Introductory Chemistry II

Hydrocarbons
 Organic Chemistry
• Organic Chemistry is the chemistry of carbon and its
compounds
• Originally compounds were divided into organic and
inorganic depending on source
• Organic: those obtained from vegetable or animal
sources (i.e., from living organisms)
• Inorganic: Those obtained from minerals
• These compounds from organic sources all
contained the element carbon
• Even after it had become known that
organic compounds could be obtained
from other sources other than living
systems, it was felt convenient to retain
the name

• That division has stayed on till today

 The Carbon
• The element, carbon, is one of the most versatile
elements on the periodic table in terms of the number
of compounds it may form.
• Carbon compounds are involved in all life processes
• E.g., Proteins, DNA, carbohydrates, vitamins, etc.
• A large No. of organic compounds are insecticides
• There are over a million known compounds of carbon
and many more are being prepared
• So there is enormous interest in the chemistry of
Carbon
• Carbon may form virtually an infinite number of
compounds.
• This is largely due to the types of bonds it can form
and the number of different elements it can join in
bonding.
• Carbon may form single, double and triple bonds.
• Formation of these bonds involve hybridization of
carbon.
 Carbon’s Hybridization
• Note: A hybrid occurs when two things are
combined and the result has characteristics of
both
• The carbon atom has four valence electrons with the
electron configuration of 1s22s22p2
• You may expect the two unpaired p electrons to
bond with other atoms and the two paired s
electrons to remain as a lone pair
• However, carbon undergoes hybridization.
• Hybridization is the combination of two or more
atomic orbitals to form the same number of hybrid
orbitals, each having the same shape and energy.
 sp3 Hybrid Orbitals
• Carbon has two core electrons, plus four valence
electrons.
• To fill atomic orbitals in the most stable
arrangement, electrons are placed in the orbitals of
lowest energy.
• For carbon, this places two in the 2s orbital and one
each in 2p orbitals.

• Note: The lowest energy arrangement of electrons

for an atom is called its ground state.
• An electron is promoted from a 2s to a vacant 2p
orbital forming four unpaired electrons for bonding.

• This process requires energy because it moves an

electron to a higher energy orbital.

• This higher energy electron configuration is called an

electronically excited state.
• Atoms like carbon do not use pure s and pure p
orbitals in forming bonds
• The 2s and 2p orbitals of carbon atoms combine (or
mix) to form four degenerate orbitals called hybrid
orbitals (i.e. orbitals of equal energy)
• The hybrid orbitals formed from one s orbital and
three p orbitals are called sp3 orbitals.
• The mixing of a spherical 2s orbital and three
dumbbell shaped 2p orbitals together produces four
hybrid orbitals, each having one large lobe and one
small lobe.
• The sp3 orbitals formed are all half-filled, with the
electron far more likely to be found in the larger lobe.
• Note that each hybrid orbital contains one electron
that it can share with another atom, giving carbon 4
bonding sites.

• The hybrid orbital is called an sp3 orbital because

the four orbitals form from one s and three p
orbitals.

• Since electrons repel each other, the four sp3

hybridised orbitals surrounding a central carbon
atom result in a familiar tetrahedral shape, with a
maximum possible angle between each orbital of
109.5°.
 Bonding in CH4
• Each bond in CH4 is formed by overlap of an sp3 hybrid
orbital of carbon with a 1s orbital of hydrogen.
• These four bonds point to the corners of a tetrahedron.
 Bonding in ethane, CH3CH3

• Carbon-to-carbon single bonds in alkanes result from

overlapping sp3 orbitals forming σ bonds.

• σ bonds are covalent bonds formed by end-on

overlap of two atomic orbitals and since σ bonds
must lie along the line joining both atoms, there will
be free rotation around these orbitals.
H
H

C C
H σ bond H

H H
 sp2 Hybridization
• One 2s orbital and two 2p orbitals form three sp2
hybrid orbitals.

The three sp2 hybrids point towards the corners of a

triangle at 120o to each other.
Each sp2 hybrid is involved in in the σ bond formation
ant the remaining p orbital forms the pi ( ) bond.
A double bond has a σ
 sp hybridizzation
sp hybridization is observed when one s and one p
orbital in the same main shell of an atom mix to form
two new equivalent orbitals. The new orbitals formed
are called sp hybridized orbitals. It forms linear
molecules with an angle of 180°
• In carbon, One 2s orbital and one 2p orbital form
two sp hybrid orbitals.
Each sp orbital is involved in a σ bond formation and
the remaining two p orbitals form two bonds.

