CH182: CHEMISTRY FOR ENGINEERS II (PART 3)

POLYMERS AND POLLUTION

Polymers: introduction

Polymers are long-chain molecules with very high molecular weight, made by joining together of many
small molecules (the repeating units called monomers). Polymers consist of giant molecules with
macromolecular extended structures.

Monomers Oligomers Polymers

(Single units) (Molecules with (Molecules with large
intermediate no. of no. of monomers)
monomers)

They are broadly classified as: (i) organic, (ii) inorganic and (iii) semi-inorganic polymers. These polymers
can be either naturally occurring or synthetically made.

Organic polymers: Large molecules containing carbon atoms in the backbone of the chain.
Inorganic polymers: Large molecules containing atoms other than carbon in the backbone of the chain.
Semi-inorganic polymers: Large molecules having both carbon as well as other inorganic elements in the
backbone of the chain.

Polymer Natural (Examples) Synthetic (Examples)

Organic Protein (monomers: amino acids) Polyethylene or polythene or poly(ethene) (monomer: ethene)
Wool, silk, muscle; Starch Cups, refrigerator bowls; Poly(chloroethene) or poly(vinyl
(monomers: glucose) Potato, chloride) (monomer: vinyl chloride) Fabric coatings,
wheat electrical insulations
Inorganic Silica (sand), clay, asbestos, talc, Polysiloxanes
mica, etc.
Semi-inorganic --- Poly(stannomethylene)

Polymerization occurs with organic compounds having multiple bonds (double or triple). Polymers vary
widely in physical properties like strength, flexibility, softening temperatures, etc. Some are very strong and
not readily stretched fibres (polyesters); some are more easily deformed plastics (poly(ethene)).

Properties

The properties of polymers vary depending on certain factors as given below:

1) Chain length: Depending on the chain length of a polymer, properties like melting point, flexibility and
tensile strength vary. Thus, strength and melting point increases with chain length. Only average chain
lengths of polymers should be considered, since individual chains vary in length even in a pure sample
of polymer.
2) Intermolecular forces: If the intermolecular forces between chains are high, then the polymer will be
strong with high melting point. The magnitude of this force depends on the nature of the size of the
groups present on the chain.
3) Branching: Highly branched polymer chains cannot pack together as regularly as straight chains: hence
such polymers tend to have lower tensile strength and melting point. In most of the polymers, there are
regions in which the chains are regularly packed. These are called crystalline regions. The regions in
which packing is irregular are called non-crystalline regions.
4) Cross-linking: Some polymers have extensive cross-linking between chains. This forms a rigid network,
making them hard. More cross-linking more rigid polymer becomes highly brittle. Such polymers
are called as thermosetting polymers.

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 Polymers with no branched chains,
Eg. High-density polythene.
Chains regularly packed with
extensive crystalline regions. High
tensile strength and melting point.
Polymers with many branched chains,
Eg. low-density polythene.
Chains irregularly packed with largely
amorphous and few crystalline regions.
Low tensile strength and melting point.
Polymers with huge cross-
linking. Eg. Bakelite
Rigid and hard, fairly
brittle.

Types of plastics

Thermosoftening plastics or thermoplastics: These are formed by addition polymerization (see below).
They become soft when heated and can be softened and moulded many times without change of properties.
These generally consist of linear chains of carbon atoms; there are comparatively few cross linkages (or
branches). Hence they are soft, weak and less brittle. As a result, they are thermally less stable. They are
soluble in organic solvents.

This can be represented as: X X X X

Thermosetting plastics: These are formed by condensation polymerization (see below). These are formed
as resins, which can be mixed with powders and moulded by heating them at high pressures. They are
infusible when set, and cannot be remoulded after manufacture. Their structure contains close network of
chains. Hence, they are hard, strong and more brittle. As a result, they are thermally more stable compared
to thermoplastics; but prolonged heating resulting in charring of the polymer. They are insoluble in organic
solvents.

X X X
X X X
This can be represented as:

Ingredients in plastic ware

The properties of plastics can be modified by adding various compounds known as plasticizers. These can
enhance flexibility and also impart properties like acid resistance and tensile strength. Fillers are used to
increase the bulk of the plastic, and thus cheapen the product, but are chosen so that the properties of the
plastic are altered as little as possible. Dyes and pigments are sometimes added to give colour to the plastic.

Types of polymerization

Addition polymerization - This involves addition reactions between monomer units. Usually, only a single
type of monomer molecule is involved. The polymerization reaction is initiated by a radical. Most addition
polymers are synthetic. Eg. Polythene, polystyrene, poly(propene), poly(vinyl chloride), etc.
H H H H H H
H H H H H H
C C C C C C
C C + C C + C C
H H H H H H
H H H H H H

Addition polymerization occurs by several steps: (a) initiation; (b) chain growth; and (c) termination.

