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Electrochemistry is the study of phenomena at electrode-solution interfaces
Two quite different aspects of the field of electrochemistry
An introduction to redox equilibria and electrode potentials
The more negative the value, the stronger reducing agent the metal is.
The more positive the value, the stronger oxidising agent the metal ion is.
33 V). • A solution containing dichromate(VI) ions in acid is almost as strong an oxidising agent (E° = +1.Redox Potentials for non-metal and other systems • Chlorine gas is the strongest oxidising agent (E° = +1. • None of these three are as strong an oxidising agent as Au3+ ions (E° = +1. .77 V).50 V). • Iron(III) ions are the weakest of the three new ones (E° = +0.36 V).
.Looking at this from an equilibrium point of view Suppose you have a piece of magnesium in a beaker of water. The electrons will be left behind on the magnesium. There will be some tendency for the magnesium atoms to shed electrons and go into solution as magnesium ions.
A dynamic equilibrium will be established when the rate at which ions are leaving the surface is exactly equal to the rate at which they are joining it again. .
.At that point there will be a constant negative charge on the magnesium. and a constant number of magnesium ions present in the solution around it.
but there will be less charge on the metal. You will still reach an equilibrium position. . and fewer ions in solution. Any ions which do break away are more likely to reclaim their electrons and stick back on to the metal again.Copper is less reactive and so forms its ions less readily.
an equilibrium is set up between hydrogen molecules and hydrogen ions in solution.standard hydrogen electrode As the hydrogen gas flows over the porous platinum. . The reaction is catalysed by the platinum.
.The standard hydrogen electrode is attached to the electrode system you are investigating .for example. a piece of magnesium in a solution containing magnesium ions.
Magnesium has a much greater tendency to form its ions than hydrogen does. That means that there will be a much greater build-up of electrons on the piece of magnesium than on the platinum. The position of the magnesium equilibrium will be well to the left of that of the hydrogen equilibrium. .
What if you replace the magnesium half cell by a copper one? .
.standard electrode potentials • The standard electrode potential of a metal / metal ion combination is the electro-motive force (emf) measured when that metal / metal ion electrode is coupled to a hydrogen electrode under standard conditions.
In the copper case: .
The two equilibria which are set up in the half cells are: .
.Obviously. and copper is the (relatively) positive one. the voltmeter will show that the zinc is the negative electrode.
(a) Galvanic and (b) electrolytic cells .
Scope Introduction of electrochemistry Introduction – Investigation of chemical phenomena associated with a charge transfer reaction – To assure electroneutrality two (or more) halfreactions take place in opposite directions (oxidation/reduction) – If the sum of free energy changes at both electrodes is negative electrical energy is released battery – If it is positive. external electrical energy has to be supplied to oblige electrode reactions electrolysis .
called the reference electrode. and the electrode at which it occurs is called the working (or indicator) electrode. coupled with an electrode that approaches an ideal nonpolarizable electrode of known potential. the current is passed between the working electrode and an auxiliary(or counter) electrode. Most of the time one is interested in only one of these reactions. which describe the real chemical changes at the two electrodes. In experiments. • . Three electrodes are frequently placed in three compartments separated by a sintered-glass disk.Reactions and electrodes • • The overall chemical reaction taking place in a cell is made up of two independent half-reactions.
. • The reference electrode acts as a reference point for the redox couple. A Luggin capillary is often used to position the sensing point of a reference electrode to a desired point in a cell.Reference electrode: • A reference electrode is used in measuring the working electrode potential of an electrochemical cell.
242 V vs. ● The internationally accepted primary reference is the standard hydrogen electrode (SHE) or normal hydrogen electrode (NHE). SCE is Hg/Hg2Cl2/KCl (sat’d in water).Reference electrode ● The potential of the working electrode is monitored relative to a separate reference electrode. NHE. positioned with its tip near the working electrode.aqueous) ●By far the most common reference is the saturated calomel electrode (SCE) and the Silver/Silver Chloride (Ag/AgCl) electrodes. . Its potential is 0. which is Pt/H2(a=1)/H+(a=1.
.The device minimizes any iR drop in the electrolyte associated with the passage of current in an electrochemical cell.
