CHAPTER I

ORGANIC COMPOUNDS AND

HYDROCARBONS

1
 INTRODUCTION

Organic chemistry is the study of carbon containing compounds and their properties. It is the
study of molecules containing the carbon-hydrogen (C-H) bond and their structures, properties and
reactions. This includes the great majority of chemical compounds on the planet,but some substances
such as carbonates and oxides of carbon are considered to be inorganic substances even though they
contain carbon.
The word “organic” was originally used by 18th century chemists to describe substances
obtained from living sources - plants and animals. These chemists believed that nature possessed a
certain vital force and that only living things could produce carbon compounds. This Romantic notion
was disproved by Friedrich Wohler, a German chemist who prepared urea, an organic compound, from
the reaction of between the inorganic compounds lead cyanate and the aqueous ammonia:
Pb(NOC)2 + 2NH3 + 2H2O → 2(NH2)2CO + Pb(OH)2
Urea
Organic chemicals are continually released into the environment in large quantities. For
example, global production of mineral oil exceeds 3 billion tonnes a year and the amount of new
organic chemicals made each year in research laboratories and industry is increasing exponentially.
There is a need to understand how these organic molecules will interact with the environment in order
to minimise their impact. To achieve this the type of reactions that organic molecules undergo needs to
be understood.

IMPORTANCE OF ORGANIC CHEMISTRY

1. It is the study of life and all of the chemical reactions related to life.
2. Several careers apply an understanding of organic chemistry, such as doctors, veterinarians,
dentists, pharmacologists, chemical engineers, and chemists.
3. It plays a part in the development of common household chemicals, foods, plastics, drugs, fuels

TIMELINE IN THE DEVELOPMENT OF ORGANIC CHEMISTRY

Year Scientist Contributions
1826 Michel Chevreul Study soaps made from fats and alkalis
1828 Friedrich Wohler Produced Urea from inorganic ammonium cyanate
(Wohler synthesis)
1856 William Henry Perkin Manufactured accidentally the organic dye (Perkin’s Mauve)
1858 Firedrich August Kekule Developed the concept of tetravalent structure of carbon
and Archibald Scott atoms in bonding to one another to form carbon lattice
Couper
1900 Bayer Manufactured Acetylsalicylic acid ( aspirin) in Germany
1914 Adolf von Baeyer Developed synthetic method of producing indigo from
petrochemicals
20th century Polymers and enzymes were shown/ development of
petrochemical industry.

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 COMPARISON BETWEEN INORGANIC AND ORGANIC COMPOUNDS
Organic Compounds Inorganic Compounds
1. Many are soluble in organic solvents such as 1. Most are not soluble in organic solvents
petroleum, benzene and hexane
2. Mostly insoluble in water (hydrophobic) 2. Many are water soluble
3. Solution in water generally do not conduct 3. When dissolved in water conducts
electricity electrical current
4. Almost all burn (flammable) 4. Most not combustible
5. Use mostly covalent bonding 5. Mostly ionic bonding
6. Slow to react with other chemicals 6. Often undergo fast chemical reactions
7. Are gases, liquids or solids with low melting 7. Are generally solids with high melting
points points

Examples of Organic Compounds:

Sugar, acetic acid, alcohol, carbohydrates, gasoline, plastics, fats, oils, dyes, soap
Examples of Inorganic Compounds
Cyanide, carbon dioxide, water, oxygen, hydrogen, metallic compounds, bicarbonates (-HCO3-)
carbonates (-CO32-) minerals

The vast majority of organic compounds are typically chains or rings of carbon atoms that
contain other elements such as O, N, P, S, Cl, Br and I. There are over five million of these compounds
known today and an almost infinite number of new compounds could possibly be synthesized. This
can be compared to the total number of inorganic compounds, which is approximately half a million.

Why does carbon form so many compounds?

Carbon has the ability to bond with itself to form long chains and ring structures; hence it can form
molecules that contain from one to an infinite number of C atoms.
Additionally C atoms may:
1. be bonded by multiple bonds (i.e. double and triple) as well as single
2. contain branches of other carbon chains
3. need additional atoms attached to them to make them stable. The most common of these is H,
but, N, O, X, P and S also commonly occurs attached to C and may even be attached in several
different ways.

THE UNIQUE CARBON ATOM

Carbon has the following properties:
 Has atomic number of 6 and has 6 electrons ● Its electronic structure is 1s2 2s2 2p2
 It has valence electrons of 4. ● ● Carbon has 4 covalent bonds
 Its Lewis -electron dot structure is ●C ●
●
 Its orbital notation is 6C- 2s ↑↓ 2p ↑ ↑

3
HYBRIDIZATION OF CARBON
Comparing Hybrid Types
Type of Hybrid sp3 sp2 sp
Atomic orbitals used s, p, p, p s, p, p s, p
Number of hybrid orbitals 4 3 2
formed
Number of atoms bonded to 4 3 2
the C
Number of sigma bonds 4 3 2
Number of left over p orbitals 0 1 2
Number of pi bonds 0 1 2
Bonding pattern | \ =C=
-C- C= or
| / -C

Example: Indicate the hyrbrid orbitals of each C in the following molecule: H3C - CH2 – CH = CH2-CH3
How many sigma and pi bonds are there? 15 sigma and 1 pi bond sp3 sp3 sp2 sp2 sp3

CLASSIFICATION OF ORGANIC COMPOUNDS

Classes of compounds can be distinguished according to functional groups they contain.
Functional group – is a group of atoms that is largely responsible for the chemical behavior of the
parent molecule.
*Different molecules containing the same kind of functional group or groups undergo similar
reactions.
*All organic compounds are derived from a group of compounds known as HYRDOCARBONS
because they are made up of only hydrogen and carbon.

Two Main Classes of Hydrocarbons:

1. Aliphatic hydrocarbons – do not contain the benzene group or benzene ring.
2. Aromatic hydrocarbons – contain one or more benzene rings.

ALIPHATIC COMPOUNDS
1. According to State of Saturation:
A. Saturated Hydrocarbons – they contain the maximum number of hydrogen atoms that can
bond with the number of carbon atoms present.

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 1. Alkanes( paraffins) – with single bond,
B. Unsaturated Hydrocarbons
2. Alkenes( olefins) - contain one or more double bonds
3. Alkynes - have one or more triple bonds.

2. According to the Functional Groups Present:

1. "straight-chain" or normal (n)
2. branched-chain
3. cyclic /ring

Saturated cyclic compounds contain single bonds only, whereas aromatic rings have an
alternating (or conjugated) double bond
*The degree of branching affects characteristics, such as the octane number or cetane number in
petroleum chemistry.

ALKANES
Alkanes are the simplest family of hydrocarbons - compounds containing carbon and
hydrogen only. They only contain carbon-hydrogen bonds and carbon-carbon single bonds. They
have the general formula, CnH2n+2 where n = 1,2, 3, . . . . They are occasionally called aliphatic
compounds a word derived from the Greek aleiphas, meaning “fat”.

Unbranched/Straight-Chain Alkanes
- each additional carbon is added to the end to form one long continuous chain and there
are only single bonds in the main chain of the molecule.
 The formulas and structures of these alkanes increase uniformly by a CH2 increment.
 A uniform variation of this kind in a series of compounds is called homologous.
 These formulas all fit the CnH2n+2 rule. This is also the highest possible H/C ratio for a stable
hydrocarbon.
 Since the H/C ratio in these compounds is at a maximum, we call them saturated (with
hydrogen).

Name Molecular Formula Structural formula Isomers

methane CH4 CH4 1
ethane C2H6 CH3CH3 1
propane C3H8 CH3CH2CH3 1
butane C4H10 CH3CH2CH2CH3 2
pentane C5H12 CH3(CH2)3CH3 3
hexane C6H14 CH3(CH2)4CH3 5
heptane C7H16 CH3(CH2)5CH3 9
octane C8H18 CH3(CH2)6CH3 18
nonane C9H20 CH3(CH2)7CH3 35
decane C10H22 CH3(CH2)8CH3 75
undecane C11H24
dodecane C12H26

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 FORMULAE OF ALKANES
A. Molecular Formula – gives the total number of atoms in a molecule. Methane, CH4
B. Structural Formula - shows how the various atoms are bonded.
a. Expanded Structural formula

b. Condensed Structure Formula – the bonds are not drawn in a molecule, the C-C and C-H
bonds are “understood” rather than shown.
Example: Butane, C4H10 CH3CH2CH2CH3

C. Skeletal Formula
In a skeletal formula, all the hydrogen atoms are removed from carbon chains, leaving just a
carbon skeleton with functional groups attached to it.
For example, butan-2-ol. The normal structural formula and the skeletal formula look like
this:

In a skeletal diagram of this sort,

a. there is a carbon atom at each junction between bonds in a chain and at the end of each bond
(unless there is something else there already - like the -OH group in the example);
b. there are enough hydrogen atoms attached to each carbon to make the total number of bonds
on that carbon up to 4.

