Beruflich Dokumente
Kultur Dokumente
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Chapter 20:
Electrochemistry
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Electrochemistry
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Oxidation-Reduction Reactions
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Mitochondrial Respiration
NADH NAD+
Methane monoxygenase
Jespersen/Brady/Hyslop
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Na
(s)
Na+ + e
Oxidizing Agent
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Oxidation-Reduction Reaction
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Reducing Agent
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Oxidation Numbers
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of
of
of
of
of
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Reduction
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Your Turn!
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Jespersen/Brady/Hyslop
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Electrochemistry
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Jespersen/Brady/Hyslop
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Half-Cells
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reduced
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Electrode Names
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Learning Check:
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Jespersen/Brady/Hyslop
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Learning Check:
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(oxidn)
(redn)
Cathode = reduction =
2CO2 (g) H2C2O4 (aq)
Anode = oxidation = H2O2 (aq) O2 (g)
Jespersen/Brady/Hyslop
half rxn
half rxn
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Your Turn!
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Jespersen/Brady/Hyslop
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Metallic Conduction
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Electrolytic Conduction
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Salt Bridge
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Salt bridge
Jespersen/Brady/Hyslop
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Jespersen/Brady/Hyslop
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Jespersen/Brady/Hyslop
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Your Turn!
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Cell Reaction
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cathode
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
27
anode
Salt Bridge
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Cell Notation
cathode
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Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
anode
electrode
anode
electrolyte
cathode
electrolyte
cathode
electrode
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Learning Check
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Learning Check
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30
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Your Turn!
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1 V = 1 J/C
Jespersen/Brady/Hyslop
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Voltage
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Jespersen/Brady/Hyslop
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Cell potential
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Electrical Potential
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cell
Of substance
red reduced
Jespersen/Brady/Hyslop
red
Of substance
oxidized
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Reference Electrode
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Jespersen/Brady/Hyslop
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(anode)
(cathode)
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Yes!!
For substances in two half-reactions
Substance with more positive Ered
always occurs as written
Reduction
Other half-reaction with less positive Ered
always forces to run in reverse
Oxidation
Jespersen/Brady/Hyslop
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Co
oxidation
]
3[
2Au3+(aq) + 3 Co(s) 2Au(s) + 3Co2+(aq) net
Jespersen/Brady/Hyslop
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Au(s) Au3+(aq) + 3e
Al3+(aq) + 3e Al(s)
E = 1.66 V
E = +1.50 V
oxidation
reduction
55
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In electrical system
Where
n = number of moles of electrons transferred
F = Faradays constant = number of Coulombs of
charge equivalent to 1 mole of e
1 F = 96,486 C
Ecell = potential of cell in Volts
Jespersen/Brady/Hyslop
57
coulombs joules
=J
mol e
coulomb
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Ecell
G = nFEcell
G = nFEcell
Jespersen/Brady/Hyslop
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96 ,485C
= (3 mol e )
1 mol e
1J
(3.16V )
1C 1V
59
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Applications of Electrochemistry
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Jespersen/Brady/Hyslop
E cell
o
RT
=
ln K C
nF
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Ecell = +0.90 V
Determine n
So n = 6
T = 298 K
R = 8.3145 J/(molK)
Jespersen/Brady/Hyslop
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RT
=
ln K C
nF
ln K C
E cell nF
=
RT
o
K C = e 210.3 = 2.1 10 90
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Your Turn!
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Jespersen/Brady/Hyslop
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ln K C
ln K C
K C = 3.2 x 10
172
Jespersen/Brady/Hyslop
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E cell = E cell
o
RT
ln Q
nF
Nernst equation
Jespersen/Brady/Hyslop
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Q = ln
[Zn ]PH 2
+ 2
[H ]
E cell = E cell
o
RT [Zn ]PH 2
ln
+ 2
nF
[H ]
Jespersen/Brady/Hyslop
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2+
E cell
E cell
(0.03125)
= 1.05 V (0.0128 V) ln
(1.0 10 4 )
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E cell = E cell
RT
2F
ln
[H + ]2
[Cu
2+
[H + ]2
0.49 V 0.34 V = 0.01284 V ln
(0.050)
Jespersen/Brady/Hyslop
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(0.050)
= 11.68
Take antilog
[H + ]2
= e 11.68 = 8.44 10 6
(0.050)
pH = log[H+] = 3.19
Jespersen/Brady/Hyslop
72
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Your Turn!
