CHAPTER 6

POLYMERS

Before discussing POLYMERS, let us introduce first ORGANIC CHEMISTRY.

Organic Chemistry designates the branch of chemistry that deals with carbon
compounds but does not imply that these compounds must originate from some form of life.
The field of organic chemistry is vast, for it includes not only the composition of all
living organisms, but also that of a great many other materials that we use daily. Examples
of organic materials are nutrients (fats, proteins, carbohydrates), fuels, fabrics (cotton, wool,
rayon, nylon), wood and paper products, paints and varnishes, dyes, soaps and detergents,
cosmetics medicinal, rubber products and explosives.

The Carbon Atom

The carbon atom is central to all organic compounds. The atomic number of carbon
is 6, and its electronic structure is 1s 2 2s2 2p2. Two stable isotopes of carbon exists 12C and
13
C. With four electron in its outer shell, carbon has ON ranging from +4 to -4, and it forms
predominantly covalent bonds. Carbon occurs as the free element in diamond, graphite,
coal, coke, carbon black, charcoal, lampblack and buckminsterfullence.
A carbon atom usually forms four covalent bonds; each bond result from two atoms
sharing a pair of electrons. The number of electron pairs that two atoms share determines
whether the bond is single or multiple. In a single bond, only one pair of electrons is shared
by the atoms. Carbon also forms multiple bonds by sharing two or three pairs of electrons
between two atoms. The double bond formed by sharing two electron pairs is stronger than
a single bond, but not twice as strong. It is also shorter than a single bond. Similarly, the
triple bond formed by sharing three electron pairs is stronger and shorter than a double
bond. An organic compound is classified as saturated if it contains only single bond and as
unsaturated if the molecules possess one or more carbon-carbon bonds.
Formulas of organic molecules are also represented differently than those of
inorganic compounds, A formula gives information about the composition of a compound. In
a structural formula, the arrangement of the atoms within a molecule is clearly shown.
Organic chemists often shorten these structural formulas into a final type called condensed
structural formulas.
H H
| |
Ex. H – C-C-H CH3CH3
| | Condensed structural formula
H H
Structural formula

HYDROCARBONS

Hydrocarbons are compounds that are composed entirely of carbon and hydrogen
atoms bonded to each other by covalent bonds. Hydrocarbons are classified into two major
categories: aliphatic and aromatic. The term aromatic refers to compounds that contain
benzene rings. All hydrocarbons that are not aromatic are often described as aliphatic. The
aliphatic hydrocarbons include the alkanes, alkenes, alkynes and cycloalkanes.

1
Saturated Hydrocarbons: Alkanes
The alkanes, also known as paraffins or saturated hydrocarbons, are straight-or-
branched-chain hydrocarbons with only single covalent bonds between the carbon atoms.

Name Molecular Formula, CnH2n+2 Condensed Structural Formula

Methane CH4 CH4
Ethane C2H6 CH3CH3
Propane C3H8 CH3CH2CH3
Butane C4H10 CH3CH2CH2CH3
Pentane C5H12 CH3CH2CH2CH2CH3
Hexane C6H14 CH3CH2CH2CH2CH2CH3
Heptane C7H16 CH3CH2CH2CH2CH2CH2CH3
Octane C8H18 CH3CH2CH2CH2CH2CH2CH2CH3
Nonane C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3
Decane C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3

Naming Organic Compounds

Alkyl groups have the general formula CnH2n+1 (one less hydrogen atom than the
corresponding alkane). The missing H atom may have detached from any carbon in the
alkane. The name of the group is formed from the name of the corresponding alkane by
simply dropping –ane and substituting a –yl ending.

Names and Formulas of Selected Alkyl Groups

CH3- methyl CH3(CH2)4CH2- hexyl
CH3CH2- ethyl CH3(CH2)5CH2- heptyl
CH3CH2CH2- propyl CH3(CH2)6CH2- octyl
CH3CH2CH2CH2- butyl CH3(CH2)7CH2- nonyl
CH3(CH2)3CH2- pentyl CH3(CH2)8CH2- decyl

IUPAC Rules for naming Alkanes

1. Select the longest continuous chain of carbon atoms as the parent compound, and
consider all the alkyl groups attached to it as branch chains that have replaced hydrogen
atoms of the parent hydrocarbon. The name of the alkane consists of the name of the parent
compound prefixed by the names of the branched-chain alkyl groups attached to it.
2. Number the carbon atoms in the parent carbon chain from one end to the other, starting
from the end closest to the first carbon atom that has a branch chain.

CH3
|
CH3CH2CHCH2CH2CH3
1 2 3 4 5 6

3. Name each branch-chain alkyl group and designate its position on the parent carbon
chain by a number (e.g., 3-methyl means a methyl group attached to carbon 3).
4. When the same alkyl-group branch chain occurs more than once, indicate this by a prefix
(di-, tri-, tetra-, etc.) written in front of the alkyl-group name (e.g., dimethyl indicates two
methyl groups). The numbers indicating the positions of these alkyl groups are separated by
a comma, followed by a hyphen and placed in front of the name (e.g., 2,3-dimethyl).

2
5. When several different alkyl groups are attached to the parent compound, list them in
alphabetical order (e.g., ethyl before methyl as in 3-ethyl-4-methyloctane).

Example:
1. How would you write the structural formula for 2-methylpentane? An analysis of its name
gives us this information:
a) The parent compound pentane, contains five carbons. Write and number the five-
carbon skeleton of pentane (at this point, numbering can either from right to left or
from left to right):
C–C–C–C–C
1 2 3 4 5

b) Put a methyl group on carbon 2 (“2-methyl” in the name gives this information)
CH3
|
C–C–C–C–C
1 2 3 4 5

c) Add hydrogen to give each carbon four bonds. The structural formula is:

H CH3 H H H CH3
| | | | | |
H-C–C–C–C–C-H CH3 – CH – CH2 – CH2 – CH3
| | | | | 2-methylpentane
H H H H H

2. Write the structural formula for 2,3-dimethylbutane.

Explanation: The name of the compound is 2,3-dimethylbutane. The longest carbon
chain is four, indicating butane, “dimethyl” indicates two methyl groups; “2,3-“ means
one CH3 is on carbon 2 and one is on carbon 3 (Rule 4)
CH3 CH3
| |
CH3 – CH – CH – CH3
1 2 3 4

2,3-dimethylbutane

3. Write the structural formula for 2,2,4-trimethylhexane

Explanation: The name hexane indicates a six-carbon chain,“trimethyl” indicates
three methyl groups; 2 methyl groups on carbon 2 and one on carbon 4.

CH3 CH3
| |
CH3 – C – CH2 – CH – CH2 – CH3
1 2 3 4 5 6
|
CH3
2,2,4-trimethylhexane

4. Write the structural formula for 3-ethylpentane

Explanation: The name pentane indicates five-carbon chain. An ethyl group is written
as CH3CH2- . Attach this group to carbon 3

3
 CH2CH3
|
C–C–C–C–C
1 2 3 4 5

Now add hydrogen atoms to give each carbon atom four bonds. Carbons 1 and 5
each need three H atoms; carbon 2 and 4 each need two H atoms; and carbon 3
needs one H atom. The formula is complete:
CH2CH3
|
CH3CH2CH CH2CH3
3-ethylpentane

5. Write the structural formula for 4-ethyl-2,4-dimethyloctane

Explanation: In this compound, the longest carbon chain is eight. The groups that are
attached on the octane chain are named in alphabetical order (Rule 5). An ethyl
group is on carbon 4; methyl groups on carbon 2 and carbon 4.
CH3 CH2CH3
| |
CH3 – CH – CH2 – C – CH2 – CH2 – CH2 – CH3
1 2 3 4
| 5 6 7 8

CH3
4-ethyl-2,4-dimethyloctane
Name the following compounds:

1. CH3
|
CH3CH2CH2CH2CHCH3
Solution: The longest continuous carbon chain contains six carbon atoms (Rule 1).
Thus, tne parent name of the compound is hexane. Number the carbon atom from right to
left so that the methyl group attached carbon 2 is given to the lowest possible number (Rule
2). With a methyl group on carbon 2, the name of the compound is 2-methylhexane (Rule 3).

2. CH2CH3
|
CH3CH2CHCH2CH2CHCH3
|
CH3
Solution: The longest continuous carbon chain contains seven carbon atoms. Thus,
the parent name of the compound is heptane. Number the carbon atom from right to left,
there is a methyl group on carbon 2 and an ethyl group on carbon 5, so the name of the
compound is 5-ethyl-2-methylheptane. Note that ethyl is name before methyl (alphabetical
order, Rule 5).

3. CH3 CH2CH3
| |
CH3CH2CHCH2CHCH2CHCH3
|
CH2CH3

4
Solution: The longest continuous carbon chain contains eight carbon atoms. Thus,the parent
name of the compound is octane .Number the carbon atom from right to left, there are two
ethyl groups on carbon 2 and carbon 4; one methyl group on carbon 6, so the name of the
compound is 2,4-diethyl-6-methyloctane.

ALKENES

Molecules of the alkene series of hydrocarbons are characterized by having two

adjacent carbon atoms joined to one another by a double bond. Any member in this series
can be represented by the general formula C nH2n.

Nomenclature of Alkenes
The names of alkenes are derived from the names of corresponding alkanes.

IUPAC Rules for Naming Alkenes

1. Select the longest continuous carbon-carbon chain that contains the double bond.
2. Name this parent compound as you would an alkane, but change the –ane ending to –ene
for example, propane is changed to propene .

CH3CH2CH3 CH3CH = CH2

propane propene
3. Number the carbon chain of the parent compound starting with the end nearer to the
double bond. Use the smaller of the two numbers on the double-bonded carbon atoms to
indicate the position of the double bond. Place this number in front of the alkene name; for
example, 2-butene means that the carbon-carbon double bond is between carbon 2 and 3.
4. Branch chains and other groups are treated as in naming alkanes, by numbering and
assigning them to the carbon atom to which they are bonded.

Study the following examples of named alkenes

CH3CH2CH = CH2 CH3CH = CHCH3

4 3 2 1 1 2 3 4

1-butene 2-butene

CH3 CH2CH2CH3
| |
CH3CHCH=CH2 CH3CH2CH2 CHCH=CH2
4 3 2 1 6 5 4 3 2 1

3-methyl-1-butene 3-propyl-1-hexene

To write a structural formula from a systematic name, the naming process is reversed
For example, how would you write the structural formula for 4-methyl-2-pentene? The name
indicates: 1. Five carbon atoms in the longest chain
2. A double bond between carbon 2 and 3
3. A methyl group on carbon 4

Write five carbon atoms in a row. Place a double bond between carbons 2 and 3, and
place a methyl group on carbon 4

5
 CH3
|
C–C=C–C–C
1 2 3 4 5

carbon skeleton
Now add hydrogen atoms to give each carbon atom four bonds. Carbons 1 and 5
each need three H atoms; carbons 2, 3 and 4 each need one H atom. The complete formula
is:
CH3
|
CH3CH=CHCHCH3
4-methyl-2-pentene

Example:
Write structural formulas for:
1. 2-pentene
Solution: The stem pent- indicates a five-carbon chain; the suffix –ene indicates a
carbon-carbon double bond; the number 2 locates the double bond between carbons 2 and
3. Write five carbon atoms in a row and place a double bond between 2 and 3:

C–C=C–C–C
1 2 3 4 5

Add hydrogen atoms to give each carbon atoms four bons. Carbon 1 and 5 need three H
atoms; carbons 2 1nd 3 each need one H atom; carbon 4 needs two H atoms. The complete
formula is:
CH3CH=CHCH2CH3

2. 4,7-dimethyl-3-octene
Solution: Octene, like octane, indicates an eight-carbon chain. The chain contains a
double bond between carbons 3 and 4; two methyl groups on carbons 4 and 7. Write eight
carbon atoms in a row, place a double bond between carbons 3 and 4 and place methyl
group on carbon 4 and carbon 7:
CH3 CH3
| |
C–C–C=C–C–C–C–C
1 2 3 4 5 6 7 8

Now add hydrogen atoms to give each carbon atom four bonds. The complete formula is:

CH3 CH3
| |
CH3CH2CHCCH2CH2CHCH3
4,7-dimethyl-3-octene

3. 3-ethyl-5-methyl-2-hexene
Solution: The stem hex- indicates a six-carbon chain. The chain contains a double
bond between carbon s 2 and 3, one ethyl group on carbon 3 and a methyl group on carbon
5. Write six carbon atoms in a row, place a double bond between carbons 2 and 3, and place
an ethyl group on carbon 3 and a methyl group on carbon 5.

6
 CH2CH3
|
C–C=C–C–C–C
|
CH3

Add hydrogen atoms to give each carbon atom four bonds. The complete formula is:

CH2CH3
|
CH3CH=CCH2CHCH3
|
CH3
3-ethyl-5-methyl-2hexene

Name this compound::

1. CH3 CH2CH3
| |
CH3CHCH=CCH2CH2CHCH2CH3
1 2
| 3 45 6 7 8 9

CH3
Solution: The longest carbon chain contains nine carbons. A double bond is between
carbons 3 and 4. Two methyl groups are attached to carbons 2 and 4 and an ethyl group on
carbon 7. The complete name is: 7-ethyl-2,4-dimethyl-3-nonane

2. CH2CH3
|
CH2=CCHCH2CHCH2CH3
1 2 3 4
| |5 6 7
CH3 CH2CH3
Solution: The longest carbon chain contains seven carbons. A double bond is between
carbons 1 and 2. One methyl group is on carbon 2 and two ethyl groups are attached to
carbons 3 and 5. The complete name of the compound is 3,5-diethyl-2-methyl-1-heptene

3. CH2CH2CH3
|
CH3CH=CHCHCH2CHCH2CH3
1 2 3 4 5
|6 7 8

CH2CH3
Solution: The longest carbon chain contains eight carbons. A double bond is between
carbons 2 and 3. An ethyl group is on carbon 6 and a propyl group is on carbon 4. The
complete name of the compound is 6-ethyl-4-propyl-2-octene

POLYMERS

The word polymer has a Greek origin, which means many units (parts). Polymer is
defined as a chemical substance of a high molar mass formed by the combination of a large
number of simple molecules, called monomers. Ex.