A triple bond = 0ne σ bond + two bonds

• sp3: Used in compounds with C-C single bonds such as
in alkanes

• sp2: Used in compounds with C=C double bonds such

as in alkenes

• Sp: used in compounds with carbon to carbon triple

bonds such as in alkynes
 Hydrocarbons
• Hydrocarbons are organic compounds composed of
carbon and hydrogen atoms only
• Two large categories: Aliphatic and aromatic
• 1. Aliphatic
• Have chains of carbon atoms sometimes folded into rings
• Open chain: Acyclic, e.g., butane:
• Cyclic: Alicyclic (or simply cyclic): CH3 CH2 CH2 CH3

Cylcobutane
• Aliphatic hydrocarbons fall into two categories – saturated and
unsaturated

• Saturated
• Contain maximum number of hydrogen atoms
• Have C-C single bonds

• Unsaturated
• Contain fewer than maximum number of hydrogen atoms
• Have multiple bonds
• Those with C=C double bonds are called alkenes
• Those with carbon to carbon triple bonds are called alkynes

• Apart from a few exceptional ring compounds, alicyclic and acyclic

hydrocarbons of similar mol. wt. have similar chemical and physical
properties
 Index of hydrogen deficiency
• Saturated hydrocarbons have max no. of hydrogen atoms
and contain C-C single bonds

• Cyclic alkanes are not fully saturated

• To avoid confusion chemists talk of the index of hydrogen

deficiency or the degree of unsaturation of a compound

• Index of hydrogen deficiency is the number of pairs of

hydrogen atoms that must be removed from a molecular
formula of an alkane to give the molecular formula of a
compound under consideration
• Compare cyclohexane and hexane

H H H
C H
H C C H
H
C C H CH3CH2CH2CH2CH2CH3
H C
H H H hexane

Cyclohexane
• 2. Aromatic hydrocarbons

• Were so named because most have strong aromas

and were found to have unusual chemical
properties

• Later it was found that their structural features

were different from those of other compounds

• So the word aromatic came to designate a type of

structure rather than aroma
• Aromatic compounds are cyclic hydrocarbons
with alternating double and single bonds

• So are unsaturated
• The simplest of them is benzene
H

H H

H H

• Benzene and other aromatic compounds are not

alkenes
• Aromatic compounds have chemical properties that are
different from those of alkenes

• For example: Alkenes undergo addition reaction with

Br2/CCl4
Br Br
CH3CH CH2 + Br2/ CCl4 CH3CH CH2

• Benzene undergoes substitution reaction in presence of a

catalyst Br

+ Br2 FeCl3 + HBr

• The bonds in benzene are not single and not double
• They are all the same
• Benzene can be drawn in two ways

or

I II
• The actual structure is intermediate between the two
• The two contributing structures are called cannonical
structures (or resonance structures)

I II
• The pi electrons are spread (delocalized) over the
entire ring

• Structure of benzene is sometimes written with a

circle inscribed inside
 SUMMARY
Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic Aromatic
Aromatic

Alkanes
Alkanes Alkenes
Alkenes Alkynes
Alkynes
 Functional groups
Apart from carbon and hydrogen, an organic compound may
also contain groupings composed of other atoms

E.g., O, N, S, P, Cl or C=C, -NH2, C=O, OH, etc

These define the structure of a particular family of organic

compounds and the same time determine their properties

They are called functional groups

A functional group is the part that determines the compound’s

chemical properties and most of its physical properties

Chemical reactions of a molecule occur at the functional

group
 Nomenclature of organic molecules
• The current system of naming organic compounds was
started at the end of the 19th century

• Before that time, several organic compounds had been

discovered

• The names given were either in Latin or Greek or

reflected the source or method of preparation with no
structural significance

•
• It soon became clear that problems would arise
• Latin or Greek names meant everybody should
learn Latin or Greek in order to understand them—
what a difficult task!!

