Electrogravimetric and Coulometric Methods

• For a cell to do any useful work or for an electrolysis to occur, a significant current must flow.
• Whenever current flows, three factors act to decrease the output voltage of a galvanic cell or to
increase the applied voltage needed for electrolysis.
• These factors are

– ohmic potential,
– concentration polarization (overpotential), and
– Kinetic polarizaton (overpotential)
Coulometry and Electrogravimetry
• A potential is applied forcing a nonspontaneous chemical reaction to take place

• How much voltage should be applied?

• Eapplied = Eback + iR

– Eback = voltage require to cancel out the normal forward reaction (galvanic cell reaction)

– iR = iR drop. The work applied to force the nonspontaneous reaction to take place. R is
the cell resistance

• Eback = Ereversible (galvanic) + Overvoltage

 • Overvoltage: it is the extra potential that must be applied beyond what we predict from the
Nernst equation
Ohmic Potential
• The voltage needed to force current (ions) to flow through the cell is called the ohmic potential
and is given by Ohm's law:
Eohmic = IR
where I is the current and R is the resistance of the cell.
• In a galvanic cell at equilibrium, there is no ohmic potential because I = 0.
• If a current is drawn from the cell, the cell voltage decreases because part of the free energy
released by the chemical reaction is needed to overcome the resistance of the cell itself.
• The voltage applied to an electrolysis cell must be great enough to provide the free energy for
the chemical reaction and to overcome the cell resistance.
• In the absence of any other effects, the voltage of a galvanic cell is decreased by IR, and the
magnitude of the applied voltage in an electrolysis must be increased by IR in order for current
to flow.
 Electrogravimetry
• In an electrogravimetric analysis, the analyte is quantitatively deposited as a solid on the cathode
or anode.

– The mass of the electrode directly measures the amount of analyte.

– Not always practical because numerous materials can be reduced or oxidized and still not plated
out on an electrode.
• Electrogravimetry can be conducted with or without a controlled potential
• When no control
• A fixed potential is set and the electrodeposition is carried out
• The starting potential must be initially high to ensure complete deposition
• The deposition will slow down as the reaction proceeds
•
In practice, there may be other electroactive species that interfere by codeposition with the
desired analyte.

•
Even the solvent (water) is electroactive, since it decomposes to H2 + ½ O2 at a sufficiently
high voltage.

Although these gases are liberated from the solution, their presence at the electrode
surface interferes with deposition of solids.

• Because of these complications, control of the electrode potential is an important feature of a

successful electrogravimetric analysis.
Examples on electrogravimetry

• Cu: is deposited from acidic solution using a Pt cathode

• Ni : is deposited from a basic solution

• Zn: is deposited from acidic citrate solution

• Some metals can be deposited as metal complexes e.g., Ag, Cd, Au

• Some metals are deposited as oxides on the anode e.g.,

• Pb2+ as PbO2 and Mn2+ as MnO2

Coulometric Methods of Analysis

•Potentiometry: Electrochemical cells under static conditions
•Coulometry, electrogravimetry, voltammetry: Electrochemical cells under dynamic methods (current
passes through the cell)
•Coulometry: an electrochemical method based on the measurement of the quantity of electricity ( in
coulombs) needed to convert the analyte quantitatively to a different oxidation state
•A potential is applied from an external source forcing a nonspontaneous chemical reaction to take place
:Electrolytic method
 • measured quantity and the mass of analyte can be computed from known physical constants :
standardization is not usually necessary
• as accurate as gravimetric and volumetric procedures
• faster and more convenient than gravimetric measurements

Example: In a mixture solution of Zn2+ and Cu2+, convert all Cu2+ to Cu metal and leave Zn2+ in the solution.
- Hold the working electrode (e.g. Cu) potential at a certain value (positive than that for Zn reduction)

• Cu2+(aq) + 2e - → Cu(s)

Units for Quantity of Electricity

• The quantity of electricity or charge is measured in units of coulombs (C).
• A coulomb is the quantity of charge transported in one second by a constant current of one ampere.
• Thus, for a constant current of I amperes for t seconds, the charge in coulombs Q is given by the
expression
• For a variable current i, the charge is given by

Faraday's law relates the number of moles of the

analyte nA to the charge
n = #moles of electrons transferred in the half-cell rxn
F = Faradays constant = 96487 C mol-1 nA = number of moles of analyte

