Republic of the Philippines Balancing Redox Reactions

NUEVA ECIJA UNIVERSITY OF SCIENCE AND TECHNOLOGY ✓ The most common method used is the half-reaction approach
Cabanatuan City ✓ Can be done in acidic or basic medium
✓ Rules on balancing under acidic medium
COLLEGE OF ARTS AND SCIENCES a. Separate the unbalanced reaction in to two half-reactions (oxidation and
Chemistry and Environmental Science Department reduction).
b. Add H2O to balance the O atoms and H+ to balance the H atoms.
c. Add the two half-reactions then equalize the number of electrons.
Chem 114 (Chemistry for Engineers) ✓ Rules on balancing under basic medium
a. Same process when balancing under acidic medium; however, OH - ions should be
Electrochemistry added on both sides of the balanced redox reaction under acidic medium. For
every H+ ion present, an equivalent number of OH- ion must be added.
Electrochemistry- branch of chemistry dealing with the interconversion of electrical and
chemical energies Types of Electrochemical Reactions
a. Electrolysis- consumes electrical energy to allow chemical changes in a system to
Electrochemical processes- involve redox reactions. In spontaneous reactions, the electrical occur.
energy is converted to chemical energy while for non-spontaneous reactions, the electrical b. Electrochemical cell reaction- involves redox reactions. Electrical energy is produced
energy is used to drive the reaction. as a result of a chemical change in a system.

Redox Reactions (Reduction-Oxidation Reactions) Galvanic/Voltaic Cell

✓ GEROA-LEORA (Gain of electrons, reduction process, oxidizing agent – loss of ✓ A cell that runs spontaneously to produce a positive cell potential.
electrons, oxidation process, reducing agent) ✓ One of the earliest forms of this cell was made by Luigi Galvani and Alessandro Volta.
✓ Also called electron-transfer reactions
✓ Common applications: combustion, metal and nonmetal extraction from ores

Oxidation Number
✓ Number of charges the atom would have in a molecule or ionic compound if electrons
were fully transferred
✓ An increase in the oxidation number signifies the oxidation of a substance
✓ A decrease in the oxidation number signifies the reduction of a substance
✓ Rules in assigning oxidation numbers
a. Elemental forms have 0 oxidation number.
b. For monatomic ions, the oxidation number is equal to the charge of the ion.
c. Oxygen usually has -2 ON but for peroxide ion (O22-) and superoxide ion (O2-), it is
-1 and -1/2, respectively.
d. Hydrogen has an oxidation number of +1 but when it is combined with metal ions
to form binary compounds such as LiH, NaH, its oxidation number becomes -1.
e. The halogen, fluorine, has a -1 ON. For other halogens (Cl, Br, I), they usually have
a negative ON but when combined with oxoacids and oxoanions, the oxidation
number becomes positive.
Figure 1. A sample set-up of a galvanic cell highlighting the reactions at a molecular level.
f. For neutral molecules, the oxidation number is 0. For polyatomic ions, the oxidation Source: Chang and Overby, 2011
number is the net charge.
✓ Half-cell – components of each half reactions which are placed in separate containers Standard Reduction Potentials
✓ The two half-cells are joined together by a circuit wire and a salt bridge. ✓ Voltage associated with a reduction reaction at an electrode when the solute is at 1 M
✓ Salt bridge – used to facilitate the continuous flow of electrons from the anode to the and the gas pressure is 1 atm, and a temperature of 25oC.
cathode ✓ Standard electromotive force of a cell: Eocell = Eocathode – Eoanode
✓ Oxidation half-cell is the anode compartment while the reduction half-cell is the
cathode compartment.
✓ In any galvanic cell, the anode is always negative while the cathode is always positive.
✓ By convention, the oxidation is at the left compartment and the reduction is at the right
compartment.
✓ Cell reactions

Figure 3. Galvanic/voltaic cell set-up for the standard hydrogen electrode (SHE).
Source: Chang and Overby, 2011

✓ Cell notations for Figure 3a and Figure 3b, respectively

Zn(s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt(s)
Pt(s) | H+ (1 M) | H2 (1 atm) || Cu2+ (1 M) | Cu(s)

