CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony

1ST SEMESTER

LESSON 2
THE BASICS OF ELECTROCHEMISTRY

Reduction - Oxidation Reaction

THE GENERAL RULES FOR ASSIGNING

OXIDATION NUMBERS

Rule (1)
The Oxidation number of any free, uncombined
element is zero. This includes multi-atomic
element such as H2 , O3 , S8 , P4 , C, Cl2 , N2
, etc.

Rule (2)
The charge on a simple (monatomic) ion is the
oxidation number of the element in that ion. In
a polyatomic ion, the sum of the oxidation The Voltaic cell or the Galvanic cell
numbers of the constituent atoms is equal to
the charge of the atom. A Galvanic cell (named after Luigi Galvani,
discovered "bioelectricity" in 1780) which is
Rule (3) also known as a Voltaic cell (named after
In compounds (whether ionic or covalent), the Alessandro Volta, invented the electric battery
sum of the oxidation numbers of all atoms in in 1799) is a type of an electrochemical cell
the compound is zero. that produce electricity as a result of
spontaneous chemical reactions.
Rule (4)
The Oxidation state of hydrogen in compounds Electrochemistry
is usually (+1), except in the case of the
metallic hydrides (CaH2 and NaH are - It is the branch of chemistry which
examples), where it is (-1). involves;

Rule (5) (1.) use of an electric current to cause

The oxidation number of monatomic ion is the chemical change – Electrolysis,
same charge on the ion. In their compounds, Example: electrolysis of water,
group IA metals (Li, Na, K, Rb, and Cs) always electroplating copper
have oxidation numbers of (+1), group IIA (2.) and generation of an electric current
elements (Be, Mg, Ca, Sr, and Ba) always by chemical change – Voltametry.
have oxidation numbers of (+2).
- It deals with the relationship between
Rule (6) electricity and chemical reactions.
The Oxidation State of oxygen in compounds is
usually (-2), except in peroxides (CaO2 and  Electricity – or sometimes referred as
H2O2 are examples) where it is (-1), or in electric current is the flow of electrical
fluorine compounds (OF2 is an example), charge, flow of electrons.
where it is (+2).
- Electricity can flow through metals by
metallic conduction.
Oxidation is loss of electron/s, which leads to
an increase in the oxidation number of the  Metallic conduction – Metallic crystals
element. may be described in terms of mobile
electron clouds permeating on relatively
Reduction is gain of electron/s, which leads to fixed structures of positive metal ions.
a decrease in the oxidation number of the When electrons are forced into one end
element. of a metal wire, (this is done by an
application of an electrical force supplied
Reducing agent (ANODE- left) is the reactant by a battery) the impressed electrons
where the oxidized element is a part of. displace other electrons of the cloud at
the point of entry. The displaced
Oxidizing agent (CATHODE- right) is the electrons, in return assume new
reactant where the reduced element is a part positions by pushing neighboring
of. electrons ahead, and this effect is
transmitted down to the end of the wire
at the opposite end. At any point
electrical neutrality is preserved, since
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

the rate of electrons moving into the wire and enter the solution as the ion M n+ . The
is equal the rate of electrons moving out metal atom is oxidized.
of the wire.
An equilibrium is quickly established between
- Electricity can flow through electrolytes the metal and the solution:
(solutions of strong acid or bases and
soluble salts) through electrolytic M (s)  M^n+ (aq) + n e-
conduction.

 Electrolytic conduction – charge can be

conducted through solutions containing
electrolytes. Ionic or electrolytic
conduction refers to the conduction of
electrical current by the motion of ions
through a solution. The positively
charged ions (cations) migrate towards
the negative electrode, while the
negatively charged ions (anions) move
toward the positive electrode.

A salt bridge – is a device used to connect the

oxidation and reduction half-cells of a galvanic
cell (voltaic cell), a type of electrochemical cell.
Salt bridges usually come in two types: glass
tube and filter paper.

A glass tube salt bridge is a U-shaped glass

tube filled with a relatively inert electrolyte;
usually potassium iodide KI, potassium nitrate,
KNO3 or sodium sulfate, Na2SO4 is used. The
Electrochemical cells electrolyte is often gellified with agar to help
prevent the intermixing of fluids which might
- is a properly connected combination of otherwise occur.
two half cells.
The following are the functions of the salt
Two kinds of electrochemical cells: bridge:
(a.) Voltaic cell or Galvanic cell – an (i) It connects the solutions of two half-
electrochemical cell that produce electricity as cells and completes the cell circuit.
a result of spontaneous chemical reactions. (ii) It prevents transference or diffusion
of the solutions from one half-cell to
(b.) Electrolytic cell – an electrochemical cell in the other.
which electricity is used to accomplish a (iii) It keeps the solutions in two half-
nonspontaneous chemical change – that is the cells electrically neutral. In anodic
reverse of a spontaneous reaction. half-cell, positive ions pass into the
solution and there shall be
Half Cell accumulation of extra positive charge
in the solution around the anode
- When a strip of metal, M is called which will prevent the flow of
electrode, and the electrode immersed electrons from anode. This does not
in a solution containing ions of same happen because negative ions are
metals M n+, the set-up is called a half provided by salt bridge. Similarly, in
cell. Two kinds of interaction is possible cathodic half-cell negative ions will
between metal atoms on the electrode accumulate around cathode due to
and metal ions in solution. deposition of positive ions by
reduction. To neutralize these
1.) A metal ion M n+, from solution will collide negative ions, sufficient number of
with the electrode, gain n electrons from it, and positive ions is provided by salt
be converted to a metal atom M. The ion is bridge. Thus, salt bridge maintains
reduced. electrical neutrality.
(iv) It prevents liquid-liquid junction-
2.) A metal atom M on the surface of the potential, i.e., the potential difference
electrode may lose n electrons to the solution which arises between two solutions
when in contact with each other.
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

makes 𝑂2 reduction less favorable. Iron in

contact with a solution whose pH is greater
than 9 does not corrode.
Module 2 The 𝐹𝑒2+ formed at the anode is eventually
oxidized to 𝐹𝑒3+, which forms the hydrated
Corrosion of metals: iron(III) oxide known as rust:*

Iron + Oxygen + Water === Hydrated Iton

(III) Oxide (Rust)
Only the surface of metal corrodes.

How to prevent iron to rust:

Barrier method:
-Preventing oxygen and water to touch the iron.
Ways: Paint, Oil/grease, and Electroplating

Sacrificial Method:
Adding a more reactive metal to the iron.

There are several methods for protecting

metals against corrosion. The most widely
used are:

1. Applying a protective coating, such as paint.

2. Plating the metal with a thin layer of a less

easily oxidized metal.

