FACT SHEETS IN CHEMISTRY FOR ENGINEERS

Hydrocarbons- are compounds of hydrogen and carbon and their derivatives. Collectively,
all carbon-containing compounds are called organic compounds. Organic compounds can be
classified as aliphatic and aromatic hydrocarbons, aldehydes, carboxylic acids, esters, ethers
and ketones. There are a number of other organic compounds but the ones mentioned
constitute a majority of the organic compounds.

Organic compounds are recognized by their functional groups. Functional groups determine
the chemical reactivity of an organic molecule. Functional groups are structural units that
determine the chemical reactivity of a molecule under a given set of conditions. Organic
compounds are classified into several major categories based on the functional groups they
contain. In the systematic names of organic compounds, numbers indicate the positions of
functional groups in the basic hydrocarbon framework. Many organic compounds also have
common names, which use the prefix form—for a compound that contains no carbons other
than those in the functional group and acet—for those that have one additional carbon
atom. The following is a summary of the functional groups of organic compounds.
The first family listed in table is the hydrocarbons. These include alkanes, with the general
molecular formula CnH2n+2 where n is an integer; alkenes, represented by CnH2n; alkynes,
represented by CnH2n−2; and arenes. Halogen-substituted alkanes, alkenes, and arenes form
a second major family of organic compounds, which include the alkyl halides and the aryl
halides. Oxygen-containing organic compounds, a third family, may be divided into two
main types: those that contain at least one C–O bond, which include alcohols, phenols
(derivatives of benzene), and ethers, and those that contain a carbonyl group (C=O), which
include aldehydes, ketones, and carboxylic acids. Carboxylic acid derivatives, the fourth
family listed, are compounds in which the OH of the –CO2H functional group is replaced by
either an alkoxy (–OR) group, producing an ester, or by an amido (–NRR′, where R and R′
can be H and/or alkyl groups), forming an amide. Nitrogen-containing organic compounds,
the fifth family, include amines; nitriles, which have a C≡N bond; and nitro compounds,
which contain the –NO2 group.

The systematic nomenclature of organic compounds indicates the positions of substituents

using the lowest numbers possible to identify their locations in the carbon chain of the
parent compound. If two compounds have the same systematic name, then they are the
same compound. Although systematic names are preferred because they are unambiguous,
many organic compounds are known by their common names rather than their systematic
names. Common nomenclature uses the prefix form—for a compound that contains no
carbons other than those in the functional group, and acet—for those that have one carbon
atom in addition [two in the case of acetone, (CH 3)2C=O]. Thus methanal and ethanal,
respectively, are the systematic names for formaldehyde and acetaldehyde.

Recall that in the systematic nomenclature of aromatic compounds, the positions of groups
attached to the aromatic ring are indicated by numbers, starting with 1 and proceeding
around the ring in the direction that produces the lowest possible numbers. For example,
the position of the first CH3 group in dimethyl benzene is indicated with a 1, but the second
CH3 group, which can be placed in any one of three positions, produces 1,2-
dimethylbenzene, 1,3-dimethylbenzene, or 1,4-dimethylbenzene ( Table 2). In common
nomenclature, in contrast, the prefixes ortho-, meta-, and para- are used to describe the
relative positions of groups attached to an aromatic ring. If the CH 3 groups in
dimethylbenzene, whose common name is xylene, are adjacent to each other, the
compound is commonly called ortho-xylene, abbreviated o-xylene. If they are across from
each other on the ring, the compound is commonly called para-xylene or p-xylene. When
the arrangement is intermediate between those of ortho- and para- compounds, the name
is meta-xylene or m-xylene.
 Figure 24.1.224.1.2: Common Nomenclature for Aromatic Ring Substitutions

How to name organic compounds using the IUPAC rules

In order to name organic compounds you must first memorize a few basic names.
These names are listed within the discussion of naming alkanes. In general, the
base part of the name reflects the number of carbons in what you have assigned
to be the parent chain. The suffix of the name reflects the type(s) of functional
group(s) present on (or within) the parent chain. Other groups which are attached
to the parent chain are called substituents.

• Alkanes - saturated hydrocarbons

The names of the straight chain saturated hydrocarbons for up to a 12

carbon chain are shown below. The names of the substituents formed by the Name
removal of one hydrogen from the end of the chain is obtained by changing
the suffix -ane to -yl. Number of Carbons
1 methane
2 ethane
3 propane
 4 butane
5 pentane
6 hexane
7 heptane
8 octane
9 nonane
10 decane
11 undecane
12 dodecane

• There are a few common branched substituents which you should

memorize. These are shown below.