Practice Exercises:
A. Write the molecular formula for each of the following:
1. CH3 – CH2 – CH2 – CH2 – CH2 – CH3 4. CH3 – CH2 – CH2 – CH2 – Br
2. CH3 – CH2 – CH2 – CH2 – Cl 5. CH3 – CH– CH2 – CH2 – CH3
I
3. CH3 – CH2 – CH2 – CH2 – CH3 CH2

B. Write condensed structural formula of the following:

H H H H H H H
H H H H
I I I I I I I
I I I I
1. H ―C ― C ―C―C― H 2. 3. H―C ― C ―C―S― H
H―C ― C ―C―C― H
I I I I I I I
I I I I
H H H H H H H
H Br H H
C. Draw the skeletal formula of the following structural formulas.
1. 2. 3. 2–methylheptane

4. (CH3)2CHCH2CH3 5. 4-ethylhexane

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 ISOMERS
Isomers are molecules that have the same molecular formula, but have a different arrangement of
the atoms in space.
Structural Isomers – molecules that have the same molecular formula, but the atoms are arranged in
a completely different order/structures.
All the alkanes with 4 or more carbon atoms in them show structural isomerism.
For example, C4H10 could be any of these four different molecules.

Types of Structural Isomerism

1. Chain isomerism
These isomers arise because of the possibility of branching in carbon chains.

For example, there are two isomers of butane, C4H10. In one of them, the carbon atoms lie in
a "straight chain" whereas in the other the chain is branched.

Pentane, C5H12, has three chain isomers.

2. Position isomerism
In position isomerism, the basic carbon skeleton remains unchanged, but important groups
are moved around on that skeleton.

For example, there are two structural isomers with the molecular formula C3H7Br. In one of
them the bromine atom is on the end of the chain, whereas in the other it's attached in the middle.

3. Functional group isomerism

In this variety of structural isomerism, the isomers contain different functional groups - that is,
they belong to different families of compounds (different homologous series).

For example, a molecular formula C3H6O could be either propanal (an aldehyde)or
propanone(a ketone).

Practice Exercises:
1. Draw the structure for the three isomers of C8H18.
2. Draw the structure for the five isomers of C6H14.

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 ALKANE NOMENCLATURE

IUPAC RULES;
1. Find and name the longest continuous carbon chain.
2. Identify and name groups attached to this chain.
3. Number the chain consecutively, starting at the end nearest a substituent group.
4. Designate the location of each substituent group by an appropriate number and name.
5. Assemble the name, listing groups in alphabetical order using the full name (e.g. cyclopropyl
before isobutyl).
The prefixes di, tri, tetra etc., used to designate several groups of the same kind, are not considered
when alphabetizing.
ALKYL GROUP
If a hydrogen is removed from an alkane, the partial structure that remains is called an ALKYL
GROUP. Alkyl groups are named by replacing the –ane ending of the parent alkane with an –yl
ending.
Examples of some common alkyl groups are given in the following table. The symbol R is used
to designate a generic (unspecified) alkyl group.

Group Name Group Name

CH3– Methyl (CH3)2CHCH2– Isobutyl
C2H5– Ethyl CH3CH2CH(CH3)– sec-Butyl
CH3CH2CH2– Propyl (CH3)3C– tert-Butyl
(CH3)2CH– Isopropyl R– Alkyl
CH3CH2CH2CH2– Butyl

Examples:

a. hexane b. 2-methylpentane c. 3-methylpentane

d. 2,2-dimethylbutane e. 2,3-dimethylbutane

Practice Exercises: Name the following compounds:

1. 2. 3. 4. 5.

IUPAC RULES FOR NAMING BRANCHED COMPOUNDS

1. Determine the longest continuous chain, this will be the parent chain. Give the parent chain a
prefix matching the number of carbon’s in it.
2. Assign #’s to each C of the parent chain so that the numbers of all attached side pieces add up to
the smallest sum.
3. Determine the correct name for each branch or other atom or group.
4. Attach the name of the alkyl group or other substituent to the name of the parent as a prefix. Place
the location # in front and separate from the name by a hyphen.
5. When 2 or more groups are attached, name each, and locate them by number. Always use hyphens
to separate the #'s from each other.

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6. When 2 or more of the substituents are identical, use special prefixes such as "di" for 2, "tri" for
three and "tetra" for 4 and specify the location #'s of every group.
7. When identical groups are on the same carbon in the parent chain, repeat the number on the
parent
carbon.
8. Halogen substituents are easily accommodated, using the names: fluoro (F-), chloro (Cl-), bromo
(Br-) and iodo (I-).
For example, (CH3)2CHCH2CH2Br would be named 1-bromo-3-methylbutane.
If the halogen is bonded to a simple alkyl group an alternative "alkyl halide" name may be
used. Thus, C2H5Cl may be named chloroethane (no locator number is needed for a two carbon chain)
or ethyl chloride. Halogenated alkyl substituents such as bromomethyl, BrCH2–, and trichloromethyl,
CCl3–, may be listed and are alphabetized according to their full names.

Practice Exercises: Give the IUPAC name of the following compounds:

1. 2. 3.

4. 5. Cl

CYCLOALKANES
Cycloalkanes contain carbon-hydrogen bonds and carbon-carbon single bonds, but this time
the carbon atoms are joined up in a ring. The smallest cycloalkane is cyclopropane.

Name Molecular Formula Structural Formula Line Formula

Cyclopropane C3H6

Cyclobutane C4H8

Cyclopentane C5H10

Cyclohexane C6H12

Cycloheptane C7H14

Cycloalkane CnH2n (CH2)n

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 IUPAC Rules for Cycloalkane Nomenclature
1. For a monosubstituted cycloalkane the ring supplies the root name (table above) and the
substituent group is named as usual. A location number is unnecessary.
2. If the alkyl substituent is large and/or complex, the ring may be named as a substituent group on
an alkane.
3. If two different substituents are present on the ring, they are listed in alphabetical order, and the
first cited substituent is assigned to carbon #1. The numbering of ring carbons then continues in a
direction (clockwise or counter-clockwise) that affords the second substituent the lower possible
location number.
4. If several substituents are present on the ring, they are listed in alphabetical order. Location
numbers are assigned to the substituents so that one of them is at carbon #1 and the other
locations have the lowest possible numbers, counting in either a clockwise or counter-clockwise
direction.
5. The name is assembled, listing groups in alphabetical order and giving each group (if there are
two or more) a location number. The prefixes di, tri, tetra etc., used to designate several groups of
the same kind, are not considered when alphabetizing.
Examples:

Practice Exercises: Name the following cycloalkanes:

1. 2. CH3 3. 4.
Cl

CIS-TRANS ISOMERISM IN CYCLOALKANES

- the same connections but differ in the spatial orientation of the atoms.
Because of their cyclic structures, cycloalkanes have two sides: a “top” side and a “bottom” side. As a
result, isomerism is possible in substituted cycloalkanes.
For example:
CH3 CH3 CH3 H

H H H CH3

Cis-1,2-Dimethylcyclopropane trans-1,2dimethylcyclopropane

Cis – is used if the substitutes are on the on the same side

Trans – is used if the substitutes are across.

Practice Exercise:
1. Draw both cis and trans isomers of 1,2-dibromocyclobutane.
2. Draw cis-1,4-dimethylcyclohexane

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 PROPERTIES AND USES OF ALKANES
Alkanes are sometimes referred to as paraffins, a word derived from the latin parum affinis,
meaning “slight affinity”.
Physical Properties of Alkanes:
1. Alkanes are colourless and odorless.
2. Alkanes are less dense than water (alkanes float on top of water).
3. Alkanes are non-polar molecules so they are more soluble in non-polar solvents than they are in
polar solvents. Alkanes are insoluble in water.
4. The melting and boiling points of the shorter chain alkanes is low, but the melting and boilings of
alkanes increase as the number of carbon atoms in the carbon chain increases.
5. The alkanes can exist as gases (lower alkane), liquids (middle alkane), or solids (higher alkane) at
room temperature. The unbranched alkanes methane, ethane, propane, and butane are
gases; pentane through hexadecane are liquids; the homologues larger than hexadecane
are solids
6. Alkanes show regular increases in both boiling point and melting point as molecular weight
increases.
7. Branched chain alkanes have decrease surface area while long chain alkanes have high surface area
8. Alkanes with even number of carbon has higher melting point while odd number of carbon have
lower melting point
9. Alkanes having higher molecular weight decreases their solubility. The higher the density the
higher the molecular weight.

The density of air is about 1.29 g/L. Because natural gas is less dense than air, it rises. When a
natural-gas leak is detected and shut off in a room, the gas can be removed by opening an upper
window. On the other hand, bottled gas can be either propane (density 1.88 g/L) or butanes (a
mixture of butane and isobutane; density about 2.5 g/L). Both are much heavier than air (density 1.2
g/L). If bottled gas escapes into a building, it collects near the floor. This presents a much more
serious fire hazard than a natural-gas leak because it is more difficult to rid the room of the heavier
gas.