3. Galvanizing, or coating steel with zinc, a

more active metal.

Corrosion reactions are spontaneous redox

reactions in which a metal is attacked
by some substance in its environment and
converted to an unwanted compound.

Rusting of metal is an Oxidation-reduction

reaction
Prevention of rust:
- Coat surface with grease, paint, or
water-repellent water layer.
- Galvanization
-
4. Cathodic protection - connecting the metal
directly to a sacrificial anode, a piece of
another metal that is more active and therefore
preferentially oxidized

The electrons produced in the oxidation

migrate through the metal from this anodic
region to another portion of the
surface, which serves as the cathode
where 𝑂2 is reduced. The reduction
of 𝑂2 requires
𝐻+, so lowering the concentration
of 𝐻+ (increasing the pH)
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

BATTERIES

CHEMICAL TO ELECTRICAL ENERGY

Positive end: cathode

Negative end: anode

Type of batteries:

Primary voltaic cells

(non rechargeable)]

Leclanche dry cell

The first dry cell was patented by Georges
Leclanche in 1866.

-Carbon rod is placed in a porous spot

maintaining a mixture of carbon and
manganese dioxide Alkaline Dry Cell
- Ammonium chloride solution is the electrolyte
and carbon and zinc rods are the electrodes.
-Sealed by pitch.

Ammonium chloride to the electrolyte split into

ammonium and chloride ions, then its electrons
travel to the zinc rod, transferring its electron
forming zinc chloride. And the ammonium ions
travel to the carbon rod, the free ions neutralize
the ammonium ions forming ammonia and
hydrogen gas.

Carbon rod becomes the anode. (positive)

Thus zinc rod becomes the cathode. (negative)

The hydrogen gas is oxidize by manganese

dioxide to form water. And polarization is
prevented.

If a external copper wire is connected it

enables the electrodes to move from the
cathode to the anode, generating electricity.

EMF: 1.5 V
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

Mercury dry cell

CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

severe burns. Alpha radiation is less damaging

and the rays can be partially blocked with a
MODULE 3: CHEM LECTURE sheet of paper. It would take a sheet of metal
to block beta rays. You need thick layers of
RADIOACTIVITY AND NUCLEAR CHANGE dense material, such as lead, to protect
yourself from gamma radiation. A nuclear
Radioactivity is the spontaneous meltdown causes acute radiation exposure that
transmutation of an atomic nucleus from one is multiplied by the fact that foodstuffs remain
state to another, which yields various contaminated for years afterwards. The
radiations. exposure limit of 200 millisieverts hints at a
level of safety that no one can guarantee.
In 1896, Henri Becquerel (a French physicist)
discovered natural radioactivity coming from RADIOACTIVE DECAY
uranium compound.
Nuclear Stability
He was investigating phosphorescence in
uranium salts. Becquerel wrapped a Parts of an atom:
fluorescent substance, potassium uranyl
sulfate, in photographic plates.

- A strong nuclear force holds the positive

protons and neutral neutrons together in the
nucleus and is what determines if a nucleus
Photographic plate exposure caused by two is stable.
uranium ore rocks.
Uranium is transformed into lead while Stable Nuclei:
releasing invisible radiation “Becquerel rays” or
- The force is strong.
radioactivity.
- Brings sufficient energy to hold the nucleus
together permanently.
Effects of nuclear radiation on the human
body:
Unstable Nuclei:
- Have too many protons or too many
Alpha radiation is shown as a worm-like
neutrons upsetting the strong nuclear
structure. The spider-web like threads in the
forces.
middle show beta radiation. The human body
- Balance themselves by giving off the
has no way of sensing radioactivity, so we do
excess proton or neutron. THIS IS
not even notice when we have been exposed
RADIOACTIVE DECAY.
to radioactivity.
- Unstable nuclei are radioactive and emit
This is why people who work in nuclear plants, radiation.
like here in the destroyed Japanese plant
Fukushima, are completely dependent on their Three types of decay:
radiation exposure detectors. Acute damage Alpha, Beta (-), & Beta (+)
can be caused when exposure reaches 200
millisieverts or more, but lower dosages can ALPHA DECAY
cause late effects. - Loss of an Alpha particle.
Dust particles in the air absorb nuclear - Alpha particle: 2 neutrons and 2 protons.
radiation and this causes stress to our lungs - Mass: 4
and thyroid glands. Even if it sounds odd, water - Charge: +2
that is contaminated with radiation can cause - Mass number: Decrease (-4)
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

- Atomic Number: Decreases (-2)

- New Element is formed, 2 places lower in
the periodic table.

BETA (-) DECAY

- Isotope has too many neutrons.
- A neutron changes into a proton and an
electron, the proton is retained by the atom
while the electron is lost.
- The lost electron is high energy, BETA
PARTICLE.
- Mass Number: remain the same
- Atomic Number: increases (+1)
- New Element is formed, 1 place higher in
the periodic table.

THREE TYPES OF RADIATION:

BETA (+) DECAY
- Isotope has too many protons. Ernest Rutherford explained the nature of the 3
- A proton changes into a neutron and an a types of radiation emitted by radioactive
positive beta particle: POSITRON substances that occur in nature.
- Positron: same mass as electrons, but the
opposite charge.
- Mass Number: remain the same
- Atomic Number: Decreases (-1)
- New Element is formed, 1 place lower? in
the periodic table.

HOW TO KNOW IF THE ATOM IS STABLE

OR UNSTABLE?

Determine if a radioactive isotope is likely

to decay by: ALPHA RADIATION (α rays)
- Are nuclei ejected from the radioactive
- By proton neutron nz graph.
substance at speeds around 16,000 km/s.
- If a radioisotope lies left or right of the
stability line it is unstable and likely to decay BETA RADIATION (β rays)
to become stable. - Are electrons ejected from the radioactive
substance at approximately 130,000 km/s.
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1ST SEMESTER

- In a nuclear reaction, particles within the

GAMMA RADIATION (γ rays) nucleus (protons and neutrons) are
- Is essentially a highly electric form of light. involved.
- Nuclear change release or absorb
tremendous amounts of energy.
- The rate of nuclear reaction is influenced by
the rate of release of neutrons.

IONIZING POWER OF α β & γ RAYS

Ionization is the physical process of converting
an atom or molecule into an ion by adding or
removing charged particles such as electrons
or other ions.

TYPES OF NUCLEAR REACTION

Nuclear change can happen in 2 ways:

(a) Nuclear fission- the splitting of heavy

and unstable nuclei to form smaller
fragments.
(b) Nuclear fusion- the union of lighter
nuclei to form a heavier and stable
nuclei.

BOTH changes are highly exothermic

processes.

