AN INTRODUCTION TO ELEGTROANALYTICAL METHODS

Electrochemical methods are based upon ue measurement of potential (potentiometry)

or the reciprocal of resistan ce, 1.e., Conducutce (Conductimetrv), diffusion ej1rrent
(polarography or voltammetry) and evatuabon of material generated at electrodes
(coulometrv). AIl these measurements are airecuy Telated to analytical concentrations.
Electroanalyticalmethods are listed below.
1 Coulometrv. In controlled potential coulometry the analyte is determined b°
electrolysis.
quantitative reaction at an electrode during
2. Potentiometry. It involves the direct appicauon to the Nernst equation The w
of single mcasurements of electrode potentials are the basis of determinations of ionic species
by standard solhutinn
in solution and these are compared with potentials developed
analyte.
8. Voltammetry. It is concerned with the study oi voltage-current-time relationshin
during electrolysis in a cell. The magnitude of limiting current is related to the concentration.
of the analyte. Hence, by using standard solutions or internal standard and standard additio.
techniques, a quantitative evaluation may be carried out.
4. Polarography. Here the working electrode is a dropping mercury electrode and the
auxiliary electrode is a pool of mercury at the base of the cell.
5. Conductimetry. Here two identical inert electrodes are employed and the
conductance (i.e., reciprocal of resistance) between the two electrodes is measured, with an
alternating current powered Wheatstone bridge. Specific effects of electrodes are eliminated.
Technique involving titrations is termed as conductometry.
6.Oscillometry or High Frequency Titrations. This permits one to observe changes
in conductance, dielectric constant or both by the use of high frequency alternating current
Electrodes are not kept in contact with the solution directly.
7. Chronopotentiometry. A known constant current is passed through the solutior
and the potential appearing across the electrodes is observed as a function of time. The related
measurement of current changes following application of a constant potential is known a
chronoamperometry.
8.Amperometry. It refers to measurement of current under a constant applied Voltage
Under these conditions it is the concentration of the analyte which determines
the magnu
of the current.
9. Controlled Potential Separation. It is
by means of possible to quantitatively Sepa th i
electrolytic oxidation or reduction at an electrode, the potential 0 w
carefully controlled. The quantity of separated species may be measured
gravimetrically. coulometricay
10. Electro-gravimetry. Analyte element is weighed after it has been electrolytical
deposited upon a suitable electrode.
11. Electro-deposition. This method is governed by Ohm's law and Faraday's laws o
electrolysis.
 Coulometric Methods
INTRODUCTION
on Michel Faraday's first
Coulometric methods of analysis are based the form that the extent of
Jaw of electrolysis which may be expressed in
electrode is directly proportional to the quantity of
chemical reaction at an change at an
clectricity passed through an electrode. For each mole of chemical
Faraday constant
are required i.e., the
electrode, 96487 + 1-6 Xn coulombs involved in the electrode reaction. The
multiplied by the number of electrons
electrolysis
the substance, W produced or consumed during an
weight of
involving Q coulombs is therefore given by the expression ...(1)
W = Mx Q/nF
liberated
is the relative atomic (or molecular) mass of the substance
M
where constant. Analytical methods based upon
Faraday
or consumed. F is a universal (1)
measurement of a quantity of electricity and the application ofequation
the Coulometric and
term derived from coulomb.
are ternmed coulometric methods-a quantitative conversion of the reactant to
electrodeposition techniques ensure fundamental
product by a process of oxidation or reduction. The
a new electrode reaction used for the
requirement of a coulometric analysis is that the the quantity of the
determination proceeds with 100% efficiency soof that Faraday's laws from the
substance reacted can be expressed by means
passed.
measured quantity of the electricity (coulomb)
PRINCIPLES OF COULOMETRY
a constant potential of
1. The first principle involves maintaining of reaction to occur at that
anode or cathode (which allows only a single indicates completion of
electrode) until zero current is realised which
produced and thus the
the reaction. The total quantity of electricity Faraday's law can be
amount of desired substance according to function of
determined by integrating the current which flows as a
coulometry.
time. This technique is known as controlled-potential
current coulometry or
2. Amperostatic coulometry, constant Twebelledy (1938)
coulometric titration introduced by Somegyi and
current
is more useful technique. It involves the passage of constant magnitude
until an indicator indicates completion of the reaction. The
helps in
of the current and time for which it has been passed
calculating the quantity of electricity required to attain the end point.
efficiency
The species determined must interact with 100% current
L.e., each Faraday of electricity must bring about a chemical change
that corresponds to one equivalent of the desired substance. The
species should not be directly involved in electrode transfer
process at the electrode. The substance determined is involved
Wholly or partly in a reaction that is secondary to the electrode
reaction.

(841)
 842 the oxidation of Fe(II)
METHODS
at platinun
electrochemical oxidation of Fe(II ). In
Consider the reaction,
anode, the current is generated from
Fe Fe +e
anode noto.
competing reaction of the decomposition of water starts when the
The concentration decreases,
polarisation as the Fe(II)
rises due to
2H,0 ’ O, + 4H +e
eveos.
current required to complete the oxidation of Fe(II) would
Hence the
can be removed by adding an excess of
theoretical amount and would create error that
the electrolysis. Since the oxidation potential of Ce(III) is lower than that of.
UID before
CeCet +e
equivalent amount of Fe(II)
So Ce(IV) diffuses rapidly from the electrode surface and an
be oxidised.
Ce + Fe2 Ce+Fet
Thus, one achieves the electrochemical oxidation of Fe(ll) with 100% current efficiency
although only a fraction of Fe(II) is oxidised directly at the electrode surface.
COULOMETRIC TECHNIQUES
1. Constant Current Coulometric Analysis.
This technique requires the knowledge of constant current and elapsed time to determine
the number of coulombs. The completeness of the reaction can be detected by a visual indicator
in the solution or by amperometric, potentiometric or spectrophotometric methods.
The amount of electricity passed is derived from the product, current (amp.) x time (seconds).
Since both current and time can be measured with high accuracy with relatively simple
equipment, this technique of coulometry is both accurate and simple. Constant current
technique is of two types.
(a) Primary Constant Current Coulometry. In this technique, the
estimated undergoes direct reaction at the electrode with 100% element to be
oxidised into ferric ion at the anode with 100% efficiency, then it is efficiency. If ferrous ion is
constant current coulometry. said to be a case of primary
(b) Secondary Con stant Current
method the titrant is quantitatively Coulometry or Coulometric Titrations. In this
produced
reacts with the ion to be estimated. A good on the iselectrode which then stoichiometrically
example
Fe by Ce* which is
produced by the oxidation of Ce provided by the oxidation of Fe in
ion at the anode.
Ce ’ Cet +e (At
A large
anode): Cet + Fe2t -’ Cet + Fet
potential of theconcentration
of cerrous ion
anode as low as not to alloweliminates
the
anodic polarisation and maintals
have used iodine as evolution of O,. Lingane and
Fernado (1956) usedelectrolytic intermediate in the titration of Bard (I90
bromine for the estimation of ascorbicantimony with hydroquinoe
coulometric analysis is further classified into acid and oxine. Seconu
generation analysis. external generation analysis and nve
2. Controlled Potential
The substance beingCoulometric Analysis.
determined
potential of which is controlled. reacts with
The completion of 100% efficiency at a
the reaction can be working electrae,
the
t
current
obtained by
 843