Physical Properties of Some Alkanes

Molecular Formula Melting Point Boiling Point Density Physical State
Name (°C) (°C) (20°C)* (at 20°C)

methane CH4 –182 –164 0.668 g/L gas

ethane C2H6 –183 –89 1.265 g/L gas

propane C3H8 –190 –42 1.867 g/L gas

butane C4H10 –138 –1 2.493 g/L gas

pentane C5H12 –130 36 0.626 g/mL liquid

hexane C6H14 –95 69 0.659 g/mL liquid

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 Molecular Formula Melting Point Boiling Point Density Physical State
Name (°C) (°C) (20°C)* (at 20°C)

octane C8H18 –57 125 0.703 g/mL liquid

decane C10H22 –30 174 0.730 g mL liquid

*Note the change in units going from gases (grams per liter) to liquids (grams per milliliter). Gas
densities are at 1 atm pressure.
Practice Exercises:
1. Without referring to a table, predict which has a higher boiling point—hexane or octane. Explain.
2. If 25 mL of hexane were added to 100 mL of water in a beaker, which of the following would you
expect to happen? Explain.
a. Hexane would dissolve in water.
b. Hexane would not dissolve in water and would float on top.
c. Hexane would not dissolve in water and would sink to the bottom of the container
3. Without referring to a table or other reference, predict which member of each pair has the higher
boiling point, a. pentane or butane? b. heptane or nonane?
4. For which member of each pair is hexane a good solvent,
a. pentane or water? b. sodium chloride or soybean oil?

Chemical Properties of Alkanes:

1. Alkanes are relatively unreactive.
2. Alkanes do not react with strong acids, bases, oxidising agents (oxidants) or reducing agents
(reductants).
3. Alkanes combust (react rapidly with oxygen) releasing energy, which makes alkanes useful as fuels.
4. Alkanes will react with halogens such chlorine gas and bromine water in the presence of ultraviolet
light.

ALKENES
Alkene is a molecule made up entirely of carbon and hydrogen where one or more carbon
atoms are connected by double bonds. The general formula for an alkene is CnH2n where n is the
number of carbon atoms in the molecule.
Alkanes are named by adding the the -ene suffix to the prefix associated with the number of
carbon atoms present in the molecule. A number and dash before the name denotes the number of
the carbon atom in the chain that begins the double bond.
For example: 1-hexene is a six carbon chain where the double bond is between the first and
second carbon atoms.
Straight –chain Alkenes
Name Molecular Structures of Name Molecular Structures of Alkenes
Formula Alkenes Formula
ethene C2H4 CH2 = CH2 hexene C6H12 CH2=CH CH2 CH2CH2CH3
propene C3H6 CH2=CHCH3 heptene C7H14 CH2=CH CH2 CH2CH2CH2CH3
butene C4H8 CH2=CH CH2CH3 octene C8H16 CH2=CHCH2CH2 CH2CH2CH2CH3
pentene C5H10 CH2=CH CH2CH2CH3 nonene C9H18 CH2=CHCH2CH2CH2CH2 CH2 CH2CH3

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 IUPAC Rules for Alkene and Cycloalkene Nomenclature
1. The ene suffix (ending) indicates an alkene or cycloalkene.
2. The longest chain chosen for the root name must include both carbon atoms of the double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If the
double bond is in the center of the chain, the nearest substituent rule is used to determine the end
where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is used as the
double bond locator. If more than one double bond is present the compound is named as a diene,
triene or equivalent prefix indicating the number of double bonds, and each double bond is assigned
a locator number.
5. In cycloalkenes the double bond carbons are assigned ring locations #1 and #2. Which of the two
is #1 may be determined by the nearest substituent rule.
6. Substituent groups containing double bonds are:
H2C=CH– Vinyl group H2C=CH–CH2– Allyl group

Examples:

Practice Exercise: Give the IUPAC name of the following compounds:

1. 2.
C2H5
CH3 ― CH ―CH ―CH=CH2
I
I I
CH3―CH=CH―CH ―CH―CH3
CH3 CH3
I
CH3
CH3
I
CH2=CH ― CH ―CH =CH2―CH3
3.
I
CH3
CIS-TRANS ISOMERS OF ALKENES
Cis-trans isomerism is not limited to disubstituted alkenes. It occurs whenever double-bond
carbons are attached to two different groups.
Example: Cis and trans isomers of 2-butene
CH3 CH3 H CH3
C=C C=C
H H CH3 H
Cis-2-Butene Trans-2-Butene

Practice exercise:
1. Draw the cis and trans isomers of 5-chloro-2-pentene
2. Draw the structure of 4-Ethyl-1,3-pentadiene.

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IMPORTANT USES OF ALKENES
Alkenes occur abundantly in nature and many have important biological roles. Ethylene, for
example, is a plant hormone that induces ripening in fruits and ∞-pinene is the major constituent of
turpentine. Another is β-carotene which contains 11 double bonds, found in carrots and is a valuable
dietary source of vitamin A.

Name of Uses Name of Uses

alkene alkene
A Flammable gas Synthetic
produced by styrene- contain in
Acetylene the reaction of butadiene bubble gums
calcium carbide and
water

TEFLON Used in Β-Carotene Found in carrots

Polytetrafluoro nonstick provides
ethylene frying pan. approximately 50% of
the vitamin A

is a plant hormone
also known as that induces ripening
Alpha-Pinene TERPENE, is found Ethylene of fruits
in eucalyptus oil

ALKYNES
An alkyne is a molecule made up entirely of carbon and hydrogen where on or more carbon
atoms are connected by triple bonds. The general formula for an alkyne is CnH2n-2 where n is the
number of carbon atoms in the molecule.
The alkyne series is very similar to the alkane and alkene series. They all have at least one
triple bond. The triple bond prevents rotation but it also prevents the formation if cis and trans
structures in the parent chain.

Straight –chain Alkynes

Name Molecular Structures of Name Molecular Structures of Alkenes
Formula Alkenes Formula
ethyne C2H2 CH ≡CH hexyne C6H10 CH ≡CCH2 CH2CH2CH3
propyne C3H4 CH ≡CCH3 heptyne C7H12 CH ≡CCH2 CH2CH2CH2CH3
butyne C4H6 CH ≡CCH2CH3 octyne C8H14 CH ≡CCH2CH2 CH2CH2CH2CH3
pentyne C5H8 CH ≡CH2CH2CH3 nonyne C9H16 CH ≡CCH2CH2CH2CH2 CH2 CH2CH3

IUPAC Rules for Alkyne Nomenclature

1. The yne suffix (ending) indicates an alkyne or cycloalkyne.
2. The longest chain chosen for the root name must include both carbon atoms of the triple bond.
3. The root chain must be numbered from the end nearest a triple bond carbon atom. If the triple
bond is in the center of the chain, the nearest substituent rule is used to determine the end

14
 where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the triple bond is used as the
triple bond locator.
5. If several multiple bonds are present, each must be assigned a locator number. Double bonds
precede triple bonds in the IUPAC name, but the chain is numbered from the end nearest a
multiple bond, regardless of its nature.
6. Because the triple bond is linear, it can only be accommodated in rings larger than ten carbons. In
simple cycloalkynes the triple bond carbons are assigned ring locations #1 and #2. Which of the
two is #1 may be determined by the nearest substituent rule.
7. Substituent groups containing triple bonds are: HC≡C– Ethynyl group HC≡CH–CH2– Propargyl
Examples:
1. 2- pentyne 2. propyne 3. 5-ethyl-4-methyl-2-hexyne
CH≡CH2 ― CH2 CH―C≡ C ―CH ―CH2―CH3
I I
Practice Exercise: Give the IUPAC name of the following compounds: CH3 C2H3
1. 2. CH3 ― CH ―CH2 ―C≡CH
CH3―CH2―CH―C≡ C―CH3 I
I C2H3
CH3

AROMATIC HYDROCARBONS
Aromatic hydrocarbons contain conjugated double bonds. This means that every carbon atom
in the ring is sp2 hybridized, allowing for added stability. The most important example is benzene, the
structure of which was formulated by Kekulé who first propose
the delocalization or resonance principle for explaining its structure.

In aromatic hydrocarbons the root word 'aroma' means

perfume. All the aromatic compounds have characteristic smell and
many of them are used as perfumes. Benzene, naphthalene are
example for aromatic hydrocarbon.
Benzene is one of the best-known aromatic
compounds as is one of the simplest and most stable aromatics.

