Chemistry General: Chapter 20: Electrochemistry

Prentice-Hall 2007 General Chemistry: Chapter 20 Slide 1 of 54
Philip Dutton
University of Windsor, Canada
Prentice-Hall 2007

CHEMISTRY
Ninth
Edition GENERAL
Principles and Modern Applications
Petrucci Harwood Herring Madura
Chapter 20: Electrochemistry
Contents
20-1 Electrode Potentials and Their Measurement
20-2 Standard Electrode Potentials
20-3 E
cell
, G, and K
eq

20-4 E
cell
as a Function of Concentration
20-5 Batteries: Producing Electricity Through
Chemical Reactions
20-6 Corrosion: Unwanted Voltaic Cells
20-7 Electrolysis: Causing Non-spontaneous Reactions
to Occur
20-8 Industrial Electrolysis Processes
Focus On Membrane Potentials
20-1 Electrode Potentials and
Their Measurement
Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2 Ag(s)
Cu(s) + Zn
2+
(aq)
No reaction
An Electrochemical Half Cell
Anode
Cathode
Oxidation
Reduction
An Electrochemical Cell
Oxidation: Cu(s) Cu
2+
(aq) + 2e
-
Recduction: 2{Ag
+
(aq) +2e
-
Ag(s)}
_______________________________________
Overall: Cu(s) + 2Ag
+
(aq) Cu
2+
(aq) + Ag(s)
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 ||.
Terminology
Zn(s) | Zn
2+
(aq) || Cu
2+
(aq) | Cu(s) E
cell
= 1.103 V
Oxd. Zn(s) Zn
2+
(aq) +2e
-
E
o
= +0.763V
Red. Cu
2+
(aq) +2e
-
Cu(s) E
o
= +0.340V
______________________________________
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
cell
= 1.103V

Terminology
Galvanic cells.
Produce electricity as a result of spontaneous reactions.
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
-
.
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)
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)
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).

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
cathode
-

E
anode
cathode anode
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
cathode
-

E
anode
E
cell
= E
Cu
2+
/Cu
-

E
H
+
/H
2
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
Measuring Standard Reduction Potential
anode anode cathode cathode
Standard Reduction Potentials
Copyright 2011 Pearson
Canada Inc.
20 - 18
Canada Inc.
20 - 19
20-3 E
cell
, G, and K
eq

Cells do electrical work.
Moving electric charge.
Faraday constant,
F = 96,485 C mol
-1

elec
= zFE
(z = number of electrons)
G = -zFE
cell
G = -zFE
cell

(in Standard state)
Michael Faraday 1791-1867
Note: Joule = volt x coulomb
Combining Half Reactions
Fe
3+
(aq) + 3e
-
Fe(s) E
Fe
3+
/Fe
= ?
Fe
2+
(aq) + 2e
-
Fe(s) E
Fe
2+
/Fe
= -0.440 V
Fe
3+
(aq) + 3e
-
Fe
2+
(aq) E
Fe
3+
/Fe
2+ = 0.771 V
Fe
3+
(aq) + 3e
-
Fe(s)
G = +0.880 J
G = -0.771 J
G = +0.109 V E
Fe
3+
/Fe
= +0.331 V
G = +0.109 V = -nFE
E
Fe
3+
/Fe
= +0.109 V /(-3F) = -0.0363 V
Spontaneous Change
G < 0 for spontaneous change.
Therefore E
cell
> 0 because G
cell
= -nFE
cell

E
cell
> 0
Reaction proceeds spontaneously as written.
E
cell
= 0
Reaction is at equilibrium.
E
cell
< 0
Reaction proceeds in the reverse direction spontaneously.
The Behavior or Metals Toward Acids
M(s) M
2+
(aq) + 2 e
-
E = -E
M
2+
/M
2 H
+
(aq) + 2 e
-
H
2
(g) E
H
+
/H
2
= 0 V
2 H
+
(aq) + M(s) H
2
(g) + M
2+
(aq)
E
cell
= E
H
+
/H
2
- E
M
2+
/M
= -E
M
2+
/M

When E
M
2+
/M
< 0, E
cell
> 0. Therefore G < 0.
Metals with negative reduction potentials react with acids.

