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Chapter

18

Electrochemistry
Chemistry 4th Edition McMurry/Fay
Dr. Paul Charlesworth
Michigan Technological University

Kinds of electrochemical cells

Galvanic (voltaic)
Spontaneous chemical reaction generates electricity with which to do work e.g. batteries

Electrolytic
Electricity used to drive nonspontaneous chemical reaction

Prentice Hall ©2004

Chapter 18

Slide 2

Redox Reactions

01

Prentice Hall ©2004

Chapter 18

Slide 3

Prentice Hall ©2004 Chapter 18 Slide 6 . OIL – Oxidation Is Loss of electrons. Oxidation and reduction must occur together. The Zn loses two electrons to form Zn2+. RIG – Reduction Is Gain of electrons. They cannot exist alone. Prentice Hall ©2004 Chapter 18 01 Slide 4 Redox Reactions 02 Prentice Hall ©2004 Chapter 18 Slide 5 Redox Reactions • • 02 Oxidation Half-Reaction: Zn(s) → Zn2+(aq) + 2 e–.Redox Reactions Redox reaction are those involving the oxidation and reduction of species.

Anode: is the electrode where oxidation takes place. Cathode: is the electrode where reduction takes place. Prentice Hall ©2004 Chapter 18 Slide 7 Galvanic cell. Salt Bridge: is a U-shaped tube that contains a gel permeated with a solution of an inert electrolyte. Chapter 18 Slide 9 • • • Prentice Hall ©2004 .Redox Reactions • 03 Reduction Half-Reaction: Cu2+(aq) + 2 e– → Cu(s) • The Cu2+ gains two electrons to form copper. example 1 • Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Prentice Hall ©2004 Chapter 18 Slide 8 Electrochemical Cells • 01 Electrodes: are usually metal strips/wires connected by an electrically conducting wire.

example 3 Fe(s) + 2Fe3+(aq) 3Fe2+(aq) Prentice Hall ©2004 Chapter 18 Slide 11 Fe(s) + Fe3+(aq) 2Fe2+(aq) Prentice Hall ©2004 Chapter 18 Slide 12 .Galvanic cell. example 2 Al(s) + Pb2+(aq) Al3+(aq) + Pb(s) Prentice Hall ©2004 Chapter 18 Slide 10 Galvanic cell.

Chapter 18 Slide 13 Prentice Hall ©2004 Cell potential. Fe2+(aq) | Pt(s) • Electrons flow from anode to cathode. Free-energy change Prentice Hall ©2004 Chapter 18 Slide 14 Driving force in electrochemical cells Name: electromotive force (emf) cell potential cell voltage Symbol: E SI units: Volt (V) (1 J = 1 C x 1 V) Prentice Hall ©2004 Chapter 18 Slide 15 . Anode is placed on left by convention.Electrochemical Cells • 02 Convention for expressing the cell: Anode Half-Cell || Cathode Half-Cell Electrode | Anode Soln || Cathode Soln | Electrode Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s) Fe(s) | Fe2+(aq) || Fe3+(aq).

5oC. What is ∆Go? Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Prentice Hall ©2004 Chapter 18 Slide 18 .10 V at 2. Eo Standard conditions aqueous solutes: 1 M gases: 1 atm solids and liquids: pure ∆Go = -nFEo Prentice Hall ©2004 Chapter 18 Slide 17 Example Problem The standard cell potential (Eo) for following reaction is 1.Relationship between ∆G and E ∆G = -nFE F = 96.500 C/mol efaraday (Faraday contant) Prentice Hall ©2004 Chapter 18 Slide 16 Standard cell potential.

E. Chapter 18 Slide 21 • • Prentice Hall ©2004 .H.00 V.76 V Eored = Eo 0V 2H+(aq) + 2e– Zn(s) + 2H+(aq) = 0.Standard oxidation and reduction potentials Eo = Eoox + Eored Example: Zn(s) Zn2+(aq) + 2e– H2(g) Zn2+(aq) + H2(g) Eoox = 0.76 V Prentice Hall ©2004 Chapter 18 Slide 19 Electrochemical Cells 05 Prentice Hall ©2004 Chapter 18 Slide 20 Electrochemical Cells • 04 The standard half-cell potentials are determined from the difference between two electrodes. The standard hydrogen electrode is assigned an arbitrary value of exactly 0. The reference point is called the standard hydrogen electrode (S.) and consists of a platinum electrode in contact with H2 gas (1 atm) and aqueous H+ ions (1 M).

Another example H2(g) 2H+(aq) + 2e– Cu(s) Eoox = 0V Cu2+(aq) + 2e– H2(g) + Cu2+( aq) Eored = 0.34 V Prentice Hall ©2004 Chapter 18 Slide 22 Standard reduction potentials Zn(s) Zn2+(aq) + 2eZn(s) Eoox = 0.76 V Eored = -0.76 V Zn2+(aq) + 2e- Eoox = -Eored Prentice Hall ©2004 Chapter 18 Slide 23 Electrochemical Cells 06 Prentice Hall ©2004 Chapter 18 Slide 24 .34 V 2H+(aq) + Cu(s) Eo = 0.