7
 n(CH2=CH2) → [ -CH2 – CH2 - ]n
ethylene polyethylene

Polymerization
The process by which the monomers get combined and transformed into polymers, is
known as polymerization.
n [ Monomer ] → Polymer

Difference Between Polymers and Macromolecules

Polymers are also called macromolecules due to their large size but converse is not
always true. A macromolecules may not contain monomer units, ex. chlorophyll
(C55H72O5N4Mg) is a macromolecule but not a polymer since there are no monomer units
present so we can conclude that all polymers are macromolecules may be not be polymers
in nature.

Classification of Polymers Based on Source of Origin

1. Natural polymers. Those polymers which occur in nature, i.e., in plants and animals are
called natural polymers.

Natural Polymer Occurrence

1. Starch Main reserve food of plants
2. Cellulose Main structure material of plants
3. Proteins Act as building blocks in animals
Occurs as latex (a colloidal dispersion
4. Natural rubber of rubber in water) in the bark of many
tropical trees

2. Synthetic polymers. The polymers which are prepared in the laboratory are known as
synthetic polymers or man-made polymers, ex., polythene, synthetic rubber, PVC, nylon-66,
teflon, orlon, etc
3. Semisynthetic polymers. Polymers obtain by making some modification in natural
polymers by artificial means, are known as semi synthetic polymers, ex., cellulose acetate
(rayon), vulcanized rubber.

Classification of Polymers Based on Mode of Polymerization

1. Addition polymers. The polymers formed by polymerization of monomers containing

double or triple bonds (unsaturated compounds) are called addition polymers. Addition
polymers have the same empirical formula as their monomers.
Addition polymers can further be classified on the basis of the types of monomers
into the following two classes:
a) Homopolymers. The polymer which are obtained by the polymerization of a single
type of monomer are called homopolymers.
n(CH2 = CH2) → ( -CH2 – CH2 -)n
ethene polythene
b) Copolymers. The polymers which are obtained by the polymerization of two or
more different types of monomers are called copolymers.
2. Condensation polymers. The polymers which are formed by the combination of

8
monomers with compound containing –COOH) to form a bond between N and C plus a H 2O
molecule.

H O H O
| || | ||
- N – H + H – O – C - → - N – C - + H2O

Classification of Polymers Based on Molecular Forces

1. Elastomer. This is a material that exhibits rubbery or elastic behaviour. When subjected
to stretching or bending, an elastomer regains its original shape upon removal of the
distorting force, if it has not been distorted beyond some elastic limit. Rubber is the most
familiar example of an elastomer.
2. Fibers. Fibers belong to a class of polymers which are thread-like and can be woven into
fabrics. These are widely used for making clothes, nets, ropes, gauzes, etc. Fibers possess
strong intermolecular forces such as hydrogen bonding. The fibers are crystalline in nature
and have sharp melting points.
3. Thermoplastic. Plastics are materials that can be formed into various shapes, usually
by the application of heat and pressure. Thermoplastic materials can be reshaped, For
example, plastic milk containers are made from the polymer polyethylene. These containers
can be melted down and the polymer recycled for some other use
4. Thermosetting plastic is shaped through irreversible chemical processes and, therefore,
cannot be reshaped readily.

POLYETHYLENE

The prevalent plastic polyethylene is the simplest and least expensive synthetic
polymer. It is familiar to us in the form of plastic bags for packaging fruits and vegetables,
garment bags for dry-cleaned clothing, garbage-can liners, and many other items.
Polyethylene is made from ethylene (CH2=CH2), an unsaturated hydrocarbon. Ethylene is
produced in large quantities from the cracking of petroleum, a process by which large
hydrocarbon molecules are broken down into simpler hydrocarbons.
With pressure and heat and in the presence of a catalyst, ethylene monomers join
together in long chains.
H H H H H H H H H H H H H H H H
| | | | | | | | | | | | | | | |
…+ C = C +C =C+C = C + C=C+… → - C - C –C – C - C –C- C - C -
| | | | | | | | | | | | | | | |
H H H H H H H H H H H H H H H H

Using condensed formulas, this becomes

…+CH2=CH2+CH2=CH2+CH2=CH2+CH2=CH2+ → -CH2CH2CH2CH2CH2CH2CH2-

9
Using abbreviated forms
H H H H
| | | |
nC=C → -C -C- or nCH2=CH2 → [-CH2CH2-]n
| | | |
H H H H n

POLYPROPYLENE

Most of the many familiar addition polymers are made from the derivatives of ethylene
in which one or more of the hydrogen atoms are replaced by another atom or group.
Replacing one of the hydrogen atoms with a methyl group gives the monomer propylene
(propene). Polypropylene molecules, except that there is a methyl group (-CH3) attached to
every other carbon atom.

-CH2 – CH – CH2 – CH – CH2 – CH – CH2 – CH or -CH2 – CH -

| | | | |
CH3 CH3 CH3 CH3 CH3 n
Polypropylene

The chain of carbon atoms is called the polymer backbone. Groups attached to the
backbone, such as the CH3 groups of polypropylene, are called pendant groups.
Polypropylene is a tough plastic material that resists moisture, oils and solvents. It is
molded into hard-shell luggage, battery cases, and various kinds of appliance parts. It is also
used to make packaging material, fibers for textiles such as upholstery fabrics and carpets,
and ropes that float. Because of polypropylene‟s high melting point (121 oC), objects made of
it can be sterilized with steam.

POLYSTYRENE

Replacing one of the hydrogen atoms in ethylene with a benzene ring gives monomer
called styrene, which has the formula C6H5CH=CH2 where C6H5 represent the benzene
ring. Polymerization of styrene produces polystyrene, which has benzene rings as pendant
group.

Polystyrene is the plastic used to make transparent disposable drinking cups. With color and
filler added, it is the material of thousands of inexpensive toys and household items. When a
gas is blown into styrene material (called Styrofoam) of ice chests and disposable coffee
cups. The polymer can easily be formed into shapes as packing material for shipping
instruments and appliances.

10
VINYL POLYMERS

Replacing one of the hydrogen atoms of ethylene with a chlorine atom gives vinyl
chloride (CH2=CHCl), a compound that is a gas at room temperature. Polymerization of vinyl
chloride yields the tough thermoplastic material PVC. A segment of the PVC molecule is
shown below

- CH2CH – CH2CH - CH2CH – CH2CH -

| | | |
Cl Cl Cl Cl
Polyvinyl chloride (PVC)

PVC is readily formed into various shapes. The clear, transparent polymer is used in plastic
wrap and clear plastic bottles. Adding color and other ingredients to a vinyl plastic yields
artificial leather. Most floor tile and shower curtains are made from vinyl plastics, which are
also widely used to simulate wood in home siding panels and window frames. About 40% of
the PVC produced is molded into pipes.

PROCESSING POLYMERS

In everyday life, many polymers are called plastics. In chemistry, a plastic material is
one that can be made to flow under heat and pressure. The material can then be shaped in
a mold or in other ways. Plastic products are often made from granular polymeric material. In
compressing molding, heat and pressure are applied directly to such grains in the mold
cavity. In transfer molding, the polymer is softened by heating before being poured into
molds to harden.

There are several methods of molding molten polymers. In injection molding, the
plastic is melted in a heating chamber and then forced by a plunger into cold molds to set. In
extrusion molding, the melted polymer is extruded through a die in continuous form to be cut
into lengths or coiled. Bottles and similar hollow objects often are blow-molded; a “bubble” of
molten polymer is blown up like a balloon inside a hollow mold.

RUBBER AND OTHER ELASTOMERS

Although rubber is a natural polymer, it was the basis for much of the development of
the synthetic polymer industry. Natural rubber can be broken down into a simple
hydrocarbon called isoprene. Isoprene is a volatile liquid, whereas rubber is a semisolid,
elastic material. Chemists can make polyisoprene, a substance identical to natural rubber,
except that the isoprene comes from petroleum refineries rather than the cells of rubber
trees.

n CH2 + C – CH = CH2 → [ - CH2 – C = CH – CH2 - ]n

| |
CH3 CH3
Isoprene Polyisoprene (rubber)

Synthetic Rubber
Natural rubber is a polymer of isoprene, and some synthetic elastomers are closely
related to natural rubber. For example, polybutadiene is made from the monomer butadiene

11
(CH2=CH-CH=CH2) which differs from isoprene only in that it lacks a methyl group on the
second carbon atom. Polybutadiene is made rather easily from this monomer.

n CH2 = CH – CH = CH2 → [ - CH2 – CH = CH – CH2 - ]n

However, this polymer has only fair tensile strength and poor resistance to gasoline and oils.
These properties limit its value for automobile tires, the main use of elastomers.
Another synthetic elastomer, polychloroprene (Neoprene), is made from a monomer
similar to isoprene, but with a chlorine in place of the methyl group on isoprene.

n CH2 = C – CH + CH2 → [ - CH2 – C = CH – C

| |
Cl Cl
Neoprene is more resistant to oil and gasoline than other elastomer are. It is used to make
gasoline pump hoses and similar items used at automobile service stations.
Styrene-butadiene rubber (SBR) is a polymer of styrene (about 25%) and butadiene
(about75%).

Polymers in Paints
A surprising use for elastomers is in paints and other coatings. The substances in a
paint that hardens to form a continuous surface coating, often called binder, or resin, is a
polymer, usually an elastomer. Paint made with elastomers is resistant to cracking. Various
kinds of polymers can be used as binders, depending on the specific qualities desired in the
paint. Latex paints, which have polymer particles dispersed in water, and thus avoiding the
use of organic solvents. Brushes and rollers are easily cleaned in soap and water.

Condensation Polymers

1. Nylon 6 – one type of nylon, is a six-carbon carboxylic acid with an amino group on the
sixth carbon atom: 6 aminohexanoic acid (HOOCCH 2CH2CH2CH2CH2NH2)
2. Nylon 66 – another nylon made by condensation of two different monomers: 1,6-hexane
diamine (H2NCH2CH2CH2CH2CH2CH2NH2) and adipic acid (HOOCCH2CH2CH2CH2COOH).
Each monomer has six carbon atoms.
Although nylon can be molded into various shapes, most nylon is made into fibers.
Some is spun into fine thread to be woven into silklike fabrics, and some is made into yard
that is much like wood. Carpeting, which was once made primarily from wool, is now made
largely from nylon.
3. Polyester – is a condensation polymer made from molecules of alcohol and carboxylic
acid functional groups. The most common polyester is made from ethylene glycol and
terephthalic acid. It is called polyethylene terephthalate (PET). PET can be molded into
bottles for beverages and other liquids. It can be formed into a film, which is used to laminate
documents and to make tough packaging tape. Polyester fibers are used on premium wood
products such as guitars, pianos, and the interiors of vehicles and boats. Polyester fibers are
strong, quick-drying and resistant to mildew, wrinkling, stretching and shrinking. They are
used in home furnishings such as carpets, curtains, sheets and pillow cases and upholstery.
Because polyester fibers do not absorb water, they are ideal for outdoor clothing to be worn
in wet and damp environments and for insulation in boots and sleeping bags. For other
clothing, they are blended with cotton for more natural feel. A familiar use of polyester film is
in the shiny balloons that are filled with helium to celebrate special occasion.

12
4. Resins – Phenolic resins are used as a substitute for porcelain and in board and tabletop
game pieces such as billiard balls, dominoes and checkers.
5. Polycarbonates are “clear as glass” polymers tough enough to be used in bulletproof
windows. They are also used in protective helmets, safety glasses and even dental crowns.

6. Polyurethanes – may be elastomeric or tough and rigid, depending on the monomers

used. They are common in foamed padding (foam rubber) in cushions, mattresses and
padded furnitures. They are also used for skate wheels, in running shoes and protective
gear for sports activities.
7. Epoxies – make excellent surface paints and coatings. They are used to protect steel
pipes and fittings from corrosion. The inside of metal cans are often coated with epoxy to
prevent rusting, especially in cans for acidic foods like tomatoes.

