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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.
Looking at this from an equilibrium point of view Suppose you have a piece of magnesium in a beaker of water. There will be some tendency for the magnesium atoms to shed electrons and go into solution as magnesium ions. The electrons will be left behind on the magnesium.
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.
Copper is less reactive and so forms its ions less readily. Any ions which do break away are more likely to reclaim their electrons and stick back on to the metal again. You will still reach an equilibrium position, but there will be less charge on the metal, and fewer ions in solution.
As the hydrogen gas flows over the porous platinum, an equilibrium is set up between hydrogen molecules and hydrogen ions in solution. 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. The position of the magnesium equilibrium will be well to the left of that of the hydrogen equilibrium. That means that there will be a much greater build-up of electrons on the piece of magnesium than on the platinum.
The two equilibria which are set up in the half cells are:
Obviously, the voltmeter will show that the zinc is the negative electrode, and copper is the (relatively) positive one.
Reference electrode:
A reference electrode is used in measuring the working electrode potential of an electrochemical cell. 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
The potential of the working electrode is monitored relative to a separate reference electrode, positioned with its tip near the working electrode. The internationally accepted primary reference is the standard hydrogen electrode (SHE) or normal hydrogen electrode (NHE), which is Pt/H2(a=1)/H+(a=1,aqueous) By far the most common reference is the saturated calomel electrode (SCE) and the Silver/Silver Chloride (Ag/AgCl) electrodes. SCE is Hg/Hg2Cl2/KCl (satd in water). Its potential is 0.242 V vs. NHE.
The device minimizes any iR drop in the electrolyte associated with the passage of current in an electrochemical cell.
working electrode
A fixed potential difference is applied between the working electrode and the reference electrode. This potential drives the electrochemical reaction at the working electrode's surface. 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.
Potential window
A working electrode will only function within a defined potential window. For example, electrolysis of many compounds will readily occur on a glassy carbon working electrode up to approximately 1300mV vs. a silver/silver chloride reference electrode. The applied potential to the working electrode is dependent upon both the working electrode material and the pH of the mobile phase.
The potential window of various working electrodes under acidic and basic conditions.
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.
(cathode) reduction ,(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
E = E0 (RT/nF) i ln ci
i : stoichiometric numbers: positive for reduced species,
negative for oxidised species
Reference
A.J. Bard, L.R. Faulkner, Electrochemical MethodsFundamentals and Applications. New York: John Wiley & Sons,1980.