• Naming by source was problematic in that the

many compounds prepared in the lab would be
difficult to name

• There are 2 C4, 3 C5, 75 C10, it would be difficult to

devise and remember each and every prefix for all
the isomers
 The 2 alkanes with C4:
CH3CHCH3
CH3CH2CH2CH3
Butane CH3
Isobutane
• It thus became obvious that a systematic way of
naming was needed
• A sub committee of the International Union of Pure
and Applied Chemistry (IUPAC) was set up
• To come up with rules for naming compounds
systematically
• Names that would describe the structures of the
compounds
• Names formed by using IUPAC rules are called IUPAC
names or systematic names
• So, a systematic name (or IUPAC name is a name
that describes the structure of a compound
Idea behind IUPAC rules:
 Each compound should have its own name Not e.g.,
butane and isobutane
 The system is simple enough to allow anybody
familiar with the rules to write the name of any
compound encountered
 One should be able to derive the structure of a
given compound from its IUPAC name
 IUPAC RULES
Names of alkanes have an ending –ane
1. Locate the longest continuous chain of carbons
This determines the base name (or parent name) of
the compound
The longest chain may not always be obvious from
the way the formula is written

2. Number the longest chain from the end close to the

substituent(s)
3. Use the Numbers obtained in rule 2 to designate the
location of the substituent groups

Base name is placed last, and the name of the

substituent group preceded by the number designating
its location on the chain is placed first

Numbers are separated from words by a hyphen and

words are written without a space between their parts
Example
CH3
4 2
3
CH3 CH2 CH2 CHCH3 5 1

2-Methylpentane
(not 4-methylpentane)
 When two or more different substituents are
attached to the parent chain, the names of the
groups are written in alphabetical order.

• if there are different substituents in equivalent

positions on opposite ends of the parent chain, give
the substituent of lower alphabetical order the
lower number
4. When two or more substituents are present,
give each substituent a number corresponding to
its location on the longest chain. E.g.

CH3 2 4 6
1 3 5
CH3 CH2 CHCH2 CHCH2 CH3 7

CH2 CH3
3-Ethyl-5-methylheptane
(not 3-methyl-5-ethylheptane)
5. When two substituents are present on the same
carbon, use that number twice

6. When two or more substituents are identical, indicate

this by the use of prefixes, di (for two), tri (for
three),tetra(for four), penta (five), etc,

CH3 CH2 CH3

2 4 6
CH3 CCH2 CHCH2 CH3 1 3 5

CH3
4-Ethyl-2,2-dimethylhexane
(not 2,2-dimethyl-4-ethylhexane)
 CH3 CH3
6 4 2
CH3 CH2 CHCH2 CHCH3 5 3 1

2,4-Dimethylhexane
(not 3,5-dimethylhexane)

Make certain that each and every substituent has a

number

Commas are used to separate numbers from each other

 More on naming
When a halogen is present in an organic compound, it is
indicated by a prefix (haloalkanes)
F fluoro-
Cl chloro-
Br bromo-
I iodo-
CH3

CH3CHCHCH2CH3

Cl
3-Chloro-2-methylpentane
Cycloalkanes: An alkane that contains a ring of
carbon atoms. Ring sizes from 3 carbons to 30 or
higher are known.

Cyclic alkanes are indicated by the prefix cyclo

 Additional Rules for Naming Cyclics

• Step 1: Use the cycloalkane name as the parent

chain. (unless the straight chain is bigger)

• Step 2: Number the carbons on the ring to give

the lowest possible numbers.

• Once you establish carbon #1, proceed around

the ring in the direction that gives the lowest
numbers. (use tie breaker if necessary)
 CH3 CH3

CH3

Methylcyclopentane 1,2-dimethylcyclopentane
CH3

CH3

CH3

1,2,4-trimethylcyclohexane
 Aromatic compounds have their own system of names
Aromatic compounds are named:
•With benzene as the parent chain.
•Name of substituent comes in front of the “benzene”.

Cl
CH3

CH2-CH3
CH2CH3 CH3 CH=CH2

Ethylbenzene Toluene Styrene

methylbenzene chlorobenzene ethylbenzene
 Test yourself
CH3 Cl

H3C

Cl

CH3

H3C

C6H5
 Alkenes

• The functional group of alkenes is a carbon to carbon

double bond (C=C)

• Are unsaturated compounds: Contain fewer than

maximum number of hydrogen atoms

• Are also referred to as olefins

• Latin (oleum = oil, faceo = to make)

• The simplest member (ethene) was once called olefiant

gas, because it reacts with Cl2 to yield 1,2-
 Naming alkenes
• The name of an alkene has an ending –ene

• The name is derived from the name of an alkane with the same
no of carbons, the ending –ane in the name of the alkane is
replaced by –ene

