1

BASIC CONCEPTS OF CRYSTALLINE STRUCTURE

Introduction

Crystal structure is a description of the ordered arrangement

of atoms, ions or molecules in a crystalline material. Ordered structures
occur from the intrinsic nature of the constituent particles to form symmetric
patterns that repeat along the principal directions of three-dimensional
space in matter.

Ice is a crystalline solid, which possesses rigid and long-range order;

its atoms, molecules, or ions occupy specific positions. The arrangement of
such particles in a crystalline solid is such that the net attractive
intermolecular forces are at their maximum. The forces responsible for the
stability of a crystal can be ionic forces, covalent bonds, van der Waals
forces, hydrogen bonds, or a combination of these forces. Amorphous
solids such as glass lack a well-defined arrangement and long-range
molecular order.

The smallest group of particles in the material that constitutes the

repeating pattern is the unit cell of the structure. The unit cell completely
defines the symmetry and structure of the entire crystal lattice, which is built
up by repetitive translation of the unit cell along its principal axes. Each
sphere represents an atom, ion, or molecule and is called lattice point. In
many crystals, the lattice point does not actually contain such particle.
Rather, there may be several atoms, ions, or molecules identically arranged
about each lattice point.

The lengths of the principal axes, or edges, of the unit cell and the
angles between them are the lattice constants, also called lattice

parameters. The symmetry properties of the crystal are described by the

concept of space groups. All possible symmetric arrangements of particles

in three-dimensional space may be described by the 230 space groups.

The crystal structure and symmetry play a critical role in determining

many physical properties, such as cleavage, electronic band structure,

and optical transparency.

 2

Content

 Unit Cell

A crystal is an array of atoms packed together in a regular pattern. A unit

cell of a pattern is a piece of the pattern which, when repeated through
space without rotation and without gaps or overlaps, reconstructs the
pattern to infinity. For filling space without holes, a unit cell must be either a
parallelogram (in 2D) or a parallelepiped (in 3D).

The symmetries of a pattern determine the shape of the unit cell. For
example, mirror symmetry requires a rectangular (in 2D) or tetragonal (in
3D) unit cell. There is an infinite number of possible unit cells for any pattern.
By custom, the unit cell is chosen to be the smallest one that reveals the
special geometry characteristic of the symmetry. Thus, although an oblique
parallelogram can be used for a pattern with 4-fold symmetry in 2D, a
square is preferred.

When a unit cell is repeatedly translated to fill all of 2D or 3D space, the

vertices of all the unit cells in the filled space constitute a lattice. A lattice is
an infinite array of regularly-spaced points. All points in the lattice have
identical "environments" - the view from every point in the lattice is identical
to that from any other point in the lattice. The absolute positions of the
points of a lattice, and hence the unit cell, are arbitrary with respect to a
pattern.

Not all lattice points need coincide with unit cell vertices. Primitive unit
cells use every lattice point as a unit cell vertex. Non-primitive unit cells,
however, contain extra lattice points not at the corners.

A primitive unit cell contains exactly one lattice point. In 2D, a non-
primitive unit cell has one additional lattice point exactly centered within it
and is called a body-centered non-primitive unit cell.

In 3D, non-primitive cells are of three kinds:

1. end-centered : an extra lattice point is centered in each of two

opposing faces of the cell

2. face-centered : an extra lattice point is centered in every face of the

cell
 3

3. body-centered : an extra lattice point is centered in the exact middle

of the cell

 Lattice and Unit Cell Parameters

A lattice may be specified by two non-coincident vectors in 2D, and by

three non-coplanar vectors in 3D. The vectors lie along the edges of the
unit cell, and are labelled as a, b, and (in 3D) c. The magnitude of the
vectors is given by the dimensions of the unit cell in the real crystal under
study.

The faces of the unit cell are labeled as follows:

1. A : edges defined by lattice vectors b and c

2. B : edges defined by lattice vectors a and c
3. C : edges defined by lattice vectors a and b

Similarly, the inter-facial angles of the unit cell are defined to be:

1. alpha : angle between edges b and c

2. beta : angle between edges a and c
3. gamma : angle between edges a and b

 Lattice Systems: the 14 Bravais Lattices

Lattices can be classified into "systems", each system being

characterized by the shape of its associated unit cell. 3D, the lattices are
categorized into seven crystal lattice "systems". Within several of these,
lattices supporting non-primitive unit cells can be defined. The classification
scheme yields a total of 14 possible lattices (called Bravais lattices).

The lattice symbols used for classification are as follows:

 P : primitive
 B : end-centered on B-face (convention for Monoclinic systems)
 C : end-centered on C-face (convention for Orthorhombic systems)
 I : body-centered
 F : face-centered
 R : rhombohedral primitive
 4

 Simple Crystal Structures

There are several types of crystal structures. The simplest one is the simple
cubic lattice (sc). Two other cubic lattices are the body-centered (bcc)
and the face-centered (fcc) cubic lattice.

Figure 1 Body-centered cubic (bcc)

Figure 2 Face-centered cubic (fcc) lattice
lattice

 Reciprocal Lattice

The electron density at each atom depends on the number of electrons

per atom, binding type and the lattice structure. The lattice structure is
periodical in 3D and therefore is the electron density periodical in 3D. A
periodic function can be expanded into a Fourier series. We are often
familiar with the concept of Fourier series in one dimension (from signal
theory), while Fourier series in 3D feels more abstract. However, the
extension of the Fourier analysis to periodical functions in 3D is
straightforward and it turns out that we can write the Fourier series in the
same way as:

To proceed futher with the Fourier analysis of the electron

concentration we must find the vectors G of the Fourier sum. G can be
constructed from the axis vectors b1, b2, b3 of the reciprocal lattice:
 5

The vectors a1, a2, a3 are primitive translation vectors or primitive basis for
the real space lattice, while b1, b2, b3 are primitive translation vectors or
primitive basis for the reciprocal lattice. G is called a reciprocal lattice
vector. All reciprocal lattice vectors can be expressed as a linear
combination ofb1, b2, b3 using integer coefficients. Examples of reciprocal
lattice vectors:

G=b1+b2+b3 G=b1-2*b2+2*b3 G=-3*b1-10*b2-2*b3

Figure 1. Real space lattice Figure 2. Reciprocal lattice

 Atomic coordination

By considering the arrangement of atoms relative to each other, their

coordination numbers (or number of nearest neighbours), interatomic
distances, types of bonding, etc., it is possible to form a general view of the
structures and alternative ways of visualizing them.

 Close packing

The hcp lattice (left) and the fcc lattice (right)

 6

The principles involved can be understood by considering the most

efficient way of packing together equal-sized spheres and stacking close-
packed atomic planes in three dimensions. For example, if plane A lies
beneath plane B, there are two possible ways of placing an additional
atom on top of layer B. If an additional layer was placed directly over plane
A, this would give rise to the following series:

...ABABABAB...

This arrangement of atoms in a crystal structure is known as hexagonal close

packing (hcp).

If, however, all three planes are staggered relative to each other and
it is not until the fourth layer is positioned directly over plane A that the
sequence is repeated, then the following sequence arises:

...ABCABCABC...
This type of structural arrangement is known as cubic close packing (ccp).

The unit cell of a ccp arrangement of atoms is the face-centered cubic

(fcc) unit cell. This is not immediately obvious as the closely packed layers
are parallel to the {111} planes of the fcc unit cell. There are four different
orientations of the close-packed layers.

The packing efficiency can be worked out by calculating the total

volume of the spheres and dividing by the volume of the cell as follows:

The 74% packing efficiency is the maximum density possible in unit

cells constructed of spheres of only one size. Most crystalline forms of
metallic elements are hcp, fcc, or bcc (body-centered cubic).
The coordination number of atoms in hcp and fcc structures is 12 and
its atomic packing factor (APF) is the number mentioned above, 0.74. This
can be compared to the APF of a bcc structure, which is 0.68.

 Crystals Grouped by Lattices (Shape)

There are seven crystal lattice systems.

1. Cubic or Isometric: These are not always cube-shaped. You'll also find
octahedrons (eight faces) and dodecahedrons (10 faces)
 7

2. Tetragonal: Similar to cubic crystals, but longer along one axis than the
other, these crystals forming double pyramids and prisms.
3. Orthorhombic: Like tetragonal crystals except not square in cross-
section (when viewing the crystal on end), these crystals form rhombic
prisms or dipyramids (two pyramids stuck together).
4. Hexagonal: When you look at the crystal on end, the cross-section is a
six-sided prism or hexagon.
5. Trigonal: These crystals possess a single 3-fold axis of rotation instead of
the 6-fold axis of the hexagonal division.
6. Triclinic: These crystals are not usually symmetrical from one side to the
other, which can lead to some fairly strange shapes.
7. Monoclinic: Like skewed tetragonal crystals, these crystals often form
prisms and double pyramids.

This is a very simplified view of crystal structures. In addition, the lattices

can be primitive (only one lattice point per unit cell) or non-primitive (more
than one lattice point per unit cell).

Combining the 7 crystal systems with the 2 lattice types yields the 14 Bravais
Lattices.

 Types of Crystals Grouped by Properties

There are four main categories of crystals, as grouped by their chemical

and physical properties.

1. Covalent Crystals: A covalent crystal has true covalent bonds between

all of the atoms in the crystal. You can think of a covalent crystal as one
big molecule. Many covalent crystals have extremely high melting
points. Examples of covalent crystals include diamond and zinc sulfide
crystals.
2. Metallic Crystals: Individual metal atoms of metallic crystals sit on lattice
sites. This leaves the outer electrons of these atoms free to float around
the lattice. Metallic crystals tend to be very dense and have high
melting points.
 8

3. Ionic Crystals: The atoms of ionic crystals are held together

by electrostatic forces (ionic bonds). Ionic crystals are hard and have
relatively high melting points. Table salt (NaCl) is an example of this type
of crystal.
4. Molecular Crystals: These crystals contain recognizable molecules
within their structures. A molecular crystal is held together by non-
covalent interactions, like van der Waals forces or hydrogen bonding.
Molecular crystals tend to be soft with relatively low melting points. Rock
candy, the crystalline form of table sugar or sucrose, is an example of a
molecular crystal.

As with the lattice classification system, this system isn't completely cut-
and-dried. Sometimes it's hard to categorize crystals as belonging to one
class as opposed to another. However, these broad groupings will provide
you with some understanding of structures.

Application

Crystal structure predictions have been used to study organic

molecules such as polymorphism of pharmaceutical molecules, where
changes in crystal form can lead to changes in important physical and
chemical properties, which must be strictly controlled in a pharmaceutical
product, or inorganic materials where the discovery and computational
design of new materials with targeted properties, such as porosity,
electronic or mechanical properties are necessary. However, the
communities addressing methods and applications in organic and
inorganic crystal structure prediction have largely remained separate, due
to the different approaches that have been used in these two areas. The
community as a whole will benefit from cross-fertilisation of ideas and
methods that would result from this Faraday Discussion meeting, as well as
bringing these theoreticians together with interested experimentalists.