13
 EXERCISES

I – Write the structural formulas for:

1. 3-ethyl pentane
2. 2,2,4-trimethyl heptane
3. 2-ethyl-3,5-dimethylhexane
4. 2,4-diethyl-3-methylhexane
5. 5,6-diethyl-2-methyl-4-propyloctane

II – Write the structural formulas for:

1. 3,5-dimethyl-2-heptene
2. 4-ethyl-2-methyl-3-hexene
3. 3-ethyl-3-methyl-1-pentene
4. 2,5-diethyl-7-methyl-3-nonene
5. 4-ethyl-3,5-dimethyl-2-octen

III – Name these compounds:

1. CH2CH2CH3
|
CH3CH2CHCH2CHCH2CHCH3
| |
CH3 CH3

2. CH2CH3 CH2CH3
| |
CH3CHCH2CH2CHCH2CHCH2CH3
|
CH3

3. CH3 CH3
| |
CH3CHCHCH2CHCH2CH3
|
CH2CH3

4. CH3 CH2CH3
| |
CH3C=CHCH2CHCH2CHCH3
|
CH2CH2CH3

14
5. CH2CH2CH3
|
CH3CH2CHCHCH2CHCH=CH2
| |
CH3 CH3

CHEMISTRY LABORATORY

ACTIVITY 6

Write the condensed structural formula for the following compounds:

1. 4-methyl-2-methylhexane
2. 4-ethyl-2,4,8-trimethyldecane
3. 2,3-diethyl-5-methylheptane
4. 2-ethyl-1,3-dimethyl-5-propyloctane
5. 5,6-diethyl-3,7-dimethylnonane
6. 3-ethyl-3,5-dimethyl-1-hexene
7. 3,4-diethyl-3-hexene
8. 4-ethyl-2,5-dimethyl-2-heptene
9. 3-ethyl-3-methyl-1-pentene
10. 2,6-diethyl-3,6-dimethyl-3-octene

15
 CHAPTER 7

ENGINEERED NANOMATERIALS

The prefix nano means 10-9. When people speak of “nanotechnology”, they usually
mean making devices that are on the 1-100 nm scale. It turns out that the properties of
semiconductors and metals change in size range. Nanomaterials – materials that have
dimensions on the 1 -100 nm scale.

What are nanomaterials?

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 a human hair. Nanomaterials are of interest
because of this scale unique optical, magnetic electrical and other properties emerge these
emergent properties have the potential for great impact in electronics, medicine and other
fields.

Where are nanomaterials found?

Some nanomaterials occur naturally, but of particular interest are engineered

nanomaterials (EN), which are designed for, and already being used in many commercial
products and processes. They can be found in such things as sunscreens, cosmetics,
sporting goods, stain resistant clothing, tires, electronics, as well as many other everyday
items, and are used in medicine for purposes of diagnosis, imaging and drug delivery.
Nanomaterials are already in commercial use, with some having been available for
several years or decades. The range of commercial products available today is very broad,
including stain-resistant and wrinkle-free textiles, cosmetics, sunscreens, electronics, paints
and varnishes. Nanocoatings and nanocomposites are finding uses in diverse consumer
products, such as windows, sports equipment, bicycles and automobiles. There are novel
UV-blocking coatings on glass bottles which protect beverages from damage by sunlight,
and longer-lasting tennis balls using butyl-rubber/nano-clay composites. Nanoscale titanium
dioxide, for instance, is finding applications in cosmetics, sun-block creams and self-cleaning
windows, and nanoscale silica is being used as filler in a range of products, including
cosmetics and dental fillings.

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 (eg. surface films), two
dimensions (eg. strands or fibers), or three dimensions (eg. particles). They can exist in
single, fused, aggregated or agglomerated forms with spherical, tubular, and irregular
shapes. 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).
Nanostructured materials are classified as zero dimensional, one dimensional, teo
dimensional, three dimensional nanostructures. Nanomaterials are materials which are
characterized by an ultra fine grain size (< 50 nm) or by a dimesionality limited to 50 nm.

16
Why so much interest in nanomaterials?

These materials have created a high interest in recent years by virtue of their unusual
mechanical, electrical, optical and magnetic properties. Some examples are given below:
● Nanophase ceramics are of particular interest because they are more ductile at

elevated temperatures as compared to the coarse-grained ceramics.

● Nanostructured semiconductors are known to show various non-linear optical
properties. Semiconductor Q-particles also show quantum confinement effects
which may lead to special properties, like the luminescence in silicon powders and
silicon germanium quantum dots as infrared optoelectronic devices. Nanostructured
semiconductors are used as window layers in solar cells.
● Nanosized metallic powders have been used for the production of gas tight
materials, dense parts and porous coatings. Cold welding properties combined
with the ductility make them suitable for metal-metal bonding especially in the
electronic industry.
● Single nanosized magnetic particles are mono-domains and one expects that also
in magnetic nanophase materials the grains correspond with domains, while
boundaries on the contrary to disordered walls. Very small particles have special
atomic structures with discrete electronic states, which give rise to special
properties in addition to the super-paramagnetism behaviour. Magnetic nano
composites have have been used for mechanical force transfer (ferrofluids), for
high density information storage and magnetic refrigeration.
● Nanostructured metal clusters and colloids of mono- or plurimetallic composition
have a special impact in catalytic applications. They may serve as prescursors for

17
 new type of heterogeneous catalysts (Cortex-catalysts) and have been shown to
offer substantial advantages concerning activity, selectivity and lifetime in chemical
transformations and electrocatalysis (fuel cells). Enantioselective catalysis was
also achieved using chiral modifiers on the surface of nanoscale metal particles.
● Nanostructured metal-oxide thin films are receiving a growing attention for the
realization of gas mentors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with
enhanced sensitivity and selectivity. Nanostructured metal-oxide (MnO2) finds
application for rechargeable batteries for cars or consumer goods. Nanocrystalline
silicon films for highly transparent contacts in thin film solar cell and nano-
structured titanium oxide porous films for its high transmission and significant
surface area enhancement leading to strong absorption in dye sensitized solar
cells.
● Polymer based composites with a high content of inorganic particles leading to a
high dielectric constant are interesting materials for photonic band gap structure.

NANOMATERIAL SYNTHESIS AND PROCESSING

We are dealing with very fine structures: a nanometer is billionth of a meter. This
indeed allows us to think in both the „bottom up‟ or „top down‟ approaches to synthesize
nanomaterials, i.e., either to assemble atoms together or to dis-assemble (break, or
dissociate) bulk solids into finer pieces until they are constituted of only a few atoms.

18
METHODS OF CREATING NANOSTRUCTURES

There are many different ways of creating nanostructures: of course, macromolecules

or nanoparticles or bucky balls or nanotubes and so on can be synthesized artificially for
certain specific materials. They can also be arranged by methods based on equilibrium or
near-equilibrium thermodynamics such as methods of self-organization and self-assembly
arranged into useful shapes so that finally the material can be applied to a certain
application.
Nanomaterials can be synthesized by any of the following methods:
1. Pyrolysis
It involves pyrolysis of hydrocarbons such as acetylene at 700 oC in the presence of
Fe-silica or Fe-graphite catalyst under inert conditions.
2. Carbon Arc Method
It is carried out by applying direct current (60-100A and 20-25V) arc between graphite
electrodes of 10-20 μm diameter.
3. Laser Evaporation Method
It involves vaporization of graphite containing small amount of Co and Ni, by exposing
it to laser beam at 1200oC in a quartz tube reactor. An inert gas like argon is allowed to pass
into the reactor to sweep the evaporated carbon atoms from the furnace to the copper
collector, on which the nanomaterials condense.
4. Chemical Vapor Deposition
It involves decomposition of vapour of hydrocarbons such as methane, ethylene,
acetylene, etc., at 1100oC in presence of catalysts like Ni, Co, Fe supported on MgO.

PROPERTIES OF NANOMATERIALS

1. Electrical Properties
The electrical properties of nanomaterials vary between metallic to semiconducting
materials. It depends on the diameter of the nanomaterials. The very high electrical
conductivity of nanomaterial is due to minimum defects in the structure.
2. Thermal Conductivity
The thermal conductivity of nanomaterials are very high, is due to the vibration of cavalent
bonds. Its thermal conductivity is 10 times greater than the metal. The very high thermal
conductivity of nanomaterial is also due to minimum defects in the structure.
3. Mechanical Properties
Nanomaterials are very strong and withstand extreme strain. Most of the materials fracture
on bending because of the presence of more defects, but nanomaterials possess only few
defects on the structure.
4. Optical Properties
The optical properties of nanomaterials depend on parameters such as feature size, shape
surface characteristics, and other variables including doping and interaction with the
surrounding environment or other nanostructures.

APPLICATIONS OF NANOMATERIALS

Below we list some key applications of nanomaterials. Most current applications

represent evolutionary developments of existing technologies: for example, the reduction of
size of electronics devices.
1. Sunscreens and Cosmetics

19
 The traditional chemical UV protection approach suffers from its poor long-term
stability. A sunscreen based on mineral nanoparticles such as titanium dioxide offer several
advantages. Titanium oxide nanoparticles have a comparable UV protection property.
Nanosized titanium dioxide and zinc oxide are currently used in some sunscreens, as they
absorb and reflect ultraviolet (UV) rays and yet are transparent to visible light and so are
more appealing to the consumer. Nanosized iron oxide is present in some lipstick as a
pigment. The use of nanoparticles in cosmetics has raised a number of concerns about
consumer safety
2. Paints
Incorporating nanoparticles in paints could improve their performance, for example by
making them lighter and giving them different properties. Thinner paint coatings
(„lightweighting‟), used for example on aircraft, would reduce their weight, which could be
beneficial to the environment.
3. Displays
The huge market for large area, high brightness, flat-panel displays, as used in
television screens and computer monitors, is driving the development of some nanomaterials
Nanocrystalline zinc selenide, zinc sulfide, cadmium sulfide and lead telluride synthesized by
sol gel techniques are candidates for the next generation of light-emitting phosphors.
4. Batteries
With the growth in portable electronic equipment (mobile phones, laptop computers,
remote sensors), there is great demands for lightweight, high-energy density batteries.
Nanocrystalline materials synthesized by sol-gel techniques are candidates for separator
plates in batteries because of their foam-like (aerogel) structure, which can hold
considerably more energy than conventional ones. Nickel-metal hydride batteries made of
nanocrystalline nickel and metal hydrides are envisioned to require less frequent recharging
and to last longer because of their large surface area.
5. Catalysis
In general, nanoparticles have a high surface area, and hence provide higher catalytic
activity. Catalysis is important for the production of chemicals. Nanoparticles serve as an
efficient catalyst for some chemical reaction, due to the extremely large surface to volume
ratio. Platinum nanoparticles are now being considered in the next generation of automotive
catalytic converters because the very high surface area of nanoparticles could reduce the
amount of platinum required. Some chemical reactions are also carried out using
nanomaterials. For example, reduction of nickel oxide to the base metal Ni.
6. Medicine
Nanotechnology has been a boon in medical field by delivering drugs to specific cells
using nanoparticles. The overall drug consumption and side effects can be lowered
significantly by depositing the active agent in the morbid region only and in no higher dose
than needed. This highly selective approach reduces costs and human suffering.
Nanotechnology can also help to reproduce or to repair damaged tissue, “Tissue
engineering” might replace today‟s conventional treatment like organ transplants or artificial
implants. For example, bones can be regrown on carbon nanotube scaffold.
7. Sensors of gases
The gases like NO2 and NH3 can be detected on the basis of increase in electrical
conductivity of nanomaterials. This is attributed to increase in hole concentration in
nanomaterials due to charge transfer from nanomaterials to NO 2 as the gas molecules bind
the nanomaterials.
8. Food

20
 Nanotechnology can be applied in the production, processing, safety and packaging of
food. A nanocomposite coating process could improve food packaging by placing anti-
microbial agents directly on the surface of the coated film. New foods are among the
nanotechnology created consumer products coming onto the market at the rate of 3 to 4 per
week.
9. Construction
Nanotechnology has the potential to make construction faster, cheaper and safer.
Automation of nanotechnology construction can allow for creation of structures from
advanced homes to massive skyscrapers much more quickly and at much lower cost. The
Silica (SiO2) is present in conventional concrete as part of the normal mix. When nano silica
is added to concrete the particle packing can be improved mechanical properties. The
addition of nano silica to cement based materials can also control the degradation of the
fundamental C-S-H (calcium silica hydrate) reaction of concrete caused by calcium
leaching in water as well as block mater penetration and therefore lead to improvements in
durability. The strength of concrete can also be increase by adding haematite (Fe2O3)
nanoparticles.
Steel has been widely available material and has a major role in the construction
industry. The use of nanotechnology in steel helps to improve the properties of steel. The
nano size steel produce stronger steel cables which can be used in bridge construction.
The glass is also an important material in construction. Titanium dioxide (TiO2)
nanoparticles are used to coat glazing since it has sterilizing and anti-fouling properties .
The particles catalyze powerful reactions which breakdown organic pollutants, volatile
organic compounds and bacterial membranes. Most of the glass in construction is on the
exterior surface of buildings. So the light and heat entering the building through glass has to
be prevented. The nanotechnology can provide a better solution to block light and heat
coming through windows.
Coatings is an important area in construction. Coatings are extensively use to paint the
walls, doors and windows. Coatings should provides a protective layer which is bound to the
base material to produce a surface of the desired protective or functional properties.
Nanotechnology is being applied to paints to obtained the coatings having self healing
capabilities and corrosion protection under insulation. Since these coatings are hydrophobic
and repels water from the metal pipe and can also protect metal from salt water attack.
10. Agriculture
Applications of nanotechnology have the potential to change the entire agriculture
sector and food industry from production to conversion, processing, packaging,
transportation, and even waste treatment.
11. Energy
The most advanced nanotechnology projects related to energy are: storage,
conversion, manufacturing improvements by reducing materials and process rates, energy
saving and enhanced renewable energy sources. Today‟s best solar cells have layers of
several different semiconductors stacked together to absorb light at different energies but
they still only manage to use 40 percent of the Sun‟s energy. Commercially available solar
cells have much lower efficiencies (15-20%). Nanotechnology could help increase the
efficiency of light conversion by using nanostructures.
12. Other Applications
Some commercial products on the market today utilizing nanomaterials include stain
resistant textiles and reinforced tennis rackets. Companies like Kraft foods are heavily
funding nanomaterials based plastic packing. Food will stay fresh longer if the packaging is

21
less permeable to atmosphere. Coors Brewing company has developed new plastic beer
bottles that stay cold for longer periods of time.