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Jespersen/Brady/Hyslop
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Electrolytic Cell
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Nonspontaneous
Use electrical energy to force nonspontaneous
reaction to occur
Electrodes switch relative to galvanic cells
What was cathode becomes anode where oxidation occurs
What was anode becomes cathode where reduction occurs
75
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cathode
anode
2Na+() + 2e 2Na()
2Na+() + 2Cl() 2Na() + Cl2(g) (Net)
Since nonspontaneous
electrolysis
2Na+() + 2Cl() 2Na() + Cl2(g)
Jespersen/Brady/Hyslop
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Electrolytic Cell
Galvanic Cell
77
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Electrical Conduction
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Electrical Conduction
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More complex
May have competing
reactions
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Jespersen/Brady/Hyslop
cathode
anode
SO42
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Cathode
K+ (aq) + e K(s)
E = 2.92 V
2H2O + 2e H2(g) + 2OH(aq)
E = 0.83 V
H2O much easier to reduce than K+
Anode
S2O82(aq) + 2e 2SO42
E = +2.01 V
O2(g) + 4H+(aq) + 4e 2H2OE = +1.23 V
S2O82 easier to reduce than O2
So H2O easier to oxidize than SO42
Jespersen/Brady/Hyslop
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K+ (aq) + e K(s)
2SO42 S2O82(aq) + 2e
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Net reaction
2 [ 2H2O + 2e H2(g) + 2OH(aq)]
2H2O O2(g) + 4H+(aq) + 4e
6H2O O2(g) + 2H2(g) + 4OH(aq) + 4H+(aq)
2
4H2O
Net = 2H2O H2(g) + O2(g)
So what is the role of K2SO4?
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Jespersen/Brady/Hyslop
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E = +1.07 V
Br2(aq) + 2e 2Br(aq)
O2(g) + 4H+(aq) + 4e 2H2OE = +1.23 V
EO2 more + so
Expected reaction
Cu2+(aq) + 2e Cu(s)
(cathode)
2Br(aq) Br2(aq) + 2e
(anode)
Cu2+(aq) + 2Br(aq) Cu(s) + Br2(aq) (net)
Jespersen/Brady/Hyslop
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Yellow-orange
color is Br2
Anode
Jespersen/Brady/Hyslop
Cathode
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Learning Check
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E = 2.71 V
E = 0.83 V
87
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E = 0.48 V
S(s) + 2e S2(aq)
O2(g) + 4H+(aq) + 4e 2H2OE = +1.23 V
EO2 more + so
Expected reaction
88
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Your Turn!
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Cl I Br Li
Eo
Eo
Eo
Eo
=
=
=
=
+1.36V
+0.54
+1.07
-3.05V
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Michael Faraday
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Coulomb (C)
SI unit of charge
1 coulomb = 1 ampere 1 second
1 C = 1A s
Faraday (F)
1F = 96,485 C/mol e
Jespersen/Brady/Hyslop
90
q = It = nF
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Faradays Equation
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Kinetics of Electrolysis
q = charge (coulombs, C)
I = current (Amperes, A, or C/s)
t = time (s)
n = moles of electrons transferred in process
F= Faradays constant (96,485 C/mol)
Jespersen/Brady/Hyslop
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Electroplating
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molesmetal coefficien te
massmetal
= ne
MMmetal coefficien tm
Jespersen/Brady/Hyslop
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Charge (C)
1mol reactant
n mol e
Mol reactant
(or product)
MM
As=C
Current
& time
Jespersen/Brady/Hyslop
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Solution
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1mol e
mol e = 109.8C
= 1.138 10 3 mol e
96,485C
Jespersen/Brady/Hyslop
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Solution (cont.)
