Professional Documents
Culture Documents
Chapter 20
Electrochemistry
John D. Bookstaver
St. Charles Community College
St. Peters, MO
2006, Prentice Hall, Inc.
Electrochemistry
Electrochemical Reactions
In electrochemical reactions, electrons
are transferred from one species to
another.
Metals tend to lose electrons and are
oxidized, non metals tend to gain
electrons and are reduced.
Electrochemistry
LEO
GER
Losing
Electrons is
Oxidation.
Gaining
Electrons is
Reduction
Electrochemistry
OIL RIG
Oxidation
Is
Loss.
Reduction
Is
Gain.
Electrochemistry
REDOX REACTIONS
Are reduction
oxidation reactions.
Electrons are
transferred.
When an atom is
losing electrons its
O.N. increases. It is
being oxidized.
When an atom gains
electrons its O.N.
decreases. It is being
reduced
Electrochemistry
Oxidation Numbers
In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.
Electrochemistry
Oxidation-Reduction
Reactions
Zn added to HCl yields the spontaneous reaction
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g).
The oxidation number of Zn has increased from 0 to 2+.
The oxidation number of H has reduced from 1+ to 0.
Zn is oxidized to Zn2+ while H+ is reduced to H2.
H+ causes Zn to be oxidized and is the oxidizing agent.
Zn causes H+ to be reduced and is the reducing agent.
Note that the reducing agent is oxidized and the oxidizing
Electrochemistry
agent is reduced.
Half Reactions
The half-reactions for
Sn2+(aq) + 2Fe3+(aq) Sn4+(aq) + 2Fe2+(aq)
are
Sn2+(aq) Sn4+(aq) +2e2Fe3+(aq) + 2e- 2Fe2+(aq)
Oxidation: electrons are products.
Reduction: electrons are reactants.
Loss of
Gain of
Electrons is
Electrons is
Oxidation
Reduction
Electrochemistry
Electrochemistry
Half-Reaction Method
Mn2+(aq) + CO2(aq)
Electrochemistry
Electrochemistry
Half-Reaction Method
First, we assign oxidation numbers.
+7
+3
MnO4 + C2O42-
+2
+4
Mn2+ + CO2
4. Adding gives:
16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq) 2Mn2+(aq) +
8H2O(l) + 10CO2(g)
5. Which is balanced!
Electrochemistry
Voltaic Cells
In spontaneous
oxidation-reduction
(redox) reactions,
electrons are
transferred and
energy is released.
Electrochemistry
Voltaic Cells
We can use that
energy to do work if
we make the
electrons flow
through an external
device.
We call such a setup
a voltaic cell.
Electrochemistry
Voltaic Cells
A typical cell looks
like this.
The oxidation occurs
at the anode.
The reduction
occurs at the
cathode.
Electrochemistry
Voltaic Cells
Once even one
electron flows from
the anode to the
cathode, the
charges in each
beaker would not be
balanced and the
flow of electrons
would stop.
Electrochemistry
Voltaic Cells
Therefore, we use a
salt bridge, usually a
U-shaped tube that
contains a salt
solution, to keep the
charges balanced.
Cations move toward
the cathode.
Anions move toward
the anode.
Electrochemistry
Voltaic Cells
In the cell, then,
electrons leave the
anode and flow
through the wire to
the cathode.
As the electrons
leave the anode, the
cations formed
dissolve into the
solution in the
anode compartment.
Electrochemistry
Voltaic Cells
As the electrons
reach the cathode,
cations in the
cathode are
attracted to the now
negative cathode.
The electrons are
taken by the cation,
and the neutral
metal is deposited
on the cathode.
Electrochemistry
Electrochemistry
Cell Potential
Cell potential is measured in volts (V).
One volt is the potential difference required
to impart 1J of energy to a charge of 1
coulomb. (1 electron has a charge of 1.6 x
10-19 Coulombs). The potential difference
between the 2 electrode provides the
driving force that pushes the electron
through the external circuit.
Electrochemistry
Electrochemistry
Electrochemistry
Electrochemistry
Electrochemistry
Cell Potentials
For the oxidation in this cell,
Ered
= 0.76 V
For the reduction,
Ered
= +0.34 V
Electrochemistry
Cell Potentials
Ecell
= Ered
(cathode) Ered
(anode)
= +0.34 V (0.76 V)
= +1.10 V
Electrochemistry
PNEUMONICS
LEO GER
OIL RIG
RED CAT
AND ALWAYS THE SOURCE OF
ELECTRONS IS THE NEGATIVE
ELECTRODE!!!
Electrochemistry
Spontaneity of Redox
Reactions
In a voltaic (galvanic) cell (spontaneous) Ered(cathode) is
more positive than Ered(anode) since
E cell E red cathode E ox anode
Or
E cell E red cathode E red anode
Electrochemistry
Electrochemistry
Eo = - 0.34 V
Eo = 0.43 V
Electrochemistry
Free Energy
G for a redox reaction can be found by
using the equation
G = nFE
where n is the number of moles of
electrons transferred, and F is a
constant, the Faraday.
1 F = 96,485 C/mol = 96,485 J/V-mol
Electrochemistry
Electrochemistry
Effect of Concentration
on Cell EMF
The Nernst Equation
A voltaic cell is functional until E = 0 at which point
equilibrium has been reached.
The point at which E = 0 is determined by the
concentrations of the species involved in the redox
reaction.
