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In chapter 5, we learned how to recognize an oxidation-reduction reaction. In this chapter we introduce electrode potentials and the Nernst equation. These allow for a quantitative treatment of electrochemistry. Chapter 12 Oxidation-Reduction Reactions. Common Oxidation-Reduction Reactions.
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In chapter 5, we learned how to recognize an oxidation-reduction reaction. In this chapter we introduce electrode potentials and the Nernst equation. These allow for a quantitative treatment of electrochemistry. Chapter 12Oxidation-Reduction Reactions
Common Oxidation-Reduction Reactions • Oxidation-reduction reactions used for heat or work: • Combustion • Metabolic • Corrosion • Photosynthesis
Common Oxidation-Reduction Reactions • Oxidation-reduction reactions involve the transfer of electrons. • Element or compound that gains electrons undergoes reduction. • Element or compound that loses electrons undergoes oxidation.
Common Oxidation-Reduction Reactions • Consider this reaction: 2Na + Cl2→ 2NaCl • The Na has been oxidized. • The Cl2 has been reduced.
Common Oxidation-Reduction Reactions • This reaction, 2Na + Cl2→ 2NaCl, can be written as the sum of two half-reactions: 2Na ⇄ 2Na+ + 2e- oxidation Cl2 + 2e-⇄ 2Cl- reduction
Common Oxidation-Reduction Reactions • The addition of oxygen atoms or hydrogen atoms to an element or compound is also classified as an oxidation-reduction reaction.
Common Oxidation-Reduction Reactions • CO2 + H2⇄ CO + H2O • The H2 is oxidized and the CO2 reduced. • C2H4 + H2⇄ C2H6 • The C2H4 is reduced and the H2 oxidized.
Common Oxidation-Reduction Reactions • In order to determine that an oxidation-reduction reaction has occurred, we must be able to assign oxidation numbers or oxidation states.
Determining Oxidation Numbers • Introduced in Chapter 5, section 16 • Two methods: • One based on Lewis structure • Good for organic compounds • Other based on set of rules • e. g., elements = 0, monatomic ions = charge • Review section 16, chapter 5
Recognizing Oxidation-Reduction Reactions • After all the oxidation numbers in a chemical reaction have been determined, look for changes. • Oxidation occurs when the oxidation number of an atom increases. • Reduction occurs when the oxidation number of an atom decreases.
Recognizing Oxidation-Reduction Reactions • In an oxidation-reduction reaction, both oxidation and reduction must occur. • If one species is being oxidized, another must be reduced. • In biochemical reactions, often only the oxidation or reduction reaction is shown explicitly.
Recognizing Oxidation-Reduction Reactions Figure 12.1
Recognizing Oxidation-Reduction Reactions • Organic reactions can be classified by examining the Lewis structures. • If the number of C-H bonds decreases, the molecule is being oxidized. • If the number of C-O bonds increases, the molecule is being oxidized. • Conversely, if the number of C-H bonds increases, the molecule is being reduced.
Voltaic Cells • Also known as galvanic cells • Physically separate the half-reactions • Force electrons to travel through an external circuit connecting the two half-reactions • Battery!
Voltaic Cells Figure 12.2
Voltaic Cells • As H+ ions leave the solution on the right, K+ ions fill in to keep the solution electrically neutral. • Salt Bridge • The voltage required to prevent the flow of electrons is measured with a voltmeter. • This voltage is called the cell potential.
Voltaic Cells • Oxidation takes place at the anode. • Reduction takes place at the cathode. • In Figure 12.2, the half-reactions involve two electrons. • The half-reactions are added to produce the overall reaction.
Voltaic Cells • What if the half reactions do not have the same number of electrons? Figure 12.3
Standard Cell Potentials • The relative half-reactions from Figure 12.2 are Zn ⇄ Zn+2 +2e- E° =+0.7628 2H+ + 2e-⇄ H2 E° =+0.0000 Figure 12.2
Standard Cell Potentials • The overall standard cell potential, E°, for the cell is the sum of the two half-reaction E°. • Expect the reaction to go as written if the overall E° >0.