• Here is a simple list of rules to follow. Some examples are given at the end
of the list.
1. Identify the longest carbon chain. This chain is called the parent
chain.
2. Identify all of the substituents (groups appending from the parent
chain).
3. Number the carbons of the parent chain from the end that gives the
substituents the lowest numbers. When compairing a series of
numbers, the series that is the "lowest" is the one which contains the
lowest number at the occasion of the first difference. If two or more
side chains are in equivalent positions, assign the lowest number to
the one which will come first in the name.
4. If the same substituent occurs more than once, the location of each
point on which the substituent occurs is given. In addition, the
number of times the substituent group occurs is indicated by a prefix
(di, tri, tetra, etc.).
5. If there are two or more different substituents they are listed in
alphabetical order using the base name (ignore the prefixes). The
only prefix which is used when putting the substituents in
alphabetical order is iso as in isopropyl or isobutyl. The prefixes sec-
 and tert- are not used in determining alphabetical order except when
compared with each other.
6. If chains of equal length are competing for selection as the parent
chain, then the choice goes in series to:
a) the chain which has the greatest number of side chains.
b) the chain whose substituents have the lowest- numbers.
c) the chain having the greatest number of carbon atoms in the
smaller side chain.
d)the chain having the least branched side chains.
7. A cyclic (ring) hydrocarbon is designated by the prefix cyclo- which
appears directly in front of the base name.

In summary, the name of the compound is written out with the substituents in alphabetical
order followed by the base name (derived from the number of carbons in the parent
chain). Commas are used between numbers and dashes are used between letters and
numbers. There are no spaces in the name.

Here are some

examples:

• Alkyl halides

The halogen is treated as a substituent on an alkane chain. The halo-

substituent is considered of equal rank with an alkyl substituent in the
numbering of the parent chain. The halogens are represented as follows:
 F fluoro-
Cl chloro-
Br bromo-
I iodo-

• Here are some examples:

• Alkenes and Alkynes - unsaturated hydrocarbons

Double bonds in hydrocarbons are indicated by replacing the suffix -ane with -ene. If
there is more than one double bond, the suffix is expanded to include a prefix that
indicates the number of double bonds present (-adiene, -atriene, etc.). Triple bonds are
named in a similar way using the suffix -yne. The position of the multiple bond(s) within
the parent chain is(are) indicated by placing the number(s) of the first carbon of the
multiple bond(s) directly in front of the base name.

Here is an important list of rules to follow:

1. The parent chain is numbered so that the multiple bonds have the
lowest numbers (double and triple bonds have priority over alkyl and
halo substituents).
2. When both double and triple bonds are present, numbers as low as
possible are given to double and triple bonds even though this may at
times give "-yne" a lower number than "-ene". When there is a choice
in numbering, the double bonds are given the lowest numbers.
3. When both double and triple bonds are present, the -en suffix follows
the parent chain directly and the -yne suffix follows the -en suffix
(notice that the e is left off, -en instead of -ene). The location of the
double bond(s) is(are) indicated before the parent name as before,
and the location of the triple bond(s) is(are) indicated between the -
en and -yne suffixes. See below for examples.
4. For a branched unsaturated acyclic hydrocarbon, the parent chain is
the longest carbon chain that contains the maximum number of
double and triple bonds. If there are two or more chains competing
for selection as the parent chain (chain with the most multiple bonds),
the choice goes to (1) the chain with the greatest number of carbon
atoms, (2) the # of carbon atoms being equal, the chain containing
the maximum number of double bonds.
 5. If there is a choice in numbering not previously covered, the parent
chain is numbered to give the substituents the lowest number at
the first point of difference.

Here are some examples:

• Alcohols

Alcohols are named by replacing the suffix -ane with -anol. If there is more than one
hydroxyl group (-OH), the suffix is expanded to include a prefix that indicates the number
of hydroxyl groups present (-anediol, -anetriol, etc.). The position of the hydroxyl
group(s) on the parent chain is(are) indicated by placing the number(s) corresponding to
the location(s) on the parent chain directly in front of the base name (same as alkenes).

