Voltage Needed for Electrolysis

To drive a reaction in the non-spontaneous direction, we must

apply a voltage at least as large as the voltage produced by
the spontaneous reaction.
Zn (s) | Zn2+ (aq) | Cu2+ (aq) | Cu (s)

discharge: E0 = 1.10 V

we need to apply at least (-)1

(-)1.10
10 V to overcome the driving force
of the standard Daniell cell and charge it.

Often the applied voltage must be larger than this minimum

(thermodynamic) value to get an uphill reaction to go at a
reasonable rate.
This excess voltage is called the overvoltage.
many
a y multi-electron
u e ec o redox
edo processes
p ocesses a
are
e sslow
o (e
(e.g.
g H2O oxidation)
o da o )
and have large overvoltages (> 0.5 V).
292

Faradays Law of Electrolysis

Faradays Law: The amounts of the substances consumed
or produced at the electrodes of an electrolysis cell is
proportional
ti
l tto the
th charge
h
th
thatt passes th
through
h th
the cell.
ll

Zn2+ (aq) + 2 e Zn (s)

stoichiometry: 2 moles of electrons to make 1 mole of Zn

We can relate:
current moles electrons amounts of products
1. Charge = current time

1C=1A1s

2. Charge of 1 mole electrons = F = 96,485 C / mol

293

EXAMPLE: Calculate the volume of H2 gas at 25 C and

1 atm that will collect at the cathode when water is
electrolyzed for 2.00 hours with a 10.0 A current.

2 H2O 2 H2 + O2
Total charge
g p
passed through
g cell:
10 Amp 2.00 hr 3600 s/hr = 72,000 C
Moles of electrons:
72,000 C / 96,485 C mol-1 = 0.746 mol eMoles of H2 (2 e- per H2):
0.746 / 2 = 0.373 moles H2
Volume at 1 atm:
V = nRT/P = (0.373)(0.08206)(298)/(1) = 9.12 L
294

Electroplating / Electrodeposition
The process of coating a cathode with a film (usually a metal)
using an electrolysis cell.

295

The metal ions are said to plate out onto the cathode.

EXAMPLE: What is the oxidation number of the osmium

ion in an unknown salt if 26.7 g
grams of osmium metal
plates out when a current of 15 amps is passed through
a solution of this salt for 1 hour?

Cathode: Osn+ + n e- Os (s)

n=?

Total charge passed through cell:

15 Amps 1.00 hr 3600 s/hr = 54,000 C

Moles of electrons:

54,000 C / 96,485 C mol-1 = 0.56 mol e-

0.56
0
56 mol e- produced 26
26.7
7 grams of osmium metal how
many moles of Os is that?

Moles of osmium: 26.7

6 g / 190.23
90 3 g mol
o -1 = 0
0.14 mol
o Os
296

4 electrons used per Os: n = 4

EXAMPLE: A constant current is passed through an

electrolysis cell containing molten Al2O3 at 900
900C
C for 18
hours. If 480,000 grams of Al are obtained, what is the
current in amperes?

Moles of aluminum produced:

480,000 g / 27 g mol-1 = 17,778 moles Al
Moles of electrons needed:
(17,778 mol Al) (3 mol e- / mol Al) = 53,333 mol eCurrent needed:
(53 333 mol e-) (96,485
(53,333
(96 485 C/mol) / 64
64,800
800 s = 79,411
79 411 A

297

Aluminum production consumes roughly 5%

of electricity generated in the U.S.

Aluminum Production
aluminum production needs lots of
electricity, so aluminum smelters are
usually sited near cheap
hydroelectric
y
power.
p
In U.S.: Columbia River, WA
Grand Coulee Dam

Electrolyte is molten Al2O3 in

cryolite (Na3AlF6)
A single cell may use 500
500,000
000 amps
operating at 3-5 V
298