The Discussion will appeal to researchers from computational

chemistry, informatics, physics (applying solid state electronic structure
methods) and materials science in the development of methods.
Applications of the methods also cover several fields, including
 9

crystallography, crystal engineering, mineralogy and pharmaceutical

materials.

METALS

Introduction

Metals is any chemical element that is an effective conductor of

electricity and heat can be defined as a metal. A metal is also good at
forming bonds and cations with non-metals. Atoms inside of a metal quickly
lose electrons in order to make positive ions or cations. The ions in turn are
surrounded by the electrons that are delocalized, which give the metal its
electric conductivity.

Metals are sometimes described as a lattice of positive ions

surrounded by a cloud of delocalized electrons. The metals are one of the
three groups of elements as distinguished by their ionization and bonding
properties, along with the metalloids and non-metals.

On the periodic table, a diagonal line drawn from boron (B) to

polonium (Po) separates the metals from the non-metals. Most elements on
this line are metalloids, sometimes called semi-metals; elements to the lower
left are metals; elements to the upper right are nonmetals.

A modern definition of metals is that they have overlapping

conduction bands and valence bands in their electronic structure. This
definition opens up the category for metallic polymers and other organic
metals, which have been made by researchers and employed in high-tech
devices. These synthetic materials often have the characteristic silvery-grey
reflectiveness of elemental metals. The traditional definition focuses on the
bulk properties of metals. They tend to be lustrous, ductile, malleable, and
good conductors of electricity, while nonmetals are generally brittle (for
solid nonmetals), lack lustre, and are insulators.
 10

Content

Metals are one of the most important types of the materials. They
have relatively high values of elastic constants and can be made strong by
alloying and proper heat treatment. What is particularly important they
combine stiffness and high strength with considerable ductility. As a result,
most metals yield before they fracture and this makes them the most widely
used engineering material.

Lattice of metal crystals can be used to explain the structure

insensitive properties which are listed in Table II. The values of structure
insensitive properties are primarily controlled by the strength of inter-atomic
bonds, which in turn are influenced by the arrangements of atoms in crystal
lattices.

 Quantitative characterization of structure

Images of the elements of microstructure of metals can be obtained with

required precision by modern imaging techniques such as transmission
 11

electron microscopy (TEM), scanning electron microscopy (SEM),

secondary-ion mass spectroscopy (SIMS), X-ray photoelectron
spectroscopy (XPS). Modern computer aided methods can be further used
to obtain a quantitative description of the microstructure of a studied
material. These methods take advantage of the progress made in recent
years in the field of image processing, mathematical morphology, and
quantitative stereology.

Characterization of the microstructure of materials involves identification

of the main microstructural elements present and a quantitative description
of their sizes, shapes, numbers and positions within the specimen of the
studied material.

In other words this is a process that answers the following questions:

1. What are the elements in the internal structure of a given material that
distinguish it from other materials of that kind (of say similar chemical
composition?

2. Where are these elements located and in what quantity;

3. What is their size and shape?

Answers to all these questions provide a comprehensive description of the

material microstructure that can be used to explain its properties and to
gain better control over its technological usage. However, the first of these
questions is a domain of material physics. In fact, microstructural elements
such as dislocations and grain boundaries by themselves have become
subjects of extensive theoretical studies.

Fig. 1. Images of microstructural

elements in metals: (a)

dislocations and grain boundaries

imaged by transmission electron

microscopy; (b) grain and inter-

phase boundaries imaged by

light optical microscopy; (c)

second phase particles revealed

by scanning electron microscopy.

 12

In the present text the focus is placed on the two last questions. Size
and shape are the attributes of 1-, 2- and 3-dimensional elements of the
microstructure. The size of microstructural elements can be quantitatively

described by:

• length, 1, for 1-dimensional elements,

• area, A, for 2-dimensional elements,

• volume, V, for 3-dimensional elements.

Direct measurements of the length, area, or volume of

microstructural elements are rarely possible. As a result, the measurements
are usually done on sections or projections of the microstructural elements.
The results of such measurements characterize the size of the elements
studied but do not define their volume, area, or length.

 Stereology

The elements of a microstructure extend into 3-dimensions and are

distributed over the volume of the specimen. This means that
characterization of the microstructural elements should be based on some
3-dimensional model for the material studied. On the other hand, in an
experimental approach they are commonly studied on 2-dimensional
cross-sections or via examination of thin slices. . On the other hand, a large
number of properties are related to microstructural elements which are
distributed over the volume of the material. In this situation, the required 3D
description of the microstructure is inferred from the 2D images by means
of the methods of quantitative stereology.

Fig. 2. Examples illustrating applications of

stereological methods: (a) estimation of
volume fraction, Vv, for a two-phase system
via measurements of area fraction, AA; (b)
estimation of grain boundary surface are, Sv,
via measurements of the density of
intersection points for a system of test lines
with traces of grain boundaries.
 13

A quantitative description of the properties of two-dimensional

images of microstructures is a prerequisite for the quantitative inference of
the properties of the 3-dimensional microstructure. In the past, a number of
methods have been developed that allow an appropriate quantitative
characterization of two-dimensional images by means of simple counting
methods. Some details of such methods are given in Fig. 2. I

Application

The most common and perhaps the most important route of

exposure to allergenic metals in modern humans is via everyday consumer
objects, such as jewelry, clothing, leather, and technological devices.
Nickel, cobalt, chromium and gold, especially, are ubiquitous in daily-use
objects. Nickel release from jewelry is common and ear piercing remains
the most important risk factor for the development of nickel contact allergy.
Cobalt and chromium are frequently found in leather products and gold is
commonly used in jewelry. There is abundant clinical evidence of allergic
contact dermatitis from metals released from daily-use objects and many
exposure studies have been performed seeking to better characterize
which allergenic metals are released from which products. Exposure to
allergenic metals via technological devices such as mobile phones,
laptops, and tablets is likely growing. The pediatric population in particular
seems at risk for metal allergic contact dermatitis from daily-use objects.
Metal exposure via daily-use objects is frequent and clinicians should be
aware of the ways these items can elicit metal allergic contact dermatitis.

POLYMERS

Introduction

Polymer, any of a class of natural or synthetic substances composed

of very large molecules, called macromolecules that are multiples of
simpler chemical units called monomers. Polymers make up many of the
materials in living organisms, including, for example, proteins, cellulose, and
nucleic acids. Moreover, they constitute the basis of such minerals as
diamond, quartz, and feldspar and such man-made materials as concrete,
glass, paper, plastics, and rubbers.
 14

The word polymer designates an unspecified number of monomer

units. When the number of monomers is very large, the compound is
sometimes called a high polymer. Polymers are not restricted to monomers
of the same chemical composition or molecular weight and structure.
Some natural polymers are composed of one kind of monomer. Most
natural and synthetic polymers, however, are made up of two or more
different types of monomers; such polymers are known as copolymers.

Organic polymers play a crucial role in living things, providing basic

structural materials and participating in vital life processes. For example, the
solid parts of all plants are made up of polymers. These include cellulose,
lignin, and various resins. Cellulose is a polysaccharide, a polymer that is
composed of sugar molecules. Lignin consists of a complicated three-
dimensional network of polymers. Wood resins are polymers of a simple
hydrocarbon, isoprene. Another familiar isoprene polymer is rubber.

Other important natural polymers include the proteins, which are

polymers of amino acids, and the nucleic acids, which are polymers of
nucleotides—complex molecules composed of nitrogen-containing bases,
sugars, and phosphoric acid. The nucleic acids carry genetic information in
the cell. Starches, important sources of food energy derived from plants,
are natural polymers composed of glucose.
 15

Polymer Synthesis

There are two major types of polymerization methods used to convert

small molecules (monomers) into polymers. These methods were originally
referred to as addition and condensation polymerization. Depending on
the author, addition polymerization is now called chain, chain-growth, or
chain reaction polymerization. Condensation polymerization is now
referred to as step-growth or step-reaction polymerization. The major
distinctions between these two methods, which, hopefully, will become
apparent from the following discussion, result from the differences in the
kinetics of the polymerization reactions.

Content

 The Structure of Polymers

Many common classes of polymers are composed of hydrocarbons,

compounds of carbon and hydrogen. These polymers are specifically
made of carbon atoms bonded together, one to the next, into long chains
that are called the backbone of the polymer. Because of the nature of
carbon, one or more other atoms can be attached to each carbon atom
in the backbone. There are polymers that contain only carbon and
hydrogen atoms. Polyethylene, polypropylene, polybutylene, polystyrene
and polymethylpentene are examples of these. Polyvinyl chloride (PVC)
has chlorine attached to the all-carbon backbone. Teflon has fluorine
attached to the all-carbon backbone.

Other common manufactured polymers have backbones that

include elements other than carbon. Nylons contain nitrogen atoms in the
repeat unit backbone. Polyesters and polycarbonates contain oxygen in
the backbone. There are also some polymers that, instead of having a
carbon backbone, have a silicon or phosphorous backbone. These are
considered inorganic polymers.

 Chemical Properties of Polymers

The chemical properties of polymers are very similar to those of

analogous small molecules. A functional group attached to a polymer
chain generally reacts the same way it would if present in a monomer. For
example, an acid group can be esterified, an aromatic ring can be
 16

sulfonated, and an ally lie hydrogen can be abstracted by free radicals.

The rates at which these pendant groups undergo reactions, however, can
be quite different. For example, due to steric effects and the
hydrophobicity of its surroundings, the ester group in poly- (methyl
methacrylate) is considerably more resistant to hydrolysis than the ester
group in methyl propionates.

Conversely, the reactivity of pendant functional group can be

substantially increased by the presence of suitable neighboring groups. For
example, the rate of transesterification of pendant phenyl-ester groups
surrounded by pendant carboxyl groups is many orders of magnitude faster
than that of analogous phenyl acetates.

 Physical Properties of Polymers

All of us are well aware that polymers display unique physical properties
for non-metals. Some are tough undergoing large permanent deformations
without breaking, some are stiff and strong, some are soft and flexible, and
others can withstand considerable impact without breaking. All of these
“mechanical properties” are peculiar to the polymer and are not
characteristic of the monomer from which it was prepared. A polymer’s
unusual physical behavior is due to the tremendous amount of interactions
between its chains. These interactions consist of various types of
intermolecular bonds and physical entanglements. The magnitude of these
interactions is dependent upon the nature of the intermolecular bonding
forces, the molecular weight, the manner in which the chains are packed
together, and the flexibility of the polymer chain. Thus, the amount of
interaction is different in different polymers and quite often different in
different samples of the same polymer.

 Characteristics of Polymers

The majority of manufactured polymers are thermoplastic, meaning

that once the polymer is formed it can be heated and reformed over and
over again. This property allows for easy processing and facilitates
recycling. The other group, the thermosets, cannot be remelted. Once
these polymers are formed, reheating will cause the material to ultimately
degrade, but not melt.
 17

Every polymer has very distinct characteristics, but most polymers

have the following general attributes.

