Electrochemistry

Electrochemical reactions are oxidation-reduction reactions.

Chapter 21a | The two parts of the reaction are physically separated.
z The oxidation reaction occurs in one cell.
Electrochemistry: The z The reduction reaction occurs in the other cell.
Electrolytic Cell

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Electrochemistry Electrical Conduction

| There are two kinds electrochemical cells. | Metals conduct electric currents well in a process called
metallic conduction.
1. Electrochemical cells containing spontaneous
z In metallic conduction there is electron flow with no atomic
chemical reactions are called voltaic or galvanic motion.
cells. z Metal atoms changing oxidation states without moving.
„ The generation of electric current from a chemical • E.g. Oxidative phosphorylation
reaction.
2. Electrochemical cells containing in nonspontaneous
chemical reactions are called electrolytic cells.
„ The use of electric current to produce a chemical change.

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Electrical Conduction Electrodes

| In ionic or electrolytic conduction ionic motion The following convention for electrodes is correct for
transports the electrons. either electrolytic or voltaic cells:
z Positively charged ions, cations, move toward the | The cathode is the electrode at which reduction
negative electrode. occurs.
z Negatively charged ions, anions, move toward the • The cathode is negative in electrolytic cells and positive
positive electrode. in voltaic cells.
| The anode is the electrode at which oxidation
occurs.
• The anode is positive in electrolytic cells and negative in
voltaic cells.

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 Electrodes Electrolytic Cells

| Inert electrodes do not react with the liquids or Electrical energy is used to force nonspontaneous
products of the electrochemical reaction. chemical reactions to occur.
| Two examples of common inert electrodes are | The process is called electrolysis.
graphite and platinum. | Two examples of commercial electrolytic reactions
are:
1. The electroplating of jewelry and auto parts.
2. The electrolysis of chemical compounds.

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Electrolytic Cells Figure 11.19:

Voltaic Cell Electrolytic Cell
| Electrolytic cells consist of:
1. A container for the reaction mixture.
2. Two electrodes immersed in the reaction mixture.
3. A source of direct current.
| Electrolytic cells uses electrical energy to produce a
chemical change.
z The electrical energy forces a current through a cell that has a
negative potential. (a) A standard galvanic cell (b) A standard electrolytic cell
z The electrical energy forces a chemical change to occur. The cell in (b) has a power source that forces the electrons in the
opposite direction from the voltaic cell in (a).
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Counting Electrons: Coulometry and Faraday’s Counting Electrons: Coulometry and Faraday’s Law of
Law of Electrolysis Electrolysis

| The stoichiometry of electrolysis processes can | Faraday’s Law - The amount of substance
quantify “how much chemical change occurs with the flow of undergoing chemical reaction at each electrode
a given current for a specific time”. during electrolysis is directly proportional to the
amount of electricity that passes through the
electrolytic cell.
| A faraday is the amount of electricity that reduces
one equivalent of a species at the cathode and
oxidizes one equivalent of a species at the anode.
1 faraday of electricity ≡ 6.022 × 1023 e-

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 Counting Electrons: Coulometry and Faraday’s Law of Counting Electrons: Coulometry and Faraday’s Law of
Electrolysis Electrolysis

| A coulomb is the amount of charge that passes a | Faraday’s Law states that during electrolysis, one
given point when a current of one ampere (A) flows faraday of electricity (96,485 coulombs) reduces and
for one second. oxidizes, respectively, one equivalent of the
| 1 ampere (amp) = 1 coulomb/second oxidizing agent and the reducing agent.
z This corresponds to the passage of one mole of electrons
1 faraday ≡ 6.022 × 1023 e-
through the electrolytic cell.
1 faraday ≡ 1.0 mol e – 1 equivalent of oxidizing agent ≡ gain of 6.022 ×1023 e –
1.0 mol e ≡ 96, 485 coulombs
–
1 equivalent of reducing agent ≡ loss of 6.022 ×1023 e –

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Counting Electrons: Coulometry and Faraday’s Law of