BALANCING NUCLEAR REACTIONS

WRITING NUCLEAR EQUATIONS

Two requirements for the equation for a

nuclear reaction:

1.) The sum of the mass numbers (the left

superscript in the nuclide symbol) of the
reactants must equal the sum of the mass
CHEMICAL CHANGE VS NUCLEAR CHANGE numbers of the products.

Chemical Change: 2.) The sum of atomic numbers (the left

- No new elements can be produced.
subscript in the nuclide symbol) of the
- Usually only the outermost electrons
reactants must equal the sum of the atomic
(valence electrons) participate during
chemical reaction. numbers of the products; this maintains charge
- Chemical changes release or absorb balance.
relatively small amounts of energy.
- The rate of chemical reaction depends on
factors such as concentration, temperature,
presence of a catalyst and the nature of its
reactants.

Nuclear Change:
- Elements may be converted form one kind
to another.
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1ST SEMESTER

Types of Radioactive Decay Processes

Material Science and Engineering

Materials science and engineering (MSE) is an

interdisciplinary field of science and engineering
that studies and manipulates the composition and Characteristics of metals / Metallic bonding
structure of materials across length scales to
control materials properties through synthesis and Metals and alloys include steels, aluminum,
processing. The term composition means the magnesium, zine, cast iron, titanium, copper, and
chemical make-up of a material. The term nickel. An alloy is a metal that contains additions of
structure means a description of the arrangement one or more metals or non-metals. In general,
of atoms, as seen at different levels of detail. metals have good electrical and thermal con-
Materials scientists and engineers not only deal ductivity. Metals and alloys have relatively high
with the development of materials, but also with the strength, high stiffness, ductility or forma- bility, and
synthesis and processing of materials and shock resistance. They are particularly useful for
manufacturing processes related to the production structural or load-bearing applications. Although
of components. The term "synthesis ' refers to how pure metals are occasionally used, alloys provide
materials are made from naturally occurring or improvement in a particular desirable property or
man-made chemicals. The term "processing 2' permit better combinations of properties.
means how materials are shaped into useful
components to cause changes in the properties of
different materials. One of the most important
functions of materials scientists and engineers is to
establish the relationships between a material or a
device's properties and performance and the
microstructure of that material, its composition, and
the way the material or the device was synthesized
and processed. In materials science, the
The Metallic Bond
emphasis is on the underlying relation- ships
The metallic elements have electropositive atoms
between the synthesis and processing, structure,
that donate their valence electrons to form a "sea"
and properties of materials. In materials
"sea" of electrons surrounding the atoms (Figure 2-
engineering, the focus is on how to translate or
11). Aluminum, for example, gives up its three
transform materials into useful devices or
valence electrons, leaving behind a core consisting
structures.
of the nucleus and inner electrons. Since three
negatively charged electrons are missing from this
Materials engineers create new materials and core, it has a positive charge of three. The valence
improve existing materials. Materials engineers electrons move freely within the electron sea and
understand the relationship between the properties become associated with several atom cores. The
of a material and its internal structure--from the positively charged ion cores are held together by
macro level to the atomic level. In many cases, mutual attraction to the electrons, thus producing a
materials engineers are the people who help a strong metallic bond.
product become cheaper, easier to produce, or
more durable. They also discover new materials. Because their valence electrons are not fixed in any
one position, most pure metals are good electrical
conductors of electricity at relatively low
There are five categories of Engineering temperatures (~ < 300 K). Under the influence of an
Materials: applied voltage, the valence electrons move,
causing a current to flow if the circuit is complete.
1. metals and alloys
Metals show good ductility since the metallic bonds
2. ceramics, glasses and glass-ceramics are non-directional. There are other important
reasons related to microstructure that can explain
3. polymers (plastics) why metals actually exhibit lower strengths and
higher ductility than what we may anticipate from
4. semiconductors their bonding. Ductility refers to the ability of
materials to be stretched or bent permanently
5. composite materials without breaking. We will discuss these concepts in
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

greater detail in Chapter 6. In general. the melting filled (or emptied) outer energy levels, but both
points of metals are relatively high. From an optical have acquired an electrical charge and behave as
properties viewpoint. metals make good reflectors ions. The atom that contributes the electrons is left
of visible radiation. Owing to their electropositive with a net positive charge and is called a cation,
character, many metals such as iron tend to while the atom that accepts the electrons acquires
undergo corrosion or oxidation. Many pure metals a net negative charge and is called an anion. The
are good conductors of heat and are effectively oppositely charged ions are then attracted to one
used in many heat transfer applications. We another and produce the ionic bond. For example,
emphasize that metallic bonding is one of the the attraction between sodium and chloride ions
factors in our efforts to rationalize the trends. (Figure 2-14) produces sodium chloride (NaCI), or
table salt.

Polymers
Polymers are typically organic materials. They are
produced using a process known as
polymerization. Polymeric materials include
rubber (elastomers) and many types of adhesives.
Polymers typically are good electrical and thermal
insulators although there are exceptions such as
Ceramics the semiconducting polymers discussed earlier in
Ceramics can be defined as inorganic crystalline this chapter. Although they have lower strength,
materials. Beach sand and rocks are examples of polymers have a very good strength-to-weight
naturally occurring ceramics. Advanced ceramics ratio. They are typically not suitable for use at high
are materials made by refining naturally occurring temperatures. Many polymers have very good
ceramics and other special processes. Advanced resist- ance to corrosive chemicals. Polymers have
ceram- is are used in substrates that house thousands of applications ranging from bullet- proof
computer chips, sensors and actuators, capacitors, vests, compact disks (CDs), ropes, and liquid
wire- less communications, spark plugs, inductors, crystal displays (LCDs) to clothes and coffee cups.
and electrical insulation. Some ceramics are used Thermoplastic polymers, in which the long
as barrier coatings to protect metallic substrates in molecular chains are not rigidly con- nected, have
turbine engines. Ceramics are also used in such good ductility and formability; thermosetting
consumer products as paints, plastics, and tires, polymers are stronger but more brittle because the
and for industrial applications such as the tiles for molecular chains are tightly linked (Figure 1-4).
the space shuttle, a catalyst support, and the Polymers are used in many applications, including
oxygen sensors used in cars. Traditional ceramics electronic devices. Thermoplastics are made by
are used to make bricks, tableware, toilets, shaping their molten form. Thermosets are typically
bathroom sinks, refractories (heat-resistant cast into molds. Plastics contain additives that
material), and abrasives. In general, due to the enhance the properties of polymers.
presence of porosity (small holes), ceramics do not
conduct heat well; they must be heated to very high
temperatures before melting. Ceramics are strong
and hard, but also very brittle. We normally prepare
fine powders of ceramics and convert these into
different shapes. New processing techniques make
ceramics sufficiently resistant to fracture that they
can be used in load-bearing applications, such as
impellers in turbine engines. Ceramics have
exceptional strength under compression. Can you
believe that an entire fire truck can be supported
using four ceramic coffee cups?
The Covalent Bond
Materials with covalent bonding are characterized
by bonds that are formed by sharing of valence
electrons among two or more atoms. For example,
a silicon atom, which has a valence of four, obtains
eight electrons in its outer energy shell by sharing
its valence electrons with four surrounding silicon
atoms, as in Figure 2-12(a) and (b). Each instance
of sharing represents one covalent bond; thus,
each silicon atom is bonded to four neighboring
atoms by four covalent bonds. In order for the
The lonic Bond
covalent bonds to be formed, the silicon atoms
When more than one type of atom is present in a
must be arranged so the bonds have a fixed
material, one atom may donate its valence
directional relationship with one another. A
electrons to a different atom, filling the outer energy
directional relationship is formed when the bonds
shell of the second atom. Both atoms now have
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