Benzene Derivatives
The nomenclature of substituted benzene ring compounds is less systematic than that of the
alkanes, alkenes and alkynes. A few mono-substituted compounds are named by using a group name
as a prefix to "benzene", as shown by the combined names listed below

15
 IUPAC Rules for Aromatic Nomenclature
1. For monosubstituted benzene,consists of 1 substituent, name the group followed by benzene.
CH3

Methyl benzene (usually called toluene)

2. For di-substituted benzenes, indicate the location of the second group relative to the first.

H3C
benzenes). They are defined as the following:
 ortho- (o-): 1,2- (next to each other in a benzene ring)
 meta- (m): 1,3- (separated by one carbon in a benzene ring)
 para- (p): 1,4- (across from each other in a benzene ring) Cl
Cl Cl
Cl

Cl

H3C
Cl
a b c
H3C
H3C

1,2 –dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene

o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene.
3. In some molecules benzene is named as a substituent. A benzene molecule minus a hydrogen atom
(C6H5) is called phenyl group. CH3 – CH2 – CH2 – CH3

Practice Exercise:
A. Draw the following aromatic hydrocarbons:
H3C

a. ethyl benzene b. m-bromoiodobenzene c. o-nitrotoluene

B. Give the name of the aromatic hydrocarbon

a. Br b. NO2
Br
Br

What are PAHs?

H3C
H3C

Short for polycyclic aromatic hydrocarbons, PAHs describe chemicals that are often found
together in groups of two or more. They are hydrocarbons made up of two or more benzene rings
fused together without any other substituents
Examples:

PAHs comprise a group of over 100 different chemicals that are produced during the
incomplete burning of fuels, garbage or other organic substances such as tobacco, plant material or
meats. These combustion processes produce a mixture of chemicals with soot being a well known
example. Tobacco smoke contains many chemicals including PAHs which are found in the tar that
accumulates in the lungs of smokers.
16
 Some of these PAHs are manufactured
for research or are used in medicines, dyes,
plastics and pesticides such as naphthalene
found in mothballs. PAHs can also be found in
coal tar, bitumen, crude oil, creosote and
roofing tar.
The distribution of PAHs in the
environment is extensive and the general public
may be exposed to PAHs found in soil/dust, air,
water, food or household products.

ORGANIC REACTIONS OF ALIPHATIC HYDROCARBONS

Organic reactions often much slower than inorganic reactions
- must break strong covalent bond
- trying to find new catalysts to use
Types of Organic Reactions:
1. Addition Reactions – oocur when two reactants add together to form a single new productwtih no
atoms ‘left over”. A + B → C
 In addition reaction, substance is added at the double or triple bond location, after it is broken
Note: In double bonded alkenes, it is easier to break a bond than in single bond alkanes
 If a halogen is added in an addition reaction, the result is a halocarbon that is disubstituted.
Example: CH2 = CH2 + HCl → CH3-CH2Cl
 Addition of water to an alkene is a hydration reaction - usually occurs with heat and an acid
(such as HCl or H2SO4 acting as a catalyst)
CH2 = CH2 + H2 O
 The hydrogenation of a double bond is a reduction reaction, which in one sense is defined as
the gain of H Example: ethene is “reduced” to ethane; cyclohexene is “reduced” to
cyclohexane
 Addition of hydrogen to produce an alkane is a hydrogenation reaction, which usually involves
a catalyst such as Pt or Pd
– common application is the manufacture of margarine from unsaturated vegetable oils
(making them solid from a liquid)
2. Elimination Reactions - are the opposite of addition reactions. They occur when a single reactant
splits into two products. A → B + C
 Alkyl halides split apart into acid and alkene when treated with base.
Example: NaOH
CH3-CH2Cl → CH2 = CH2 + HCl
3. Substitution Reactions - occur when two reactants exchange parts to give to new products.
A -B + C-D → A–C + B-D
 In a substitution, an atom (or group of atoms) replaces another atom or group of atoms
 A halogen (shown as “X”) can replace a hydrogen to make a halocarbon: R-H + X2 Õ R-X + HX
Example: light
CH4 + Cl2 → CH2Cl + HCl

17
4. Rearrangement Reactions – occur when a single reactant undergoes a reorganization of bonds and
atoms to yield a single isomeric product. A → B
Example: cis-2-butene can be converted into its isomeric trans-2-butene by treatment with an acid

CH3 CH3 H CH3

acid catalyst C=C
C=C
H H CH3 H
Cis-2-Butene Trans-2-Butene

Practice exercises:
A. Classify the following organic reactions :
1. CH3Br + KOH → CH3OH + KBr 3. CH3 CH2OH → CH2 = CH2 + H2O
2. CH2 = CH2 + H2 → CH3CH3

B. Predict the products and classify the type of reaction

1. Propane reacts with fluorine
2. Bromine and ethene react to form an alkyl halide.
3. Chloromethane is produced by reacting methane and chlorine.

18
 Chapter 2
FUNCTIONAL GROUPS

19
 FUNCTIONAL GROUPS

FUNCTIONAL GROUPS are specific groups of atoms within molecules, that are responsible for
the characteristic chemical reactions of those molecules. The same functional group will undergo the
same or similar chemical reaction(s) regardless of the size of the molecule it is a part of.
They consist of one or more atoms, and they can be atoms of identical or different
elements. The simplest organic molecule is one carbon bonded covalently to four hydrogens, CH4.
Functional groups are attached to the carbon backbone of organic molecules. They determine
the characteristics and chemical reactivity of molecules. Functional groups are far less stable than the
carbon backbone and are likely to participate in chemical reactions.

LIST OF COMMON FUNCTIONAL GROUPS

Functional Name Functional Name Functional Name

Group Group Group
Halogen
R-X Derivatives Aldehyde Ketone

Alcohol Carboxylic
Ether Acid

Ester Amine Amide

1. HALOALKANES (ALSO KNOWN AS HALOGENOALKANES) (ALKYL HALIDES)

20
 Haloalkanes are a group of chemical compounds, consisting of alkanes, such as methane or
ethane, with one or more halogens linked, forming an organic halide. The most widely known family
within this group are the chlorofluorocarbons (CFCs). They have the general formula R-X where R-
represents some alkyl or aryl group and -X represents one of the members of the halogen family:
fluorine, chlorine, bromine and/or iodine.

R-X R-F R-Cl R-Br R-I

Halogen Derivatives Fluoro- Chloro- Bromo- Iodo-

IUPAC Rules for HaloAlkane Nomenclature

1. Identify the longest alkane chain, ending with -ane.
2. Locate the position of carbon where the halogen
group is attached. Halogen functional groups are
prefixed with the bonding position and take
the form fluoro-, chloro-, bromo-, iodo-, etc.,
depending on the halogen.
3. Multiple groups are dichloro-, trichloro-, etc.,
and dissimilar groups are ordered alphabetically as before.
For example, CHCl3 (chloroform) is trichloromethane. The anesthetic Halothane (CF3CHBrCl) is
2-bromo-2-chloro-1,1,1-trifluoroethane.

Practice Exercise: Name the following:

1. 2. CH3 ― CH ―CH ―CH ─ CH2 3.
[Grab your reader’s attention with a great quote I I from the
document or use this space to emphasize a key point. To
Cl Cl
place this text box anywhere on the page, just drag it.]

2. ALCOHOL
Alcohols are compounds in which one or more
hydrogen atoms in an alkane have been replaced by
an -OH group (Hydroxyl Group). It can be regarded as
a derivative of water, with an alkyl group replacing
one of the hydrogens.
Example: CH3CH2OH - ethanol (grain alcohol)

IUPAC Rules for Alcohol Nomenclature

1. The name of the alkane chain loses the terminal "e"
and adds "ol",
Example: "methanol" and "ethanol".
2. The position of the hydroxyl group is indicated by
a number between the alkane name and the
"ol": propan-1-ol for
CH3CH2CH2OH, propan-2-ol for
CH3CH(OH)CH3.

21
3. The position number is written before the IUPAC name: 1-propanol and 2-propanol.
4. Alcohol called with the name of the corresponding alkyl group followed by the word "alcohol",
e.g., methyl alcohol, ethyl alcohol.
5. Propyl alcohol may be n-propyl alcohol or isopropyl alcohol, depending on whether the hydroxyl
group is bonded to the 1st or 2nd carbon on the propane chain.
6. If an aryl group is present rather than an alkyl, the compound is generally called a phenol rather
than an alcohol.

KINDS OF ALCOHOLS
Alcohols fall into different classes depending on how the -OH group is positioned on the chain
of carbon atoms. There are some chemical differences between the various types.
1. Primary alcohols
In a primary (1°) alcohol, the carbon which carries the -OH group is only attached to one alkyl
group. Example: CH3 CH2OH - ethanol
2. Secondary alcohols
In a secondary (2°) alcohol, the carbon with the -OH group attached is joined directly
to two alkyl groups, which may be the same or different. Example: OH - 2- propanol
|
3. Tertiary alcohols CH3CHCH3
In a tertiary (3°) alcohol, the carbon atom holding the -OH group is attached directly
to three alkyl groups, which may be any combination of same or different.
OH
Example: CH3 -C- CH3 - 2-methyl- 2-propanol
CH3
Practice Exercise: Classify and give the IUPAC name of the following alcohol.