cOULOMETRIC METHODS
of a
determined either from the reading
zero. The amount of substance can becurrent time integrating device.
docreasing to by means of a
moter in series with the cellor COULOMETER
CURRENT MEASURING DEVICE, determining the amount
of electricity by
measuring quantity the unknown is
Couiometer is a device for current. The electrolytic cell containing action
ohange brought about by the that the amount of electrochemical
f another cell so designed coulometers gas coulometer,
silver
Rnocted in series with types of
determined. Of the various coulometers can be replaced by
oan be precisely are important. Chemical more
Jometer and iodine coulometersintegrators which show equal precision and are
loctronic or electromechanical
convenient to operate.
or Water Coulometer.
Hydrogen-Oxygen Coulometer
upon the volume of Thermometer
H,-O, coulometer depends cell
produced by passing the current through a Burette
gas
electrolysis of water occurs. This highly
where consists ofa graduated glass
sensitive device (Fig. 1) cm and an external
a length of about 40
tube having electrodes are sealed
diameter of 20 cm. Two platinum of the tube is
upper part
into the lower end. The
Water
jacket to maintain the bath
provided with a water connected to the
0.5 F NaSO4
temperature. The calibrated tube is
rubber tube so that by
electrolytic tube by a pressure
the collected gas
moving it vertically the pressure of pressure before
atmospheric
can be adjusted to The tube and its
measuring the volume of the gas.
sodium sulphate
levelling bulbs are filled with 0-5 F 100% current
ensure
solution of highest purity to
errors below Pt. electrode
eficiency. Such coulometer give negative
difficulty can be
50 milliampere current. This electrolyte
removed by using hydrazinium sulphate as a 5 cmn°
in
and evolved H, and No may be measured Fig. 1. Hydrogen-oxygen
microburette. In order to obtain precise and coulometer.
reproducible results the electrolyte must be freshly
Saturated with hydrogen-oxygen mixture, which can
be done by a 5-minute electrolysis with the stopcock open.
Precautions.
Following precautions should be taken while operating a gas coulometer.
in the series with electrolytic cell.
ecoulometer should be connected in the circuit
perature and pressure should be noted before and after the electrolysis.
.
" The electrolyte should be of 100% efficiency.
considerable error. The lower
ees of iron (Fe and F3+) or other metal will cause a
valence state oxidation at the anode followed by reduction atthe cathode.
undergoes
" As electrolysis proceeds, the graduated tube should be lowered periodically so that the
" liquid levelsprecise
To obtain are maintained equal. results the electrolyte
and reproducible must be tfreshlysaturated with
H-O, mixture before use.
 ELECTROANALY YTICAL METHOD

844
It consists of in reducing iodine at a platinum electrode acting as cathode or generatine
lodine Coulometer.
with standard arsenous solution.
an anode. The liberated LL is titrated precise coulometer (Fig. 2), The first reliable
10dine at
measurement Coulomneter. This is the
with silver coulometer was most
due to Kohlrausch. The coulometer consists of apure
Silver
(O000
anode suspended inside a platinum
silver cathode. The silver anode
crucible which acts as catch any
0000
surrounded with a porous cup to
Is may drop off. The Ag anode
particle of metallicsilver whichsilver nitrate. The
electrolyte is a pure solution of weighed both
Pt crucible

crucible is washed, dried and The increase in (cathode)

before and after the electrolysis. AgNO, solution
the amount of
weight after the experiment gives Since one
Porous Cup
silver deposited in the coulometer. electricity
Faraday or 96,500 coulombs of Fig. 2. Silver coulometer.
deposits, 107-88 g of silver thus the quantity of
electricity used to deposit the amount of silver
the coulometer can be easily calculated.
CURRENT OR
COULOMETRIC TITRATIONS OR COULOMETRY AT CONSTANT
AMPEROSTATIC COULOMETRY
electrochemical
Coulometric titrations are based on the principle of constant currentdetermined. The
generation of a titrant which reacts quantitatively with the substance to be
magnitude of the constant current and time required to generate an amount of titrant
stoichiometrically equivalent to the desired substance are used to calculate the weight a
concentration of the substance using Faraday's laws.
Principles of Titration.
Coulometric titration involves the electrolytic generation of a reagent that reacts with
the species to be determined. The technique is termed titration, although the titrant is not
added as such from a burette (like titrimetric analysis). Here the reagent is generald
electrically and its amount is evaluated from a knowledge of current and the generating t
The electron becomes the standard reagent. The electrode reaction may involve only reag
preparation, i.e., precipitation of halides and preparation of silver ions. Some other titrau
may involve direct determination of species at the
generator electrode. An example coud
coulometric oxidation of Fe(II) both by electrolytically generated Ce(IV) and also bydired
electrode reaction. The current is maintained at a fixed value. The product of this Currenti
amperes and the time in seconds regquired to reach the equivalence point for the reactiongives
the number of coulombs and, thus, the number of equivalents involved in the electrolysis.#
the concentration of species being
Fundamnental Requirementsdetermined
of a
decreases, polarisation sets in.
Coulometric Titration are :
1.
2. The
Reagent-generating
electrode reaction should proceed with 100% etie bein

generated reagent should react substance

3.
determined.
The reagent may be generated directly stoichiometrically with
within the test solution
the
or it may be generate