The Nernst equation relates emf to concentration using
G G RT ln Q
and noting that
nFE nFE RT ln Q
Electrochemistry
0.0592
0 E
log K eq
n
nE
log K eq
0.0592
Electrochemistry
Examples
1. Calculate Ecell for the following reaction:
Zn (s) + Cu2+ Zn2+ + Cu (s)
2. Calculate Ecell if [Zn2+] = 1.88 M and [Cu2+] =
0.020 M
3. Calculate Ecell for the following reaction:
IO3- (aq) + Fe2+ (aq) Fe3+ (aq) + I2 (aq)
4. Calculate Ecell if [IO3-] = 0.20 M, [Fe2+] = 0.65
M, [Fe3+] = 1.0 M, and [I2] = 0.75 M
Electrochemistry
Concentration Cells
Electrochemistry
Concentration Cells
We can use the Nernst equation to generate a cell that has
an emf based solely on difference in concentration.
One compartment will consist of a concentrated solution,
while the other has a dilute solution.
Example: 1.00 M Ni2+(aq) and 1.00 10-3 M Ni2+(aq).
The cell tends to equalize the concentrations of Ni2+(aq)
in each compartment.
The concentrated solution has to reduce the amount of
Ni2+(aq) (to Ni(s)), so must be the cathode.
Electrochemistry
Concentration Cells
Electrochemistry
PROBLEM
Use the Nernst equation to
determine the (emf) at 25oC of
the cell. Zn(s)Zn2+(0.00100M
Cu2+(10.0M)Cu(s).
The standard emf of this cell is
1.10 V.
Electrochemistry
Applications of
Oxidation-Reduction
Reactions
Electrochemistry
Batteries
A battery is a galvanic cell or,
more commonly, a group of
galvanic cells connected in
series.
Electrochemistry
Batteries
Electrochemistry
17_370
H2SO4
electrolyte
solution
Anode (lead
grid filled with
spongy lead)
Cathode (lead
grid filled with
spongy PbO2)
Anode reaction:
Pb(s) +H2SO4(aq) ---> PbSO4(aq) + 2H+(aq) + 2e-
Cathode reaction:
PbO2(s)+H2SO4(aq)+ 2e-+2H+(aq)->PbSO4(aq)+2H2O(l)
Overall reaction:
Pb(s)+ PbO2(s) + 2H2SO4(aq)-->PbSO4(aq)+ 2H2O (l)
Electrochemistry
17_371
Anode
(zinc inner case)
Cathode
(graphite rod)
Paste of MnO2,
NH4CL, and
carbon
Electrochemistry
Alkaline Battery
Anode: Zn cap:
Zn(s) Zn2+(aq) + 2e Cathode: MnO2, NH4Cl and C paste:
2NH4+(aq) + 2MnO2(s) + 2e- Mn2O3(s) + 2NH3(aq) +
2H2O(l)
The graphite rod in the center is an inert cathode.
For an alkaline battery, NH4Cl is replaced with KOH.
Electrochemistry
Electrochemistry
Electrochemistry
Fuel Cells
Direct production of electricity from fuels occurs in a
fuel cell.
On Apollo moon flights, the H2-O2 fuel cell was the
primary source of electricity.
Cathode: reduction of oxygen:
2H2O(l) + O2(g) + 4e- 4OH-(aq)
Anode:
2H2(g) + 4OH-(aq) 4H2O(l) + 4eElectrochemistry
17_372
Insulation
Cathode (steel)
Anode (zinc container)
Electrochemistry
Fuel Cells
...
galvanic cells for which the
reactants are continuously supplied.
2H2(g) + O2(g) 2H2O(l)
Electrochemistry
17_369
Reference solution of
dilute hydrochloric acid
Thin-walled membrane
Corrosion
Corrosion of Iron
Since Ered(Fe2+) < Ered(O2) iron can be oxidized by
oxygen.
Cathode: O2(g) + 4H+(aq) + 4e- 2H2O(l).
Anode: Fe(s) Fe2+(aq) + 2e-.
Dissolved oxygen in water usually causes the oxidation
of iron.
Fe2+ initially formed can be further oxidized to Fe3+
which forms rust, Fe2O3.xH2O(s).
Electrochemistry
Electrochemistry
Electrochemistry
Electrochemistry
Electrochemistry
Electrochemistry
Corrosion
Some metals, such as copper, gold,
silver and platinum, are relatively difficult
to oxidize. These are often called noble
metals.
About 1/5 of all iron and steel produced
each year is used to replace rusted
metal.
Electrochemistry
Self-protecting Metals
Some metals such as aluminum,
copper, and silver form a protective
coating that keeps them from
corroding further.
The protective coating for iron and
steel flakes away opening new
layers of metal to corrosion.
Electrochemistry
Prevention of Corrosion
Redox Titrations
Same as any other titration.
the permanganate ion is used often because
it is its own indicator. MnO4- is purple, Mn+2 is
colorless. When reaction solution remains
clear, MnO4- is gone.
Chromate ion is also useful, but color change,
orangish yellow to green, is harder to detect.
Electrochemistry
Example
The iron content of iron ore can be
determined by titration with standard
KMnO4 solution. The iron ore is dissolved
in excess HCl, and the iron reduced to
Fe+2 ions. This solution is then titrated with
KMnO4 solution, producing Fe+3 and Mn+2
ions in acidic solution. If it requires 41.95
mL of 0.205 M KMnO4 to titrate a solution
made with 10.613 g of iron ore, what
percent of the ore was iron?
Electrochemistry