Elektrolisis

Lecture 25 Electrolysis
Define electrolysis?
Some examples.
What are the values of G and Ecell?
Electrolysis of water.
Some industrial applications.
Corrosion
Houghton Mifflin Company and G.

Hall. All rights reserved.
Two Types of Cells

Cell 1: does work by releasing free
energy from a spontaneous reaction to
produce electricity such as a battery.
Cell 2: does work by absorbing free
energy from a source of electricity to
drive a non-spontaneous reaction such
as electroplating.

Electrolysis
Previously our lectures on electrochemistry
were involved with voltaic cells i.e. cells
with Ecell > 0 and G < 0 that were
spontaneous reactions.
Today we discuss electrochemical cells
where Ecell < 0 and G > 0 that are nonspontaneous reactions and require
electricity for the reactions to take place.
We can take a voltaic cell and reverse the
electrodes to make an electrochemical cell.
Electrolysis
The splitting (lysing) of a substance
or decomposing by forcing a current
through a cell to produce a chemical
change for which the cell potential
is negative.

Voltaic
Electrolytic

Fig. 21.17


A voltaic (Galvanic) cell can power an

electrolytic cell


Fig. 21.18: Car battery, both voltaic and

electrochemical cell.

10
Increase
oxidizing
power
Increase
reducing
power

11
A standard electrolytic cell. A power source

forces the opposite reaction

12
Electrolysis

13
(a) A silver-plated teapot. (b) Schematic

of the electroplating of a spoon.

14
Schematic of the
electroplating of a spoon.
AgNO3(aq)

15
The electrolysis of water produces

hydrogen gas at the cathode (on the
right) and oxygen gas at the anode
(on the left).

16
Fig. 21.19
Electrolysis of
water

17
Electrolysis of water
At the anode (oxidation):
2H2O(l) + 2e- = H2(g) + 2OH-(aq) E=-0.42V
At the cathode (reduction):
2H2O(l) = O2(g) + 4H+(aq) + 4e- E= 0.82V
Overall reaction after multiplying anode
reaction by 2,
2H2O(l) = 2H2(g) + O2(g)
Eocell = -0.42 -0.82 = -1.24 V
18
Electrolysis: Consider the electrolysis of a

solution that is 1.00 M in each of CuSO4(aq) and
NaCl(aq)
Oxidation possibilities follow.

2Cl(aq) = Cl2(g) + 2e
E = 1.358 V
2SO42(aq) = S2O82(aq) + 2e
E = 2.01 V
2H2O = 4H+(aq) + O2(g) + 4e
E = 1.229 V
Reduction possibilities follow:

Na+(aq) + e = Na(s)
E = 2.713 V
Cu2+(aq) + 2e = Cu(s)
E = +0.337 V
2H2O + 2e = H2(g) + 2OH(aq)
E = +0.828 V

19
Electrolysis
We would choose the production of O2(g) and Cu(s).
But the voltage for producing O2(g) from solution is
considerably higher than the standard potential, because of
the high activation energy needed to form O2(g).
The voltage for this half cell seems to be closer to 1.5 V in
reality.
The result then is the production of Cl2(g) and Cu(s).
anode, oxidation: 2Cl(aq) = Cl2(g) + 2e
E = 1.358 V
cathode, reduction: Cu2+(aq) + 2e : Cu(s) E = +0.337 V
overall: CuCl2(aq) : Cu(s) + Cl2(g) E = 1.021 V
We must apply a voltage of more than +1.021 V to cause
this reaction to occur.

20
E = -2.37 V
21
E = 1.07 V
Ecell = -2.37-1.07 = -3.44V

22

23
Prob. 21.9

24
Stoichiometry of electrolysis: Relation

between amounts of charge and product
Faradays law of electrolysis relates
to the amount of substance produced
at each electrode is directly
proportional to the quantity of charge
flowing through the cell (half
reaction).
Each balanced half-cell shows the
relationship between moles of
electrons and the product.
25
Application of Faradays law

1. First balance the half-reactions to find
number of moles of electrons needed per
mole of product.
2. Use Faraday constant (F = 9.65E4 C/mol
e-) to find corresponding charge.
3. Use the molar mass of substance to find
the charge needed for a given mass of
product.
1 ampere = 1 coulomb/second or 1 A = 1 C/s
A x s = C
26
Stoichiometry of Electrolysis
How
much chemical change occurs with

the flow of a given current for a
specified time?
current and time quantity of charge

moles of electrons moles of analyte
grams of analyte

27
Fig. 21.20

28
Doing work with electricity.

29

30
Industrial Applications of Electrolysis

31
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.

http://academic.pgcc.edu/~ssinex/
E_cells.ppt.. All rights reserved.
32
Molten NaCl
Observe the reactions at the electrodes
battery
Cl2 (g) escapes

Na (l)
Cl-
electrode
half-cell
Na+ + e- Na
NaCl (l)
Na+
(-)
ClCl-
Na+
(+)
Na+
All rights reserved.

electrode
half-cell
2Cl- Cl2 +33 2e-
Molten NaCl
At the microscopic level
e-
battery
NaCl (l)
cations
migrate
toward
(-)
electrode
cathode
Na+ + e- Na
Na+
Cl(-)
Cl
Cl-
Na+
e(+)
Na+
E_cells.ppt. All rights reserved.
anions
migrate
toward
(+)
electrode
anode
2Cl- Cl2 +34 2e-
Molten NaCl Electrolytic Cell

cathode half-cell (-)
REDUCTION Na+ + e- Na
X2
anode half-cell (+)

OXIDATION 2Cl- Cl2 + 2eoverall cell reaction
2Na+ + 2Cl- 2Na
Non-spontaneous
reaction!
E_cells.ppt. All rights reserved.
Cl2
35
The Downs Cell for the Electrolysis of Molten Sodium Chloride

36
If the products are mixed, the result is household bleach.

2 NaOH(aq) + Cl2(g) = NaCl(aq) + NaOCl(aq) + H2O

37
The Mercury Cell for Production of Chlorine and Sodium Hydroxide

38
A schematic diagram of an electrolytic

cell for producing aluminum by the HallHeroult process.

