CHE102

General Chemistry II Notes

Lecturers: Prof Singh 237/227

Prof Masesane 237/218
Carbon in the periodic table
 Introduction to organic chemistry
• Subdivision of chemistry involving study of structures, properties and reactions of
carbon-containing compounds called organic compounds.
• Organic compounds form the basis of all life = biological molecules are carbon-
containing compounds.
• The simplest carbon compounds is made up of one carbon with four hydrogens
substituents and called methane
H BUT The electronic configuration of C is 1S22S22p2 and has only 2 unpaired
H C H 1S2 2S2 2p2
electrons and one
H empty p-
orbital.
In theory, C can from only three bonds and will not complete its octet. For
methane it can only for two bonds since each hydrogen atom has only one
electron (covalent bonds are formed by two shared electrons)

SOLUTION: Consider promotion of one electron from 2s to the 2p orbital =

excited state
1S2 2S2 2p2 1S2 2S1 2p3

4 unpaired electrons will form 4 covalent bonds

 C-H bond lengths and other characters
Expectation: the bond formed from the s-orbital would be different from the three formed with
p-orbitals.
Fact: The four C-H bonds in methane are identical
Solution: hybrid orbitals that result from combining atomic orbitals
2S2 2p2 sp3 sp3 sp3 sp3

4 Atomic orbitals are hybridized 4 hybrid orbitals

Each hybrid orbital has 25% s-character and 75% p-

character and is said to ‘s-p-three’ hybridised

The 4 sp3 orbitals adopt a special arrangement that keep them as far from each as possible
because of the electrons repelling each other = Point toward the corners of a regular
tetrahedron
H

Tetrahedral carbon and H-C-H bond angles

C
H are all 109.5
o
H

H
 Carbon-Carbon bonds
Consider Ethane H H One sp 3 orbital of one carbon overlaps an sp3 of the
H C C H other carbon to form the C-C bond. The
remaining 3 H H
sp3 orbitals of each carbon overlaps with the s-
orbitals
Orbital description of formation of C-C
of hydrogens double
to form bonds
C-H bonds
hene H carbon
Each H atom is bonded to three atoms. To achieve
C C this, three hybridised orbitals are required.
H H achieved by hybridisation of one s-orbital
ive three sp2 hybridised orbitals and one unhybridized p-orbital.

2s 2p sp2 sp2 sp2 p

Three orbitals are hybridised Three hybrid orbital are formed + one
unhybridised p-orbital

Consequently, one sp2 orbital of one carbon overlaps with an sp2 of another carbon to form a C-
C bond.
The remaining two sp2 orbitals on each carbon overlap with the s-orbitals of hydrogens to form
C-H bonds.
The unhybridized p-orbitals of the carbon atoms then overlap to form a second C-C bond
sp2-sp2 C-C bond = sigma (d) bond
H H

sp2-s C-H bond = sigma bond H H

p-p orbital overlap C-C bond = pi (p) bond

Two bonds connecting two atoms = double bond. The two bonds connecting the carbon atoms in
ethene are not identical. Since the rotation around the C-C bond is restricted due to the double
bond, the ethene molecule is planar and each carbon atom of ethene adopt a trigonal planar
shape with H-C-H or H-C-C angle of 120o.
Orbital description of formation of C-C triple bonds
Consider ethyneH C C H Each carbon is bonded to two other atoms. Two hybrid
orbitals are therefore required. Hybridisation of an s-orbital and one p-orbital will give two
hybrid orbital and two unhybridized orbitals.
2s 2p sp sp p

p-p orbital overlap pi bond 2

Two orbitals are Two hybridised sp orbitals and
hybridised Two unhybridised p-orbitals
sp-sp C-C sigma bond

Ethyne adopts a linear shape with H-C-C H H sp-s C-H sigma bond
angle of 180o p-p orbital overlap pi bond 1
Fractional distillation of crude oil
Hydrocarbons: Carbon compounds that
contain carbon and hydrogen atoms only. Four
subgroups of hydrocarbons; 1. alkane, 2.
alkenes, 3. alkynes, 4. aromatic compounds.
Major sources of hydrocarbons: Petroleum and
natural gas.

Petroleum or crude oil is separated into

different hydrocarbons by fractional
distillation.

