DETERMINATION OF

ELECTRODE POTENTIALS
Electrochemistry

Electrochemistry deals with the chemical
changes produced by electric current and
with the production of electricity by chemical
reactions

=> all electrochemical reactions involve the
transfer of of electron and are therefore
redox reactions

=> the sites of oxidation and reduction are
separated physically so that oxidation occurs
at one location and reduction occurs at the
other
Electrochemical cells: 2
types

1. Galvanic or Voltaic cells-
spontaneous chemical reactions
produce electricity and supply it to
sn external circuit, provides a
useful source of energy

2. Electrolytic cells- electrical
energy from an external source
causes nonspontaneous reactions to
occur, no need for a salt bridge!!
Galvanic vs. Electrolytic
cell
ANODE CATHODE
Rxn
Ion moving
towards it
Sign Rxn
Ion moving
towards it
Sign
Galvanic Cell oxidation anions _ reduction cations +
Electrolytic
cell
oxidation anions + reduction cations _

=> the difference between the anode and cathode of
galvanic and electrolytic cells is their polarity!!!

Flow of electrons: ANODE CATHODE (always!!!) →
What are we measuring?

Electromotive force (emf) or Cell
potential – measures the tendency of
whether a reduction-oxidation reaction will
proceed and in what direction; measured by
E
cell
• i.e. • E
cell
= (+) => reaction proceeds from
left to right (Product
Favored)
• E
cell
= (-) => reaction proceeds from
right to left (Reactant
Favored)
• • E
cell
= 0 => system is at equilibrium
• • E
cell
= E
o
cell
=> all species are in their
standard concentrations
What are we measuring?

Note: standard electrode potentials are
relative values based on the standard
reference hydrogen electrode: H
+
(aq)

+ 2e- → ½H
2
, which has an assigned
half-cell potential of zero

* Standard states- the standard
concentration for 1.) pure substances
like pure solid and pure liquid (ex. H
2
O)
is equal to 1,
2.) ionic species (ex. Cu
2+
) is 1 M,
3.) gases is 1 atm
GALVANIC
CELLS
- useful energy is produced

Consider the reaction
• Zn
(s)
+ Cu
2+
(aq)
Cu →
(s)
+ Zn
2+
(aq)

=> in a mixed system, there is a
direct transfer of electrons from the
Zn atom to each Cu
2+
ion => work
done by the system is not harnessed

=> but if contact between the Cu
2+
and
Zn is confined to a wire connection,
electron transfer is converted to useful
electrical work through the wire

=> equivalent to the Gibbs free energy
(ΔG) of the reaction system

=> this useful electrical work is
harnessed through a galvanic cell. So,
how should a galvanic cell be set up?
Galvanic cell
• Cell notation: Zn
(s)
|Zn
2+
(1M)||Cu
2+
(1M)|Cu
(s

Anodic reaction: Zn(s) Zn →
2+
+ 2 e
-

E
o
= -0.76 V

Cathodic reaction: Cu
2+
+ 2 e
-
Cu(s) → E
o
=
0.34 V
• Overall reaction: Zn
(s)
+Cu
2+
(aq)
Cu →
(s)
+Zn
2+
(aq)
E
o
= 1.1 V
A galvanic
cell is a device
that converts
electron
transfer into
useful electrical
work
The Salt Bridge

Maintains electroneutrality

Provides the contact between the 2 solutions

=> without the salt bridge, no reaction
will occur since no ions will replenish the
charge imbalance in the half-cells

Ideal salt for salt bridge: the mobility of the
cation and the anion of the salt should be
nearly equal (ex: KNO
3
)

