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Chang, 6th Edition, Chapter 19, Worksheet #4

S. B. Piepho, Spring 1999

Electrolysis Many nonspontaneous reactions may be forced to occur electrolytically. All that is required are two electrodes, a battery, and a conducting solution. Graphite pencil leads work well as electrodes since they are excellent conductors and are non-reactive. To produce an electrolytic cell, graphite electrodes are hooked up to the terminals of a nine-volt battery and then dipped in an electrolyte solution in a Petri dish. A battery is a voltaic cell and thus has a positive cell potential (Ecell). The spontaneous reaction occurring in the battery pumps electrons out of the negative battery terminal and pulls electrons into the positive battery terminal. Thus reduction in the solution in the Petri dish occurs at the electrode attached to the (-) terminal, and oxidation occurs at the electrode attached to the (+) terminal. The cell potential of the solution being electrolyzed is always negative since the reaction is nonspontaneous. If the battery is to be successful in forcing this nonspontaneous reaction to occur, the battery voltage must be large enough to overcome the negative electrolytic cell potential so that the sum of the battery potential and electrolytic cell potential is greater than zero. In practice, some "overvoltage" is also required. A nine volt battery gives sufficient voltage to electrolyze most solutions of interest. Predicting Electrolysis Products To predict the products of electrolysis, begin by writing down all the possible reactants that are present in significant amounts in the solution being electrolyzed (we assume here that the electrodes themselves are inert). A possible reactant that it is easy to forget about is water! Water can be either oxidized or reduced (or both!): Reduction: 2 H2O + 2 e- H2(g) + 2 OH-(aq) Eored = - 0.83 v ( - 0.42 v at pH = 7) Eoox = - 1.23 v ( - 0.81 v at pH = 7) (1)

Oxidation:

2 H2O O2(g) + 4 H+(aq) + 4 e-

(2)

Note that both of these reactions have a gaseous product, but the reduction of water produces OH - (aq) while the oxidation of water produces H+(aq). Other possible reactants are the dissolved anions and cations in the solution. Metal ions are good candidates for reduction (see Chang, Table 19.1, pg 766), while halide ions are good candidates for oxidation: 2 Cl-(aq) Cl2(g) + 2 e2 Br-(aq) Br2(l) + 2 e2 I-(aq) I2(s) + 2 eEoox = - 1.36 v Eoox = - 1.07 v Eoox = - 0.53 v (3) (4) (5)

All three halogens are easily detected. Chlorine, Cl2(g), is recognized by the observation of gas 1

S. B. Piepho, Spring 1999

bubbles and its distinctive odor. Bromine dissolved in water gives a yellowish color, while in cyclohexane it turns orange. Iodine dissolved in water gives a reddish-brown color, while it turns lavender in cyclohexane. If sufficient iodine is produced, crystals of I2(s) will form on the anode: these look metallic. If more than one reactant is available for reduction, the one with the highest Eored potential is most likely to be reduced. Similarly, if more than one reactant is available for oxidation, the one with the most positive (least negative) Eoox potential is most likely to be oxidized. However, if two possible reduction reactions have similar Eored values, kinetic effects may become the deciding factor; either reduction reaction, or both, may occur. The same applies if two possible oxidation reactions have Eoox values which are close. Careful observation and testing of products is essential to determine which oxidation and reduction reactions have occurred. ______________________________________________________________________________ Exercises 1. A student has run an electrolysis reaction of an aqueous solution of MgBr2(aq) in a petri dish using inert electrodes and a 9 volt battery. Observations are made and the following data is recorded: At the electrode attached to the (-) terminal of the battery, bubbles are observed. A white precipitate forms around the electrode. At the electrode attached to the (+) terminal of the battery, a small amount of bubbles are also observed. The solution near the electrode has turned yellowish. When a few drops of the yellowish liquid are mixed with cyclohexane, an orange layer forms at the top of the mixture. When a few drops of phenolphthalein are added to the petri dish, a magenta pink color is observed near the electrode attached to the (-) terminal of the battery. Account for all the observations above. Write equations for the redox reactions which occurred and account for the colors, precipitate, and bubbles.

Answer: At the cathode (the (-) terminal) the possible reductions are: 2 H2O + 2 e- H2(g) + 2 OH-(aq) Mg+2 + 2 e - Mg(s) At the anode (the (+) terminal) the possible oxidations are: 2 Br (aq) Br2(l) + 2 e2 H2O O2(g) + 4 H+(aq) + 4 e-

Eored = - 0.83 v Eored = - 2.37 v

( - 0.42 v at pH = 7)

Eoox = - 1.07 v Eoox = - 1.23 v ( - 0.81 v at pH = 7)

The reduction reaction which occurs is usually the one with the more (+) Eored, and the oxidation reaction is usually the one with the more (+)Eoox. Thus here we expect that H2O is reduced at the cathode and Br - (aq) is oxidized at the anode. The data indicates, however, that some H2O is also oxidized at the anode. This is not surprising since the Eoox values are close.

S. B. Piepho, Spring 1999

The bubbles at the (-) terminal are due to H2(g) and the white precipitate is Mg(OH)2(s). The magenta pink color at the (-) electrode is due to phenolphthalein which turns that color in the presence of OH (aq), one of the products of the reduction of H2O. The small amount of bubbles at the (+) electrode are O2(g). The other product at the (+) electrode is Br2 which is yellowish in water but turns orange when dissolved in an organic solvent such as cyclohexane. The cyclohexane layer is on top since cyclohexane is less dense than water.

______________________________________________________________________________ 2. Suppose that molten MgBr2(l) is electrolyzed. What reactions would take place, and what is the minimum emf required for reaction?

Answer: No water is present in a molten salt, so only the salt ions are available to react. Thus, Mg+2 would be reduced: Mg+2 + 2 e - Mg(s) Eored = - 2.37 v would be oxidized: 2 Br (aq) Br (l) + 2 e_ Br Eoox = - 1.07 v 2 The minimum emf required is equal to - Eocell = - (Eored + Eoox) = - (- 2.37 v + - 1.07 v) = + 3.44 v