• Alkane  Alkene

• Rules are the same as for alkanes

• But: Start numbering the longest chain from the end close to
the double bond

• We have to locate the position of the double bond

• Since the double bond is between two carbons, we take
the lower number to designate its location
• Indicate location of substituents by the number of the
carbons to which they are attached
CH3

CH3CH2CH2CH CHCH2CH3 CH3CHCH2CH CHCH2CH3

3- Heptene 6-Methyl-3-heptene
Hept-3-ene 6-Methylhept-3-ene

Cl

2,3-Diethyl-1-pentene
2,3-Diethylpent-1-ene
• If more than one double bond is present, use di, tri, etc,
and indicate positions of all of them

Br
CH3 CH CHCH CHCCH2CH3
Cl
6-Bromo-6-chloro-2,4-octadiene

6-Bromo-6-chloroocta-2,4-diene
• For cyclic alkenes, number the ring in such away that
gives the carbons of the double bond the 1 and 2
positions and that gives the location of substituents
the lower numbers

6
4 1
3 5
5
4
2
1 2 3

3-Methylcyclopentene 4-Ethyl-1-methylcyclohexene
(not 5-methylcyclopentene) (not 5-ethyl-2-methylcyclohexene)
• If two double bonds are attached to a single
carbon, they are said to be cummulated and these
substances are called allenes (or cumulenes)

• They are very reactive and difficult to prepare

• So few members are known

• Examples are encountered in antibiotics from

fungi
• If double bonds alternate with single bonds the
compound is called a conjugated diene, triene, etc,
depending on the number of double bonds

2-Methylhepta-1,3,5-triene

• The double bonds interact with each other and this

affects their properties
• The compounds absorb visible light and appear coloured
• Carotenes found in carrots are orange/yellow in colour
 Carotene

• Double bonds act independently of each other when

separated by more than one single bond
• They are said to be unconjugated (or isolated)

Hepta-2,5-diene This is an unconjugated diene

 Properties of alkenes
• Physical
• Similar to alkanes although slightly polar
• C2-C4 are gas at 25oC
• C5-C17 are liquid
• >C18 are solids
• Restricted rotation about C=C bond results in two
different compounds
• They are insoluble in water but soluble in non polar
solvents, e.g., benzene, chloroform
• Chemical

• Remember the pi-bond is exposed

• There is a region of negative charge outside the plane
• Anything that is positively charged will be attracted to
this region
• Such an ‘’electron lover’’ is called an electrophile
• An electrophile adds to the carbons of the double bond
• Most characteristic reactions of alkenes are
electrophilic additions
• In addition reactions a substance XY adds to the
carbons of the double bond with no loss of
atom(s).
• General equation for an addition reaction:
H H
H H
C C + XY H C C H
H H X Y

• Several substances add to the alkenes

• 1. Hydrogenation
• Addition of hydrogen to C=C is effected by a catalyst,
Palladium (Pd), Platinum (Pt) or Nickel (Ni) metal
H H
H H
C C + H2 H C C H
H H H H
• A very important industrial reaction:
Pt
Margarine for
example, is made in this way
• A vegetable oil (kazinga) is partially hydrogenated, living
a semisolid --margarine
• Halogen acids, HX (e.g., HCl, HBr, HI, etc)
• Halogen acids add to alkenes to give alkyl halides
• Addition of a halogen acid to ethene is straightforward
H Cl

H2C CH2 + HCl H2C CH2

• Addition of say HCl to an unsymmetric alkene can give

two possible products (isomeric)
H Cl
CH3CH CH2
CH3CH CH2 + HCl
Cl H
CH3CH CH2
• Which of these two products predominates?
• A Russian chemist Vladimir Markovnikov studied a
number of such reactions and observed a certain pattern

• Where two isomeric products are possible, only one

predominates

• From this he came up with a rule called Markovnikov’s

rule
• This can be likened to a bible verse: Mathew 13 Vs 12 or
25 Vs 29 wich says:

• To those who have more shall be added and from those

who don’t have even the little they have shall be taken
away
• In simple terms, the hydrogen atom adds to a carbon that
already has more hydrogen atoms
Cl H Cl
• So the correct product is: CH3CH CH2
ie
CH3CH CH3
3. Addition of Halogens