between atoms in a covalently bonded material

form specific angles, depending on the material. In
the case of silicon, this arrangement produces a
tetrahedron, with angles of 109.5° between the BONDING SOLIDS
covalent bonds Figure 2-12(c)].
What is Chemical Bond?
A chemical bond is any of the interactions that
account for the association of atoms into
molecules, ions, crystals, and other stable species
that make up the familiar substances of the
everyday world.

Lewis theory of chemical bonding describes a

chemical bond as a region that forms when
Weak intermolecular forces in polymers electrons from different atoms interact with each
There are three types of van der Waals other.
interactions, namely London forces, Keesom
forces, and Debye forces. If the interactions are Covalent Bonds
between two dipoles that are induced in atoms or If one or more pairs of electrons are shared
molecules, we refer to them as London forces between atoms; is called a covalent bonds.
(e.g., carbon tetrachlo- ride) (Figure 2-15). When
an induced dipole (that is, a dipole that is induced Interatomic interactions:
in what is otherwise a non-polar atom or molecule) Electron – electron repulsion
interacts with a molecule that has a permanent Nucleus – nucleus repulsion
dipole moment, we refer to this interaction as a Electron – nucleus attraction
Debye interaction. An example of Debye
interaction would be forces between water Electronegativity
molecules and those of carbon tetrachloride. If the Electronegativity is a measure of the relative
interactions are between molecules that are tendency of an atom to attract electrons toward
permanently polarized (e.g.. water molecules itself when it is chemically combined with another
attracting other water molecules or other polar atom. Electronegativities of the elements are
molecules), we refer to these as Keesom expressed on a somewhat arbitrary scale, called
interactions. The attraction between the positively the Pauling Scale.
charged regions of one water molecule and the
negatively charged regions of a second water
molecule provides an attractive bond between the
two water molecules (Figure 2-16).
The bonding between molecules that have a
permanent dipole moment, known as the Keesom
force, is often referred to as a hydrogen bond,
where hydrogen atoms represent one of the
polarized regions. Thus, hydrogen bonding is
essentially a Keesom force and is a type of van der
Waals force. The relatively strong Keesom force
between water molecules is the reason why surface
tension (72 mJ/m? or dyne/cm at room Non-Polar Covalent Bonds
temperature) and the boiling point of water (100°C) In a non-polar covalent bond, the electron density is
are much higher than those of many organic liquids symmetrical about a plane that is perpendicular to
of comparable molecular weight (surface tension the line between the two nuclei. This is true for all
~20 to 25 dyne/cm, boiling points up to 80°C). homonuclear diatomic molecules (such as H2 , O2 ,
Note that van der Waals bonds are secondary N2 , F2 , Cl2 , Br2 , and I2 ) because the two
bonds, but the atoms within the mol- ecule or identical atoms have identical electronegativities.
group of atoms are joined by strong covalent or
ionic bonds. Heating water to the boiling point A bond in which the distribution of bonding electron
breaks the van der Waals bonds and changes density is symmetrical, or centered, is said to be
water to steam, but much higher temperatures are non-polar.
required to break the covalent bonds joining oxygen
and hydrogen atoms. The covalent bond in all homonuclear diatomic
molecules must be non-polar.

Polar Covalent Bond

When different kinds of atoms combine, as in HCl,
one nucleus usually attracts the electrons in the
bond more strongly than the other. The effect of
unequal attractions for the bonding electrons in an
unbalanced distribution of electron density with in
the bond.

A bond that carries partial positive and negative

charges on opposite ends is called a polar bond.
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

Because there are two poles of charges involved,

the bond is said to be dipole.

A bond with an unsymmetrical distribution of

bonding electron charge is a polar covalent
bond.
Ionic Bond
 Electrons are transferred from one atom to
another. Positive and negative ions are formed,
and attract each other through electrostatic
Hydrogen Bonding
forces called ionic bonds.
• Hydrogen bonding is a special type of dipole -
dipole attraction that exists between the hydrogen
Metallic Bond
atom in a polar bond (particularly an H-F, H-O, or
 In metals, the valence electron of each of the H-N bonds) and an unshared electron pair on a
metal atoms overlaps with a large number of nearby small electronegative ion or atom (usually
neighboring atoms. As a consequence, these an F, O, or N atom on another molecule).
electrons continually move from one atom to
another. Strengths of Intermolecular Forces
 In short, the valence electrons in metals, unlike
those in covalently bonded substances, are
nonlocalized, capable of wandering relatively
freely throughout the entire crystal.
 The atoms that the electrons leave behind
become positive ions, and the interaction
between such ions and valence electrons gives
rise to the cohesive or binding force that holds
the metallic crystal together.
Ionic Crystals
Intermolecular Bond • Ionic crystals have high melting points, brittle,
 The forces holding molecules together are soluble in water, good conductors of electricity
generally called intermolecular forces (van der when molten or in solution but not in the crystalline
Waals’ forces). The energy required to break state, where ions are not free to move.
molecules apart is much smaller than a typical
bond-energy, but intermolecular forces play Metallic Crystals
important roles in determining the properties of • Metallic crystals have high melting points, high
a substances. densities, malleable and ductile, and are good
conductors of electricity in solid or molten state
London dispersion force – present in all
substances, the most significant bonding in Covalent network Crystals
nonpolar molecules • Atoms occupy positions in crystals and they are
held by a network of covalent bonds. Covalent
bonds extend throughout the crystal structure; the
entire crystal can be looked upon at as one great
giant molecule.
• Network crystals have high melting points,
Dipole – dipole interaction : bonding between extremely hard, and do not conduct electricity.
polar molecules
Molecular Crystals
• Molecules occupy positions in crystals of covalent
compounds, van der Waals forces of attraction
holds the molecules together.
• Molecular crystals are soft, has low melting points,
usually below 300 °C, do not conduct electricity in
Hydrogen bonding – interaction of a polar solid or liquid state.
molecules having an NH, O-H and H-F bonds
Bonding in solids / Crystal structures

Types of solids (by bonding type)

Ion – dipole interaction – bonding between

ions and polar molecules.
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1ST SEMESTER

network solids. Nanomaterials are solids in which

the dimensions of individual crystals have been
reduced to the order of 1-100 nm. As we will see,
the properties of conventional materials change
when their crystals become this small

Bond triangles or van Arkel–Ketelaar triangles

(named after Anton Eduard van Arkel and J. A. A.
Ketelaar) are triangles used for showing different
compounds in varying degrees of ionic, metallic
and covalent bonding.

