Electrolysis and Electrolytic cell
Preferential Discharge Theory
If an electrolytic solution consists of more than two ions and the electrolysis is done, it is observed that all the ions are not discharged at the electrodes simultaneously but certain ions are liberated at the electrodes in preference to others. This is explained by preferential discharge theory. It states that if more than one type of ions are attracted towards a particular electrode, then the one discharged is the ion which requires least energy. The potential at which the ion is discharge or deposition potential. The values of discharge potential are different for different ions. For example, the discharge potential of H+ ions is lower than Na+ ions when platinum or most of the other metals* are used as cathodes. Similarly, discharge potential of Cl-ions is lower than that of OH-ions. This can be explained by some examples given below:
(i)  Electrolysis of sodium chloride solution:
The solution of sodium chloride besides Na+and Cl-ions possesses H+and OH-ions due to ionization of water. However, the number is small as water is a weak electrolyte. When potential difference is established across the two electrodes, Na+and H+ions move towards cathode and Cl-and OH-ions move towards anode. At cathode H+ions are discharged in preference to Na+ions as the discharge potential of H+ions is lower than Na+ions. Similarly at anode, Cl-ions are discharged in preference to OH-ions.
NaCl <--> Na++ Cl-
H2O <--> H++ OH-
 At cathode  At Anode
 H++ e---> H Cl---> Cl + e-
	 2H --> H2            	 2Cl --> Cl2
Thus, Na+and OH-ions remain in solution and the solution when evaporated yields crystals of sodium hydroxide.
(ii)  Electrolysis of copper sulphate solution using platinum electrodes:
CuSO4<--> Cu2++ SO42-
H2O <--> H++ OH-
 At cathode  At Anode
 Cu2++ 2e---> Cu 2OH---> H2O + O + 2e-
	 O + O --> O2
Copper is discharged at cathode as Cu2+ions have lower discharge potential than H+ions. OH-ions are discharged at anode as these have lower discharge potential than ions. Thus, copper is deposited at cathode and oxygen gas is evolved at anode.

(iii) Electrolysis of sodium sulphate solution using inert electrodes:
Na2SO4<--> 2Na++ SO42-
H2O <--> H++ OH-
 At cathode  At Anode
 H++ e---> H 2OH---> H2O + O + 2e-
	 2H --> H2 O + O --> O2
Hydrogen is discharged at cathode as H+ ions have lower discharge potential than Na+ions. OH-ions are discharged at anode as these have lower discharge potential than ions. Thus, hydrogen is evolved at cathode and oxygen is evolved at anode, i.e., the net reaction describes the electrolysis of water. The ions of Na2SO4conduct the current through the solution and take no part in the overall chemical reaction.
The decreasing order of discharge potential or the increasing order of deposition of some of the ions is given below:
For cations:K+, Na+, Ca2+, Mg2+, Al3+, Zn2+, H+, Cu2+, Hg2+, Ag+
For anions:SO42-, NO3-, OH-, Cl-, Br-, I-
(iv)  Electrolysis of copper sulphate solution using copper electrodes:
CuSO4<--> Cu2++ SO42-
 At cathode, copper is deposited.
 Cu2++ 2e-Cu
 At anode, the copper of the electrode is oxidised to Cu2+ions or ions solution dissolve equivalent amount of copper of the anode.
 Cu Cu2++ 2e-
or  Cu +  CuSO4+ 2e-
 Thus, during electrolysis, copper is transferred from anode to cathode.
(v)  Electrolysis of silver nitrate solution using silver electrodes:
AgNO2<--> Ag++ NO42-
At cathode, silver is deposited.
 Ag++ e---> Ag
At anode, the silver of the electrode is oxidised to Ag+ions which go into the solution or ions dissolve equivalent amount of silver of the electrode.
  Ag --> Ag++ e-
 Ag + NO3---> AgNO3+ e-
 Table 12.1 Some more examples of electrolysis
Electrolyte
Electrode
Cathodic reaction
Anodic reaction
Aqueous acidified CuCl2solution
Molten PbBr2
Sodium chloride solution
Silver nitrate solution
Sodium nitrate solution
Pt
Pt
Hg
Pt


Pt
 Cu2++ 2e---> Cu
 Pb2++ 2e---> Pb
 2Na++ 2e---> 2Na

 Ag++ e---> Ag


 2H++ 2e---> H2
 2Cl---> Cl2+ 2e-


 2br---> Br2+ 2e-
 2Cl---> Cl2+ 2e-

 2OH--->
1/2 O2+ H2O + 2e-
 2OH--->
1/2 O2+ H2O + 2e-


Thanks & Regards
Rinkoo Gupta
AskIITians Faculty