Oxidizing and Reducing Agents • Reducing agent donates electrons: its oxidation number increases. • Oxidizing agent accepts electrons: its oxidation number decreases.
Oxidizing and Reducing Agents • In Figure 12.2, zinc metal is the reducing agent. • Hydrogen ions are the oxidizing agent. Figure 12.2
Oxidizing and Reducing Agents • As with acids and bases, there are conjugate oxidizing and reducing agents. • When Zn is oxidized to Zn+2, Zn+2 becomes the conjugate oxidizing agent because its oxidation number drops in the reverse reaction: Zn ⇄ Zn+2 + 2e-
Oxidizing and Reducing Agents • Strong reducing agents produce weak conjugate oxidizing agents. • Strong oxidizing agents produce weak conjugate reducing agents.
Relative Strengths of Oxidizing Agents and Reducing Agents • Oxidation-reduction reactions should occur when they convert the stronger of a pair of oxidizing agents and the stronger of a pair of reducing agents into a weaker oxidizing agent and a weaker reducing agent.
Relative Strengths of Oxidizing Agents and Reducing Agents Table 12.1
Relative Strengths of Oxidizing Agents and Reducing Agents • Standard electrode potentials, E°red • Half-reactions written as reductions • Standard means gases at 1 bar, solutions at 1 M • When written as oxidations, the sign on E°red is reversed.
Batteries • Alkaline dry cells, ubiquitous • Lead-Acid, cars • NiCd, rechargeable • NiMH, hybrids • Lithium ion, compact • Fuel cells, hydrogen
Batteries • Lead-Acid
Batteries • NiMH
Electrochemical Cells at Nonstandard Conditions: The Nernst Equation • To determine E when a cell is not at standard conditions, the Nernst Equation is used.
Electrochemical Cells at Nonstandard Conditions: The Nernst Equation • n is the number of electrons transferred. • Qc is the reaction quotient. • Notice that if all concentrations are 1 M, E=E°. • F is the Faraday constant.
Electrochemical Cells at Nonstandard Conditions: The Nernst Equation Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) Figure 12.8
Electrochemical Cells at Nonstandard Conditions: The Nernst Equation • At equilibrium Qc = K and E = 0. • This provides an alternate equation for expressing equilibrium.
Electrolysis and Faraday’s Law • Voltaic cells operate spontaneously. • Electrolytic cells require an external power supply. • e. g. electroplating
Electrolysis and Faraday’s Law Figure 12.9
Electrolysis and Faraday’s Law • 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.
Electrolysis and Faraday’s Law • Amps × time (in secs) = Coulombs, C • F = 96,485 C/mol of e- • C/F = mol of e- passed • Grams of silver plated out can be determined from [Ag(CN)2]-(aq) + e-⇄ Ag(s) + 2CN-(aq)
Electrolysis of Molten NaCl Figure 12.11
Electrolysis of Molten NaCl • CaCl2 added to the NaCl to lower the melting point. No effect on half reactions. • Na(l) less dense than NaCl(l). • Cl2(g) and Na(l) kept apart. Why?
Electrolysis of Aqueous NaCl Figure 12.13
Electrolysis of Aqueous NaCl • Chloride is oxidized instead of water. • Water is reduced, not sodium ion. • Hydrogen gas and NaOH(aq) are produced and sold.
Electrolysis of Water Figure 12.15
Electrolysis of Water • A salt which resists electrolysis is added to improve conductivity. • Similar (but not exactly) half reactions running in reverse describe a fuel cell. • If the gases were collected, what would their volume ratio be?
The Hydrogen Economy • Using hydrogen gas as a common fuel. • Solar energy for electrolysis of water. • Fuel cells to generate electricity from hydrogen and reproduce the water. • No drain on fossil fuels. • No carbon emissions. • Water (seawater) already has the electrolyte for improved conductivity added! • Plenty of solar radiation.
The Hydrogen Economy • Not a new idea. • Big challenges. • Economical production of hydrogen. • Storage. • Distribution. • Better fuels cells. • Cheaper. • More robust.