In 1941 van Arkel recognized three extreme

materials and associated bonding types. Using 36
main group elements, such as metals, metalloids
Metallic solids are held together by a delocalized and non-metals, he placed ionic, metallic and
"sea" of collectively shared valence electrons. This covalent bonds on the corners of an equilateral
form of bonding allows metals to conduct electricity. triangle, as well as suggested intermediate species.
It is also responsible for the fact that most metals The bond triangle shows that chemical bonds are
are relatively strong without being brittle. Ionic not just particular bonds of a specific type. Rather,
solids are held together by the mutual electrostatic bond types are interconnected and different
attraction between cations and anions. Differences compounds have varying degrees of different
between ionic and metallic bonding make the bonding character (for example, polar covalent
electrical and mechanical properties of ionic solids bonds).
very different from those of metals: Ionic solids do
not conduct electricity well and are brittle.
Covalent-network solids are held together by an
extended network of covalent bonds. This type of
bonding can result in materials that are extremely
hard, like diamond, and it is also responsible for the
unique properties of semiconductors. Molecular
solids are held together by the intermolecular
forces we studied in Chapter 11: dispersion forces,
dipole-dipole interactions, and hydrogen bonds.
Because these forces are relatively weak,
molecular solids tend to be soft and have low
melting points.

We will also consider two classes of solids that do

not fall neatly into the preceding categories:
polymers and nanomaterials. Polymers contain
long chains of atoms (usually carbon), where the
atoms within a given chain are connected by
covalent bonds and adjacent chains are held to one
another largely by weaker intermolecular forces.
Polymers are normally stronger and have higher
melting points than molecu- lar solids, and they are
more flexible than metallic, ionic, or covalent-
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

Solids in which atoms are arranged in an orderly

repeating pattern are called crys- talline solids.
These solids usually have flat surfaces, or faces,
that make definite angles with one another. The
orderly arrangements of atoms that produce these
faces also cause the solids to have highly regular
shapes (> Figure 12.2). Examples of crystalline two dimensions the unit cells must tile, or fit
solids include sodium chloride, quartz, and together in space, in such a way that they
diamond. completely cover the area of the lattice with no
gaps. In three dimensions the unit cells must stack
Amorphous solids (from the Greek words for together to fill all space.
"without form") lack the order found in crystalline
solids. At the atomic level the structures of In a two-dimensional lattice, the unit cells can take
amorphous solids are similar to the structures of only one of the five shapes shown in Figure 12.4.
liquids, but the molecules, atoms, and/or ions lack The most general type of lattice is the oblique
the free- dom of motion they have in liquids. lattice. In this lat tice, the lattice vectors are of
Amorphous solids do not have the well-defined different lengths and the angle y between them is of
faces and shapes of a crystal. Familiar amorphous arbi- trary size, which makes the unit cell an
solids are rubber, glass, and obsidian (volcanic arbitrarily shaped parallelogram. A square lattice
glass). results when the lattice vectors are equal in length
and the angle between them is 90°. A rectangular
Examples of crystalline and amorphous solids. The lattice is formed when the angle between the lattice
atoms in crystalline solids repeat in an orderly, vectors is 90° but the vectors have different
periodic fashion that leads to well-defined faces at lengths. The fourth type of two-dimensional lattice,
the macroscopic level. This order is lacking in where a and b are of the same length and y is 120°,
amorphous solids like obsidian (volcanic glass). is a hexagonal lattice." If a and b are of the same
length but the angle between them is any value
The geometrical pattern of points on which the unit other than 90° or 120° a rhombic lattice results. For
cells are arranged is called a crystal lattice. The a rhombic lattice an alternative unit cell can be
crystal lattice is, in effect, an abstract (that is, not drawn, a rectangle with lat- tice points on its
real) scaffolding for the crystal structure. We can corners and its center (shown in green in Figure
imagine forming the entire crystal structure by first 12.4). Because of this the rhombic lattice is
building the scaffolding and then filling in each unit commonly referred to as a centered rectangular
cell with the same atom or group of atoms. lattice. The lat- tices in Figure 12.4 represent five
basic shapes: squares, rectangles, hexagons,
Before describing the structures of solids, we need rhombuses (diamonds), and arbitrary
to understand the properties of crystal lattices. It is parallelograms. Other polygons, such as
useful to begin with two-dimensional lattices pentagons, cannot cover space without leaving
because they are sim- pler to visualize than three- gaps, as Figure 12.5 shows.unit cell can be drawn,
dimensional ones. > Figure 12.3 shows a two- a rectangle with lat- tice points on its corners and
dimensional array of lattice points. Each lattice its center (shown in green in Figure 12.4). Because
point has an identical environment. The positions of of this the rhombic lattice is commonly referred to
the lattice points are defined by the lattice vectors a as a centered rectangular lattice. The lat- tices in
and b. Beginning from any lattice point it is possible Figure 12.4 represent five basic shapes: squares,
to move to any other lattice point by adding rectangles, hexagons, rhombuses (diamonds), and
together whole-number multiples of the two lattice arbitrary parallelograms. Other polygons, such as
vectors. * pentagons, cannot cover space without leaving
gaps, as Figure 12.5 shows.
The parallelogram formed by the lattice vectors, the
shaded region in Figure 12.3, defines the unit cell. A crystalline lattice in two dimensions. An
In two dimensions the unit cells must tile, or fit infinite array of lattice points is generated by adding
together in space, in such a way that they together the lattice vectors a and b. The unit cell is
completely cover the area of the lattice with no a parallelogram defined by the lattice vectors.
gaps. In three dimensions the unit cells must stack
together to fill all space. If we place a lattice point at each corner of a unit
cell, we get a primitive lattice. All seven lattices in
The parallelogram formed by the lattice vectors, the Figure 12.6 are primitive lattices. It is also possible
shaded region in Figure 12.3, defines the unit cell. to generate
In
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

what are called centered lattices by placing

additional lattice points in specific loca- tions in the
unit cell. This is illustrated for a cubic lattice in >
Figure 12.7. A body- centered cubic lattice has one
lattice point at the center of the unit cell in addition
to the lattice points at the eight corners. A face-
centered cubic lattice has one lattice point at the
center of each of the six faces of the unit cell in
addition to the lattice points at the eight corners.
Centered lattices exist for other types of unit cells
as well. For the crystals discussed in this chapter
we need consider only the lattices shown in Figures
12.6 and 12.7.