The product obtained when a halogen adds to an

alkene depends on the solvent the halogen is
dissolved in

One can use a reactive solvent (e.g., water) or an

inert one (e.g., carbon tetrachloride, CCl4)
• Inert solvent
• When Br2 dissolved in CCl4 is added to an alkene, both
atoms of the halogen add to the carbons of the double
bond Br Br
CH3CH CH2 + Br2/ CCl4 CH3CH CH2
• Reaction is observed by the instant disappearance the
red-brown colour of bromine
• This is the reaction that is used to detect whether a
compound is an alkene or not (Test for Alkenes)
• Reactive solvent
• When a halogen dissolved in say, water is added to an
alkene, only one halogen atom adds to one of the
carbons of the double bond
• To the other carbon is added a group from the solvent
(in case of water its the OH group)
• The product in this case is a halo alcohol also called a
halohydrin
OH

CH3CH2C CH2Br
CH3CH2C CH2 + Br2/H2O

CH3 CH3
• 4. Addition of Hydroxylic compounds

• All hydroxylic compounds add to alkenes in

presence of acid as catalyst (H2SO4 or H3PO4)

• Hydration (addition of water) is a very important

process used for preparation of alcohols

• Reaction follows Markovnikov’s rule

 Examples of Hydration of alkenes
H3C H OH
CH3 H2SO4
+ H2O H3 C C C CH3
C C
H CH3
H CH3
1 H bonded to C
No H bonded to C
the hydrogen atom adds to the carbon atom of the double
bond that already has the greater number of hydrogen
atoms. OH
H+
CH3CH2CH CH2 + H2O CH3CH2CH CH3
 Markovnikov’s rule

In the addition of HX to an alkene, the hydrogen

atom bonds to the alkene carbon that has fewer alkyl
substituents.
• 5 Polymerization
• A compound is said to polymerize when two or
more small molecules combine to form a more
complex molecule (called the polymer)

• Molecules (monomers) can unite to give a dimer,

trimer, tetramer, etc.
• Up to 10 monomers, we get an oligomer
• More than ten monomers, we get a polymer
• Ethene polymerizes to give polyethylene (polyethene)
• Used for sealing or packaging materials
• Also vinylchloride (chloroethene) can polymerize to give
polyvinylchloride (PVC)
• Material is used for making plastic pipes, etc.
• Same units uniting (A-A-A-A) give a homopolymer,
different units (A-B-A-B)- give copolymer
 Oxidation of alkenes
• Alkenes are readily oxidized by various oxidizing
compounds

• One oxidizing substance frequently used is a mild solution

of potassium permanganate (KMnO4)

• Products obtained depend on whether the KMnO4

solution is cold or hot or whether the C=C bond is terminal
or internal
• With cold KMnO4 solution
• Products are 1,2-diols (glycols) OH OH

CH3CH2C CH2 + cold KMnO4 CH3CH2C CH2

CH3 CH3
2-methylbutane-1,2-diol
CH2OH
CH2
OH

+ cold KMnO4

1-(hydroxymethyl)cyclopentanol
CH2CH3 CH2CH3

OH

+ cold KMnO4

OH
3-ethylcyclohexane-1,2-diol
 • With hot KMnO4 solution
• Terminal C=C
• We are looking at an alkene of the type C-C-C=CH2
• The terminal carbon (C-C-C=C) is oxidized to CO2 and
H2O
O O O O
CH3C + H C CH3C + H C
CH3CH CH2 + hot KMnO4
H H
OH
OH

O
CH3C + CO2 + H2O
OH
• Internal C=C
• We are looking at an alkene of the type C-C=C-C
• Products depend on what is attached to the two middle
carbons, C-C=C-C
Aldehydes (alkanals) are oxidized to carboxylic acids while
ketones (alkanones) are not oxidized
O O O O
CH3CH2C CH3C CH3CH2C + CH3C
CH3CH2C CHCH3 + hot KMnO4 +
OH
H CH3
CH3
CH3

CH3
CH3 CH3
+ hot KMnO4 O O

O H O OH
 Diels-Alder reaction
The Diels-Alder reaction is a very useful synthetic reaction in that
it produces cyclic compounds.
In this reaction, a conjugated diene (called a diene) is reacted
with a compound containing a double bond (called a
dienophile),

CH2 CH2 CH2

HC CH2 HC CH2 CH CH2
+
HC CH2 HC CH2 CH2
CH
CH2 CH2
ethene C
H2
(A dinophile)
Buta-1,2-diene Cyclohexene
(A diene)