1. Polymers can be very resistant to chemicals. Consider all the cleaning

fluids in your home that are packaged in plastic. Reading the warning
labels that describe what happens when the chemical comes in contact
with skin or eyes or is ingested will emphasize the need for chemical
resistance in the plastic packaging. While solvents easily dissolve some
plastics, other plastics provide safe, non-breakable packages for
aggressive solvents.
2. Polymers can be both thermal and electrical insulators. A walk through
your house will reinforce this concept, as you consider all the appliances,
cords, electrical outlets and wiring that are made or covered with
polymeric materials. Thermal resistance is evident in the kitchen with pot
and pan handles made of polymers, the coffee pot handles, the foam
core of refrigerators and freezers, insulated cups, coolers, and
microwave cookware. The thermal underwear that many skiers wear is
made of polypropylene and the fiberfill in winter jackets is acrylic and
polyester.
3. Generally, polymers are very light in weight with significant degrees of
strength. Consider the range of applications, from toys to the frame
structure of space stations, or from delicate nylon fiber in pantyhose to
Kevlar, which is used in bulletproof vests. Some polymers float in water
while others sink. But, compared to the density of stone, concrete, steel,
copper, or aluminum, all plastics are lightweight materials.
4. Polymers can be processed in various ways. Extrusion produces thin fibers
or heavy pipes or films or food bottles. Injection molding can produce
very intricate parts or large car body panels. Plastics can be molded into
drums or be mixed with solvents to become adhesives or paints.
Elastomers and some plastics stretch and are very flexible. Some plastics
are stretched in processing to hold their shape, such as soft drink bottles.
Other polymers can be foamed like polystyrene (Styrofoam™),
polyurethane and polyethylene.
5. Polymers are materials with a seemingly limitless range of characteristics
and colors. Polymers have many inherent properties that can be further
enhanced by a wide range of additives to broaden their uses and
 18

applications. Polymers can be made to mimic cotton, silk, and wool

fibers; porcelain and marble; and aluminum and zinc. Polymers can also
make possible products that do not readily come from the natural world,
such as clear sheets and flexible films.
6. Polymers are usually made of petroleum, but not always. Many polymers
are made of repeat units derived from natural gas or coal or crude oil.
But building block repeat units can sometimes be made from renewable
materials such as polylactic acid from corn or cellulosics from cotton
linters. Some plastics have always been made from renewable materials
such as cellulose acetate used for screwdriver handles and gift ribbon.
When the building blocks can be made more economically from
renewable materials than from fossil fuels, either old plastics find new raw
materials or new plastics are introduced.
7. Polymers can be used to make items that have no alternatives from other
materials. Polymers can be made into clear, waterproof films. PVC is
used to make medical tubing and blood bags that extend the shelf life
of blood and blood products. PVC safely delivers flammable oxygen in
non-burning flexible tubing. And anti-thrombogenic material, such as
heparin, can be incorporated into flexible PVC catheters for open heart
surgery, dialysis, and blood collection. Many medical devices rely on
polymers to permit effective functioning.

 Molecular Arrangement of Polymers

Think of how spaghetti noodles look on a plate. These are similar to

how linear polymers can be arranged if they lack specific order, or are
amorphous. Controlling the polymerization process and quenching molten
polymers can result in amorphous organization. An amorphous
arrangement of molecules has no long-range order or form in which the
polymer chains arrange themselves. Amorphous polymers are generally
transparent. This is an important characteristic for many applications such
as food wrap, plastic windows, headlight lenses and contact lenses.

Obviously not all polymers are transparent. The polymer chains in

objects that are translucent and opaque may be in a crystalline
arrangement. By definition, a crystalline arrangement has atoms, ions, or in
this case, molecules arranged in distinct patterns. You generally think of
 19

crystalline structures in table salt and gemstones, but they can occur in
plastics. Just as quenching can produce amorphous arrangements,
processing can control the degree of crystallinity for those polymers that
are able to crystallize. Some polymers are designed to never be able to
crystallize. Others are designed to be able to be crystallized. The higher the
degree of crystallinity, generally, the less light can pass through the
polymer. Therefore, the degree of translucence or opaqueness of the
polymer can be directly affected by its crystallinity. Crystallinity creates
benefits in strength, stiffness, chemical resistance, and stability.

Scientists and engineers are always producing more useful materials

by manipulating the molecular structure that affects the final polymer
produced. Manufacturers and processors introduce various fillers,
reinforcements and additives into the base polymers, expanding product
possibilities.

Application

The polymers that occur in nature. Our body is made up of many

natural polymers like nucleic acids (DNA, RNA - which have genetic codes),
proteins (collagen), etc. The following are some examples of other naturally
occurring polymers – Cellulose (an important structural component of
plants), keratin, silk, cotton, hair, latex (a kind of natural rubber), starch etc.

The following are the most useful polymers in our daily life:

 The polymer called Polyethylene is used in plastic bags and film

wraps.
 Polyethylene is utilized in the bottles, electrical insulation, toys, etc.
 Polyvinyl Chloride (PVC) is used in siding, pipes, flooring purposes.
 The synthetic polymer Polystyrene is used in cabinets, petri dishes,
CD cases, plastic cutlery and in packaging.
 Polyvinyl acetate is used in adhesives and latex paints.
 20

ENGINEERED NANOMATERIALS

Introduction

Nanomaterials are cornerstones of nanoscience and

nanotechnology. Nanostructure science and technology is a broad and
interdisciplinary area of research and development activity that has been
growing explosively worldwide in the past few years. It has the potential for
revolutionizing the ways in which materials and products are created and
the range and nature of functionalities that can be accessed. It is already
having a significant commercial impact, which will assuredly increase in the
future.

Nanoscale materials are defined as a set of substances where at

least one dimension is less than approximately 100 nanometers. A
nanometer is one millionth of a millimeter - approximately 100,000 times
smaller than the diameter of a human hair. Nanomaterials are of interest
because at this scale unique optical, magnetic, electrical, and other
properties emerge. These emergent properties have the potential for great
impacts in electronics, medicine, and other fields.

Content

 Classification of Nanomaterials

Nanomaterials have extremely small size which having at least one

dimension 100 nm or less. Nanomaterials can be nanoscale in one
dimension (e.g. surface films), two dimensions (e.g. strands or fibres), or
three dimensions (e.g. particles). They can exist in single, fused, aggregated
or agglomerated forms with spherical, tubular, and irregular shapes.
 21

Common types of nanomaterials include nanotubes, dendrimers, quantum

dots and fullerenes. Nanomaterials have applications in the field of nano
technology, and displays different physical chemical characteristics from
normal chemicals (i.e., silver nano, carbon nanotube, fullerene,
photocatalyst, carbon nano, silica). According to Siegel, Nanostructured
materials are classified as Zero dimensional, one dimensional, two
dimensional, three dimensional nanostructures.

Nanomaterials are materials which are characterized by an ultrafine

grain size (< 50 nm) or by a dimensionality limited to 50 nm. Nanomaterials
can be created with various modulation dimensionalities as defined by
Richard W. Siegel: zero (atomic clusters, filaments and cluster assemblies),
one (multilayers), two (ultrafine-grained over layers or buried layers), and
three (nanophase materials consisting of equiaxed nanometer sized
grains).

Fig2

 Examples of Nanomaterials

Nanomaterials (gold, carbon, metals, meta oxides and alloys) with

variety of morphologies (shapes)
 22

 Types of Nanomaterials

For the purpose of this article, most current nanomaterials could be

organized into four types:

1. Carbon Based Materials. These nanomaterials are composed mostly of

carbon, most commonly taking the form of a hollow spheres, ellipsoids,
or tubes. Spherical and ellipsoidal carbon nanomaterials are referred to
as fullerenes, while cylindrical ones are called nanotubes. These particles
have many potential applications, including improved films and
coatings, stronger and lighter materials, and applications in electronics.

2. Metal Based Materials. These nanomaterials include quantum dots,

nanogold, nanosilver and metal oxides, such as titanium dioxide. A
quantum dot is a closely packed semiconductor crystal comprised of
hundreds or thousands of atoms, and whose size is on the order of a few
nanometers to a few hundred nanometers. Changing the size of
quantum dots changes their optical properties.

3. Dendrimers. These nanomaterials are nanosized polymers built from

branched units. The surface of a dendrimer has numerous chain ends,
which can be tailored to perform specific chemical functions. This
property could also be useful for catalysis. Also, because three-
dimensional dendrimers contain interior cavities into which other
molecules could be placed, they may be useful for drug delivery.

4. Composites. Composites combine nanoparticles with other

nanoparticles or with larger, bulk-type materials. Nanoparticles, such as
nanosized clays, are already being added to products ranging from
auto parts to packaging materials, to enhance mechanical, thermal,
barrier, and flame-retardant properties.

5. Unique Properties. The unique properties of these various types of

intentionally produced nanomaterials give them novel electrical,
catalytic, magnetic, mechanical, thermal, or imaging features that are
highly desirable for applications in commercial, medical, military, and
environmental sectors. These materials may also find their way into more
 23

complex nanostructures and systems. As new uses for materials with

these special properties are identified, the number of products
containing such nanomaterials and their possible applications continues
to grow.

Application

Though nanotechnology is a relatively new science, it already has

numerous applications in everyday life, ranging from consumer goods to
medicine to improving the environment.

Here are a few examples:

Medicine
One application of nanotechnology in medicine currently being
developed involves employing nanoparticles to deliver drugs, heat, light or
other substances to specific types of cells, such as cancer cells. Particles
are engineered so that they are attracted to diseased cells, which allow
direct treatment of those cells. This technique reduces damage to healthy
cells in the body and allows for earlier detection of disease. For example,
nanoparticles that deliver chemotherapy drugs directly to cancer cells are
under development.

Electronics
Nanoelectronics holds some answers on expanding the capabilities of
electronics devices can be expanded while reducing their weight and
power consumption. These include improving display screens on
electronics devices and increasing the density of memory chips.
Nanotechnology can also reduce the size of transistors used in integrated
circuits. One researcher believes it may be possible to put the power of all
of today’s present computers in the palm of your hand.

Environment

Nanotechnology is being used in several applications to improve the

environment. This includes cleaning up existing pollution, improving
manufacturing methods to reduce the generation of new pollution, and
 24

making alternative energy sources more cost effective. Potential

applications include:

 Cleaning up organic chemicals polluting groundwater. Researchers

have shown that iron nanoparticles can be effective in cleaning up
organic solvents that are polluting groundwater. The iron
nanoparticles disperse throughout the body of water and
decompose the organic solvent in place. This method can be more
effective and cost significantly less than treatment methods that
require the water to be pumped out of the ground.
 Generating less pollution during the manufacture of materials.
Researchers have demonstrated that the use of silver nanoclusters as
catalysis can significantly reduce the polluting by products
generated in the process used to manufacture propylene oxide.
Propylene oxide is used to produce common materials such as
plastics, paint, detergents and brake fluid.
 Increasing the electricity generated by windmills. Epoxy containing
carbon nanotubes is being used to make windmill blades. The
resulting blades are stronger and lower weight and therefore the
amount of electricity generated by each windmill is greater.
 Producing solar cells that generate electricity at a competitive cost.
Researchers have demonstrated that an array silicon nanowires
embedded in a polymer results in low-cost but high-efficiency solar
cells. This may result in solar cells that generate electricity as cost
effectively as coal or oil.