in an external solution which is allowed to run

into the test soluion
 845
Consider coulometric
containing HBr by
COULOMETRIC DETERMINATION
determination the
of
cathode. The anodicelectrolytic reduction
half reaction is
concentration
to the ferrous of ferric ion in
state using silver a
solution
anode and platinum
In the Ag Br ’ AgBr
+
current +e
voltage
EoBra ion and of the H" ion incurves (Fig. 3) the curve i
HBr includes the reduction waves of
solution. Now if the current
Dassed through the solution, the cathode
potential of constant
be 0-40 V versus
standard will
calomel electrode (SCE) magnitude a,
where curve a and 1 intersect.
the process of electrolysis, the As iron reduces with
to the plateau corresponding
diffusion current of FeBr,
cathode potential jumps to -0-3 Vis lowered
(curve
until
2). (a)
corresponds to reduction of H ions. Since Fe3t jonsIt
continue to reduce and H, is liberated, the
efficiency decreases to below 100%. The current
repeated by adding excess of Ti(IV) processis 0.8 0.6 0.4 0,2
Ti(III) in presence of acid at the Ptwhich is reduced -0.2 -0.4 -0.6
cathode. It has Cathode potential, Vvs SCE
a slightly more negative
potential
(curve 3). The current efficiency than that of SCE Fig. 3. Current voltage curves as
there is no loss. reaches 100% and observed with a platinum cathode
Vs standard calomel electrode.
The equivalence point in this reaction is the point in time when the
electricity is just equivalent to generate the total amount of ferric quantity of
The equivalence point can be identified by iron present the samnple.
in
potentiometric or amperometric, photometric or
conductometric methods of analysis. In the above reaction it is assumed that no
electrochemical reaction at the anode and cathode occurs. Such an interaction can interaction of
be avoided
by shielding the counter electrode (viz., anode) with a
glass tube
discourage convection currents. Ag or agar agar salt bridges can having also be
a fritted tip to
closed by anion exchange membrane (cation or anion exchanger) can also be used. A shield
a glass fritt. Thus cations or anions are not allowed to escape from the
used instead of
anodic compartment.
ADVANTAGES OF COULOMETRIC TITRIMETRY
1. The most important advantage of this titrimetry is that extremely minute quantities
of the titrant can be accurately generated. Addition of 1 x 10*3 cm² of 0-01 N titrant
from the burette is made for 1x 10- meg. Since a small quantity of electricity can
be measured readily with a high degree of precision, the method has high sensitivity.
2 Only a very small amount of titrant need be prepared. Preparation, storage, handling
and standardisation of samples is thus completely eliminated. This advantage is
particularly important with labile reagents like Cl, Brg, T, Ag and Mn owing
Ouneir instability. These substances are inconvenient as volumnetric reagents. Since
these ions are generated and consumed immediately, there is no loss on storage or
change of titre.
d. Standard solutions are not required and in their place the coulomb becomes the
primary working standard.
Small amounts of titrants may be generated when required. This dispenses with
e aifficulties involved in the standardisation and storage of dilute solutions. The
veuure is ideally adopted for use on a micro or semi microscale.
 846 ELECTROANALYYTICAL METHOOS

5. The sample solution is not diluted in the internal generation proced ure.
6. By pre-titration of the generating solutionthebefore tB:e addition of the sample, m
effect of impurities in the
accurate results can be obtained. Since
solution is minimised.
7. This electrical method is easily adopted to automatic operation and onerai:
generating
remote locations. This is significant in the titration of radioactive or
materials.
Errors in Coulometric Titrations. Possible errors may be due to
dangerous
1. Variation in current efficiency from 100%.
2. Wrong measurement of current or time.
3. Variation in current during electrolysis and measurement of time.
4 Departure of equivalence point from end point. The error due to Curre.
measurement can be avoided with simple instrumentation which provides curten
constant to 0-2 to 0-5%. Sophisticated instruments offer current constant to 0.1% A
electric stop watch in which relative errors are as small as 0-1% can be employed or
time measurement.
INSTRUMENTATION FOR COULOMETRIC TITRATORS
The basic components of coulometric titrators (Fig. 4) include a suitable source af
constant current, an accurate timing device, coulometric cell and an integrator.
Potentiometer B-Batteries 90-180 volts
for current
measurement

R, Standard
Generator electrode resistance
Cell

20000
Auxiliary electrode
R2
R

Clock
Constant current lo potentiometer
sOurce 110 volts AC O o

Fig. 4. Coulometric titration apparatus. Fig. 5. Source for constant current

1. Constant Current Sources.
In coulometric titrations, generating currents of 5 to 20 milliamperes are used, althoug
currents as high as l00 ma and as low as l ma are required. Current source is shown in Fig
5. The power supply consists of two or more high capacity, 45 volt B-batteries, the curren
from which passes through a calibrated standard resistance R,. (R, when multipiea y
potential
current, Ishould be -1 V). The potentiometer across this resistance measures the
drop. The variable resistance should be 20,000 ohms. On putting the switch to position Z, u
crrent passing through the cell is,
Eg Ecell ...(2)
R, +R +Rg +Reell
where Ep is potential of the B-batteries. The Ell COmprises the cathode and anode poten
of the titration cell plus any overvoltage. Rp and Rall are the resistances of the battery
COULOMETRIC METHODs 847

the cell. Assuming E, and Rg CoIstant during the course of titration, E.all and Rcell result
variation in current. Changes in Ecel affect the current considerably. Aresistance Ra is
employed that has about the same magnitude as Roll.
2. Timing Device.
An electric stopcock powered by a synchronous motor, which in turn is actuated through
the same switch (s), is used to start and stop the titration. The start-stop error is reduced to
about 0-01% by using solenoid operated brakes.
3. Coulometric Titration Cell.
The cell (Fig. 6) consists of a generator electrode, where the reagent is formed, and a
second electrode for completing the Gas indicator
circuit. Provision is made for magnetic electrode
stirring and for passing a stream of inert Pt. generator Auxiliary
cathode
anode
gas (e.g.. N, He, Ar and also CO, for Salt bridge to Pure
removing dissolved O, from the sample reterence
electrode
nitrogen
solution) through the solution. The
interference usually arises from the
products formed at the second electrode,
For instance, when an oxidising agent is
generated at the anode, hydrogen is
liberated at the cathode. If not removed,
it would react with an oxidising agent.
For removing this interference the second
electrode is isolated by a sintered disc or
some other porous medium. The cell is
provided with other electrodes depending Magnetic stirrer
upon the type of titration. For example,
for acid-base titration, a glass membrane Fig. 6. A cell for coulometric titrations.
indicator electrode and a salt bridge tbe
leading to a suitable reference electrode is used.
The indicator electrodes may consist of a tungsten pair for a biamperometric end point.
rOr an amperometric end point, the electrodes may be of Pt foil or one of Pt and the other a
saturated calomel reference electrode. Indicator electrodes should be positioned outside the
electrie field (eurrent path) between the generator electrodes, otherwise spurious indicator
nts may be produced, particularly in the amperometric detection of the equivalence
point.
4. An Integrator.
Iis is an electronic device for measuring the product (current x time), i.e., the number
coulombs. If necessary this mav be replaced by an accurately calibrated millhammever wmcn
ouped with a quartz crystal clock to record the duration of electrolysis.
General Procedure.
The electrolytic cell is set up with both generator and indicator electrodes in position and
provision is made for
solution from which thepassing inert gas through the solution. Titration cell is charged with the
be titrated. The titrant will be generated electrolytically, together with the solution to
auxiliary electrode compartment is filled with a solution of electrolyte at a
 ELECTROANALYTICAL METHODS
848 electrodes are
The indicator connected
level than the solution in the titration cell. point. Stirring is effectod0a
higher of the end
pH meter or a
galvanometer for the detection counter and pH meter as the enda
are taken of the integrating
magnetic stirrer. Readings switch off the electrolysis currert
before the
readings of pH
approached. It is necessary to
is
meter are recorded.

