GENERAL CHEMISTRY

Principles and Modern Applications PETRUCCI HERRING MADURA

TENTH EDITION

BISSONNETTE

Electrochemistry
PHILIP DUTTON
UNIVERSITY OF WINDSOR DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

20

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Spontaneous Change: Entropy and Gibbs Energy

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20-1 Electrode Potentials and Their Measurement

Cu(s) + 2Ag+(aq)

Cu(s) + Zn2+(aq)

Cu2+(aq) + 2 Ag(s)

No reaction

FIGURE 20-1 Behavior of Ag+(aq) and Zn+(aq) in the presence of copper

Anode

electrode half-cell Cathode

FIGURE 20-2 An electrochemical half cell

anode

cathode

FIGURE 20-3 Measurement of the electromotive force of an electrochemical cell

Zn(s) + Cu2+(aq) E

Zn2+(aq) + Cu(s) = 1.103 V

Cell Diagrams and 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 (commonly a salt bridge) shown by ||.

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Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) Ecell = 1.103 V

FIGURE 20-4 The reaction Zn(s) + Cu2+(aq) an electrochemical cell Zn2+(aq) + Cu(s) in

Galvanic (or voltaic) 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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20-2 Standard Electrode Potentials Cell voltages, the potential differences between electrodes, are among the most precise scientific measurements. The potential of an individual electrode is difficult to establish. Arbitrary zero is chosen.
The Standard Hydrogen Electrode (SHE)

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2 H+(a = 1) + 2 e-

H2(g, 1 bar)

E = 0 V

Pt|H2(g, 1 bar)|H+(a = 1)

FIGURE 20-5 The standard hydrogen electrode (SHE)

Standard Electrode Potential, E Ecell = Ecathode (right) Eanode,(left) The tendency for a reduction process to occur at an electrode.

All ionic species present at a=1 (approximately 1 M) All gases are at 1 bar (approximately 1 atm). Where no metallic substance is indicated, the potential is established on an inert metallic electrode (ex. Pt).
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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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Pt|H2(g, 1 bar)|H+(a = 1) || Cu2+(1 M)|Cu(s) Ecell = 0.340 V Ecell = Ecathode - Eanode Ecell = ECu2+/Cu - EH+/H2 0.340 V = ECu2+/Cu - 0 V ECu2+/Cu = +0.340 V H2(g, 1 atm) + Cu2+(1 M) H+(1 M) + Cu(s) Ecell = 0.340 V

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anode

cathode

cathode

anode

FIGURE 20-6 Measuring standard reduction potential

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20-3

Ecell, G, and Keq

elec = -zFEcell
G = -zFEcell Faraday constant, F = 96,485 C mol-1 When products are in their standard states G = -zFEcell

Michael Faraday 1791-1867

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Combining Reduction Half-Equations

Fe3+(aq) + 3e- Fe(s) Fe2+(aq) + 2e- Fe(s) Fe3+(aq) + 1e- Fe2+(aq) Fe3+(aq) + 3e- Fe(s)

EFe3+/Fe = ?
can add G

EFe2+/Fe = -0.440 V EFe3+/Fe2+ = 0.771 V

G = +0.880 J G = -0.771 J

EFe3+/Fe = +0.331 V G = +0.109 J

but cannot simply add E

G = +0.109 J = -nFE

EFe3+/Fe = +0.109 J /(-3F) = -0.0363 V

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Spontaneous Change in Oxidation-Reduction Reactions

G < 0 for spontaneous change. Therefore Ecell > 0 because Gcell = -nFEcell Ecell > 0

G = H - T S

Reaction proceeds spontaneously as written. Ecell = 0 Reaction is at equilibrium. Ecell < 0 Reaction proceeds in the reverse direction Slide 27 of 53 spontaneously.

The Behavior or Metals Toward Acids

M(s) M2+(aq) + 2 e2 H+(aq) + 2 e- H2(g) 2 H+(aq) + M(s) H2(g) + M2+(aq) Ecell = EH+/H2 - EM2+/M = -EM2+/M When EM2+/M < 0, Ecell > 0. Therefore G < 0. Metals with negative reduction potentials react with acids.
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E = -EM2+/M EH+/H2 = 0 V

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Relationship Between Ecell and Keq

G = -RT ln Keq = -zFEcell RT ln Keq zF

Ecell =

Ecell =

0.25693 ln K eq = 0.0592/n X log z Keq

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General Chemistry: Chapter 20

Copyright 2011 Pearson Canada Inc.