Here is an important list of rules to follow:

1. The hydroxyl group takes precedence over alkyl groups and halogen
substituents, as well as double bonds, in the numbering of the parent
chain.
2. When both double bonds and hydroxyl groups are present, the -en
suffix follows the parent chain directly and the -ol suffix follows the -
en suffix (notice that the e is left off, -en instead of -ene). The location
of the double bond(s) is(are) indicated before the parent name as
before, and the location of the hydroxyl group(s) is(are) indicated
between the -en and -ol suffixes. See below for examples. Again, the
hydroxyl gets priority in the numbering of the parent chain.
3. If there is a choice in numbering not previously covered, the parent
chain is numbered to give the substituents the lowest number at
the first point of difference.
 Here are some examples:

• Ethers

You are only expected to know how to name ethers by their commmon names. The two
alkyl groups attached to the oxygen are put in alphabetical order with spaces between the
names and they are followed by the word ether. The prefix di- is used if both alkyl groups
are the same.

Here are some examples:

• Aldehydes

Aldehydes are named by replacing the suffix -ane with -anal. If there is more than one -
CHO group, the suffix is expanded to include a prefix that indicates the number of -CHO
groups present (-anedial - there should not be more than 2 of these groups on the parent
chain as they must occur at the ends). It is not necessary to indicate the position of the -
CHO group because this group will be at the end of the parent chain and its carbon is
automatically assigned as C-1.

Here is an important list of rules to follow:

1. The carbonyl group takes precedence over alkyl groups and halogen
substituents, as well as double bonds, in the numbering of the parent
chain.
2. When both double bonds and carbonyl groups are present, the -en
suffix follows the parent chain directly and the -al suffix follows the -
en suffix (notice that the e is left off, -en instead of -ene). The location
of the double bond(s) is(are) indicated before the parent name as
 before, and the -al suffix follows the -en suffix directly. Remember it is
not necessary to specify the location of the carbonyl group because it
will automatically be carbon #1. See below for examples. Again, the
carbonyl gets priority in the numbering of the parent chain.
3. There are a couple of common names which are acceptable as
IUPAC names. They are shown in the examples at the end of this list
but at this point these names will not be accepted by the computer.
Eventually they will be accepted.
4. If there is a choice in numbering not previously covered, the parent
chain is numbered to give the substituents the lowest number at
the first point of difference.

Here are some examples:

• Ketones

Ketones are named by replacing the suffix -ane with -anone. If there is more than one
carbonyl group (C=O), the suffix is expanded to include a prefix that indicates the number
of carbonyl groups present (-anedione, -anetrione, etc.). The position of the carbonyl
group(s) on the parent chain is(are) indicated by placing the number(s) corresponding to
the location(s) on the parent chain directly in front of the base name (same as alkenes).

Here is an important list of rules to follow:

1. The carbonyl group takes precedence over alkyl groups and halogen
substituents, as well as double bonds, in the numbering of the parent
chain.
2. When both double bonds and carbonyl groups are present, the -en
suffix follows the parent chain directly and the -one suffix follows the -
en suffix (notice that the e is left off, -en instead of -ene). The location
of the double bond(s) is(are) indicated before the parent name as
 before, and the location of the carbonyl group(s) is(are) indicated
between the -en and -one suffixes. See below for examples. Again,
the carbonyl gets priority in the numbering of the parent chain.
3. If there is a choice in numbering not previously covered, the parent
chain is numbered to give the substituents the lowest number at
the first point of difference.

Here are some examples:

• Carboxylic Acids

Carboxylic acids are named by counting the number of carbons in the longest
continuous chain including the carboxyl group and by replacing the suffix -ane of the
corresponding alkane with -anoic acid. If there are two -COOH groups, the suffix is
expanded to include a prefix that indicates the number of -COOH groups present (-
anedioic acid - there should not be more than 2 of these groups on the parent chain as
they must occur at the ends). It is not necessary to indicate the position of the -COOH
group because this group will be at the end of the parent chain and its carbon is
automatically assigned as C-1.

Here is an important list of rules to follow:

1. The carboxyl group takes precedence over alkyl groups and halogen
substituents, as well as double bonds, in the numbering of the parent
chain.
2. If the carboxyl group is attached to a ring the parent ring is named
and the suffix -carboxylic acid is added.
3. When both double bonds and carboxyl groups are present, the -en
suffix follows the parent chain directly and the -oic acid suffix follows
the -en suffix (notice that the e is left off, -en instead of -ene). The
location of the double bond(s) is(are) indicated before the parent
name as before, and the -oic acid suffix follows the -en suffix directly.
Remember it is not necessary to specify the location of the carboxyl
group because it will automatically be carbon #1. See below for
 examples. Again, the carboxyl gets priority in the numbering of the
parent chain.
4. There are several common names which are acceptable as IUPAC
names. They are shown in the examples at the end of this list but at
this point these names will not be accepted by the computer.
Eventually they will be accepted.
5. If there is a choice in numbering not previously covered, the parent
chain is numbered to give the substituents the lowest number at
the first point of difference.

