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Slide 1 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 1 of 53
PHILIP DUTTONUNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY ANDBIOCHEMISTRY
TENTH EDITION
GENERAL CHEMISTRYPrinciples and Modern Applications
PETRUCCI HERRING MADURA BISSONNETTE
Electrochemistry 20
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Slide 2 of 53
Spontaneous Change:
Entropy and Gibbs Energy
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 2 of 53
ONTENTS19-1 Electrode Potentials and Their
Measurement
19-2 Standard Electrode Potentials
19-3 Ecell, G, and K
19-4 Ecellas a function of
Concentrations
19-5 Batteries: Producing ElectricityThrough Chemical Reactions
19-6 Corrosion: Unwanted Voltaic
Cells
19-7 Electrolysis: Causing
Nonspontaneous Reactions toOccur
19-8 Industrial Electrolysis Processes
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Slide 3 of 53
20-1 Electrode Potentials and Their Measurement
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 3 of 53
FIGURE 20-1
Behaviour of Ag+(aq) and Zn+(aq) in the presence of copper
Cu(s) + 2Ag+(aq)
Cu2+(aq) + 2 Ag(s)
Cu(s) + Zn2+(aq)
No reaction
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Slide 4 of 53
An electrochemical half cell
FIGURE 20-2
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Anode
Cathode
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Slide 5 of 53
Measurement of the electromotive force of an electrochemical cell
FIGURE 20-3
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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Slide 6 of 53
The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an electrochemical cell
FIGURE 20-4
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Ecell= 1.103 V
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Slide 7 of 53
Cell Diagrams and Terminology
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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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Slide 8 of 53
The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an electrochemical cell
FIGURE 20-4
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
Ecell= 1.103 V
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Slide 9 of 53
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-.
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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Slide 12 of 53
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.
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
The Standard Hydrogen Electrode (SHE)
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Slide 13 of 53
The standard hydrogen electrode (SHE)
FIGURE 20-5
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
2 H+(a = 1) + 2 e- H2(g, 1 bar) E= 0
V
Pt|H2(g, 1 bar)|H+(a = 1)
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Slide 14 of 53
Standard Electrode Potential, E
Ecell= Ecathode(right)Eanode,(left)
The tendency for a reductionprocess 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).
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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Slide 15 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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
Standard cell potential: the potential difference of a
cell formed from twostandardelectrodes.
E
cell=E
cathode -E
anode
cathodeanode
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Slide 16 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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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Slide 17 of 53
Measuring standard reduction potential
FIGURE 20-6
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
anodeanode cathode cathode
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Slide 18 of 53
TABLE 20.1 Some Selected Standard Electrode (Reduction)
Potentials at 25C
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 18 of 53
Reduction Half-Reaction E, V
Acidic Solution
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Slide 19 of 53
TABLE 20.1 Some Selected Standard Electrode (Reduction)
Potentials at 25C (continued)
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 19 of 53
Reduction Half-Reaction E, V
Acidic Solution
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Slide 20 of 53
TABLE 20.1 Some Selected Standard Electrode (Reduction)
Potentials at 25C (continued)
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 20 of 53
Reduction Half-Reaction E, V
Acidic Solution
Basic Solution
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Slide 23 of 53
20-3 Ecell, G, and Keq
Faraday constant,
F = 96,485 C mol-1
When products are in their
standard states
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
elec= -zFEcellG= -zFEcell
G= -zFEcell
Michael Faraday 1791-1867
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Slide 24 of 53
Combining Reduction Half-Equations
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Fe3+(aq) + 3e- Fe(s) EFe3+/Fe= ?
Fe2+(aq) + 2e- Fe(s) EFe2+/Fe= -0.440 V
Fe3+
(aq) + 1e-
Fe2+
(aq) E
Fe3+/Fe2+= 0.771 V
Fe3+(aq) + 3e- Fe(s)
G= +0.880 J
G
= -0.771 J
G= +0.109 JEFe3+/Fe= +0.331 V
G= +0.109 J = -nFE
EFe3+/Fe= +0.109 J /(-3F)= -0.0363 V
but cannot simply add E
can add G
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Slide 25 of 53
Spontaneous Change in
Oxidation-Reduction Reactions
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
G < 0 for spontaneous change.
ThereforeEcell> 0 because Gcell= -nFEcell
E cell> 0Reaction proceeds spontaneously as written.
E cell= 0Reaction is at equilibrium.
E cell< 0Reaction proceeds in the reversedirection spontaneously.
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Slide 28 of 53
The Behavior or Metals Toward Acids
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
M(s) M2+(aq) + 2 e- E= -EM2+/M
2 H+(aq) + 2 e- H2(g) EH+/H2= 0 V
2 H+(aq) + M(s) H2(g) + M2+(aq)
Ecell=EH+/H2-EM2+/M= -EM2+/M
WhenEM2+/M < 0,Ecell> 0. Therefore G< 0.