Consumer Products

Nanotechnology has already found its way into numerous consumer

products you use every day, from clothing to skin lotion. They include:

 Silver nanoparticles in fabric that kill bacteria making clothing odor-

resistant.
 Skin care products that use nanoparticles to deliver vitamins deeper
into the skin
 Lithium ion batteries that use nanoparticle-based electrodes
powering plug-in electric cars
 25

 Flame retardant formed by coating the foam used in furniture with

carbon nanofibers.

Sporting Goods

If you’re a tennis or golf fan, you’ll be glad to hear that even sporting goods
have been improved by nanotechnology. Current nanotechnology
applications in the sports arena include:

 Increasing the strength of tennis racquets by adding nanotubes to

the frames which increases control and power when you hit the ball.
 Filling any imperfections in golf club shaft materials with
nanoparticles; this improves the uniformity of the material that makes
up the shaft and thereby improving your swing.
 Reducing the rate at which air leaks from tennis balls so they keep
their bounce longer.

THE CHEMISTRY OF THE ATHMOSPHERE

Introduction

Many of us picture the earth‘s life-giving atmosphere, the oxygen,

nitrogen, carbon dioxide, water, methane, and the multitude of other trace
gases it contains, as a relatively unchanging, indestructible gaseous
mixture. We have considered its relative vastness to be an infinite sink for
any and all waste products of our civilization which we might wish to vent
into it. That the relatively finite emissions from human activity might
noticeably perturb its properties, particularly in a global sense, is still not
accepted readily by some people. However, we recognize today,
particularly in urban areas with a high density of population, indisputable
evidence of some very significant perturbations which result from human
activity: the generation of high levels of ozone, the high acidity of rain, the
density of the haze, the irritation of our eyes, evidence of stress on plants
and trees, etc. Some environmental problems are less tangible than those
of urban pollution, and surprisingly, they are not yet fully accepted as major
concerns by some of the public. For example, the notion that the very
 26

unreactive chlorofluorocarbons (CFCs) released at the surface of the earth

can lead to serious destruction of our protective stratospheric ozone layer
is debated in some circles as an unsubstantiated theory. However the
appearance of the “ozone hole” over Antarctica in recent years has
renewed interest of many previous skeptics in the possible truth in the
scientific theories of stratospheric ozone destruction. Today, atmospheric
scientists, industrial and academic scientists and engineers of many
disciplines are becoming more aware of the importance of understanding
the changes which are occurring in the atmosphere as a result of human
activities. We are all interested in minimizing the occurrence of surprises
such as the “ozone hole”, forest damage, etc. The leaders of our countries
require advice in designing scientifically sound yet economically realistic
solutions to the many problems which result from the perturbations that we
induce on our natural system. Clearly the knowledge of atmospheric
chemistry as derived from both fundamental and applied chemical studies
by scientists from many disciplines can form the basis for sound scientific
solutions to these problems. In this discussion, we will review briefly the
chemistry of the atmosphere and attempt to identify critical elements
which can alter this chemistry. The scope of our present discussions will be
necessarily limited to only a few of the perturbations in our atmosphere. In
addition, some specific contributions will be identified that IUPAC scientists
can make in our continued search for understanding of atmospheric
chemistry and in the control of harmful air pollution.

Content

 Significance of the Atmosphere

The atmosphere protects life on earth by serving the following functions:

 Absorbs the energetic ultraviolet radiation while allow the passing of

important visible radiations.
 Keeps the earth’s surface warm through heat retention, making
possible a comfortable mean temperature of ±15°C.
 Prevents excessive heating of surface of the earth at day and
excessive cooling at night thereby reducing the temperature
variations.
 27

 Contains nitrogen, oxygen and carbon dioxide gases essential for

plant growth and for respiration.
 It protects the surface of earth and all life existing on earth from small
meteorites that heat up in the atmosphere due to friction.
 Serves an integral part in the bio-geo chemical cycles of C, N, O, P
and S
 Helps in flow of energy and water vapours through dynamic
processes of air flow.
 Helps in radio communication.
 Helps in movement of air crafts.
 Aids in dissipation, dispersion and decomposition of pollutants.

 Composition of the Atmosphere

The atmosphere is having 78.08% nitrogen (N2), 20.95% oxygen (O2) and
about 1% other gases.

• Structure of Atmosphere
1. Troposphere. It is closest layer to the earth’s surface. So, the layer in which
we live is troposphere. It is about 18 km above the sea level at the
equator and 7 km at poles.75% of the atmospheric gases are present in
this layer and almost all of the dust particles and water vapors. All
weather phenomenon like cloud formation, winds, rainfall, snowfall takes
place in this layer. The air below this layer is warmer than any other layer
because it is heated from the earth’s surface below. The layer of air
which is warm tends to rise up, and a pocket of cold air flows to cover
the space, giving rise to wind movement. The temperature will decrease
at a rate of about 6.5 °C per km as the altitude increases. The average
temperature near the surface is 15°C while it is -57° C at the top. Pressure,
 28

moisture content and density of air also decrease with height thinning of
air. That is why people experience breathlessness at high altitudes in
mountains. The troposphere ends when there is variation in temperature
with height. This area, which is the top of troposphere and bottom of
stratosphere, is known as tropopause. The inversion of temperature
beyond tropopause prevents further convection of air thereby confining
most of the weather phenomenon in troposphere.
2. Stratosphere. It is the second layer of earth’s atmosphere. It starts at the
top of tropopause and is 50 km above the sea level. The term
stratosphere is derived from a Greek word “strata” which means
arrangement in horizontal layers. Approximately 99% of the atmosphere
is located up to this height which includes almost all the gases. Weather
balloons and jet aircrafts fly in this region as the air present in this layer is
very thin. This increases the fuel efficiency of the aircrafts. The
stratosphere also contains the ozone layer; at a height of about 30 km.
The density or thickness of ozone layer above the surface of earth is
measured in Dobson Units (DU). The ozone layer is thinnest near the
equator (~260 DU) and its thickness increases towards the poles, though
there are seasonal fluctuations. Ozone – which is a mainly formed
photochemical smog – is considered to be dangerous for health if
reached the ground level or near the surface of earth. However, in the
stratosphere, the high energy UV radiation is absorbed by the ozone
layer and heats up the stratosphere. This also prevent skin cancer and
damage to vegetation. The ozone layer is created in the stratosphere
when the oxygen molecules (O2) absorb UV radiations (240 nm) and
dissociate to give atomic oxygen (O) which immediately react with
another O2 molecule and results in the formation of an ozone (O3)
molecule:

Although, the absorption of UV radiation in the stratosphere leads to

dissociation of ozone molecules, the ozone layer density is maintained
by the reformation of ozone:
 29

As the height increases temperature in the stratosphere also increases, with

the base temperature being close to −60 °C and close to freezing at the
top. This is because, the top layer is hottest and bottom is coldest, the
temperature stratification takes place with little or no mixing of layers. The
stratification has a disadvantage too. Because there is no vertical
convection in the stratosphere, so dissipation and dispersion of materials do
not take place. Chlorofluorocarbons (CFCs) and aerosols from volcanic
eruptions and meteorite impacts can stay in the stratosphere for prolonged
periods of time resulting in damage to the ozone layer and alteration of
global climate. The periods of existence of ozone hole have also seen a
considerable increase in the reported incidents of skin cancer. The layer
which is top of the stratosphere and bottom of mesosphere (the next layer
to stratosphere) is known as stratopause. Here, the temperature becomes
constant with altitude till it again starts increasing in the mesosphere.

3. Mesosphere. It is the middle layer of the earth’s atmosphere. The name

derives from the Greek word ‘misos’ meaning middle. This layer starts at
50 km above the sea level and extends to about 85 km. The air in this
layer is very thin and molecules are at long distance from each other.
Not much is known about this layer because weather balloons and jet
aircrafts do not fly so high and it is too low an orbit for satellites and space
 30

shuttles. Some scientific studies have been made using sounding rockets
that are not required to go into orbit. It is found that meteors generally
burn up in the mesosphere. Thus, this layer protects the surface of earth
from being pockmarked with craters.
The temperature of this layer also decreases with increase in altitude. The
temperature of upper layer of mesosphere is even less than -100°C. At
these low temperatures, freezing of water vapour will take place and
polar-mesospheric clouds are formed. They are known to be the highest
water-based aerosols and ends at mesopause. It marks the minimum
temperature of mesosphere (making it the coldest part of earth also) and
is the bottom of the next layer – the thermosphere − of the atmosphere.
4. Thermosphere. It is the fourth and widest among all layers of the
atmosphere. It is at 90 km or starts from the top of mesopause to between
500 and 1,000 km, varying with solar activity. When more high energy
radiations are emitted by the sun, the thermosphere expands under heat
and thus, its height at top varies. The air is so thin in this layer, that it is
generally considered to be part of outer space. The Kármán Line at
about 100 km is called as boundary of the atmosphere also lies in this
region. Layer is consist of many satellites and space shuttles orbit.
Temperature inversion takes place in thermosphere and temperature
increases as one goes up. The temperatures can range from 500 °C to
2,000 °C or higher, depending upon the position and activity of the sun.
However, the air feels cold because the molecules are so far apart that
a molecule may travel up to 1 km before collision with another molecule.
Most of the X-rays and UV radiations emitted by the sun are absorbed in
the thermosphere. In this layer dissociation of the molecules into atoms,
ions and free electrons is done by high energy radiation. The ionization
process increases with increase in sun’s activity. The ions create an
electrical layer, known as the ionosphere, which can reflect radio waves
back to the earth making radio communication possible. In the
thermosphere theatoms and molecules get excited to higher energy
states after collisions with charged particles from space. Transfer of
thermal energy takes place during the collisions. The excess energy of
atoms and molecules are lost as radiations in the visible region of
spectrum. The top of thermosphere is called thermopause. It is also called
as exobase, because it is the bottom of the exosphere.
 31

5. Exosphere. This is the outermost layer of earth’s atmosphere. It starts from

the top of thermosphere and extends up to a height of 10,000 km into
space. The atmosphere mainly consists of hydrogen and helium which
can escape into space. So, the air is so thin here that it is almost a
vacuum. Thus, the atoms and molecules have to cover hundreds of
kilometers before colliding with each other. Temperature of exosphere is
very high because the particles are directly heated from solar radiation.
However, it doesn’t appear so high because there are too few particles
and so there is not much transfer of energy because inter-molecular
collisions are limited.

Application

We do this by integrating measurements, data, models and new

understanding of complex interactions. Our research supports policy
development for the mitigation of air pollutants and greenhouse gas (GHG)
emissions.