Here are some examples:

• Esters
Systematic names of esters are based on the name of the corresponding carboxylic acid.
Remember esters look like this:

The alkyl group is named like a substituent using the -yl ending. This is
followed by a space. The acyl portion of the name (what is left over) is
 named by replacing the -ic acid suffix of the corresponding carboxylic acid
with -ate.

Here are some examples:

Esters are formed through reactions between an acid and an alcohol with the elimination
of water. An example of this is the reaction of acetic acid with an alcohol, which yields an
acetic ester and water.

The part enclosed by the red circle represents the ethyl group from the alcohol and the
part enclosed by the green rectangle represents the acetate group from the acid.

Esters can be named using a few steps

Esters are named as if the alkyl chain from the alcohol is a substituent. No number is
assigned to this alkyl chain. This is followed by the name of the parent chain from the
carboxylic acid part of the ester with an –e remove and replaced with the ending –oate.

Example
Esters are formed through reactions between an acid and an alcohol with the elimination
of water. An example

1. First, identify the oxygen that is part of the continuous chain and bonded to carbon on
both sides. (On one side of this oxygen there will be a carbonyl present but on the other
side there won't be.)

2. Second, begin numbering the carbon chains on either side of the oxygen identified in
step 1.

3. Next, use this format: [alkyl on side further from the carbonyl] (space) [alkane on the
side with the carbonyl] - (In this case: [methyl] [methane])

4. Finally, change the ending of the alkane on the same side as the carbonyl from -e to -
oate. (In this case: methyl methanoate)
When an ester group is attached to a ring, the ester is named as a substituent on the
ring.

Benzenecarboxylic acid (Benzoic acid)

Other substituents that exist on either side of the ester are named in the same way as they
are on regular alkane chains. The only thing you must make sure of is placing the
substituent name on the part of the name that corresponds to the side of the ester that it
is on.
1-chloromethyl ethanoate

methyl 2-chloroethanoate

CH3COOCH2CH3

methyl propanoate

CH3COOCH2CH2CH2CH2CH2CH2CH2CH3

octyl ethanoate

• Amines

You are only expected to know how to name amines by their common names . They are
named like ethers, the alkyl (R) groups attached to the nitrogen are put in alphabetical
order with no spaces between the names and these are followed by the word amine. The
prefixes di- and tri- are used if two or three of the alkyl groups are the same.
NOTE: Some books put spaces between the parts of the name, but we will not. Follow the
examples.

Here are some examples:

POLYMERS

The simplest definition of a polymer is a useful chemical made of many repeating units. A
polymer can be a three dimensional network (think of the repeating units linked together left and
right, front and back, up and down) or two-dimensional network (think of the repeating units linked
together left, right, up, and down in a sheet) or a one-dimensional network (think of the repeating
units linked left and right in a chain). Each repeating unit is the “-mer” or basic unit with “poly-mer”
meaning many repeating units. Repeating units are often made of carbon and hydrogen and
sometimes oxygen, nitrogen, sulfur, chlorine, fluorine, phosphorous, and silicon. To make the chain,
many links or “-mers” are chemically hooked or polymerized together. Linking countless strips of
construction paper together to make paper garlands or hooking together hundreds of paper clips to
form chains, or stringing beads helps visualize polymers. Polymers occur in nature and can be made
to serve specific needs. Manufactured polymers can be three-dimensional networks that do not melt
once formed. Such networks are called THERMOSET polymers. Epoxy resins used in two-part
adhesives are thermoset plastics. Manufactured polymers can also be one-dimensional chains that can
be melted. These chains are THERMOPLASTIC polymers and are also called LINEAR polymers.
Plastic bottles, films, cups, and fibers are thermoplastic plastics.

Polymers abound in nature. The ultimate natural polymers are the deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA) that define life. Spider silk, hair, and horn are protein polymers. Starch can
be a polymer as is cellulose in wood. Rubber tree latex and cellulose have been used as raw material
to make manufactured polymeric rubber and plastics. The first synthetic manufactured plastic was
Bakelite, created in 1909 for telephone casing and electrical components. The first manufactured
polymeric fiber was Rayon, from cellulose, in 1910. Nylon was invented in 1935 while pursuing a
synthetic spider silk.