Condensation polymerization - This involves a condensation reaction between two monomers. A small
molecule (usually water) is eliminated from between two larger molecules, thus forming a bond between
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them. Most natural polymers are condensation polymers. Eg. Polyester, nylon, proteins, starch, cellulose,
nucleic acids, etc.

A OH + H B A B + H2O
Condensation polymerization usually involves two or more different monomers joined in a chain by
condensation.

HO A OH + H B H + HO A OH + H B H

HO A B A B H + 3 H2O

Thermosoftening plastics

Poly(vinylchloride) (PVC)

Vinyl chloride is manufactured from either ethylene or acetylene.

HCl
C2H4 + Cl2 Cl-CH2CH2-Cl H2C=CH-Cl C2H2
600C

Vinyl chloride is then refluxed using benzoyl peroxide, C6H5CO-O-O-COC6H5 as catalyst. The polymer
chain and hence the properties of the polymer is controlled by the original concentration of the monomer
and the amount of catalyst used. PVC is an example of a homopolymer, which is made up of only one type
of monomer.
Cl Cl
H2 H2
H2C=CH-Cl + H2C=CH-Cl + ....... C C C C
H H

PVC is tough and a plasticizer (tricresyl phosphate) is added to soften it. PVC is resistant to weathering, fire,
chemicals and is a good electrical insulator. It is easy to colour. A heat stabilizer is added and the plastic is
used to make household goods like curtains, tablecloths, toys, etc. It is also used for electrical insulation
(cables), leathercloth (in cars), drain-pipes and gutters.

Poly(vinylacetate) - PVA

Vinyl acetate is manufactured from acetylene and acetic acid. It is then refluxed with benzoyl peroxide
catalyst. PVA is an example of a copolymer (discussed later).

OOCCH3 OOCCH3
H2 H2
C C C C
C2H2 + CH3COOH H H

A solution of this thermoplastic in acetone is used as an adhesive and for grease-proofing paper. Large
quantities of the solid are used in USA as chewing gum base.

Polythene or poly(ethylene)

When ethene is heated to 200C and 1200 atmospheric pressure in the presence of traces of oxygen as
catalyst produces low-density polythene (LDPE). It has branched chain which cannot pack closely together

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and so possesses low melting point and it is easily deformed. It is used for making film and sheeting for bags
and wrappers and for making moulded articles such as washing-up bowls and squeezy bottles.

Another method (Ziegler method) of preparing is, by heating ethene gas at about 60C and 1 atm pressure in
the presence of aluminium alkyl as catalyst with titanium tetrachloride as promoter. The molecules produced
have few branches and can pack closely together. This is called the high-density polythene (HDPE). It is
more rigid, denser and stronger and possesses high melting point. It is used for making moulding rigid
articles such as bleach bottles and milk bottle crates.

Thermosetting plastics

Phenol-formaldehyde plastics or resins (Bakelite)

Bakelite is the first synthetic polymer prepared by Baekeland. This is made by the condensation reaction
between phenol and formaldehyde in the presence of a mineral acid or an alkali as catalyst. This resin is
milled with a filler (eg. wood shavings, asbestos fibre), pigment and with hexamethylenetetramine or hexa (a
hardener to provide more formaldehyde and crosslink the units with methylene bridges; as a catalyst). The
powder is then moulded under high pressures to various sizes and shapes. The Novolac does not contain
methylol groups (-CH2OH) and so no water is produced when the mixture is heated. This dry process has the
advantage because water present in moulded resin decreases the electrical insulating properties.

It has resistance to solvents and possesses electrical insulating properties. Hence, they are used for making
electrical switches and plug points. Novolacs are used as photoresists.

OH H2 OH
C

OH OH OH OH
H2
C
catalyst (CH2)6N4 CH2 CH2
+ CH2O +
- H2O
n
Thermoplastic
Linear: no crosslinking
Novolac C
OH H2 OH
Thermosetting plastic
Crosslinked
Bakelite

Urea-formaldehyde plastics or resins

Urea and formaldehyde condense in aqueous solution in the presence of a mild base (usually ammonia or
pyridine) to form a thermosetting plastic or resin, which is filtered. It has high tensile strength, low water
absorption and high surface hardness. The polymer absorbs dyes easily and the powders can be moulded
under pressure to form tableware, trays, decorative laminates and many household utensils. This is used as
adhesives to glue wood together. They are used, in solution, to strengthen paper and to improve the shrink
resistance of cotton, wool and rayon. It is used as ion-exchange resins to demineralize water, where the
nitrogen can combine with the acidic groups in water.