1. CH3 CH2CH2CH(OH)CH2CH3 2. 3.

Common names of Alcohol

Chemical Formula IUPAC Name Common Name

CH3OH Methanol Wood alcohol
C2H5OH Ethanol Alcohol
C3H7OH Isopropyl alcohol Rubbing alcohol
C4H9OH Butyl alcohol Butanol
C5H11OH Pentanol Amyl alcohol
C16H33OH Hexadecan-1-ol Cetyl alcohol

Physical and Chemical Properties of Alcohol

1. Alcohols have an odor that is often described as “biting” and as “hanging” in the nasal passages.
Ethanol has a slightly sweeter (or more fruit-like) odor than the other alcohols.
2. Solubility of alcohols in water
In general, the hydroxyl group makes the alcohol molecule polar. This hydrogen bonding
means that alcohols can be used as protic solvents. Two opposing solubility trends in alcohols are: the
tendency of the polar OH to promote solubility in water, and the tendency of the carbon chain to
resist it.

22
  methanol, ethanol, and propanol are miscible in water because the hydroxyl group wins out
over the short carbon chain.
 Butanol, with a four-carbon chain, is moderately soluble because of a balance between the
two trends.
 Alcohols of 5 or more carbons (pentanol & higher) are effectively insoluble in water because
of the hydrocarbon chain's dominance. All simple alcohols are miscible in organic solvents.
3. Boiling Points
Because of hydrogen bonding, alcohols tend to have higher boiling points than
comparable hydrocarbons and ethers.
 The boiling point of the alcohol ethanol is 78.29 °C, compared to 69 °C for the
hydrocarbon hexane (a common constituent of gasoline), and 34.6 °C for diethyl ether.
 The boiling point of an alcohol is always much higher than that of the alkane with the same
number of carbon atoms.
 The boiling points of the alcohols increase as the number of carbon atoms increases.
4. Alcohols, like water, can show either acidic or basic properties at the -OH group.
 They are slightly weaker acids than water, but they are still able to react with strong bases
such as sodium hydride or reactive metals such as sodium. The salts that result are
called alkoxides, with the general formula RO- M+.

Important Uses of Alcohol

An important class of alcohols are the simple acyclic alcohols, the general formula for which is
CnH2n+1OH.
a. Alcoholic beverages
Alcoholic beverages, typically containing 1–50% ethanol by volume, have been produced and
consumed by humans since pre-historic times. Ethanol (C2H5OH) is the alcohol found in alcoholic
beverages. Other alcohols such as 2-methyl-2-butanol and γ-hydroxybutyric acid are also consumed
by humans for their psychoactive effects.
b. Antifreeze
A 50% v/v (by volume) solution of ethylene glycol in water is commonly used as an antifreeze.
c. Antiseptics
Ethanol can be used as an antiseptic to disinfect the skin before injections are given, often
along with iodine. Isopropyl alcohol (propan-2-ol) or wood alcohol (methyl alcohol, or methanol).
Ethanol-based soaps are becoming common in restaurants and are convenient because they do not
require drying due to the volatility of the compound. Alcohol based gels have become common
as hand sanitizers.
d. Fuels
Some alcohols, mainly ethanol and methanol, can be used as an alcohol fuel. Fuel
performance can be increased in forced induction internal combustion engines by injecting alcohol
into the air intake after the turbocharger or supercharger has pressurized the air. This cools the
pressurized air, providing a denser air charge, which allows for more fuel, and therefore more power.
 Denatured alcohol- means it has been made poisonous by the addition of other chemicals,
often methyl alcohol (methanol, or wood alcohol). As little as 10 mL of methanol has been
known to cause permanent blindness, and 30 ml has resulted in death!!!
e. Preservative It is often used as a preservative for specimens in the fields of science and medicine.
f. Solvents

23
 Alcohols have applications in industry and science as reagents or solvents. Because of its
relatively low toxicity compared with other alcohols and ability to dissolve non-polar substances,
ethanol can be used as a solvent in medical drugs, perfumes, and vegetable essences such as vanilla.
 Glycerol (1,2,3-propanetriol) - used as a moistening agent in cosmetics, foods, and drugs; also
a component of fats and oils

3. ALDEHYDE
Aldehydes are considered the most
important functional group. They are often
called the formyl or methanoyl group.
Aldehydes derive their name from
the dehydration of alcohols.
Aldehydes contain the terminal
carbonyl group( O=CH- aldehyde group),
bonded to at least one hydrogen atom
. The aldehyde group is also called
the aldo, formyl or methanoyl group. The
word aldehyde seems to have arisen
from alcohol dehydrogenated..

IUPAC NAMING ALDEHYDES

1. Aldehydes take their name from their
parent alkane chains. The -e is removed
from the end and is replaced with -al.

2. The aldehyde funtional group is given the #1 numbering location and this number is not included
in the name.
3. For the common name of aldehydes start with the common parent chain name and add the
suffix aldehyde.
4. When the -CHO functional group is attached to a ring the suffix -carbaldehydeis added, and the
carbon attached to that group is C1.
5. If an aldehyde is attached to a benzene and is the main functional group, the suffix becomes
benzaldehyde.

IMPORTANT USES OF ALDEHYDES

1. Used as flavoring agent, synthesized other compounds including
dyes and perfumes,
2. Formalin, 40% formaldehyde solution, is used in preserving tissue
specimens.
3. Formaldehyde is used as disinfectant and monomer of polymers.
4. Ethanal is used in the synthesis of other compounds including
butanol, perfumes, flavours and dyes.

24
4. ETHER
Ether is the general name for a class of chemical compounds which contain an oxygen atom
connected to two (substituted) alkyl groups. The general formula R1-O-R2 where R1 and R2 are
hydrocarbon groups.
A typical example is the solvent and Alkyl Group Name Alkoxy Name
anesthetic, diethyl ether, commonly referred to Group
simply as "ether". CH3– Methyl CH3O– Methoxy
CH3CH2– Ethyl CH3CH2O– Ethoxy
IUPAC RULES for Ether Nomenclature: (CH3)2CH– Isopropyl (CH3)2CHO– Isopropoxy
1. Name the alkyl groups alphabetically followed (CH3)3C– tert- (CH3)3CO– tert-Butoxy
by the word "ether". or Butyl
C6H5– Phenyl C6H5O– Phenoxy
2. Name ethers by adding -oxy- to the prefix for
the smaller hydrocarbon group and joining it to the alkane name of the larger hydrocarbon group.
The smaller, shorter alkyl group becomes the alkoxy substituent. The larger, longer alkyl group side
becomes the alkane base name
Example: CH3-O-CH2-CH3 – ethyl methyl ether or methoxyethane
3. If just two alkyl groups are identical in its molecular formula, use the prefix di-, tri-, tetra-, etc to
signify these branches.
Example: CH3CH2-O-CH2CH3 - diethyl ether or ethoxyethane

Practice Exercise: Name the following ethers.

1. CH3CH2CH2CH2CH2-O-CH2CH2CH3 2. 3. CH3 CH2 CH2-O-CH2CH3

5. Ketones
Ketones are either the functional group characterized by a carbonyl group (O=C) linked to two
other carbon atoms or a compound that contains this functional group. A ketone can be generally
represented by the formula: R1(CO)R2. The simplest ketone is acetone, dimethyl ketone or
propanone.

IUPAC Rules For Ketone Nomenclature

1. Ketones take their name from their parent alkane chains.
The ending -e is removed and replaced with -one.
2. The common name for ketones are simply the substituent
groups listed alphabetically + ketone.
3. Some common ketones are known by their generic names.

Practice Exercise: Name the following ketone.

1. CH3(CH2)3COCH3 2. CH3COCH3 3.

25
Important Ketones
1. Propanone – used as paint and polish remover.
2. Progesteron – female hormone

6. Carboxylic Acids
Carboxylic acids are organic acids characterized by the presence of a carboxyl group, which
has the formula -C(=O)OH, usually written -COOH or -CO2H. Carboxylic acids are Bronsted Acids —
they are proton donors. Salts and anions of carboxylic acids are called carboxylates.

IUPAC Rules for Carboxylic Acid Nomenclature

1. Carboxylic acids are named with the suffix -oic acid.
2. They take the "1" position on the parent chain, but do not have their position number indicated .
For example, CH3CH2CH2CH2COOH (valeric acid) is named pentanoic acid.
3. For carboxylic acids attached to a benzene ring such as Ph-COOH, these are named as benzoic acid
or its derivatives.
4. If there are multiple carboxyl groups on the same parent chain, the suffix "-carboxylic acid" can be
used (as -dicarboxylic acid, -tricarboxylic acid, etc.).
Citric acid is one example; it is named 2-hydroxypropane- 1,2,3-tricarboxylic acid, rather than
3-carboxy-3-hydroxypentanedioic acid.

Practice Exercise: Name the following carboxylic acids.

1. 2. 3.