The Structure of Polymers

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

Other common manufactured polymers have backbones that include elements other than
carbon. Nylons contain nitrogen atoms in the repeat unit backbone. Polyesters and polycarbonates
contain oxygen in the backbone. There are also some polymers that, instead of having a carbon
backbone, have a silicon or phosphorous backbone. These are considered inorganic polymers. One of
the more famous silicon-based polymers is Silly Putty®.

Molecular Arrangement of Polymers

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

Obviously not all polymers are transparent. The polymer chains in objects that are translucent and
opaque may be in a crystalline arrangement. By definition, a crystalline arrangement has atoms, ions,
or in this case, molecules arranged in distinct patterns. You generally think of crystalline structures
in table salt and gemstones, but they can occur in plastics. Just as quenching can produce amorphous
arrangements, processing can control the degree of crystallinity for those polymers that are able to
crystallize. Some polymers are designed to never be able to crystallize. Others are designed to be
able to be crystallized. The higher the degree of crystallinity, generally, the less light can pass through
the polymer. Therefore, the degree of translucence or opaqueness of the polymer can be directly
affected by its crystallinity. Crystallinity creates benefits in strength, stiffness, chemical resistance,
and stability.

Scientists and engineers are always producing more useful materials by manipulating the molecular
structure that affects the final polymer produced. Manufacturers and processors introduce various
fillers, reinforcements and additives into the base polymers, expanding product possibilities.

PROPERTIES OF POLYMERS

Metals, polymers and ceramics have contrasting physical and chemical properties. Cotton t-
shirts and plastic spoons do not have much in common with bicycle frames or coffee mugs.
Polymers have low densities; do not reflect or absorb light (they are white or colorless); do not
conduct electricity; and are flammable.
A primary reason that polymer properties are different is because the chemical compositions of
metals, polymers and ceramics are totally different. Polymers are composed of non-metallic elements,
found at the upper right corner of the periodic table. Carbon is the most common element in polymers.
The chemical bonds in polymers are also different than those found in metals and ceramics.
5.1 FUNCTIONAL GROUPS IN POLYMERS

Carbon is the most important element in polymers. Because it starts with only four
valence electrons, and wants to share four more, carbon forms a wide variety of covalent bonds.
Most importantly, carbon forms strong bonds with itself. Long, strong chains or nets made of
thousands of carbon atoms form the backbone of a polymer.

C C C C C C C C

C C
C C

carbon backbones
 Polyethylene is the simplest polymer. In addition to the carbon backbone, only hydrogen
atoms are used to achieve four covalent bonds per carbon atom.

H H H H

polyethylene C C C C

H H H H

Although silicon is in the same group as carbon, it does not form strong bonds with itself.
Silicones, long chains of alternating silicon and oxygen atoms, can be synthesized.

silicone Si O Si O Si

Many different nonmetal atoms could be covalently attached to a polymer backbone.

Groups of atoms that contribute something besides C-C and C-H bonds are called functional
groups. They affect the chemical and physical properties of a polymer.

Examples of Functional Groups

acid group (-COOH) C H

O

alcohol group (-OH) O H

H
amino group (-NH2) N
H

chloride (-Cl ) fluoride (-F)

styrene (-C6H6)
SKELETON STRUCTURES

Simplified or "skeleton" structures can be used to emphasize the functional groups.

Carbon-carbon bonds of the framework are represented by line segments. Each vertex is the
location of a carbon atom. Most hydrogen atoms and all lone pairs are omitted. This type of
diagram deemphasizes the hydrocarbon skeleton; since it is so strongly bonded as to be
unreactive, it does not affect the chemical properties of the polymer.
Polyethylene is the simplest polymer. Since it has no functional groups, the skeleton
structure of a polyethylene fragment looks like it does not have any atoms! (Remember that a
real polyethylene molecule is more often 100 or 1000 atoms long.)

polyethylene
It is possible to figure out the missing information. There should be a carbon atom at the
end of each line segment; six are needed, connected by five single bonds.
C C C

C C C
Since each carbon atom must have four bonds in a molecule, there must be missing bonds
to hydrogen atoms. For the carbon atoms on the ends of the molecule, adding three C-H bonds to
each will achieve octets. Two C-H bonds should be added to each of the inner carbons.
H H
H H H H
C C C
H H
C C C
H H H H H
H

complete Lewis structure for polyethylene fragment

three dimensional model of polyethylene

 When functional groups are added to a simplified backbone it is easy to notice the change
in structure. Polyfluoroethylene, often sold as Teflon, is similar in structure to polyethylene
except that all the hydrogen is replaced with fluorine. It is a very slippery polymer.