Detection of End Point.

point of the titration is evaluated from the plot of the reading of indicat:
The end counter reading. The first or second derivative
e8
instrument (in millivolts) against the
locate the equivalence point accurately. The titration is repeated with a fresh vol
drawn to determined potentiometrically and t
of the test solution, if the end point is to be
determinations may be stopped at the potential found for the equivalence noint:
subsequent species are involved in coulometric titratione
the initial titration. When light absorbing
with visual indicators can be employed. Coulometric titrations are
spectrophotometry
addition of titrant is different. Bo
analogous to volumetric titrations except that the mnode of
titrations a gold or platinum indicator is used while for complexometric titration
redox electrode is used. For a precipitation
(where EDTA is electrogenerated), mercury indicator is used. In coulometric titrations
titration either silver or mercury indicator electrode
involving acids, conductivity is used for end point detection.
Limitations of Coulometric Titration or Internal generation of Titrant.
present in solution
1. The side reaction between generator electrode and other substance
formed during the
poses problems for coulometric titrations. A base at the cathode is
titration of acids.
2. When applied on a macro scale-samples of1 to 5 millimoles with generation rates of
100 to 500 milliamps are required. Parasitic currents may be induced in the indicato
electrode at currents in excess of about 10 to 20 mH. Consequently precise location o
the equivalence point by amperometric method is not reliable.
To overcome these limitations, the reagent can be generated at constant current witi
100% efficiency in an external generator cell and subsequently delivered to the titration cel
To reservoir of
EXTERNAL GENERATION OF TITRANT. NazSO4 solution
The reagent is generated
electrolytically in the electrolytic cell
(Fig. 7.) The generator electrodes Lonsist
of two platinum spirals. The sintered glass
disc between the electrodes prevent
turbulent mixing. A beaker containing Platinum
the substance to be titrated is placed Cathode spiral Ianod
beneath the delivery tip and the solution
For
from the other tip is run to waste. acts Sintered
the titration of acids, a electrode glass disc
cathode in sodium sulphate
as
and the OH io
generator electrolyte
the reaction flows into the
generated by
test solution.
H,0+ 2 e 2OH +H, Fig. 7. Cell for external generation
2 of the titrant.
is emploved as the anode. For titrations with electrolytically generated iodine, the generator
The
olectrolvte consisis of KI solution. formed at anode flows into the titration vessel.
Disadvantage. A minor disadvantage of external generation of titrant is the dilution
Cbe contents of the titration cell. Care is therefore taken in adjusting therate of 1ow and
the
concentration of generator solution. The procedure is, however, most suited for
the
automatic control.

APPLICATIONS OF COULOMETRIC TITRATIONS

Coulometric titrations have been developed for all types of volumetric reactions.
1. Redox Titrations.
Avariety of determinations
As3t
(Table 1) have been carried out by the constant current
generation of halogens. and I are determined with electrogenerated chlorine whereas
Sb), Se(iV), S,0; and H,S have been determined using electrogenerated iodine or
bromine.
2Br’ Br, +2e (Anode) ; 2H,0+ 2e ’ 20H +H, (Cathode)
AsO +Br, +20H ’ Aso +2Br +H,0 uranium,
Electrogenerated bromine is also used to determine phenol, salicylic acid,
ammonia, aniline, iodide, oxine and thiodiglycol etc.
Table 1. Some redox coulometric titrations.
Electrolyte Generator electrode Substance titrated
End point
Reagent composition reaction detection
2C1 Cl2 + 2e As(Ill), I A
HCI (2 M)
Br, + 2e Sb(ll ), TI(I) I, SCN, A
Br KBr (02 M) 2Br
N,H, NH,OH
As(Il), Sb(!II), S? A, P,I
KI(0-1 M), PO, 21 l, +2e
buffer pH 8 S,0, Ascorbic acid
Fe Cr(V), Mn(VI), P
Fe,(S04): (NH),SO4 Fe +e Fe
|Ce(IV), VV)
(03 M), H,SO, (2 M)
Mn' P
MnSO, (0-5 M) Mn2t = Mn* +e Fe(l), As(III), H,C,04
H,SO, (1-8 M)
Ag' AgNO, (0 1M) As(III), Ce(lII), V(IV) P
Ag Ag' +e
HNO, (5 M) H,C,04
Fe(ll), T(IID, As(III), P
|Ce(S04)3 (0-1 M) Ce Ce+e UIV), |Fe(CN);]*
T P
TiIV) S0, (06 M) Ti0 +2H +e
Fe(lIl), Ce(IV), UV),
H,SO, (6 M) +2 H0 VV)
HNO, (2 M) UO} +4H + 2e Ce(IV), Cr(VI) P

U + 2H20
CuClk CuSO, (0-1 M) |Cu+3CI +e CuCl%VOV), CrV), IO3, Br
Note. A=
Amperometric. I= Indicator, P= Potentiometric.
 L METH

850 water.
reduction of Both weak
2. Neutralisation Titrations.
is
oxidation and
hydroxide ion. At
the cathode water is and str
such titrations
The basis
acids can be
of
titrated using
electrogenerated
H, + 20H
reduced
follows. 2H,0 + 2e
reduce directly at the electrode
under similar conditions surlac
Hydrogen ions of acid
2H* +2e H,
must be isolated from the main samal
anode is used, it determination
If platinum auxiliaryduring oxidation of water hinders the
because hydrogen formed 2H,04H"+ 4e +O
avoided by using silver auxiliary electrode which is dipped
Anodic generation of H, is
containing 0-04 M NaBr.
a solution of acid
Ag + BrAgBr +e
bromide so produced at anode forms a coating on the electrode. For the tit
Silver from the oxidation of water.
of bases, H ion is generated at the Pt anode
H,0 1/20, + 2H* + 2e
reduction of anodi
It is essential to isolate the auxiliary cathode in order to check the
generated H" ions at the cathode. The H ions can be electrogenerated at the platinum ano
by adding little water to a non-aqueous solvent for the titration of weak bases. The mam
advantage of the coulometric titration of acid using OH is that one need not undergo t
cumbersome protection of the standard base solution from CO,.