CATCH: YOU DO NOT NEED A SALT BRIDGE IN
AN ELECTROLYTIC CELL. DID WE?
ELECTROLYTIC
CELLS
- forcing a non-spontaneous reaction to
happen at the expense of energy
-no salt bridge is required
Electrolytic cell
• Cell notation: C
(graphite)
|I
2(s)
|I
-
(1M)||OH
-
(10
-7
M)|H
2
(1atm)|C
(graphite)
• Anodic reaction: 2 I
-
I →
2
+ 2 e
-
• Cathodic reaction: 2 H
2
O + 2 e
-
2 H →
2
+ 2 OH
-
• Overall reaction: 2 I
-
+ 2 H
2
O 2 H →
2
+ 2 OH
-
Zero
oxidation
states must
be placed
near the
electrode
No need to write
water in the cell
notation
This process
is called
electrolysi
s
Note that
graphite was
used since it
does not react
with the
solution and it
is a good
conductor of
electricity
Cell Potential, E
cell
• E
cell
= E
cathode
– E
anode

At standard conditions,
• E
cell
= E
o
cell
= E
o
cathode
– E
o
anode
• Example: E
o
cell for Zn
(s)
+ Cu
2+

(aq)
Cu →
(s)
+ Zn
2+

(aq)
Zn(s) Zn →
2+
+ 2 e
-
E
o
= -0.76 V
Cu
2+
+ 2 e
-
Cu(s) → E
o
= 0.34 V
• E
o
cell
= E
o
cathode
– E
o
anode
= 0.34 V – (-0.76 V) = 1.10 V
The Nernst Equation

used to measure the cell potential for
species not in their standard conditions (not
1M, not 1 atm, etc)

For any temperature:

At 25
o
C (298 K):
Q log
nF
RT 303 . 2
E E
cell
o
cell
− ·
where R = 8.314 J/mol
K, F = 96485 C/mol e
-
,
n = no. of e
-

transferred, T = temp.
in K
Q log
n
0592 . 0
E E
cell
o
cell
− ·
For Cu
2+
+ 2 e
-
Cu(s), →
] Cu [
1
log
n
0592 . 0
E E
2
cell
o
cell
+
− ·
Equilibrium constants from the
nernst equation
• At equilibrium, ΔG = 0, E
cell
= 0, and Q =
K
eq
thus,
becomes
• Solving for K
eq
, we get:
• Note that Keq can be K
sp
, K
a
, K
b
, K
f
, etc.
Q log
n
0592 . 0
E E
cell
o
cell
− ·
eq
cell
o
K log
n
0592 . 0
E ·
1
1
]
1

¸

·
0592 . 0
) E )( n (
log anti K
cell
o
eq
ΔG and E
cell

Thus, the reaction is spontaneous only if ΔG is
negative and E
cell
is positive

Example: Calculate the ΔG
o
in J/mol for
3 Sn
4+
+ 2Cr
(s)
3 Sn →
2+
+ 2 Cr
3+
Cathode: 3(Sn
4+
+ 2e
-
Sn →
2+
) E
o
= + 0.15 V
Anode: 2(Cr
(s)
Cr →
3+
+3e
-
) E
o
= - 0.74 V
E
o
cell
= (+0.15 V) –(-0.74 V) = + 0.89 V
=> The very negative value of ΔG indicates that the
reaction is product-favored. This is consistent with the
positive value of E
cell
cell
nFE G − · ∆
where F = 96485
C/mol e
-
, n = no.
of e
-
transferred
( ) mol / J 230 , 515 V 89 . 0
e mol
C 485 , 96
rxn mol
e mol 6
nFE G
cell
o o
− · +

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− · − · ∆
Note: 1 J = 1
CV
Equilibrium constant?
• Let us now calculate for the K
eq
of the
previous example
• Recall: E
o
cell
= (+0.15 V) –(-0.74 V) = + 0.89
V

Thus,
• => the very large value of K
eq
reinforces our
previous conclusion that the reaction is
product-favored
90
eq
10 x 59 . 1
0592 . 0
) 89 . 0 )( 6 (
log anti K ·
1
]
1

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EXPERIMENT
PROPER

Part A
Cell Notation Anode Cathode
Cu
(s)
|Cu
2+
(aq)
(0.01 M)|| Cu
2+
(aq)

