3.

1 Electrochemistry
Electrochemistry is best defined as the study of the interchange of chemical and electrical energy. It is primarily
concerned with two processes that involve oxidation-reduction reactions: the generation of an electric current from a
spontaneous chemical reaction and the opposite process, the use of a current to produce chemical change.

Lesson 1: Oxidation-Reduction Reaction

In this reaction, solid sodium, which contains neutral sodium atoms,
reacts with chlorine gas, which contains diatomic Cl2 molecules, to form the
ionic solid NaCl, which contains Na+ and Cl- ions.

Reactions like this one, in which one or more electrons are transferred, are called oxidation-reduction reactions or
redox reactions.

Oxidation State
The concept of oxidation states (also called oxidation numbers) provides a way to keep track of electrons in
oxidation-reduction reactions, particularly redox reactions involving covalent substance. The oxidation states of atoms in
covalent compounds are obtained by arbitrarily assigning the electrons (which are actually shared) to particular atoms.

We define the oxidation states (or oxidation numbers) of the atoms in a covalent compound as the imaginary charges
the atoms would have if the shared electrons were divided equally between identical atoms bonded to each other or, for
different atoms, were all assigned to the atom in each bond that has the greater attraction for electrons. Of course, for ionic
compounds containing monatomic ions, the oxidation states of the ions are equal to the ion charges.

Rules for Assigning Oxidation States

Application of these simple rules allows the assignment of oxidation states in most compounds. To apply these rules,
recognize the sum of the oxidation states must be zero for an electrically neutral compound.

It is worthwhile to note at this point that the convention is to write actual charges on ions as n+ or n-, the number
being written before the plus or minus sign. On the other hand, oxidation states (not actual charges) were written +n or –n,
the number being written after the plus or minus sign.
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Characteristics of Redox Reaction
Oxidation-reduction reactions are characterized by a transfer of electrons. Oxidation is an increase in oxidation state
(a loss of electrons). Reduction is a decrease in oxidation state (a gain of electrons).

Sodium is oxidized and chlorine is reduced. Thus Cl2 is called the oxidizing agent (electron acceptor), and Na is
called the reducing agent (electron donor).

Balancing Oxidation-Reduction Equations

Redox reactions in aqueous solutions are often complicated, which means that is can be difficult to balance their
equations by simple inspection. In this section we will discuss a special technique for balancing the equations of redox
reactions that occur in aqueous solutions. It is called the half-reaction method.

The Half Reaction Method for Balancing Redox
Reaction in Aqueous Solutions
1. Write separate equations for the oxidation and
reduction half-reactions
2. For each half-reaction:
a. Balance all the elements except hydrogen and oxygen
b. Balance oxygen using H2O
c. Balance hydrogen using H+
d. Balance the charge using electrons
3. If necessary, multiply one or both balanced half-
reactions by an integer to equalize the number of
electrons transferred in the two half-reactions
4. Add the half-reactions, and cancel identical species
5. Check that the elements and charges are balanced
The Half-Reaction Method for Balancing Equations for
Redox Reaction in Basic Solution
1. Use the half-reaction method as specified for acidic
solution to obtain the final balanced equation as if H +
ions were present
2. To both sides of the equation obtained above, add a
number of OH- ions that is equal to the number of H+
ions. (We want to eliminate H+ by forming H2O.)
3. Form H2O on the side containing both+ and OH- ions,
and eliminate the number of H2O molecules that
appear on both sides of the equation.
4. Check that elements and charges are balanced.

Lesson 2: Galvanic Cell

Under these conditions, no useful work is obtained from the
chemical energy involved in the reaction, which instead released
as heat. To harness this energy, we have to separate the oxidizing
agent from the reducing agent thus, requiring the electron transfer
to occur through a wire. To sustained electron flow, the solutions
must be connected so that ions can flow to keep the net charge I
each compartment zero. This connection might involve a salt
bridge (a U-tube filled with an electrolyte) or a porous disk ion to
flow without extensive mixing of the solutions. When we make the provision for ion flow, the circuit is complete. Electrons flow
through the wire from reducing agent to oxidizing agent, and ions flow from one compartment to the other to keep the net
charge zero.

