ELECTROCHEMISTRY
Electrochemistry
Chemistry and Energy Relations
Lecture Notes 12
Chemistry for Engineers
ELECTROCHEMISTRY
ELECTROCHEMISTRY is the branch of chemistry that deals with the relationship
between electrical energy and chemical energy.
ELECTROCHEMICAL PROCESSES – are (redox) oxidation–reduction reactions in
which the energy released by a spontaneous reaction is converted to electricity
REDOX (oxidation-reduction) reactions –occurs when electrons are transferred
from an atom that is oxidized to an atom that is reduced.
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OXIDATION NUMBER (OXIDATION STATE) – signifies the number of charges the
atom would have in a molecule or in an atomic compound if electrons were
transferred completely.
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RULES IN ASSIGNING OXIDATION NUMBERS
• The oxidation number of a free element is always 0.
• The oxidation number of a monatomic ion equals the charge of the ion.
• Fluorine in compounds is always assigned an oxidation number of -1.
• The alkali metals (group I) always have an oxidation number of +1.
• The alkaline earth metals (group II) are always assigned an oxidation number of +2.
• Oxygen almost always has an oxidation number of -2, except in peroxides (H2O2) where it is -
1 and in compounds with fluorine (OF2) where it is +2.
• Hydrogen has an oxidation number of +1 when combined with non-metals, but it has an
oxidation number of -1 when combined with metals.
• The algebraic sum of the oxidation numbers of elements in a compound is zero.
• The algebraic sum of the oxidation states in an ion is equal to the charge on the ion.
Source: www.periodni.com
ELECTROCHEMISTRY
OXIDATION REACTION – refers to the half-reaction that involves the loss of electrons
REDUCTION REACTION – refers to the half-reaction that involves the gain of electrons
OXIDIZING AGENT - the one that accepts electrons; the one that is reduced
REDUCING AGENT – the one that donates electrons; the one that is oxidized
OILRIG: Oxidation Is Loss (of electrons). Reduction Is Gain (of electrons).
LEOGER: Loss Electron – Oxidation. Gain Electron - Reduction
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SAMPLE PROBLEM 01:
Identify the oxidizing and reducing agents in the reaction
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BALANCING REDOX REACTIONS
1. The amount of each element must be the same on both sides of the
equation.
2. The gains and losses of electrons must be balanced.
HALF-REACTIONS – equations that show either oxidation or reduction alone.
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BALANCING REDOX REACTIONS BY THE METHOD OF HALF-REACTIONS
A. For balancing of redox reaction that occurs in acidic aqueous solution.
1. Divide the equation into one oxidation half-reaction and one reduction half-
reaction.
2. Balance each half-reaction.
(a) Balance elements other than H and O.
(b) Balance O atoms by adding H2O as needed.
(c) Balance H atoms by adding H+ as needed.
(d) Balance charge by adding e- as needed.
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3. Multiply half-reactions by integers as needed to make the number of electrons
lost in the oxidation half-reaction equal the number of electrons gained in the
reduction half-reaction.
4. Add half-reactions and, if possible, simplify by cancelling species appearing on
both sides of the combined equation.
5. Check to make sure the atoms and charges are balanced.
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SAMPLE PROBLEM 02:
Balance the following equations occurring in an acidic medium:
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B. For balancing of redox reaction that occurs in basic aqueous solution.
1. Divide the equation into one oxidation half-reaction and one reduction half-
reaction.
2. Balance each half-reaction.
(a) Balance elements other than H and O.
(b) Balance O atoms by adding H2O as needed.
(c) Balance H atoms by adding H+ as needed.
(d) Balance charge by adding e- as needed.
(e) Count the number of H+ in each half-reaction and add the same number of
OH- to each side of the reaction.
(f) Neutralize H+ and OH- by forming H2O when they are on the same side of
either half-reaction.
(g) Cancel water molecules that both appear in the product and reactant sides.
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3. Multiply half-reactions by integers as needed to make the number of electrons
lost in the oxidation half-reaction equal the number of electrons gained in the
reduction half-reaction.
4. Add half-reactions and, if possible, simplify by cancelling species appearing on
both sides of the combined equation.
5. Check to make sure the atoms and charges are balanced.
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SAMPLE PROBLEM 03:
Balance the following equations occurring in a basic medium:
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ELECTROCHEMICAL CELLS: systems that incorporate redox reaction to produce or
utilize electrical energy
TYPES OF ELECTROCHEMICAL CELLS:
1. VOLTAIC (GALVANIC CELL): cells that uses spontaneous reaction resulting
from the difference in chemical potential energy between higher- and lower-
energy products to generate electrical energy
2. ELECTROLYTIC CELL: uses electrical energy to drive nonspontaneous reaction.
The electrical energy from the external source converts lower energy
reactants to higher energy products.
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PARTS OF ELECTROCHEMICAL CELLS:
1. ELECTRODES: conduct electricity between the cell and its surroundings
a. ANODE: the occurrence of the oxidation half-reaction
b. CATHODE: the occurrence of the reduction half-reaction
2. ELECTROLYTES: a mixture of ions usually in aqueous solution that are involved
in the reaction or that carry the charges. This is where the electrodes are
dipped.
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The energy released in a spontaneous redox
reaction can be used to perform electrical
work.
GALVANIC (VOLTAIC) CELL – a device in which
the transfer of electrons takes place in an
external pathway rather than directly
between the reactants present in the same
reaction vessel.
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Anions always migrate toward the anode and
cations toward the cathode through an
external circuit.
