CM 1502 1

Electrochemistry
1. Introduction
2. Oxidation Numbers
3. Balancing Redox Equations
4. Voltaic/Galvanic Cells
5. Cell Diagrams
6. Cell Potentials
7. Free Energy and Nernst Equations
8. Latimer Diagrams
9. Electrolytic Cells
CM 1502 2
Electrochemistry
In electrochemical reactions, electrons are transferred from
one species to another.

Electron transfer reactions oxidation-reduction (redox) are
reactions.

The electron transfer results in the generation of an electric
current (electricity).

The electron transfer can be caused by imposing an electric
current.
3
Definitions
Oxidation:
- Loss of electrons
- Increase in oxidation number
- Gain of oxygen
- Loss of hydrogen


Oxidising Agent:
- Species is reduced


Reduction:
- Gain of electrons
- Decrease in oxidation number
- Loss of oxygen
- Gain of hydrogen

Reducing Agent:
- Species is oxidised

CM 1502 4
You cannot have one without the other!
Reduction (gaining electrons) cant happen without an
oxidation to provide the electrons.
You cant have 2 oxidations or 2 reductions in the same
equation. Reduction has to occur at the cost of oxidation.
Hence, redox reactions!
LEO the lion says GER!
OIL RIG
GER!
CM 1502 5
Oxidation Numbers (O.N.)
In order to keep track of
what loses electrons and
what gains them, assign
oxidation numbers.
Zn is oxidised as it loses
two electrons to go from
neutral Zn (O.N. = 0) metal
to the Zn
2+
(O.N. = 2) ion.
Each of the H
+
is reduced
as it gains an electron each
to go from H
+
(O.N. = 1)
ions to combine to form H
2
(O.N. = 0) gas.
CM 1502 6
Assigning Oxidation Numbers
1. Elements in their elemental form have an oxidation
number of 0. e.g. Hg (O.N. = 0)

2. The oxidation number of a monoatomic ion is the
same as its charge. e.g. Cu
2+
(O.N. = 2)


CM 1502 7
Assigning Oxidation Numbers
3. Non-metals tend to have negative oxidation numbers, although some
are positive in certain compounds or ions.

Oxygen has an oxidation number of 2, except in the
peroxide ion (e.g. in H
2
O
2
) in which it has an oxidation number of
1.

Hydrogen has an oxidation number of +1, except when bonded to a
metal ( hydride ion, H
-
) in which it has an oxidation number of 1.

Fluorine always has an oxidation number of 1.

The other halogens have an oxidation number of 1 when they are
negative; they can have positive oxidation numbers, however, most
notably in oxyanions. e.g. HClO
4
(Cl O.N. = 7)



CM 1502 8
Assigning Oxidation Numbers
4. The sum of the oxidation numbers in a neutral
compound is 0.

5. The sum of the oxidation numbers in a polyatomic
ion is the charge on the ion.
*


1 + x + 4(-2) = 0
x = +7

O.N. of Mn is +7



2x + 2(-1) = 0
x = +1

O.N. of H is +1

O.N of Mn in CsMnO
4

O.N of H in H
2
O
2

O.N of l in lO
6
5-
x + 6(-2) = -5
x = +7

O.N. of I is +7

CM 1502 9
Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the equation of an
oxidation-reduction reaction is via the half-reaction
method.

This involves treating (on paper only) the oxidation and
reduction as two separate processes, balancing these
half reactions, and then combining them to attain the
balanced equation for the overall reaction.
1 oxidation half reaction + 1 reduction half reaction =>
Overall reaction
CM 1502 10
Half-Reaction Method
This must be done in sequential order.

1. Assign oxidation numbers to determine what is oxidised
and what is reduced.

2. Write the oxidation and reduction half-reactions.

3. Balance each half-reaction.
a. Balance elements other than H and O.
b. Balance O by adding H
2
O.
c. Balance H by adding H
+
.
d. Balance charge by adding electrons.

CM 1502 11
Half-Reaction Method
4. Multiply the half-reactions by integers so that the
electrons lost and gained are the same for oxidation
and reduction, respectively.

