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

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Chapter 18

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Redox Reactions

01

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Chapter 18

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Redox Reactions
Redox reaction are those involving the oxidation and reduction of species. OIL Oxidation Is Loss of electrons. RIG Reduction Is Gain of electrons. Oxidation and reduction must occur together. They cannot exist alone.
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Redox Reactions

02

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Chapter 18

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Redox Reactions

02

Oxidation Half-Reaction: Zn(s) Zn2+(aq) + 2 e. The Zn loses two electrons to form Zn2+.

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Chapter 18

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Redox Reactions

03

Reduction Half-Reaction: Cu2+(aq) + 2 e Cu(s) The Cu2+ gains two electrons to form copper.

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Galvanic cell, example 1

Overall: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

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Chapter 18

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Electrochemical Cells

01

Electrodes: are usually metal strips/wires connected by an electrically conducting wire. Salt Bridge: is a U-shaped tube that contains a gel permeated with a solution of an inert electrolyte. Anode: is the electrode where oxidation takes place. Cathode: is the electrode where reduction takes place.
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Galvanic cell, example 2

Al(s) + Pb2+(aq) Al3+(aq) + Pb(s)

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Chapter 18

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Galvanic cell, example 3

Fe(s) + 2Fe3+(aq) 3Fe2+(aq)

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Chapter 18

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Fe(s) + Fe3+(aq)

2Fe2+(aq)

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Chapter 18

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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), Fe2+(aq) | Pt(s)

Electrons flow from anode to cathode. Anode is placed on left by convention.

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Cell potential, Free-energy change

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Chapter 18

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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)

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Relationship between G and E

G = -nFE F = 96,500 C/mol efaraday (Faraday contant)

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Chapter 18

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Standard cell potential, Eo

Standard conditions aqueous solutes: 1 M gases: 1 atm solids and liquids: pure Go = -nFEo

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Chapter 18

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Example Problem
The standard cell potential (Eo) for following reaction is 1.10 V at 2.5oC. What is Go? Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

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Chapter 18

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Standard oxidation and reduction potentials

Eo = Eoox + Eored
Example: Zn(s) Zn2+(aq) + 2e H2(g) Zn2+(aq) + H2(g) Eoox = 0.76 V Eored = Eo 0V

2H+(aq) + 2e Zn(s) + 2H+(aq)

= 0.76 V

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Chapter 18

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Electrochemical Cells

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Chapter 18

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Electrochemical Cells

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The standard half-cell potentials are determined from the difference between two electrodes. The reference point is called the standard hydrogen electrode (S.H.E.) and consists of a platinum electrode in contact with H2 gas (1 atm) and aqueous H+ ions (1 M). The standard hydrogen electrode is assigned an arbitrary value of exactly 0.00 V.
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Another example

H2(g)

2H+(aq) + 2e Cu(s)

Eoox =

0V

Cu2+(aq) + 2e H2(g) + Cu2+( aq)

Eored = 0.34 V

2H+(aq) + Cu(s) Eo = 0.34 V

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Chapter 18

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Standard reduction potentials

Zn(s) Zn2+(aq) + 2eZn(s) Eoox = 0.76 V Eored = -0.76 V

Zn2+(aq) + 2e-

Eoox = -Eored

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Electrochemical Cells

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Chapter 18

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Learning Goal

Determine Eo for a cell from a table of standard reduction potentials.

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Chapter 18

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Electrochemical Cells

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When selecting two half-cell reactions the more negative value will form the oxidation half-cell. Consider the reaction between zinc and silver:
Ag+(aq) + e Ag(s) Zn2+(aq) + 2 e Zn(s) E = 0.80 V E = 0.76 V

Therefore, zinc forms the oxidation half-cell:

Zn(s) Zn2+(aq) + 2 e E = (0.76 V)
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Chapter 18

Electrochemical Cells

08

What is the standard emf of an electrochemical cell made of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr electrode in a 1.0 M Cr(NO3)2 solution?

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Chapter 18

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Electrochemical Cells

08

What is the standard emf of an electrochemical cell made of a Mg electrode in a 1.0 M Mg(NO3)2 solution and a Ag electrode in a 1.0 M AgNO3 solution?

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What is Eo for the following cell?

Fe(s) | Fe2+(aq) || Pb2+(aq) | Pb(s)

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Chapter 18

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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 = 0.0257 V (at 25oC)

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Spontaneity of a Reaction
Equivalent forms of equation: Ecell = (0.0257/n) ln K Ecell = (0.0592/n) log K

02

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Chapter 18

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Learning Goal

Determine equilibrium constant for a redox reaction from Eo.

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Chapter 18

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Spontaneity of a Reaction

03

Calculate the standard free energy change (G) and the equilibrium constant (K) for the following reactions at 25C: Sn2+(aq) + 2 Cu+(aq) Fe(s) + 2 Ag+(aq) 4 Fe3+(aq) + 2 H2O(l)
Slide 33

1. Sn(s) + 2 Cu2+(aq) 2. Fe2+(aq) + 2 Ag(s)

3. 4 Fe2+(aq) + O2(g) + 4 H+(aq)

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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
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Learning Goal

Determine a cell potential under nonstandard-state conditions using Nernst equation (given: table of standard reduction potentials).

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Chapter 18

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The Nernst Equation

03

Consider the reaction of metallic zinc with hydrochloric acid. Calculate the cell potential at 25C when [H+] = 1.0 M, [Zn2+] = 0.0010 M, and PH = 0.10 atm. 2

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Chapter 18

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What is E for the following cell?

Zn(s) | Zn2+(2.0 M) || Cu2+(0.010 M) | Cu(s)

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Practical Use: pH Meter

What is pH of the solution in the anode half-cell below? Given: E is measured to be 0.78 V, and Eo[Cu+(aq) Cu(s)] is 0.52 V. Pt(s) | H2(g,1 atm) | H+(aq,? M) || Cu+(aq,1 M) | Cu(s)

Solution with unknown pH

Reference electrode

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Chapter 18

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Actual pH meter
One electrode (glass electrode): Ag(s) | AgCl(s) | Cl(aq) Ag(s) + Cl(aq) AgCl(s) + e Eoox = -0.22 V

Reference electrode (calomel electrode): Hg2Cl2(s) | Hg(l), Cl(aq) Hg2Cl2(s) + 2e

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2Hg(s) + 2Cl(aq)
Chapter 18

Eored = 0.28 V
Slide 39

E depends on pH via potential across glass membrane, as well as on Eoox and Eored.
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