High molecular weight hydrocarbons are

converted into low molecular weight
hydrocarbons thermal or catalytically through a
process called cracking
 hydrocarbons
Carbon compounds that contain carbon and hydrogen atoms only. Four subgroups of
hydrocarbons; 1. alkane, 2. alkenes, 3. alkynes, 4. aromatic compounds
Alkanes
General formula = CnH2n+2; Carbon Geometry = tetrahedral
Naming straight chain alkanes
1. Straight chain alkanes: All the carbon atoms in alkanes are sp3 hybridised.

Number of carbons formula name

1 CH 4 Methane
2 CH 3CH3 Ethane
3 CH 3CH2CH3 Propane
4 CH 3CH2CH2CH3 Butane
5 CH3CH2CH2CH2CH3 Pentane
6 CH3CH2CH2CH2CH2CH3 Hexane
7 CH3CH2CH2CH2CH2CH2CH3 Heptane
8 CH3CH2CH2CH2CH2CH2CH2CH3 Octane
9 CH3CH2CH2CH2CH2CH2CH2CH2CH3 Nonane
10 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 Decane
Homologous series = a sequence of organic compounds with the same function groups with each
compound in the series differing from the next by a defined structural unit.
 2. Branched chain alkanes

These are isomers of straight chain alkanes with four or more carbon atoms. Isomers are
Compounds with the same molecular formula but different structures.
Straight chain alkane Branched isomer
CH3CH2CH2CH3 Condesed formula (CH3)2CHCH3
C4H10 Molecular formula C4H10
Line formula

Butane Name?

To name a branched alkane, the following rules must be followed.

1. Identify the longest continuous chain in the molecule and this will give the parent name

e.g

Longest continues chain

is in brackets and has
3 carbon atoms;
Parent name = propane
 2. Number the longest continuous chain from the end nearest to a substituent.

e.g 2 1
CH2CH3 End of longest
CH3 End of continous chain
CH3CHCH3 longest chain CH3CH2CH2CHCH3
1 2 3 6 5 4 3 Substituent
For this example, For this example, numbering can
numbering from any end only be as shown. Numbering from the
of the longest chain end up other end places the substituent on C-4
with the substituent on C-2

3. Identify the substituent and their position and place the name together with the position of
the substituent before the parent name. This will be name of the substituted alkane.
A substituents is named by replacing the –ane adding of the corresponding alkane with the
-yl ending. E.g methane as a substituent will be methyl.
e.g 2 1
CH3 CH2CH3
CH3CHCH3 CH3CH2CH2CHCH3
1 2 3 6 5 4 3
Substituent: 2-methyl Substituent: 3-methyl
Parent name: propane Parent name: hexane
Name: 2-methylpropane Name: 3-methylhexane
 4. Suppose the longest continuous chain has two or more substituents, these are arranged
In alphabetic order in the name.
End of longest
8 9 continous chain
CH2CH3 Parent name: nonane
substituent Br CHCH2CH2CHCH2CH3 Substituent
Substituents: 2-methyl; 4-ethyl; 7-bromo
7 5 CH CHCH
2 3 Name: 7-bromo-4-ethyl-2-methylnonane
3 CH End of longest
3
1 continous chain
Arranged in alphabetic order

5. If two or more identical substituents are on the longest continuous chain, the prefixes di-
For two, tri- for three, tetra- for four etc are used.

CH2CH3
CH3CHCHCHCH3
• A carbon attached to one other carbon is
CH3 CH3
classified as a primary carbon
Identical substituents • A carbon attached to two other carbons is
classified as a secondary carbon
Name: 3-Ethyl-2,4-dimethylpentane • A carbon attached to three other carbons is
Positions of
methyl classified as a tertiary carbon
substituents • A carbon attached to four other carbons is
classified as
 NAMING CYCLOALKANES
For cyclic alkanes the preffix cyclo- is added to the alkane name

e.g

Cyclopropane Cyclobutane Cyclopentane Cyclohexane

Substituted cycloalkanes

=
1,2-dimethylcylobutane 1-ethyl-2-methylcyclopentane cis-1-ethyl-2-methylcyclopentane
OR

1,3-dimethylcyclobutane 1-ethyl-3-methylcyclopentane
Trans-1-ethyl-2-methylcyclopentane

The substituted cycloalkanes exhibit geometric isomerism. The ring has two faces and the
Substituent can be on the same of the ring or different faces.
If the substituents are on the same side of the molecule = cis
If the substituents are on different sides of the molecule = trans
These isomers are not interchangeable and are distinctly different compounds.
Geometric isomerism will be discussed again in alkenes
 REACTIONS OF ALKANES
Alkanes are relatively inert organic compounds. They do not react with common acids, bases
Or oxidising and reducing agents. They are therefore used as solvents. Alkanes however
Undergo two reactions;
1. Combustion or reaction with oxygen to give carbodioxide, water and energy
2. Free-radical halogenation reactions that envolve substitution of hydrogen atoms with
halogens.

