Electrochemistry: Brady and Senese 5th Edition
Electrochemistry: Brady and Senese 5th Edition
Electrochemistry: Brady and Senese 5th Edition
Electrochemistry
Brady and Senese
5th Edition
Index
19.1 Galvanic cells use redox reactions to generate electricity
19.2 Cell potentials can be related to reduction potentials
19.3 Standard reduction potentials can predict spontaneous re
actions
19.4 Cell potentials are related to free energy changes
19.5 Concentrations in a galvanic cell affect the cell potential
19.6 Electrolysis uses electrical energy to cause chemical reac
tions
19.7 Stoichiometry of electrochemical reactions involves elect
ric current and time
19.8 Practical applications of electrochemistry
2
Galvanic Reactions
Are spontaneous redox reactions
Release energy as heat if no resistance is met
May be separated into compartments to harness
energy as a battery
Electrochemical Cells
In all cells, electrons transfer between the cathode
(the reduction half-cell) and the anode (the
oxidation half-cell)
Electrical current is conducted through the passage
of electrons and ions
To prevent charge buildup,
a salt bridge allows ions
to move between the
cells
Your Turn
Towards which compartment will electrons flow in
an electrochemical cell?
A. Toward the cathode
B. Toward the anode
C. It depends on the reaction
Your Turn
Through which components of the cell will ions not
flow?
A. The electrodes
B. The solution
C. The salt bridge
Learning Check
Balance and identify the cathode and anode
CrO3(s) + MnO2(s) MnO4-(aq) + Cr3+(aq) (basic)
CrO3 + 3H2O + 3e- Cr3+ + 6OHMnO2 + 4OH- MnO4- + 2H2O + 3eCrO3(s) + MnO2(s) + H2O MnO4-(aq) + Cr3+(aq) +
2OH-(aq)
Cathode: CrO3
Anode: MnO2
19.1 Galvanic cells use redox reactions to generate electricity
Learning Check:
Balance and identify the cathode and anode
H2O2(aq) + CO2(g) H2C2O4(aq) + O2(g) (acidic)
H2O2 O2 + 2H+ + 2e2H+ + 2e- + 2CO2 H2C2O4
(acidic)
10
Learning Check
Where there are no conductive metals involved in a
process, an inert electrode is used.
C(gr) and Pt are often used. Write the standard cell
notation for the reactions
CrO3(s) + MnO2(s) MnO4-(aq) + Cr3+(aq) (basic)
H2O2(aq) + CO2(g) H2C2O4(aq) + O2(g) (acidic)
C(gr);MnO2(s) | MnO4-(aq) || CrO3(s) | Cr3+(aq) | C
C(gr)|H2O2(aq), H+(aq) | O2(g) || CO2(g) | H2C2O4(aq), H+(aq) | C(gr)
11
Your Turn!
In the reaction MnO2(s) + 2H+(aq) Mn2+(aq) + H2O2(aq)
which is the correct standard cell notation?
A. Pt, MnO2(s)|H+(aq), Mn2+(aq)||H2O|H2O2(aq), H+(aq)|Pt
B. Pt|H2O2(aq), H+(aq)|H2O||H+(aq), Mn2+(aq)|MnO2(s)Pt
C. Both are correct
D. Neither is correct
12
Electrical Potential
Every substance has the potential to gain
electrons, or be reduced in oxidation state
The relative ease of gaining electrons is termed the
reduction potential, and is symbolized Ered
If the matter being observed is in standard state
then E is termed the standard reduction potential
and is symbolized as Ered
Units are Volt 1 V = 1 J C-1
13
14
Cell Potentials
The standard cell potential is calculated as:
Ecell = Ecathode - Eanode
15
Your Turn
Given the two half reactions, what would be Ecell for
the reaction:
Ni(s) + H2O2(aq) + 2H+(aq) 2H2O + Ni2+(aq)
A.
B.
C.
D.