39
Fig. 22.19 A
schematic diagram
of an electrolytic
cell for producing
aluminum by the
Hall-Heroult
process.

40
The Hall Process for Aluminum

Electrolysis of molten Al2O3 mixed with
cryolite lowers melting point
Cell operates at high temperature
1000oC
Aluminum was a precious metal in 1886.
A block of aluminum is at the tip of
the Washington Monument!
E_cells.ppt.
41
graphite anodes
CO2
bubbles
From: http://academic.pgcc.edu/~ssinex/E_cells.ppt.
Al2O3 (l)
from
power
source
Al+3
O-2
e-
Al+3
O-2
O-2
e-
Al (l)
carbon-lined steel vessel

acts as cathode
Cathode: Al+3 + 3e- Al (l)

Anode: 2 O-2 + C (s) CO2 (g) + 4e-
Draw
off
Al (l)
42
The Hall Process

Cathode: Al+3 + 3e- Al (l)
x4
Anode: 2 O-2 + C (s) CO2 (g) + 4e- x 3

4 Al+3 + 6 O-2 + 3 C (s) 4 Al (l) + 3 CO2 (g)
The graphite anode is consumed in the process.
E_cells.ppt.
43
Fig. 22.21: Production of solid Mg

44
Corrosion
Electrochemistry plays a major role in
corrosion and protection against it.

45
Calculating the cell potential, Eocell, at

standard conditions
H2O with O2
Consider a drop of oxygenated

water on an iron object
Fe
Fe+2 + 2e- Fe
2x
Eo = -0.44 v
reverse
Fe Fe+2 + 2e- -Eo = +0.44 v
O2 (g) + 2H2O + 4e- 4 OH-
Eo = +0.40 v
2Fe + O2 (g) + 2H2O 2Fe(OH)2 (s) Eocell= +0.84 v

This is corrosion or the oxidation of a metal.
From: http://academic.pgcc.edu/~ssinex/E_cells.ppt.
46
Cathodic Protection Against Corrosion
Underground steel pipes offer the strength to transport fluids at high pressures,
but they are vulnerable to corrosion driven by electrochemical processes. A
measure of protection can be offered by driving a magnesium rod into the
ground near the pipe and providing an electrical connection to the pipe. Since
the magnesium has a standard potential of -2.38 volts compared to -.41 volts
for iron, it can act as a anode of a voltaic cell with the steel pipe acting as the
cathode. With damp soil serving as the electrolyte, a small current can flow in
the wire connected to the pipe. The magnesium rod will be eventually
consumed by the reaction
Mg(s) -> + Mg2+(aq) + 2ewhile the steel pipe as the cathode will be protected by the reaction
O2(g) + 2H2O(l) + 4e- -> 4OH-(aq).
From: http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/corrosion.html#c2
47
Lecture summary
Electrolysis is often the reverse of voltaic
cell in that Ecell < 0, and G >0 and
reaction is non-spontaneous.
Electrolysis of water to produce O2 and H2.
Faradays law allows us to determine how
much current is needed to produce a
certain amount of an element.
Industrial applications are numerous for
producing a variety of solid elements (Al,
Mg, Na, etc).
48

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Lecture 25 Electrolysis

Houghton Mifflin Company and G.

Two Types of Cells

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

A voltaic (Galvanic) cell can power an

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Fig. 21.18: Car battery, both voltaic and

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

A standard electrolytic cell. A power source

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

(a) A silver-plated teapot. (b) Schematic

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

The electrolysis of water produces

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Electrolysis: Consider the electrolysis of a

Oxidation possibilities follow.

Reduction possibilities follow:

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Ecell = -2.37-1.07 = -3.44V

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Stoichiometry of electrolysis: Relation

Application of Faradays law

much chemical change occurs with

current and time quantity of charge

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Doing work with electricity.

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

Industrial Applications of Electrolysis

Houghton Mifflin Company and G.

What chemical species would be present in a

Lets examine the electrolytic cell for molten NaCl.

Observe the reactions at the electrodes

Cl2 (g) escapes

All rights reserved.

At the microscopic level

Molten NaCl Electrolytic Cell

anode half-cell (+)

The Downs Cell for the Electrolysis of Molten Sodium Chloride

Houghton Mifflin Company and G.

If the products are mixed, the result is household bleach.

Houghton Mifflin Company and G.

The Mercury Cell for Production of Chlorine and Sodium Hydroxide

Houghton Mifflin Company and G.

A schematic diagram of an electrolytic

Houghton Mifflin Company and G.

Houghton Mifflin Company and G.

The Hall Process for Aluminum

carbon-lined steel vessel

Cathode: Al+3 + 3e- Al (l)

The Hall Process

Anode: 2 O-2 + C (s) CO2 (g) + 4e- x 3