FIGURE 20-8 A summary of important thermodynamic, equilibrium and electrochemical relationships under standard conditions.

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20-4 Ecell as a Function of Concentration

G = G - RT ln Q -zFEcell = -zFEcell - RT ln Q RT Ecell = Ecell ln Q zF
Convert to log10 and calculate constants.
Variation of Ecell with ion concentrations

0.0592 V Ecell = Ecell log Q z

The Nernst Equation

Concentration Cells
Two half cells with identical electrodes but different ion concentrations. Pt|H2 (1 atm)|H+(x M)||H+(1.0 M)|H2(1 atm)|Pt(s) 2 H+(1 M) + 2 e- H2(g, 1 atm) H2(g, 1 atm) 2 H+(x M) + 2 e2 H+(1 M) 2 H+(x M) Ecell = EH+/H - EH+/H = 0
2 2

FIGURE 20-11 A concentration cell Slide 37 of 53

2 H+(1 M) 2 H+(x M) Ecell = EH+/H2 - EH+/H2 = 0

0.0592 V Ecell = Ecell log Q z 0.0592 V x2 Ecell = Ecell log 12 z 0.0592 V x2 Ecell = 0 log 1 2 Ecell = - 0.0592 V log x Ecell = (0.0592 V) pH

but we can calculate using the Nernst Equation

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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)
Work Example 20-11 as an exercise to understand the process.
FIGURE 20-12 A concentration cell for determining Ksp of AgI Slide 39 of 53 of 54 Slide 39

The Glass Electrode and the Electrochemical Measurement of pH

Ag|AgCl(s)|Cl-(1.0M),H+(1.0M)|glass membrane|H+(unknown)|| Cl-(1.0 M)|AgCl(s)|Ag(s) Ag(s) + ClH+(1.0 M) AgCl(s) + eAgCl(s) + eH+(unknown) Ag(s) + Cl-(aq)

G = G(unknown) G(1.0M) = G + RTln[unknown] G - RTln(1.0) =RTln[unknown] Ecell = -RTln[unknown]/zF pH = -log[unknown]=zFEcell/RT

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aH+(inside) is fixed
TMHsiung@2008 42/45

a) Glass Electrode for measuring pH A pH glass combination electrode for example: AH+(inside) is fixed

Reference electrode || Test solution |

Indicator electrode

Eref(outer)

Elj

E(membrane)

Eref(inner)

E cell = E ref(inner) E ref(outer)+ E lj E (m em brane)

Asymmetry potenial (): The (measured = K '+ (0.05916 log ) = K + (0.05916 loga H + (outside of a galvanic cell, ) voltage/theoretical voltage) ratio a H + (intside) value close to 1.0 (>0.98). )

a H + (outside )

= K (0.05916 pH )

TMHsiung@2008 43/45

pH glass membrane electrode structure: SiO4 framework with charge balancing cations SiO2 72 %, Na2O 22 %, CaO6 %

O Si Na+

Na+

TMHsiung@2008 44/45

Example 2: (membrane potential calculation)

exterior [K+] = 15 mM interior [K+] = 400 mM

Cathode: K+int(400 mM) + e Anode: overall: E cell K+ext (15 mM) + e K+int(400 mM)

K(s) K(s) K+ext(15 mM)

[K + ]ex 0.0592 0.0592 15 = Eo log + = 0 log = 0.084 V cell 1 1 400 [K ]in

TMHsiung@2008 45 /45

(a) The silversilver chloride electrode (b) The standard calomel electrode

(c) A glass electrode (d) A modern pH electrode

Reference Electrodes

Indicator electrode: responds to analyte concentration Reference electrode: maintains a fixed (reference) potential The cell voltage in Figure 14-8 responds only to changes in the quotient [Fe2 ]/[Fe3 ]. Everything else is constant.

The half-cell on the left in Figure 14-8 can be Slide 47 of 53 thought of as a reference electrode.

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Figure 14-9
Reference electrode Indicator electrode

Figure 14-9 Another view of Figure 14-8. The contents of the dashed box in Figure 14-8 are now considered to be a reference electrode dipped into the analyte solution. Slide 48 of 53
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Silver-Silver Chloride Reference Electrode

The half-cell enclosed by the dashed line in Figure 14-8 is called a silver-silver chloride electrode. Figure 14-10 shows how the halfcell is reconstructed as a thin, glassenclosed electrode that can be dipped into the analyte solution in Figure 14-9.