1.52 V
-1.52 V
2.02 V
-2.02 V
Reaction
Ecell
Ni2+ + 2e- Ni
-0.25
1.77
16
17
18
Learning Check
Calculate Ecell. Which are spontaneous?
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)
[0.80 - 0.34] V = 0.46 V
Pb + Cu2+ Pb2+ + Cu
[0.34 - (-0.13)] V = 0.47 V
0.34 V
Cr2O72-/Cr3+
1.33 V
Ag+/Ag
0.80 V
MnO4-/MnO2 1.695 V
Pb2+/Pb
-0.13 V
19
Your Turn
Which of the following is not spontaneous?
A. Ni2+ + Pb Pb2+ + Ni
B. Ni + Pb2+ Pb + Ni2+
C. Zn + Pb2+ Pb + Zn2+
D. All are spontaneous
Ered
Ni2+ + 2e- Ni
Zn2+ + 2e- Zn
Pb2+ + 2e- Pb
19.3 Standard reduction potentials can predict spontaneous reactions
-0.25
-0.76
-0.13
20
21
Learning Check
Calculate G in kJ. Which are spontaneous under standard
conditions?
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)
G = -2 mol 96,500 C mol-1 0.46 J C-1 = -88.8 kJ
Pb + Cu2+ Pb2+ + Cu
G = -2 mol 96,500 C mol-1 0.47 J C-1 = -80.7 kJ
Cr2O72-(aq) + MnO2(s) MnO4-(aq) + Cr3+(aq)
G = -6 mol 96,500 C mol-1 (-0.365 J C-1) = 211 kJ
Not spontaneous
Cu2+/Cu 0.34 V
Cr2O72-/Cr
1.33 V
Ag+/Ag 0.80 V
MnO4-/MnO2
1.695 V
Pb2+/Pb -0.13 V
19.4 Cell potentials are related to free energy changes
22
Your Turn
Given that G = 65.3 kJ , what is the value for Ecell
for the reaction Cu2+(aq) + Hg(l) Hg2+(aq) + Cu(s)?
A. 6.53 V
B. .+0.338 V
C. -0.338 V
D. -0.676 V
E. None of these
23
RT ln K
E
nF
o
K e
nFE
RT
24
Learning Check:
Calculate K for the following cells.
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)
nFE
RT
8.314
J
mol
K
298.15
K
nFE
RT
E = 0.46 V
3.58 1015
E = 0.47 V
-1
-1
7.8 1015
25
nFE
RT
-1
-1
1.1 1037
26
Your Turn!
What is the value of K for the reaction at 298.15 K:
Ecell = 4.33 V
3PbO2 + 4Al 3Pb + 2Al2O3
A.
-1
-1
B.
-1
-1
C.
-1
-1
1
1
12
mol
96500
Cmol
4
.
33
JC
1 1
8
.
314
Jmol
K
298
.
15
K
27
G = G + RT ln Q
conditions,
Substituting for the free nFE = nFE + RT ln Q
energy, G, terms gives us
Dividing by nF, we get
o RT
the Nernst Equation
EE
ln Q
nF
When the temperature is
298 K and ln is converted
o 0.0592 log Q
to log,
EE
n
19.5 Concentrations in a galvanic cell affect the cell potential
28
Zn2+/Zn -0.76 V
29
Learning Check
Al|Al3+(aq) (0.5 M)||Al3+(aq) (0.2 M)|Al Al3+/Al -1.662 V
E o (1.66 (1.66)) 0 V
0.0592
[0.5]
E 0
log
7.85 103 V
3
[0.2]
Al|Al3+(aq) (0.5 M, 25 C )||Al3+(aq) (0.5 M, 50 C )|Al
8.314 (323 K)
1
ln
1.6664 V
3 96,500
[0.5]
8.314 (298 K)
1
E (-1.66)
ln
1.6659 V
3 96,500
[0.5]
Ecell Ecathode Eanode 0.0005 V
E (-1.66)
30
0.0592
[x]2
0.494 (0.25 (0.74))
log
6
[0.5]3
0.222 M = x
0.0592
[x]2
0.000571 (0.00 0.00)
log 2
2
[1]
0.978 M = x; pH = 0.00965
H+/H2
0.00 V
Cr3+/Cr
-0.74 V
Ni2+/Ni
-0.25 V
Cu2+/Cu
0.34 V
31
Your Turn
Consider the reaction shown. What is the value of Ecell?