Dicarboxylic acids - compounds that contain two -CO2H functional groups

Examples: Tartaric acid - is a by-product of the fermentation of wine,
Succinic, fumaric, malic, and oxaloacetic acid are intermediates in the metabolic pathway
used to oxidize sugars to CO2 and H2O.

- oxalic acid tartaric acid fumaric acid

Properties of Carboxylic Acids

1. The higher boiling points than the equivalent chain length alcohols.
2. Unbranched acids made up of an even number of carbon atoms have melting points higher than
the odd numbered homologs having one more or one less carbon.
3. As the length of the alkyl chain increases, the odor of carboxylic acids becomes more unpleasant.

26
4. Water soluble up to a chain length of 6 carbons. They become less soluble in water as the length of
the alkyl chain increases

Important Carboxylic Acids

1. Formic acid (Latin formica, "an ant)- sharp, pungent odor first obtained by distilling ants
- used in tanning and dyeing
2. acetic acid (Latin acetum, "vinegar") – a sharp, pungent odor
- is contained in vinegar as food preservative
3. Butyric acid (Latin butyrum, "butter") - is found in sweat and in rancid butter
- used in varnishes
4. Caproic, caprylic, and capric acids (Latin caper, "goat") - are all obtained from goat fat
5. Benzoic acid – used as food preservative and in dyeing

7. Esters
Esters are organic compounds in which an organic group from an alcohol (symbolized by R')
replaces a hydrogen atom in the hydroxyl group of an organic acid. The general formula is (R-CO-O-R')
The most common esters are the carboxylate esters, where the acid in question is a carboxylic
acid.
Esters are formed through reactions between an acid and an alcohol with the elimination of water
Alcohol + Carboxylic Acid Ester + Water
R'OH + RCOOH RCOOR' + H2O
IUPAC Rules for Ester Nomenclature
1. Identify the alkyl group that is attached to the oxygen atom
2. Number according to the end closest to the -CO- group regardless of where alkyl substituents are.
3. Determine the alkane that links the carbon atoms together. If there is a separation of a continuous
link of carbon atoms due to the oxygen atom, individually name the two alkanes before and after the
oxygen atom.
4. The longer structural alkane is the one that should contain the carbonyl atom. The format is as
follows: (alkane further from carbonyl) (alkane closest to carbony)(parent chain)
5. The R-CO-O part is then named as a separate word based on the carboxylic acid name, with the
ending changed from -oic acid to -oate.
For example: CH3CH2CH2CH2COOCH3 is methyl pentanoate,
(CH3)2CHCH2CH2COOCH2CH3 is ethyl 4-methylpentanoate.
3. For esters such as ethyl acetate (CH3COOCH2CH3), ethyl formate (HCOOCH2CH3) or dimethyl
phthalate that are based on common acids, IUPAC recommends use of these established names,
called retained names. The -
oate changes to -ate. Examples:
4. If the alkyl group is not attached at
the end of the chain, the bond position
to the ester group is infixed before "-
yl": CH3CH2CH(CH3)OOCCH2CH3 may be
called but-2-yl propanoate or but-2-yl propionate.
Practice Exercise: Name the following carboxylic acids.
1. CH3 CH3COOCH2CH3 2. CH3 COOCH2 CH2CH3 3. CH3 CH2 COOCH2 CH2 CH2CH3

27
Properties and Important Uses of Esters
1. Small esters are fairly soluble in water but solubility decreases with increasing chain length
2. Natural occurring esters of organic acids in fruits and flowers give their distinctive odors.
3. It also used for food aroma and taste, perfumes, synthetic fibers and solvents.
Common Name IUPAC Name Fruit Source
Propyl acetate Pentyl ethanoate pear
Ethyl butyrate pineapple
Octyl acetate Octyl ethanoate orange
Benzyl acetate peach
Isobutyl formate raspberry
Isoamyl valerate Pentyl pentanoate apple
Isoamyl acetate banana
Methyl anthranilate grape

8. Amines
Amines are derivatives of ammonia in which one or more of the hydrogens has been replaced
by an alkyl or aryl group. They are organic compounds whose functional group contains nitrogen as
the key atom.
Structurally amines resemble ammonia,
wherein one or more hydrogen atoms are
replaced by organic substituents such as alkyl
and aryls groups.

IUPAC Rules for Amine Nomeclature

1. Amines (R-NH2) are named for the attached
alkane chain with the suffix "-amine" (e.g.
CH3NH2 Methyl Amine).

2. If necessary, the bonding position is infixed:

CH3CH2CH2NH2 propan-1-amine,
CH3CHNH2CH3 propan-2-amine.
3. For secondary amines (of the form R-NH-R), the longest carbon chain attached to the nitrogen atom
becomes the primary name of the amine; the other chain is prefixed as an alkyl group with location prefix
given as an italic N: CH3NHCH2CH3 is N-methylethanamine
.4. Tertiary amines (R-NR-R)
are treated similarly: CH3CH2N(CH3)CH2CH2CH3 is N-ethyl-N-methylpropanamine. Again, the
substituent groups are ordered alphabetically.

Practice Exercise: Name the following amines.

1. CH3 CH3NHCH2CH3 2. CH3CH2CH2NH2 3. CH3 CH2 CH2 NHCH2 CH2CH3

Properties of Amine:
1. The boiling points of amines are less than those of alcohols. This is because they form H-bonds with
each other, but these are not as strong as those formed by alcohols.
2. Amines are more soluble in water than alcohols of comparative molecular weights due to their basicity.

28
Important Amines
Alkaloids are amines that are isolated from plants. They include poisons such as nicotine,
coniine, and strychnine. Nicotine has a pleasant, invigorating effect when taken in minuscule
quantities, but is extremely toxic in larger amounts. Coniine is the active ingredient in hemlock, a
poison that has been used since the time of Socrates. Strychnine is another toxic alkaloid that has
been a popular poison in murder mysteries.
The alkaloids also include a number of drugs, such as morphine, quinine, and cocaine.
Morphine is obtained from poppies; quinine can be found in the bark of the chinchona tree; and
cocaine is isolated from coca leaves.

Nicotine Coniine

9. Amide
Amides are compounds of the type RC(O)NR2, where the C(O) refers to a carbonyl group.
Amide is one of two kinds of compounds:
-a carbonyl group (C=O) linked to a nitrogen atom (N), or
- a compound that contains this functional group; or a particular kind of nitrogen anion.
Amides are the most stable of all the carbonyl functional groups.

Properties of Amide:
1. Amides (R-CO-NH2) take the suffix "-amide", or "-
carboxamide" if the carbon in the amide group cannot be
included in the main chain. The prefix form is both
"carbamoyl-" and "amido-".
2. Amides that have additional substituents on the nitrogen
are treated similarly to the case of amines: they are ordered alphabetically with the location prefix N:
HCON(CH3)2 is N,N-dimethylmethanamide.
Practice Exercise: Name the following amines.
1. CH3 CH3 CONHCH2CH3 2. CH3 CH2 CH2 CONH2 3. CH3 CH2 CH2 CONHCH2 CH3

Properties of Amides
1. They are neutral compounds which are basic.
2. Tertiary amides have high boiling points due to the high polarity.
3. Tertiary amides have less solubility in water.

Important Amides:
1. Sodium Amide (NaNH2)– commonly called sodamide is used in the industrial production of indigo,
hydrazine, and sodium cyanide
2. Dimethylformamide(CH3)2NC(O)H – use in the production of acrylic fibers and plastics
3. Potassium amide (KNH2) – used as a pesticide.

29
 Functional groups in Some Drugs

ORGANIC REACTIONS OF FUNCTIONAL GROUPS

1. Synthesis of Alcohol
 Alcohols are synthesized by reduction of aldehyde with lithium aluminum hydride. Reduction
of aldehyde generally gives primary alcohols. For example acetaldehyde on reduction gives
ethyl alcohol.
Example: CH3-CHO → CH3-CH2-OH
 Reduction of ketones give secondary alcohols. O OH
Example: 2-propanone on reduction gives 2-propanol. CH3-C-CH3 → CH3- CH-CH3
 Alcohol is prepared by adding water to an alkene in the presence of a strong acid such as
concentrated sulfuric acid
Example : ethylene on hydration gives ethyl alcohol . CH2=CH2 + H2O → CH3-CH2-OH

2. Synthesis of Esters
 Alcohols condense with acids in the presence of concentrated sulfuric acid to give ester.
Example: ethyl alcohol condense with acetic acid to give ethyl acetate.
CH3-CH2-OH + CH3-COOH → CH3-CH2-O-CO-CH3 + H2O

3. Synthesis of Amine
 Alcohols react with ammonia to give a mixture of amines.
The reaction yields depend on the concentration of ammonia and alcohol.
CH3-OH + NH3 → CH3-NH2 + H2O

4. Synthesis of Ethers
 Ethers are prepared by dehydration of alcohols
Example: 2 CH3CH2OH → CH3CH2OCH2CH3 + H2O

30
5. Synthesis of Aldehydes
 Aldehydes can be formed by oxidizing a primary alcohol