Copolymers

Copolymers are prepared by polymerizing two or more different monomers. Copolymerization leads to
polymers with properties entirely different from those of their corresponding homopolymer. The following
table gives the well known examples.
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 Monomers Formula Trade name Applications
Vinyl chloride (20%) CH2=CHCl Saran Food wrappings,
Vinylidene chloride (80%) CH2=CCl2 fibres
Styrene (25%) CH2=CH-C6H5 SBR (styrene Tyres, rubber
1,3-Butadiene (75%) CH2=CH-CH=CH2 butadiene rubber) articles
Isobutylene CH2=C(CH3)2 Butyl rubber Inner tubes
Isoprene CH2=C(CH3)-CH=CH2

Types of copolymers

Depending upon the distribution of monomers in the chain, copolymers are categorized into random and
alternating copolymers. If monomer A is copolymerized with monomer B, the resultant product might
have a random distribution of these monomers throughout the chain, or it might have an alternating
distribution.

The other two types of copolymers are block and graft copolymers. Block copolymers are those in which
different blocks of identical monomer units alternate with each other. Graft copolymers are those in which
homopolymer branches of one monomer unit are grafted onto a homopolymer chain of another monomer
unit.

Type of copolymer Structure

Random
A A A B A B B A B A A A
n
Alternating
A B A B A B A B A B A B
n
Block
A A A A A A B B B B B B
n
Graft

Pollution: definition of common terms

Pollutant: If the concentration of a substance already present in nature is increased to undesirable

proportion by human action, so that it spoils the environment and reduces quality of life or affects health,
then it is called as a pollutant. Eg. CO, SO2, NOx, pollen, dust, etc.

Contaminant: A substance that does not occur in nature but is introduced in significant amounts into the
environment by human action is known as a contaminant. A contaminant also reduces quality of life and
affects our health. Eg. Chlorofluorocarbons (CFC), methylisocyanate (MIC).

Primary and secondary pollutants: The primary pollutants discharged into the atmosphere suffer chemical
changes in the presence of H2O, O2 and ultraviolet ray of sunlight to form secondary pollutants. Some
examples are summarized below.

Primary pollutants Reaction Secondary pollutants

CO2 + H2O H2CO3
SO2 + H2O H2SO3
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Pollutants

Pollutants are in one way categorized into two classes: (i) organic; and (ii) inorganic. These pollutants get
discharged into the environment both by natural and well as human causes. They cause pollutions to the air,
water, land and biological systems.

Organic pollutants

Organic chemicals available in the environment or introduced into the environment are constantly subjected
to various physical, chemical, and biological processes. However, these processes act in a combined way in
environmental systems to determine the overall fate of these compounds.

They can be divided into two major categories:

Processes like transport and mixing phenomena within a given environmental compartment (like
water body) or transfer processes between different phases and/or compartments (like water-air
exchange) that leave the structure of the organic chemical unchanged
Processes (like chemical, photochemical, biological, microbial reactions) that transform the chemical
into one or several products (alters the structures of the compound) of different environmental
behaviour and effects

However, in a given environmental system, all of these processes may occur simultaneously and different
processes may strongly influence each other.

Inorganic pollutants

Most of the inorganic pollutants are either gaseous (CO2, CO, (NO)x nitrogen oxides, SO2, H2S) or solids or
particulates (heavy metals and metalloids, anions like F-, CN-, PO43-, etc.). So transport and mixing
phenomena play vital roles in making them move from one place to another. Some of the solids can get
leached away during the wet and dry deposition processes thus getting transported and affecting vast areas.
Carbon particles (soot) emitted from chimneys of industries usually act as a carrier of these gaseous and
heavy metal pollutants for transportation.

Common organic pollutants

1. Methane (natural) and global warming

Sources: (a) Natural: end-product of the metabolism from an anaerobic bacteria, methanogen, Natural
wetlands, enteric fermentation (wild animals), termites, biomass burning, ocean/fresh water; (b) Man-made:
rice paddies, gas drilling and transmission, landfills, coal mining, biomass burning.

Effects: Methane is referred to as greenhouse gas because it contributes for the global warming. The CH4
molecule absorbs strongly in the infrared region, and its presence in the atmosphere decreases the loss of
heat from the earth by radiation. This global warming is called the greenhouse effect.