F F F F
polyfluoroethylene
F F F F

Amino acids, the monomers that build proteins, contain amino groups and acid groups,
separated by one carbon. In the model nitrogen atoms are blue and oxygen atoms are red. The
carbon between the amino group and the acid group always has one hydrogen on it (pointing up
in the model) but the fourth group is variable. The symbol R is used when the exact identity of
the group is not important. More than twenty different groups, as simple as a single hydrogen
atom, are found on amino acids in nature.
O
amino acid H
C H
N O
H
R

The photo shows a model of alanine, which has a -CH3 group.

three dimensional model of amino acid alanine

Polysaccharides are sugar polymers. Cellulose (found in wood, cabbages, cotton, and
linen) is composed of long chains of sugar rings. They are covered with alcohol groups.
 OH

O
OH
OH
O
OH O
cellulose OH OH
O O
OH
OH

OH

Starch contains the same functional groups, but the sugar rings are connected at different
angles. The structural change makes it possible for the human digestive system to digest the
polymer into sugar. Starch polymers are often branched.

OH
O
OH
OH OH

starch O
O
OH OH
O
OH OH OH

5.2 INTERMOLECULAR FORCES

A molecule is a group of atoms connected by covalent bonds. Chemical reactions are

required to form or break covalent bonds. Weaker attractions often form between molecules,
encouraging them to stick together in groups. The weaker attractions are called secondary
bonds or intermolecular forces. These can be overcome by adding heat or dissolving in a
liquid. The functional groups on a polymer determine the type(s) and strength of its secondary
bonds.

POLAR INTERACTIONS

The valence electrons moving around a molecule may not be symmetrically distributed.
The nonmetallic elements closest to the right top corner of the periodic table - nitrogen, oxygen,
fluorine and chlorine - tend to shift shared electrons away from carbon and hydrogen. When
there is a functional group with one of those elements, it has a slight negative charge and the rest
of the molecule (carbon and hydrogen) is slightly positive. The molecule is polarized (or polar,
for short). Its positive sections are attracted to negative sections of neighboring polymers.
 poly(ethylene terephthalate)
"PET"

Poly(ethylene terephthalate) or PET, a polymer used to make bottles for carbonated

beverages, has oxygen-containing functional groups that make it polar. Protein and cellulose
chains are also polar.
Polyfluoroethylene is nonpolar (not polar) because it is completely covered with fluorine
atoms; there is no exposed positive section to interact with a neighboring molecule's negative
section.
Positive and negative charges can be localized on a covalent molecule since they have no
path for conduction of electrons. The carbon atoms in the backbone always follow the octet rule
with four covalent bonds, so can't pass extra electrons along the chain. If polymer fibers are
rubbed together they can build up a static electricity charge.

HYDROGEN BONDS

Molecules with either -N-H or -O-H groups will form strong secondary bonds. This
phenomenon is responsible for the relatively high boiling point of water, and for the fact that its
solid form (ice) is less dense than its liquid form. Polymers with hydrogen-bonding groups will
soak up water.
Fabric softeners are added to laundry to change the properties of cotton and linen fabrics.
The fabric softener molecules have one end that binds to OH groups on cellulose. The other end
of the fabric softener is a long, nonpolar chain. This exposed end feels smooth and slippery.
Softened fabrics are less able to build up a static charge. However softened fabrics will not
absorb as much water. This is an issue for the performance of cotton towels.

NONPOLAR INTERACTIONS

As valence electrons move around the nuclei in a nonpolar polymer, like polyethylene or
polyfluoroethylene, they can become temporarily imbalanced. For a brief moment of time one
part of a molecule would be negative, another part positive; it is temporarily polar. These
occasional imbalances are enough to allow nonpolar molecules to attract each other, but the
interaction is much weaker than that observed for polar or hydrogen bonding polymers.

5.3 POLYMER CLASSES

The most common carbon polymers can be divided into four classes based on the
structures of their carbon backbones, and the resulting physical properties.
FIBERS

Fibers are thread formers, often used to make cloth. Silk, nylon, polyester, and cotton
are all fibers. They are usually flexible, and can be tightly woven without breaking. At the
molecular level they are composed of long carbon chains with few or no branches.
In a fiber strand, multiple polymer molecules line up in parallel. Their intermolecular
forces encourage an ordered, rather crystalline, arrangement. If you pull on both ends of a
strand, it will not stretch very much since the chains are already aligned. Wool is an exception to
this; sulfur atoms in adjacent chains find each other and form sulfur bonds, crosslinking the
chains. This gives wool its crinkly texture.