DISADVANTAGES OF NANOMATERIALS

● Instability of the particles - Retaining the active metal nanoparticles is highly challenging,
as the kinetics associated with nanomaterials is rapid. In order to retain nanosize of
particles, they are encapsulated in some other matrix. Nanomaterials are thermodynamically
metastable and lie in the region of high-energy local-minima. Hence they are prone to attack
and undergo transformation. These include poor corrosion resistance, high solubility, and
phase change of nanomaterials. This leads to deterioration in properties and retaining the
structure becomes challenging. Fine metal particles act as strong explosives owing to their
high surface area coming in direct contact with oxygen. Their exothermic combustion can
easily cause explosion.
● Impurity - Because nanoparticles are highly reactive, they inherently interact with
impurities as well. In addition, encapsulation of nanoparticles becomes necessary when they
are synthesized in a solution. The stabilization of nanoparticles occurs because of a non-
reactive species engulfing the reactive nano-entities. Thereby, these secondary impurities
become a part of the synthesized nanoparticles, and synthesis of pure nanoparticles
becomes a highly difficult. Formation of oxides, nitides, etc. can also get aggravated from the
impure environment/ surrounding while synthesizing nanoparticles. Hence retaining high
purity in nanoparticles can become a challenge hard to overcome.
● Biologically harmful – Nanomaterials are usually considered harmful as they become
transparent to the cell-dermis. Toxicity of nanomaterials also appears predominant owing to
their high surface area and enhanced surface activity. Nanomaterials have shown to cause
irritation, and have indicated to be carcinogenic. If inhaled, their low mass entraps them
inside lungs, and in no way they can be expelled out of body. Their interaction with
liver/blood could also prove to be harmful.
● Recycling and disposal – There are no hard-and-fast safe disposal policies evolved for
nanomaterials. Issues of their toxicity are still under question, and result of exposure
experiments are not available. Hence the uncertainty associated with affects of
nanomaterials is yet to be assessed in order to develop their disposal policies.

SELF-ASSESSMENT QUESTIONS

1. How nanotechnology applies to food production?

2. What are nanoparticles, nanotubes and nanofilms?

3. Describe the similarities and differences of carbon fibers and carbon nanotubes?

4. Why are nanomaterials used in cosmetics?

5. What are the advantages of nanocomposite packages?

6. What are the advantages and disadvantages of nanomaterials?

7. What are the potential risks of nanomaterials to the human health and the environment?

8. Explain why carbon nanotubes are considered to be an ideal nanoparticles for

nanocomposite materials.

22
9. What are the dangers of nanotechnology?

10. Explain the advantages of nanocomposites compared to classical (macro) composites.

CMEMISTRY LABORATORY

INDIVIDUAL ACTIVITY: RESEARCH WORK # 3

ENGINEERED NANOMATERIALS

23
 CHAPTER 8

THE CHEMISTRY OF THE ATMOSPHERE

EARTH‟S ATMOSPHERE

The temperature of the atmosphere varies with altitude, and the atmosphere is divided
into four regions based on this temperature profile. Just above the surface , in the
troposphere, the temperature normally decreases with increasing altitude, reaching a
minimum of 215K at about 10 km. Nearly all of us live our entire lives in the troposphere.
Howling winds and soft breezes, and sunny skies - all that we normally think of as “weather”
occur in this region. Commercial jet aircraft typically fly about 10 km (33,000 ft) above Earth,
an altitude that defines the upper limit of the troposphere, which we call the tropopause.
Above the tropopause, air temperature increases with altitude, reaching a maximum of
about 275K at about 50 km. The region from 10 km to 50 km is the stratosphere, and above
it are the mesosphere and thermosphere. Notice in figure 8.1 that the temperature
extremes that form the boundaries between adjacent regions are denoted by the suffix –
pause. The boundaries are important because gases mix across them relatively slowly. For
example, pollutant gases generated in the troposphere pass through the tropopause and find
their way into the stratosphere only very slowly.
Atmospheric pressure decreases with increasing elevation (fig. 8.1), declining much
more rapidly at lower elevations than at higher ones because of the atmosphere
compressibility. Thus the pressure decreases from an average value of 760 torr (101 kPa) at
sea level to 2.3 x 10-3 torr (3.1 x 10-4 kPa) at 100 km, to only 1.0 x 10 -6 torr (1.3 x 10-7 kPa) at
200 km.
The troposphere and stratosphere together account for 99.9% of the mass of the
atmosphere, 75% of which is the mass of the troposphere. Consequently, most of the
chemistry that follows focuses on these two regions.

COMPOSITION OF THE ATMOSPHERE

Earth‟s atmosphere is constantly bombarded by radiation and energetic particles from

the Sun. This barrage of energy has profound chemical and physical effects, especially in
the upper regions of the atmosphere, above about 80 km. In addition, because of Earth‟s
gravitational field, heavier atoms and molecules tend to sink in the atmosphere, leaving
lighter atoms and molecules at the top of the atmosphere. This is why 75% of the
atmosphere‟s mass is in the troposphere. Because of all these factors, the composition of
the atmosphere is not uniform. Table 8.1 shows the composition of dry air near sea level.
Note that although traces of many substances present, N 2 and O2 make up about 99% of
sea-level air. The noble gases and CO2 make up most of the remainder.

Table 8.1 The Major Components of Dry Air Near Sea Level

Component Content (mole fraction) Molar Mass (g/mole)

Nitrogen 0.78084 28.013
Oxygen 0.20948 31.998
Argon 0.00934 39.948
Carbon dioxide 0.000382 44. 0099
Neon 0.00001818 20.183
Helium 0.00000524 4.003

24
 Methane 0.000002 16.043
Krypton 0.00000114 83.80
Hydrogen 0.0000005 2.0159
Nitrous oxide 0.0000005 44.0128
Xenon 0.0000000087 131.30

Figure 8.1 Temperature and pressure in the atmosphere vary as a function

of altitude above sea level

When applied to substances in aqueous solution, the concentration unit parts per
million refers to grams of substance per million parts of solution. When dealing with gases,
however, 1 ppm means one part by volume in 1 million volumes of the whole. Because
volume is proportional to number of moles of gas via the ideal gas equation (PV=nRT),
volume fraction and mole fraction are the same. Thus, 1ppm of a trace constituents of the
atmosphere amounts to 1 mole of that constituent in 1 million moles of air; that is, the
concentration in parts per million is equal to the mole fraction times 10 6. For example, Table
8.1 lists mole fraction of CO 2 in the atmosphere as 0.000382, which means its concentration
in parts per million is 0.000382 x 10 6 = 382 ppm.

Sample Exercises: Calculating the Concentration of Water in Air

1. What is the concentration, in parts per million, of water vapour in a sample of air if the
partial pressure of the water is 0.80 torr and the total pressure of the air is 735 torr?

Given: PH2O = 0.80 torr

PT = 735 torr

25
 Solution:

PH2O = ꭕH2O PT where; ꭕH2O = mole fraction of water vapor

ꭕH2O = PH2O
PT
= 0.80 torr = 0.0011
735 torr
The concentration in ppm is the mole fraction times 10 6
= 0.0011 x 106 = 1100 ppm

2. The concentration of CO in a sample of air is 4.3 ppm. What is the partial pressure of the
CO if the total air pressure is 695 torr?

Solution:

4.3 ppm = ꭕH2O x 106

ꭕH2O = 4.3 = 4.3 x 10-6
106
PH2O = ꭕH2O PT
= (4.3 x 10-6)(695 torr)
= 3.0 x 10-3 torr

3. The average concentration of carbon monoxide in air in Ohio City in 2006 is 3.5 ppm.
Calculate the number of CO molecules in 1.0 L of this air at a pressure of 759 torr and
a temperature of 22oC

Solution:

mole fraction of CO = 3.5 ppm = 3.5 x 10-6

106
V = 1.0 L
P = 759 torr x 1 atm = 0.9987 atm
760 torr
T = 22oC + 273 = 295K
Using the Ideal Gas Equation
PV = nRT
n = PV = (0.9987 atm)(1.0L)
RT (0.0821 L-atm/moleK)(295K)
n = 0.04123 mole
mole fraction of CO = nCO
nT
nCO = (3.5 x 10-6)(0.04123 mole)
nCO = 1.44 x 10-7 mole
no. of CO molecules = 1.44 x 10 -7 mole x 6.022 x 1023 molecules
1 mole
16
= 8.69 x 10 molecules

4. a) From the data in Table 8.1, what is the concentration of neon in the atmosphere in
ppm.? b) What is the concentration of neon in the atmosphere in molecules per L,
assuming an atmospheric pressure of 730 torr and a temperature of 296K?

26
 Solution:

For Ne
mole fraction = 0.00001818 = 1.818 x 10 -5
molar mass = 20.183 g/mol
a) ppm = mole fraction x 106
ppm of Ne = 1.818 x 10-5 x 106 = 18.18 ppm
b) P = 730 torr x 1 atm__ = 0.96 atm
760 torr
T = 296 K
V = 1L
PV = nRT
n = PV = (0.96 atm)(1 L)
RT (0.0821 L-atm/mole K)(296 K)
n = 0.04 mole
mole fraction of Ne = nNe
nT
nNe = (1.818 x 10 )(0.04 mole) = 7.272 x 10 -7 mole
-5

no. of Ne molecules = 7.272 x 10 -7 mole x 6.022 x 1023 molecules

1 mole
17
= 4.38 x 10 molecules

Other minor constituents if the troposphere, in addition to CO 2, are listed in the table.

Table 8.2 Sources and Typical Concentrations of Some Minor

Atmospheric Constituents
Constituents Sources
Carbon dioxide, CO2 Decomposition of organic
matter, release from
oceans, fossil-fuel
combustion
Carbon monoxide, CO Decomposition of organic
matter, industrial processes,
fossil-fuel combustion
Methane, CH4 Decomposition of organic
matter, natural-gas seepage,
livestock emission
Nitric oxide, NO Atmospheric electrical
discharges, internal
combustion engines,
combustion of organic matter
Ozone, O3 Atmospheric electrical
discharges, diffusion
from the stratosphere,
photochemical smog
Sulfur dioxide, SO2 Volcanic gases, forest fires,
bacterial action, fossil-fuel
combustion, industrial
Typical Concentration
382 ppm
throughout
troposphere
0.05 ppm in
unpolluted air; 1-50
ppm in urban areas
1.77ppm
throughout
troposphere
0.01 ppm in unpolluted
air, 0.2 ppm in smog
0 to 0.01 ppm in
unpolluted air; 0.5 ppm
in photochemical smog
0 to 0.01 ppm in
unpolluted air; 0.1-2
ppm in polluted

27
PHOTOCHEMICAL REACTIONS IN THE ATMOSPHERE

Although the atmosphere beyond the stratosphere contains only a small fraction of the
atmospheric mass, it forms the outer defense against the hail of radiation and high energy
particles that continuously bombard earth, As the bombarding radiation passes through the
upper atmosphere, it causes two kinds of chemical changes: photodissociation and
photoionization. These processes protect us from high-energy radiation by absorbing most
of the radiation before it reaches the troposphere. If it were not for these chemical
processes, plant and animal life as we know it could not exist on Earth.
The Sun emits radiant energy over a wide range of wavelength (Fig. 8.2). To
understand the connection between the wavelength of radiation and its effect on atoms and
molecules, recall the electromagnetic radiation can be pictured as a stream of photons. The
energy of each photon is given by E = hv, where h is the Planck‟s constant v is the radiation
frequency. For a chemical change to occur when radiation strikes atoms or molecules, two
conditions must be met. First, the incoming photons must have sufficient energy to break a
chemical bond or remove an electron from the atom or molecule. Second, the atoms or
molecules being bombarded must absorb these photons. When these requirements are met,
the energy of the photons is used to do work associated with some chemical change.
The rupture of a chemical bond resulting from absorption of a photon by a molecule is
called photodissociation. No ions are formed when the bond between two atoms is cleaved
by photodissociation. Instead, half the bonding electrons stay with one atom and half stay
with other atom. The result is two electrically neutral particles.
One of the most important processes occurring above an altitude of about 120 km is
photodissociation of the oxygen molecule:
O = O + hv → O + O
The minimum energy required to cause this change is determined by the bond energy (or
dissociation energy) of O2, 495 kJ/mole.

Fortunately for us, O2 absorbs much of the high-energy, short wavelength radiation
from the solar spectrum before that radiation reaches the lower atmosphere. As it does,
atomic oxygen, O2, is formed. The dissociation of O2 is very extensive at higher elevations.
At 400 km, for example, only 1% of the oxygen is in the form of O 2; 99% is atomic oxygen. At
130 km, O2 and atomic oxygen are just equally abundant. Below 130 km, O 2 is more
abundant than atomic oxygen because most of the solar energy has been absorbed in the
upper atmosphere.

Sample Exercise: Calculating the Wavelength Required to Break a Bond

1. What is the maximum wavelength of light, in nanometers, that has enough energy per
photon to dissociate the O2 molecule?