This device in which chemical energy is changed to electrical energy is called galvanic cell. The reaction in an
electrochemical cell occurs at the interface between the electrode and the solution where the electron transfer occurs. The

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electrode compartment in which oxidation occurs is called the anode; the electrode
compartment in which reduction occurs is called the cathode.
Cell Potential
A galvanic cell consists of an oxidizing agent in one compartment that pulls
electrons through a wire from a reducing agent in the other compartment. The “pull”,
or driving force, on the electrons is called the cell potential (Εcell) or the electromotive
force (emf) of the cell. The unit of electrical potential is volt (V), which defined as 1
Joule of work per coulomb of charge transferred.
The instrument used to measure cell potential is a crude voltmeter which works by drawing current through a known
resistance.
Lesson 3: Standard Reduction Potentials
The reaction in a galvanic cell is always a redox reaction that can be broken down into two half-reactions. It would be
convenient to assign a potential to each half-reaction so that when we construct a cell from a given pair of half-reactions we
can obtain the cell potential by summing the half-cell potentials.
The Eo values corresponding to reduction half-reaction with all solutes at 1M and all gases at 1atm are called
standard reduction potentials. Standard reduction potentials for the most common half-reactions are given in the table:

Combining two half-reactions to obtain a balanced redox reaction often requires two manipulations:
1. One of the reduction half-reactions must be reversed (since redox reactions must involve a substance being oxidized and
a substance being reduced). The half-reaction with the largest positive
potential will run as written (as a reduction), and the other half-reaction will
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 be forced to run in reverse (will be the oxidation reaction). The net potential of the cell will be the difference between the
two. Since the reduction process occurs at the cathode and the oxidation process occurs at the anode, we can write:

Because subtraction means “change the sign and add,” in the example done here we will change the sign of the
oxidation (anode) reaction) when we reverse it and add it to the reduction (cathode) reaction.

2. Since the number of electrons lost must equal the number gained, the half-reactions must be multiplied by integers as
necessary to achieve the balanced equation. However, the value of E o is not changed when a half-reaction is multiplied
by an integer. Since a standard reduction potential is an intensive property (it does not depend on how many times the
reaction occurs), the potential is not multiplied by the integer required to balance the cell reaction
Lesson 3: Electrolysis
A galvanic cell produces current when a redox reaction proceeds spontaneously. A similar apparatus, an electrolytic
cell, uses electrical energy to produce chemical change. The process of electrolysis involves forcing a current through a cell
to produce a chemical change for which the cell potential is negative; that I s electrical work causes an otherwise non-
spontaneous chemical reaction to occur. Electrolysis has great practical importance; for example, charging a battery,
producing aluminum metal, and chrome plating an object are all done electrolytically.

Lesson 3: Application of Galvanic Cell

Battery
A battery is a galvanic cell or, more commonly, a group of galvanic cells connected in series, where the potentials of
the individual cells add to give the total battery potential. Batteries are a source of direct current and have become an essential
source of portable power in our society.

Lead Storage Battery

Since about 1915 when self-starters were first used in automobiles, the lead storage battery has been a major factor
in making the automobile a practical means of transportation. This type of battery can function for several years under
temperature extremes from -30oF to 120oF and under incessant punishment from rough roads.

In this battery, lead serves as the

anode, and lead coated with lead dioxide
serves as the cathode. Both electrodes dip into
an electrolyte solution of sulfuric acid. The electrode reactions are:

Typical automobile lead storage battery has a six cells connected in series. Each cell contains multiple electrodes in
the form of grids and produces approximately 2V, to give a total battery potential of about 12V.

Dry Cell Battery

The calculators, electronic games, digital watches, and portable CD players that are so familiar to us are all powered
by small, efficient batteries. The common dry cell battery was invented more than 100 years ago by George Lanclanche
(1839-1882), a French chemist.