Types of Coulometric Methods:

1. Controlled potential coulometry:

2. Controlled current coulometry:

Fundamental requirement for both methods is 100% current efficiency

- all e- go to participate in the desired electrochemical process

- If not, then takes more current over-estimate amount of analyte

• Current efficiency of 100% does not, however, imply that the analyte must necessarily participate
directly in the electrontransfer process at the electrode. Indeed,more often than not, the analyte
participates, at least in part, in a reaction that is secondary to the electrode reaction.
1) Controlled potential (Potentiostatic) coulometry):

• The working electrode will be kept at constant potential that analyte’s quantitative reduction or
oxidation occurs without simultaneously reducing or oxidizing other species in the solution

• The current flowing through the cell is proportional to the analyte’s concentration. As the reactants are
consumed, the current decreases. When the reaction is complete,the current is negligible.

• The quantity of electricity is usually measured with an electronic integrator.

Controlled potential coulometry
➢ An analysis of this kind has all the advantages of an electrogravimetric method, but it is not necessary to weigh a product. The
technique can therefore be applied to systems that yield deposits with poor physical properties as well as to reactions that yield no
solid product at all. For example, arsenic may be determined coulometrically by the electrolytic oxidation of arsenous acid
(H3AsO3,) to arsenic acid (H3As04) at a platinum anode. Similarly, the analytical conversion of iron(lI) to iron(lII) can be
accomplished with suitable control of the anode potential.
➢ controlled-potential coulometry is carried out in
small-volume electrochemical cells, using electrodes with large surface areas
with high stirring rates.
Instrumentation:
•The instrumentation for potentiostatic coulometry consists
of an:
•electrolysis cell,
•a potentiostat and
•an electronic integrator for determining the
charge consumed.

Potentiostat is an electronic device that maintains the

potential of a working electrode at a constant level with a
feedback circuitry which adjust the potential of the
variable DC voltage source to maintain Ew - Eref constant

Working electrode is where the electrolysis takes place. Ew is fixed vs the Eref • Two types of working electrodes are commonly used:
• a Pt electrode manufactured from platinum-gauze and fashioned into a cylindrical tube, and
• an Hg pool electrode
Ref. electrode is
often either
SCE or Ag/AgCl
connected to
bulk solution by a
salt bridge
• Auxiliary electrode is part of the other half-cell and it is often made from the same material as the working electrode

• Usually separated from the solution in contact with the working electrode to prevent reaction between species produced at Aux.
Electr. and species in the bulk of solution
•
The auxiliary electrode, which is often a Pt wire, is separated by a salt bridge from the
solution containing the analyte.

• This is necessary to prevent electrolysis products generated at the auxiliary electrode from
reacting with the analyte and interfering in the analysis.

• A saturated calomel or Ag/AgCI electrode serves as the reference electrode.

• A means of determining the total charge passed during electrolysis. One method is to monitor
the current as a function of time and determine the area under the curve.

• Modern instruments, however, use electronic integration to monitor charge as a function of

time. The total charge can be read directly from a digital readout or from a plot of charge
versus time
 FIGURE 24-6 Schematic of a system for controlled-potential coulometry.
(a) Equivalent circuit. (b)Resistances within the cell. The cell current Ic passes to the integrator readout module, which provides a number
proportional to the total quantity of charge that passes through the cell.

Rs: cell resistance between counter electrode and tip of the reference electrode Ru: uncompansated cell resistance between the ref. Elec. And working
electr.

Controlled-Current (amperostatic) Coulometry:

• The current is kept constant until an indicator signals completion of the analytical reaction.

• The quantity of charge required to attain the end point is calculated from the magnitude of the
current and the time of its passage. Q=i x t
 • Controlled-current coulometry, also known as amperostatic coulometry or coulometric titrimetry

– When called coulometric titration, electrons serve as the titrant.

– An example is the titration of halides by silver ions produced at a silver anode.

• The current in a coulometric titration is carefully maintained at a constant and accurately known level by means of an amperostat.

• Controlled-current coulometry, has two advantages over controlled-potential coulometry.

– First, using a constant current leads to more rapid analysis since the current does not decrease over time. Thus, a
typical analysis time for controlled current coulometry is less than 10 min, as opposed to approximately 30-60 min
for controlled-potential coulometry.