5. Add the half-reactions, subtracting things that appear
on both sides.

6. Check that the equation is balanced on both sides
according to elements present.

7. Check that the equation is balanced on both sides
according to charge.

CM 1502 12
Redox Reaction
Consider the reaction between MnO
4

(permanganate) and
C
2
O
4
2
(oxalate):

MnO
4

(aq) + C
2
O
4
2
(aq) Mn
2+
(aq) + CO
2
(aq)
NOT BALANCED
Reaction
complete
Excess
permanganate
CM 1502 13
Half-Reaction Method
First, assign oxidation numbers.
MnO
4

+ C
2
O
4
2-
Mn
2+
+ CO
2

+7 +3 +4 +2
Manganese is reduced.
Carbon is oxidised.
x + 4(-2) = -1
x = +7

2x + 4(-2) = -2
x = +3

x + 2(-2) = 0
x = +4

CM 1502 14
Oxidation Half-Reaction
C
2
O
4
2
CO
2


To balance the carbon, add a coefficient of 2:

C
2
O
4
2
2CO
2

The oxygen is now balanced as well. To balance the
charge, add 2 electrons to the right side.

C
2
O
4
2
2CO
2
+ 2e

CM 1502 15
Reduction Half-Reaction
MnO
4

Mn
2+


The manganese is balanced; to balance the oxygen, add 4 waters to
the right side.

MnO
4

Mn
2+
+ 4H
2
O

To balance the hydrogen, add 8 H
+
to the left side.

8H
+
+ MnO
4

Mn
2+
+ 4H
2
O

To balance the charge, add 5 e

to the left side.

5e

+ 8H
+
+ MnO
4

Mn
2+
+ 4H
2
O
CM 1502 16
Combining the Half-Reactions
Now combine the two half-reactions together:
C
2
O
4
2
2CO
2
+ 2e

5e

+ 8H
+
+ MnO
4

Mn
2+
+ 4H
2
O

To attain the same number of electrons on each side, multiply the first
reaction by 5 and the second by 2.

5C
2
O
4
2
10CO
2
+ 10e

10e

+ 16H
+
+ 2MnO
4

2Mn
2+
+ 8H
2
O

Add these together, subtracting things that appear on both sides and get:

16H
+
+ 2MnO
4

+ 5C
2
O
4
2
2Mn
2+
+ 8H
2
O + 10CO
2

X 5
X 2
17
1. In a redox process, H
2
SO
4
is converted to H
2
SO
3
and Fe is
converted to Fe
2+
. Write the equation for the redox reaction.






2. Balance the following reaction:
Cr
2
O
7
2-
(aq) + I
-
(aq) Cr
3+
(aq) + I
2
(aq)

Fe + H
2
SO
4
+ 2H
+
Fe
2+
+ H
2
SO
3
+ H
2
O
14H
+
+ Cr
2
O
7
2-
+ 6I
-
2Cr
3+
+ 3I
2
+ 7H
2
O

CM 1502 18
Balancing in Basic Solution
If a reaction occurs in basic solution, one can balance it
as if it occurred in acid.

Once the equation is balanced, add OH

to each side to
neutralize the H
+
in the equation and create water in
its place.

If this produces water on both sides, subtract water
from each side.
CM 1502 19
+ 14OH
-
(aq) + 14OH
-
(aq)
Cr
2
O
7
2-
+ 6I
-
2Cr
3+
+ 3I
2
+ 7H
2
O + 14OH
-
14H
2
O +
Reconcile the number of water molecules.
+ 14OH
-
Cr
2
O
7
2-
+ 6I
-
2Cr
3+
+ 3I
2
7H
2
O +
*
7
Cr
2
O
7
2-
(aq) + 6I
-
(aq) 2Cr
3+
(aq) + 3I
2
(s) + 7H
2
O(l) 14H
+
(aq) +
20
Energy is absorbed to drive a
nonspontaneous redox reaction
Figure 21.3
General characteristics of voltaic and electrolytic cells.
VOLTAIC CELL ELECTROLYTIC CELL
Energy is released from
spontaneous redox reaction
Reduction half-reaction
at electrode Y
+
+ e
-
Y
Oxidation half-reaction
X X
+
+ e
-
from electrode
Reduction half-reaction
in solution B
+
+ e
-
B
Oxidation half-reaction
A
-
A + e
-
in solution
Overall (cell) reaction
X + Y
+
X
+
+ Y; G < 0
Overall (cell) reaction
A
-
+ B
+
A + B; G > 0
Inert
electrodes
CM 1502 21
Electrolytic vs. Voltaic Cells
Voltaic cell: electric current produced
Electrolytic cell: electric current used to cause chemical change