Thermodynamics of Redox Reactions

✓ Cell potential (Ecell) – also called the cell voltage or electromotive force. It is basically
the difference of the potentials between the electrodes.
• Units of measurement
1 𝐽𝑜𝑢𝑙𝑒 (𝐽)
1 𝑉𝑜𝑙𝑡 (𝑉) =
1 𝐶𝑜𝑢𝑙𝑜𝑚𝑏 (𝐶)
✓ Galvanic cells have positive values of cell potential.
✓ The change in Gibbs free energy (ΔG) for a galvanic cell is always negative, that is,
indicating a spontaneous reaction. It is given by the equation below
𝛥𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
Figure 2. A sample set-up of a galvanic cell highlighting the half-cell reactions. where
Source: Silberberg, 2009 ΔG is the Gibbs free energy change of the system which can also be interpreted as
the maximum work that can be derived from the redox reaction taking place
✓ Cell diagram notation (referring to the previous diagram) n is the number of moles of electrons
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s) F is the Faraday’s constant (96485 C/ mol electrons)
Ecell is the cell potential
✓ Active electrodes – electrodes that can participate in redox reactions such as the zinc
bar and copper bar shown in the illustrations At standard conditions, the equation above becomes
✓ Inactive electrodes – electrodes that are used to permit electron flow but do not 𝑜
𝛥𝐺 𝑜 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
participate in the redox reaction such as platinum and graphite
 ✓ Efficiency of a galvanic cell
𝑤
% 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = 𝑥 100%
𝑤𝑚𝑎𝑥
where
w is the actual work obtained from the system
wmax is the maximum amount of work that can be generated from the cell
✓ Relationship of the equilibrium constant, K and Eocell
𝑜 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾
𝑛𝐹
where
R is the universal gas constant (8.314 J/mol-K)
T is temperature (in Kelvin)
K is the equilibrium constant Figure 5. Components of an alkaline battery.
✓ Concentration dependence of emf Source: Silberberg, 2009
The dependence of the cell potential on concentration is given by the Nernst equation.
Mathematically, the equation is written as 2. Mercury and silver (button) batteries – usually used in calculators, watches,
𝑅𝑇 hearing aids, and cameras
𝐸 = 𝐸𝑜 − ln 𝐾
𝑛𝐹
The Gibbs free energy change can also be dependent of the concentration and its
dependency is given by the equation below
∆𝐺 = 𝑅𝑇 ln 𝐾
This free energy change accounts for the movement of the system from non-standard
to standard conditions.
✓ Concentration cells – cells having the same composition in both compartments but at
different concentrations.
Figure 6. Redox reactions taking place in mercury and silver batteries.
Batteries Source: Silberberg, 2009
✓ A group of galvanic cells arranged in series; thus, its total electric potential is simply
the sum of the voltages of each cell
✓ Types of batteries
a. Primary/ non-rechargeable batteries – when these batteries are deemed “dead,”
they are eventually discarded.
Some primary batteries:
1. Alkaline battery – previously known as Leclanche cell. This is the most
common dry cell which finds its way in flashlights, radios, watches, and more.

Figure 7. Components of a silver (button) battery.

Source: Silberberg, 2009
Figure 4. Redox reaction taking place inside an alkaline battery.
Source: Silberberg, 2009
 3. Primary lithium battery – commonly used in watches as well and implanted
medical devices such as a heart pacemaker.
Figure 10. Redox reaction in a lead-acid battery.
Source: Silberberg, 2009

Figure 8. Redox reaction taking place in primary lithium batteries.

Source: Silberberg, 2009

Figure 11. Components of a lead-acid battery.

Source: Chang & Overby, 2011

2. Nickel-metal hydride battery – commonly used in wireless/cordless razors,

camera flash units, and even in power tools such as a handheld drilling
machine.
Figure 9. Components of a primary lithium battery.
Source: Silberberg, 2009

b. Secondary/ rechargeable batteries – as electrical energy is supplied, the reversal

of the cell reaction takes place which favors the reformation of the reactant. Most
common secondary battery is the ones used in vehicles. Figure 12. Redox reaction in a nickel-metal hydride battery.
Some secondary batteries: Source: Silberberg, 2009
1. Lead-acid battery – a battery used in cars. Typical structure of this battery is
six-celled connected in series which has a total voltage of 12.
 Figure 16. Redox reaction in a hydrogen-oxygen fuel cell.
Source: Silberberg, 2009

Figure 13. Components of a nickel-metal hydride battery.

Source: Silberberg, 2009

3. Lithium-ion battery – commonly used in laptop computers, cellular phones, and

digital cameras

Figure 14. Redox reaction in a lithium-ion battery.

Source: Silberberg, 2009
Figure 17. Mechanism of a hydrogen-oxygen fuel cell.
Source: Silberberg, 2009

Figure 18. Redox reaction in a propane-oxygen fuel cell.

Source: Chang & Overby, 2011

Corrosion
✓ A natural phenomenon occurring on metals resulting to their deterioration due to
Figure 15. Components of a lithium-ion battery set-up. electrochemical means.
Source: Silberberg, 2009 ✓ This process results to the formation of metal oxides and sulfides.
✓ It can be viewed as the oxidation of metals.
c. Fuel cell – a type of galvanic cell wherein the reactants must be continuously
✓ Corrosion of iron
supplied to keep the system functioning.
 References:
Chang, R. & J. Overby. (2011). General chemistry: The essential concepts (6 th ed.). McGraw-
Hill Companies, Inc.: New York, United States of America.
Silberberg, M. S. (2009). Chemistry: The molecular change of nature and matter (5 th ed.).
McGraw-Hill Companies, Inc.: New York, United States of America.
Zumdahl, S. S. & S. A. Zumdahl. (2010). Chemistry (8th ed.). Brooks Cole: California, United
States of America.

Figure 19. Illustration of the rusting of iron.

Source: Zumdahl & Zumdahl, 2010

Figure 20. Redox reaction involved in the rusting of iron.

Source: Zumdahl & Zumdahl, 2010

✓ Corrosion prevention
a. Galvanizing – application of zinc as a coating on steel which forms an oxide-
carbonate coating.
b. Alloying – mixing two or more types of metals to form a more durable and rust-
resistant steel or alloys.
c. Cathodic protection – used to protect steel that are buried underground.

Figure 21. Illustration of cathodic protection of storage tanks.

Source: Chang & Overby, 2011
Figure 22. Standard reduction potential table.
Source: Chang and Overby, 2011