– Second, with a constant current the total charge is simply the product of current and time. A method for integrating
the current-time curve, therefore, is not necessary.
Experimental problems with constant current coulometry
1) as electrolysis occurs the analyte's concentration and, therefore, the current due to its oxidation or reduction steadily decreases.

– To maintain a constant current the cell potential must change until another oxidation or reduction reaction can occur at the working
electrode.

– Unless the system is carefully designed, these secondary reactions will produce a current efficiency of less than 100%.

• Second problem is the need for a method of determining when the analyte has been exhaustively electrolyzed.
– In controlled-potential coulometry this is signaled by a decrease in the current to a constant background or residual current.

• In controlled-current coulometry, a constant current continues to flow even when the analyte has been completely oxidized or reduced. A
suitable means of determining the end-point of the reaction, is needed. Most of the end-point detection methods applicable to volumetricanalysis
 are equally satisfactory here. Visual observations of color changes of indicators, as well as potentiometric, amperometric, and photometric
measurements have all been used successfully.

Instrumentation
• Controlled-current coulometry normally is carried out using a
amperostat and an electrochemical cell consisting of a working
electrode and a counter electrode.

• The working electrode is constructed from Pt, is also called the

generator electrode since it is where the mediator reacts to generate
the species reacting with the analyte.
Should have a large surface area

• The counter electrode is isolated from the analytical solution by a salt

bridge or porous frit to prevent its electrolysis products from reacting
with the analyte.
Method for the external generation of oxidizing and
reducing
 agents in coulomtric titration

• The other necessary instrumental component for controlled-current coulometry is an accurate clock
for measuring the electrolysis time, te, and a switch for starting and stopping the electrolysis.
 • Analog clocks can read time to the nearest ±0.01 s, but the need to frequently stop and start the
electrolysis near the end point leads to a net uncertainty of ±0.1 s.

• Digital clocks provide a more accurate measurement of time, with errors of ±1 ms being possible.
• The switch must control the flow of current and the clock, so that an accurate determination of the
electrolysis time is possible.
Applications of Coulometric Titrations:

a) Can be used for Acid-Base Titrations

b.) Can be used for Complexation Titrations (EDTA)

c.) Can be used for Redox Titrations

Ce3+ ↔ Ce4+ + e-

Ce4+ + Fe2+ ↔ Ce3+ + Fe3+

Comparison of Coulometric and Volumetric Titrations

• Both require a detectable end point and are subject to a titration error as a consequence
• regarding the apparatus and solutions employed:
– The timer and switch correspond closely to the buret, the switch performing the same function as a stopcock.

• Coulometry, advantages is the elimination of problems associated with the preparation, standardization, and storage of standard
solutions. (instability of Br, Cl and Ti)
• With coulometry, by proper choice of current, microquantities of a substance can be introduced with ease and accuracy

• the coulometric method adapts easily to automatic titrations, because current can be controlled quite easily.

Coulometric titrations are subject to five potential sources of error:

(1) variation in the current during electrolysis,

(2) departure of the process from 100% current efficiency,
(3) error in the current measurement,
(4) Error in the measurement of time, and
(5) titration error due to the difference between the equivalence point and the end point.

The last of these difficulties is common to volumetric methods as well. For situations in which the indicator error is the limiting
factor, the' two methods are likely to have comparable reliability.
Quantitative calculations:Example 1

• The purity of a sample of Na2S2O3 was determined by a coulometric redox titration using I- as a
mediator, and 13- as the "titrant“. A sample weighing 0.1342 g is transferred to a 100-mL volumetric
flask and diluted to volume with distilled water. A 10.00-mL portion is transferred to an
electrochemical cell along with 25 ml, of 1 M KI, 75 mL of a pH 7.0 phosphate buffer, and several
drops of a starch indicator solution. Electrolysis at a constant current of 36.45 mA required 221.8 s to
reach the starch indicator end point. Determine the purity of the sample.
 Example 2

• A 0.3619-g sample of tetrachloropicolinic acid, C6HNO2CI4, is dissolved in distilled water,

transferred to a 1000-ml, volumetric flask, and diluted to volume. An exhaustive controlled-
potential electrolysis of a 10.00-mL portion of this solution at a spongy silver cathode
requires 5.374 C of charge. What is the value of n for this reduction reaction?