Analyze: We are asked to determine the wavelength of a photon that has just enough
energy to break O=O double bond in O2.
The dissociation energy of O2 is 495 kJ/mole
E = 495 kJ x 1000J x 1 mole______
mole 1 kJ 6.022 x 1023 molecules
E = 8.22 x 10-19 J/molecule

28
 frequency v of a photon
v = E_ h(Plank‟s constant) = 6.629 x 10 -34 J-s
h
v = 8.22 x 10-19 J
6.629 x 10-34 J-s
v = 1.24 x 1015 s-1
wavelength of light, λ
λ = c = ( 3.0 x 108 m/s )( 109 nm )
v 1.24 x 1015/s 1m
λ = 242 nm
Thus, light of wavelength 242 nm, which is in the UV region of the electromagnetic
spectrum, has sufficient energy per photon to photodissociate an O2 molecule. Because
photon energy increases as wavelength decreases, any photon of wavelength shorter than
242 nm will have sufficient energy to dissociate O 2.

Figure 8.2 The solar spectrum above Earth‟s atmosphere compared to

that at sea level. The more structured curve at sea level is due to gases in
in the atmosphere absorbing specific wavelengths of light. “Flux”, the unit
on the vertical axis, is light energy per area per unit of time.

The dissociation energy of N2 is very high, 941 kJ/mole, only photons having a
wavelength shorter than 127 nm possess sufficient energy to dissociate N 2. Furthermore, N2
does not readily absorb photons, even when they possess sufficient energy. As a result, very
little atomic energy is formed in the upper atmosphere to photodissociation of N 2.
The electrons in the upper atmosphere result mainly from photoionization, which
occurs when a molecule in the upper atmosphere absorbs solar radiation and the absorbed
energy causes an electron to be rejected from the molecule. The molecule then becomes a

29
positively charged ion. For photoionization to occur, therefore, a molecule must absorb
photon, and the photon must have enough energy to remove an electron.

2. The bond energy of N2 is 941 kJ/mol. What is the longest wavelength a photon can have
and still have sufficient energy to dissociate N2?

Solution:
E = 941 kJ x 1 mole
mole 6.022 x 1023molecules
E = 1.5626 x 10-21 kJ/molecule = 1.5626 x 10-18 J/molecule

E = hv
v = E = 1.5626 x 10-18 J
h 6.629 x 10-34 J-s
v = 2.357 x 1015 /s
λ = c = ( 3.0 x 108 m/s )( 109 nm )
v 2.357 x 1015/s 1m
λ = 127.27 nm

Four important photoionization processes occurring in the atmosphere above 90 km

are shown in the table below. Photons of any wavelength shorter than the maximum lengths
given in the table have enough energy to cause photoionization. A look back at Fig. 8.2,
however, shows you that virtually all of these high-energy photons are filtered out of the
radiation reaching Earth because they are absorbed by the upper atmosphere.

Table 8.3 Photoionization Reactions for Four Components in the

Atmosphere

Processes Ionization Energy (kJ/mole) (nm)

max
N2 + hv → N2+ + e- 1495 80.1
O2 + hv → O2+ + e- 1205 99.3
O + hv → O+ + e- 1313 91.2
NO + hv → NO+ + e- 890 134.5

Ozone in the Stratosphere

Although N2, O2 and atomic oxygen absorb photons having wavelengths shorter than
240 nm, ozone, O3, is the key absorber of photons having wavelengths ranging from 240 to
310 nm, in the ultraviolet region of the electromagnetic spectrum. Ozone in the upper
atmosphere protects us from these harmful high-energy photons, which would otherwise
penetrate to Earth‟s surface. Let‟s consider how ozone forms in the upper atmosphere and
how it absorbs photons.
By the time radiation from the Sun reaches an altitude of 90 km above Earth‟s surface,
most of the short-wavelength radiation capable of photoionization has been absorbed. At this
altitude, however, radiation capable of dissociating the O 2 molecule in sufficiently intense for
photodissociation of O2 is much greater that the concentration of atomic oxygen. From this
finding, we conclude that the oxygen atoms formed by photodissociation of O 2 in this region
frequently collide with O2 molecules and form ozone.
O + O2 → O3*
The asterisk on O3 denotes that the molecule contains an excess of energy. This reaction

30
releases 105 kJ/mole. This energy must be transferred away from the O3* molecule quickly
or else the molecule will fly apart into O 2 and atomic O – a decomposition that is the reverse
of the reaction by which O3* is formed. An energy-rich O3* molecule can release its excess
energy by colliding with another atom or molecule and transferring some of the excess
energy to it.

The Ozone Layer and Its Depletion

The ozone layer protects Earth‟s surface from damaging ultraviolet (UV) radiation.
Therefore, if the concentration of ozone in the stratosphere decreases substantially, more
UV radiation will reach Earth‟s surface, causing unwanted photochemical reactions,
including reactions correlated with skin cancer. Satellite monitoring of ozone, has revealed a
depletion of ozone in the stratosphere that is particularly severe over Antarctica, a
phenomenon known as ozone hole.
In the study of ozone depletion showed that naturally occurring nitrogen oxides
catalytically destroy ozone. Another study showed that chlorine from chloroflourocarbons
(CFCs) may deplete the ozone layer. These substances, principally CFCl 3 and CF2CL2 do
not occur in nature and have been widely used as propellants in spray cans, as refrigerant
and air-conditioner gases, and as foaming agents for plastics. They are virtually unreactive
in the lower atmosphere. Furthermore, they are relatively insoluble in water and are
therefore not removed from the atmosphere by rainfall or by dissolution in the oceans.
Unfortunately, the lack of reactivity that makes them commercially useful allows them to
survive in the atmosphere and to diffuse into the stratosphere. It is estimated that several
million tons of chloroflourocarbons are now present in the atmosphere.
As CFCs diffuse into the stratosphere, they are exposed to high-energy radiation
which cause photodissociation. Because C-Cl bonds are considerably weaker than C-F
bonds, free chlorine atoms are formed readily in the presence of light with wavelengths in
the range from 190 to 225 nm, as shown in the typical reaction:
CF2CL2(g) + hv → CF2Cl (g) + Cl(g)
Calculations suggest that chlorine atom formation occurs at the greatest rate at an altitude of
about 30 km, the altitude at which ozone is at its highest concentration.

SELF-ASSESSMENT QUESTIONS

1. a) What is the primary basis for the division of the atmosphere into different regions? (b)
Name the regions of the atmosphere, indicating the altitude interval for each one.
2. (a) What is the difference between the troposphere and the tropopause? (b) Explain why
the stratosphere, which is more than 20 mi thick, has a smaller total mass than the
troposphere, which is less than 10 mi thick?
3. Give two reasons why photodissociation of N2 is a relatively unimportant process
compared to photodissociation of O 2.
4. In terms of the energy requirements, explain why photodissociation of oxygen is more
important than photoionization of oxygen at altitudes below about 90 km.
5. (a) Why is the temperature of the stratosphere higher near the stratopause than near the
tropopause? (b) Explain how ozone is formed in the stratosphere.
6. What does CFC stand for? Give a chemical formula for a representative CFC. Why are
these compounds harmful to the environment?

31
 CHEMISTRY LABORATORY

ACTIVITY 7

Solve the following problems:

1. Air pollution in Mexico City metropolitan area is among the worst in the world. The
concentration of ozone in Mexico City has been measured at 441 ppb (0.441ppm). Mexico
City sits at an altitude of 7400 feet, which means its atmospheric pressure is only 0.67 atm.
(a) Calculate the partial pressure of ozone at 441 ppb if the atmospheric pressure is 0.67
atm. (b) How many ozone molecules are in 1.0 L of air in Mexico City? Assume T = 25 oC.

2. The estimated average concentration of NO2 in air in the United States in 2006 was 0.016
ppm. (a) Calculate the partial pressure of the NO 2 in a sample of this air when the
atmospheric pressure is 755 torr. (b) How many molecules of NO 2 are present under these
conditions at 20oC and a volume of 1.0 L of air.

3. From the data in Table 8.1, calculate the number of helium atoms in 1.0 l of air at a
pressure of 0.97 atm and a temperature of 295 K.

4. What is the energy of a photon of electromagnetic radiation having a wavelength of 436

nm?

5. What is the wavelength of a photon that has an energy of 3.36 x 10 -19 J?

6. Calculate the energy of a photon of electromagnetic radiation whose frequency is

2.81 x 1014/sec.

7. If a quantum of light (photon) has a wavelength of 450 nm, how much energy is carried by
that photon?

8. Calculate the energy of photon of light having frequency of 2.7 x 10 13 s-1.

9. Calculate the frequency and wavelength of photon with energy 3.98 x 10 -15 J.

10. What is the energy of a photon of light with a wavelength of 575 nm?

32
 CHAPTER 9

THE CHEMISTRY OF WATER

EARTH‟S WATER

Water covers 72% of Earth‟s surface and is essential to life. Our bodies are about 65%
water by mass. Because of extensive hydrogen bonding, water has unusually high melting
point and boiling points and a high heat capacity. Water‟s highly polar character is
responsible for its exceptional ability to dissolve a wide range of ionic and polar-covalent
substances. Many reactions occur in water, including reactions in which H 2O can participate
in acid-base reactions as either a proton donor or a proton acceptor. All these properties
play a role in our environment.

The Global Water Cycle

All the water on Earth is connected in a global water cycle (Fig. 9.1). Most of the
processes depicted here rely on the phase changes of water. For instance, warmed by the
Sun, liquid water in the oceans evaporates into the atmosphere as water vapour and
condenses into liquid water droplets that we see as clouds. Water droplets in the clouds can
crystallize to ice, which can precipitate as hail or snow. Once on the ground, the hail or snow

Figure 9.1 The Global Water Cycle

33
melts to liquid water, which soaks into the ground. If conditions are right, it is also possible
for ice on the ground to sublime to water vapour in the atmosphere.

Salt Water: Earth‟s Oceans and Seas

The vast layer of salty water that covers so much of the planet is in actuality one large
connected body and is generally constant in composition. For this reason, oceanography
speak of a world ocean rather than of the separate oceans we learn about in geography
books.
The world ocean is huge, having a volume of 1.35 x 10 9 km3 and containing 97.2% of
all the water on Earth. Of the remaining 2.8%, 2.1% is in the form of ice caps and glaciers.
All the freshwater – in lakes, in rivers, and in the ground – amounts to only 0.6%.
Seawater is often referred to as saline water. The salinity of seawater is the mass in
grams of dry salts present in 1 kg of seawater. In the ocean world, salinity averages about
35. To put it another way, seawater contains about 3.5% dissolved salts by mass. The list of
elements present in seawater is very long. Most, however, are present only in very low
concentrations. The Table below lists the 11 ionic species most abundant in seawater.

Table 9.1 Ionic Constituents of Seawater Present in Concentration

Greater Than 0.001 g/kg (1 ppm)

Ionic Constituent Salinity Concentration (M)

Chloride, Cl- 19.35 0.55
Sodium, Na+ 10.76 0.47
Sulfate, SO42- 2.71 0.028
Magnesium, Mg2+ 1.29 0.054
Calcium, Ca2+ 0.412 0.010
Potassium, K+ 0.40 0.010
Carbon dioxide* 0.106 2.3 x 10-3
Bromide, Br- 0.067 8.3 x 10-4
Boric acid, H3BO3 0.027 4.3 x 10-4
Strontium, Sr2+ 0.0079 9.1 x 10-5
Flouride, F- 0.0013 7.0 x 10-5
*
CO2 is present as HCO3- and CO32-

Seawater temperature, salinity, and density vary as a function of depth (Fig. 9.2).
Sunlight penetrates well only 200 m into the water; region between 200 m and 1000 m deep
in the “twilight zone”, where visible light is faint. Below 1000 m, the ocean is pitch-black and
cold, about 4oC. The transport of heat, salt and other chemicals throughout the ocean is
influence by these changes in the physical properties of seawater, and in turn the changes in
the way heat and substances are transported affects ocean currents and the global climate.
The sea is so vast that if the concentration of a substance in seawater is 1 part per
billion (1 x 10-6 g per kilogram of water), there is 1 x 10 12 kg of substance in the world ocean.
Nevertheless, because of high extracting costs, only three substances are obtained from
seawater in commercially important amounts: sodium chloride, bromine (from bromide salts),
and magnesium (from its salts).
Absorption of CO2 by the ocean plays a large role in global climate. Because carbon
dioxide and water form carbonic acid. The H 2CO3 concentration in the ocean increases as
the water absorbs atmospheric CO 2. Most of the carbon in the ocean, however, is in the form

34
of HCO3- and CO32- ions, which form a buffer system that maintains the ocean‟s pH between
8.0 and 8.3. The pH of the ocean is predicted to decrease as the concentration of CO 2 in the
atmosphere increases.

Figure 9.2 Average temperature, salinity, and density of seawater

as a function of depth.