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 In its acid version, the dry cell battery contains a zinc inner case that acts as the anode and a carbon rod in contact
with a moist paste of solid MnO2, solid
NH4Cl, and carbon that acts as the
cathode. The half-reactions are complex
but can be approximated as follows:

This cell produces a potential of about 1.5V

In the alkaline version of the dry cell battery, the solid NH4Cl is replaced with KOH or NaOH. In this case the half-
reactions can be approximated as follows:

The alkaline dry cell lasts longer mainly because the zinc anode corrodes less rapidly under basic conditions than
under acidic conditions.

Other types of useful batteries include the silver cell, which has a Zn anode and a cathode that employs Ag2O as
the oxidizing agent in a basic environment. Mercury cells, often used in calculators have a Zn anode and a cathode involving
HgO as the oxidizing agent in a basic medium.

An especially important type of battery is the nickel-cadmium battery, in which the electrode reactions are:

Fuel Cells
A fuel cell is a galvanic cell for which the reactants are
continually supplied. To illustrate the principles of fuel cells,
let’s consider the exothermic redox reaction of methane with oxygen:

Corrosion
Corrosion can be viewed as the process of
returning metals to their natural state – the ores from
which they were originally obtained. Corrosion involved
oxidation of the metal. Since corroded metal often loses
its structural integrity and attractiveness, this
spontaneous process has great economic impact.
Approximately one-fifth of the iron and steel produced
annually is used to replace rusted metal.
2.2 Nuclear Chemistry and Energy
Lesson 2.2: Nuclear Chemistry and Energy
Nuclear chemistry is the sub discipline of chemistry that is concerned with changes in the nucleus of elements.
These changes are the source of radioactivity and nuclear power.
There are essentially three sources of radioactive elements.

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1. Primordial nuclides are radioactive elements whose half-lives are comparable to the age of our solar system and were
present at the formation of Earth. These nuclides are generally referred to as naturally occurring radioactivity and are
derived from the radioactive decay of thorium and uranium.
2. Cosmogenic nuclides are atoms that are constantly being synthesized from the bombardment of planetary surfaces by
cosmic particles (primarily protons ejected from the Sun), and are also considered natural in their origin.
3. Anthropogenic nuclides and results from human activity in the production of nuclear power, nuclear weapons, or through
the use of particle accelerators.
Nuclear energy, also called atomic energy, energy that is released in significant amounts in processes that
affect atomic nuclei, the dense cores of atoms. It is distinct from the energy of other atomic phenomena such as ordinary
chemical reactions, which involve only the orbital electrons of atoms.
One method of releasing nuclear energy is by controlled nuclear fission in devices called reactors, which now
operate in many parts of the world for the production of electricity. Another method for obtaining nuclear energy, controlled
nuclear fusion, holds promise but has not been perfected by 2020.
Nuclear energy has been released explosively by both nuclear fusion and nuclear fission.
Radioactive Decay:
Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration or nuclear disintegration)
is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is
considered radioactive. Three of the most common types of decay are alpha decay, beta decay, and gamma decay, all of
which involve emitting one or more particles or photons. The weak force is the mechanism that is responsible for beta decay.

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 Alpha Decay
Many nuclei with mass numbers greater than 200 undergo alpha (α) decay,
which results in the emission of a helium-4 nucleus as an alpha (α) particle, 42𝛼 .
The general reaction is as follows:

The daughter nuclide contains two fewer protons and two fewer neutrons than the parent. Thus α-particle emission produces
a daughter nucleus with a mass number A − 4 and a nuclear charge Z − 2 compared to the parent nucleus.

 Beta Decay
Nuclei that contain too many neutrons often undergo beta (β) decay, in
which a neutron is converted to a proton and a high-energy electron that is ejected
from the nucleus as a β particle:
The general reaction for beta decay is therefore
Although beta decay does not change the mass number of the nucleus, it does result in an increase of +1 in the
atomic number because of the addition of a proton in the daughter nucleus. Thus beta decay decreases the neutron-to-proton
ratio, moving the nucleus toward the band of stable nuclei.
 Positron Emission
Because a positron has the same mass as an electron but opposite charge, positron
emission is the opposite of beta decay. Thus positron emission is characteristic of neutron-
poor nuclei, which decay by transforming a proton to a neutron and emitting a high-energy
positron:
The general reaction for positron emission is therefore