Metals with negative reduction potentials react with acids.
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Slide 30 of 53
Relationship Between Ecelland Keq
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
G= -RTlnKeq= -zFEcell
Ecell = zF
RT
lnKeq
Ecell =z
0.25693lnKeq
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Slide 31 of 53
A summary of important thermodynamic, equilibrium and electrochemical
relationships under standard conditions.
FIGURE 20-8
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Slide 33 of 53
20-4 Ecellas a Function of Concentration
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-9
Variation of Ecellwith ion concentrations
G= G-RTln Q
-zFEcell= -zFEcell-RTln Q
Ecell=Ecell- ln QzF
RT
Convert to log10and calculate constants.
Ecell=Ecell- log Qz
0.0592 VThe Nernst Equation
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Slide 34 of 53
Concentration Cells
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-11
A concentration cell
Two half cells with identical electrodes but different ion concentrations.
2 H+(1 M) 2 H+(xM)
Pt|H2(1 atm)|H+(xM)||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+(xM) + 2 e-
Ecell=EH+/H2-EH+/H2
= 0
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Slide 35 of 53Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20Slide 35 of 54
Ecell=Ecell- logz
0.0592 V x2
12
Ecell= 0 - log2
0.0592 V x2
1
Ecell= - 0.0592 V logx
Ecell= (0.0592 V) pH
2 H+(1 M) 2 H+(xM)
Ecell=Ecell
- log Qz
0.0592 V
Ecell=EH+/H2-EH+/H2
= 0
but we can calculateusing the Nernst Equation
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Slide 38 of 53
Measurement of Ksp
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20Slide 38 of 54
FIGURE 20-12
A concentration cell for determining Kspof AgI
Ag+(0.100 M) Ag+(satd M)
Ag|Ag+(satd AgI)||Ag+(0.10 M)|Ag(s)
Ag+(0.100 M) + e- Ag(s)
Ag(s) Ag+(satd) + e-
Work Example 20-11 as an exerciseto understand the process.
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Slide 40 of 53
Schematic diagrams of some common electrodes
FIGURE 20-13
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20Slide 40 of 54
0.22233 V
0.2680 V (satd KCl)
or
0.2412 V (1 M KCl)
Th Gl El t d d th El t h i l
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Slide 41 of 53
The Glass Electrode and the Electrochemical
Measurement of pH
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Ag|AgCl(s)|Cl-(1.0M),H+(1.0M)|glass membrane|H+(unknown)|| Cl-(1.0 M)|AgCl(s)|Ag(s)
Ag(s) + Cl- AgCl(s) + e-
H+(1.0 M) H+(unknown)
AgCl(s) + e- 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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Slide 42 of 53
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 energy.
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
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Slide 43 of 53
The Leclanch (dry) cell
FIGURE 20-14
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
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Slide 44 of 53
The Leclanch Dry Cell
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Zn(s) Zn2+(aq) + 2 e-Oxidation:
2 MnO2(s) + H2O(l) + 2 e- Mn2O3(s) + 2 OH
-Reduction:
NH4+ + OH- NH3(g) + H2O(l)Acid-base reaction:
NH3 + Zn2+(aq)+ Cl- [Zn(NH3)2]Cl2(s)
Precipitation reaction:
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Slide 45 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Zn2+(aq)+ 2 OH- Zn (OH)2(s)
Zn(s) Zn2+(aq) + 2 e-
Oxidation reaction can be thought of in two steps:
2 MnO2(s) + H2O(l) + 2 e- Mn2O3(s) + 2 OH-Reduction:
Zn(s)+ 2 OH- Zn (OH)2(s) + 2 e-
The alkaline cell
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Slide 46 of 53
The Lead-Acid(Storage) Battery
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20
The lead-acid (storage) cell
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Slide 47 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
PbO2(s) + 3 H+(aq) + HSO4
-(aq) + 2 e- PbSO4(s) + 2 H2O(l)
Oxidation:
Reduction:
Pb (s) + HSO4-(aq) PbSO4(s) + H
+(aq) + 2 e-
PbO2(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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Slide 48 of 53
The Silver-Zinc Cell: A Button Battery
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20-16
The silver-zinc button (miniature) cell
Zn(s) + Ag2O(s) ZnO(s) + 2 Ag(s) Ecell= 1.8 V
Zn(s),ZnO(s)|KOH(satd)|Ag2O(s),Ag(s)
The Nickel Cadmium Cell: A Rechargeable
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Slide 49 of 53
The Nickel-Cadmium Cell: A Rechargeable
Battery
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) 2 Ni(OH)2(s) + Cd(OH)2(s)
A rechargeable nickel-cadmium cell, or nicad battery
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Slide 50 of 53
The Lithium-Ion Battery
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20Slide 50 of 53
FIGURE 20-17
The electrodes of a lithium-ion battery
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The positive electrode consists of lithium cobalt(III) oxide, LiCoO2, and the
negative electrode is highly crystallized graphite. To complete the battery an
electrolyte is needed, which can consist of an organic solvent and ions, such as
LiPF6. The structure of LiCoO2, and graphite electrode is illustrated in Figure 20-17.
