Discovering

Electrochemical Cells
PGCC CHM 102 Sinex
Part I Electrolytic Cells
Many important industrial processes
battery
+ -
inert
electrodes
power
source
vessel
e
-

e
-

conductive
medium
Cell
Construction
Sign or polarity of electrodes
(-) (+)
What chemical species would be
present in a vessel of molten
sodium chloride, NaCl (l)?
Na
+
Cl
-
Lets examine the electrolytic cell for molten NaCl.
+ -
battery
Na (l)
electrode
half-cell
electrode
half-cell
Molten NaCl
Na
+
Cl
-
Cl
-
Na
+
Na
+
Na
+
+ e
-
Na 2Cl
-
Cl
2
+ 2e
-
Cl
2
(g) escapes
Observe the reactions at the electrodes
NaCl (l)
(-)
Cl
-
(+)
+ -
battery
e
-

e
-

NaCl (l)
(-) (+)
cathode
anode
Molten NaCl
Na
+
Cl
-
Cl
-
Cl
-
Na
+
Na
+
Na
+
+ e
-
Na
2Cl
-
Cl
2
+ 2e
-
cations
migrate
toward
(-)
electrode
anions
migrate
toward
(+)
electrode
At the microscopic level
Molten NaCl Electrolytic Cell
cathode half-cell (-)
REDUCTION Na
+
+ e
-
Na

anode half-cell (+)
OXIDATION 2Cl
-
Cl
2
+ 2e
-

overall cell reaction
2Na
+
+ 2Cl
-
2Na + Cl
2

X 2
Non-spontaneous reaction!
Definitions:
CATHODE

REDUCTION occurs at this electrode
ANODE

OXIDATION occurs at this electrode
What chemical species would be
present in a vessel of aqueous
sodium chloride, NaCl (aq)?
Na
+
Cl
-
H
2
O
Will the half-cell reactions be the same or different?
battery
+ - power
source
e
-

e
-

NaCl (aq)
(-) (+)
cathode
different
half-cell
Aqueous NaCl
anode
2Cl
-
Cl
2
+ 2e
-
Na
+
Cl
-
H
2
O
What could be
reduced at the
cathode?
Aqueous NaCl Electrolytic Cell
possible cathode half-cells (-)
REDUCTION Na
+
+ e
-
Na
2H
2
0 + 2e
-
H
2
+ 2OH
-

possible anode half-cells (+)
OXIDATION 2Cl
-
Cl
2
+ 2e
-
2H
2
O O
2
+ 4H
+
+ 4e
-

overall cell reaction
2Cl
-
+ 2H
2
0 H
2
+ Cl
2
+ 2OH
-

e
-
Ag
+
Ag
For every electron, an atom of
silver is plated on the electrode.
Ag
+
+ e
-
Ag
Electrical current is expressed
in terms of the ampere, which
is defined as that strength of
current which, when passed
thru a solution of AgNO
3
(aq)
under standard conditions, will
deposit silver at the rate of
0.001118 g Ag/sec
1 amp = 0.001118 g Ag/sec
Faradays Law
The mass deposited or eroded from an
electrode depends on the quantity of electricity.
Quantity of electricity coulomb (Q)
Q is the product of current in
amps times time in seconds
Q = It
coulomb
current in amperes (amp)
time in seconds
1 coulomb = 1 amp-sec = 0.001118 g Ag
Ag
+
+ e
-
Ag
1.00 mole e
-
= 1.00 mole Ag = 107.87 g Ag
107.87 g Ag/mole e
-
0.001118 g Ag/coul
= 96,485 coul/mole e
-
1 Faraday (F )
mole e
-
= Q/F
mass = mole
metal
x MM
mole
metal
depends on the half-cell reaction
Examples using Faradays Law
How many grams of Cu will be deposited in
3.00 hours by a current of 4.00 amps?
Cu
+2
+ 2e
-
Cu

The charge on a single electron is 1.6021
x 10
-19
coulomb. Calculate Avogadros
number from the fact that 1 F = 96,487
coulombs/mole e
-
.


A series of solutions have 50,000 coulombs
passed thru them, if the solutions were
Au
+3
, Zn
+2
, and Ag
+
, and Au, Zn, and Ag were
plated out respectively, calculate the
amount of metal deposited at each anode.
battery
- +
+ + + - - -
1.0 M Au
+3
1.0 M Zn
+2
1.0 M Ag
+
Au
+3
+ 3e
-
Au Zn
+2
+ 2e
-
Zn Ag
+
+ e
-
Ag
e
-
e
-
e
-
e
-
The Hall Process for Aluminum
Electrolysis of molten Al
2
O
3
mixed with
cryolite lowers melting point

Cell operates at high temperature
1000
o
C

Aluminum was a precious metal in 1886.