World-class science and innovation:

 Flagship monitoring sites and national-scale monitoring networks

(e.g. GHG Flux Network) generate long-term, high frequency time
series of atmospheric composition change and its key drivers.
 We develop state-of-the-art process-based models from our
measurements and field experiments.
 Our models quantify the emissions, dispersion and
deposition/removal of pollutants from the atmosphere and their
environmental fate.
 We investigate the impact of changes in meteorology and
atmospheric composition on the biodiversity and biogeochemical
cycling of macro and micronutrients in natural and managed
ecosystems.
 32

THE CHEMISTRY OF WATER

Introduction

Water is abundant in all living things and, consequently, is in almost all

foods, unless steps have been taken to remove it. It is essential for life, even
though it contributes no calories to the diet. Water also greatly affects the
texture of foods, as can be seen when comparing grapes and raisins (dried
grapes), or fresh and wilted lettuce. It gives crisp texture or turgor to fruits
and vegetables, and it also affects perception of the tenderness of meat.
For some food products, such as potato chips, salt, or sugar, lack of water
is an important aspect of their quality, and keeping water out of such foods
is important to maintain quality. Almost all food processing techniques
involve the use of water or modification of water in some form: freezing,
drying, emulsification (trapping water in droplets or trapping oil in a water
phase to give salad dressings their characteristic mouth- feel),
breadmaking, thickening of starch, and making pectin gels are a few
examples. Further, because bacteria cannot grow without water, the water
content has a significant effect on maintaining quality of the food. This
explains why freezing, dehydration, or concentration of foods increases
shelf life and inhibits bacterial growth. Water is important as a solvent or
dispersing medium, dissolving small molecules to form true solutions, and
dispersing larger molecules to form colloidal solutions. Acids and bases
ionize in water; water is also necessary for many enzyme catalyzed and
chemical reactions to occur, including hydrolysis of compounds such as
sugars. It is also important as a heating and cooling medium and as a
cleansing agent. Since water has so many functions that are important to
a food scientist, it is important to be familiar with some of its unique
properties. When modifying the water content of a food, it is necessary to
understand these functions in order to predict the changes that are likely
to occur during processing of such foods. Drinking water is available to the
consumer in convenient bottled and aseptic containers in addition to the
tap.
 33

Content

 Chemistry of Water

The chemical formula for water is H2O. Water contains strong

covalent bonds that hold the two hydrogen atoms and one oxygen atom
together. The oxygen can be regarded to be at the center of a
tetrahedron, with a bond angle of 105° between the two hydrogen atoms
in liquid water and a larger angle of 109° 60 between the hydrogens in ice.
The bonds between oxygen and each hydro- gen atom are polar bonds,
having a 40 % partial ionic character. This means that the outer-shell
electrons are unequally shared between the oxygen and hydrogen atoms,
the oxygen atom attracting them more strongly than each hydro- gen
atom. As a result, each hydrogen atom is slightly positively charged and
each oxygen atom is slightly negatively charged. Therefore they are able
to form hydrogen bonds.

A hydrogen bond is a weak bond between polar compounds where

a hydrogen atom of one molecule is attracted to an electronegative atom
of another molecule. It is a weak bond relative to other types of chemical
bonds such as covalent or ionic bonds, but it is very important because it
usually occurs in large numbers and, therefore, has a significant cumulative
effect on the properties of the substance in which it is found. Water can
form up to four hydrogen bonds (oxygen can hydrogen bond with two
hydrogen atoms). Water would be expected to be gas at room
temperature if compared with similar compounds in terms of their positions
in the periodic table, yet due to the many hydrogen bonds it contains, it is
liquid. Hydrogen bonds between hydrogen and oxygen are common, not
just between water molecules, although between many other types of
molecules that are important in foods, such as sugars, starches, pectins,
and proteins. Due to its V-shape, each molecule of water can form up to
four hydrogen bonds with its nearest neighbors. Each hydrogen atom can
form one hydrogen bond, and the oxygen atom can form two, which
 34

results in a three- dimensional lattice in ice. The structure of ice—frozen

water, is dynamic, and hydrogen bonds are continually breaking and
reforming between different water molecules. Liquid water also contains
hydrogen bonds and, there- fore, has a variety of ordered structures that
are continually changing as hydrogen bonds break and re-form. In liquid
water, it is estimated that about 80 % of water molecules are involved in
hydrogen bonding at any one time at 212 F (100°C), whereas 90 % are
involved in liquid water at 32°F (0°C). For the reason that liquid water has
a smaller bond angle than ice, the molecules can be packed together
more tightly, and so the coordination number or, in other words, the
average number of nearest neighbors is higher for water than for ice. The
average distance between water molecules is also affected by

temperature and increases with temperature as the molecules have more

kinetic energy and can move around faster and further at higher
temperatures. Both of these affect the density of water, although the
coordination number has a much more dramatic effect. Ice is less dense
than water because the molecules have a smaller coordination number
and cannot be packed together as tightly as water. Therefore, ice floats.

As water freezes, its density decreases and its volume increases by

about 9 %. This is very significant when freezing foods with high water
content. Containers and equipment must be designed to accommodate
the volume increase when the product freezes, for example, molds for
popsicles must allow room for expansion. This volume increase also
contributes to the damage to the structure of soft fruits on freezing. As
water is heated above 39°F (4°C), the increase in the average distance
between molecules causes a slight decrease in density.
 35

 Water’s Physical Property:

Water is unique in that it is the only natural substance that is found in

all three states -- liquid, solid (ice), and gas (steam) -- at the temperatures
normally found on Earth. Earth's water is constantly interacting, changing,
and in movement.

Water freezes at 32°Fahrenheit (F) and boils at 212°F. In fact, water's

freezing and boiling points are the baseline with which temperature is
measured: 0°on the Celsius scale is water's freezing point, and 100° is
water's boiling point. Water is unusual in that the solid form, ice, is less dense
than the liquid form, which is why ice floats.

Water has a high specific heat index. This means that water can
absorb a lot of heat before it begins to get hot. This is why water is valuable
to industries and in your car's radiator as a coolant. The high specific heat
index of water also helps regulate the rate at which air changes
temperature, which is why the temperature change between seasons is
gradual rather than sudden, especially near the oceans.

Water has a very high surface tension. In other words, water is sticky
and elastic, and tends to clump together in drops rather than spread out in
a thin film. Surface tension is responsible for capillary action, which allows
water (and its dissolved substances) to move through the roots of plants
and through the tiny blood vessels in our bodies.

 Specific Heat and Latent Heat of Water

When ice is heated, the temperature increases in proportion to the

amount of heat applied. The specific heat of water is the energy (in calories
or in joules) required to raise the temperature of 1 g of water by 1 °C, and
is the same whether heating water or ice. It is relatively high com- pared to
other substances due to the hydrogen bonds. The specific heat of water is
1 cal/g/°C. This means that it takes 100 cal to raise the temperature of 1 g
of water from 0 to 100 °C. Once ice has reached 0 °C, energy needs to be
put in to break the hydrogen bonds and enable ice to change to the liquid
form. Until the ice has been converted to liquid, there is no further change
in temperature until liquid water created.
 36

The latent heat of fusion is the energy required to convert 1 g of ice

to water at 0 °C and is 80 cal; that is, 1 g of ice at the freezing point absorbs
approximately 80 cal as it changes to the liquid state. The latent heat of
vaporization is the energy required to convert 1 g of water into vapor at 100
°C and is 540 cal; that is, 1 g of water at the boiling point absorbs
approximately 540 cal as it becomes steam.

Both the specific heat and latent heat for water are fairly high
compared with most substances, and this is an important consideration
when water is used as a medium of heat transfer. It takes considerable
energy to heat water, and that energy is then available to be transferred
to the food. Foods heated in water are slow to heat. Water also must take
up considerable heat to evaporate. It takes heat from its surroundings, thus,
it is a good cooling agent. When ice is subjected to vacuum and then
heated, it is converted into vapor without going through the liquid phase.
This phenomenon is known as sublimation, and is the basis for the food
processing method known as freeze drying. Coffee is an example of a food
product that is freeze-dried. The process is expensive and is only used for
foods that can be sold at a high price, such as coffee. The coffee beans
are frozen and then subjected to a high vacuum, after which radiant heat
is applied until almost all of water is removed by sublimation. Freezer burn is
also the result of sublimation.

 Vapor Pressure and Boiling Point

Vapor Pressure

If a puddle of water is left on the ground for a day or two, it will dry
up because the liquid evaporates. The water does not boil, yet individual
water molecules gain enough energy to escape from the liquid as vapor.
Over a period, an open, small pool of water will dry up in this way. If the
liquid is in a closed container, at equilibrium, some molecules are always
evaporating and vapor molecules are condensing, so there is no overall
change in the system. The vapor(gaseous) molecules that have escaped
from the liquid state exert a pressure on the surface of the liquid known as
the vapor pressure. When the vapor pressure is high, the liquid evaporates
(is vaporized) easily and many molecules exist in the vapor state; the boiling
point is low. Conversely, a low vapor pressure indicates that the liquid does
 37

not vaporize easily and that there are few molecules existing in the vapor
state. The boiling point for these liquids is higher. The liquid boils when the
vapor pressure reaches the external pressure. The vapor pressure increases
with increasing temperature. At higher temperatures, the molecules have
more energy and it is easier for them to overcome the forces holding them
within the liquid and to vaporize, and so there are more molecules in the
vapor state. The vapor pressure decreases with addition of solutes, such as
salt or sugars. In effect, the solutes dilute the water; therefore, there are less
water molecules (in the same volume) available for vaporization and, thus,
there will be fewer molecules in the vapor state, and the vapor pres- sure
will be lower. Attraction to the solute also limits evaporation.

Boiling Point

Anything that lowers the vapor pressure (pres- sure by gas above the
liquid) increases the boiling point. This is due to the fact that as the vapor
pressure is lowered at a particular temper- ature, more energy must be put
in; in other words, the temperature must be raised to increase the vapor
pressure again. The external pressure does not change if salts or sugars are
added, although it becomes harder for the molecules to vaporize and so
the temperature at which the vapor pressure is the same as the external
pres- sure (boiling point) will be higher. One mole of sucrose elevates the
boiling point by 0.52 C, and 1 mol of salt elevates the boiling point by 1.04
C. Salt has double the effect of sucrose because it is ionized, and for every
mole of salt, there is 1 mol of sodium ions and 1 mol of chloride ions. Salts
and sugars depress the freez- ing point of water in a similar fashion. If the
external pressure is increased by heating in a pressure cooker or retort
(commercial pres- sure cooker), the boiling point increases and a shorter
time than normal is required to cook a particular food (the basis of
preserving foods by canning). For example, food may be heated in cans in
retorts, and the steam pressure is increased to give a boiling point in the
range 239–250 F (115–121 C). Conversely, if the external pressure is
decreased, for example, at high altitude, water boils at a lower
temperature and so food may require a longer time to cook
 38

 The polarity of water

Water has a simple molecular structure. It is composed of one oxygen

atom and two hydrogen atoms. Each hydrogen atom is covalently bonded
to the oxygen via a shared pair of electrons. Oxygen also has two unshared
pairs of electrons. Thus there are 4 pairs of electrons surrounding the oxygen
atom, two pairs involved in covalent bonds with hydrogen, and two
unshared pairs on the opposite side of the oxygen atom. Oxygen is an
"electronegative" or electron "loving" atom compared with hydrogen.