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Figure 14-10

Figure 14-10

Figure 14-10 Silver-silver chloride reference electrode.

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Example: Using a Reference Electrode Calculate the cell voltage in Figure 14-9 if the reference electrode is a saturated silversilver chloride electrode and [Fe2 ]/[Fe3 ]=10. SOLUTION:

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Calomel Reference Electrode

If the cell is saturated with KCl, it is called a saturated calomel electrode and the cell potential is 0.241 V at 25.

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20-5 Batteries: Producing Electricity Through Chemical Reactions

Primary Cells (or batteries). Cell reaction is not reversible. Secondary Cells. Cell reaction can be reversed by passing electricity through the cell (charging). Flow Batteries and Fuel Cells. Materials pass through the battery which converts chemical energy to electric Slide 53 of 53 General Chemistry: Chapter 20 energy.

Copyright 2011 Pearson Canada Inc.

FIGURE 20-14 The Leclanch (dry) cell

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The Leclanch Dry Cell

Oxidation: Reduction: Zn(s) Zn2+(aq) + 2 e2 MnO2(s) + H2O(l) + 2 e- Mn2O3(s) + 2 OHNH4+ + OH- NH3(g) + H2O(l)

Acid-base reaction:

Precipitation reaction: NH3 + Zn2+(aq) + Cl- [Zn(NH3)2]Cl2(s)

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The alkaline cell

Reduction: 2 MnO2(s) + H2O(l) + 2 e- Mn2O3(s) + 2 OH-

Oxidation reaction can be thought of in two steps: Zn(s) Zn2+(aq) + 2 eZn2+(aq) + 2 OH- Zn (OH)2(s) Zn (s) + 2 OH- Zn (OH)2(s) + 2 e-

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The Lead-Acid (Storage) 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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The Silver-Zinc Cell: A Button Battery

FIGURE 20-16 The silver-zinc button (miniature) cell

Zn(s),ZnO(s)|KOH(satd)|Ag2O(s),Ag(s) Zn(s) + Ag2O(s) ZnO(s) + 2 Ag(s) Ecell = 1.8 V

The Nickel-Cadmium Cell: A Rechargeable Battery

A rechargeable nickel-cadmium cell, or nicad battery

Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) 2 Ni(OH)2(s) + Cd(OH)2(s)

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The Lithium-Ion Battery

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
FIGURE 20-18 Slide 63 of 53

= G/ H = 0.83

A hydrogen-oxygen fuel cell

Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- 4 [Al(OH)4](aq)

FIGURE 20-19 A simplified aluminum-air battery

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20-6 Corrosion: Unwanted Voltaic Cells

In neutral solution: O2(g) + 2 H2O(l) + 4 e- 4 OH-(aq) 2 Fe(s) 2 Fe2+(aq) + 4 eEO2/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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FIGURE 20-21
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Protection of iron against electrolytic corrosion

Magnesium sacrificial anodes The small cylindrical bars of magnesium attached to the steel ship provide cathodic protection against corrosion. Slide 69 of 53

20-7 Electrolysis: Causing Non-spontaneous Reactions to Occur

Voltaic Cell: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Electrolytic Cell: Cu(s) + Zn2+(aq) Cu2+(aq) + Zn(s) EO2/OH- = -1.103 V E0 = 1.103 V

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Predicting Electrolysis Reaction

An Electrolytic Cell e- is the reverse of the voltaic cell. The battery must have a voltage in excess of 1.103 V in order to force the nonspontaneous reaction.
FIGURE 20-22 An electrolytic cell Slide 71 of 53

Complications in Electrolytic Cells

Overpotential. Competing reactions. Non-standard states. Nature of electrodes.

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Quantitative Aspects of Electrolysis

1 mol e- = 96485 C

Charge (C) = current (C/s) time (s)

ne- =

I t F

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20-8 Industrial Electrolysis Processes

The refining of copper by electrolysis.

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Electrorefining Electroplating Electrosynthesis

A rack of metal parts being lifted from the electrolyte solution after electroplating.

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Chlor-Alkali Process

FIGURE 20-24 Slide 77 of 53

FIGURE 20-25

The A diaphragm chlor-alkali cell mercury-cell chlor-alkali process

End of Chapter Questions Dont just read examples, work them!! If you write: Information is going through your fingers, Your muscles, Your nerves, Directly to your brain. Physically experience the solution. Your eyes and ears are not enough.
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