Table 2. Neutralisation reactions.

Reagent Electrolyte
Electrode reaction Analytical Substances
generated composition reaction titrated
H Na2SO4 (02 M) H20 2H + 1/2 O2 + 2e H +OH ’ H20 OH,Organic
bases
OH NapSO4 (0-2 M) 2H20 + 2e 20H + HT OH +H" ’ H)0 H, Organic
acids
Note. End point is detected by
3. Precipitation Titrations.
potentiometric method.
In these titrations, the glass
electrode for titrations with anodicallymembrane electrode replaces a silver wire
accurately determined. The end point generated
is
silver ion. Halide ions can be analyseda
mercury (I) is used to titrate Cl, determined Electrogenerate
potentiometrically.
titrated by an indirect coulometric Br,I individually from their mixtures. Thiourea has be
an uncertainty cf only 0-01 mg. procedure, i.e.. 0-4 to 4 mg amount being determ
4. Complexometric Titrations.
C. N. Reilley
and W.
titration of several cattions byW. Proterfied (1959) have applied methodto
cathode in an EDTA. Here coulometric
ammonia-ammonium+ HgII)-EDTA-amine
nitrate buffer is reduced to formcomplex
EDTA.
at a
mercury P

HgNH,Y" NH, +2e Hg +2NH, + HY

COULOMETRIC METHODSs 851

Mhe liberated HY reacts with the cation being determined. For example, for divalent
jons, the reaction occurs as follows : M* + HY- + NH, ’ MX' + NH;
Since mercury chelate is more stable than the corresponding complexes with
2 C2+ Zn2+, Pb* etc., complexation of these ions cannot occur until the electrode process
frees the complexing agent. The accuracy is within ±0-5% for substances ranging from 2 to
40 mg.
Table 3. Some typical coulometric titrations.
Kind of Reagent Electrolyte Substances End point
generated composition titrated Note**
titration detection*
Precipitation Ag(I) KNO, (0-5 M) CI, Br,I, P 1
Reactions |Mercaptans
Hg(l) HCIO, (0-5 M) CI, Br P 2
KNO, (0-4 M)
Fe(CN)l* KFe(CN)s (0-2 M) Zn(II) P
H,S0, (0-1 M)
|Complexation EDTA Hg(NH3)y (0-1 M) Ca(I), Cu(II), P 3

Reaction NH,NO3 (01 M) Zn(II), Pb(II)

pH 83
KBr (0-2 M) Phenols, Oxine, A
Substitution Br2
Reactions Aromatic amines

Addition Br2 KBr (0-2 M) Unsaturated A 4

Reactions hydrocarbons e.g.,

Alkenes, Cyclohexene
P= Potentiometric, A = Amperometric.
Note.** 1. Silver anode; 2. Mercury anode; 3. Mercury cathode.
For mercury.EDTA reagent. Prepare a stock solution containing 8-4 HgII) nitrate
and 93 g disodium EDTA in 250 cm³ (01 M). Mix 25 cm stock solution with 75 cm
NH,NO, solution (0-1 M) and adjust to pH 8:3 with concentrated NHg solution.
4. Trace of mercury (II) acetate dissolved in acetic acid/methanol mixture is added as
catalyst.
DETERMINATIONS INVOLVING CoULOMETRIC TITRATIONS AT CONSTANT CURRENT
Coulometric titration is vezy suitable for the determinations of substances present in the
Order of 10 to 10 mole. Large amount of substances require long electrolysis times unless
aperostat capable of delivering large currents (upto 2A) is available. In such cases, a
lon procedure
lower is to start the electrolysis with a large current and then to switeh to a much
output as the end pointis
approached.
CHLORIDE, BROMIDE AND IODIDE.
from Principle.
mercury poolHg(l)anodes
ions can be generated at 100% efficiency from mercury coated gold or
and used for coulometric titration of halides. End point is
determinedof potentiometrically.
solubility In the The
mercury (I) chloride. titration of C1 ion,
standard 70% methanol
potentials of the isfundamental
added to reduce the
couples
involving uncomplexed Hg(l) and Hg(l) ions are :
 ELECTROANALYTICAL METHODS

852 E' = + 0-80 V

Hg + 2e ’ 2Hg EO= +0-88 V
Hg2t + 2e -’ Hg E= +0-91 V
(ii)
2Hg2 +2e ’ Hg (less oxidising) potential than to T
smaller
to Hg, requires a is subjected to
anodic
The
ions
oxidation
are the
of Hg
main product when
a mercurv
electrode polarisation
a.
Hgl)
non-complexing nmedium. bromide, the mercury pool generator
in a chloride and a saturated calomel
Apparatus. For titrations of
acts also as the
indicator electrode. It is used
through
in conjunction
a
with
saturated potassium
reference
nitrate salt
bridge.
electrode which is connected
to the cell consists of a silver rod. The solutit
electrode
iodide, the indicator
For the titrations of magnetic stirrer during
titration. perchloric aid
stirred vigorously with a
Electrolyte. For Cl and Br , use 0-5 M
Reagents. (i) Supporting The reagents must be chloride free.
+ 0-4 M KNO. compartment may be either the
I ion, use 0-1 MHCIO, in the isolated cathode
(ii) Catholyte. The electrolyte
same supporting electrolyte or 0-1 M H,S0,.
Determination of Chloride lon.
HCI. Pipette 5 cm methanol and 10 cm° of stock solution of
Standardise 0-005 M
compartment with supporting electrolyte or
supporting electrolyte. Fill the isolated cathode
liquid must be kept above that in the titration cell
with 0-1 M sulphuric acid. The level of the
counter reading, stir magnetically and commence the electrolysis at about 50 mA
Note the
the counter reading. Observe the potential
Stop the generating current periodically and note electrode.
etween the mercury pool and standard calomel Plot a potential-counter reading
second differential graph.
rurve. Evaluate the equivalence point from the first or
Determination of Bromide lon.
Prepare 0-01 M solution of KBr. The procedure is similar to that of chlorideof the
ion
determination except that no methanol is added. The tit ration cell may contain 10 cm
bromide solution, 30 cm of water and 10 cm of the stock solution of supporting electrolyte.
Determination of lodide lon.
Prepare 0-01 Msolution of KI. The procedure is similar to those described for Br, except
that the indicator electrode consists of a silver rod immersed in the solution. The titration cell
may be charged with 10 cm of KI solution, 30 cm of water and 10 cm of the stock solution
of HCIO, +KNO,. In the neighbourhood of the equivalence point it is necessary to allow a1
least 30s to elapse before steady potentials are obtained.
CONTROLLED POTENTIAL COULOMETRY OR POTENTIoSTATIC CoULOMETRY
Most controlled-potential coulometric experiments are conducted under conditios
which the current is controlled by diffusion. Thus, the relationship between
time, t, and concentration, C,, is given by current, I, a
nFADC, ...3)

where A is the area of the working electrode (in cm), D is the diffusion
"oactive species (in cm min ), and 8 is the thickness of the Nernstcoefiicient
diffusiOn
e
(in cm). From Faraday's law, the rate of change of
concentration with time is gven Dy
dC,
dt nFV
initial concentration, Co
C; = Co ..(5)
ond current as a function of the initial current. I

