Electrolysis

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. 1

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.

A voltaic (Galvanic) cell can power an
electrolytic 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.

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 non-
spontaneous 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.
Electrolytic
Voltaic

Fig. 21.17

Fig. 21.18: Car battery, both voltaic and
electrochemical cell.

Increase
oxidizing
power
Increase
reducing
power

A standard electrolytic cell. A power source
forces the opposite reaction

Electrolysis

(a) A silver-plated teapot. (b) Schematic
of the electroplating of a spoon.

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

The electrolysis of water produces
hydrogen gas at the cathode (on the
right) and oxygen gas at the anode
(on the left).

Fig. 21.19
Electrolysis of
water

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

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

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.

E = -2.37 V

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

Prob. 21.9

Stoichiometry of electrolysis: Relation
between amounts of charge and product
Faraday’s 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.

Application of Faraday’s 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

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

Fig. 21.20

Doing work with electricity.

Industrial Applications of Electrolysis

What chemical species would be present in a
vessel of molten sodium chloride, NaCl (l)?
Na+ Cl-
Let’s examine the electrolytic cell for molten NaCl.
http://academic.pgcc.edu/~ssinex/ 32
E_cells.ppt.. All rights reserved.
Molten NaCl
Observe the reactions at the electrodes
- +
battery
Cl2 (g) escapes
Na (l)
NaCl (l)
Na+
Cl- Na+
(-) Cl- (+)

electrode electrode
half-cell Cl- Na+ half-cell
Na+ + e-  Na All rights reserved. http://academi
c.pgcc.edu/~ssinex/E_cells.ppt.
2Cl-  Cl2 +33 2e-
Molten NaCl
At the microscopic level
- +
battery
e-
NaCl (l)
cations anions
migrate Na+ migrate
toward Cl- Na+ toward
(-) (+)
Cl e-
electrode (-)
-
(+) electrode
cathode Cl- Na+ anode

Na+ + e-  Na http://academic.pgcc.edu/~ssinex/ 2Cl-  Cl2 +34 2e-
E_cells.ppt. All rights reserved.
Molten NaCl Electrolytic Cell
cathode half-cell (-)

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

OXIDATION 2Cl-  Cl2 + 2e-
overall cell reaction

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

If the products are mixed, the result is household bleach.
2 NaOH(aq) + Cl2(g) = NaCl(aq) + NaOCl(aq) + H2O

The Mercury Cell for Production of Chlorine and Sodium Hydroxide

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

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

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.
graphite anodes From: http://academic.pgcc.edu/~ssinex/E_cells.ppt. e- 
+
from
power
CO2 source
bubbles Al+3 Al+3 -
O-2  e-
O-2 O-2
Al2O3 (l)
Al (l)
Draw
carbon-lined steel vessel off
acts as cathode Al (l)
Cathode: Al+3 + 3e-  Al (l)
Anode: 2 O-2 + C (s)  CO2 (g) + 4e- 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.
Fig. 22.21: Production of solid Mg

Corrosion
Electrochemistry plays a major role in

corrosion and protection against it.

Calculating the cell potential, Eocell, at
H2O with O2 standard conditions
Consider a drop of oxygenated
Fe water on an iron object
Fe+2 + 2e-  Fe Eo = -0.44 v reverse
2x 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.
46
From: http://academic.pgcc.edu/~ssinex/E_cells.ppt.
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) + 2e-
while 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
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 and to produce O2 and
H2.
Faraday’s 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).


Electrolysis

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Electrolysis

Diunggah oleh

Hak Cipta:

Format Tersedia

Lecture 25 Electrolysis

Houghton Mifflin Company and G. 1

Cell 1: does work by releasing free

Houghton Mifflin Company and G. 2

Houghton Mifflin Company and G. 3

 The splitting (lysing) of a substance

Houghton Mifflin Company and G. 4

Previously our lectures on electrochemistry

Houghton Mifflin Company and G. 6

Houghton Mifflin Company and G. 9

Houghton Mifflin Company and G. 10

Houghton Mifflin Company and G. 11

Houghton Mifflin Company and G. 12

Houghton Mifflin Company and G. 13

Houghton Mifflin Company and G. 14

Houghton Mifflin Company and G. 15

Houghton Mifflin Company and G. 16

Houghton Mifflin Company and G. 17

At the anode (oxidation):

At the cathode (reduction):

Houghton Mifflin Company and G. 18

 Reduction possibilities follow:

Houghton Mifflin Company and G. 19

 We would choose the production of O2(g) and Cu(s).

 overall: CuCl2(aq) : Cu(s) + Cl2(g) E = –1.021 V

Houghton Mifflin Company and G. 20

Houghton Mifflin Company and G. 21

Ecell = -2.37-1.07 = -3.44V

Houghton Mifflin Company and G. 22

Houghton Mifflin Company and G. 24

Houghton Mifflin Company and G. 25

1. First balance the half-reactions to find

Houghton Mifflin Company and G. 26

Houghton Mifflin Company and G. 27

Houghton Mifflin Company and G. 28

Houghton Mifflin Company and G. 29

Houghton Mifflin Company and G. 31

Let’s examine the electrolytic cell for molten NaCl.

Cl2 (g) escapes

(-) Cl- (+)

cathode Cl- Na+ anode

cathode half-cell (-)

anode half-cell (+)

overall cell reaction

Houghton Mifflin Company and G. 36

Houghton Mifflin Company and G. 37

Houghton Mifflin Company and G. 38

Houghton Mifflin Company and G. 39

Houghton Mifflin Company and G. 40

Electrolysis of molten Al2O3 mixed with

Cell operates at high temperature –

Aluminum was a precious metal in 1886.

A block of aluminum is at the tip of

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.

Houghton Mifflin Company and G. 44

Electrochemistry plays a major role in

Houghton Mifflin Company and G. 45

Fe+2 + 2e-  Fe Eo = -0.44 v reverse

2x Fe  Fe+2 + 2e- -Eo = +0.44 v

O2 (g) + 2H2O + 4e-  4 OH- Eo = +0.40 v