6. Synthesis of Ketone
 oxidation of a secondary alcohol gives a ketone.

7. Substitution Reactions of Benzene

 Nitration - Benzene reacts with a mixture of concentrated nitric and sulfuric acids to produce
Nitrobenzene
 Alkylation - Substitution of an alkyl group onto a benzene ring.
An alkyl halide RX is used in the substitution to produce an alkyl-benzene.
Example: Benzene + chloroethane → ethyl benzene + HCl
 Halogenation - Both bromine and chlorine react with benzene if iron is present.
Example : Benzene + Br2 → bromobenzene + HBr

Practice Exercises:
Write the reaction and name the product.
1. Butanoic acid + Propanol 4. Pentanol
2. Benzene + Chlorine 5. Methyl butanoate
3. 2-Hexanone

31
 Chapter 3
POLYMERS

INTRODUCTION TO POLYMERS

Prior to the early 1920's, chemists doubted the existence of molecules having molecular
weights greater than a few thousand. This limiting view was challenged by Hermann Staudinger, a
German chemist with experience in studying natural compounds such as rubber and cellulose. In
contrast to the prevailing rationalization of these substances as aggregates of small molecules,
Staudinger proposed they were made up of macromolecules composed of 10,000 or more atoms. He
formulated a polymeric structure for rubber, based on a repeating isoprene unit (referred to as a
monomer). For his contributions to chemistry, Staudinger received the 1953 Nobel Prize. The
terms polymer and monomer were derived from the Greek roots poly (many), mono (one)
and meros (part).
Polymers are substances containing a large number of structural units joined by the same type
of linkage. These substances often form into a chain-like structure. Polymers in the natural world
have been around since the beginning of time. Starch, cellulose, and rubber all possess polymeric
properties. Man-made polymers have been studied since 1832.

32
 Today, polymers already have a range of applications that far exceeds that of any other class
of material available to man. Current applications extend from adhesives, coatings, foams, and
packaging materials to textile and industrial fibers, elastomers, and structural plastics. Polymers are
also used for most composites, electronic devices, biomedical devices, optical devices, and precursors
for many newly developed high-tech ceramics.

What are Polymers?

Polymers are high molecular mass macromolecules composed of repeating structural units
derived from monomers. They have a high molecular mass (103 – 107 U). In a polymer, various
monomer units are joined by strong covalent bonds.
Examples: polyethene, rubber, nylon 6,6

What are monomers?

Monomers are simple reactive molecules that combine with each other in karge numbers
through covalent bonds to give rise to polymers.
Examples: ethene, propene, styrene, vinyl chloride

TIMELINE OF THE DEVELOPMENT OF POLYMERS

Year Event
1500 British explorers discovered that Mayan civilization were the fist to find an application for
polymers as their children were fond of playing balls made from local rubber trees.
1839 Charles Goodyear discovers vulcanization by combining natural rubber with sulfur and
heating it to 270 degree Fahrenheit. Vulcanized rubber is a polymeric substances that is
much more durable than its natural counterpart. Its most common use today is in
automobile tires.
1907 The oldest recorded synthetic plastic is fabricated by Leo Bakeland. Bakelite’s hardness
and high heat resistivity made it an excellent choice as an electrical insulator.
1917 X-ray crystallography is invented as a method of analyzing crystal structure. Eight years
later, this method is used by M. Polanyi to discover the chemical structure of cellulose.
This establishes the fact that polymer unit cells contain sections of long chain molecules
rather than small molecular species.
1920 Staudinger published his classic paper entitled ‘Uber Polymerization” Publication of this
paper heralded a decade of intense research and presented to the world the development
of modern polymer theory.
1927 Large scale production of vinyl-chloride resins begins. This polymeric compound continues
to widely used today to make plumbing (PVC) pipe , Euttery tile and bottle.
1930 Polystyrene is invented. This polymeric material is used in videocassettes and other
packaging. Expanded polysterene (commonly called Styrofoam) is used in cups, packaging
and thermally insulated containers.
1938 Wallace Carothers of the Duport company produces another well known polymeric
product, nylon. Nylon is a common material used today for such applications as ropes and
clothes.
1941 Polyethylene is developed. Billions of pounds of both high and low density versions of
these materials are produced annually for everything from packaging film to piping to toys.

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 1970 James Economy develops one of the pioneer moldable high temperature polymers
(EKONOL) . This polymeric material paved the way for the development of liquid crystal
polymers one year later. Ekonol’s most common applications occur in electronic devices
and aircraft engines.
1971 S Kwolek, who has been awarded more than 37 patents in polymer science, develops
KEVLAR. Kevlar is a high strength material that can withstand temperatures up to 300 oC,
and used in applications such as bullet proof vests, and fire proof garments for firefighting
and auto racing.
1976 The polymer /plastics industry outstripped steel as the nation’s most widely used material
per unit volume. We now use more plastic than steel, aluminum and copper combined.

CLASSIFICATION OF POLYMERS

A. Based on the source or origins

1. Natural polymers are polymers found in nature. They are formed by plants and animals.
Examples: protein, cellulose, starch
2. Synthetic polymers are polymers prepared by man in laboratories.
Examples: plastic (polyethene), synthetic fibers (nylon 6,6) Synthetic rubbers (Buna-S)

Practice Exercise: Classify the following as natural or synthetic.

1. nucleic acids 6. PAN
2. PVC 7. silicone
3. Kevlar 8. shellac
4. collagen 9. Dacron
5. Teflon 10. wool

B. Based on Monomer Composition

1. Homopolymers are polymers that are formed by the polymerization of a single type of monomer.
Its repeating units are derived only from one monomer. This can be represented by: [-A-A-A-A-A-]
Examples: polyethene is a homopolymer of ethene.
Polyvinyl chloride is a homopolymer of vinyl chloride
2. Copolymers contain repeating units which have derived from two types of monomers.
This can be represented by: [-A-B-A-B-A-B-A-B-A-]
Examples: Butadiene - Styrene rubber is a copolymer of 1,3 butadiene and styrene.
Copolymers are classify as
a. Statistical copolymer (random) – two or more different
repeating units are distributed randomly.
ABAABABBBAABAABB
b. Alternating polymer – are made of alternating sequences
of the different monomers.
ABAABABABABABA
c. Block copolymer – long sequences of a monomer are followed
by long sequences of another monomer.
AAAAAAABBBBBBB

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 d. Graft copolymer – consist of a chain made from one type of
monomers with branches of another type.
AAAAAAAAAAAAAAAA
B B B
B B B
Practice Exercise: Classify the following as homopolmer or copolymer.
1. Polyethylene
2. polytetrafluoroethylene
3. poly(vinyl chloride)
4. Kevlar
5. Saran

C. Based on Chain Structure

1. Linear Chains – a polymer consisting of a single continuous chain of repeat units
2. Branched Chains – a polymer that includes side chains of repeat units connecting onto the main
chain of repeat units
3. Hyper branched polymer – consist of a constitutional repeating unit including a branching group.
4. Crosslinked polymer – a polymer that includes interconnections between chains
5. Network polymer – a cross linked polymer that includes interconnection between chains,

D. Based on Thermal Behavior

1. Thermoplastic - can be soften by heat, hardened by cooling, and then soften by heat over and
over again. They are not cross-linked. Examples: polyethylene , nylon, PVC
2. Thermosetting Plastic - become permanently hard and rigid when heated or cured. They are hard
and rigid at room temperature and do not soften on heating.
Examples: epoxy resins – used as coating materials, manufacture of insulating materials
Phenolic resins – tools handles, billiard balls, sprockets, insulation
Unsaturated polyesters resins – manufacture of plastics reinforced fiberglass
commonly known as polyester, fillers
Practice Exercise: Classify the following as thermosets or thermoplastics
1. HDPE (High density polyethylene)
2. MF (melamine formaldehyde)
3. PET (polyethylene terepthalate)
4. PAN ( polyacrylonitrile)
5. glass reinforced plastic

E. Based on Molecular Forces

1. Elastomers or rubbers have the weakest intermolecular forces of attraction.

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2. Fibers have the strongest intermolecular forces of attraction.
3. Thermoplastics polymers inter mediate intermolecular forces attraction
4. Thermosetting plastics polymers

Practice Exercise: Arrange the following polymers in increasing order of their intermolecular forces.
1. Nylo6,6 ,Buna-S , Polyethene
2, Nylon 6, Neoprene , PVC

Configuration Isomers of Polymers

1. Isotactic - If all the substituents lie on one side of

the chain the configuration Examples:
polypropylene

2. Syndiotactic - If the substituents alternate from

one side to another in a regular manner the
configuration

3. Atactic - a random arrangement of

substituent groups. Examples: Polystyrene,
PAN, PVC

POLYMERIZATION
Polymerization is the chemical reaction in which high molecular mass molecules are formed
from monomers. It is process of forming high molecular mass macromolecules, which consist of
repeating structural units derived from monomers. In a polymer, various monomer units are joined
by strong covalent bonds.