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3. Calculate amount of Ni in g
1.138 10
mol e
1mol Ni
2mol e
58.69 g Ni
1mol Ni
= 0.033 g Ni
Could also do the entire calculation in one
step:
1mol e
1C
= 0.033g Ni
1mol Ni
2mol e
Jespersen/Brady/Hyslop
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n mol e
Mol reactant
(or product)
MM
Faradays
(mole e)
Charge (C)
As=C
Jespersen/Brady/Hyslop
Current
& time
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Solution
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1mol Ag 1mol e
mol e = 2.500 g Ag
107.9 g Ag 1mol Ag
= 0.02317 mol e
2. Calculate quantity of charge
0.02317mol e
Jespersen/Brady/Hyslop
96,485 C
1mol e
= 2236 C
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Solution
= 46.6 min
current (A ) 0.800 A
1C
60s
1mol Ag
1mol e
2.500 g Ag
107.9 g Ag 1mol Ag
96 , 485 C
1s /C
1 min
= 46 .6 min
0.800 A
60 s
1mol e
Jespersen/Brady/Hyslop
98
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Your Turn!
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Jespersen/Brady/Hyslop
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1mol Au
2mol e
1.00 g Au
196.97 g Au 1mol Au
96, 485 C
1
1min
=i
65.3min 60s
1mol e
i = 0.250 amps
Jespersen/Brady/Hyslop
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Batteries
Galvanic cells in action
Electroplating
Electrolysis in action
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Applications of Electrochemistry
Jespersen/Brady/Hyslop
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Batteries
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Jespersen/Brady/Hyslop
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Primary Cell
Secondary Cell
Non-rechargeable
Rechargeable
Ex. Alkaline dry cell Pb storage Battery
Jespersen/Brady/Hyslop
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Alkaline Battery
Reactions:
Anode
Zn (s) + 2OH (aq) ZnO (s) + H2O + 2e
Cathode
2MnO2 (s) + H2O + 2e Mn2O3 (s) + 2OH
Net
Zn (s) + 2MnO2 (s) ZnO (s) + Mn2O3 (s)
Jespersen/Brady/Hyslop
(aq)
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(aq)
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Shelf-life
Energy density
Specific energy
Jespersen/Brady/Hyslop
106
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Ni-MH Batteries
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Reactions:
107
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108
Charge cycle
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Lithium Ion
Discharge cycle
Uncharged state
When charged
Charging rxn:
LiCoO2 + C6 Li1xCoO2 + LixC6
When cell discharges to provide electrical power
109
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Fuel Cells
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Clean burning
No electrode loss
Easily replenished
High operational temperature
Highly efficient
Jespersen/Brady/Hyslop
110
Early design
Cathode: O2(g) + 2H2O + 4e 4OH(aq)
Anode:
H2(g) + 2OH(aq) 2H2O + 2e
Net:
2H2(g) + O2(g) 2H2O
Electrolyte
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111
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Application of Electrolysis
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Electroplating
Jespersen/Brady/Hyslop
anode
Bar of Silver
112
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Uses of Electrolysis
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113
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Uses of Electrolysis
ly
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Jespersen/Brady/Hyslop
114
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Electrorefining of
Metals
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Application of Electrolysis
Purifying metals such as
Cu
Ultrapure Cu sheets =
cathodes
Lower between slabs of
impure Cu = anodes
Aqueous CuSO4 electrolyte
solution
4 weeks for anodes to
dissolve and pure Cu to
plate onto cathodes
Jespersen/Brady/Hyslop
115
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Refining Copper
Jespersen/Brady/Hyslop
116
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Corrosion of Iron
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Jespersen/Brady/Hyslop
117
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Prevention of Corrosion
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Jespersen/Brady/Hyslop
118
Cathodic Protection
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Prevention of Corrosion
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Jespersen/Brady/Hyslop
119
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Your Turn!
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120
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Extra Practice
121
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Learning Check
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Cu2+/Cu
0.337V
1.33V
Ag+/Ag
0.799V
0.126V
Pb2+/Pb
Jespersen/Brady/Hyslop
Cr2O72/Cr
MnO4/MnO2
1.695V
122
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Learning Check
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Cu2+/Cu
Ag+/Ag
Pb2+/Pb
0.337V
0.799V
-0.126V
Jespersen/Brady/Hyslop
Cr2O72/Cr
MnO4/MnO2
1.33V
1.695V
123
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Learning Check:
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124
1.662V
Zn2+/Zn
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Al3+/Al
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0.02569V [0.5]2
E = 0.899V
ln
6
[0.2]3
125
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Learning Check:
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Jespersen/Brady/Hyslop
126