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elec
= nFE
G = -nFE
G = -nFE
Slide 18
Problem Determining E
o
from an E
o
cell
measurement
PROBLEM: A voltaic cell houses the reaction between aqueous bromine
and zinc metal:
PLAN:
SOLUTION:
Br
2
(aq) + Zn(s) Zn
2+
(aq) + 2Br
-
(aq) E
0
cell
= 1.83V
Calculate E
0
bromine
given E
0
zinc
= -0.76V
The reaction is spontaneous as written since the E
0
cell
is (+).
Zinc is being oxidized and is the anode. Therefore the
E
0
bromine
can be found using E
0
cell
= E
0
cathode
- E
0
anode
.
anode: Zn(s) Zn
2+
(aq) + 2e
-
E = +0.76
E
0
Zn
as Zn
2+
(aq) + 2e
-
Zn(s) is -0.76V
E
0
cell
= E
0
cathode
- E
0
anode
= 1.83 = E
0
bromine
- (-0.76)
E
0
bromine
= 1.83 - 0.76 = +1.07 V
Slide 17
Problem Calculating E
o
cell
for a reaction
A new battery system currently under study for possible use in
electric vehicles is the zinc-chlorine battery. The overall reaction
producing electricity in this cell is Zn(s) + Cl
2
(g) ZnCl
2
(aq).
What is E
o
cell
of this voltaic cell?
Slide 16
Standard Reduction Potentials
Slide 15
Measuring Standard Reduction Potential
cathode cathode anode anode
Slide 14
Standard Cell Potential
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
E
cell
= E
right
- E
left
E
cell
= E
Cu
2+
/Cu
- E
H
+
/H2
0.340 V = E
Cu
2+
/Cu
- 0 V
E
Cu
2+
/Cu
= +0.340 V
H
2
(g, 1 atm) + Cu
2+
(1 M) H
+
(1 M) + Cu(s) E
cell
= 0.340 V
Slide 13
Reduction Couples
Cu
2+
(1M) + 2 e
-
Cu(s) E
Cu
2+
/Cu
= ?
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
Standard cell potential: the potential difference of a
cell formed from two standard electrodes.
E
cell
= E(right)
cathode
- E(left)
anode
cathode anode
Slide 12
Standard Electrode Potential, E
E defined by international agreement.
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).
Slide 11
Standard Hydrogen Electrode
2 H
+
(a = 1) + 2 e
-
H
2
(g, 1 bar) E = 0 V
Pt|H
2
(g, 1 bar)|H
+
(a = 1)
Slide 10
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)
Slide 9
Problem - Representing a Redox Reaction by
Means of a Cell Diagram
PROBLEM: Diagram, show balanced equations, and write the notation for a
voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO
3
)
3
solution, another half-cell with an Ag bar in an AgNO
3
solution, and
a KNO
3
salt bridge. Measurement indicates that the Cr electrode is
negative relative to the Ag electrode.
PLAN:
SOLUTION:
Identify the oxidation and reduction reactions and write each half-
reaction. Associate the (-)(Cr) pole with the anode (oxidation) and
the (+) pole with the cathode (reduction).
Voltmeter
Oxidation half-reaction
Cr(s) Cr
3+
(aq) + 3e
-
Reduction half-reaction
Ag
+
(aq) + e
-
Ag(s)
Overall (cell) reaction
Cr(s) + 3Ag
+
(aq) Cr
3+
(aq) + 3Ag(s)
Cr
Cr
3+
Ag
Ag
+
K
+
NO
3
-
salt bridge
e
-
Cr(s) | Cr
3+
(aq) || Ag
+
(aq) | Ag(s)
Slide 8
A voltaic (galvanic) cell based on the zinc-copper reaction.
Oxidation half-reaction
Zn(s) Zn
2+
(aq) + 2e
-
Reduction half-reaction
Cu
2+
(aq) + 2e
-
Cu(s)
Overall (cell) reaction
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
Slide 7
Terminology
Galvanic cells.
Produce electricity as a result of spontaneous
reactions, e.g. Cells on slides 4 & 6
Electrolytic cells.
Non-spontaneous chemical change driven by
electricity.
Couple, M|M
n+
A pair of species related by a change in number of e
-
.
Slide 6
Terminology
E
cell
= 1.103 V
Slide 5
Terminology
Electromotive force, E
cell
.
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
(usually a salt bridge) shown by ||.
Slide 4
An Electrochemical Cell
Slide 3
An Electrochemical Half-Cell
Anode
Cathode
Slide 2
Electrode Potentials and Their Measurement
Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2 Ag(s)
Cu(s) + Zn
2+
(aq)
No reaction
General Chemistry
Principles and Modern Applications
Petrucci Harwood Herring Madura
9
th
Edition
Chapter 20: Electrochemistry
Fran Kerton
Memorial University of Newfoundland,
St. Johns, Canada
A1B 3X7