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17.7 Electrolysis  (Page 2/7)

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Now consider the cathode. Three reductions could occur:

( iii ) 2H + ( a q ) + 2 e − ⟶ H 2 ( g ) E cathode ° = 0 V ( iv ) 2H 2 O ( l ) + 2 e − ⟶ H 2 ( g ) + 2 OH − ( a q ) E cathode ° = −0.8277 V ( v ) Na + ( a q ) + e − ⟶ Na ( s ) E cathode ° = −2.71 V

Reaction (v) is ruled out because it has such a negative reduction potential. Under standard state conditions, reaction (iii) would be preferred to reaction (iv). However, the pH of a sodium chloride solution is 7, so the concentration of hydrogen ions is only 1 × 10 −7 M . At such low concentrations, reaction (iii) is unlikely and reaction (iv) occurs. The overall reaction is then

overall: 2 H 2 O ( l ) + 2 Cl − ( a q ) ⟶ H 2 ( g ) + Cl 2 ( g ) + 2 OH − ( a q ) E cell ° = −2.186 V

As the reaction proceeds, hydroxide ions replace chloride ions in solution. Thus, sodium hydroxide can be obtained by evaporating the water after the electrolysis is complete. Sodium hydroxide is valuable in its own right and is used for things like oven cleaner, drain opener, and in the production of paper, fabrics, and soap.

Electroplating

An important use for electrolytic cells is in electroplating    . Electroplating results in a thin coating of one metal on top of a conducting surface. Reasons for electroplating include making the object more corrosion resistant, strengthening the surface, producing a more attractive finish, or for purifying metal. The metals commonly used in electroplating include cadmium, chromium, copper, gold, nickel, silver, and tin. Common consumer products include silver-plated or gold-plated tableware, chrome-plated automobile parts, and jewelry. We can get an idea of how this works by investigating how silver-plated tableware is produced ( [link] ).

This figure contains a diagram of an electrochemical cell. One beakers is shown that is just over half full. The beaker contains a clear, colorless solution that is labeled “A g N O subscript 3 ( a q ).” A silver strip is mostly submerged in the liquid on the left. This strip is labeled “Silver (anode).” The top of the strip is labeled with a red plus symbol. An arrow points right from the surface of the metal strip into the solution to the label “A g superscript plus” to the right. A spoon is similarly suspended in the solution and is labeled “Spoon (cathode).” It is labeled with a black negative sign on the tip of the spoon’s handle above the surface of the liquid. An arrow extends from the label “A g superscript plus” to the spoon on the right. A wire extends from the top of the spoon and the strip to a rectangle labeled “Voltage source.” An arrow points upward from silver strip which is labeled “e superscript negative.” Similarly, an arrow points down at the right to the surface of the spoon which is also labeled “e superscript negative.” A plus sign is shown just outside the voltage source to the left and a negative is shown to its right.
The spoon, which is made of an inexpensive metal, is connected to the negative terminal of the voltage source and acts as the cathode. The anode is a silver electrode. Both electrodes are immersed in a silver nitrate solution. When a steady current is passed through the solution, the net result is that silver metal is removed from the anode and deposited on the cathode.

In the figure, the anode consists of a silver electrode, shown on the left. The cathode is located on the right and is the spoon, which is made from inexpensive metal. Both electrodes are immersed in a solution of silver nitrate. As the potential is increased, current flows. Silver metal is lost at the anode as it goes into solution.

anode: Ag ( s ) ⟶ Ag + ( a q ) + e −

The mass of the cathode increases as silver ions from the solution are deposited onto the spoon

cathode: Ag + ( a q ) + e − ⟶ Ag ( s )

The net result is the transfer of silver metal from the anode to the cathode. The quality of the object is usually determined by the thickness of the deposited silver and the rate of deposition.

Quantitative aspects of electrolysis

The amount of current that is allowed to flow in an electrolytic cell is related to the number of moles of electrons. The number of moles of electrons can be related to the reactants and products using stoichiometry. Recall that the SI unit for current ( I ) is the ampere (A), which is the equivalent of 1 coulomb per second (1 A = 1 C s ). The total charge ( Q , in coulombs) is given by

Questions & Answers

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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