Channel Electrodes A Review

Jonathan A. Cooper and Richard G. Compton* Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, UK

Submitted by Ganesh Parajuli Roll No: 31 M. Sc. Second Year

Central Department of Chemistry Tribhuvan University Kirtipur, Kathmandu

Contents:
Abstract Introduction Experimental Theory Applications References Acknowledgement

Abstract:
Recent progress in the development of channel electrode voltammetry is reviewed. Both experimental and fundamental aspects are addressed, and the power of the approach is illustrated with a variety of applications.

Introduction:
A channel electrode consists of an electrode embedded smoothly in one wall of a rectangular duct through which electrolyte flows. Such electrodes offer many advantages in diverse application. First, in analytical procedures where their flow-through nature facilitates continuous monitoring. For e.g. Chromatographic Separation

Second their well-defined hydrodynamics permits rigorous mechanistic investigations of electrode processes via voltammetric methods. Third ,they can readily be used for spectroelectrochemistry with little modification. Fourth, the possibility of irradiating the electrode surface through the solution permits photoelectrochemical studies to be readily undertaken in the channel electrode.

Merits of channel electrodes

Channel electrodes offer several clear merits as compared to alternative possible electrode systems. The rate of mass transport is controllable over a very wide range. For example volume flow rates over three orders of magnitude from 104 to over 101 cm3s1 are readily attainable. the mass-transport coefficient can be controlled by altering the cell depth, h, and in particular the electrode length, xe, comparison the range of mass transport rates attainable at alternative hydrodynamic electrodes such as rotating disks is much more limited.

Under laminar flow conditions the flow is well defined and calculable so that electrode processes can be accurately simulated so as to permit discrimination between candidate Mechanisms.This permits the easy interpretation of electrochemical data in terms of a variety of possible mechanisms. The channel electrode is immediately compatible with spectroelectrochemical methods, permitting the ready detection of intermediates and products of electrolytic reactions. The cells are easy to construct for a wide diversity of electrode materials.

Experimental:
The practical design of many channel flow cells, as shown in Figure1,

It consists of first a base-plate. The base-plate has outlet tubes for connecting (normally) to silicone or other tubing, through which the electrolyte solution flows, usually either under gravity or via pumping, but it can also be driven by pressurized gas. The base plate is most commonly made of an inert material such as Teflon, but it can be made of silica for spectroelectrochemical applications. Second there is a top plate of similar dimensions. The top plate can also be silica, as this not only allows for photochemistry to be carried out by shining light onto the surface of the electrode.

The electrode(s) are embedded either into the base-plate or attached to the cover-plate where it can be connected to a lead, either design is Practicable. The electrode itself is situated in the center of the cell, with a slight gap of at least ca. 1mm between it and the edge of the cell to negate any edge-effects and ensure a constant velocity across the width (w) of the cell. The reference electrode is not usually situated directly in the flowing solution, but rather in a compartment with electrolytic connection to the main flow, upstream of the working electrode. The counter electrode is situated downstream, to avoid contamination of the working electrode by any reaction products formed.

Theory
The channel flow cell lends itself particularly well to theoretical modeling since there is a precisely defined, parabolic hydrodynamic flow regime and the dimensions of the cell are accurately determinable. The convention is that the direction of flow is designated as the x-direction and the y-direction is normal to the electrode (see Fig. 1).

Appropriate dimensions are easily and practically designed so that certain conditions (see below) which allow useful simplifications to be made with no significant loss of accuracy. These are introduced later. We start the theoretical discussion with macroelectrodes. The general equation describing diffusion and convection for a species A at an electrode of any dimensions in a channel flow cell is as follows

where a is the concentration of A, D is the diffusion coefficient, x, y and z are the coordinates as defined above and in Figure 1 and vx, vy and vz are the solution velocity profiles in those directions. The equation can be simplified in a number of ways. First at steady state time dependence is removed. Second in case of macroelectrode axial diffusion is neglected.

It can be seen that at faster flow rate, the diffusion layer is smaller. Last, the Leveque approximation may be made which approximates the parabolic flow to a linear one near the electrode surface, where the concentration changes are taking place. For a parabolic flow, where v0 is the velocity at the centre of the channel, and h is the halfheight of the cell. The quadratic y is removed making the flow linear.

Solution of the Mass-Transport Equation

The convective-diffusion equation can now be solved analytically for the case of a transport-limited oxidation/reduction with no coupled kinetics.