Relationship Between E
cell
and K
eq

G = -RT ln K
eq
= -nFE
cell
E
cell
=
nF
RT
ln K
eq

Canada Inc.
20 - 25
Summary of Thermodynamic, Equilibrium
and Electrochemical Relationships.
20-4 E
cell
as a Function of Concentration
at Nonstandard Conditions
G = G -RT ln Q

-nFE
cell
= -nFE
cell
-RT ln Q
E
cell
= E
cell
- ln Q
nF
RT
Convert to log
10
and calculate constants.
E
cell
= E
cell
- log Q
n
0.0592 V
The Nernst Equation:
Pt|Fe
2+
(0.10 M),Fe
3+
(0.20 M)||Ag
+
(1.0 M)|Ag(s)
Applying the Nernst Equation for Determining E
cell
. What
is the value of E
cell
for the voltaic cell pictured below and
diagrammed as follows?

EXAMPLE 20-8
E
cell
= E
cell
- log Q
n
0.0592 V
Pt|Fe
2+
(0.10 M),Fe
3+
(0.20 M)||Ag
+
(1.0 M)|Ag(s)
E
cell
= E
cell
- log
n
0.0592 V [Fe
3+
]
[Fe
2+
] [Ag
+
]
Fe
2+
(aq) + Ag
+
(aq) Fe
3+
(aq) + Ag

(s)
E
cell
= 0.029 V 0.018 V = 0.011 V
EXAMPLE 20-8
Canada Inc.
20 - 30
Concentration Cells
Two half cells with identical electrodes
but different ion concentrations.
2 H
+
(1 M) 2 H
+
(x M)
Pt|H
2
(1 atm)|H
+
(x M)||H
+
(1.0 M)|H
2
(1 atm)|Pt(s)
2 H
+
(1 M) + 2 e
-
H
2
(g, 1 atm)
H
2
(g, 1 atm) 2 H
+
(x M) + 2 e
-
Concentration Cells
E
cell
= E
cell
- log
n
0.0592 V x
2

1
2

E
cell
= 0 - log
2
0.0592 V x
2

1
E
cell
= - 0.0592 V log x
E
cell
= (0.0592 V) pH
2 H
+
(1 M) 2 H
+
(x M) E
cell
= E
cell
- log Q
n
0.0592 V
Measurement of K
sp

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
-
Using a Voltaic Cell to Determine K
sp
of a Slightly Soluble
Solute. With the date given for the reaction on the previous
slide, calculate K
sp
for AgI.

AgI(s) Ag
+
(aq) + I
-
(aq)
Let [Ag+] in a saturated Ag
+
solution be x:
Ag
+
(0.100 M) Ag
+
(satd M)
E
cell
= E
cell
- log Q =
n
0.0592 V
E
cell
- log
n
0.0592 V
[Ag
+
]
0.10 M soln

[Ag
+
]
satd AgI

EXAMPLE 20-10
E
cell
=
E
cell
- log
n
0.0592 V
[Ag
+
]
0.10 M soln

[Ag
+
]
satd AgI

E
cell
=
E
cell
- log
n
0.0592 V
0.100
x
0.417 = 0 - (log x log 0.100)
1
0.0592 V
0.417
log 0.100 -
0.0592
log x = = -1 7.04 = -8.04
x = 10
-8.04

= 9.110
-9
K
sp
= x
2
= 8.310
-17
EXAMPLE 20-10
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.

The Leclanch (Dry) Cell
Dry Cell
Zn(s) Zn
2+
(aq) + 2 e
-
Oxidation:
2 MnO
2
(s) + H
2
O(l) + 2 e
-
Mn
2
O
3
(s) + 2 OH
-
Reduction:
NH
4
+
+ OH
-
NH
3
(g) + H
2
O(l)

Acid-base reaction:
NH
3

+ Zn
2+
(aq)

+ Cl
-
[Zn(NH
3
)
2
]Cl
2
(s)

Precipitation reaction:
Alkaline Dry Cell
Zn
2+
(aq)

+ 2 OH
-
Zn (OH)
2
(s)

Zn(s) Zn
2+
(aq) + 2 e
-

Oxidation reaction can be thought of in two steps:
2 MnO
2
(s) + H
2
O(l) + 2 e
-
Mn
2
O
3
(s) + 2 OH
-
Reduction:
Zn