80 V E° = – 0.Learning Goal Determine Eo for a cell from a table of standard reduction potentials. Prentice Hall ©2004 Chapter 18 Slide 25 Electrochemical Cells • 07 When selecting two half-cell reactions the more negative value will form the oxidation half-cell. zinc forms the oxidation half-cell: Zn(s) → Zn2+(aq) + 2 e– E° = – (–0.76 V) Slide 26 Prentice Hall ©2004 Chapter 18 Electrochemical Cells • 08 What is the standard emf of an electrochemical cell made of a Cd electrode in a 1.0 M Cr(NO3)2 solution? Prentice Hall ©2004 Chapter 18 Slide 27 . Consider the reaction between zinc and silver: Ag+(aq) + e– → Ag(s) Zn2+(aq) + 2 e– → Zn(s) E° = 0.0 M Cd(NO3)2 solution and a Cr electrode in a 1.76 V • • Therefore.

0 M AgNO3 solution? Prentice Hall ©2004 Chapter 18 Slide 28 What is Eo for the following cell? Fe(s) | Fe2+(aq) || Pb2+(aq) | Pb(s) Prentice Hall ©2004 Chapter 18 Slide 29 Spontaneity of a Reaction • 01 The value of E˚ is related to the thermodynamic quantities of ∆G˚ and K. ∆G˚ = –nFE˚ and ∆G˚ = –RT ln K combine to give: n = moles of electrons E˚ = –(RT/nF) ln K Prentice Hall ©2004 Chapter 18 RT/F = 0.0 M Mg(NO3)2 solution and a Ag electrode in a 1.Electrochemical Cells • 08 What is the standard emf of an electrochemical cell made of a Mg electrode in a 1.0257 V (at 25oC) Slide 30 .

Prentice Hall ©2004 Chapter 18 Slide 32 Spontaneity of a Reaction • 03 Calculate the standard free energy change (∆G˚) and the equilibrium constant (K) for the following reactions at 25°C: Sn2+(aq) + 2 Cu+(aq) Fe(s) + 2 Ag+(aq) 4 Fe3+(aq) + 2 H2O(l) Slide 33 1.Spontaneity of a Reaction Equivalent forms of equation: E˚cell = (0. 4 Fe2+(aq) + O2(g) + 4 H+(aq) Prentice Hall ©2004 Chapter 18 .0592/n) log K 02 Prentice Hall ©2004 Chapter 18 Slide 31 Learning Goal Determine equilibrium constant for a redox reaction from Eo.0257/n) ln K E˚cell = (0. Fe2+(aq) + 2 Ag(s) 3. Sn(s) + 2 Cu2+(aq) 2.

10 atm. Calculate the cell potential at 25°C when [H+] = 1. and PH = 0.0010 M.The Nernst Equation • 01 Cell potentials can be modified by temperature and composition changes according to the equation: ∆G = ∆G° + RT lnQ ∴ • –nFE = –nFE° + RT lnQ Giving: E = Eo − Chapter 18 RT ln Q nF Slide 34 Prentice Hall ©2004 Learning Goal Determine a cell potential under nonstandard-state conditions using Nernst equation (given: table of standard reduction potentials). 2 Prentice Hall ©2004 Chapter 18 Slide 36 . [Zn2+] = 0. Prentice Hall ©2004 Chapter 18 Slide 35 The Nernst Equation • 03 Consider the reaction of metallic zinc with hydrochloric acid.0 M.

Cl–(aq) Hg2Cl2(s) + 2e– Prentice Hall ©2004 2Hg(s) + 2Cl–(aq) Chapter 18 Eored = 0.28 V Slide 39 .22 V Reference electrode (“calomel electrode”): Hg2Cl2(s) | Hg(l).What is E for the following cell? Zn(s) | Zn2+(2.010 M) | Cu(s) Prentice Hall ©2004 Chapter 18 Slide 37 Practical Use: pH Meter What is pH of the solution in the anode half-cell below? Given: E is measured to be 0.1 atm) | H+(aq.78 V.0 M) || Cu2+(0.52 V. and Eo[Cu+(aq) Cu(s)] is 0.? M) || Cu+(aq. Pt(s) | H2(g.1 M) | Cu(s) Solution with unknown pH Reference electrode Prentice Hall ©2004 Chapter 18 Slide 38 Actual pH meter One electrode (“glass electrode”): Ag(s) | AgCl(s) | Cl–(aq) Ag(s) + Cl–(aq) AgCl(s) + e– Eoox = -0.

Prentice Hall ©2004 Chapter 18 Slide 40 . as well as on Eoox and Eored.E depends on pH via potential across glass membrane.