I,- I,eR or 2.3 log lo kt ...(6)

The constant k is given by DA/VS. These relations provide a logical basis for the optimum
dosien of cclls and the choice of experimental conditions to obtain rapid electrolysis.
Note that the cquation (5) corresponds to a first order rcaction and rate of electrolysisof
ie. the decadic change in concentration) is independent of the initial concentration
reactant.
The number of coulombs, Q, that pass up to time t is obtained by integration :

Q,-J 1dt -Jet dt = ...(7)

Equation (7) is useful for estimating the total number of coulombs required for the
complete reaction before the reaction is actually completed. Q, is read at several values of t,
Dreferably in the range of 90%-99% completion, and then these values of Q, are plotted versus
L. Q. is determined by extrapolation of the straight line so obtained to the coulomb axis. The
limiting values of Q is lo/k.
INSTRUMENTATION FOR CONTROLLED POTENTIAL COULOMETRY
Instrumental units involve a DC current supply, a potentiostat, an electrolytic cell
and a coulometer. A mercury pool is most often used as a working electrode for electrolyses
that involve reduction processes. Oxidations can be performed at a platinum working
electrode. Because the current is continuously changing, decreasing from a relatively large
value at the beginning to essentially zero at the completion of the reaction, the charge transfer
during this process must be integrated by a coulometer. A potentiostat is necessary to control
is
the potential of the working electrode with 1-5 mV of the desired value. The clectrolysis
terminated when the current has diminished to 0-1% or less of the initial valuc or when the
Current becomes equal to the residual current as measured on a sample of supporting
electrolyte alone.
Current integration can be performed digitally by a 50 kHz voltage to frequency
CUnverter and counter system. The integrator is preceded by a chopper-stabilized current to
voltage converter with crrent ranges of 1 uA to 1 Aavailable in decade steps. The frequency
uput of this converter is then digitally counted to yield the current integral.
e digital normalization can be used to evaluate the background current. While an
Cietronic logarithmic display of the digitally recurded data is viewed, a constant number of
hts Is subtracted from cach data channel until al! the data points in the decay curve tall
ContllB ine. The summation of the counts subtracted is cqual to the background current
contribution. Software
programs carry out the normalization automatically.
Selection of Experimental Conditions in Controlled Potential Coulometry.
"The experimental conditions are so chosen so as to obtain desired accuracy, selectivity
and speed of analysis, e.g- (i) cell geometry (ii) stirring efficiency (ii) electrode potential
 ELECTROANALYTICAL METHO
854
concentration of
(v) solvent (vi) nature
and supporting
(Iv) electrode material
(Vn) temperature(viii) complexing agent or
surface active agents.
APPLICATIONS OF CONTROLLED POTENTIAL
COULOMETRy electroly
1. potential electrolysis has been found extremely useful in many
Controlled fields
chemistry, e.g.. organic and inorganic preparations, separation of Se and Te,
and W(V). and NH,OH. separation of radioactive
It also provides a valuable method for the
2
w leve.
Arsenic can be determined by oxidising HgAsOz to HgAsO4 at a
nuclides
3.
platin
Anode potential control also allows the conversion of Fe(II) to Fe(III)
4. Metals can be separated by electrodeposition on a mercury
um anode
than mercury can be deposited on a mercury surface, e.g., Al, Sc, v w cathode
employing controlled potential coulometry. Any metal with a deposition potential )
Alkali and alkaline earths can be deposited if the solution is basic. But a TI and y
potential leads to concentration polarisation and consequently we change in notice
5.
other species
of and
loss selectivity.
of
Lead in presence of cadmium, copper in
presence of bismuth and nickel in presence of
0.6
Potential
codepostig
0.4
cobalt have been determined by this
technique. Fig. 8 indicates that at point A lead 0.2
co)
can be deposited, at B cadmium and at point
C there is evolution of H, gas. 0.0
Such (Pb)
interference can be avoided by decreasing the 0.2
applied potential to avoid a negative drift of
cathode potential but in this process the 0.4
current decreases. 10 20 30
6. Organic compounds can be determined by Time (min)
controlled potential coulometry. For instance Fig. 8. Changes in potential
(i) trichloroacetic acid and during electrolysis.
(ii) picric acid are
quantitatively
have been suitably controlled.
reduced at a mercury cathode whose potentia:
(i)
Cl,CC00 + H" +2eCI,HCCO + CI
OH
OH
O;N NO,
+ 18 H" + 18 e H,N NH,
+ 6 Hz0

7.
NO;
Separation of Nickel and NH,
Reagents. (i) Prepare standard Cobalt.
solutions
ammonium nickel sulphate and
of N2 and
Co2t ion (10 mg cm ")
(ii) ammonium
Redistil pyridine and collect the cobalt sulphate respectively.
(iii) Supporting
to a pH of 7-0 + electrolyte is
middle fraction at 388 K.
0-2 for use composed of 1 M
with a silver anode. ion.Adiu
pyridine and 0-50 Mchloride
with Procedure.
pure nitrogen Take 90 cm of the supporting electrolyte inthe cell. Remove dissolved
and subject the meru
solution to
electrolysis with the potential
of
COULOMETRIC METHODS
855

