BISSONNETTE
Electrochemistry
PHILIP DUTTON
UNIVERSITY OF WINDSOR DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
20
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Cu(s) + 2Ag+(aq)
Cu(s) + Zn2+(aq)
Cu2+(aq) + 2 Ag(s)
No reaction
Anode
anode
cathode
Zn(s) + Cu2+(aq) E
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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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)
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.
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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
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20-3
elec = -zFEcell
G = -zFEcell Faraday constant, F = 96,485 C mol-1 When products are in their standard states G = -zFEcell
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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
G = +0.880 J G = -0.771 J
G = +0.109 J = -nFE
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.
E = -EM2+/M EH+/H2 = 0 V
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Ecell =
Ecell =
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FIGURE 20-8 A summary of important thermodynamic, equilibrium and electrochemical relationships under standard conditions.
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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
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
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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
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
Indicator electrode
Eref(outer)
Elj
E(membrane)
Eref(inner)
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
Cathode: K+int(400 mM) + e Anode: overall: E cell K+ext (15 mM) + e K+int(400 mM)
TMHsiung@2008 45 /45
(a) The silversilver chloride electrode (b) The standard calomel 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.
P.327
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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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.
P.327
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Figure 14-10
Figure 14-10
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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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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P.328
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.
Acid-base reaction:
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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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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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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
Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- 4 [Al(OH)4](aq)
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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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Magnesium sacrificial anodes The small cylindrical bars of magnesium attached to the steel ship provide cathodic protection against corrosion. Slide 69 of 53
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1 mol e- = 96485 C
ne- =
I t F
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Chlor-Alkali Process
FIGURE 20-25
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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