Chapter 17:

Electrochemistry
 Electrochemistry
• Electrochemistry is the study of redox reactions that produce or
require an electric current.

• The conversion between chemical energy and electrical energy is

carried out in an electrochemical cell.

• Spontaneous redox reactions take place in a galvanic/voltaic cell.

• Nonspontaneous redox reactions can be made to occur in an

electrolytic cell by the addition of electrical energy.

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 Oxidation-Reduction
• Reactions in which electrons are transferred from one
atom to another are called oxidation–reduction reactions.

• Atoms that lose electrons are being oxidized; atoms that

gain electrons are being reduced.

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A Spontaneous Redox Reaction:
Zn(s) + Cu2+(aq) → Zn2+ + Cu(s)
 Voltaic (Galvanic) Cells: Spontaneous Redox Reactions
• Electrical current: The amount of electric charge that passes a point in a given period of
time
• Whether as electrons flowing through a wire or as ions flowing through a solution

• Redox reactions involve the movement of electrons from one substance to another.
• Therefore, redox reactions have the potential to generate an electric current.

• A spontaneous redox reaction does not require external energy to proceed.

• The reaction’s ΔG is negative.

• Voltaic (galvanic) cells produce an electrical current from spontaneous redox reactions.
• To use that current, we need to separate the place where oxidation is occurring from
the place where reduction is occurring.
 Electrochemical Cells
• Oxidation and reduction half-reactions are kept as separate in half-cells in an
electrochemical cell.

• The flow of electrons require a conductive solid electrode to allow the transfer of
electrons either through:
• An external circuit or
• Metal or graphite electrode

• An electrochemical cell requires the exchange of ions between the two half-cells of the
system via a salt bridge.
 Voltaic Cell

The salt bridge is required to complete the circuit and maintain

charge balance.
 Cell Notation
• Shorthand description of a voltaic cell is written as follows:

electrode | electrolyte || electrolyte | electrode

• Oxidation half-cell on the left; reduction half-cell on the right

• Single line | = phase barrier
• If multiple electrolytes in same phase, a comma is used rather than |
• Often use an inert electrode
• Double line || = salt bridge

• Example:
 Voltaic Cell
Anode = Zn(s) Cathode = Cu(s)
The anode is oxidized to Cu2+ ions are reduced at
Zn2+ ions. the cathode.
 Electrodes
• When the half-reaction involves
a gas, an inert electrode can be
used.
• An inert electrode, such as
platinum, is one that does not
participate in the reaction but
provides a surface for the
transfer of electrons to take
place on.
• Hydrogen electrode written as a
cathode:
• H+(aq) | H2(g) | Pt
• Hydrogen electrode written as
an anode:
• Pt | H2(g) | H+(aq) 10
 Electrochemical Cell Notation with an Inert Electrode
• The half-reaction involves reducing Mn oxidation state from +7 to +2.
• An inert electrode (Pt) will provide a surface for the electron transfer without reacting
with the MnO4−.

Fe(s) | Fe2+(aq) || MnO4– (aq), Mn2+(aq), H+(aq) | Pt(s) 11

 Standard Reduction Potential
• The absolute tendency of
a half-reaction standard reduction
potential cannot be measured.
• Only the potentials relative to
another half-reaction can be
measured.

• To overcome this limitation, a standard

half-reaction for the reduction of H+ to
H2 is selected and assigned a potential
difference of 0 V.
• Standard hydrogen electrode, SHE

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13
 Half-cell Potentials
• Standard reduction potentials compare the tendency for
a particular reduction half-reaction to occur relative to
the reduction of H+ to H2.

• Half-reactions with a stronger tendency toward

reduction than the SHE have a positive value for E°red.
• Half-reactions with a stronger tendency toward
oxidation than the SHE have a negative value for E°red.

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Table of Standard Reduction Potentials
(from Pearson Education, Inc.)
• A redox reaction will be spontaneous
when there is a strong tendency for the
oxidizing agent to be reduced and the
reducing agent to be oxidized.

• Higher on the table of standard

reduction potentials = stronger
tendency for the reactant to be
reduced

• Lower on the table of standard

reduction potentials = stronger
tendency for the product to be
oxidized
 Calculating Cell Potentials under Standard Conditions
• Cell potentials are intensive properties of matter.
• Because cell potentials are intensive physical properties, when
determining the cell potential, do not multiply the half-cell E°
values, even if you need to multiply the half-reactions to
balance the redox equation.
• The cell potential of an electrochemical cell (Eocell) is the
difference between the electrode potential of the cathode and that
of the anode.
• Cell potentials can be determined using the following equation:
E°cell = E°cathode – E°anode
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 Predicting Spontaneity of Redox
• When E is
° Reactions
cell
• positive, the redox reaction of the cell is spontaneous.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) spontaneous
• When E°cell is
• negative, the redox reaction of the cell is nonspontaneous.

Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s) nonspontaneous

Cu2+(aq) + 2 e− → Cu(s) E°red = +0.34 V
Zn2+(aq) + 2 e− → Zn(s) E°red = −0.76 V

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Example

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 E°cell, ΔG°, and K
• For a spontaneous reaction, one that proceeds
in the forward direction with the chemicals in
their standard states,
• ΔG°: negative
• E°: positive
• K>1

• ΔG° = −RT ln K = −nFE°cell

• n = the number of electrons
• F = Faraday’s constant = 96,485 C/mol e−

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Dependence of Cell Potential on Concentration
ΔG = ΔG° + RT ln Q

(–) nFEcell = (–) nFE°cell + RT ln Q

RT
Ecell = E°cell – ln Q This is the Nernst equation.
nF
At 25 °C (T),
Faraday’s constant (F) = 96,500 C/mol e–
n = the number of electrons
Converting from ln to log (2.303),
the Nernst equation becomes

0.0592 V
Ecell = E°cell – log Q
n
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 Corrosion
• Corrosion is the spontaneous oxidation of a
metal by chemicals in the environment.
• Mainly O2

• Because many materials used are active

metals, corrosion can be a very big problem.
• Metals are often used for their strength
and malleability, but these properties are
lost when the metal corrodes.
• For many metals, the product of corrosion
does not adhere to the metal, and as it
flakes off more metal can corrode.
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 Reduction of O2
• O2 is very easy to reduce in moist conditions.

O2(g) + 2 H2O(l) + 4 e− → 2 OH−(aq) E° = 0.40 V

• O2 is even easier to reduce under acidic conditions.

O2(g) + 4 H+ + 4 e− → 2 H2O(l) E° = 1.23 V

• Because the reduction of most metal ions lies below O2 on the table of
standard reduction potentials, the oxidation of those metals by O2 is
spontaneous.
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 Rusting
• At the anodic regions, Fe(s) is oxidized to Fe2+.
• The electrons travel through the metal to a
cathodic region where
O2 is reduced.
• In acidic solution from gases dissolved in the
moisture

• The Fe2+ ions migrate through the moisture to the

cathodic region, where they are further oxidized
to Fe3+, which combines with the oxygen and
water to form rust.
• Rust is hydrated iron(III) oxide, Fe2O3 · nH2O.
• Moisture must be present. Water acts as a
reactant.
• It is required for ion flow between
cathodic and anodic regions. 23
 Preventing Corrosion
• One way to reduce or slow corrosion is to
coat the metal surface to keep it from
contacting corrosive chemicals in the
environment.
• Paint
• Some metals, such as Al, form an
oxide that strongly attaches to the
metal surface, preventing the rest from
corroding.

• Another method to protect one metal is to

attach it to a more reactive metal that is
cheap.
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Voltaic vs Electrolytic Cells

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 Electrolysis

• Electrolysis is the process of

producing a chemical change in
an electrolytic cell.

• Electrolytic cells can be used to

separate elements from their
compounds.
 Electrolysis
• In electrolysis we use electrical energy to overcome the energy
barrier of a nonspontaneous reaction, allowing it
to occur.
• The reaction that takes place is the opposite of the spontaneous
process.
2 H2(g) + O2(g) → 2 H2O(l) spontaneous
2 H2O(l) → 2 H2(g) + O2(g) electrolysis
• Some applications of electrolysis are the following:
(1) Metal extraction from minerals and purification
(2) Production of H2 for fuel cells
(3) Metal plating
 Electrolytic Cells
• The source of energy is a battery or DC power supply.
• The positive terminal of the source is attached to the anode.
• The negative terminal of the source is attached to the cathode.
• Electrolyte can be either an aqueous salt solution or a molten
ionic salt.
• Cations in the electrolyte are attracted to the cathode and anions
are attracted to the anode.
• Cations pick up electrons from the cathode and are reduced;
anions release electrons to the anode and are oxidized.
 Electrolysis of Aqueous Solutions
• Possible cathode reactions:
• Reduction of cation to metal
• Reduction of water to H2
• 2 H2O + 2 e− → H2 + 2 OH− E° = −0.83 V at standard conditions
E° = −0.41 V at pH 7
• Possible anode reactions:
• Oxidation of anion to element
• Oxidation of H2O to O2
• 2 H2O → O2 + 4 e− + 4H+ E° = −1.23 V at standard conditions
E° = −0.82 V at pH 7
• Oxidation of electrode:
• Particularly Cu
• Graphite doesn’t oxidize

• Half-reactions that lead to least negative Ecell will occur.

• Unless overvoltage changes the conditions
Electrolysis of Water
 Electrolysis of Pure Compounds
• The compound must be in
molten (liquid) state.
• Electrodes are normally
graphite.
• Cations are reduced at the
cathode to metal element.
• Anions are oxidized at the
anode to nonmetal
element.
Electrolysis of NaCl(l)
 Electroplating
In electroplating, the work
piece is the cathode.

Cations are reduced at

cathode and plate to the
surface of the work piece.

The anode is made of the

plate metal. The anode
oxidizes and replaces the
metal cations in the solution.
 Mixtures of Ions and Electrolysis

• When more than one cation is present, the cation that is easiest to
reduce will be reduced first at the cathode.
• Least negative or most positive E°red

• When more than one anion is present, the anion that is easiest to
oxidize will be oxidized first at the anode.
• Least negative or most positive E°ox
 Stoichiometry of Electrolysis
• In an electrolytic cell, the amount of product made is related to the
number of electrons transferred.
• Essentially, the electrons are a reactant.

• The number of moles of electrons that flow through the electrolytic

cell depends on the current and length of time.
• 1 amp = 1 coulomb of charge/second
• 1 mole of e− = 96,485 coulombs of charge
• Faraday’s constant

Conceptual plan:
time (in seconds) → coulombs → moles of electrons →
moles of metal → grams of metal
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