Abode -1-20 V versus SCE to remove traces of reducible impurities. Discontinue the
olvsis when the background current (2 mA) has decreased to a constant value (30 to 60
minutes).
Pronarc the coulometer, adjust the potentiostat (at -0-95 V us SCE for nickel) and
3foach of the standard solutions to the cell. Electrolyse until the current has decreased
value of background current. Record the number of coulombs passed and calculate the
tght of nickel deposited. Now adjust the potential to -1-20 V. Continue electrolysis until
the eurrent falls to the background current value. From the number of coulombs passed in the
eond electrolysis, calculate the weight of cobalt present.
NON ANALYTICAL APPLICATIONS OF CONTROLLED POTENTIAL COULOMETRY
1. Determination of n-Values.
Controlled potential coulometry can be employed for the direct measurement of n-values
.. the number of faradays of electricity required for the reaction by using Faradays laws.
i dt = Q n wF
M

where the quantity ofelectricity Q coulombs is given by the integral of current iamperes over
the time interval s sec. w is the weight in grams of the species that is consumed or produced
during electrolysis. M is given molecular weight. w can be calculated by evaluating Q
accurately.
2. Determination of Formal Potentials.
Scott et al. have determined formal redox potentials by plotting the extent of reaction
as a function of zero current electrode potential.
3. The technique is also used for studying the kinetics and mechanism of reactions.
OTHER COULOMETRIC METHODS
1. Flowing Stream Coulometry.
In flowing stream technique, the electrode is a cylinder of reticular vitreous carbon
which is amaterial of porous structure having a porosity factor of 0-95. This working electrode
IS Ssurrounded by steel cylinder which acts as the auxiliary electrode. The solution is pumped
through the electrode at a flow rate of 1 cm per sec. The assembly is mounted inside a small
chamber in which connection to the reference electrode is made.
Procedure. Take 0-02 cm3 of the solution to be analysed. Inject this into a stream of
UPporting electrolyte flowing in a tube of 0-5 mm diameter. Mixing occurs and at the entry
e working electrode the diluted test. solution mav occupy a volume of about 0-2 cm". All
Lernal to be determined will pass through the electrode in 12 to 15 seconds and thus a
rapid rate of
in which aa determination
potentiostat
has been achieved. The electrode will be incorporated in a circuit
a controls the potentials of the working electrode and may also provide
counteinr-current
included the facility to nullify the background current. An electronic integrator is also
circuit. Thus thetime reqquired for a coulometric determination can be reduced
0y using a
flowing stream technique.
2.
Thin-layer
Acell is Cavity Cell
(metal-plate) is constructed Coulometry.
to give a cavity on one wall of which the working electrode
mounted. This wall isthinseparated by a teflon sheet in which a central aperture
 856

has been cut out fronn the opposite

ELECTROANALYTICAL METHO
wall of the cavity. Thus tho wall
tubes for the test solution
made for the connections to
which is caused to flow past the
theother clectrodes.
workingcontains
clectrodeentry and
laver of the electrolyte during electrolysis and so
Ifthe teflon
distance between the two walls of the cavity is less than the sheet is thin
normal thickness (0-05
elcctrolysis within
of
Prtheovisionthe
mm),
3. Predictive Coulometry.
The time required for conventional
the cavity is
rapid. dif usion,
controlled potential coulometry can be
adopting the procedure of predictive coulometry. The determination
of coulombs (Q,) for
completion. If at time t, Q, conlombs have
coulombs will be required to complete the
requires a
been reduced
passed, certain number
by
number of times t1, t, ta separated by 10 determination, i.e., Qr= Q-.then QR further
By selcct
seconds and
has been observed thatmeasuring the corresponding ni
of coulombs passed Q1, Q. Q3 it

A computer is
Q=329, -(Q1 +3)
of 10 s until programmed
a constant value of
to calculate Q from the
).. is obtained. value of Q, at successive interyal.
4. Voltage Scanning Coulometry.
In this
is scanned technique,
the electrolysis is carried out at
through the potential region in such a a working electrode whose potential
maintained at all times. The way that
rate. The solution is mixed equilibrium is maintained by scanningelectrolytic equilibrium is
vigourously. A plot of the voltage at a constant
(Q) against electrode instantaneous current
for a reagent blank. The potential is () or total
recorded during the scan and a similar type of electricity
coulogram
species. If I is plotted against E, we of Q aagainst E provides the weight of thegraph is noted
of I at derivative have time derivative of the electrolysed
The electrode maximum the weight of the coulogram. From the value
potential can be scanned at a electrolysed species can be
of iron and
plutonium can be analysed by thisrate inversely proportional todetermined directly.
the current. Traces
5. Stripping Coulometry. technique.
In stripping analysis the analyte is
clectrode. It is
stripped or collected by electrode positioned at a
redissolved
solution. Quantitative analysis from the mercury or solia
is based either on electrode to produce a more con centrated
10Gto 109or microgram
on
concentration of solution. Such elcctrical analytical measurements durims
to
nanogram methods are useful in trace
analysis work irou
Usually a micro mercury
electrode
voltametric analysis of the sample to be
concentration.
is used for Analysis
the
is feasible with greatest accuracy

analysis. analysed. deposition

Consider
process followed by
following two steps du
(A)
Electrodeposition
quantitative Step. Part of the analyte is
results depend on control deposited
deposition, stirring rate for sample and of the electrode potential, during this step.f
electrode
i.sod as the electrode (Fig. 9). The standard solution. Mercury drop with a size, time
platinum r
donosition of an analyte species. A hanging concentration of mercury is
kept
drop electrode is preferred asminimum to fac
Acapillary supplies
by mercury tor drop transfer. Then a
rotating the transte scoop and contacting
microelectroo
hanging drop electrode is to e
solution is stirred and the drop can be mercury with platinum wire in a glass tubeend ot
dislodged by tapping the at the
COULOMETRIC METHODS
857

analvsis. After tormation of a drop. a J1

less than the half
potentia, equal to
potential ( E ) of the Pt wire
analvtical metal ion is applied.
SCE
minutes
Deposition is allOwed for 5 DC
B), Voltammetric Analysis. SOurce
in the
The analvte which is collected
DME
determined
hanging drop electrode is
quantitatively by voltammetric Dron
analvsis. The voltage is decreased at transferer
value to
afixed rate from the cathodic -Hg
the anodic value. The resulting anodic
of
Current is recorded as a function
Glass tube
current Fig. 9. Stripping analysis assembly.
the applied voltage. A plot ofplotted
a) (s potential ('s SCE) is
Exercise., Analyse cudmium by stripping coulometry.
Solution. Cadmium is deposited from a 10 M solution by applying a potential of
-09V(Us SCE). It is 0-3 V mere negative than E/2 of Cd. After 10 minutes the electrolysis
ntential was diminished at a raie of 21 mV/s. Arapid increase in anodiccurrent occurred at
reaction
-0-65 V due to the
Cd(Hg) ’ Cd +Hg + 2e
The current depleted after reaching a maximum. The peak current is proportional to the
concentration by Cd and inversely proportional to the deposition time. A standard curve of
cadmiumn is of course necessary.

