Coulometry

Dynamic Electrochemical Methods of analysis Electrolysis 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 called the ohmic potential, concentration overpotential (polarization), and activation overpotential.

Coulometry
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.

Overvoltage or overpotential
The electrochemical cell is polarized if its actual potential is different than that expected according to Nernst equation. The extent of polarization is measured as overpotential = Eapplied Ereversible(equilib) What are the sources of overpotential?

1. Concentration overpotential (polarization)

This takes place when the concentration at the electrode surface is different than that in the bulk solution. This behavior is observed when the rate of electrochemical reaction at the electrode surface is fast compared to the rate of diffusion of electroactive species from the solution bulk to the electrode surface

Example on concentration polarization

Cd Cd2+ + 2e

 The anode potential depends on [Cd2 +]s, not [Cd2 +]o, because [[Cd2 +]s is the actual concentration at the electrode surface. Reversing the electrode reaction to write it as a reduction, the anode potential is given by the equation
E(anode) = E(anode) ( 0.05916/2) log [Cd2+]s

If [Cd2 +]s = [Cd2+]o, the anode potential will be that expected from the bulk Cd2+ concentration. If the current is flowing so fast that Cd2+ cannot escape from the region around the electrode as fast as it is made, [Cd2 +]s will be greater than [Cd2 +]o. When [Cd2 +]s does not equal [Cd2 +]o, we say that concentration polarization exists. The anode will become more positive and the Cell voltage = E (cathode) -E (anode) will decrease.

the straight line shows the behavior expected. When ions are not transported to or from an electrode as rapidly as they are consumed or created, we say that concentration polarization exists if only the ohmic potential (IR) affects the net cell voltage.

 The deviation of the curve from the straight line at high currents is due to concentration polarization. In a galvanic cell, concentration polarization decreases the voltage below the value expected in the absence of concentration polarization. In electrolysis cells, the situation is reversed; reactant is depleted and product accumulates. Therefore the concentration polarization requires us to apply a voltage of greater magnitude (more negative) than that expected in the absence of polarization. Concentration polarization gets worse as [Mn+] gets smaller.

Example on Concentration overpotential

Assume:

Factors that affect concentration polarization

Among the factors causing ions to move toward or away from the electrode are
diffusion, convection, electrostatic attraction or repulsion.

Raising the temperature increases the rate of diffusion and thereby decreases concentration polarization. Mechanical stirring is very effective in transporting species through the cell. Increasing ionic strength decreases the electrostatic forces between ions and the electrode. These factors can all be used to affect the degree of polarization. Also, the greater the electrode surface area, the more current can be passed without polarization.

How can we reduce the concentration overpotential? Increase T Increase stirring Increase electrode surface area: more reaction takes place Change ionic strength to increase or decrease attraction between electrode and reactive ion.

Activation Overpotential
Activation overpotential is a result of the activation energy barrier for the electrode reaction.
The faster you wish to drive an electrode reaction, the greater the overpotential that must be applied. More overpotential is required to speed up an electrode reaction.

How to calculate the potential required to reverse a reaction

Example 1 on electrolysis

Assume that 99.99% of each will be quantitatively deposited Then 0.01% (10-5 M) will be left in the solution Given that:

Example 2

Suppose that a solution containing 0.20 M Cu2+ and 1.0 M H+ is electrolyzed to deposit Cu(s) on a Pt cathode and to liberate O2 at a Pt anode. Calculate the voltage needed for electrolysis. If the resistance of this cell is 0.44 ohm. Estimate the voltage needed to maintain a current of 2.0 A. Assume that the anode overpotential is 1.28 V and there is no concentration polarization.

Example 2

A solution containing 0.1M Cu2+ and 0.1 M Sn2+ calculate:

the potential at which Cu2+ starts deposition. The potential at which Cu2+ is completely deposited (99.99% deposition). The potential at which Sn2+ starts deposition.

Would Sn2+ be reduced before the copper is completely deposited? From the standard potentials given below we expect that Cu2+ be reduced more easily than Sn2+

Cu2+ + 2e- Cu (s);

Eo = 0.339 V

Example 3

Coulometric Methods of Analysis

Potentiometry: Electrochemical cells under static conditions Coulometry, electrogravimetry, voltammetry and amperometry: Electrochemical cells under dynamic methods (current passes through the cell) Coulomteric methods are based on exhaustive elctrolysis of the analyte: that is quantitative reduction or oxidation of the analyte at the working electrode or the analyte reacts quantitatively with a reagent generated at the working electrode A potential is applied from an external source forcing a nonspontaneous chemical reaction to take place ( Electrolytic cell)

Types of Coulometry
1. Controlled potential coulometry: constant potential is applied to electrochemical cell 2. Controlled current coulometry: constant current is passed through the electrochemical cell Faradays law: Total charge, Q, in coulombs passed during electrolysis is related to the absolute amount of analyte: Q = nFN n = #moles of electrons transferred per mole of analyte F = Faradays constant = 96487 C mol-1 N = number of moles of analyte Coulomb = C = Ampere X sec = A.s

 For a constant current, i: (t = electrolysis time) Q = ite ; e For controlled potential coulometry: the current varies with time: Q=

t t e

t 0

i (t )dt

What do we measure in coulometry? Current and time. Q & N are then calculated according to one of the above equations Coulometry requires 100% current efficiency. What does this mean?
All the current must result in the analytes oxidation or reduction

Controlled potential coulometry (Potentiostatic coulometry)

The working electrode will be kept at constant potential that allows for the analyts reduction or oxidation without simultaneously reducing or oxidizing other species in the solution The current flowing through the cell is proportional to the analyts concentration With time the analytes concentration as well as the current will decrease The quantity of electricity is measured with an electronic integrator.

