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Chapter 17. Electrochemistry – part 2. Electrolysis and Electrolytic Cells. Anode: where oxidation takes place Anions are oxidized at this electrode labeled positive to reflect anions attraction to anode Cathode: where reduction takes places Cations are reduced at this electrode
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Chapter 17 Electrochemistry – part 2
Electrolysis and Electrolytic Cells • Anode: where oxidation takes place • Anions are oxidized at this electrode • labeled positive to reflect anions attraction to anode • Cathode: where reduction takes places • Cations are reduced at this electrode • Labeled negative to reflect the cations attraction to cathode
Electrolysis and Electrolytic Cells • Electrolysis: The process of using an electric current to bring about chemical change. • Process occurring in galvanic cell and electrolytic cells are the reverse of each other • In an electrolytic cell, two inert electrodes are dipped into an aqueous solution
Electrolysis and Electrolytic Cells Electrolysis: The process of using an electric current to bring about chemical change.
Quantitative Aspects of Electrolysis Charge(C) = Current(A) × Time(s) 1 mol e Moles of e = Charge(C) × 96,500 C Faraday constant
Example • God can be plated out of a solution containing Au3+ according to the following half-reaction: Au3+(aq) + 3e- Au(s) What mass of gold (in grams) will be plated by the follow of 5.5A of current for 25 minutes?
Example • Silver can be plated out of a solution containing Ag+ according to the following half-reaction: Ag+(aq) + e- Ag(s) How much time (in minutes) would it takes to plate 12.0 g of silver using a current of 3.0A?
Led-acid storage batteries • Consists of six cells wired in series. • Each cell contains a porous lead anode and a lead oxide cathode, both immersed in sulfuric acid. • An electric current is drawn from the battery, both the anode and cathode become coated with PbSO4(s) • Can be recharged by running electric current through it in reverse direction
Batteries Lead Storage Battery Anode: Pb(s) + HSO4(aq) PbSO4(s) + H+(aq) + 2e Cathode: PbO2(s) + 3H+(aq) + HSO4(aq) + 2e PbSO4(s) + 2H2O(l) Overall: Pb(s) + PbO2(s) + 2H+(aq) + 2HSO41(aq) 2PbSO4(s) + 2H2O(l)
Dry-Cell Batteries • Zinc acts as the anode and a graphite rod immersed in a moist, slightly acidic pasted of MnO2 and NH4Cl acts a cathode. Anode: Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e Cathode: 2MnO2(s) + H2O(l) + 2e Mn2O3(s) + 2OH(aq)
Batteries Dry-Cell Batteries Leclanché cell Anode: Zn(s) Zn2+(aq) + 2e 2MnO2(s) + 2NH4+(aq) + 2e Mn2O3(s) + 2NH3(aq)+ H2O(l) Cathode:
Batteries Nickel-Cadmium (“ni-cad”) Batteries Anode: Cd(s) + 2OH(aq) Cd(OH)2(s) + 2e Cathode: NiO(OH)(s) + H2O(l) + e Ni(OH)2(s) + OH(aq) Nickel-Metal Hydride (“NiMH”) Batteries Anode: MHab(s) + OH(aq) M(s) + H2O(l) + e Cathode: NiO(OH)(s) + H2O(l) + e Ni(OH)2(s) + OH(aq) Overall: MHab(s) + NiO(OH)(s) M(s) + Ni(OH)2(s)
Batteries Lithium and Lithium Ion Batteries Lithium Anode: xLi(s) xLi+(soln) + xe Cathode: MnO2(s) + xLi+(soln) + xe LixMnO2(s) Lithium Ion Anode: LixC6(s) xLi+(soln) + 6C(s) + xe Cathode: Li1-xCoO2(s) + xLi+(soln) + xe LiCoO2(s)
Fuel cells Hydrogen-Oxygen Fuel Cell • Like batteries, but the reactants must be constanly replenished. • Normal batteries los their ability to generate voltage with use because the reactants become depleted as electric current is drawn from the battery. • In fuel cell, the reactant – the fuel-constanly flow through the battery, generating electric current as they undergo redox reaction.
Corrosion Corrosion: The oxidative deterioration of a metal. • Moisture must be present for rusting to occur • Additional electrolytes promote more rusting • Such as NaCl, on the surface of iron because it enhances current flow • The presence of acid promotes rusting. (H+ ions are involved in the reduction of oxygen, lower pH enhances the cathodic reaction and leads to faster rusting.
Preventing Corrosion • Keep dry • Coat the iron with a substance that is impervious to water • Painting • Placing a sacrificial electrode in electrical contact with the iron. • For some metals, oxidation protects the metal (aluminum, chromium, magnesium, titanium, zinc, and others).
Zn2+(aq) + 2e Fe2+(aq) + 2e Fe(s) Zn(s) Corrosion Prevention of Corrosion Galvanization: The coating of iron with zinc. When some of the iron is oxidized (rust), the process is reversed since zinc will reduce Fe2+ to Fe: E° = 0.45 V E° = 0.76 V
Corrosion Prevention of Corrosion Cathodic Protection: Instead of coating the entire surface of the first metal with a second metal, the second metal is placed in electrical contact with the first metal: Anode: Mg(s) Mg2+(aq) + 2e E° = 2.37 V Cathode: O2(g) + 4H+(aq) + 4e 2H2O(l) E° = 1.23 V Attaching a magnesium stake to iron will corrode the magnesium instead of the iron. Magnesium acts as a sacrificial anode.
Molten salt- mixture of cations and anions • In general: • The cation that is most easily reduced (the one with least negative, or most positive, reduction-half cell potential) is reduced first • The anion is most easily oxidize ( the one has the least negative, or most positive, oxidation half-cell potential) is oxidized first • The cations of active metals-those that are not easily reduced, such as Li+, K+, Na+, Mg2+, Ca2+, and Al3+ - Cannot be reduced from aqueous solution by electrolysis because water is reduced at lower voltage.
Electrolysis and Electrolytic Cells Electrolysis of Molten Sodium Chloride Anode: 2Cl(l) Cl2(g) + 2e Cathode: 2Na+(l) + 2e 2Na(l) Overall: 2Na+(l) + 2Cl(l) 2Na(l) + Cl2(g)