Two Kinds of Polymerization

1. Addition Polymerization – monomers with double bond are joined together to form polymer
without loss of a small molecule.
In the formation of polymers, the carbon-carbon double bond in each monomer is broken
open and replaced by a carbon-carbon single bond.
Three steps involves:
a. initiation- the first active center (radical, anion or cation) is formed and the growth of the
chain is initiated. C = C ↔ C+ - C- ↔ C- C
b. propagation – growth of the polymer chain occurs by the successive addition of monomers

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 to the active center at the end of the chain. - C- C - C- C - C- C -
c. termination – growth is terminated by either neutralization or transfer of the active center.
Example: Polyethylene : CH2=CH2 → [– CH2 – CH2 – CH2 – CH2 – CH2 – CH2 –]

Some Common Addition Polymers

Name(s) Formula Monomer Properties Uses
Polyethylene –(CH2- ethylene soft, waxy solid film wrap, plastic bags
low density (LDPE) CH2)n– CH2=CH2
Polyethylene –(CH2- ethylene rigid, translucent solid electrical insulation
high density (HDPE) CH2)n– CH2=CH2 bottles, toys
Polypropylene –[CH2- propylene atactic: soft, elastic solid similar to LDPE
(PP) different grades CH(CH3)]n CH2=CHCH3 isotactic: hard, strong solid carpet, upholstery
Poly(vinyl chloride) –(CH2- vinyl chloride strong rigid solid pipes, siding, flooring
(PVC) CHCl)n– CH2=CHCl
Poly(vinylidene –(CH2- vinylidene chloride dense, high-melting solid seat covers, films
chloride)(Saran A) CCl2)n– CH2=CCl2
Polystyrene –[CH2- styrene hard, rigid, clear solid toys, cabinets
(PS) CH(C6H5)]n CH2=CHC6H5 soluble in organic solvents packaging (foamed)
Polyacrylonitrile –(CH2- acrylonitrile high-melting solid rugs, blankets
(PAN, Orlon, Acrilan) CHCN)n– CH2=CHCN soluble in organic solvents clothing
Polytetrafluoroethyle –(CF2- Tetrafluoroethyle resistant, smooth solid non-stick surfaces
ne (PTFE, Teflon) CF2)n– ne CF2=CF2 electrical insulation
Poly(methyl metha –[CH2- methyl metha hard, transparent solid lighting covers, signs
crylate)(PMMA, C(CH3)CO2C crylate CH2=C skylights
Lucite, Plexiglas) H3]n– (CH3)CO2CH3
Poly(vinyl acetate) –(CH2-CHO vinyl acetate soft, sticky solid latex paints, adhesives
(PVAc) COCH3)n– CH2=CHOCOCH3
cis-Polyisoprene –[CH2-CH= isoprene soft, sticky solid requires vulcanization
natural rubber C(CH3)CH2]n CH2=CHC(CH3)=CH2 for practical use
Polychloroprene (cis –[CH2 CH= chloroprene tough, rubbery solid synthetic rubber
+ trans)(Neoprene) CCl-CH2]n– CH2=CHCCl=CH2 oil resistant
2. Condensation polymerization – process in which two monomers react to form a larger molecule
and eliminate a smaller molecule (usually water, ammonia, HCl)
Example: CH3-NH2 + HOOC-CH2-CH3 → CH3-NH-CO-CH2-CH3 + H2O
Amine acid amide water

Practice Exercise: Classify the following addition polymers or condensation polymers.

1. Teflon
2. Kevlar
3. PVC
4. Terylene
5. Polypropylene

B. Draw the polymers of the following monomers:

1. CH2=CHCN
2. H2N (CH2)6NH2 + HOOC(CH2)4COOH

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3. H2C=CH-CH=CH2 + C6H5CH=CH2
4. CH2=CHCl
5. CH2=CHCH3

PROPERTIES OF POLYMERS
The physical properties of a polymer, such as its length and flexibility depend on:
1. Chain length – in general, the longer the chains the stronger the polymers
2. Side groups – polar side groups give stronger attraction between polymer chains, making the
polymer stronger
3. Branching – straight, unbranched chains can pack together more closely than highly branched
chains, giving polymers that are more crystalline and therefore stronger.
4. Cross-linking – if polymer chains are linked together extensively by covalent bonds, the polymer is
harder and more difficult to melt.

CHARACTERISITCS OF POLYMERS

Low density Excellent surface finish can be obtained

Low coefficient of friction Economical
Good corrosion resistance Can be produced with close dimensional tolerances
Good mould ability Can be produced transparent or in different colors.
Low mechanical properties Poor temperature resistance
Poor tensile strength

Practice Exercise: Explain why the following products useful in the following:
1. electrical insulator
2. plastic container
3. clothing fiber
4. toys
5. food wrappers

POLYMER PROCESSING
There are five basic processes to form polymer products or parts. These include; injection
molding, compression molding, transfer molding, blow molding, and extrusion. Compression molding
and transfer molding are used mainly for thermosetting plastics. Injection molding, extrusion and
blow molding are used primarily with thermoplastics.

Comparison of polymer processing techniques for thermoplastics and thermosets.

Process Thermoplastic (TP) Advantages Disadvantages

or Thermoset (TS)

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 Injection TP, TS It has the most precise control It has high capital cost, is only
Molding of shape and dimensions, is a good for large numbers of parts,
highly automatic process, has and has large pressures in mold
fast cycle time, and the widest (20,000 psi).
choice of materials.
Compressi TS It has lower mold pressures It requires more labor, longer cycle
on (1000 psi), does minimum than injection molding, has less
Molding damage to reinforcing fibers shape flexibility than injection
(in composites), and large molding, and each charge is loaded
parts are possible. by hand.
Transfer TS It is good for encapsulating There is some scrap with every
Molding metal parts and electronic part and each charge is loaded by
circuits. hand.
Blow TP It can make hollow parts It has no direct control over wall
Molding (especially bottles), stretching thickness, cannot mold small
action improves mechanical details with high precision, and
properties, has a fast cycle, requires a polymer with high melt
and is low labor. strength.
Extrusion TP It is used for films, wraps, or It must be cooled below its glass
long continuos parts (ie. transition temperature to maintain
pipes). stability.

Application of Polymers
1. Agriculture – polymers are used in and on soil to improve aeration, provide mulch and promote
plant growth and health.
2. Medicine - Many biomaterials, especially heart valve replacement and blood vessels are made of
polymers like Dacron, Teflon and polyurethane.
3. Consumer Science- Plastic containers of all shapes and sizes are light weight and economically less
expensive than the more traditional containers. Clothing, floor coverings, garbage disposal bags and
packaging.
4. Industry -Automobile parts, windshields for fighter planes, pipes, tanks, packing materials,
insulation wood substitutes adhesives, matrix for composites, and elastomers.
5. Sports - Playground equipment, various balls, golf clubs, swimming pools, and protective helmets.

Practice Exercise: Enumerate at least five polymeric materials used in the following:
1. medicine
2. sports
3. consumer products

RECYCLING OF PLASTICS

Reason for not discarding plastics:

1. viable means for disposal
2. conservation of energy

Major Plastic Resins and Their Uses

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Resin Code Resin Name Common Uses Examples of Recycled Products
Soft drink bottles, peanut Liquid soap bottles, strapping,
Polyethylene butter jars, salad dressing fiberfill for winter coats, surfboards,
1 Terephthalate bottles, mouth wash jars paint brushes, fuzz on tennis balls,
(PET or PETE) soft drink bottles, film
Milk, water, and juice Soft drink based cups, flower pots,
High density containers, grocery bags, drain pipes, signs, stadium seats,
2 Polyethylene (HDPE) toys, liquid detergent trash cans, re-cycling bins, traffic
bottles barrier cones, golf bag liners, toys
Clear food packaging, Floor mats, pipes, hoses, mud flaps
Polyvinyl Chloride shampoo bottles
3 or Vinyl
(PVC-V)
Bread bags, frozen food Garbage can liners, grocery bags,
Low density bags, grocery bags multi purpose bags
4 Polyethylene (LDPE)

Ketchup bottles, yogurt Manhole steps, paint buckets,

containers, margarine, tubs, videocassette storage cases, ice
5 Polypropylene medicine bottles scrapers, fast food trays, lawn
(PP) mower wheels, automobile battery
parts.
Video cassette cases, License plate holders, golf course
compact disk jackets, coffee and septic tank drainage systems,
Polystyrene cups, cutlery, cafeteria desk top accessories, hanging files,
6 (PS) trays, grocery store meat food service trays, flower pots, trash
trays, fast-food sandwich cans
container

Practice Exercise: Identify the Resin Code of the following:

1. plastic mineral bottle
2. lego toy
3. plastic food wrapper
4. plastic vegetable oil bottle
5. VC disks

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