The crystal structures of many metals are simple

enough that we can generate the
structure by placing a single atom on each lattice
point. The structures corresponding
to the three cubic lattices are shown in V Figure
12.11. Metals with a primitive cubic
structure are rare, one of the few examples being the
radioactive element polonium.
Body-centered cubic metals include iron,
chromium, sodium, and tungsten. Examples
of face-centered cubic metals include aluminum,
lead, copper, silver, and gold.

The crystal structures of many metals are simple

enough that we can generate the structure by
placing a single atom on each lattice point. The
structures corresponding to the three cubic lattices
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

are shown in V Figure 12.11. Metals with a

primitive cubic structure are rare, one of the few
examples being the radioactive element polonium.
Body-centered cubic metals include iron,
chromium, sodium, and tungsten. Examples of face-
centered cubic metals include aluminum, lead,
copper, silver, and gold.

The structures of (a) primitive cubic, (b) body-

centered cubic, and (c) face- centered cubic metals.
Each structure can be generated by the combination X-ray crystallography is used extensively to
of a single-atom motif and the appropriate lattice. determine the structures of molecules in crystals.
(d) Corner atoms (one shown in red) are shared The instruments used to measure X-ray diffrac-
among eight neighboring cubic unit cells. tion, known as X-ray diffractometers, are now
computer controlled, mak- ing the collection of
diffraction data highly automated. The diffraction
pattern of a crystal can be determined very
accurately and quickly (some- times in a matter of
hours), even though thousands of diffraction spots
are measured. Computer programs are then used
to analyze the diffrac- ton data and determine the
arrangement and structure of the molecules in the
crystal. X-ray diffraction is an important technique
in industries ranging from steel and cement
manufacture to pharmaceuticals.

Alloys
An alloy is a material that contains more than one
element and has the characteristic properties of a
metal. The alloying of metals is of great importance
because it is one of the primary ways of modifying
the properties of pure metallic elements. Nearly all
the com- mon uses of iron, for example, involve
alloy compositions (for example, stainless steel).
Bronze is formed by alloying copper and tin, while
brass is an alloy of copper and zinc. Pure gold is
too soft to be used in jewelry, but alloys of gold are
much harder (see' "Chemistry Put to Work: Alloys
of Gold"). Other common alloys are described in
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

Alloys can be divided into four categories:

substitutional alloys, interstitial alloys,
heterogeneous alloys, and intermetallic
compounds. Substitutional and interstitial alloys are
both homogeneous mixtures in which components
are dispersed randomly and uniformly (A Figure
12.15). coo (Section 1.2) Solids that form
homogeneous mix tures are called solid solutions. known as cementite. In general, the properties of
When atoms of the solute in a solid solution occupy heterogeneous alloys depend on both the
positions normally occupied by a solvent atom, we composition and the manner in which the solid is
have a substitutional alloy. When the solute atoms formed from the molten mix- ture. The properties of
occupy interstitial positions in the "holes" between a heterogeneous alloy formed by rapid cooling of a
solvent atoms, we have an interstitial alloy (Figure molten mix- ture, for example, are distinctly
12.15). different from the properties of an alloy formed by
slow cooling of the same mixture.
Substitutional alloys are formed when the two
metallic components have similar atomic radii and Intermetallic compounds are compounds rather
chemical-bonding characteristics. For example, than mixtures. Because they are compounds, they
silver and gold form such an alloy over the entire have definite properties and their composition
range of possible compositions. When two metals cannot be varied. Further- more, the different types
differ in radii by more than about 15%, solubility is of atoms in an intermetallic compound are ordered
generally more limited. rather than randomly distributed. The ordering of
For an interstitial alloy to form, the solute atoms atoms in an intermetallic compound generally leads
must have a much smaller bonding atomic radius to better structural stability and higher melting
than the solvent atoms. Typically, the interstitial points than what is observed in the constitu- ent
element is a nonmetal that makes covalent bonds metals. These features can be attractive for high-
to the neighboring metal atoms. The presence of temperature applications. On the nega tive side,
the extra bonds provided by the interstitial intermetallic compounds are often more brittle than
component causes the metal lat- tice to become substitutional alloys.
harder, stronger, and less ductile. For example,
steel, which is much harder and stronger than pure Intermetallic compounds play many important roles
iron, is an alloy of iron that contains up to 3% car- in modern society. The inter- metallic compound
bon. Other elements may be added to form alloy NizAl is a major component of jet aircraft engines
steels. Vanadium and chromium may be added to because of its strength at high temperature and its
impart strength, for instance, and to increase low density. Razor blades are often coated with
resistance to fatigue and corrosion. CrPt, which adds hardness, allowing the blade to
stay sharp longer. Both compounds have the
One of the most important iron alloys is stainless structure shown on the left-hand side of y Figure
steel, which contains about 0.4% carbon, 18% 12.17. The compound Nb3Sn, also shown in Figure
chromium, and 1% nickel. The chromium is 12.17, is a superconductor, a substance that, when
obtained by carbon reduction of chromite (FeCrO,) cooled below a critical temperature, conducts
in an electric furnace. The product of the reduction electricity with no resistance. In the case of Nb;Sn
is ferrochrome (FeCr2), which is added in the superconductivity is observed only when the
appropriate amount to molten iron to achieve the temperature falls below 18 K. Supercon- ductors
desired steel composition. The ratio of elements are used in the magnets in MRI scanners widely
present in the steel may vary over a wide range, employed for medical imaging. coo (Section 6.7,
imparting a variety of specific physical and "Nuclear Spin and Magnetic Resonance Imaging")
chemical properties to the materials. The need to keep the magnets cooled to such a low
temperature is part of the reason why MRI devices
In a heterogeneous alloy the components are not are expensive to operate. The hexagonal
dispersed uniformly. For exam- ple, the intermetallic compound SmCo, shown on the right-
heterogeneous alloy pearlite contains two phases hand side of Figure 12.17, is used to make the
(> Figure 12.16). One phase is essentially pure permanent magnets found in lightweight headsets
body-centered cubic iron, and the other is the and high-fidelity speakers. A related compound with
compound FezC the same structure, LaNis, is used as the anode in
nickel-metal hydride batteries.
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

