ELECTROCHEMISTRY

STEM 12

GENERAL CHEMISTRY 2

Members:

Anthoneth Piege C. Padama

Jerwin Guina-ob

Joeny Uminyad
Electrochemistry

Section 1

Redox Reactions

 A type of chemical change where electron transfer occurs is classified as an oxidation-

reduction (redox) process. The ability of the electrons to be transferred from one species
to another is dependent on the species’ reduction or oxidation potential. Fluorine, being
the most non-metallic element, has the greatest tendency to undergo reduction or to gain
electrons during a redox process. On the other hand, metallic elements possess great
tendency or potential to lose electrons or undergo oxidation.

Balancing Redox Reactions

Redox reactions can be balanced in two ways: by the change in oxidation state method or by the
ion-electron method.

The following steps are involved in balancing redox reactions by the change in oxidation state
method:

1. Write the skeleton equation.

2. Assign oxidation state of all elements using the following rules:

a.) The oxidation state of all elements in the free, uncombined state is zero.

Examples: Cl in Cl 2, H in H 2, O in O 2, Mg as Mg metal

b.) The oxidation state of H in compounds is +1 except in hydrides where it is -1.

Examples: H is +1 in HCl, NaOH, CH 3COOH; H is -1 in NaH, Mg H 2

c.) The oxidation state of O in compounds is -2, except in peroxides where it is -1 and when

combined with F where it is +2.

Examples: O is -2 in NaOH, H₂O, HNO₃; -1 in H₂O₂, Na₂O₂; +2 in OF₂

d.) The oxidation state of a representative element is equal to its valence.

Examples: Na is +1 in NaOH, Mg is +2 in MgO, Cl is -1 in HCl, S is -2 in H 2S

e.) The sum of the oxidation states in a radical is equal to its charge.

Example: Mn is +7 in the permanganate ion, (MnO₄)⁻¹. The oxidation state of O is -2.

The sum of all oxidation states in the permanganate radical must be equal to -1. It follows

that the oxidation state of Mn must be +7.

f.) The sum of oxidation states in a compound is zero.

Examples: S is +6 in sulphuric acid, H₂SO₄. 2 H atoms give 2(+1) or +2, 4 O atoms give
 4(-2) or -8 which give a total of -6 for H and O. Since the sum of oxidation states must be

zero, the oxidation states of S must be +6.

3. Determine the element/s which show an increase or decrease in oxidation state. The oxidizing agent
shows a decrease in oxidation state while the reducing agent shows an increase in oxidation state. One
unit decrease in oxidation state means a gain of one electron while one unit increase in oxidation state
means the loss of one electron.

4. Determine the number electrons gained or lost per molecule or unit from the change in oxidation
state.

5. Balance the number of electrons gained and electrons lost.

6. Balance the number of atoms of the element oxidized or reduced.

7. Balance the rest of the equation by inspection, balancing H and O last if they are not the element
oxidized or reduced.

Exercise:

Assign oxidation states to the underlined element.

a.) Cl₂ c.) Na₂S e.) NaN₃ g.) NH₄Cl

b.) K₂O₂ d.) Na₂S₂O₃ f.) CH₄ h.) OF₂

Solution:

Assign oxidation states to all elements.

0+1-1 +3-1 0

Al+HCl → AlCl₃ + H₂

Section 2

Galvanic Cells

 An electrochemical cell that converts the chemical energy of spontaneous redox reactions into
electrical energy is known as a galvanic cell or voltaic cell.

Principle of Galvanic (Voltaic) Cell

Electric work done by a galvanic cell is mainly due to the Gibbs energy of spontaneous redox reaction
in the voltaic cell. It generally consists of two half cells and salt bridge. Each half cell further consists
of a metallic electrode dipped into an electrolyte. These to half-cells are connected to a voltmeter and
a switch externally with the help of metallic wires. In some cases, when both the electrodes are dipped
in the same electrolyte, a salt bridge is not required.
 Galvanic Cell (Voltaic Cell) Diagram

Section 3

Standard Reduction Potentials

The cell voltage or cell potential is the potential difference between the electrodes of a galvanic cell
when no current flows. It is observed as the voltage reading in the voltmeter that is connected in series
to the galvanic cell at zero current (no current flows). When the cell potential is positive, electrical
energy is generated during the process and the cell is galvanic (or voltaic). Galvanic cells result from
the conversion of chemical energy into electrical energy during a spontaneous reaction. When the cell
potential is negative, the cell is not galvanic but electrolytic, the reaction is nonspontaneous and
requires electrical energy to carry out redox process.

Consider the following reactions:

Anode oxidation half-reaction Zn(s ) → Zn2+¿¿ + 2e−¿¿ ε ° red = - 0.76 V

Cathode reduction half-reaction 2e + Cu2+¿ ¿ → Cu(s) ε ° red = + 0.34 V

Cell reaction: Zn(s ) + Cu2+¿ ¿ → Zn2+¿¿ + Cu(s) ε ° cell = 0.34 – (-0.76) = 1.10 V

Section 4

Spontaneity of Redox Reactions

In section 3 of this chapter, it was established that for a galvanic cell, the cell reaction is obtained
either by adding the anode oxidation half-reaction to the cathode reduction half-reaction or by
subtracting the anode reduction half-reaction from the cathode reduction half-reaction. The standard
cell potential is the sum of the reduction potential of the cathode and the oxidation potential of the
anode or the difference obtained between the cathode reduction potential and the anode reduction
potential, which gives:

ε ° cell = ε ° reduction ,cathode −ε ° reduction ,anode

Therefore, for the reaction of the Zn-Cu cell given in Section 3, ε ° cell = 1.10 V, which is the quatity of
electrical energy generated by the galvanic cell at the standard [Link] was evaluated from the
standard half-cell potential of each half-reaction. Since the cell potential is positive, the cell is
classified as galvanic at the standard state. Whether a cell is galvanic or electrolytic can be determined
just by comparing the values of the electrode potentials. If the cathode potential is more positive
(greater reduction potential), that the anode reduction potential, then the cell potential is positive and
the cell is galvanic.

Section 5

Commercial Cells and Batteries

 Commercial batteries are galvanic cells that use solids or pastes as reactants to
maximize the electrical output per unit mass.
 A battery is a contained unit that produces electricity, whereas a fuel cell is a galvanic
cell that requires a constant external supply of one or more reactants to generate
electricity.

The Leclanché Dry Cell

 This is the most common cell used in flashlights, radios, some calculators, and the like.
 It is one of the modern electrical batteries that was invented by the French electrical engineer
Georges Leclanché.
 The zinc casing acts as the anode and a graphite rod is the cathode.

Mercury and Silver Button Battery

 Mercury is used to inhibit corrosion that can lead to gas build up which in turn can cause
bulging and leakage or can adversely affect battery performance.
Fuel cells
 This cells convert the energy of a fuel to electrical energy and are used for portable power
generation, stationary power generation, and power for transportation.
Lead Storage Battery
 This is the battery used in cars and trucks.

Section 6

Corrosion
 Refers to the process of deterioration of metals.
 Although this process is usually described in terms of metal iron, it is not limited to
iron but can happen to any metal that has lower reduction potential than hydrogen.
Section 7

Electrolysis
 It uses electricity to separate chemical compounds causing the chemical
reaction of oxidation-reduction to occur.
 During electrolysis, reduction occurs at the cathode while oxidation occurs at
the anode of electrolytic cell.