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# 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).
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## 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

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

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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?

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?

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

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## 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
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