A block of aluminum is at the tip of the
Washington Monument!
carbon-lined steel vessel
acts as cathode
CO
2

bubbles
Al (l)
Al
2
O
3
(l)
Draw
off
Al (l)
-
+
Cathode: Al
+3
+ 3e
-
Al (l)
Anode: 2 O
-2
+ C (s) CO
2
(g) + 4e
-
from
power
source
Al
+3
O
-2
O
-2
Al
+3
O
-2
graphite anodes
e
-
e
-

The Hall Process
Cathode: Al
+3
+ 3e
-
Al (l)
Anode: 2 O
-2
+ C (s) CO
2
(g) + 4e
-
4 Al
+3
+ 6 O
-2
+ 3 C (s) 4 Al (l) + 3 CO
2
(g)
x 4
x 3
The graphite anode is consumed in the process.
Part II Galvanic Cells
Batteries and corrosion
Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
Salt bridge
KCl in agar
Provides conduction
between half-cells
Cell
Construction
Observe the
electrodes
to see what
is occurring.
Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
Cu
plates out
or
deposits
on
electrode
Zn
electrode
erodes
or
dissolves
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
Zn Zn
+2
+ 2e
-
- +
What about half-cell
reactions?
What about the sign
of the electrodes?
What
happened
at each
electrode?
Why?
Galvanic cell
cathode half-cell (+)
REDUCTION Cu
+2
+ 2e
-
Cu

anode half-cell (-)
OXIDATION Zn Zn
+2
+ 2e
-

overall cell reaction
Zn + Cu
+2
Zn
+2
+ Cu
Spontaneous reaction that produces electrical current!
Now for a standard cell composed of
Cu/Cu
+2
and Zn/Zn
+2
, what is the voltage
produced by the reaction at 25
o
C?
Standard Conditions
Temperature - 25
o
C
All solutions 1.00 M
All gases 1.00 atm
Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
Zn Zn
+2
+ 2e
-
- +
Now replace the light bulb with a volt meter.
1.1 volts
H
2
input
1.00 atm
inert
metal
We need a standard electrode
to make measurements against!
The Standard Hydrogen Electrode (SHE)
Pt
1.00 M H
+
25
o
C
1.00 M H
+
1.00 atm H
2
Half-cell
2H
+
+ 2e
-
H
2
E
o
SHE
= 0.0 volts
H
2
1.00 atm
Pt
1.0 M H
+
Cu
1.0 M CuSO
4
0.34 v
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
H
2
2H
+
+ 2e
-
KCl in agar
+
Now lets combine the copper half-cell with the SHE
E
o
= + 0.34 v
H
2
1.00 atm
Pt
1.0 M H
+
1.0 M ZnSO
4
0.76 v
cathode half-cell
2H
+
+ 2e
-
H
2
anode half-cell
Zn Zn
+2
+ 2e
-

KCl in agar
Zn
-
Now lets combine the zinc half-cell with the SHE
E
o
= - 0.76 v
Al
+3
+ 3e
-
Al E
o
= - 1.66 v

Zn
+2
+ 2e
-
Zn E
o
= - 0.76 v

2H
+
+ 2e
-
H
2
E
o
= 0.00 v

Cu
+2
+ 2e
-
Cu E
o
= + 0.34

Ag
+
+ e
-
Ag E
o
= + 0.80 v
Assigning the E
o
Write a reduction half-cell, assign the voltage
measured, and the sign of the electrode to the
voltage.
I
n
c
r
e
a
s
i
n
g

a
c
t
i
v
i
t
y

105
Db
107
Bh
The Non-active Metals
Metal + H
+
no reaction
since E
o
cell
< 0
Calculating the cell potential, E
o
cell
, at
standard conditions
Fe
+2
+ 2e
-
Fe E
o
= -0.44 v
O
2
(g) + 2H
2
O + 4e
-
4 OH
-
E
o
= +0.40 v
This is corrosion or the oxidation of a metal.
Consider a drop of oxygenated
water on an iron object
Fe
H
2
O with O
2
Fe Fe
+2
+ 2e
-
-E
o
= +0.44 v 2x
2Fe + O
2
(g) + 2H
2
O 2Fe(OH)
2
(s) E
o
cell
= +0.84 v
reverse
Is iron an active metal?
What would happen if iron is exposed to
hydrogen ion?
How does acid rain influence the corrosion
of iron?
Fe + 2H
+
Fe
+2
+ H
2
(g) E
o
cell
= +0.44 V
Fe Fe
+2
+ 2e
-
-E
o
= +0.44 v
O
2
(g) + 4H
+
+ 4e
-
2H
2
0 E
o
= +1.23 v
2x
2Fe + O
2
(g) + 4H
+
2Fe
+2
+ 2H
2
O E
o
cell
= +1.67 v
Enhances the corrosion process
What happens to the electrode potential if
conditions are not at standard conditions?
The Nernst equation adjusts for non-standard conditions
For a reduction potential: ox + ne red
at 25
o
C: E = E
o
- 0.0591 log (red)
n (ox)
Calculate the E for the hydrogen electrode
where 0.50 M H
+
and 0.95 atm H
2
.
in general: E = E
o
RT ln (red)
nF (ox)
DG
o
= -nFE
o
cell
Free Energy and the Cell Potential
Cu Cu
+2
+ 2e
-
-E
o
= - 0.34
Ag
+
+ e
-
Ag E
o
= + 0.80 v 2x
Cu + 2Ag
+
Cu
+2
+ 2Ag
E
o
cell
= +0.46 v
where n is the number of electrons for
the balanced reaction
What is the free energy for the cell?
1F = 96,500 J/v
and the previous relationship:
DG
o
= -nFE
o
cell
from thermodynamics:
DG
o
= -2.303RT log K

-nFE
o
cell
= -2.303RT log K
at 25
o
C: E
o
cell
= 0.0591 log K
n
where n is the number of electrons for the balanced reaction
galvanic electrolytic
need
power
source
two
electrodes
produces
electrical
current
anode (-)
cathode (+)
anode (+)
cathode (-)
salt bridge vessel
conductive
medium
Comparison of Electrochemical Cells
DG < 0
DG > 0