Pb SO42-(0.1 M) PbSO4 Ni2+(0.2 M) Ni
A.
B.
C.
D.
0.998 V
-0.998 V
-0.101 V
None of these
Ecell
0.060 V
0.0592
1
(0.25 (0.36))
log
2
[0.1][0.2]
Ni2+ Ni -0.25 V
PbSO4 Pb
-0.36 V
32
Learning Check
Consider the following reaction. Is favored at high or low
temperatures?
Pt|H2(1 atm)|H+(pH = 4)||Cu2+(0.1 M)|Cu
Eo (0.34 0.00)
8.314 T
[0.0001]2
E 0.34
ln
2 96,500
[0.1]2
33
34
Galvanic Cell
35
Learning Check
In the electrolysis of aqueous K2SO4 The products of the
electrolysis are H2 and O2 gas, not the expected products solid
K and S2O82-. Why?
Cathode
Anode
K+ + e- K -2.92 V
H2O + 2e- H2 + OH- -0.83 V
Water competes
36
Learning Check
Predict the likely products of the following, when an
electrode is dipped into:
A solution of NaCl
H2(g), O2(g)
Molten NaCl
Cl2(g), Na(l)
A solution of HCl
H2(g), O2(g)
37
Your Turn
An electrode is dipped into an aqueous solution
containing K+(aq) , NO3-(aq), H2O(l) and Cl2(aq).
Which is the cathode?
A. K+(aq)
B. NO3-(aq)
C. H2O(l)
D. Cl2(aq)
Ered
-0.83
0.94
-2.92
1.36
38
39
Electroplating
In Faradays equation, we use the number of
moles of electrons transferred, ne
Because we cant see electrons, we gauge this by
the amount of metal deposited or lost
Using the half-reaction and stoichiometry, we can
relate the metal to the number of moles of
electrons
moles metal
mass metal
MM metal
coefficient e
ne
coefficient m
40
Learning Check
What current must be supplied to deposit 3.00 g Au from a
solution of AuCl3 in 200.0 s?
1 mol Au 3 mol e- 96,500 C
3.00 g Au
4410 C = I 200.0 s
196.97 g 1 mol Au
mol e
22.1 A
How much time (in s) does it take to plate 10.2 g of Ag+
using a 0.1 mA power source?
1mol Ag 1 mol e- 96,500 C
10 3 A
10.2 g Ag
0.1 mA
t
107.87 g 1 mol Ag
mA
mol e
t = 9 107 s
41
Your Turn
In Chrome Plating, Cr3+ is plated as Cr. How long will the
process take if 1.50 g Cr (MM = 52.00) are required and
the current is 50 mA?
A. 1.2 106 s
B. 4.1 105 s
C. 6.5 107 s
D. 1.7 105 s
Ered
Cr3+ +3e- Cr(s)
-0.744 V
42
Secondary Cell
Non-rechargeable
Alkaline dry cell
Rechargeable
Pb storage Battery
43
44
Lithium Batteries
Lithium can be used in batteries with high
specific energy (because of its low mass) and
high energy density (because of its very (-) Ered)
Can be either non-rechargeable (primary cells) or
rechargeable (secondary cells)
45
46
Clean burning
No electrode loss
Easily replenished
High operational
temperature
Highly efficient
47
Application: Refining
Al2O3 is electrolyzed in cryolite, AlF6.
48
Purification of Copper
49
50