The greenhouse effect is the rise in temperature that the Earth experiences because certain gases in the
atmosphere trap energy from the sun. Without these gases, heat would escape back into space and Earths
average temperature would be about 60F colder. These gases are referred to as greenhouse gases. Some
examples are CO2, N2O, CH4, H2O vapour, etc.

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Consequences of global warming

Sea level rise - Beach erosion, coastal wetland loss, loss of low-lying territories
Effects on agriculture - Changes in the length of growing season, growth of undesirable plant species
Effects on air quality - Concentration of certain atmospheric species, widespread forest fire, worsen air
quality, change in how pollutants are dispersed
Impacts on human health - Changes in patterns of sickness and death, respiratory problems affected by
air quality change

2. Polyaromatic hydrocarbons, PAH (man-made)

PAH contains two or more fused six membered carbon atom aromatic rings. These compounds have low
water solubility and most of them are solids with increase in melting point with molecular weight. They
have low vapour pressure (low volatility).
PAH are xenobiotic lipophilic compounds [xenobiotic: substances that are foreign to an entire biological
system (i.e., artificial substances) which did not exist in nature before their synthesis by humans; lipophilic:
fat soluble].
Sources: Natural - forest fires, volcanic activities; Man-made - power plants, auto-exhaust emissions,
incomplete combustion of coal, fuel oils and petrol.

PAH are abundantly present in sediments. Their persistence is proportional to their size. Some examples of
PAH are provided below:

Pyrene Chrysene Benzopyrene Pentacene

Toxicity: All are prone to produce cancer (carcinogenic). Compounds like benzanthracene and benzopyrene
are converted by certain enzymes into polar water soluble products (dihydrosol epoxides) which bind to
haemoglobin and DNA. The reaction proceeds very slowly and over long periods of time. Presence of solar
radiation increases the toxicity of PAH compounds.

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Effects on health: Mutagenic (birth defects; DNA is affected) and carcinogenic effects are seen with PAH.
Benzopyrene induces chromosome aberrations. They can persist in atmosphere for longer duration of time
because they are lipophilic and hence bioaccumulates in the food chain.

3. Pesticides (man-made)

The term "pesticide" is a composite term that includes all chemicals that are used to kill or control pests. In
agriculture, this includes herbicides (weeds), insecticides (insects), fungicides (fungi), nematocides
(nematodes), and rodenticides (vertebrate poisons). A range of highly chlorinated aromatic compounds were
developed and used as pesticides. Some well known examples of this category are
dichlorodiphenyltrichloroethane (DDT) and benzene hexachloride (BHC). The gamma isomer of BHC is
known as gammexane or Lindane which is used as pesticide.

When such pesticides are sprayed on the land, insect-borne diseases like malaria were eliminated and also
led to huge improvements in the quality and yield of crops. But, these compounds are so stable and they
remain unchanged on the crops and accumulate in the soil. These compounds are also fat-soluble and not
water-soluble. Hence, after ingestion in birds (that eat seeds) and domestic animals (cows that graze), they
concentrate in the fatty tissues and reach hazardous levels. Along the food chain, the toxicity level gets
magnified.
DDT BHC
Cl H
H H Cl

Cl H
Cl C Cl
H Cl

CCl3
Cl H
H Cl

4. Chlorofluorocarbons (CFCs, organic / inorganic, man-made) and Ozone depletion

Compounds containing C-F and C-Cl bonds are referred to as chlorofluorocarbons. Some important CFCs
and their uses are given below:

Formula Name Uses

CCl3F Trichlorofluoromethane Blowing agent for making foam plastics
CCl2F2 Dichlorodifluoromethane Refrigerant fluid, aerosol propellant
CCl2F-CClF2 1,1,2-Trichloro-1,2,2-trifluoroethane Solvent for degreasing in electronic industries

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CFCs are useful in these applications because they are non-inflammable, non-toxic and very unreactive. But,
it has been then found that CFCs are responsible for serious damage in the stratospheric ozone layer which
filters out most of the suns harmful ultraviolet (UV) radiation before it reaches the earth.

It is calculated that a CFC molecule takes an average of 15 years to go from the ground level up to the upper
atmosphere, and it can stay there for about a century, destroying up to one hundred thousand ozone
molecules during that time. The relatively weak C-Cl bond in CFCs get broken by homolytic fission to form
Cl radicals. Ozone is continuously formed in the stratosphere by reaction between O radicals and O2
molecules. O radicals are formed when UV radiation splits up O2 molecules.
O2 (g) 2 O (g) O (g) + O2 (g) O3 (g)

When Cl radicals are present in the stratosphere, they react with ozone, forming O2 and ClO radicals.
O3 (g) + Cl (g) O2 (g) + ClO (g) ClO (g) + O (g) Cl (g) + O2 (g)

It is evident that both O3 and O are removed from the stratosphere. At the same time, Cl radical is
regenerated and they act as catalyst in converting O3 and O to O2. Measurements of the ozone concentration
in the stratosphere showed that the ozone layer was thinning and developing a hole especially over the
Antarctic.

