The Electrolysis of Aqueous NaCl
The figure below shows an idealized drawing of a cell in which an aqueous solution of sodium chloride is electrolyzed.
diagram
Once again, the Na+ ions migrate toward the negative electrode and the Cl- ions migrate toward the positive electrode. But, now there are two substances that can be reduced at the cathode: Na+ ions and water molecules.
Cathode (-):
Na+ + e- ----> Na Eored = -2.71 V
2 H2O + 2 e- ----> H2 + 2 OH- Eored = -0.83 V
Because it is much easier to reduce water than Na+ ions, the only product formed at the cathode is hydrogen gas.
Cathode (-): 2 H2O(l) + 2 e- ----> H2(g) + 2 OH-(aq)
There are also two substances that can be oxidized at the anode: Cl- ions and water molecules.
Anode (+):
2 Cl- ----> Cl2 + 2 e- Eoox = -1.36 V
2 H2O ----> O2 + 4 H+ + 4 e- Eoox = -1.23 V
The standard-state potentials for these half-reactions are so close to each other that we might expect to see a mixture of Cl2 and O2 gas collect at the anode. In practice, the only product of this reaction is Cl2.
Anode (+): 2 Cl- ----> Cl2 + 2 e-
At first glance, it would seem easier to oxidize water (Eoox = -1.23 volts) than Cl- ions (Eoox = -1.36 volts). It is worth noting, however, that the cell is never allowed to reach standard-state conditions. The solution is typically 25% NaCl by mass, which significantly decreases the potential required to oxidize the Cl- ion. The pH of the cell is also kept very high, which decreases the oxidation potential for water. The deciding factor is a phenomenon known as overvoltage, which is the extra voltage that must be applied to a reaction to get it to occur at the rate at which it would occur in an ideal system.
Under ideal conditions, a potential of 1.23 volts is large enough to oxidize water to O2 gas. Under real conditions, however, it can take a much larger voltage to initiate this reaction. (The overvoltage for the oxidation of water can be as large as 1 volt.) By carefully choosing the electrode to maximize the overvoltage for the oxidation of water and then carefully controlling the potential at which the cell operates, we can ensure that only chlorine is produced in this reaction.
In summary, electrolysis of aqueous solutions of sodium chloride doesn't give the same products as electrolysis of molten sodium chloride. Electrolysis of molten NaCl decomposes this compound into its elements.
electrolysis
2 NaCl(l) ----> 2 Na(l) + Cl2(g)
Electrolysis of aqueous NaCl solutions gives a mixture of hydrogen and chlorine gas and an aqueous sodium hydroxide solution.
electrolysis
2 NaCl(aq) + 2 H2O(l) ----> 2 Na+(aq) + 2 OH-(aq) + H2(g) + Cl2(g)
Because the demand for chlorine is much larger than the demand for sodium, electrolysis of aqueous sodium chloride is a more important process commercially. Electrolysis of an aqueous NaCl solution has two other advantages. It produces H2 gas at the cathode, which can be collected and sold. It also produces NaOH, which can be drained from the bottom of the electrolytic cell and sold.
graphic
The dotted vertical line in the above figure represents a diaphragm that prevents the Cl2 produced at the anode in this cell from coming into contact with the NaOH that accumulates at the cathode. When this diaphragm is removed from the cell, the products of the electrolysis of aqueous sodium chloride react to form sodium hypo-chlorite, which is the first step in the preparation of hypochlorite bleaches, such as Chlorox.