Freshwater and Groundwater

Freshwater is the term used to denote natural waters that have low concentration (less
than 500 ppm) of dissolved salts and solids. Freshwater includes the waters of lakes, rivers,
ponds and streams. The total amount of freshwater on earth is not a very large fraction of
the total water present. Indeed, freshwater is one of our precious resources. It forms by
evaporation from the oceans and the land. The water vapour that accumulates in the
atmosphere is transported by global atmospheric circulation, eventually returning to the
Earth as rain, snow and other forms of precipitation. (Fig. 9.1)
As water runs off the land on its way to the oceans, it dissolves a variety of cations
(mainly Na+, K+, Mg2+, Ca2+, and Fe2+), anions (mainly Cl-, SO42-, and HCO3-), and gases
(principally O2, N2, and CO2). As we use water, it becomes laden with additional dissolved
material, including waste of human society. As our population and output of environmental
pollutants increase, we find that must spend ever-increasing amounts of money and
resources to guarantee a supply of freshwater.
Approximately 20% of the world‟s freshwater is under the soil, in the form of
groundwater. Groundwater resides in aquifers which are layers of porous rock that hold
water. The water in quifers can be very pure and accessible for human consumption if near
the surface (Fig. 9.3). Dense rocks that does not allow water to readily penetrate can hold
groundwater for years or even millennia. The nature of the rock that contains the
groundwater has a large influence on the water‟s chemical composition, If minerals in the
rock are water soluble to some extent, ions can leach out of the rock and remain dissolved in
groundwater

35
 Figure 9.3 Groundwater is water located in aquifers below the soil.

HUMAN ACTIVITIES AND EARTH‟S WATER

All life on Earth depends on the availability of suitable water. Some organisms can
thrive under the temperature, pH, and ionic conditions where other organisms would die.
Many human activities where organisms would die. Many human activities rely on waste
disposal via Earth‟s water, even today, and this practice can be detrimental to aquatic
organisms.

Dissolved Oxygen and Water Quality

The amount of O2 dissolved in water is an important indicator of water quality. Water

fully saturated with air at 1atm and 20 oC contains about 9 ppm of O2. Oxygen is necessary
for fish and most other aquatic life. Cold-water fish require water containing at least 5 ppm of
dissolved oxygen for survival. Aerobic bacteria consume dissolved oxygen to oxidize organic
materials for energy. The organic material the bacteria are able to oxidize is said to be
biodegradable.
Excessive quantities of biodegradable organic materials in water are detrimental
because they remove the oxygen necessary to sustain normal animal life. Typical sources of
these biodegradable materials, which are called oxygen-demanding wastes, include sewage,
industrial wastes from food-processing plants and paper mills, and liquid waste from
meatpacking plants.
In the presence of oxygen, the carbon, hydrogen, nitrogen, sulfur, and phosphorus in
biodegradable material end up mainly as CO2, HCO3-, H2O, NO3-, SO42-, and phosphates.
The formation of these oxidation products sometimes reduces the amount of dissolved
oxygen to the point where aerobic bacteria can no longer survive. Anaerobic bacteria then
take over the decomposition process, forming CH4, NH3, H2S, PH3, and other products,
several of which contribute to the offensive odors and some polluted waters.
Plant nutrients, particularly nitrogen and phosphorus, contribute to water pollution by
stimulating excessive growth of aquatic plants. The most visible results of excessive plant
growth are floating algae and murky water. What is more significant, however, is that as
plant growth becomes excessive, the amount of dead and decaying plant matter increases
rapidly, a process called eutrophication. The process by which plants decay consumes O 2,

36
and without sufficient oxygen, the water cannot sustain animal life.
The most significant sources of nitrogen and phosphorus compounds in water are
domestic sewage (phosphate-containing detergents and nitrogen-containing body wastes),
runoff from agricultural land (fertilizers contain both nitrogen and phosphorus), and runoff
from livestock areas (animal wastes contain nitrogen).

Water Purification: Desalination

Because of its high salt content, seawater is unfit for human consumption and for most
of the uses to which we put water. The removal of salts from seawater or brackish water to
make water usable is called desalination.
Seawater can also be desalinated using reverse osmosis. Recall that osmosis is the
net movement of solvent molecules, but not solute molecules, through a semipermeable
membrane. In osmosis, the solvent passes from the dilute solution into the more
concentrated one. However, if sufficient external pressure is applied, osmosis can be
stopped and, at still higher pressure, reversed. When reverse osmosis occurs, solvent
passes from the more concentrated into the more dilute solution. In a modern reverse-
osmosis facility, hollow fibers are used as semipermeable membrane. Water is introduced
under pressure into the fibers, and desalinated water is recovered.

Water Purification: Municipal Treatment

The water needed for domestic, agricultural, and industrial use is taken either from
lakes, rivers and underground sources or from reservoirs. Much of the water that find its way
into municipal water system is “used” water, meaning it has already passed through one or
more sewage systems or industrial plants. Consequently, this water must be treated before it
is distributed to our faucets.
Municipal water treatment usually involves five steps (Fig. 9.4). After coarse filtration
through a screen, the water is allowed to stand in large sedimentation tanks where sand and
other minute particles settle out. To aid in removing very small particles, the water may first
be made slightly basic with CaO. The Al(SO 4)3 is added and reacts with OH- ions to form a
spongy, gelatinous precipitate of Al(OH)3 (Ksp = 1.3x10-33). This precipitate settles slowly,
carrying suspended particles down with it, thereby removing nearly all finely divided matter
and most bacteria. The water is then filtered through a fine sand bed. Following filtration, the
water may be sprayed into the air (aeration) to hasten oxidation of dissolved organic
substances.
The final step normally involves treating the water with a chemical agent to ensure the
destruction of bacteria. Ozone is more effective, but chlorine is less expensive. Liquified Cl 2
is dispensed from tanks through a metering device directly into the water supply. The
amount used depends on the presence of other substances with which the chlorine might
react and on the concentrations of bacteria and viruses to be removed. The sterilizing action
of chlorine is probably due to Cl2 itself but to hypochlorous acid, which forms when chlorine
reacts with water.
Cl2(aq) + H2O(l) → HCLO(aq) + H+(aq) + Cl-(aq)

Water Softening

Water containing a relatively high concentration of Ca 2+, Mg2+, and other divalent
cations is called hard water.. Although the presence of these ions is generated not a health

37
 Figure 9.4 Common steps in treating water for a public water system.

threat, they can make water unsuitable for some household and industrial uses. For
example, these ions react with soap to form insoluble soap scum, the stuff of bathtub rings.
In addition, mineral deposits may form when water containing these ions is heated.
When water containing calcium ions and bicarbonate ions is heated, some carbon dioxide is
driven off. As a result the solution becomes less acidic and insoluble calcium carbonate
forms.
Ca2+(aq) + 2HCO3-(aq) → CaCO3(s) + CO2(g) + H2O(l)
The solid CaCO3 coats the surface of hot-water systems and teakettles, reducing
heating efficiency. These deposits, called scale, can be especially serious in boilers where
water is heated under pressure in pipes running through a furnace.
Removal of the ions that cause hard water is called water softening. In the lime- soda
process used for large-scale municipal water-softening operations, the water is treated with
calcium hydroxide (prepared from lime) and, sodium carbonate (sometimes called soda ash)
to precipitate Ca2+ as CaCO3 and Mg2+ as Mg(OH)2
Ca2+(aq) + CO2-(aq) → CaCO3(s)
Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)

Calculations of Parts per Million and Parts per Billion

For solutions that are extremely dilute, we often express concentrations in parts per
million (ppm), parts per billion (ppb), parts per billion (ppb), or even parts per trillion (ppt).
For aqueous solution, ppm, ppb and ppt are generally based on mass. Thus, 1 ppm of
solute in a solution is the same as 1 g of solute per 1 x 10 6 g (1 million grams) of solution
and 1ppb is 1 g of solute per 109 g ( 1 billion grams) of solution.

1 ppm = 1 g solute 1 ppb = 1 g solute

6 9
10 g solution 10 g solution

Example: Contaminant Concentrations

1. According to standards, the EPA maximum allowable level of fluoride ion in drinking
water is 4 mg F- per liter. What is this level expressed in ppm?

38
 Solution: density of water = 1.0 g/mL
1 L of water = 1000 g

4 mg F- x 1 g water = 4 mg F-
1000g water 1000 mg water 100000 mg water
= 4 ppm F-

EPA - Environmental Protection Agency

2. What is the concentration in ppb that is equivalent to a maximum allowable level in water
of 0.1 μg/L of gasoline additive MTBE ( methyl tert-butyl ether)

Solution: density of water = 1.0 g/mL 1 g = 106

1 L of water = 1000g

0.1 μg MTBE x 1L water x 1g = 1.0 x 10-10 ppb

L 1000 g water 10 6 μg

MTBE – is a volatile, flammable and colorless liquid that is sparingly soluble in water, a
gasoline additive

3. Express each aqueous concentration in the unit indicated:

a) 11 μg of benzene per liter of water, as ppb of benzene
b) 0.014% BaCO3 by mass, as ppm BaCO3
c) 25 μg of trichloroethylene in 9.5 L of water, as ppb of trichloroethylene
d) 38 g of Cl2 in 1.0 x 104 L of water, as ppm Cl2

Solution:

a) 11 μg C6H6 x 1 L of water x 1 g C6H6

1 L water 1000 g water 106 μg C6H6
-8
= 1.1 x 10 ppb of benzene

b) Basis: 1 L of water = 1000 g water

mass of BaCO3 = 0.00014 (1000 g) = 0.14 g = 140 mg

140 mg BaCO3 x 1L of water x 1 g BaCO3

1 L water 1000 g water 1000 mg BaCO3
= 1.4 x 10-4 ppm of BaCO3

c) 25 μg C2H4Cl3 x 1L of water x 1 g C2H4Cl3

9.5 L of water 1000 g water 106 μg C2H4Cl3
= 2.63 x 10-9 ppb of trichloroethylene

d) 38 g = 38000 mg

38000 mg of Cl2 x 1 L water x 1 g Cl2

4
1.0 x 10 L of water 1000 g water 1000 mg Cl2
= 3.8 x 10-6 ppm of Cl2

39
 EXERCISES

Solve the following problems:

1. A sample of drinking water is found to contain 38 mg Pb. What is the concentration

in ppm?
2. What is the concentration in ppm if 18.5 g of solute are dissolved in a 25 L water?
3. Given a 6.174 g mass of sodium sulfate that is dissolved in a 1 L volume, what is
the concentration with respect to sodium ion?
4. What is the ppm concentration of salt in a solution composed of 3.5 g salt and 96.5
g water?
5. What is the concentration in ppm of a 500 g sample of drinking water that contains
4 mg of lead?
6. A solution has a concentration of 2250 μg/kg. What is the concentration in ppm?
7. A solution has a concentration of 0.5 mg/mL. What is its concentration in ppm?
8. A solution has a concentration of 1.25 g/L. What is its concentration in ppm?
9. A solution has a concentration of 0.033 g/kg. What is its concentration in ppm?
10. What is the concentration of a solution, in ppm, if 0.02 g of NaCl is dissolved in
1000g of solution?

MULTIPLE CHOICE: Choose the corresponding letter of the correct answer.

1. How does global warming affect the hydrologic cycle?

a) It causes random variation in the cycle
b) It doesn‟t affect the cycle at all
c) It causes the cycle to accelerate
d) It causes the cycle to decelerate
2. Where does the energy to drive the hydrologic cycle come from?
a) Earth‟s interior c) Sun
b) Plate tectonics d) Photosynthesis
3. A(n) __________ is an underground rock formation that holds water.
a) Reservoir c) Aquifer
b) Porosity d) Aeration
4. Approximately ______ percent of the world supply of freshwater is groundwater.
a) 0.6 b) 5 c) 22 d) 50
5. An underground area that holds water is called ___________ .
a) Permeable b) Aquifer c) Groundwater d) Aeration
6. Hardness of water is due to the presence of salts of ___________ .
a) Potassium b) Chlorine c) Magnesium d) Boron
7. Hardness of water is conventionally expressed in terms of equivalent amount of ____ .
a) H2CO3 b) MgCO3 d) CaCO3 d)Na2CO3
8. What is the best definition of desalination?
a) Removing harmful chemicals from water
b) Filtering dirty water
c) Cleaning natural water spring
d) Removing salt and minerals from sea water
9. What are the main water treatments?
a) Coagulation, flocculation and sedimentation, filtration and disinfection
b) Radiation, filtration and flocculation

40
 c) Coagulation, flocculation and sedimentation, closed systems and radiation
d) None of the above
10. What is sediment?
a) Another word for mud
b) Filtered sand
c) Matter heavier than water that collects on the bottom of the tank
d) None of the above

41
 CHAPTER 10

SOIL CHEMISTRY

Soil is a medium for plant growth can be describes as a complex natural material
derived from weathering of rocks and decomposition of organic materials, which provide
nutrients, moisture and anchorage for plants.
Soil is a mixture of minerals, organic matter (humus), air and water. An ideal soil for
plant growth is about 50% solids consisting of minerals and organic material. The organic
portion consists of residues from plants, animals and other living organisms. Under optimum
conditions for plant growth, about half of the space between soil particles- pore particles-is
filled with water, and the remainder with air. Soil compaction reduces pore space and the
amount of water and air the soil can hold, thereby restricting rot growth and the ability of
plants to take up nutrients from the soil.

PHYSICAL PROPERTIES

Soil Color
The color of the soil has little effect on plant growth but is an indicator of soil properties
that do not affect plant development. Color is an indicator of organic matter content,
drainage and aeration.
● Black: High in organic matter (4% or more)
● Brown: Good organic matter and well drained
● Red: Low in organic matter, well drained. Red color is due to the presence of iron
(often ferric oxide, Fe2O3)
● Gray: Low in organic matter, poorly drained. Gary color is due to an excess of
water and poor aeration. Gray color is due to the presence of iron (often ferrous
oxide, FeO)
● Yellow: Low in organic matter, well drained
● Mottling effect in subsoil: Indicated both well and poorly drained conditions
during the year due to fluctuations in water table.