Effects: (a) On humans - The ozone layer is important as it filters the radiation from the sun and prevents
most of the harmful UV radiation from reaching the earth. Excessive exposure to UV radiation should be
avoided as it causes skin cancer melanoma in humans; (b) On crops: An increase of UV radiation would
be expected to affect crops. A number of economically important species of plants, such as rice, depend on
cyanobacteria residing on their roots for the retention of nitrogen. These bacteria are sensitive to UV light
and they would be affected by its increase.

Inorganic pollutants

1. Arsenic (metalloid or semimetal)

Compounds of arsenic are tasteless and hence it is a popular material for committing suicide, however the
death is slow.

Sources: Pharmaceutical, paper pulp, glass, cotton, electronic, photocopying and computer industries.

Effects: It causes dermatitis (skin inflammation) and irritation of upper respiratory passage, ulceration and
perforation of nasal septum, jaundice and anemia. Mutagenesis and carcinogenesis are also most common
effects of arsenic poisoning and exposure. The inorganic and methylated arsenic compounds are the most
toxic ones. But, the latter can be excreted in the form of urine and is less toxic compared to the former.

2. Cadmium (metal)

Growing plants acquire zinc and they also take up and concentrate Cd with the same biochemical setup. The
outbreak of Cd poisoning occurred in Japan in the form of itai itai or ouch ouch disease where the bones
become fragile.

Sources: Natural: Cd is associated with Zn minerals; Synthetic: electroplating, battery & paper industries.

Effects: At high levels, Cd causes kidney problems, anaemia, cancer and bone marrow disorders. The major
portion of Cd ingested into our body is trapped in the kidneys and eliminated. A small fraction is bound
most effectively by the body proteins, metallothionein present in the kidneys, while the rest is stored in the
body and gradually accumulates with age. When excessive amounts of Cd(II) are ingested, it replaces Zn(II)
at key enzymatic sites, causing metabolic disorders.

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3. Mercury (metal)

Mercury is well known toxic metal which came to the limelight after the incidence of Minamata disease in
1953-60 in Japan. Those who had eaten Hg-contaminated fish from Minamata Bay suffered from this
disease. The sea fish in the bay were found to have 27-102 ppm of Hg in the form of methyl mercury. This
mercury source was the effluent from a vinyl chloride plant, Minamata Chemical Company, which was
discharged into the bay.

Sources: Hg occurs as a trace component of many minerals, for example, cinnabar, HgS, fossil fuels, coal
and lignite (natural). The Chloralkali industry that manufactures Cl2 and NaOH by an electrolytic process
uses Hg electrodes (man-made). Some of the electrical apparatus (Hg vapour lamp, electrical switches, Hg
batteries) contain significant amounts of mercury. Agricultural industry uses a large number of fungicides
for seed dressings (methylmercurynitrile, ethylmercury chloride, etc.).

Mercury undergoes translocation in plants and animals and then finds its way into the human food chain.

Types of mercury and effects

The toxicity depends on its chemical species as shown below:

Type Particulars
Hg Elemental mercury; relatively inert and nontoxic; vapour highly toxic. Hg vapour, when inhaled,
enters the brain through the blood stream, leading to severe damage of the central nervous system.
Hg22+ Mercurous ion; insoluble as chloride; low toxicity. As our stomach contains a fairly high
concentration of chloride, mercurous ion is not toxic.
2+
Hg Mercuric ion; toxic. It has high affinity for S atoms and hence easily attaches itself to the S-
containing aminoacids of proteins. It also forms bonds with haemoglobin and serum albumin, both
of which contain sulphydryl groups (-SH). This ion, however, does not travel across biological
membranes and hence does not get access into biological cells.
RHg Organomercurials; highly toxic, particularly CH3Hg+ (methyl mercury); causes irreversible
+

nerve and brain damage; soluble in fat and easily transported across biological membranes; stored in
fat tissues. The covalent Hg-C bond is not easily disrupted and the alkyl mercury is retained in cells
for prolonged periods of time. The most dangerous aspect is the ability of RHg+ to move through the
placental barrier and enter fetal tissues.
R2Hg Diorganomercurials; low toxicity but can be converted to RHg+ in acidic medium.
HgS Mercuric sulphide; highly insoluble and non-toxic; trapped in soil in this form.

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