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BACKGROUND: Different reactivity of metals. Example of magnesium and copper to understand the
reactivity. Electrode potential and its aspects. Need of standard value to calculate electrode potential Standard hydrogen electrode. Standard electrode potentials. Electrode potentials and its measurement. Calculation of cell potentials. Example.
When metals react, they give away electrons and form positive ions. This particular topic sets about comparing the ease with which a metal does this to form hydrated ions in solution.
For example we compare the tendency to lose electrons in magnesium and copper.
These reactions shows the tendency of the two metals to lose electrons.
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.
Some of them will be attracted enough that they will reclaim their electrons and stick back on to the piece of metal
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.
out of the magnesium, you would be left with a situation like this:
between the negativeness of the metal and the positiveness of the solution around it. In the copper case, the difference is much less. This potential difference could be recorded as a voltage - the bigger the difference between the positiveness and the negativeness, the bigger the voltage. Unfortunately, that voltage is impossible to measure!
So consecutively there was need for a standard
equilibrium lies further to the left than the copper one. We need to know that magnesium sheds electrons and forms ions more readily than copper does. That means that we don't need to be able to measure the absolute voltage between the metal and the solution. It is enough to compare the voltage with a standardised system called a reference electrode.
What is happening? 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. This is the equilibrium that we are going to compare all the others with. Standard conditions The position of any equilibrium can be changed by changing conditions. That means that the conditions must be standardised so that you can make fair comparisons. The hydrogen pressure is 1 bar (100 kPa). (You may find 1 atmosphere quoted in older sources.) The temperature is 298 K (25C). The concentration of the hydrogen ions in solution is also important. Changing concentrations is one of the ways of changing the position of an equilibrium. Throughout this topic, all ion concentrations are taken as being 1 mol dm-3.
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
In Case of copper, there is less difference between the electrical charges on the two electrodes, so the voltage measured will be less. This time it is only 0.34 volts. This emf of a cell measured under standard conditions called Standard Electrode Potential and is given the symbol Ecell.
cells are actually the standard electrode potentials of the Mg2+ / Mg and Cu2+ / Cu systems.
electrode is coupled to a hydrogen electrode under standard conditions is known as the standard electrode potential of that metal / metal ion combination.
solution or electrolyte in which it is immersed. The equilibrium potential difference between two conducting phases in contact, most often an electronic conductor such as a metal or semiconductor on the one hand, and an ionic conductor such as an electrolyte solution (a solution containing ions) on the other. In short, it is the interfacial potential difference between the electrode and the electrolyte.
consequence of the transfer of some charge carriers from one conducting phase to the other. For a metal in contact with its metal ions of valence z, the potential difference E can be expressed in terms of a standard potential E and the concentration c of these ions in solution through the Nernst equation, where R is the gas constant, T is the absolute temperature, and F is the Faraday.
Calculation of the half cell potential using standard oxidation or reduction potential and the Nernst Equation. Write one as oxidation and other as reduction. The oxidation potentials above hydrogen in the series have a positive sign while those below these have negative sign. The total cell reaction and cell e.m.f are obtained by the algebraic sum of the half cell reactions and the potentials. A positive cell potential indicates that cell reaction written is spontaneous.
For Zn Zn+2 + 2e
Ecell = 0.762. Therefore for zinc electrode, we calculate the half cell potential from nernst equation as Zn Ecell= -0.7915 For Cu+2 +2e Cu Ecell = 0.345 Similarly from nernst equation Cu Ecell =+0.286 Therefore the total cell potential = Zn Ecell + Cu Ecell.
Zn + Cu+2 Cu + Zn+2 Cell e.m.f = +1.07756 volts. This reaction is spontaneous. In this way we can find out the feasibility of the reactions by using the electrode potentials.
References:
Class discussion Introduction to electrometallurgy and corrosion. By sharan and naryain. Internet search