The result is the Levich equation

where, in addition to the quantities defined earlier, n is the number of electrons transferred, F the Faraday constant, abulk the bulk concentration of species A, vf the solution volume flow rate, and xe the length of the electrode The reaction scheme for this mechanism in case of an electroreduction is given below

We can define an effective number of electrons transferred, Neff as follows

Under steady state neglecting axial diffusion, and making Leveque approximation the equation tends to

Where,

the response of a channel electrode of arbitrary geometry at any flow rate by a working curve which plots theoretical values of Neff as a function of the normalized parameter Knorm. Since b and c depends only on , and Knorm. the general DISP process

If the second step [k(1)] in the above scheme is rate determining then it is a DISP1 process, whilst if the fourth [k(2)] is rate determining then it is a DISP2 process.

First the limiting current is measured, and from this Neff is determined by comparison with the current expected for a simple one-electron process. The working curves then gives the corresponding values of Knorm for candidate mechanisms, which are assessed by plotting Knorm against the flow rate raised to an appropriate power, depending on the precise nature of the expression for Knorm. For example, for a homogeneous ECE or DISP 1 process, Knorm is plotted against vf 2/3 . A direct dependence consistent with Equation 20 is supportive of the proposed mechanism. If the plot is not a straight line then alternative mechanisms need to be explored. This procedure is repeated until a fit of experimental and simulated data is obtained and the kinetics and mechanism of the system are ascertained. The rate constant can be determined from the slope of the relevant Knorm/flow rate plot.

Some Applications of the Channel Flow Cell

Voltammetric Waveshapes
In the above the use of voltammetric half-wave potentials to give kinetic information was outlined for the specific case of an EC reaction. In other cases the full voltammetric wave shape contains additional useful information about coupled homogeneous kinetics.

Diffusion Coefficients of Electrogenerated Species

Diffusion coefficients of electroactive species can be readily measured in a number of ways voltammetrically, including via the channel flow cell, but measuring the diffusion coefficients of electrochemically generated species, is more difficult. A modified channel flow cell has recently been developed for this purpose. The cell is designed to fit inside an ordinary UV/vis spectrometer, and it is possible to set up a flow system to incorporate the cell. The experiment involves a potential step from a potential where no current flows to one where the limiting current would flow, and the monitoring of an absorbance in the spectrum of the electrogenerated product as a function of time, starting at the time when the step is made.

Spectroelectrochemistry
Channel flow cells can easily be made from optically transparent materials, often silica, to facilitate infra-red or UV/vis spectrometry. One of the simplest applications is to measure the UV/vis spectrum of a radical species.

Photoelectrochemistry
As described above, channel flow cells can be constructed to allow irradiation of the electrode area with UV or visible light. The addition of light to excite species involved in electrochemical processes can often promote further reactions, including electron transfer, bond dissociation, possibly followed by further reduction/ oxidation, disproportionation, or simply enhanced reactivity. Entirely new reaction pathways can be opened up as a result, and novel intermediates and products generated and characterized.

Initial analysis in terms of a DISP2 scheme was unsuccessful, due to the inverse dependence of Knorm on the concentration of 4chlorobiphenyl, as determined from plots of Knorm against (vf)2/3 as discussed generally above. A pure DISP2 scheme would be expected to have a linear dependence on the concentration. Detailed numerical simulation led to the conclusion that if all the steps in the above apply, and that k5[A]>>k7 and k4[A]>>k6, then theory and experiment matched up well.

Acknowledgement:
I am very grateful to respected Asst. Prof. Dr. Amar Prasad Yadav, CDC, for providing me the required articles and for giving me valuable suggestions to complete this work. I am thankful to the Central Department of Chemistry for giving me this opportunity to attend in the seminar. I would also like to acknowledge my dearest friends Mr. Bimal Koirala and Mr. Sanjip Kumar Sapkota for their best efforts in editing and designing this paper.

References
[1] A.M. Waller, R.G. Compton, Comprehensive Chemical Kinetics 1989, 29, 297. [2] R.A.W. Dryfe, R.G. Compton, Prog. Reaction Kinetics 1995, 20, 245. [3] R.G. Compton, J.C. Ball, J.A. Cooper, J.Electroanal. Chem. in press. [4] S.G. Weber, J. Electroanal. Chem. 1987, 222, 117. [5] P.R. Unwin, J. Electroanal. Chem. 1991, 297, 103. [6] K. Tokuda, J. Electroanal. Chem. 1988, 84, 2155. [7] R.G. Compton, P.R. Unwin, J. Electroanal. Chem. 1986, 206, 57. [8] K. Aoki, K. Tokuda, H. Matsuda, J. Electroanal. Chem. 1986, 209, 247.