Like beta decay, positron emission does not change the mass number of the nucleus. In this case, however, the
atomic number of the daughter nucleus is lower by 1 than that of the parent. Thus the neutron-to-proton ratio has increased,
again moving the nucleus closer to the band of stable nuclei.
 Electron Capture
A neutron-poor nucleus can decay by either positron emission or electron capture (EC),
in which an electron in an inner shell reacts with a proton to produce a neutron:
When a second electron moves from an outer shell to take the place
of the lower-energy electron that was absorbed by the nucleus, an x-ray is
emitted. The overall reaction for electron capture is thus
Electron capture does not change the mass number of the nucleus because both the proton that is lost and the
neutron that is formed have a mass number of 1. As with positron emission, however, the atomic number of the daughter
nucleus is lower by 1 than that of the parent. Once again, the neutron-to-proton ratio has increased, moving the nucleus
toward the band of stable nuclei.
 Gamma Emission
Many nuclear decay reactions produce daughter nuclei
that are in a nuclear excited state, which is similar to an atom in
which an electron has been excited to a higher-energy orbital to
give an electronic excited state. Just as an electron in an electronic
excited state emits energy in the form of a photon when it returns
to the ground state, a nucleus in an excited state releases energy in the form of a photon when it returns to the ground state.
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 Spontaneous Fission
Only very massive nuclei with high neutron-to-proton ratios can undergo spontaneous fission, in which the nucleus
breaks into two pieces that have different atomic numbers and atomic masses. This process is most important for the
transactinide elements, with Z ≥ 104. Spontaneous fission is invariably accompanied by the release of large amounts of
energy, and it is usually accompanied by the emission of several neutrons as well.
Half-life:
Radioactive decay proceeds according to
a principle called the half-life. The half-life (T½) is the
amount of time necessary for one-half of the radioactive
material to decay.
The fraction of parent material that remains after
radioactive decay can be calculated using the equation:

Nuclear Reaction:
The two general kinds of nuclear reactions are nuclear decay reactions and nuclear transmutation reactions.
 In a nuclear decay reaction, also called radioactive decay, an unstable nucleus emits radiation and is transformed into
the nucleus of one or more other elements. The resulting daughter nuclei have a lower mass and are lower in energy
(more stable) than the parent nucleus that decayed.
 In a nuclear transmutation reaction, a nucleus reacts with a subatomic particle or another nucleus to form a product
nucleus that is more massive than the starting material.
Classes of Radioactive Nuclei
The three general classes of radioactive nuclei are characterized by a different decay process or set of processes:
1. Neutron-rich nuclei. The nuclei on the upper left side of the band of stable nuclei have a neutron-to-proton
ratio that is too high to give a stable nucleus. These nuclei decay by a process that converts a neutron to a proton,
thereby decreasing the neutron-to-proton ratio.
2. Neutron-poor nuclei. Nuclei on the lower right side of the band of stable nuclei have a neutron-to-proton ratio
that is too low to give a stable nucleus. These nuclei decay by processes that have the net effect of converting a proton to a
neutron, thereby increasing the neutron-to-proton ratio.
3. Heavy nuclei. With very few exceptions, heavy nuclei (those with A ≥ 200) are intrinsically unstable regardless
of the neutron-to-proton ratio, and all nuclei with Z > 83 are unstable. This is presumably due to the cumulative effects of
electrostatic repulsions between the large number of positively charged protons, which cannot be totally overcome by the
strong nuclear force, regardless of the number of neutrons present. Such nuclei tend to decay by emitting an α particle (a
helium nucleus, 42𝐻𝑒, which decreases the number of protons and neutrons in the original nucleus by 2. Because the neutron-
to-proton ratio in an α particle is 1, the net result of alpha emission is an increase in the neutron-to-proton ratio. Nuclear decay
reactions always produce daughter nuclei that have a more favorable neutron-to- proton ratio and hence are more stable than
the parent nucleus.
(Combining two light nuclei to form a heavier, more stable nucleus. This process is called fusion. Splitting a heavy nucleus
into two nuclei with smaller mass numbers. This process is called fission.)
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