathode - Eanode
= -0.28 – (l.ll2) = -1.39 V
b) IR 3.l5 × l.0 = − 3.l5V
59
Electroanalytical X = 2.77 × l0−6 M
Methods-II
The concentration of Co2+ when cadmium begins to deposit
= 2.77 × l0−6 M.
60