Electrolysis - Electrolytic cells - Quantitative aspects of electrolysis

Electrolysis
Electrolysis is the passage of a direct current through an ionic substance that is either molten or dissolved in a suitable solvent, resulting in chemical reactions at the electrodes and separation of materials. The main components required to achieve electrolysis are : An electrolyte : a substance containing free ions which are the carriers of electric current in the electrolyte. If the ions are not mobile, as in a solid salt then electrolysis cannot occur. Electrodes of metal, graphite and semiconductor material are widely used. Choice of suitable electrode depends on chemical reactivity between the electrode and electrolyte and the cost of manufacture.

Process of electrolysis An electrical potential is applied across a pair of electrodes immersed in the electrolyte. Each electrode attracts ions that are of the opposite charge. Positively charged ions (cations) move towards the electron-providing (negative) cathode, whereas negatively charged ions (anions) move towards the positive anode. At the electrodes, electrons are absorbed or released by the atoms and ions. Those atoms that gain or lose electrons to become charged ions pass into the electrolyte. Those ions that gain or lose electrons to become uncharged atoms separate from the electrolyte.

Oxidation and reduction at the electrodes

Oxidation of ions or neutral molecules occurs at the anode, and the reduction of ions or neutral molecules occurs at the cathode. For example, it is possible to oxidize ferrous ions to ferric ions at the anode: Fe2+(aq) Fe3+aq + e

Electrolysis reactions involving H+ ions are fairly common in acidic solutions. In alkaline water solutions, reactions involving OH- (hydroxide ions) are common. The substances oxidised or reduced can also be the solvent (usually water) or the electrodes. It is possible to have electrolysis involving gases.

The Electrolysis of Molten NaCl An idealized cell for the electrolysis of sodium chloride is shown in the figure below. A source of direct current is connected to a pair of inert electrodes immersed in molten sodium chloride. Because the salt has been heated until it melts, the Na+ ions flow toward the negative electrode and the Cl- ions flow toward the positive electrode. When Na+ ions collide with the negative electrode, the battery carries a large enough potential to force these ions to pick up electrons to form sodium metal.

Electrolysis of NaCl:
Negative electrode (cathode): Na+ + eNa

Positive electrode (anode): 2 ClCl2 + 2 eThe net effect of passing an electric current through the molten salt in this cell is to decompose sodium chloride into its elements, sodium metal and chlorine gas. The potential required to oxidize Cl- ions to Cl2 is -1.36 volts and the potential needed to reduce Na+ ions to sodium metal is -2.71 volts. The battery used to drive this reaction must therefore have a potential of at least 4.07 volts.

The Electrolysis of Aqueous NaCl

Cathode (-): Na+ + e2H2O + 2 e-

Na H2 + 2OH-

Eored = -2.71 V 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 (-): Anode (+): 2 H2O(l) + 2 e2 Cl2 H 2O H2(g) + 2 OH-(aq) Eoox = -1.36 V Eoox = -1.23 V

Cl2 + 2 eO2 + 4H+ + 4 e-

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 ClCl2 + 2 e-

Exercise:
1. Write a net ionic equation for the expected reaction when the electrolysis of NiSO4(aq) is conducted using (a) a nickel anode and an iron cathode (b) a nickel anode and an inert platinum cathode (c) an inert platinum anode and a nickel cathode

2. Use electrode potential data to predict the probable products and the minimum voltage required in the elctrolysis with inert electrodes of each of the following:
(a) ZnSO4(aq) (b) MgBr2(l) (c) NaNO3(aq)

Electrolysis of Water A standard apparatus for the electrolysis of water is shown in the figure below.

2 H2O + 2 e2 H2O

H2 + 2OHO2 + 4H+ + 4 e-

Eored = -0.83 V Eoox = -1.23 V

Faraday's Law of Electrolysis The amount of a substance consumed or produced at one of the electrodes in an electrolytic cell is directly proportional to the amount of electricity that passes through the cell. By definition, one coulomb of charge is transferred when a 1-amp current flows for 1 second. 1 C = 1 amp-s
Example: To illustrate how Faraday's law can be used Calculate the number of grams of sodium metal that will form at the cathode when a 10.0-amp current is passed through molten sodium chloride for a period of 4.00 hours. We start by calculating the amount of electric charge that flows through the cell. Amount of charges = 10.0A x (4x3600s) = 144 000C

Faraday's constant = 96 484.56 C/mol Thus, the number of moles of electrons transferred when 144,000 coulombs of electric charge flow through the cell = 144 000/96484.56 mol = 1.49 mole of electrons According to the balanced equation for the reaction that occurs at the cathode of this cell, we get one mole of sodium for every mole of electrons. Cathode (-): Na+ + eNa Thus, we get 1.49 moles, or 34.3 grams, of sodium in 4.00 hours. The consequences of this calculation are interesting. We would have to run this electrolysis for more than two days to prepare a pound of sodium.

Exercise:
1. In the electrolysis of a gold sample to obtain gold, the half reaction at the cathode is Au3+ + 3e Au(s)

What mass of gold can be deposited at the cathode in 1.00 hour by a current of 1.50A?
2. How many grams of silver are deposited at a platinum cathode in the electrolysis of AgNO3(aq) by 1.73A of electric current in 2.05 hr? 3. How many coulomb of electric charge are required to deposit 25.0 g Cu(s) at the cathode in the electrolysis of CuSO4(aq) 4. For how many minutes must the electrolysis of a solution of CuSO4(aq) be carried out, at a current of 2.25A, to deposit 1.00g of Cu(s) at the cathode?