Alloys of Gold surrounded by six ions of the opposite type, lead-

Gold has long been a metal of choice for decorative ing to an octahedral coordination environment. In
objects, jew- elry, and coins. The popularity of gold zinc blende, each cation and
is driven by its unusual color (for a metal), its
resistance to many chemical reactions, and the fact
that it can easily be worked. However, pure gold is
too soft for many applications, including jewelry. To
increase its strength and hardness, as well as to
modify its color, gold is of- ten alloyed with other
metals. In the jewelry trade pure gold is termed 24
karat. The karat number decreases as the mass
percent of gold decreases. The most common
alloys used in jewelry are 14 karat, which is (14/24)
X 100 = 58% gold, and 18 karat, which is (18/24) X
100 = 75% gold. The color of gold varies depending
on the metals it is alloyed with. Gold is typically
alloyed with silver and/or copper. All three elements
crystallize with a face-centered cubic structure. The
fact that all three elements have similar radii (Au Semiconductors
and Ag are nearly the same size; Cu is roughly
11% smaller) and crystallize with the same type of Properties of semiconductors
structure make it possible to form substitutional
alloys with nearly any composition. The variations Metals conduct electricity extremely well. Many
in color of these alloys as a function of composition solids, how- ever, conduct electricity somewhat, but
are shown in > Figure 12.18. Gold alloyed with nowhere near as well as metals, which is why such
equal parts silver and copper takes on the golden materials are called semiconduc- tors. Two
yellow color we asso- ciate with gold jewelry. Red examples of semiconductors are silicon and germa
or rose gold is a copper- rich alloy. Silver-rich alloys nium, which lie immediately below carbon in the
take on a greenish hue, eventually giving way to periodic table. Like carbon, each of these elements
silvery-white colors as silver becomes the majority has four valence electrons, just the right number to
constituent. satisfy the octet rule by forming single covalent
bonds with four neighbors. Hence, sil- icon and
germanium, as well as the gray form of tin,
crystallize with the same infinite network of covalent
bonds as diamond.
When atomic s and p orbitals overlap, they form
bond- ing molecular orbitals and antibonding
molecular orbitals. Each pair of s orbitals overlaps
to give one bonding and one antibonding molecular
orbital, whereas the p orbitals overlap to give three
bonding and three antibonding molecular orbit- als.
oco (Section 9.8) The extended network of bonds
leads to the formation of the same type of bands
we saw for metals in Section 12.4. However, unlike
metals, in semiconductors an energy gap develops
between the filled and empty states, much like the
energy gap between bonding and antibonding
orbitals. coo (Section 9.6) The band that forms from
bonding molecular orbitals is called the valence
band, and the band that forms the antibonding
Three common ionic structure types are shown in V orbitals is called the conduction band (4 Figure
Figure 12.25. The cesium chloride (CsCl) structure 12.30). In a semiconductor, the valence band is
is based on a primitive cubic lattice. Anions sit on filled with electrons and the conduction band is
the lattice points at the corners of the unit cell, and empty. These two bands are separated by the
a cation sits at the center of each cell. (Remember, energy band gap Eg. In the semiconductor
there is no lattice point inside a primitive unit cell.) community, energies are given in electron
With this arrangement, both cations and anions are
surrounded by a cube of eight ions of the opposite volts (eV); 1 eV = 1.602 X 10 J. Band gaps greater
type. than ~ 3.5 eV are so large that the material is not a
The sodium chloride (NaCl; also called the rock salt semiconductor; it is an insulator and does not
structure) and zinc blende (ZnS) structures are conduct electricity at all. Semiconductors can be
based on a face-centered cubic lattice. In both divided into two classes, elemental
structures the anions sit on the lattice points that lie semiconductors, which contain only one type of
on the corners and faces of the unit cell, but the atom, and compound semiconductors, which
two-atom motif is slightly different for the two contain two or more elements. The elemental
structures. In NaCl the Nat ions are displaced from semiconductors all come from group 4A. As we
the Cl ions along the edge of the unit cell, whereas move down the periodic table, bond distances
in ZnS the Zn?+ ions are displaced from the S?- increase, which decreases orbital overlap. This
ions along the body diagonal of the unit cell. This decrease in overlap reduces the energy difference
difference leads to different coordination numbers. between the top of the valence band and the
In sodium chloride, each cation and each anion are bottom of the conduction band. As a result, the
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

band gap decreases on going from diamond (5.5 It is also possible to dope semiconductors with
eV, an insulator) to silicon (1.11 V) to germanium atoms that have fewer valence electrons than the
(0.67 eV) to gray tin (0.08 eV). In the heaviest host material. Consider what happens when a few
group 4A element, lead, the band gap collapses aluminum atoms replace silicon atoms in a silicon
altogether. As a result, lead has the structure and crystal. Aluminum has only three valence electrons
properties of a metal. compared to silicon's four. Thus, there are electron
vacancies, known as holes, in the valence band
when silicon is doped with aluminum (Figure 12.31
(c)]. Since the neg- atively charged electron is not
there, the hole can be thought of as having a
positive charge. Any adjacent electron that jumps
into the hole leaves behind a new hole. Thus, the
positive hole moves about in the lattice like a
particle.* A material like this is called a p-type
semiconductor, p signifying that the number of
positive holes in the material has increased.

As with n-type conductivity, p-type dopant levels of

only parts per million can lead to a millionfold
increase in conductivity-but in this case, the holes
in the valence band are doing the conduction
[Figure 12.31(c)].

The junction of an n-type semiconductor with a p-

type semiconductor forms the basis for diodes,
transistors, solar cells, and other devices.

