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Contents
21-1 21-2 21-3 21-4 21-5 21-6 21-7 21-8 Electrode Potentials and Their Measurement Standard Electrode Potentials Ecell, G, and Keq Ecell as a Function of Concentration Batteries: Producing Electricity Through Chemical Reactions. Corrosion: Unwanted Voltaic Cells Electrolysis: Causing Non-spontaneous Reactions to Occur Industrial Electolysis Processes Focus On Membrane Potentials
General Chemistry: Chapter 21 Slide 2 of 52
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Cu(s) + 2Ag+(aq)
Cu(s) + Zn2+(aq)
Cu2+(aq) + 2 Ag(s)
No reaction
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Cathode
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An Electrochemical Cell
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Terminology
Electromotive force, Ecell.
The cell voltage or cell potential.
Cell diagram.
Shows the components of the cell in a symbolic way. Anode (where oxidation occurs) on the left. Cathode (where reduction occurs) on the right. Boundary between phases shown by |. Boundary between half cells (usually a salt bridge) shown by ||.
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Terminology
Ecell = 1.103 V
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Terminology
Galvanic cells.
Produce electricity as a result of spontaneous reactions.
Electrolytic cells.
Non-spontaneous chemical change driven by electricity.
Couple, M|Mn+
A pair of species related by a change in number of e-.
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Pt|H2(g, 1 bar)|H+(a = 1)
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Reduction Couples
Cu2+(1M) + 2 e- Cu(s) ECu2+/Cu = ?
Pt|H2(g, 1 bar)|H+(a = 1) || Cu2+(1 M)|Cu(s) Ecell = 0.340 V anode cathode Standard cell potential: the potential difference of a cell formed from two standard electrodes. Ecell = Ecathode - Eanode
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ECu2+/Cu = +0.340 V
H2(g, 1 atm) + Cu2+(1 M) H+(1 M) + Cu(s)
Prentice-Hall 2002 General Chemistry: Chapter 21
Ecell = 0.340 V
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anode
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cathode
cathode
anode
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elec = -nFE
G = -nFE G = -nFE
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Fe3+(aq) + 3e- Fe2+(aq) EFe3+/Fe2+ = 0.771 V G = -0.771 J Fe3+(aq) + 3e- Fe(s) EFe3+/Fe = +0.331 V G = +0.109 V
Spontaneous Change
G < 0 for spontaneous change. Therefore Ecell > 0 because Gcell = -nFEcell Ecell > 0
Reaction proceeds spontaneously as written.
Ecell = 0
Reaction is at equilibrium.
Ecell < 0
Reaction proceeds in the reverse direction spontaneously.
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E = -EM2+/M EH+/H2 = 0 V
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Example 21-8
Applying the Nernst Equation for Determining Ecell.
What is the value of Ecell for the voltaic cell pictured below and diagrammed as follows? Pt|Fe2+(0.10 M),Fe3+(0.20 M)||Ag+(1.0 M)|Ag(s)
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Example 21-8
0.0592 V Ecell = Ecell log Q n 0.0592 V [Fe3+] Ecell = Ecell log [Fe2+] [Ag+] n
Concentration Cells
Two half cells with identical electrodes but different ion concentrations.
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Concentration Cells
0.0592 V Ecell = Ecell log Q n
Ecell = Ecell 0.0592 V
2 H+(1 M) 2 H+(x M)
x2 log 2 1
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Measurement of Ksp
Ag|Ag+(satd AgI)||Ag+(0.10 M)|Ag(s) Ag+(0.100 M) + e- Ag(s) Ag(s) Ag+(satd) + eAg+(0.100 M) Ag+(satd M)
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Example 21-10
Using a Voltaic Cell to Determine Ksp of a Slightly Soluble Solute.
With the date given for the reaction on the previous slide, calculate Ksp for AgI. AgI(s) Ag+(aq) + I-(aq) Let [Ag+] in a saturated Ag+ solution be x: Ag+(0.100 M) Ag+(satd M) 0.0592 V [Ag+]satd AgI 0.0592 V log Ecell = Ecell log Q = Ecell [Ag+]0.10 M soln n n
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Example 21-10
0.0592 V [Ag+]satd AgI Ecell = Ecell log [Ag+]0.10 M soln n
Ecell = Ecell 0.0592 V log x 0.100
0.0592 V (log x log 0.100) 0.417 = 0 1 0.417 log x = log 0.100 = -1 7.04 = -8.04 0.0592 x = 10-8.04 = 9.110-9
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Ksp = x2 = 8.310-17
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Secondary Cells.
Cell reaction can be reversed by passing electricity through the cell (charging).
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Dry Cell
Zn(s) Zn2+(aq) + 2 e2 MnO2(s) + H2O(l) + 2 e- Mn2O3(s) + 2 OH-
Oxidation: Reduction:
Acid-base reaction:
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Lead-Acid Battery
Reduction: PbO2(s) + 3 H+(aq) + HSO4-(aq) + 2 e- PbSO4(s) + 2 H2O(l)
Oxidation: Pb (s) + HSO4-(aq) PbSO4(s) + H+(aq) + 2 ePbO2(s) + Pb(s) + 2 H+(aq) + HSO4-(aq) 2 PbSO4(s) + 2 H2O(l) Ecell = EPbO2/PbSO4 - EPbSO4/Pb = 1.74 V (-0.28 V) = 2.02 V
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Zn(s),ZnO(s)|KOH(satd)|Ag2O(s),Ag(s)
Ecell = 1.8 V
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Fuel Cells
O2(g) + 2 H2O(l) + 4 e- 4 OH-(aq) 2{H2(g) + 2 OH-(aq) 2 H2O(l) + 2 e-} 2H2(g) + O2(g) 2 H2O(l) Ecell = EO2/OH- - EH2O/H2 = 0.401 V (-0.828 V) = 1.229 V = G/ H = 0.83
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Air Batteries
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EO2/OH- = 0.401 V
EFe/Fe2+ = -0.440 V
2 Fe(s) + O2(g) + 2 H2O(l) 2 Fe2+(aq) + 4 OH-(aq) Ecell = 0.841 V In acidic solution: O2(g) + 4 H+(aq) + 4 e- 4 H2O (aq) EO2/OH- = 1.229 V
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Corrosion
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Corrosion Protection
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Corrosion Protection
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ne- = I t F
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Electroplating
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Chlor-Alkali Process
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Nernst Potential,
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Chapter 21 Questions
Develop problem solving skills and base your strategy not on solutions to specific problems but on understanding.
Practice good techniques and get coaching from people who have been here before.
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