Controlled potential coulometry

Selecting a Constant Potential

The potential is selected so that the desired oxidation or reduction reaction goes to completion without interference from redox reactions involving other components of the sample matrix. Cu2+(aq) + 2e Cu(s)

This reaction is favored when the working electrode's potential is more negative than +0.342 V. To maintain a 100% current efficiency, the potential must be selected so that the reduction of H+ to H2 does not contribute significantly to the total charge passed at the electrode.

Calculation of the potential needed for quantitative reduction of Cu2+

Cu2+ would be considered completely reduced when

99.99% has been deposited. Then the concentration of Cu2+ left would be 1X10-4 [Cu2+ ]0

If [Cu2+ ]0 was 1X10-4 M

then the cathode's potential must be more negative than +0.105 V versus the SHE (-0.139 V versus the SCE) to achieve a quantitative reduction of Cu2+ to Cu. At this potential H+ will not be reduced to H2 I.e., Current efficiency would be 100% Actually potential needed for Cu2+ are more negative than +0.105 due to the overpotential

Minimizing electrolysis time

Current decreases continuous

throughout electrolysis. An exhaustive electrolysis, therefore, may require a longer time The current at time t is i = i0 e-kt i is the initial current k is a constant that is directly proportional to the area of the working electrode rate of stirring and inversely proportional to volume of the solution.

 For an exhaustive electrolysis in which 99.99% of the analyte is oxidized or reduced, the current at the end of the analysis, te, may be approximated i (10-4)io Since i = i0 e-kt
te = 1/k ln (1X10-4) = 9.21/k Thus, increasing k leads to a shorter analysis time. For this reason controlled-potential coulometry is carried out in

A quantitative electrolysis typically requires approximately 30-60 min, although shorter or longer times are possible.

small-volume electrochemical cells, using electrodes with large surface areas with high stirring rates.

Instrumentation

Athree-electrode potentiostat system is used. 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. The large overpotential for reducing H+ at mercury makes it the electrode of choice for analytes requiring negative potentials. For example, potentials more negative than -1 V versus the SCE are feasible at an Hg electrode (but not at a Pt electrode), even in very acidic solutions. The ease with which mercury is oxidized prevents its use at potentials that are positive with respect to the SHE. Platinum working electrodes are used when positive potentials are required.

 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

Controlled-Current Coulometry (amperstatic)

The current is kept constant until an indicator signals completion of the analytical reaction. The quantity of electricity required to attain the end point is calculated from the magnitude of the current and the time of its passage. Controlled-current coulometry, also known as amperostatic coulometry or coulometric titrimetry When called coulometric titration, electrons serve as the titrant.

 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

Using a constant current does present two important experimental problems that must be solved if accurate results are to be obtained. First, 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, te, is needed.

Maintaining Current Efficiency

Why changing the working electrode's potential can lead to less than 100% current efficiency? let's consider the coulometric analysis for Fe2+ based on its oxidation to Fe3+ at a Pt working electrode in 1 M H2S04. Fe2+(aq) = Fe3+(aq) + e The diagram for this system is shown. Initially the potential of the working electrode remains nearly constant at a level near the standard-state potential for the Fe 3+/Fe 2+ redox couple. As the concentration of Fe 2+ decreases, the potential of the working electrode shifts toward more positive values until another oxidation reaction can provide the necessary current. Thus, in this case the potential eventually increases to a level at which the oxidation of H2O occurs. 6H2O(l) O2(g) + 4H3O+(aq) + 4e

 Since the current due to the oxidation of H2O does not contribute to the oxidation of Fe2+, the current efficiency of the analysis is less than 100%. To maintain a 100% current efficiency the products of any competing oxidation reactions must react both rapidly and quantitatively with the remaining Fe2+. This may be accomplished, for example, by adding an excess of Ce3+ to the analytical solution. When the potential of the working electrode shifts to a more positive potential, the first species to be oxidized is Ce3+. Ce3+(aq) = Ce4+(aq) + e The Ce4+ produced at the working electrode rapidly mixes with the solution, where it reacts with any available Fe2+.

 Ce4+(aq) + Fe2+(aq) = Fe 3+(aq) + Ce3+(aq) Combining these reactions gives the desired overall reaction Fe 2+(aq) = Fe3+(aq) + e Thus, a current efficiency of 100% is maintained. Since the concentration of Ce3+ remains at its initial level, the potential of the working electrode remains constant as long as any Fe 2+ is present. This prevents other oxidation reactions, such as that for H2O, from interfering with the analysis. A species, such as Ce3+ which is used to maintain 100% current efficiency is called a Mediator.

End Point Determination

How do we judge that the analyats electrolysis is complete? When all Fe2+ has been completely oxidized, electrolysis should be stopped; otherwise the current continues to flow as a result of the oxidation of Ce3+ and, eventually, the oxidation of H2O. How do we know that the oxidation of Fe 2+ is complete? We monitor the reaction of the rest of iron (II) with Ce (IV) by using visual indicators, and potentiometric and conductometric measurements.

Instrumentation

Controlled-current coulometry normally is carried out using a galvanostat 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. 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. Alternatively, oxidizing or reducing the mediator can be carried out externally, and the appropriate products flushed into the analytical solution.

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.

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?