Water is a "polar" molecule, meaning that there is an uneven

distribution of electron density. Water has a partial negative charge ( )
near the oxygen atom due the unshared pairs of electrons, and partial
positive charges near the hydrogen atoms.

An electrostatic attraction between the partial positive charge near

the hydrogen atoms and the partial negative charge near the oxygen
results in the formation of a hydrogen bond as shown in the illustration.
The ability of ions and other molecules to dissolve in water is due to
polarity. For example, in the illustration below sodium chloride is shown in its
crystalline form and dissolved in water.
 39

Many other unique properties of water are due to the hydrogen

bonds. For example, ice floats because hydrogen bonds hold water
molecules further apart in a solid than in a liquid, where there is one less
hydrogen bond per molecule. The unique physical properties, including a
high heat of vaporization, strong surface tension, high specific heat, and
nearly universal solvent properties of water are also due to hydrogen
bonding. The hydrophobic effect, or the exclusion of compounds
containing carbon and hydrogen (nonpolar compounds) is another unique
property of water caused by the hydrogen bonds. The hydrophobic effect
is particularly important in the formation of cell membranes. The best
description is to say that water "squeezes" nonpolar molecules together.
 Acids and Bases, Ionization of Water

 Acid release H+

 Bases accept H+

We define the pH of a solution as the negative logarithm of the hydrogen

ion concentration.

 at pH 7.0, a solution is neutral

 at lower pH (1-6), a solution is acidic

 at higher pH (8-14), a solution is basic

 40

Application

Water (H2O) is one of the most common molecules on earth and a

critical one for the existence of life. As such, there are countless uses for
water. Not only does water sustain life through several uses, but it is a critical
component in manufacturing, transport and energy. Water also is a key
component in many recreational activities. Water is one of the most used
compounds on earth.

Everyday Living. The most common use of water is through drinking. People
drink water almost every day and would not be able to survive without
doing so. Water is also used in everyday life for cooking, cleaning, washing
and playing. These activities use on average 90 gallons of water per day
for the average American. Except when asleep, it is rare to go more than
a couple of hours without some interaction with water.

Agriculture. Agricultural use of water is one of the most common uses of

water. Not only are crops watered through various applications of water,
but livestock also require daily use of water. Techniques such as irrigation,
spraying, flooding and relying on natural precipitation all aid agriculture.
Water is provided from reservoirs, canals and wells as key sources for
agriculture. Fisheries and open water harvesting of seafood is a further
example of how water is a part of agriculture.

Energy. Many often initially think of hydroelectric power generation when

considering the use of water in energy generation. However, the use of
water goes far beyond that. Water wheels are still used around the world
to produce mechanical energy. Water is also a critical function in the
production of energy in fossil fuel-based generation plants. The fossil fuels
are burned in order to convert water into steam, which in turn is used to turn
the turbines that generate the electricity.

Manufacturing. Water plays a critical role in numerous industries. It is the

most common cooling agent for many heat-intensive industrial
applications. It is a common solvent in many chemical processes and is also
a common component in washing and cleaning steps in many processes.
Water also is used in transportation on several scales in industry. Not only
are goods transported by ships and barges, but raw materials are often
 41

transported by slurry in many industries, most especially mining. There are

very few heavy industries that do not use water in part of their process.

SOIL CHEMISTRY

Introduction

Soil Chemistry is a mixture of inorganic and organic solids, air and

water. Soil chemistry involves the chemical reactions and processes
between these components and particularly focuses on investigating the
fate of contaminants and nutrients within soils. Knowledge of soil chemistry
allows scientists to monitor, control and predict the effects of pollutants in
the environment. Chemical knowledge combined with understandings
from the Earth sciences, physics and biology are needed to understand,
prevent and remediate environmental issues with soils.

Soils transport and move water, provide homes for thousands of

bacteria and other creatures, and have many different arrangements of
weathered rock and minerals. When soils and minerals weather over time,
the chemical composition of soil also changes. However, nothing changes
the chemistry of soils faster than humans do.

Many of today’s soil chemistry problems have to do with

environmental sciences. What happens when a chemical is accidentally
spilt in the soil? How fast does it break down? What does it break down into?
Where does it go and how fast does it move? A soil chemist may ask these
example questions. Sol chemists research concerns about organic and
inorganic soil contamination, pesticides and other pollutants, and
environmental health risks.

Soil chemistry has traditionally focused on the chemical reactions in

soils that affect plant growth and plant nutrition. However, beginning in the
1970s and certainly in the 1990s, as concerns increased about inorganic
and organic contaminants in water and soil and their impact on plant,
animal, and human health, the emphasis of soil chemistry is now on
environmental soil chemistry. Environmental soil chemistry is the study of
chemical reactions between soils and environmentally important plant
nutrients, radionuclides, metals, metalloids, and organic chemicals.
 42

Content

 pH

One of the most important components of soil is

the pH. The pH of soil can be modified by adding
different chemicals. Soil pH indicates how acid or
alkaline the soil is. The pH scale ranges from 0 to 14.
Any substance with a pH near the lower end of the
scale is very acidic. Substances in the upper range of
the scale have a high alkalinity or are very basic. The
pH of a soil is crucial because crops grow best in a
narrow pH range which can vary among crops. For
example, blueberries and a few types of flowers grow
best when the pH is 5.5 or less. Potatoes, a more
familiar crop, grow best with a soil pH range of 5.5 to

6.0. Most garden vegetables, shrubs, trees and lawns grow best when the
soil pH is over 6.0 or 6.5. The range between 5.5 and 7.5 is favorable for two
reasons. It allows sufficient microorganisms to break down organic matter.
It is also the best range for nutrient availability. Organic matter and nutrients
will be discussed later. Areas that were formerly covered by trees, such as
Prince Edward Island, develop acidic soils. This helps explain how Prince
Edward Island farmers can grow the best potatoes in the world.

 Ion exchange

Ion exchange involves the movement of cations (positively charged

elements like calcium, magnesium, and sodium) and anions (negatively
charged elements like chloride, and compounds like nitrate) through the
soils. In the United States, cation exchange is much more common.
 43

Cation exchange is the interchanging between a cation in the

solution of water around the soil particle, and another cation that is stuck
to the clay surface. The number of cations in the soil water solution is much
smaller than the number that is attached to soil particles.

The total amount of positive charges that the soil can absorb is called
the cation exchange capacity (CEC). CEC impacts how quickly nutrients
move through the profile. A soil with a low CEC is much less fertile because
it cannot hold on to many nutrients, and they usually contain less clays. If
your soil has a low CEC, it is important to apply fertilizer small doses so it does
not infiltrate into the groundwater. A soil with a low CEC is less able to hold
spilt chemicals.

 Soil Organic Matter Interactions

Soil chemists also study soil organic matter (OM), which are materials
derived from the decay of plants and animals. They contain many
hydrogen and carbon compounds. The arrangement and formation of
these compounds influence a soils ability to handle spilt chemicals and
other pollutants.

 Oxidation and Reduction Reactions

Soils that alternate between wet and dry go from having a lot of
oxygen to not a lot of oxygen. The presence or absence of oxygen
determines how soils chemically react. Oxidation is the loss of electrons,
and reduction is the gaining of electrons at the soil surface. These type of
reactions occur every day, and are responsible for creating things like rust.
 44

Soils, because they contain a lot of iron, can also rust, or if they contain a
lot of water, can turn a light gray color. This is partially responsible for all of
the different colors that are found, and creates the speckles usually found
deeper in the soil.

 Liming

When farmers originally cleared the lands on the Island, the soil
quality was adequate for growing potatoes. However, potatoes were not
the only crop at that time. Therefore, farmers needed a way to increase
the pH of the soil to make it suitable for other crops. The pH of soil can be
increased by liming. This is why people sometimes spread white powder on
their lawns or gardens. This white powder is lime. Calcitic limestone

(CaCO3) provides a good source of Calcium (Ca) and helps neutralize soil
acidity. Dolomitic limestone functions similarly but also adds Magnesium
(Mg). The best limestone will have the greatest calcium and magnesium
content and will be ground into very tiny particles. The smaller particles
allow the limestone to correct soil acidity more rapidly. The chemistry to
liming is quite simple. Hydrogen ions (H) are attracted to soil and organic
material which have a negative + charge. When lime is applied, these
hydrogen ions are exchanged for calcium or magnesium (Ca or Mg ) ions
which have a greater positive charge. This helps to neutralize the acidity 2+
2+ of the soil. The free hydrogen ions are taken out of solution. This also helps
to increase the pH. This reaction demonstrates the process of liming.

 Nutrients
 45

Each year the soil undergoes a series of cycles in which materials are
added and then taken away. Organic matter and nutrients, in various
forms, are constantly being added to the soil. Nutrients are the minerals
required by plants to survive. It is very important that plants receive all the
required nutrients. There are a total of sixteen elements required for plant
growth. Each is required in different amounts. The most important nutrients
are called macronutrients. Nutrients which are essential, but only needed
in small quantities are called micronutrients. Carbon, Hydrogen, and
Oxygen are the big three macronutrients. These are obtained in almost
unlimited amounts from the atmosphere and from the water around the
plant. The other macronutrients are nitrogen (N), phosphorus (P), potassium
(K), calcium (Ca), magnesium (Mg), and sulfur (S). These nutrients should be
available for plant uptake from the soil. Micronutrients are obtained from
the soil. They are boron (B), copper (Cu), chlorine (Cl), iron (Fe), manganese
(Mn), molybdenum (Mo), and zinc (Zn). They are all essential because the
absence of any one of these will cause the plant to grow poorly or develop
disease.

 Organic Matter

Many pleasant drives in the country have been affected when the
passengers of a car are hit with an unpleasant, but familiar odor. Many
people complain about the smell without questioning why it exists. There is
actually a very good reason for this practice. Although they are often given
more unpleasant names, these animal wastes are known as organic
fertilizers. These fertilizers have a very high content of organic matter.
Organic matter is simply dead decaying matter that originated from a living
source. It prevents nutrients from being lost from the soil by binding these
nutrients. Therefore, the best soil for crop production will have a very high
organic content. Most organic fertilizer originates from livestock such as
 46

cows, pigs, and poultry. Compost is also an organic fertilizer. Compost can
be made up of grass clippings, table scraps, ashes, seaweed, and many
other types of food products. Organic fertilizers contain high levels of
Nitrogen and moderate levels of Phosphorus and Potassium. The nutrient
content of organic fertilizer can vary according to the animal that
produced it (agri-science text). The process of spreading organic fertilizers
gives farmers the opportunity to rid themselves of accumulated livestock
waste. It also provides farmers with a free source of fertilizer which is
sometimes sufficient to meet the needs of the desired crop. Organic
fertilizers are also less harmful to the environment. This may be one of the
first recycling practices that ever developed.