Electrolysis
The Electrolysis of Water
| Example: Calculate the mass of palladium produced by the
reduction of palladium (II) ions during the passage of 3.20 | Hydrogen and oxygen combine spontaneously to
amperes of current through a solution of palladium (II) form water.
sulfate for 30.0 minutes.
z The decrease in free energy that accompanies this
Cathode : Pd 2+ + 2e- → Pd 0 spontaneous reaction can be used to run fuel cells to
1 mol 2 mol 1 mol produce electricity.
106 g 2(96, 485) 106 g
C
| The reverse process, which is not spontaneous,
3.20 amp = 3.20 requires energy to occur.
s
1 mol e− = 96, 485 C | The formation of oxygen and hydrogen gases from
?g = ( 30.0  60 s   3.20 C   1 mol e   mol Pd  106 g Pd
min ) 
−
= 3.16 g Pd
water can be forced by electrolysis.
   - 
 min   s   96, 485 C   2 mol e  mol Pd

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Counting Electrons: Coulometry and Faraday’s Law of

The Electrolysis of Water Electrolysis
| Example: Calculate the volume of oxygen (measured at STP)
Anode reaction 2 H 2O → O2( g ) + 4 H + + 4 e –
produced by the oxidation of water during the passage of 3.20
Cathode reaction 2(2 H 2O + 2e – → H 2( g ) + 2OH – ) amperes of current for 30.0 minutes.
Anode : 2 H 2O → O2( g ) + 4 H + + 4e -
H + + 
Cell reaction 6 H 2O → 2 H 2( g ) + O2( g ) + 4 4 OH
– 2 mol 1 mol 4 mol 4 mol
4 H 2O
22.4 LSTP 4 ( 96,500 C )
The overall reaction is 2 H 2O → 2 H 2( g ) + O2( g ) C
? LSTP O2 = 3.20 amp = 3.20
s
−
1 mol e = 96, 485 C
1.0 mol = 22.4 LSTP
 60 s   3.20 C   1 mol e   mol O2   22.4 LSTP O2 
−
( 30.0 min )     -  =
 min   s   96, 485 C   4 mol e   mol O2 
= 0.334 LSTP O2 or 334 mLSTP O2
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 The Electrolysis of Molten Sodium Chloride The Electrolysis of Molten Sodium Chloride

| Liquid sodium is produced at one electrode.

| In all electrolytic cells, electrons are forced to flow
z Indicates that the reaction Na+(A) + e- → Na(A) occurs at
this electrode. from the positive electrode (anode) to the negative
z Is this electrode the anode or cathode? electrode (cathode).
z Reduction occurs at the cathode.
| Gaseous chlorine is produced at the other electrode.
z Indicates that the reaction 2 Cl- → Cl2(g) + 2 e- occurs at
this electrode.
z Is this electrode the anode or cathode?
z Oxidation occurs at the anode.

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The Electrolysis of Molten Sodium Chloride The Electrolysis of Molten Sodium Chloride

Diagram of this electrolytic cell.

e- | The nonspontaneous redox reaction that occurs is:
e- Generator-source
e–
of DC Anode reaction 2 Cl - → Cl2( g ) + 2 e-
- electrode
e–
e–
+ electrode
(
Cathode reaction 2 Na + + e- → Na( A ) )
chloride loses e– +
Na+ gainse–
e–
2e– generating Cl2 Cell reaction 2 Cl + 2 Na
-
→ Cl2( g ) + 2 Na( A )
generating Na+ + Cl2 2Cl–
Na (A) gas
liquid Na0.
molten NaCl
Na+ + e- → Na(A) 2Cl- → Cl2 (g) + 2e-
cathode reaction Porous barrier anode reaction

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Figure 11.25: The Downs cell for the electrolysis of molten sodium
chloride.
Sodium metal is The Electrolysis of Aqueous Sodium Chloride
produced by the
electrolysis of molten
sodium chloride.
| In this electrolytic cell, hydrogen gas is produced at
NaCl is mixed with
CaCl2 to lower the one electrode.
melting point (from z The aqueous solution becomes basic near this electrode.
800oC to 600oC).
z What reaction is occurring at this electrode? Gaseous
The liquid sodium is chlorine is produced at the other electrode.
drained, cast into
blocks and stored in
inert solvents.