Soil Structure
Soil structure refers to the arrangement of soil particles into aggregates. Any physical
disturbance influences soil structure. The addition of calcium(Ca), magnesium (Mg) or
organic matter improves the structure of soil by enhancing aggregation, the ability of the soil
particles to hold together as a coherent mixture. Organic matter acts as a bonding agent in
holding soil particles together to form aggregates. Excessive sodium (Na) levels in soils
cause dispersion of soil particles that can result in poor soil structure. Development of
erodibility and improves water-holding capacity, root penetration and ease if tillage.

Soil Texture
Soil texture refers to the percentage of sand (2.0 to 0.05 mm), silt (0.05 to 0.002 mm)
and clay particles (less than 0.002 mm) that make up the mineral portion of the soil. Loam is
a variable mix of these three textural classes.
● Sand adds porosity. Silt adds body to the soil. Clay adds chemical and physical
properties that affect the ability of the soil to take up nutrients through absorption to
oil particles.

42
 ● Soil texture affects the following soil characteristics:
• Water-holding capacity
• Nutrient-holding capacity
• Erodibility
• Workability
• Root penetration
• Porosity
● Soil texture affects soil fertility and nutrient management:
• Most sulfur deficiencies occur in sandy soils
• Nitrogen is easily leached from sandy soils. Loss of soil nitrogen (dinitrifi-cation)
is more common on heavy, clay soils.
• Potassium can leach from sandy solis but is immobile in medium to fine-textured
soils.

Soil Organic Matter

Soil organic matter, or humus, is the partially decomposed residue of plants, animals
and other organisms. Organic matter refers to all organic material in the soil, including fresh
crop residues.
Organic matter improves soil structure by acting as a bonding agent that hols soil
particles together in aggregates. Without organic matter, aggregates are less stable and can
be easily broken apart. Good soil structure promotes water movement and root penetration
while reducing soil crusting, clod formation and erosion.
Organic matter provides plant nutrients, mainly nitrogen and sulfur and small amount
of phosphorus. About 20 pounds of nitrogen are released by decomposition of every one
percent of organic matter in the soil. Organic matter is a primary reservoir for available forms
of nutrients (mainly zinc and boron)

Table 10.1 Soil Texture as Defined by Soil Texture Class and Estimated by a
Hand-Feel Method

Soil Textural Group Soil Textural Class Feel

Coarse to very coarse (more Sand, loamy sand Feels gritty, does not ribbon or
than 70% sand) leave smear on hand

Moderately coarse Sandy loamy Feels gritty, leaves smear on

hand, does not ribbon, breaks
into small pieces

Medium Silt, loam, silt loam Feels smooth and flourlike, does
not ribbon, breaks into pieces
about ½ inch or less

Moderately fine Sandy clay loam, clay Forms ribbon that breaks into
loam, silty clay loam pieces about ¾ inch long, sandy
clay loam will feel gritty

Fine (more than 40% clay Sandy clay, silty clay, Forms long,pliable ribbon more
clay than 2 inches long; sandy clay
will feel gritty

43
Soil Organisms
Soil organisms vary in size from microscopic bacteria, fungi and algae to those visible
to the naked eye, such as earthworms and insects. They perform both beneficial and
detrimental functions in the soil.
Microbes decompose organic matter and release nutrients for plant uptake. Bacteria
called rhizobia are responsible for fixing atmospheric nitrogen as plant-available forms in
root nodules on legumes. Some fungi and nematodes are responsible for plant diseases,
and many soil insects damage crops.
Fertilizer has positive effects on soil microorganisms by providing more nutrients and
increased crop residues. Application of anhydrous ammonia will temporarily reduce
populations of microorganisms in the zone of application.

CHEMICAL PROPERTIES

Soil pH
Soil pH is a relative measure of the hydrogen ion concentration [H+] in the soil. The pH
value vary from a minimum value of 0 to a maximum value of 14.
● Acidic: pH less than 7
● Nuetral: pH = 7
● Basic: pH greater than 7
Soil pH affects the availability of nutrients to plants. In acid soils (pH is low) calcium
and magnesium become more available in plants, whereas the micronutrients iron,
aluminium and manganese become soluble and can reach level toxic to plants. These
micronutrients also can react with phosphorus to form compounds that are insoluble and not
available to plants. In alkaline soils (pH is high), several soil micronutrients, including zinc,
copper and cobalt, becomes less available to plants. Also at high pH, phosphorus
precipitates (becomes insoluble) with the higher levels of calcium in the soil and therefore
becomes less available to plants.
Soil pH affects the population and activity of microorganisms. The activity of nitrogen-
fixing bacteria associated with legumes is impaired in acid soils, resulting in less nitrogen
fixation.
Several natural processes cause most soils to become more acidic over time:
● Soils formed from acidic rock parent material like sandstone or shale will be more acidic
than those formed from limestone.
●The higher the rainfall, the more leaching of alkaline elements such as calcium and
magnesium, leaving acidic elements such as hydrogen, manganese and aluminum. Acid rain
can also acidify the soil.
● Nitrogen from fertilizer (ammonium sulfate), decomposing organic matter, and manure as
well as nitrogen fixation by legume roots all increase soil acidity.
● Crop removal of nutrients such as calcium and magnesium causes acidity to develop. This
effect is more pronounced with legumes than with nonlegumes.

CORRECTING SOIL ACIDITY

Soil acidity is corrected by adding a liming material to reduce the hydrogen ion
concentration and increase the level of alkaline/basic cations (positively charged ions) in the
soil. Acid-producing hydrogen ions are adsorbed on exchange sites or present in soil
solution. These hydrogen ions are in equilibrium between absorbed and solution states. The

44
hydrogen ions adsorbed to the cation exchange sites serves as a reservoir for neutralizable/
reserve acidity that rapidly replaces the hydrogen ions in the soil solution that are neutralize
by lime. A soil pH test tells how acidic a soil is, but it does not measure the neutralizable/
reserve acidity. Thus, to determine how much lime is required to raise the pH, the soil must
be tested for neutralizable acidity. This is done in soil testing labs by measuring buffer pH.
Two soils with the same pH may have very different lime requirements. In general, the lime
requirement of a soil increases with the content of clay and organic matter.
● To raise pH, add:
• Limestone before planting. It will take 3 to 6 months for results.
CaCO3 + H2O to Ca + H2CO3
Ca + 2H+ + CO3- to Ca + H2O + CO2
● To lower pH, add:
• Iron sulfate (FeSO4) or aluminium sulfate, Al2(SO4)3 – chemical reaction, quick
results .
• Elemental sulphur – biological reaction, takes 3 to 6 months to show results.
• Acids (use with caution)
H2SO4 to 2H+ + SO42-

Table 10.2 Liming Material, Its Composition and Relative

Nuetralizing Value

Relative Nuetralizing
Liming Material Composition
Value

Calcium carbonate CaCO3 100

Calcitic limestone CaCO3 + impurities 50 to 100

Dolomitic limestone CaCO3 + MgCO3 +

90 to 109
impurities

Quick (burned) lime CaO 150 to 180

Hydrated (slaked) lime Ca(OH)2 115 to 135

Ground sheels 80 to 90

Wood ashes 40 to 80

Cation Exchange Capacity

Cation exchange capacity (CEC) is a measure of the total amount of exchangeable
cations (positively charged ions) a soil can absorb. Nutrient cations in the soil include
positively charged ions such as calcium (Ca 2+), magnesium (Mg2+), potassium (K+), sodium
(Na+) and hydrogen (H+). In soil tests, CEC is reported in milliequivalents (meq) per 100
grams of soil. The exchangeable cations in the soil are in equilibrium with those in the soil
solution, they are replenished from the absorbed cations, which are then available for plant
uptake.
● The higher the CEC, the more cations a soil can retain.

45
● Soil differ in CEC depending on clay and organic matter content. CEC of clay varies from 4
to 100 meq per 100 g. Humus has an average CEC of 200 meq per 100 g.
● Soil texture affects CEC. The more clay, the higher the CEC (Table 10.3)
● Soils with low CEC (1 to 10) have high sand content and low-water holding capacity. They
require less lime to correct a given pH and leaching of nitrogen and potassium is more likely.
● Soils with high CEC (15 to 40) have high clay or humus content and high water-holding
capacity to hold nutrients.

Anion Retention in Soils

Anions are negatively charged ions. They are retained by positively charged surfaces
in the soil, but only in negligible amounts. Negatively charged ions, such as nitrate and
phosphate anions, are repelled by clay /humus particles, which are also negatively charged.
For this reason, anions are susceptible to leaching losses in soil solutions.
● Anions such as nitrate (NO3-), sulfate (SO42-) and chloride (Cl-) and highly soluble and
move with water.
● The phosphate anion (PO43-) does not move freely in soils largely because it forms
relatively insoluble compounds with iron and aluminium in acid soils (low pH) and with
calcium in alkaline soils (high pH).

Table 10.3 The Higher the Clay Content of the Soil, the Greater its
Cation Exchange Capacity (CEC)

Soil CEC (meq/100g)

Sand 2 to 5

Sandy loam 5 to 12

Loams 10 to 18

Silt and Silt clay loams 15 to 30

Clay and clay loams 25 to 40

PLANT NUTRITION
Seventeen elements are considered essential nutrients for plant growth, and 14 of
these elements come from the soil (Table 10.4). If there is a deficiency of any essential
element, plants cannot complete their vegetative or reproductive cycles. Some of these
nutrients combine to form compounds that make up cells and enzymes. Other nutrients are
necessary for certain chemical processes to occur.

Table 10. 4 Seventeen Plant Nutrients Derived from Air, Water and Soils

Source
Plant Nutrient
Air Water Soil
Carbon X

46
Oxygen X X
Hydrogen X
Primary Nutrients
Nitrogen X
Phosphorus X
Potassium X
Secondary Nutrients
Calcium X
Magnesium X
Sulfur X
Micronutrients
Boron X
Chlorine X
Copper X
Iron X
Manganese X
Molybdenum X
Nickel X
Zinc X

ESSENTIAL PLANT NUTRIENTS FROM THE SOIL

1. Nitrogen. Nitrogen is a building block of plant proteins. It is an integral part of chlorophyll

and is a component of amino acids, nucleic acids and coenzymes.
Most nitrogen in the soil is tied up in organic matter. It is taken up by plants as nitrate
(NO3 ) and ammonium (NH4+) ions from inorganic nitrate and ammonium compounds. These
-

compounds can enter the soil as a result of bacterial action (nitrogen fixation), application of
inorganic nitrogen fertilizer, or conversion of organic matter into ammonium and nitrate
compounds.
2. Phosphorus. Plants use phosphorus to form nucleic acids DNA and RNA and to store
and transfer energy. Phosphorus promotes early plant growth and root formation through its
role in the division and organization of cells. Phosphorus is essential to flowering and
fruiting.
3. Potassium. Potassium is necessary to plants for translocation of sugar and for starch
formation. It is important for efficient use of water through its rule in opening and closing
small aperture (stomata) on the surface of the leaves. Potassium increases plant resistance
to diseases and assists in enzyme activation and photosynthesis.
4. Calcium. Calcium provides a building block (calcium pectate) for cell walls and
membranes and must be present for the formation of new cells. It is a constituent of
important plant carbohydrates, such as starch and cellulose. Calcium promotes plant vigor
and rigidity and is important to proper root and stem growth.
5. Magnesium. Magnesium is a component of the chlorophyll molecule and is therefore
essential for photosynthesis. Magnesium serves as an activator for many plant enzymes

47
required for sugar metabolism and movement and for growth and processes. Plants take up
magnesium as the Mg2+ ion.
6. Sulfur. Sulfur is a constituent of three amino acids (cystine, methionine and cysteine) that
play an essential role in protein synthesis. Sulfur is present in oil compounds responsible for
characteristic odors of plants such as garlic and onion. It is also essential for nodule
formation of legumes.
7. Zinc. Zinc is an essential component of several enzymes in plants. It controls the
synthesis of indoleacetic acid, an important plant growth regulator, and it is involved in the
production of chlorophyll and protein. Zinc is taken up in plants as the zinc ion (Zn 2+).
8. Iron. Iron is taken up by plants as ferrous ion (Fe 2+). Iron is required for the formation of
chlorophyll in plant cells. It serves as an activator for biochemical processes such as
respiration, photosynthesis and symbiotic nitrogen fixation. Symptoms of iron deficiency can
occur in soil with pH greater than 7.0. Specific needs for iron can be determined by soil test
and visual symptoms.
9. Manganese. Manganese serves as an activator for enzymes in plant growth processes,
and it assists iron in chlorophyll formation. Plants obtain these nutrient from the soil in the
form of manganous ion (Mn2+).
10. Copper. Copper is an activator of several enzymes in plants. It may play a role in
production of vitamin A. Deficiency interferes with protein synthesis.
11. Boron. Boron regulates the metabolism of carbohydrates in plants. It is essential for the
process by which meristem cells (cells that divide) differentiate to form specific tissues. With
boron deficiency, plant cells may continue to divide, but structural components are not
differentiated.
12. Molybdenum. Molybdenum is taken up by plants as molybdate ions (MoO 4-). It is an
essential micronutrient that enable plants to make use of nitrogen. Without molybdenum,
plants cannot transform nitrate to amino acids and legumes cannot fix atmospheric nitrogen.
13. Chlorine. Chlorine is required in photosynthetic reactions. Deficiency of chlorine in soils
is rare because of its universal presence in nature. Plants take up chlorine as chloride ion
(Cl-).
14. Nickel. Nickel is taken up by plants as Ni2+. Nickel is a component of the enzyme
urease, which is needed to prevent toxic accumulation of urea, a product of nitrogen
metabolism in plants.