In the charging cycle at the positive electrode, lithium ions are released into
the electrolyte solution as electrons are removed from the electrode. To
maintain a charge balance, one cobalt(III) ion is oxidized to cobalt(IV) foreach lithium ion released.
LiCoO2(s)+Li(1-x) = 2CoO2(s) + xLi+(solvent) + x e-
C(s) + xLi+(solvent) + x e- = LixC(S)
The layered graphite electrode is shown with lithium ions (violet) intercalated. The
LiCoO2is shown as a face-centered cubic lattice, with the oxygen atoms (red)
occupying the corners and the faces, the cobalt atoms (pink) occupying half of the
edges, and the lithium atoms occupying half of the edges and the central octahedral
hole. This arrangement leads to planes of oxygen, cobalt, oxygen, lithium, oxygen,
cobalt, and oxygen atoms, as indicated in the figure.
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Slide 52 of 53
Fuel Cells
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20-18
A hydrogen-oxygen fuel cell
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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Slide 53 of 53
Air Batteries
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20-19
A simplified aluminum-air battery
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- 4 [Al(OH)4](aq)
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Slide 54 of 53
20-6 Corrosion: Unwanted Voltaic Cells
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
O2(g) + 2 H2O(l) + 4 e- 4 OH-(aq)
2 Fe(s) 2 Fe2+(aq) + 4 e-
2 Fe(s) + O2(g)+ 2 H2O(l)
2 Fe2+(aq) + 4 OH-(aq)
Ecell= 0.841 V
EO2/OH-= 0.401 V
EFe/Fe2+= -0.440 V
I n neutral solution:
I n acidic solution:
O2(g) + 4 H+(aq) + 4 e- 4 H2O (aq) EO2/OH-= 1.229 V
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Slide 55 of 53
Demonstration of corrosion and methods of corrosion protection
FIGURE 20-20
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
The pink color
results from the
indicatorphenolphthalein in
the presence of base.
The dark blue color
results from the
formation of
Turnbulls blue
KFe[Fe(CN)6].
Zn
Cu
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Slide 56 of 53
Protection of iron against electrolytic corrosion
FIGURE 20-21
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
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Slide 57 of 53 Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
The small cylindrical bars of magnesium attached to the steel ship
provide cathodic protection against corrosion.
Magnesium sacrificial anodes
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Slide 58 of 53
20-7 Electrolysis: Causing Non-spontaneous
Reactions to Occur
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Voltaic Cell :
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) EO2/OH-= 1.103 V
Electolytic Cell:
Cu(s) + Zn2+(aq) Cu2+(aq) + Zn(s) EO2/OH-= -1.103 V
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Slide 59 of 53
Predicting Electrolysis Reaction
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20-22
An electrolytic cell
An Electrolytic Cell
e- is the reverse of the
voltaic cell.
The battery must have a
voltage in excess of 1.103V in order to force the
non-spontaneous reaction.
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Slide 60 of 53
Complications in Electrolytic Cells
Overpotential.
Competing reactions.
Non-standard states.
Nature of electrodes.
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Q f
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Slide 61 of 53
Quantitative Aspects of Electrolysis
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
ne-= It
F
1 mol e-= 96485 C
Charge (C) = current (C/s) time (s)
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20 8 I d t i l El t l i P
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Slide 64 of 53
20-8 Industrial Electrolysis Processes
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
The refining of copper by electrolysis.
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Slide 65 of 53
Electrorefining
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
Electroplating
Electrosynthesis
A rack of metal parts being lifted from theelectrolyte solution after electroplating.
Chl Alk li P
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Slide 66 of 53
Chlor-Alkali Process
Copyright 2011 Pearson Canada Inc.General Chemistry: Chapter 20
FIGURE 20-24
A diaphragm chlor-alkali cell
FIGURE 20-25
The mercury-cell chlor-alkali process
E d f Ch t Q ti
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End of Chapter Questions
Dont just read examples, workthem!!
If you write:
Information is going through your fingers,
Your muscles,
Your nerves,
Directlyto your brain.
Physically experience the solution.
Your eyes and ears are not enough.