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 The Electrolysis of Aqueous Potassium Chloride
The Electrolysis of Aqueous Potassium Chloride Cell diagram
– pole of battery + pole of battery
Battery, a source
What reaction is occurring at this electrode? of direct current e- flow
e- flow
These experimental facts lead us to the following
nonspontaneous electrode reactions:
- electrode + electrode
Anode reaction 2 Cl – → Cl2( g ) + 2 e –
Cathode reaction 2 H 2O + 2 e – → H 2( g ) + 2 OH – H2 gas Cl2 gas
Cell reaction 2 Cl – + 2 H 2O → H 2( g ) + Cl2( g ) + 2 OH –
Na + is a spectator ion. Note that water is electrolyzed ! aqueous NaCl
2 H2O + 2e- → H2 (g) + 2 OH- 2Cl- → Cl2 (g) + 2e-
cathode reaction anode reaction
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Electrolytic Cells Commercial Applications of Electrolytic Cells

| In all electrolytic cells the most easily reduced Electrolytic Refining and Electroplating of Metals
species is reduced and the most easily oxidized | Impure metallic copper can be purified
species is oxidized. electrolytically to ≈ 100% pure Cu.
z The impurities commonly include some active metals
plus less active metals such as: Ag, Au, and Pt.
| The cathode is a thin sheet of copper metal
connected to the negative terminal of a direct
current source.
| The anode is large impure bars of copper.

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Commercial Applications of Electrolytic Cells Commercial Applications of Electrolytic Cells

| The electrolytic solution is CuSO4 and H2SO4 | Any active metal impurities are oxidized to cations
| The impure Cu dissolves to form Cu2+. that are more difficult to reduce than Cu2+.
| The Cu2+ ions are reduced to Cu at the cathode. z This effectively removes them from the Cu metal.

Zn 0 → Zn 2 + + 2e −
Anode ( impure ) Cu (0s ) → Cu (2aq+ ) + 2e −
Fe0 → Fe2 + + 2e −
Cathode ( very pure ) Cu (2+aq ) + 2e− → Cu (0s)
And so forth for other
Net rxn. No net rxn.
active metals

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 Figure 11.24: Schematic of the electroplating of a
Commercial Applications of Electrolytic Cells spoon.

The spoon is the cathode and

is plated out by the Ag+ ions
Metal Plating that are released from the solid
| Objects can be plated by making a particular object silver bar that is the anode.
a cathode in a tank with ions of the plating metal. A salt bridge is not required
because Ag+ are at acting at
both electrodes.

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Copper Plating
Commercial Applications of Electrolytic Cells

| The less active metals are not oxidized and

precipitate to the bottom of the cell.
| These metal impurities can be isolated and separated
after the cell is disconnected.
| Some common metals that precipitate include:
Ag , Au, Pt , Pd
( Se, Te )

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Corrosion Corrosion

| Metallic corrosion is the oxidation-reduction reactions | Corrosion of iron

of a metal with atmospheric components such as CO2, | The importance of steel in many of our structures,
O2, and H2O.
controlling corrosion is a very important issue.
| Metals corrode because they oxidize easily.
z The corrosion mechanism involves electrochemical
z Many common metals that are used for structural and processes.
decorative purposed have standard reduction potentials that
are more negative and oxygen. 4 Fe0 + 3 O20 → 2 Fe2O3 ( overall reaction )
The reaction occurs rapidly at exposed points.

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 Corrosion
steel

| The surface of steel is not uniform.

z The chemical composition of steel is not a homogeneous
mixture.
z Stress points are produced on the surface due to physical
strains. Fe2+ ions travel through the surface moisture to the region
acting as a cathode.
z At these stress areas, iron can be more easily oxidized in
some regions than in other regions. In the region of the cathode, the Fe2+ ions react with O2 to
form rust.
o Oxidized areas act as anodes
The moisture acts as a salt bridge in the process of corrosion.
o The other areas act as cathodes
Without moisture, steel does not rust.

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Corrosion Protection Corrosion Protection

| Some examples of corrosion protection. 2. Galvanizing, the coating of steel with zinc, provides
1. Plate a metal with a thin layer of a less active (less easily a more active metal on the exterior.
oxidized) metal. The thin coat of Zn must be oxidized before Fe begins to rust.
"Tin plate " or " chromium plate " for steel.

Zinc
Steel

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Corrosion Protection Corrosion Protection

3. Connect the metal

to a sacrificial
anode, a piece of a
more active metal.

Soil pipes and ship hulls have Mg and Zn on the exterior as sacrificial anodes. Magnesium is easily
oxidized; protecting the iron
from oxidation.

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 Corrosion Protection Corrosion Protection

4. Allow a protective film to form naturally. 5. Paint or coat with a polymeric material such as
plastic or ceramic.
4 Al 0 + 3 O20 → 2 Al2O3
Al2O3 forms a hard , transparent film on exterior of aluminum foil. Steel bathtubs are coated with ceramic.

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End of Chapter 11b

| Electrochemistry is an important part of the

electronics industry.

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