O
O
H
H
N N

O O O

Sulfur bonds crosslink chains of amino acids

THERMOPLASTICS

The name thermoplastic is given to polymeric materials that are flexible at high
temperatures. Usually they are simply referred to as plastics. For example, a polyethylene milk
jug can be dented without much force. Polymers such as polyethylene can form either fibers or
thermoplastics, depending on how they are processed. A thermoplastic sample has chains going
in random directions, held together by weak secondary bonds. A small amount of force can
make the chains slide around, thus changing the shape of the sample.
If a plastic is cooled it will become stiffer, and eventually brittle. The temperature at
which a plastic becomes brittle is its glass transition temperature. At low temperatures the
polymer chains will not slide past each other because they do not have enough energy to
overcome the secondary bonds.
Small molecules called plasticizers are often mixed into thermoplastics. They reduce the
number of secondary bonds that can form between long polymer chains, making it easier to
modify the shape. The glass transition temperature for a sample with plasticizer is lower.
Plasticizers may evaporate over time (a process that is faster at high temperatures), increasing a
sample's brittleness.

Samples of polymer classes, clockwise from top left: skeins

of wool (fiber), polyethylene jug (thermoplastic),
rubber bands (elastomer), polycarbonate lenses (thermoset).

ELASTOMERS

Stretchy polymers like rubber and spandex are elastomers. They demonstrate the property
of elastic deformation: when force is applied the fiber stretches, but when the force is removed
the fiber returns to its original shape and size. The molecular structure includes chains that prefer
being tangled. If they are stretched and straightened, a restoring force pulls them back into the
shorter, tangled position. Some chains in elastomers may be crosslinked. Rubber can be
vulcanized by heating with sulfur, to create new sulfur crosslinks. This changes flowing latex into
a stiffer material, suitable for automobile tires.

THERMOSETS

With certain polymers, heat can cause crosslinks to form irreversibly. The sample hardens
so its shape is "set." Epoxy resins and some polycarbonates belong in this category. Unlike
thermoplastics, thermoset samples will not soften upon heating.
Characteristics of Polymers

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

Every polymer has very distinct characteristics, but most polymers have the following general
attributes.

1. Polymers can be very resistant to chemicals. Consider all the cleaning fluids in
your home that are packaged in plastic. Reading the warning labels that describe
what happens when the chemical comes in contact with skin or eyes or is ingested
will emphasize the need for chemical resistance in the plastic packaging. While
solvents easily dissolve some plastics, other plastics provide safe, non-breakable
packages for aggressive solvents.

2. Polymers can be both thermal and electrical insulators. A walk through your
house will reinforce this concept, as you consider all the appliances, cords,
electrical outlets and wiring that are made or covered with polymeric materials.
Thermal resistance is evident in the kitchen with pot and pan handles made of
polymers, the coffee pot handles, the foam core of refrigerators and freezers,
insulated cups, coolers, and microwave cookware. The thermal underwear that
many skiers wear is made of polypropylene and the fiberfill in winter jackets is
acrylic and polyester.

3. Generally, polymers are very light in weight with significant degrees of

strength. Consider the range of applications, from toys to the frame structure of
space stations, or from delicate nylon fiber in pantyhose to Kevlar, which is used
in bulletproof vests. Some polymers float in water while others sink. But,
compared to the density of stone, concrete, steel, copper, or aluminum, all plastics
are lightweight materials.

4. Polymers can be processed in various ways. Extrusion produces thin fibers or

heavy pipes or films or food bottles. Injection molding can produce very intricate
parts or large car body panels. Plastics can be molded into drums or be mixed with
solvents to become adhesives or paints. Elastomers and some plastics stretch and
are very flexible. Some plastics are stretched in processing to hold their shape, such
as soft drink bottles. Other polymers can be foamed like polystyrene
(Styrofoam™), polyurethane and polyethylene.
 5. Polymers are materials with a seemingly limitless range of characteristics and
colors. Polymers have many inherent properties that can be further enhanced by a
wide range of additives to broaden their uses and applications. Polymers can be
made to mimic cotton, silk, and wool fibers; porcelain and marble; and aluminum
and zinc. Polymers can also make possible products that do not readily come from
the natural world, such as clear sheets and flexible films.

6. Polymers are usually made of petroleum, but not always. Many polymers are
made of repeat units derived from natural gas or coal or crude oil. But building
block repeat units can sometimes be made from renewable materials such as
polylactic acid from corn or cellulosics from cotton linters. Some plastics have
always been made from renewable materials such as cellulose acetate used for
screwdriver handles and gift ribbon. When the building blocks can be made more
economically from renewable materials than from fossil fuels, either old plastics
find new raw materials or new plastics are introduced.