Cells E
cell
Electrode
name
Process at
electrode
Sign of
electrode
Electrodes
Voltaic/
Galvanic
>0
Spontaneous
Anode
Cathode
Ox.
Red.
-
+
Redox
process
involves
electrodes
Electrolytic <0
Non-spontaneous
Anode
Cathode
Ox.
Red.
+
-
Electrodes
are (usually)
inert
CM 1502 22
In spontaneous oxidation-
reduction (redox) reactions,
electrons are transferred and
energy is released.

The energy can be used to do
electrical work when the electrons
are channeled through an
external device => voltaic cell.
Voltaic Cells
CM 1502 23
Voltaic Cells
Separate the species
(i.e. Zn and Cu) into two
compartments. One for
oxidation other for reduction.

Connect electrodes by a
wire/voltmeter.

Connect solutions by a salt
bridge.


Ox. Red.
-ve
+ve
24
Salt Bridge
Once even just 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. (right half cell will be -ve, preventing further electron flow)

Therefore, a salt bridge is used, usually a U-shaped tube that contains
a salt solution, to keep the charges balanced.

Left half cell: net + ve charge in solution so anions move toward the
anode.

Right half cell: net - ve charge in solution so cations move toward
the cathode.
25
Cell Diagrams
Cell diagram: Zn
(s)
I Zn
2+
(aq)
II Cu
2+
(aq)
I Cu
(s)

Ox. first then red.
If both ox. and red. species are ions, then use Pt (or graphite) as
the electrode. e.g Zn(s) I Zn
2+
(aq) II Fe
3+
(aq), Fe
2+
(aq) I Pt(s)

Cannot dip wire into solution, need an electrode.
Phase boundary Salt bridge
26
Write the balanced equation and the cell diagram for a voltaic cell that
consists of one half-cell with a Cr rod in a Cr(NO
3
)
3
solution, another half-
cell with an Ag rod in an AgNO
3
solution and a KNO
3
salt bridge.
Measurement indicates that the Cr is the negative electrode and Ag is
the positive electrode.
Oxidation half-reaction
Cr(s) Cr
3+
(aq) + 3e
-

Reduction half-reaction
3Ag
+
(aq) + 3e
-
3Ag(s)
Overall (cell) reaction
Cr(s) + 3Ag
+
(aq) Cr
3+
(aq) + 3Ag(s)
Cr(s) | Cr
3+
(aq) || Ag
+
(aq) | Ag(s)
CM 1502 27
Electromotive Force (emf)
Water only spontaneously
flows one way in a
waterfall.

Likewise, electrons only
spontaneously flow one
way in a redox reaction.

Which species gives
(anode) and which takes
(cathode)?
28
Standard Reduction Potentials (E
red
)
Standard:
g = 1 atm
aq = 1 molL
-1
Higher red.
potential, more
easily reduced,
half-cell will be
the cathode.
Strong oxidising
agents.
Lower red.
potential, more
easily oxidised,
half-cell will be the
anode.
Strong reducing
agents.
CM 1502 29
Standard Hydrogen Electrode:
the other half-cell
Their values are referenced to a standard hydrogen electrode
(SHE).

By definition, the standard reduction potential (E
red
) for the
hydrogen ion is 0 V:
2H
+
(aq, 1 M) + 2e

H
2
(g, 1 atm)
aq = 1 molL
-1
i.e. pH = 0
30
V 0 E
o
red
=
by convention, E
red
of SHE = 0
Standard Hydrogen Electrode
Cu
2+
is more readily
reduced cf. H
+
E
red
(Cu
2+
) > 0


H
+
is more readily
reduced cf. Zn
2+
E
red
(Zn
2+
) < 0
31
Standard Cell Potentials
Referenced against the SHE, all species with E
red
> 0 were
reduced and all species with E
red
< 0 were oxidised.