Semiconductor doping
The electrical conductivity of a semiconductor is
influenced by the presence of small numbers of
impurity atoms. The process of adding controlled
amounts of impurity at- oms to a material is known
as doping. Consider what happens when a few
phosphorus atoms (known as dopants) replace Polymers / recycling plastics
silicon atoms in a silicon crystal. In pure Si all of the
valence-band molecular orbitals are filled and all of Polymers
the conduction-band molecular orbitals are empty, In nature we find many substances of very high
as A Figure 12.31(a) shows. Because phosphorus molecular weight, running up to mil lions of amu,
has five valence electrons but silicon has only four, that make up much of the structure of living
the "extra" electrons that come with the dopant organisms and tissues. Some examples are starch
phos- phorus atoms are forced to occupy the and cellulose, which abound in plants, as well as
conduction band [Figure 12.31 (b)]. The doped proteins, which are found in both plants and
material is called an n-type semiconductor, n animals. In 1827 Jons Jakob Berzelius coined the
signifying that the number of negatively charged word polymer (from the Greek polys, "many," and
electrons in the conduction band has increased. meros, "parts") to denote molecular sub- stances of
These extra electrons can move very easily in the high molecular weight formed by the polymerization
conduction band. Thus, just a few parts per million (joining together) of monomers, molecules with low
(ppm) of phospho- rus in silicon can increase molecular weight.
silicon's intrinsic conductivity by a factor of a million!
Historically natural polymers, such as wool, leather,
The dramatic change in conductivity in response to silk, and natural rubber, were processed into usable
the addition of a trace amount of a dopant means materials. During the past 70 years or so, chemists
that extreme care must be taken to control the impu have learned to form synthetic polymers by
rities in semiconductors. The semiconductor polymerizing monomers through controlled
industry uses "nine-nines" silicon to make chemical reactions. A great many of these synthetic
integrated circuits; what this means is that Si must polymers have a backbone of carbon-carbon bonds
be 99.999999999% pure (nine nines after the because carbon atoms have an exceptional ability
decimal place) to be technologically useful! Doping to form strong stable bonds with one another.
provides an opportunity for controlling the electrical
conductivity through precise control of the type and Plastics are polymeric solids that can be formed
concentration of dopants. into various shapes, usually by the application of
heat and pressure. There are several types of
plastics. Thermoplastics can be reshaped. For
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

example, plastic milk containers are made from the

thermoplas- tic polymer polyethylene. These Polyethylene is an important material; its annual
containers can be melted down and the polymer production exceeds 170 bil- lion pounds each year.
recy- cled for some other use. In contrast, a Although its composition is simple, the polymer is
thermosetting plastic (also called a thermoset) is not easy to make. The right manufacturing
shaped through irreversible chemical processes conditions were identified only after many years of
and, therefore, cannot be reshaped readily. Another research. Today many forms of polyethylene,
type of plastic is the elastomer, which is a material varying widely in physical properties, are known.
that exhibits rubbery or elastic behavior. When
subjected to stretching or bending, an elastomer A second general reaction used to synthesize
regains its original shape upon removal of the commercially important polymers is condensation
distorting force, if it has not been dis- torted beyond polymerization. In a condensation reaction two
some elastic limit. Rubber is the most familiar molecules are joined to form a larger molecule by
example of an elastomer. elimination of a small molecule, such as H2O. For
example, an amine (a compound containing - NH,)
Some polymers, such as nylon and polyesters, both reacts with a carboxylic acidA second general
of which are thermosetting plastics, can be formed reaction used to synthesize commercially important
into fibers that, like hair, are very long relative to polymers is condensation polymerization. In a
their cross- sectional area. These fibers can be condensation reaction two molecules are joined to
woven into fabrics and cords and fashioned into form a larger molecule by elimination of a small
clothing, tire cord, and other useful objects. molecule, such as H2O. For example, an amine (a
compound containing - NH,) reacts with a
carboxylic acid

end, is reacted with a diacid, a compound with the -

COOH group at each end. For example, the
copolymer nylon 6,6 is formed when a diamine that
has six carbon atoms and an amino group on each
end is reacted with adipic acid, which also has six
carbon atoms (V Figure 12.37). A condensation
reaction occurs on each end of the diamine and the
acid. Water is released, and N -C bonds are formed
between molecules.
Polymerization reactions
A good example of a polymerization reaction is the Table 12.5 lists nylon 6,6 and some other common
formation of polyethylene from ethylene molecules
polymers obtained by conden- sation
(V Figure 12.34). In this reaction, the double bond
in each ethylene molecule "opens up," and two of polymerization. Notice that these polymers have
the electrons originally in this bond are used to form backbones containing N or O atoms as well as C
new C -C single bonds with two other ethylene atoms.
molecules. This type of polymerization, in which
monomers are coupled through their multiple
bonds, is called addition polymerization.

We can write the equation for the polymerization Recycling Plastics

reaction as follows: If you look at the bottom of a plastic container, you
are likely to see a recycle symbol containing a
number, as shown in V Figure 12.36. The number
and the letter abbreviation below it indicate the kind
of polymer from which the container is made, as
summarized in V Table 12.6. (The chemical
structures of these polymers are shown in Table
12.5.) These symbols make it possible to sort
containers by composition. In general, the lower the
Here n represents the large number-ranging from number, the greater the ease with which the material
hundreds to many thousands of monomer
can be recycled.
molecules (ethylene in this case) that react to form
one polymer mol ecule. Within the polymer, a
repeat unit (the unit shown in brackets in the
previous equation) appears over and over along the
entire chain. The ends of the chain are capped by
carbon-hydrogen bonds or by some other bond, so
that the end carbons have four bonds.
CHEMISTRY LECTURE 1035 NOTES (5-2-937) - Mindo, Roland Anthony
1ST SEMESTER

all the colors of the rainbow can be obtained from

just one material, as shown for CdSe in > Figure
12.44.

Recycling symbols. Most plastic containers

manufactured today carry a recycling symbol
indicating the type of polymer used to make the
container and the polymer's suitability for recycling.

Nanomaterials
The prefix nano means 10?. coo (Section 1.4)
When people speak of "nanotechnology" they
usually mean making devices that are on the 1-
100-nm scale. It turns out that the properties of
semiconductors and metals change in this size
range. Nanomaterials- materials that have
dimensions on the 1-100-nm scale- -are under
intense investigation in research laboratories
around the world, and chemistry plays a central role
in this investigation.

One of the most spectacular effects of reducing the

size of a semiconductor crys. tal is that the band
gap changes substantially with size in the 1-10-nm
range. As the particle gets smaller, the band gap
gets larger, an effect observable by the naked eye,
as shown in V Figure 12.43. On the macro level,
the semiconductor cadmium phosphide looks black
because its band gap is small (Eg = 0.5 eV), and it
absorbs all wavelengths of visible light. As the
crystals are made smaller, the material
progressively changes color until it looks white! It
looks white because now no visible light is
absorbed. The band gap is so large that only high-
energy ultraviolet light can excite electrons into the
conduction band (Eg > 3.0 eV).

As we learned in Section 12.7, some

semiconductor devices can emit light when a
voltage is applied. Another way to make semicon-
ductors emit light is to illuminate them with light
whose photons have energies larger than the
energy of the band gap of the semiconductor, a
process called photoluminescence. A valence-band
electron absorbs a photon and is promoted to the
conduction band. If the excited electron then falls
back down into the hole it left in the valence band, it
emits a photon having energy equal to the band
gap energy. In the case of quan- tum dots, the
band gap is tunable with the crystal size, and thus