(s)

+ 2 OH
-
Zn (OH)
2
(s) + 2 e
-
Lead-Acid (Storage) Battery
The most common secondary battery.
Lead-Acid Battery
PbO
2
(s) + 3 H
+
(aq) + HSO
4
-
(aq) + 2 e
-
PbSO
4
(s) + 2 H
2
O(l)
Oxidation:
Reduction:
Pb (s) + HSO
4
-
(aq) PbSO
4
(s) + H
+
(aq) + 2 e
-

PbO
2
(s) + Pb(s) + 2 H
+
(aq) + HSO
4
-
(aq) 2 PbSO
4
(s) + 2 H
2
O(l)
E
cell
= E
PbO
2
/PbSO
4
- E
PbSO
4
/Pb
= 1.74 V (-0.28 V) = 2.02 V

The Silver-Zinc Cell: A Button Battery
Zn(s),ZnO(s)|KOH(satd)|Ag
2
O(s),Ag(s)
Zn(s) + Ag
2
O(s) ZnO(s) + 2 Ag(s) E
cell
= 1.8 V
The Nickel-Cadmium Cell
Cd(s) + 2 NiO(OH)(s) + 2 H
2
O(L) 2 Ni(OH)
2
(s) + Cd(OH)
2
(s)
Fuel Cells
O
2
(g) + 2 H
2
O(l) + 4 e
-
4 OH
-
(aq)
2{H
2
(g) + 2 OH
-
(aq) 2 H
2
O(l) + 2 e
-
}
2H
2
(g) + O
2
(g)

2 H
2
O(l)

E
cell
= E
O
2
/OH
- - E
H
2
O/H
2

= 0.401 V (-0.828 V) = 1.229 V
= G/ H = 0.83
Fuel Cells
Lithium Ion Batteries Cells
LiCoO
2
Li
1-n
CoO
2
+ nLi + ne
-
positive electrode
nLi
+
+ ne
-
+ C Li
n
C negative electrode
The lithium ion is transported to and from the cathode and
anode with metal Co in the Li
x
CO
2
. During discharge the
cobalt is reduced from Co
+4
to Co
+3
and during charging it is
oxidized from Co
+3
to Co
+4
.
Air Batteries
4 Al(s) + 3 O
2
(g) + 6 H
2
O(l) + 4 OH
-
4 [Al(OH)
4
](aq)

20-6 Corrosion: Unwanted Voltaic Cells
O
2
(g) + 2 H
2
O(l) + 4 e
-
4 OH
-
(aq)
2 Fe(s) 2 Fe
2+
(aq) + 4 e
-
2 Fe(s) + O
2
(g)
+
2 H
2
O(l)

2 Fe
2+
(aq) + 4 OH
-
(aq)
E
cell
= 0.841 V
E
O
2
/OH
- = 0.401 V
E
Fe/Fe
2+ = -0.440 V
In neutral solution:
In acidic solution:
O
2
(g) + 4 H
+
(aq) + 4 e
-
4 H
2
O (aq) E
O
2
/OH
- = 1.229 V
Corrosion
Corrosion Protection
Corrosion Protection
20-7 Electrolysis: Causing
Non-spontaneous Reactions to Occur
Galvanic Cell:
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
O
2
/OH
- = 1.103 V
Electolytic Cell:
Zn
2+
(aq) + Cu(s) Zn(s) + Cu
2+
(aq) E
O
2
/OH
- = -1.103 V
Predicting Electrolysis Reaction
An Electrolytic Cell
e
-
is the reverse of the
voltaic cell.
Battery must have a
voltage in excess of
1.103 V in order to force
the non-spontaneous
reaction.
Complications in Electrolytic Cells
Overpotential.
Competing reactions.
Non-standard states.
Nature of electrodes.

Quantitative Aspects of Electrolysis
1 mol e
-
= 96485 C
Charge (C) = current (C/s) time (s)
n
e
- =
I t
F
Canada Inc.
20 - 55
Canada Inc.
20 - 56
20-8 Industrial Electrolysis Processes
Chlor-Alkali Process
Focus On Membrane Potentials
Nernst Potential,
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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Prentice-Hall 2007 General Chemistry: Chapter 20 Slide 1 of 54

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