Because of this directional flow, the anode in
a voltaic cell is labeled with a negative sign
and the cathode is labeled with a positive
sign.
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ANODE – the electrode in a galvanic cell is the electrode in which oxidation
occurs
CATHODE – electrode at which reduction occurs
HALF-CELL REACTION
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SAMPLE PROBLEM 04:
The two half-reaction in a voltaic cell are
(a) Indicate which reaction occurs at the anode and which at the cathode.
(b) Which electrode is consumed in the cell reaction?
(c) Which electrode is positive?
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Cell diagram – the conventional notation for representing galvanic cells
CELL POTENTIALS UNDER STANDARD CONDITIONS
• Potential energy is higher at the anode than at the cathode; thus, electrons
flow spontaneously toward the electrode with the more positive electrical
potential.
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One volt (V) is the potential difference required to impart 1 Joule of energy to a
charge of 1 coulomb, C
Cell potential (Ecell) is the potential difference between the two electrodes of a
voltaic cell. Also called the electromotive force, emf and voltage of the cell.
The magnitude of the cell potential depends on the reactions that occur at the
cathode and anode, the concentrations of reactants and products and the
temperature.
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Standard cell potential or standard emf, E°cell, is the cell potential under standard
conditions (1M concentrations of products and reactants in solution, 1 atm
pressure and 25°C.
Standard reduction potentials are intensive properties.
The more positive the value of E°red, the greater tendency for reduction under
standard conditions.
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SAMPLE PROBLEM 05:
The standard cell potential is 1.46V for a voltaic cell based on the following half-
reactions:
Using Table 20.1, calculate E°red for the reduction of In3+ to In+.
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SAMPLE PROBLEM 06:
Using date in Table 20.1, calculate the standard emf for a cell that employs the
overall cell reaction:
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SAMPLE PROBLEM 07:
A voltaic cell is based on Co2+/Co half-cell and an AgCl/Ag half cell.
a. What half reaction occurs at the anode?
b. What is the standard cell potential?
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SAMPLE PROBLEM 08:
Using Table 20.1, rank the following species from the strongest to the weakest
reducing agent:
I-(aq), Fe(s), Al(s)
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FREE ENERGY AND REDOX REACTIONS
A positive value of E indicates a spontaneous process; a negative value of E
indicates a non-spontaneous process.
*E is used to represent the emf under non-standard conditions.
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SAMPLE PROBLEM 09:
Using the standard potentials listed in Appendix E, determine which of the
following reactions are spontaneous under standard conditions:
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Emf, Energy and the equilibrium constant
n = a positive number without units that represents the number of moles of
electrons transferred according to the balanced equation for the reaction
F = Faraday’s constant
At standard conditions:
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SAMPLE PROBLEM 10:
For the reaction
a) What is the value of “n”?
b) Use the data in Appendix E to calculate ∆G°.
c) Calculate K at T=298K
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Electrical work
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CELL POTENTIAL UNDER NON-STANDARD CONDITIONS
As voltaic cell is discharged, reactants are consumed and products are generated, so
concentrations change. The emf progressively drops until E = 0, at which point, the cell
is “dead”.
Nernst Equation:
Q = reaction quotient
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SAMPLE PROBLEM 11:
Calculate the emf generated by the cell described in the given reaction when
[Al3+]=4.0x10-3M and [I-]=0.010M.
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CONCENTRATION CELLS – cells based solely on the emf generated because of a
difference in a concentration
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Lead-Acid Battery
A 12-V lead-acid automotive battery consists of
six voltaic cells in series, each producing 2V.
The cathode of each cell is lead dioxide (PbO2)
packed on a lead grid. The anode of each cell is
lead. Both electrodes are immersed in sulfuric
acid.
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ALKALINE BATTERY – the most common non-rechargeable battery. The anode is
a powdered zinc metal immobilized in a gel in contact with a concentrated KOH.
The cathode is a mixture of MnO2 and graphite, separated from the anode by a
porous fabric. The battery is sealed with in a steel can to reduce the risk of any of
the concentrated KOH escaping.
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NICKEL-CADMIUM, NICKEL-METAL-HYDRIDE, LITHIUM-ION BATTERIES
HYDROGEN FUEL CELLS
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CORROSION REACTIONS are spontaneous redox reactions in which a metal is
attacked by some substance in its environment and converted to an unwanted
compound
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ELECTROLYSIS – It is possible for nonspontaneous redox reaction to occur by
using electrical energy to drive them.
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SAMPLE PROBLEM 12:
a) The half-reaction for formation of magnesium metal upon electrolysis of
molten MgCl2 is given in the above reaction. Calculate the mass of
magnesium formed upon passage of a current of 60.0 A for a period of 4.00
x103 s.
b) How many second would be required to produce 50.0g of Mg from MgCl2 if
the current is 100.0A?
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REFERENCES
Brown, T.L., Lemay Jr., H.E., Bursten, B.E., Murphy, C.J., and Woodward, P.M. (2012)
Chemistry: The Central Science, 12th Ed., USA: Pearson Education, Inc.
Brown, L.S. and Holme, T.A. (2011) Chemistry for Engineering Students, 2nd Edition,
USA, Brooks/Cole, Cengage Learning
Chang, R. (2010) Chemistry, 10th Ed., New York, McGraw Hill
Maron, S.H and Lando, J.B. (1974) Fundamentals of Physical Chemistry. Macmillan
Publishing Co. Inc. New York, USA
Spielberg, M.S. (c2007) Principles of General Chemistry, 2nd Edition, New York,
USA.