This potential drives the electrochemical reaction at the working electrode's surface.working electrode A fixed potential difference is applied between the working electrode and the reference electrode. . The current produced from the electrochemical reaction at the working electrode is balanced by a current flowing in the opposite direction at the counter electrode.
gold. Originally the carbon paste electrode was developed but this was soon replaced by more "convenient" and stable carbon-based working electrodes including those made from glassy carbon. gold-amalgam and a variety of alloys are now also commonly used as working electrode materials. pyrolytic carbon and porous graphite. .Materials of working electrode • A wide variety of working electrodes are now available. nickel. silver. Metals such as platinum. mercury.
including the usable applied potential range.Choice of working electrode • Carbon paste electrodes cannot be used with mobile phases containing high amounts of organic modifier because the electrode will dissolve unless a polymeric binder is used. involvement of the electrode in the redox reaction. . • The optimal working electrode choice is dependent upon many factors. and kinetics of the electron transfer reaction.
Three-electrode cell and notation for the different electrodes .
• The applied potential to the working electrode is dependent upon both the working electrode material and the pH of the mobile phase. For example. .Potential window • A working electrode will only function within a defined potential window. a silver/silver chloride reference electrode. electrolysis of many compounds will readily occur on a glassy carbon working electrode up to approximately 1300mV vs.
The potential window of various working electrodes under acidic and basic conditions. .
To drive the electrolytic reaction at a faster rate a much higher potential or "overpotential" must be used.Kinetics of the Electron Transfer Reaction • Electron-transfer reactions can be either kinetically fast or slow. For slow reactions not all of the analyte reaching the working electrode's surface will have time to react. It is usually found that organic species react more favorably on one particular working electrode material than another. For a fast reaction most of an analyte will react at the working electrode's surface. .
. (3)Chemical reactions preceding or following the electron transfer. from the bulk solution to the electrode surface). (2) Electron transfer at the electrode surface. ◆ The magnitude of this current is often limited by the inherent sluggishness of one or more reactions called rate-determining steps.g. (4)Other surface reactions.Factors affecting electrode reaction rate In general.. the electrode reaction rate is governed by rates of processes such as: (1) Mass transfer (e.
Conditions for electrochemical experiments .Reproducible experimental conditions must be given Interfering side effects must be avoided as Migration effects High solution resistance -these effects can be minimised by adding an inert supporting electrolyte (around 1 mol/L) Undefined or large diffusion layer – A complete study of the electrode process requires the measurement of kinetic as well as thermodynamic parameters.
. . and the structure of the electrode-solution interface can change with changing potential or solution composition. processes such as adsorption and desorption can occur.Faradaic and nonfaradaic processes • Charges (e. these processes are called nonfaradaic processes. Since these reactions are governed by Faraday’s law.g. electrons) are transferred across the electrode-solution interface and causes oxidation or reduction to occur. • Under some conditions. they are called faradaic processes.
and a charge in the solution. charge will accumulate on its electrode plates.Capacitance and charge of an electrode • The behavior of the electrode-solution interface is analogous to that of a capacitor. qM. qM=-qs. • At a given potential the electrode-solution interface is characterized by a double-layer capacitance. • At a given potential there will exist a charge on the metal electrode. typically in the range of 10 to 40μF/cm2. When a potential is applied across a capacitor. . At all times. Cd. qs.
(2) a sink of electrons transferred from species in solution (anode) oxidation The amount of electrons transferred is related to the current flowing between the two electrodes • .The nature of electrode reactions • • • • Electrode reactions are heterogeneous and take place in the interfacial region between electrode and solution diffusion layer The charge separation at each electrode is represented by a capacitance the difficulty of charge transfer by a resistance The electrode can act as (1) a source of electrons (cathode) reduction .
Thermodynamics and kinetics • Thermodynamics and kinetics – The potential at which a reduction or oxidation takes place (measured relative to the normal hydrogen electrode) is given by the Nernst equation E = E0 – (RT/nF) i ln ci i : stoichiometric numbers: positive for reduced species. negative for oxidised species E0 : standard electrode potential ci : concentration (ai has to be applied if activity coefficient is not 1) .
Thermodynamics and kinetics ●The concentration of species at the electrode interface depends on its mass transport coefficient kd ●The rate of the electrode reaction is expressed by the standard rate constant kf0 which is the rate when E = E0 – reversible reaction kf0 >> kd – irreversible reversible reaction kf0 << kd. an overpotential has to be applied additionally to overcome this kinetic barrier ●A behaviour in between these extremes is called quasireversible reaction .
L. Electrochemical Methods—Fundamentals and Applications. . New York: John Wiley & Sons.1980. Bard.R.Reference • A.J. Faulkner.