After a half-cell is referenced against the SHE, its E
red
can be
compared against other half-cells.

For a given voltaic cell, the cell potential at standard conditions
can be written as this equation:
E
cell


= E
red
(cathode) E
red
(anode)

Standard reduction potentials
Larger E
red
,
Reduction process
Smaller E
red
,
Oxidation process
32
Cell Potentials
E
cell


= E
red


(cathode) E
red


(anode)
= +0.34 V (0.76 V)
= +1.10 V
For the oxidation (anode) in this cell,


For the reduction (cathode),
E
red
= +0.34 V

E
red
= 0.76 V

CM 1502 33
Consider the following two electrode reactions and their
standard electrode potentials:

Al
3+
(aq)
+ 3e
-
Al
(s)
E
0
= -1.66 V
Cd
2+
(aq)
+ 2e
-
Cd
(s)
E
0
= -0.40 V

Write the cell reaction for a voltaic cell based on these two
electrodes, and calculate the standard cell potential, E
0
cell
.

2Al
(s)
+ 3Cd
2+
(aq)
2Al
3+
(aq)
+ 3Cd
(s)

E
0
cell
= -0.40 (-1.66) = 1.26 V
34
Free Energy
G
o
for a redox reaction under standard conditions, can be
written as the equation:

G
o
= total charge x E
o
cell

G
o
= nF x E
o

G
o
= nFE
o


where:
n is the number of moles of electrons transferred per mole
of reaction
F is the Faraday constant (1 F = 96,485 Cmol
-1
)
E
o
is in V = J /C

For redox reaction to be
spontaneous, G < 0, so E > 0.
CM 1502
35
Nernst Equation
By dividing both sides of nFE = nFE + RT ln Q by nF,
we obtain the Nernst equation:
E
cell
= E
cell
E
cell
= E
cell


RT
nF
ln Q
0.059
n
log Q
At 298 K,
In log
x 2.303
Recall that G = G + RT ln Q
then nFE = nFE + RT ln Q
CM 1502
CM 1502 36
A voltaic cell consists of Mn/Mn
2+
and Cd/Cd
2+
half-cells with
concentrations [Mn
2+
] = 0.75 M and [Cd
2+
] = 0.15 M. Use the
Nernst equation to calculate the cell potential, E
cell
, at 25
o
C.
(F = 96485 Cmol
-1
)

Data: Cd
2+
(aq)
+ 2e
-
Cd
(s)
E
o
= -0.40 V
Mn
2+
(aq)
+ 2e
-
Mn
(s)
E
o
= -1.18 V


From E
red
, Cd
2+
undergoes reduction and Mn
2+
oxidation.

Overall: Cd
2+
+ Mn Cd + Mn
2+

E
cell
= -0.40 (-1.18) = 0.78 V




E
cell
= 0.78 [(8.314 x 298)/(2 x 96485)] In (0.75/0.15) = 0.76 V
[ ]
[ ] reactants
products
nF
RT
For a cell reaction, E
cell
= E
cell
ln

CM 1502 37
Concentration Cells
Notice that the Nernst equation implies that a cell could be created that
has the same substance at both electrodes.
For such a cell, E
cell
would be 0, but Q would not.

Therefore, as long as the concentrations are different,
E
cell
will not be 0.
*
E
cell
= E
cell

RT
nF
ln Q
Given the following cell: Fe(s) I Fe
2+
(aq, 2 x 10
-2
M) II Fe
2+
(aq, 1 M) I Fe(s)
and that the standard reduction potential of Fe
2+
(aq) to Fe(s) is -0.44 V,
calculate E
cell
.
Oxidation: Fe(s) Fe
2+
(2 x 10
-2
M) + 2e
-