Application

 Life beneath the Surface

The ground beneath our feet—that is, the topmost layer, the A
horizon—is full of living things. In fact, there are more creatures below Earth's
surface than there are above it. The term creatures in this context includes
microorganisms, of which there might be several billion in a sample as small
as an acorn. These include decomposers, such as bacteria and fungi,
which feed on organic matter, turning fresh leaves and other material into
humus. In addition, both bacteria and algae convert nitrogen into forms
usable by plants in the surrounding environment.

Worms

We cannot see bacteria, of course, but almost anyone who has ever
dug in the dirt has discovered another type of organism: worms. These slimy
creatures might at first seem disgusting, but without them our world could
not exist as it does. As they burrow through soils, earthworms mix organic
and mineral material, which they make available to plants around them.
They also may draw leaves deep into their middens, or burrows, thus
furnishing the soil with nutrients from the surface. In addition, earthworms
provide the extraordinarily valuable service of aerating the soil, or supplying
it with air: by churning up the soil continuously, they expose it to oxygen
from the surface and allow air to make its way down below as well.

Nor are these visible, relatively large worms the only ones at work in
the soil. Colorless worms called nematodes, which are only slightly larger
 47

than microorganisms, also live in the soil, performing the vital function of
processing organic material by feeding on dead plants. Some, however,
are parasites that live off the roots of such crops as corn or cotton.

Ants and Larger Creatures

Likewise there are "bad" and "good" ants. The former build giant, teeming
mounds and hills that rise up like sores on the surface of the ground, and
some species have the capacity to sting, causing welts on human victims.
But a great number of ant species perform a positive function for the
environment: like earthworms, they aerate soil and help bring oxygen and
organic material from the surface while circulating soils from below.

In some areas, much larger creatures call the soil home. Among these
creatures are moles, who live off earthworms and other morsels to be found
beneath the surface, including grubs (insect larvae) and the roots of plants.
As with ants and earthworms, by burrowing under the ground, they help
loosen the soil, making it more porous and thus receptive both to moisture
and air. Other large burrowing creatures include mice, ground squirrels,
and prairie dogs. They typically live in dry areas, where they perform the
valuable function of aerating sandy, gravelly soil.

 Soils and Environments

In discussing our imaginary journey through the depths of the soil, it

has been necessary to use vague terms concerning depths: "less than a
foot," for instance. The reason is that no solid figures can be given for the
depth of the soil in any particular area, unless those figures are obtained by
a soil scientist who has studied and measured the soil.

Depth is just one of the ways that the soil may vary from one place
to another. Earlier we mentioned five factors that affect the character of
the soil: parent material, climate, living organisms, topography, and time.
These factors determine all sorts of things about the soil—most of all, its
ability to support varied life-forms. Collectively, these five factors constitute
the environment in which a soil sample exists.

Poor Soils

A desert environment might be one of immature soil, defined as a

sample that has only A and C horizons, with no B horizon between them.
 48

On the other hand, the soil in rainforests suffers from just the opposite
condition: it has gone beyond maturity and reached old age, when plant
growth and water percolation have removed most of its nutrients.

Whether in the desert or in the rainforest, soils near the equator tend
to be the "oldest," and this helps explain why few equatorial regions are
noted for their agricultural productivity, even though they enjoy otherwise
favorable weather for growing crops. Soils there have been leached of
nutrients and contain high levels of iron oxides that give them a reddish
color. Moreover, red soil is never good for growing crops: the ancient
Egyptians referred to the deserts beyond their realm as "the red land," while
their own fertile Nile valley was "the black land."

Rainforests

If soil is so poor at the equator, why do equatorial regions such as the

Congo or the Amazon River valley in Brazil support the dense, lush rain-forest
ecosystems for which they are noted? The answer is that the abundance
of organic material at the surface of the soil continually replenishes its
nutrient content. The rapid rate of decay common in warm, moist regions
further supports the process of renewing minerals in the ground.

This also explains why the clearing of tropical rainforests, an issue that
environmentalists called to the world's attention in the 1990s, is a serious
problem. When the heavy jungle canopy of tall trees is removed, the heat
of the sun and the pounding intensity of monsoon rains fall directly on
ground that the canopy would normally protect. With the clearing of trees
and other vegetation, the animal life that these plants support also
disappears, thus removing organisms whose waste products and bodies
would have decayed eventually and enriched the soil. Pounded by heat
and water and without vegetation to resupply it, the soil in an exposed
rainforest becomes hard and dry.

Deserts

In deserts the soil typically comes from sandstone or shale parent

material, and the lack of abundant rainfall, vegetation, or animal life gives
the soil little in the way of organic sustenance. For this reason, the A horizon
level is very thin and composed of light-colored earth. Then, of course,
there are desert areas made up of sand dunes, where conditions are much
 49

worse, but even the best that deserts have to offer is not very good for
sustaining abundant plant life.

Only those species that can endure a limited water supply—for

example, the varieties of cactus that grow in the American Southwest—are
able to survive. But lack of water is not the only problem. Desert subsoils
often contain heavy deposits of salts, and when rain or irrigation adds water
to the top soil, these salts rise. Thus, watering desert top-soil can make it a
worse environment for growth.

Rich Soils

In striking contrast to the barren soil of the deserts and the potentially
barren soil of the rainforest is the rich earth that lies beneath some of the
world's most fertile crop-producing regions. On the plains of the midwestern
United States, Canada, and Russia, the soil is black—always a good sign for
growth. Below this rich topsoil is a thick subsoil that helps hold in moisture
and nutrients.

The richest variety of soil on Earth is alluvial soil, a youngish sediment

of sand, silt, and clay transported by rivers. Large flowing bodies of water,
such as the Nile or Mississippi, pull soil along with them as they flow, and with
it they bring nutrients from the regions through which they have passed.
These nutrients are deposited by the river in the alluvial soil at its delta, the
place where it enters a larger body of water—the Mediterranean Sea and
the Gulf of Mexico, respectively. Hence the delta regions of both rivers are
extremely fertile.

CHEMICAL SAFETY

Introduction

Chemical safety is the application of the best practices for handling

chemicals and chemistry processes to minimize risk, whether to a person,
facility, or community. It involves understanding the physical, chemical,
and toxicological hazards of chemicals.

Wide range of chemicals are used in research laboratories of the

Institute, each with its own inherent hazards. An understanding of the
 50

potential hazards and precautions required in handling of chemicals is of

outmost importance in preventing exposure to chemicals and mishaps.

Safely managing the chemicals in your workplace is good for

business and it is good for everyone! It will improve your employees’ safety
and health. It will potentially introduce cost savings, through more effective
work practices such as correct storage, handling, use and disposal
procedures. Potential harm to the environment will also be reduced

In most cases you will be able to manage your chemical safety in-
house. You will be familiar with the types of chemicals involved and the
type of work activities in which these chemicals are used. In addition, your
employees will have experience and knowledge that you can use when
deciding on the precautions you are going to take. You will probably
already have precautions in place. You are now checking if these are
sufficient and if you need to take further steps to protect people. Small or
low-risk businesses will find it straightforward to identify their chemical
hazards and put in place appropriate control measures. Larger businesses,
and particularly those working in high-risk sectors, may need more
resources and competency to manage their chemical safety.

Content

 Chemical Substance

A chemical substance is a material with a specific chemical

composition. Water is an example of a chemical substance - it always
hasthe same number of hydrogens and oxygen (e.g. H2O). Some everyday
chemicals include cleaning materials, cosmetics, plastics, paint, dyestuffs,
sugar, solvents, etc. A chemical substance can exist as a solid, liquid or gas
and still be the same substance. For example, water and steam are
different forms of the same substance.

 Characteristics of Potentially Harmful Substances Used in Homes

The potentially harmful substances used daily in homes usually have

one or more of the following characteristics:

 Corrosive - They eat or wear away at many materials;

 Flammable - They easily ignite;
 51

 Reactive - They can cause an explosion or produce deadly vapors;

and
 Toxic - They are poisonous to humans and animals.

Corrosives

 Corrosive substances causes destructive burns on the tissue by

chemical action at the site of contact.
 Corrosive effect can also occur in the respiratory tract in case of
inhalation and in the gastrointestinal tract in case of ingestion.
 Typical examples are sulfuric acid, nitric acid, potassium hydroxide
(caustic potash), sodium hydroxide (caustic soda), bromine and
phenol.

Oxidisers

 Oxidisers are chemicals which decompose readily under certain

conditions to yield oxygen.
 They can cause a fire to burn violently.
 Oxidisers must not be stored with flammables.
 Typical examples include hydrogen peroxide, nitric acid, perchloric
acid, sulphuric acid, chlorates, chromates, nitrates, peroxides,
permanganates and picrates.

Flammables

 The vapours released from a flammable liquid are a common fire

hazard in a laboratory.
 The degree of hazard associated with a flammable liquid depends
on its flash point, flammability limit and ignition temperature.
 Flammable substances are those that readily catch fire and burn in
air.

Toxic chemicals

 Toxic effects of a chemical may occur after a single (acute)

exposure or long term repeated (chronic) exposure.
 Examples of acute toxins are sodiumcyanide, sodium azide and
dimethyl mercury.
 Benzene is an example of a chronic toxin which can cause damage
after repeated or long term exposure.
 52

Types of toxins - target organ/tissue - examples

 Neurotoxins (nervous system) - mercury (metallic, inorganic and

organic), xylene, carbon disulphide, n-hexane, trichloroethylene.
 Hematotoxins (blood) - carbon monoxide, nitrates aromatic amine
compounds.
 Hepatotoxins (liver) - chloroform, dinitrobenzene
 Nephrotoxins (kidney) - cadmium, mercury, carbon tetrachloride
 Dermatotoxins (skin) - organic solvents
 Storage of chemicals
 Bulk stocks must be stored in a separate building.
 A spill or fire involving bulk containers will be difficult to tackle when
compared with that involving smaller bottles.
 Chemicals must not be placed indiscriminately in the storage shelf.
They must be grouped based on their compatibility.
 Separate chemicals into compatible groups and store alphabetically
within compatible groups.
 In the event of an accidental breakage or seismic activity,
incompatible chemicals that are stored in close proximity can mix to
start a fire, hazardous fumes or explosions.
 The following chemical groups must be separated by storing them in
different cabinets/shelves or by providing secondary containment
(trays).
o Oxidisers, including peroxides
o Acids
o Bases
o Flammable materials
o Reproductive toxins
o Carcinogens

Any incompatibles within the above group must be stored

separately.