7. Polymers can be used to make items that have no alternatives from other
materials. Polymers can be made into clear, waterproof films. PVC is used to
make medical tubing and blood bags that extend the shelf life of blood and blood
products. PVC safely delivers flammable oxygen in non-burning flexible
tubing. And anti-thrombogenic material, such as heparin, can be incorporated into
flexible PVC catheters for open heart surgery, dialysis, and blood collection. Many
medical devices rely on polymers to permit effective functioning.

Solid Waste Management

In addressing all the superior attributes of polymers, it is equally important to discuss some of the
challenges associated with the materials. Most plastics deteriorate in full sunlight, but never
decompose completely when buried in landfills. However, other materials such as glass, paper, or
aluminum do not readily decompose in landfills either. Some bioplastics do decompose to carbon
dioxide and water, however, in specially designed food waste commercial composting facilities
ONLY. They do not biodegrade under other circumstances.

For 20051 the EPA characterization of municipal solid waste before recycling for the United States
showed plastics made up 11.8 percent of our trash by weight compared to paper that constituted
34.2 percent. Glass and metals made up 12.8 percent by weight. And yard trimmings constituted
13.1 percent of municipal solid waste by weight. Food waste made up 11.9 percent of municipal
solid waste. The characteristics that make polymers so attractive and useful, lightweight and
almost limitless physical forms of many polymers designed to deliver specific appearance and
functionality, make post-consumer recycling challenging. When enough used plastic items can be
gathered together, companies develop technology to recycle those used plastics. The recycling rate
for all plastics is not as high as any would want. But, the recycling rate for the 1,170,000,000
pounds of polyester bottles, 23.1%, recycled in 2005 and the 953,000,000 pounds of high density
polyethylene bottles, 28.8%, recycled in 2005 show that when critical mass of defined material is
available, recycling can be a commercial success2.

Applications for recycled plastics are growing every day. Recycled plastics can be blended with
virgin plastic (plastic that has not been processed before) without sacrificing properties in many
applications. Recycled plastics are used to make polymeric timbers for use in picnic tables, fences
and outdoor playgrounds, thus providing low maintenance, no splinters products and saving
natural lumber. Plastic from soft drink and water bottles can be spun into fiber for the production
of carpet or made into new food bottles. Closed loop recycling does occur, but sometimes the most
valuable use for a recycled plastic is into an application different than the original use.

An option for plastics that are not recycled, especially those that are soiled, such as used food wrap
or diapers, can be a waste-to-energy system (WTE). In 2005, 13.6% of US municipal solid waste
was processed in WTE systems1. When localities decide to use waste-to-energy systems to manage
solid waste, plastics can be a useful component.

The controlled combustion of polymers produces heat energy. The heat energy produced by the
burning plastic municipal waste not only can be converted to electrical energy but also helps burn
the wet trash that is present. Paper also produces heat when burned, but not as much as do plastics.
On the other hand, glass, aluminum and other metals do not release any energy when burned.

To better understand the incineration process, consider the smoke coming off a burning item. If
one were to ignite the smoke with a lit propane torch, one would observe that the smoke disappears.
This exercise illustrates that the by-products of incomplete burning are still flammable. Proper
incineration burns the material and the by-products of the initial burning and also takes care of air
and solid emissions to insure public safety.

Some plastics can be composted either because of special additives or because of the construction
of the polymers. Compostable plastics frequently require more intense conditions to decompose
than are available in backyard compost piles. Commercial composters are suggested for
compostable plastics. In 20051, composting processed 8.4% of US municipal solid waste.

Plastics can also be safely land filled, although the valuable energy resource of the plastics would
then be lost for recycling or energy capture. In 20051, 54.3% of US municipal solid waste was
land filled. Plastics are used to line landfills so that leachate is captured and groundwater is not
polluted. Non-degrading plastics help stabilize the ground so that after the landfill is closed, the
land can be stable enough for useful futures.

Polymers affect every day of our life. These materials have so many varied characteristics and
applications that their usefulness can only be measured by our imagination. Polymers are the
materials of past, present and future generations.
1 United States Environmental Protection Agency, “Municipal Solid Waste in the United States,
2005 Facts and Figures, EPA530-R-06-011, October 2006
2 American Chemistry Council, “2005 National Post-Consumer Plastics Bottle Recycling

Report”

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