(0.1M)|Cu
(s)
Cu
(s)
|Cu
2+
(aq)
(0.01M) Cu
2+
(aq)
(0.1M)|Cu
(s)
Zn
(s)
|Zn
2+
(aq)
(0.1M)|| Cu
2+
(aq)
(0.1M)|
Cu
(s)
Zn
(s)
|Zn
2+
(aq)
(0.1M) Cu
2+
(aq)
(0.1M)|Cu
(s)
C
(graphite)
|Fe
2+
(aq)
(0.5M), Fe
3+
(aq)

(1M)|| Cu
2+
(aq)
(0.5M)|Cu
(s)
C
(graphite)
|Fe
2+
(aq)
(0.5M),
Fe
3+
(aq)
(0.5M)
Cu
2+
(aq)
(0.5M)|Cu
(s)

Note that [Fe
2+
] and [Fe
3+
] are both 1 M not 2 M!!!

Theoretical E
cell
= E
o
cell
= E
o
cathode
- E
o
anode


since the
cells have standard concentrations (all 1 M)
Concentration cell

Concentration cells- cells wherein
both half cells are composed of the
same species but in different ion
concentrations
• E
o
cell
in concentration cells is always 0
• For Cu
(s)
|Cu
2+
(aq)
(1M)|| Cu
2+
(aq)
(0.1M)|
Cu
(s)
] solution ed concentrat [
] solution dilute [
log
n
0592 . 0
0 E
cell
− ·
V 030 . 0
1
1 . 0
log
2
0592 . 0
0 E
cell
+ · − ·
Concentration cell

As the reaction proceeds, [Cu
2+
]
decreases in the more concentrated
half-cell and increases in the more dilute
half-cell until the two concentrations are
equal
• At that point, E
cell
= 0, and equilibrium
has been reached

=> in any concentration cell, the
spontaneous reaction is always in the
direction that equalizes the
concentrations
ELECTROLYSIS OF
HALIDES
We did the
same thing to
KBr and KCl
It may be
assumed that the
concentration of
the halide ion, X
-
,
does not
significantly
change with the
electrolysis of the
solution
ELECTROLYSIS
• Next, we connected this C
(graphite)
| Cl
2(g)

(1M)|Cl
-
(aq)
(1M)|| half-cell to a ||Cu
2+
(aq)
(1M)|Cu
(s)
half-cell and measured
its potential
Cell Notation of Sample
Half Cell
Half-reaction
(reduction)
Standard
Reduction
Potential
Experimental
Value
C
(graphite)
| Cl
2(g)
|Cl
-
(aq)
(0.1M)||
Cu
2+
(aq)
(0.1M)|Cu
(s)
Cl
2
+ 2 e
-
2 Cl →
-
0.89 V
C
(graphite)
| Br
2(l)
,Br
-
(aq)
(0.1M)||
Cu
2+
(aq)
(0.1M)|Cu
(s)
Br
2
+ 2 e
-
2 Br →
-
0.96 V
C
(graphite)
| I
2(s)
,I
-
(aq)
(0.1M)||Cu
2+
(aq)
(0.1M)|Cu
(s)
I
2
+ 2 e
-
2 I →
-
0.92 V
Quantitative Aspects of
Electrolysis

Example: Calculate the mass
of copper metal produced at
the cathode during the
passage of 2.50 amperes of
current through a solution of
copper(II) sulfate for 50.0
minutes.

Cu
2+
(aq) + 2e
-
→ Cu(s)
Current X
Time
no. of
Coulombs
Useful
Conversions
:
1 J = 1 CV
1 A = 1 C/s
Mass of
substance
Mol. of e
-

passed
( ) Cu g 47 . 2
e mol 2
Cu g 5 . 63
C 485 , 96
e mol 1
s
C 50 . 2
min 1
s 60
min 0 . 50 Cu g ·

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