SELF-ASSESSMENT QUESTIONS

1. How do you determine the chemical composition of soil?

2. Why is soil texture important?

3. Briefly explain what is the cation exchange capacity (CEC) of a soil.

4. Describe and estimate cation exchange capacity based on soil organic matter content,
clay content and clay mineralogy.

5. Identify the major factors that contribute to soil acidity.

6. Describe the principal roles of the following essential nutrients in plant growth: nitrogen,
potassium, phosphorus.

7. Discuss the effects of soil pH on soil biological activity and crop production.

48
8. Discuss the nutrient mobility with the soil and plant.

9. Briefly explain the relationships between pH and ion toxicity.

10. Discuss the physical properties of soil.

True or False. Write TRUE when the statement is correct and FALSE when the statement is
incorrect.

1. The bulk of a plant is made up of minerals extracted from the soil.

2. Clay soils can hold more nutrients than sandy soils.

3. The main source of nitrogen in the soil is rocks.

4. Soil with low CEC (1 to 10) have low sand content and high-water holding capacity.

5. Crop removal of nutrients such as calcium and magnesium causes acidity to develop.

6. Addition of lime causes decomposition of organic material.

7. Certain plant nutrients are called micronutrients because they are too small to see with
the naked eye.

8. Nutrients needed in large quantities by plants are called macronutrients.

9. pH is used to measure water content in the soil.

10.Color of the soil is an indicator of organic matter content, drainage and aeration.

49
 CHAPTER 11

CHEMICAL SAFETY

Chemicals are all around us.

● In the food we eat
● The clothes we wear
● The vehicles we drive
● In the products we use everyday
Chemicals can help us live better lives, but we must understand and respect their
potential hazard.
Otherwise, the can harm us.

More than 30 million workers are potentially exposed to one or more chemical hazards.
There are an estimated 650,000 existing hazardous chemical products, and hundreds of
new ones are being introduced annually.
This can pose a potential serious problem for exposed workers and their employees.

Chemical – any element, chemical compound, or mixture of elements and /or compounds
Safety – being secured from undergoing or causing hurt, injury or loss
Hazard – an item or condition which poses potential risk to safety or health

Chemical Safety – being secured from undergoing or causing hurt, injury or loss when
working with elements, chemical compounds, or mixture of elements and/or
compounds
Chemical Hazards – elements, chemical compounds, or mixture of elements and/or
compounds which poses potential risk to safety or health.

What is a Physical Hazard?

“Physical Hazard” means a chemical for which there is a scientifically valid evidence that is
a:
Combustible liquid Compressed Gas
Explosive Flammable
Organic peroxide Oxidizer
Pyrophoric Unstable (reactive) or water reactive

Hazardous Chemical
Physical Hazard Categories
Fire Hazard
Flammable gas Combustible
Flammable aerosol Oxidizer
Flammable solid Pyrophoric
Flammable liquid
Explosive Hazard
Compressed gas
Explosive
Reactive Hazards
Organic peroxide
Unstable (reactive)
Water-reactive

50
 What is a Health Hazard?
“Health Hazard” means a chemical for which there is statistically significant evidence based
on at least one study conducted in accordance with established scientific principles that
acute or chronic healthy effects may occur in exposed employees.
Carcinogens Toxic or highly toxic agents
Irritants Corrosives
Hepatotoxins Nephrotoxins
Hematopoietic system agents Reproductive toxins
Agents which damage the lungs, Sensitizers
skin, eyes or mucous membrane Neurotoxins

Routes of Entry
The main routes of entry of the chemicals into the human body:
● Inhalation into lungs
● Absorption through skin membrane
● Ingestion via mouth into the gastrointestinal system

Corrosive
● Typical examples are sulfuric acid, nitric acid, potassium hydroxide (caustic
potash), sodium hydroxide (caustic soda), bromine and phenol.
● Corrosive substances causes destructive burns on the tissue by chemical action
on 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.

Oxidizers
● Typical examples include hydrogen peroxide, nitric acid, perchloric acid, sulfuric
acid, chlorates, chromates, nitrates, peroxides, permanganates and picrates
● Oxidizers are chemicals which decompose readily under certain condition to yield
oxygen
● They can cause a fire to burn violently
● Oxidizers must not be stored with flammable

Flammables
● Flammable substances are those that readily catch fire and burn in air.
● The vapors released from a flammable liquid are a common fire hazard in a
laboratory.
● The degree of hazard associated with a flammable liquid depend on its flash point,
flammability limit and ignition temperature.

Potentially Explosive Chemicals

● Chemicals when subjected to heat, impact or friction, undergoes rapid chemical
change, evolving large volumes of gases which cause sudden increase in
pressure.
● Heat, light, mechanical shock and certain catalysts can initiate explosive reactions.
● Shock sensitive substances include acetylides, azides, nitrogen triiodide, organic
nitrates, nitro compounds, perchlorate salts,and organic peroxides.
● Perchloric acid, if allowed to dry on wood or other combustibles, will explode and
cause a fire on impact or friction.

51
 ● Picric acid and picrates are detonated by heat and impact.
● Ethers that have aged and dried to catalysts are extremely unstable and
potentially explosive.

Toxic Chemicals
● Toxic chemicals produce injurious or lethal effects upon contact with body cells due
to their chemical properties.
● The toxic effects depend upon the extent of exposure and the inherent toxicity of a
chemical.
● The extent of exposure is determined by the dose, duration and frequency of
exposure and the route of exposure.
● Toxic effect of a chemical may occur after a single (acute) exposure or long term
repeated (chronic) exposure.
● Examples of acute toxins are sodium cynide, sodium azide and dimethyl mercury.
● Benzene is an example of a chronic toxin which cause damage after repeated or
long term exposure.

Types of Toxins – Target Organ/Tissue – Examples

● Neurotoxins (nervous system) – mercury (metallic, inorganic and organic), xylene,
carbon disulfide, 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

Pyrophoric Chemicals
● The rapid oxidation of a pyrophoric chemical by oxygen or moisture in air causes
the compound to ignite spontaneously.
Example: butyl lithium

Water Reactive Chemicals

● These chemicals react violently when they come in contact with moisture or water.
● Examples include lithium, sodium, potassium, aluminum bromide, calcium oxide,
sulfur trioxide and phosphorus pentachloride.

“Irritant”. A chemical which is not corrosive, but which causes a reversible inflammatory
effect on living tissue by chemical action at the site of contact.
“Sensitizer”. A chemical that causes a substantial proportion of exposed people or animals
to develop an allergic reaction in normal tissue after repeated exposure to the
chemical.

Hazard Information
How can you tell if the chemical you are working is hazardous?
● Perform a Hazard Determination
● Review the Container Label
● Review the Material Safety Data Sheet
● Contact EHS

52
 Hazard Determination
Chemical manufacturers and importers are required to evaluate chemicals they
produce or import to determine if they are hazardous. This includes assessment for both
physical and health hazards.

Container Labelling
The chemical manufacturer, importer, or distributor is required to ensure that each
container of hazardous chemical leaving their workplace is labelled, tagged or marked with
the following information.
● Identity of the hazardous chemical(s)
● Appropriate hazard warning
● Name and address of the responsible party (manufacturer, importer, others)

MSDS Information
What is an MSDS?
“Material Safety Data Sheet” (MSDS) means written or printed material connecting a
hazardous chemical which is prepared in accordance with the OSHA Hazard
Communication Standard.
Chemical manufacturers and importers shall obtain or develop a material safety data
sheet for each hazardous chemical they produce or import.
Employees shall have the material safety data sheet in the workplace for each
hazardous chemical which they use.

Ordering Chemicals
● Always order the smallest possible quantity of chemical. This reduce hazards and
chemical waste.
● Understand the hazardous properties of the chemical that is to be purchased.
● Where possible, purchase a less hazardous chemical.

Receipt of Chemicals
● Received packages must be checked to ensure that the containers are in good
condition.
● Details of new chemicals must be entered in the laboratory inventory and stored in
a designated area.
● The date of receipt and date of first usage must be recorded on the bottles of
peroxide forming chemicals.
● Ensure that the Material Safety Data Sheet (MSDS) is obtained with the chemical
and is readily available for reference.

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 according to 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

53
 that are stored in close proximity can mix to start a fire, hazardous fumes or
explosions.

Handling of Chemicals
● Bench tops must 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 formula or short forms must be used for labelling chemical bottles.
● Labels must include the full name of the chemical, hazard pictogram and a brief
description of the hazard and precautions to be taken.
● 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 be stored in drinking water bottles.

Chemical Inventory
The inventory of stored chemicals must be examined at least annually. Annual
inventory checks helps in many ways:
● It ensures that chemicals are segregated according to their compatibility.
● Discarding expired chemicals and help to save space.
● Help to quickly locate the chemicals.
● The expiration date of peroxides can be monitored.
● Help to identify bottles with worn out labels or those which are leaking.

Chemical Spill
The following actions must be taken in the event of a chemical spill:
● Evacuate non-essential personnel in the area.
● Ventilate the areas by opening the windows.
● If the spilled material is flammable, extinguish all open flames. Do not operate
electric switches near the spill.
● Avoid inhaling vapour from spilled material.
● Use personal protective equipment.
● Ensure that there is an exit near by.
● Use spill containment kits to clean up the spill.

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 at all times in the laboratory.
● Wear suitable gloves when handling chemicals. Inspect all gloves for defects
before usage.
● Know the location of the emergency equipment.
● Be aware of the hazards posed by the work of others in the laboratory.
● Make others in the laboratory aware of any specific hazards associated with your
work.

54
 ● 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.
● Laboratory equipment must be regularly inspected and serviced as per
manufacturer‟s recommendations.
● 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.

Emergency Measures
● All chemical splashes on the skin must be immediately flushed under running water
● Contaminated clothing must be removed while flushing the body. Flushing must be
continued for at least 15 minutes.
● 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.

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.

ASSESSMENT OF LEARNING

MULTIPLE CHOICE:Choose the corresponding letter of the correct answer.

1. The ___________ process determine whether exposure to a chemical can increase the
incidence of adverse health effect
a) Hazard identification c) Toxicity assessment
b) Exposure assessment d) Risk characterization
2. What is the first stage of risk assessment?
a) Exposure assessment c) Toxicity study
b) Hazard identification d) Risk characterization
3. Which of the following is not a characteristic of hazardous waste?
a) Toxicity c) Ignitibility
b) Corrosivity d) Leakage
4. The severity of toxic exposure on an individual depends on ___________.
a) Age and health c) Dose and susceptibility
b) Genetics d) Diet
5. Labelling refers to ___________.
a) Information must be displayed c) Capacity

55
 b) Physical attributes d) Quantity
6. Material Safety Data Sheets provide information about
a) Hazards about a specific chemical c) Information on chemical reactions
b) Emergency information d) All of the above
7. Flammable chemicals are stored
a) Where ever it is easy to get to c) Near water resources
b) In special flammable storage lockers d) In glass containers
8. What is the main objective of toxicity assessment?
a) To determine the source of pathway c) To determine chemical concentration
b) To estimate how much of a substance d) To analyse chemical exposure
does what kind of harm
9. What is the main objective of exposure assessment?
a) To estimate chemical concentrations c) To study site history
b) To estimate exposure of chemicals by d) Chemical assessment
the population at risk
10. Without proper labelling, it is difficult for ____________.
a) Proper handling c) Analysis
b) Maintaining d) Transportation

TRUE OF FALSE. Write TRUE if the statement is correct and FALSE if the statement is
incorrect.

1. The longer the chemical exposure, the more likely you will become affected.
2. Hazard is defined as the probability of suffering harm or loss.
3. The purpose of risk management is to identify potential problems before they occur so
the risk-handling activities may be planned.
4. Toxicity test is the experimental study of the adverse effects of exposure of a living
organism to a substance for a defined duration under defined conditions.
5. Result from long-term exposure to lower doses of a chemical is known as acute toxicity.
6. Exposure is a state in which a person can potentially be influence by a force or situation
but not necessarily affected.
7. Ingestion can be called secondary exposure pathway after skin contact happens.
8. The only way a chemical can enter the body is if I drink it.
9. Heat, light, mechanical shock and certain catalysts can initiate explosive reactions.
10. Estimation of short-term and long-term exposure are usually in terms of doses by
exposure rate.

56
REFERENCES:

Brown, Theodore L., LeMay, Eugene H., Bursten, Bruce. E.(2000), Chemistry, The
Central Science, 8th ed., Prentice Hall, Upper Saddle River, New Jersey

Hill, John W., McCreary, T. W., Kolb, D. K., (2013), Chemistry for Changing Times, 13 th ed.,
Pearson Education South Asia Pte Ltd.

Jenkins, F., Kessel, H. V., Tompkins, D., Lantz, O.,(2007), Chemistry, Nelson, Thomson
Canada Limited

Burdge, J. (2014), Chemistry, 3rd ed., New York McGraw Hill

Godberg, D. E. (2001). Fundamentals of Chemistry. Boston: McGraw Hill Co.

Wood, Jesse H., Keenan, Charles W., Bull, William E., Fundamentals of College Chemistry,
3rd ed., Harper & Row, Publishers, New York

Keenan, Charles W., Kleinfelter, Donald C., Wood, Jesse H., General College Chemistry
6th ed., Harper & Row, Publishers, New York

Hein, Morris, Best, Leo R., Pattison, Scott, Arena, Susan, Introduction to General, Organic
and Biochemistry, 8th ed., John and Wiley & Sons, Inc

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