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Electrochemistry 1
Electrochemistry 1
ELECTROCHEMISTRY
&
CORROSION
Electrochemistry
Electrochemical
cell
Electrolytic
cell
Electrolytic cell Electrical energy
NaCl → Na + + Cl -
Anode - Oxidation
Cl - → Cl + e
Cl + Cl → Cl2
Cathode - Reduction
Na + + e → Na
Anode
Zn → Zn 2+ + 2e
Cathode
Cu 2+ + 2e → Cu
Net reaction
Zn + Cu 2+ → Zn 2+ + Cu
Single electrode potential
▪ Double layer formed is known as Helmholtz electrical double layer
▪ A difference in potential is set up between the metal and the solution – Single
electrode potential
▪ The tendency of the electrode to lose electrons – Oxidation potential
▪ The tendency of the electrode to gain electrons – Reduction potential
▪ This potential difference is constant at equilibrium
▪ The potential difference developed when a metal is in contact with its own salt
solution of concentration 1M at 25oC – Standard electrode potential
▪ In general reduction potential is taken as the electrode potential
Electrochemical Series / Activity Series
❖Reactivity of metals-
From top to bottom reactivity decreases
❖Displacement reaction- metals above in the series(low E0) can displace a metal below
it from its salt solution.
Eg- Zn can displace Cu from CuSO4 solution
Zn + CuSO4 → ZnSO4 + Cu
❖Reaction with H2 - metals having negative E0 value can
liberate from dil.acids
Case1 [Zn 2+ ] = [Cu 2+ ] , Q=1 logarithmic term-zero Ecell = E0 cell EMF is independent on temperature
Case2 [Zn 2+ ] > [Cu 2+ ] Q >1 logarithmic term-negative Ecell < E0 cell EMF decreases with rise of temperature
Case3 [Zn 2+ ] < [Cu 2+ ] Q <1 logarithmic term-positive Ecell > E0 cell EMF increases with rise of temperature
Variation of EMF of hydrogen electrode with pH of solution
For hydrogen electrode at 250C H+ + e → ½ H2
E = E 0 - .0591 log 1
[H+ ]
E = E 0 - .0591 pH
E = 0 - .0591 pH = -.0591pH
E = E 0 - .0591 log 4
4
E = E 0 - .0591 pH = 1.23 - .0591 pH
▪ Finding the valency of an ion or the number of electrons involved in a electrode reaction
iv. Redox electrode- Pt dipped in a solution containing mixture of FeCl2 and FeCl 3
Reduction Oxidation
H+ + e → ½ H 2 ½ H2 → H+ + e
Limitations
▪ Very cumbersome to set up
▪ Requires considerable volume of solution
▪ Hydrogen electrode will be poisoned by compounds like Hg ,As ,S etc
▪ Difficult to maintain pressure of H2 gas at 1 atm and conc 1M HCl
Calomel electrode • Secondary reference electrode
• Metal/insoluble metal salt/common ion electrode
• Hg/Hg2Cl2(s)/KCl
Reduction
Hg2Cl 2(s) + 2e → 2Hg(l) + 2Cl-(aq)
• For measuring the pH of a test solution the glass electrode is immersed in the test
solution and coupled with saturated calomel electrode