Reduction: Fe
2+
(1 M) + 2e
-
Fe(s)
Overall: Fe
2+
(1 M) Fe
2+
(2 x 10
-2
M)
E
cell
= E
o
cell
RT/nF In Q
E
cell
= 0 RT/nF In (2 x 10
-2
/ 1)
E
cell
= 0.05 V
CM 1502
CM 1502 39
Latimer diagrams summarise the standard potential (in V)
between species of an element.
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-

in acid
+7 +5 +3 +1 0 -1
+1.20 +1.18 +1.65 +1.67 +1.36
From the Latimer Diagram, we can write the half reaction
and the potential connecting any two adjacent species. For
example,
Latimer Diagrams
ClO
3
-
+ 3H
+
+ 2e
-
HClO
2
+ H
2
O E
o
red
= +1.18V
CM 1502 40
Suppose we are interested in the potential between two
non-adjacent couples. What is the E
red
?
G
o
overall
= G
o
individual steps

-n
overall
FE
o
overall
= -n
1
FE
o
1
+ -n
3
FE
o
3
+ -n
2
FE
o
2
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-

in acid
+1.20 +1.18 +1.65 +1.67 +1.36
+7 +5 +3 +1 0 -1
What about non-adjacent species?
CM 1502 41
E
o
overall
=
-n
1
FE
o
1
+ -n
3
FE
o
3
+ -n
2
FE
o
2
-n
overall
F
E
o
overall
=
-F (n
1
E
o
1
+ n
3
E
o
3
) + n
2
E
o
2
-n
overall
F
+ n
3
E
o
3
n
1
+ n
2
+ n
3

E
o
overall
=
n
1
E
o
1
+ n
2
E
o
2
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-

in acid
+1.20 +1.18 +1.65 +1.67 +1.36
+7 +5 +3 +1 0 -1
CM 1502 42
HClO
2
+ 2H
+
+ 2e
-
HClO +H
2
O
2HClO + 2H
+
+ 2e
-
Cl
2
+ 2H
2
O
Cl
2
+ 2e
-
2Cl
-
For reaction: HClO
2
Cl
-
+ 2H
2
O + 3H
+
+ 4e
-
2 + 1 + 1
E
o
red
=
2 x 1.65

+ 1 x 1.67

+ 1 x 1.36

= 1.58 V
Note: per atom/ion!
Or follow O.N!
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-

in acid
+1.20 +1.18 +1.65 +1.67 +1.36
+7 +5 +3 +1 0 -1
CM 1502 43
Find the E
red
of IO
4
-
to HOI:

- V 0.535
2
V 1.430 V 1.154 -
3
V 1.589 -
4
I I HOI IO IO
(+7) (+5) (+1) (0) (-1)
n
1
+ n
2

E
o
red
=
n
1
E
o
1
+ n
2
E
o
2
6
2 x 1.589 + 4 x 1.154

=
= 1.299 V
CM 1502 44
Electrolysis
Electrolysis is the splitting (lysis) of a
compound using electrical energy,
typically to form elements from ions.

Say +1 V is applied at the anode
(active) to promote oxidation, -1 V will
occur at the cathode (passive).



MgBr
2
and NaCl molten salt mixture electrolysis. What is the order in which
the species will undergo oxidation or reduction?

Species that can be reduced:
Mg
2+
(E
o
red
= -2.37 V) and Na
+
(E
o
red
= -2.71 V) (cations)
Species that can be oxidised:
Br
-
(E
o
red
= 1.06 V) and Cl
-
(E
o
red
= 1.36 V) (anions)
1. Br
-
2. Cl
-
3. Mg
2+
4. Na
+
CM 1502 45
A technician is plating a faucet with 0.86 g of Cr from an electrolytic bath
containing aqueous Cr
2
(SO
4
)
3
. If 12.5 min is allowed for the plating,
what current is needed?
1 A = 1 Cs
-1
Current = Charge per sec

divide by M
96485 Cmol
-1
e
-

3 mol e
-
/mol Cr
divide by time
mass of Cr needed
mol of Cr needed
mol of e
-
transferred
current (A)
charge (C)
Cr
3+
(aq) + 3e
-
Cr(s)
0.86g x 3 mol e
-

52.00 gmol
-1

= 0.050 mol e
-

0.050 mol e
-
(96485

Cmol
-1
e
-
) = 4787

C
4787 C
12.5 min x 60 s
= 6.4 A
Electroplating
i = Q/t