 To prevent accidents caused by overreaching do not store

chemicals on shelves higher than 1.5 meter (from floor level).
 Fix the shelf to the wall to prevent its fall. Storage of chemicals
 Store heavier or larger bottles on lower racks.
 Store flammable chemicals in approved safety cabinets.
 53

 There must be a fixed storage place for each chemical and the same
must be returned to that location after each use. Storage of
chemicals
 Toxic or odoriferous chemicals must be stored in a ventilated cabinet.
 Chemicals must not be exposed to heat or direct sunlight.
 Heat and sunlight can degrade chemicals, deteriorate storage
containers and labels. Storage of chemicals
 Chemicals must not be stored at locations where they can be
knocked over. Storage of chemicals
 Rim guards must be fixed on the edge of shelves to prevent bottles
from falling.
 Flammable chemicals must not be stored on bench tops.
 After use they must be immediately removed to a safety cabinet.
 Flammable solvents must not be left open in containers or beakers.
 Same must be stored and handled away from sources of ignition and
oxidisers. Storage of chemicals
 Flammable chemicals must not be stored in domestic refrigerators.
 Vapours can leak out from the bottles and form a flammable vapour
air mixture.
 The bulb or thermostat can be a source of ignition.
 Flammable chemicals must be stored only in intrinsically safe lab
purpose refrigerators.
 Safety precautions
 Do not work alone in the laboratories particularly when performing
hazardous procedures.
 Do not perform unauthorised experiments.
 Plan appropriate procedures and the positioning of all equipment
before beginning any experiment.
 Wear appropriate personal protective equipment, a laboratory
apron or coat, safety glasses and toe covered footwear at all
times in the laboratory.
 Wear suitable gloves when handling chemicals. Inspect all gloves
for defects before usage. Safety precautions Safety precautions
 Know the location of emergency equipment.
 Be aware of the hazards posed by the work of others in the
laboratory.
 54

 Make others in the laboratory aware of any specific hazards

associated with your work.
 When heating a test tube or other apparatus, never point it
towards yourself or others.
 Be sure that glassware has cooled before touching it.
 Dilute concentrated acids and bases by slowly pouring the acid
or base into the water while stirring.
 Keep work area clean and uncluttered. Maintaining good
housekeeping helps to prevent accidents. Safety precautions
 Laboratory equipment must be regularly inspected and serviced
as per manufacturer’s recommendations. Safety precautions
 Store coats, bags and other personal items in a designated area,
not on bench tops.
 Keep drawers and cabinets closed when not in use.
 Never heat flammable substances with an open flame. Use a
water bath.
 How do I know if a chemical is hazardous?

The container that the chemical is supplied in should have a label

that describes the properties of that chemical and should also include
instructions on how to use it safely. Labelling is a visual representation of the
hazards and the most important and immediate safety information
associated with a specific chemical.

As space is limited on a label, additional information can be found in

the Safety Data Sheet (SDS); in particular the general health symptoms
associated with the identified hazard(s) are in Section 2. An SDS is normally
supplied on delivery of the chemical in question, but if you didn’t receive
one, you are entitled to ask your supplier to provide you with one.

Chemical Hazards – In relation to chemicals, a hazard is a set of inherent

properties of the substance, mixture, article or process that may cause
adverse effects to organisms or the environment. There are two broad types
of hazards associated with hazardous chemicals which may present an
immediate or long term injury or illness to people. These are:

Health Hazards – These are properties of a chemical that have the potential
to cause adverse health effects. Exposure usually occurs through
 55

inhalation, skin contact or ingestion. Adverse health effects can be acute

(short term) or chronic (long term). Typical acute health effects include
headaches, nausea or vomiting and skin corrosion, while chronic health
effects include asthma, dermatitis, nerve damage or cancer.

Physicochemical Hazards – These are physical or chemical properties of

the substance, mixture or article that pose risks to workers other than health
risks, as they do not occur as a consequence of the biological interaction
of the chemical with people. They arise through inappropriate handling or
use and can often result in injury to people and/or damage to property as
a result of the intrinsic physical hazard. Examples of physicochemical
hazards include flammable, corrosive, explosive, chemically reactive and
oxidizing chemicals. Many chemicals have both health and
physicochemical hazards.

 Information on chemical labels

The container that the chemical is supplied in should have a label

that describes the properties of the chemical. At the moment as a result of
new EU legislation the label and the SDS are changing. Below is an example
of a label where you can find safety information, one side shows the existing
system and the other showing the new system. Note: Only one type, i.e.
CPL or CLP, will appear on the label.

 Emergency measures
 Eyes must be immediately flushed with copious amount of water
for at least 15 minutes.
 In case of contact with hydrofluoric acid, apply 2.5% calcium
gluconate gel on the skin after flushing the affected part with
water. Refer safety data sheets for more information.
 Disposal of chemicals
 Laboratories must maintain labelled carboys/cans for collecting
spent chemicals.
 Care must be taken to prevent mixing of incompatible chemicals
while transferring spent chemicals.
 There should be at least 2 inch head space above the liquid
surface in the chemical container.
 56

Application

 Bench tops must not be used as storage area to prevent clutter.

Keep only chemical bottles that is for immediate use on bench
tops.
 All chemical bottles must be tightly closed after use and must not
be placed on edge of the bench or shelf from which they can fall.
 Chemical formulae or short forms must not be used for labelling
chemical bottles. Labels must include the full name of the
chemical, hazard pictogram and a brief description of the hazards
and precautions to be taken.
 It will not be possible to identify the chemical in case of a spill or
body contact due to inadequate labelling.
 Worn out labels must be immediately replaced by new ones.
Unlabelled chemical bottles can create difficulty at the time of
disposal of chemical bottle.
 Chemicals must not be stored in drinking water bottles.
 Handling of chemicals Transporting chemicals.
 Use secondary containment when transporting chemicals.
 57

APPENDICES

BASIC CONCEPTS OF CRYSTALLINE STRUCTURES:

“Basic Crystal Concepts” Retrieved from http://home.iitk.ac.in/~sangals/

crystosim/crystaltut.html. (11 October 2018)

Helmenstine, A.M. (September 2018). “Type of Crystals.” ThoughtCo.

Retrieved from https://www.thoughtco.com/types-of-crystals-602156.

(11 October 2018)

Nilsson, H.E. “Self study material in Solid State Electronics using Multimedia”

Retrieved from https://people.seas.harvard.edu/~jones/ap216/

lectures/ls_2/ls2_u7/sse_tut_1/solid1.html. (11 October 2018)

Cambridge (July 2018). “Methods and applications of crystal structure

prediction Faraday Discussion” Events. Retrieved from

http://www.rsc.org/events/detail/24508/methods-and-applications-of-

crystal-structure-prediction-faraday-discussion. (11October 2018)

METALS:

“Metal: Chemistry Guide.” Thomas. Retrieved from

https://www.thomasnet.com/articles/metals-metal-products/metal-

chemistry-guide. (11 October 2018)

“Metals.” ScienceDaily. Retrieved from

https://www.sciencedaily.com/terms/metal.html. (11 October 2018)

KURZYDŁOWSKI, K.J. (1999) “STRUCTURE AND PROPERTIES OF METALS.”

Retrieved from http://przyrbwn.icm.edu.pl/APP/PDF/96/a096z1p05.pdf.

(11 October 2018)

Hamann, C., Hamann, D. (April 2018) “Metals in Everyday Life.” Springer

Link. Retrieved from https://link.springer.com/chapter/10.1007/978-3-

 58

319-58503-1_13. (11 October 2018)

POLYMERS:

Harris, F. (1981) “Introduction to Polymer Chemistry.” Retrieved from

https://pubs.acs.org/doi/pdf/10.1021/ed058p837. (11 October 2018)

“The Basics: Polymer Definition and Properties.” American Chemistry

Council. Retrieved from https://plastics.americanchemistry.com

/plastics/The-Basics/. (11 October 2018)

“Polymer.” Britannica. Retrieved from https://www.britannica.com/

science/polymer. (11 October 2018)

ENGINEERED NANOMATERIALS:

Alagarasi, A. (December 2011) “Introduction to Nanomaterials.”

ResearchGate. Retrieved from https://www.researchgate.net/

publication/259118068_Chapter_-_INTRODUCTION_TO_

NANOMATERIALS. (11 October 2018)

“Classification of Nanomaterials, The Four Main Types of Intentionally

Produced Nanomaterials” Azonano. Retrieved from

https://www.azonano.com/article.aspx?ArticleID=1872. (11 October

2018)

Bradley, P. (October 2011) “Everyday Applications of Nanotechnology”

Community College Week. Retrieved from http://ccweek.com/article-

2630-everyday-applications-of-nanotechnology.html. (11 October

2018)

THE CHEMISTRY OF THE ATMOSPHERE:

Calvert, J. (1997) “The chemistry of the atmosphere and its

perturbations through human activities.” Retrieved from

https://www.iupac.org/publications/pac/pdf/1997/pdf/6901x0001.pdf.
 59

(15 October 2018)

Sidhwani, I.T., Garg, A. “ENVIRONMENTAL CHEMISTRY” Retrieved from

http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/

chemistry/04.environmental_chemistry/01.atmosphere/et/

5503_et_et.pdf. (15 October 2018)

“Atmospheric Chemistry and Effects” Centre for Ecology & Hydrology.

Retrieved from https://www.ceh.ac.uk/our-science/science-

areas/atmospheric-chemistry-and-effects. (15 October 2018)

THE CHEMISTRY OF WATER:

“The Chemistry of Water.” The Biology Project-Biochemistry. Retrieved from

http://www.biology.arizona.edu/biochemistry/tutorials/ chemistry/

page3.html. (15 October 2018)

“Water Chemistry.” Retrieved from https://imnh.iri.isu.edu/

digitalatlas/hydr/basics/main/chmtxt.htm. (15 October 2018)

Vaclavik, V., Christian, E.W. (2014) “Essential of Food Science.” Springer.

Retreived from https://www.springer.com/cda/content/document/

cda_downloaddocument/9781461491378-c1.pdf?SGWID=0-0-45-

1445145-p175454542. (15 October 2018)

SOIL CHEMISTRY:

“SOIL CHEMISTRY.” Soil Science Teacher Resources. Retrieved from

https://www.soils4teachers.org/chemistry. (15 October 2018)

Sparks, D. (2003) “Environmental Soil Chemistry: An Overview.”

ScienceDirect. Retrieved from https://www.sciencedirect.com/topics/

earth-and-planetary-sciences/soil-chemistry. (15 October 2018)

Rate, A. (January 2011) “Environmental Chemistry.” ResearchGate.

Retrieved from https://www.researchgate.net/publication/

 60

258521390_Soil_Chemistry. (15 October 2018)

“Soil Chemistry” Retrieved from http://www.edu.pe.ca/

agriculture/soil.pdf. (15 October 2018)

“Soil-Real-life applications.” Science Clarified. Retrieved from

http://www.scienceclarified.com/everyday/Real-Life-Earth-Science-

Vol-3/Soil-Real-life-applications.html. (15 October 2018)

CHEMICAL SAFETY:

Archibong, U. (April 2017) “CHEMICAL SAFETY(INTRODUCTION); Chemical

safety is good for business.” Linkedin. Retreived from

https://www.linkedin.com/pulse/chemical-safety-introduction-udeme-

archibong. (16 October 2018)

Health and Safety Authority (2010). “Chemical Safety Information Sheet.”

Retrieved from https://www.hsa.ie/eng/Publications_and_Forms/

Publications/Chemical_and_Hazardous_Substances/Chemical

%20Safety%20Information%20Sheet.pdf. (16 October 2018)

Cable, J. (October 2006)” Home Chemical Safety Tips from the American

Society of Safety Engineers.”EHSToday. Retrieved from

https://www.ehstoday

.com /safety/chemical/ehs_imp_39314. (16 October 2018)