COULOMETRY IN CONJUGATION WITH OTHER TECHNIQUES

Controlled potential coulometry can be used in conjugation with volumetry, gravimetry
and polarography in order to carry out the simultaneous determinations of two substances
which can not be determined independently. Following three steps are involved in the
procedure
(i) A controlled potential coulometric determination of the quantity of electricity
consumed by electrolytic reaction of both substances.
n) Evaluation of some other concentration dependent quantity for both substances.
m) Setting up and solving simultaneous equation to obtain the respective weight of the
tuo substances.
1.Coulometry and Gravimetry.
i a
Br in 1on coprecipitates on AgB:. the controlled coulometric determination of Cl and
AgBr are mixture is not accurate. Asimultaaneous determination is carried out if both AgCl and
coulometrically
and the total deposited on a tared electrode. Thus the electrode can be weighed
weight the halide deposit may be calculated. Two equations (one in terms of
of
weight and other in of coulombs) in two unknowns can be set up and solved
siutmilulisedtaneousl terms
y for the individual weight of CI and Br ion. MacNevin and Melver (1955)
this
coulogravimclectrode.
Caimium using mercury etric technique for the simultaneous determination of zinc and
 ELECTROANALY TICAL METHO0s

858
and Volumetry. employed coulovolumetric technique in
2. Coulometry (1956) have Coulometric the
of
Meites
L. Meites and T. picric acid and dinitrophenol. -NO,
all the
reduction gave a
groups present
analysis of mixtures
coulombs of electricity required to reducetotal milli-equivalents of in the
measure of the
sample, while
volumetric titration gave a measure
sample.
of
replaceable
hydrogern present in the
Polarography.
L. Meitesand(1955) have employed this combined method for the ssimultaneous
3. Coulometry
Ous
thallium and lead. He evaluated the polarographic diffusion current
determination of number of coulombs required to
total reduction of two ions
in addition to the
these two data, the two unknoureduce oth
both
electrolysis. Using
species in a controlled potential
individual weights of thallium and lead.
solved simultaneously for the
SELECTED TIPS
low currents (usually below 50 ,
" Hydrogen-oxygen coulometers give negative errors at
Coulometric methods are rapid, selective and equally sensitive. These are based
electrode reaction including dissolution, electrodeposition, oxidation reduction etc.
Coulometric methods are much faster than volumetric and gravimetric methods and need
no standardisation.
The most important criterion in choosing the best method whether amperostatic or
potentiostatic is that there should be 100% current efficiency.
" Potentiostatic methods are used for deposition of substances with poor physical properbies
and reactions giving no solid product, e.g., HAsO, to H,AsO4.
" The equivalence point in coulometric titration can be identified by potentiometric or
amperometric, photometric or conductometric methods of analysis.
SHORT ANSWER QUESTIONS
1. How does the current vary in case of controlled potential
Ans. Current generally decreases exponentially with coulometric analysis?
time according to the equation
I, = Ihe or 1, =I, 10-kt
where Io is the initial current, I, the
2. Sketch a typical time vs
current at time t and k (k') are constants.
current
Ans. The curve in Fig. 10 showscurve. Explain.
to zero. In many
that the current decreases more or less
cases an appreciable exponentialy
observed with the supporting electrolyte. background current is
current finally decays to the In such cases the
zero. A correction can be background current rather than to
background applied by
is constant during the assuming that the
current
3. Explain
different components of backgroundelectrolysis.
Ans. Background
currents.
current is divided intocurrent.five component
(a) Charging
double layercurrent
is required to
existing at the charge the electrical
The magnitude of solution-electrode
charging current depends upon interface. Time
experimental
potential. conditions, cell design, medium and the
electrode
Fig. 10. Typical
time vs c°rent
curve.
COULOMETRIC METHODS 859

(b) ContinuOus faradic current is due to the electrolysis of some component of the
medium itself.
(e) Impurity faradic current arises from the electrolysis of impurities present in the
medium.
) Kinetic background current arises when the product of electrolysis slowly
converts to the starting material,
Ia) Induced background current arises when the electrode reaction induces another
reaction to take place.
What are the fundamental requirements ofa coulometric titration ?
Ans. (i) The reagent-generating electrode reaction should proceed with 100% efficiency.
i) The generated reagent should react stoichiometrically with the substance to be
determined.
MULTIPLE CHOICE QUESTIONS
1. Coulometric methods
(a) Eliminate the need for burette and balances
(b) Do not require preparation, storage and standardization of standard solutions
(c)Can be automated and adaptable to remote operation and control
id) Allstatements are correct
2. Current potentiai diagrams are obtained by plotting current against
(a) Cathode-reference electrode potential (b) Cathode-anode potential
(c) Anode-reference electrode potential (d) Working electrode
3. A
constant electrode potential is maintained by a
(a) Two electrode potentiostat (b)Three electrode potentiostat
(c) Reference electrode (d) All
4. Acontrolled-potential coulometric electrolysis is like a
(a) First order reaction (b) Zero order reaction
(c) Second order reaction (d) Pseudo order reaction
5. Primary coulometric titration technique is attempted only with electrodes of
(a) Ag metal (b) Ag/AgX
(c) Hg amalgams (d) All
6. In situ generation of known amounts of chemical reagents from a titrant precursor forms
the basis of
(a) Controlled potential coulometry (b) Constant current coulometry
(c) Coulometric titrations (d) All
the initial silver concentration in a sample is 1 x 10 M, what time should be required
for acontrolled potential coulometric procedure, assuming a diffusion layer thickness of
2x 10 cm, a diffusion coefficient, of 4-2 x 10- cm min, solution volume of 20 cm° and
an electrode area of 15
(a) 1-014 min cm?
(b) 1-15 min
(c) 58 s
(d) 30 s
|Hint. kt =
2:303 log k=
0-434 (4-2 x 10 cm min (15 cm)
i,' (2 x 103 cm) (20 cm)
=0-684 minin1
L2=0-693/0-684 =1-014 min).
860
is
FLECTROANALYTICAL
by a current of 2 amperes
8. Cadmium deposited in 4 hours (b) 16-7 g
(a) 155 g (d) 18-9 g
(c) 13-2g 28800 coulombs
|Hint. Q=ixt=2x 14400 s =
56 g Cd
1Faraday would deposit Ca/2 = 112/2 =
56
So 28800 coulombs would
deposit = 28800 x 96500 16-712 g of Cd].

9. How many seconds will it take for a current of 0-5 ampere to deposit 0.59 g of
the basis of 80% current efficiency? silver
(b) 15-9 min
(a) 18-6 min
(e) 16-S min (d) 19-5 min
10. The possible errors in case of coulometric titrations may be due to
(a)Variation in the value of current and lack of 100%% current efficiency
(b) Wrong measurement of time or current
(c) Departure of equivalence point from the end point
(d) All

ANSWERS
1. (d) 2. (a) 3. (b) 4. (a) 5. (d) 6. (b) 7. (a) 8. (b) 9. (a) 10. (d