CHEMISTRY 122 Chapter 11 Electrochemistry

Overview:
• Oxidation Numbers and Redox Reactions
• Galvanic cells
• Standard Reduction Potentials (Eo)

Electrochemistry – Ch. 11.1 – 11.2

Recall:
We can assign oxidation number of an atom in a molecule or ion in order of priority:
1) Free elements have an oxidation state = 0.
Na = 0 and Cl2 = 0 in 2 Na(s) + Cl2(g)
2) Monatomic ions have an oxidation state equal to their charge.
Na = +1 and Cl = −1 in NaCl
3a) The sum of the oxidation states of all the atoms in a compound is 0.
Na = +1 and Cl = −1 in NaCl, (+1) + (−1) = 0
3b) The sum of the oxidation states of all the atoms in a polyatomic ion equals the charge on the ion.
N = +5 and O = −2 in NO3–, (+5) + 3(-2) = −1
4a) Group I metals have an oxidation state of +1 in all their compounds.
Na = +1 in NaCl
4b) Group II metals have an oxidation state of +2 in all their compounds.
Mg = +2 in MgCl2
5) In their compounds, nonmetals have oxidation states according to the table below.

Nonmetal Oxidation State Example

F −1 CF4

H +1 CH4

O −2 CO2

Group 7A −1 CCl4

Group 6A −2 CS2

Group 5A −3 NH3

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J. Zhou Spring 2018
CHEMISTRY 122 Chapter 11 Electrochemistry

Example:
Determine the oxidation state of Mn in the following:
a) MnO2

b) MnO4-

Oxidation state of elements can change through in an oxidation-reduction reaction:

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

In this example, Cu2+ is ________________________ and is referred to as the ________________________

agent. Zn is ________________________ and is referred to as the ________________________ agent.
We can write the oxidation and reduction half reactions:

You are responsible to review determination of oxidation numbers, redox reactions and balancing half-
reactions (in both acidic and basic conditions).

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CHEMISTRY 122 Chapter 11 Electrochemistry

Oxidation-reduction reactions involve, either the ________________________of an electric current from a

spontaneous chemical reaction, or (the opposite process) the ________________________ of electric current to
produce non-spontaneous chemical changes.

In these reactions, ________________________ are transferred and ________________________

________________________ are changed.

Electrochemistry is the study of the interchange of ________________________ and

________________________ ________________________.

There are two types of electrochemical cells:

• Galvanic cells
• Electrolytic cells

Galvanic Cell
Galvanic cell is a device that converts chemical energy to electrical energy.

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

There are two half-reactions taking place in two half-cells

• Anode (Oxidation): Zn(s) → Zn2+(aq) + 2e–
• Cathode (Reduction): Cu2+(aq) + 2e– → Cu(s)

Electrons flow from ________________________ to ________________________.

A galvanic cell diagram is usually drawn.

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CHEMISTRY 122 Chapter 11 Electrochemistry

The cell symbol for this cell can be written as follows

Standard Reduction Potentials (Eo)

Standard potentials (Eo) is an indication of how easily species are reduced or oxidized:
• All ionic species present at 1 M
• All gases are at 1 atm
• Where no metallic substance is indicated, the potential is established on an inert metallic electrode
(ex. Pt).
This must be measured with respect to a ________________________ ________________________
________________________. The potential for the Standard Hydrogen Electrode (SHE), Eo = 0.0 V.

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CHEMISTRY 122 Chapter 11 Electrochemistry

The more positive E0 the greater the tendency for the substance to be ________________________

By convention, half-cell potentials are reported as standard ________________________ potentials.

Cu2+(aq) + 2e– → Cu(s), E° = +0.34 V.
As oxidation, the Eo changes sign
Cu(s) → Cu2+(aq) + 2e–, E° =
Note: Eo does not change when reaction is multiplied by an integer
2Cu2+(aq) + 4e– → 2Cu(s), E° =

The list of standard reduction potential for different substances will be provided to you.

Cell potential, E°cell , is the difference in standard electrochemical (reduction) potentials of the two half cells.

The larger the E°cell ,the ________________________ the voltage produced.

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CHEMISTRY 122 Chapter 11 Electrochemistry

Example:
Determine the E°cell for the following galvanic cells:
a) Zn(s) | Zn2+(aq, 1M) || Cu2+(aq, 1M) | Cu(s)

b) Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Example:
Predict what will happen if molecular bromine (Br2) is added to a solution containing NaCl and NaI at
25°C. Assume all species are in their standard states.
Cl2(1 atm) + 2e- → 2Cl-(1 M) E° = 1.36 V
Br2(l) + 2e- → 2Br-(1 M) E° = 1.07 V
I2(s) + 2e- → 2I-(1 M) E° = 0.53 V

Note: in a galvanic cell the E°cell is ________________________ and the process is

________________________.

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