Combustion of alkanes
The reaction is initiated by a spark or a flame. All hydrocarbons undergo this reaction. The
Concept you must learn under this reaction is balancing chemical reactions.
CnH2n+2 + O2 CO2 + H2O
Free-radical halogenation reaction
This reaction is initiated by light. It is important to understand the mean of arrows in reactions
Before discussing the mechanism of this reaction.

Curved arrows are used to show the movement of a pair of electrons in reactions and
Resonance structures (this will discussed later)

A curved arrow with a half head is called a fish hook and is used to show the movement of a
Single electron
 General representation of a free radical monohalogenation reaction of alkanes
light
R H + X-X R X + HX
Where X-X =
Cl2, Br2, I2
Examples of monohalogenation of alkenes
Light
CH4 + Cl2 CH3Cl + HCl
Light
CH3CH3 + Cl2 CH3CH2Cl + HCl
Cl
Light
CH3CH2CH3 + Cl2 CH3CHCH3 + CH3CH2CH2Cl + HCl

Two possible organic products

What is the mechanism of the halogenation reaction of alkanes? A mechanism shows

The sequence of bond breaking and bond making in a chemical reaction.
The mechanism of halogenation of alkanes involves three steps;
1. Initiation step involving bond breakage
2. Propagation step involving both bond breaking and bond formation
3. Termination step involving bond formation
 MECHANISM OF HALOGENATION OF ALKANES

Remember: The reaction involves a halide substituting a hydrogen in an alkane. The reaction
Can therefore occur only on carbon atoms that have at least one hydrogen attached to them.

Consider the chloronation of ethane

Light
CH3CH3 + Cl2 CH3CH2Cl + HCl

The mechanism of this reaction is as follows;

1. Initiation
Light
Cl Cl Cl + Cl

Fish hook arrows Free radicals

Each Cl atom gets have an unpaired
one of the bonding electron
electrons and this is
called Homolytic
clevage.
2. Propagation
1. CH3CH2 + Cl CH3CH2 + HCl
H
Carboradical = presence
From the Initiation of a carbon with an unpaired
step electron
2. CH3CH2 + Cl Cl CH3CH2Cl + Cl
Goes back to step 1 of
Product propagation and start the
From step 1 of propagation again.
propagation Propagation is cyclic.

3. Termination. An reaction that terminates the cycle of propagation belongs to this step

Cl + Cl Cl2

CH3CH2 + Cl CH3CH2Cl

CH3CH2 + CH3CH2
 ALKENES
These hydrocarbons contain at least two sp2 carbons connected to each other by a double
Bond. While the alkanes are saturated (cannot take up any hydrogen atoms), alkenes are
Unsaturated hydrocarbons.

Naming alkenes
The names of alkenes have the ending –ene.

Number of carbon atoms formula Name

1 N/A N/A
2 CH 2CH2 Ethene
3 CH 2CHCH3 Propene
Alkenes with 4 and more carbons exhibit positional isomerism. (Remember: Isomers are
Compound with the same chemical formula but different structures).
e.g
With 4 carbon atoms we get CH2CHCH2CH3 or CH3CHCHCH3 and the names are 1-butene
And 2-butene respectively. The numbers denote the positions of the double bonds.

Naming branched alkenes

The IUPAC Rules apply.
1. Identify the longest continuous chain that includes the sp2 carbon atoms (parent name).
2. Number the longest continuous chain such that one of the sp2 carbon atoms gets the
smallest possible number.
3. Identify the substituents and their positions in the longest continuous chain.
e.g CH2C(CH2CH3)2
The simplest approach is to extend this condensed structure. Remember: carbon must have
4 bonds around it unless it is carrying a charge or is a radical. You will find that the longest
Continuous chain containing the double bond is not necessarily the longest continuous
Chain in the molecule.
3 4
1 CH2CH3 Parent name: 1-butene
H2C C substituent: 2-ethyl
2 CH2CH3 Name: 2-ethyl-1-butene

GEOMETRIC ISOMERISM IN ALKENES

Each of sp2 carbons of alkenes has two substituents. If the two substituents on each of the
Sp2 carbons can be distinguished in terms of size (big and small), the molecule will exhibit
Geometric isomerism. There will be two possible arrangements of the substituents in
To the planar double bond;
1. The big groups on the same side of the double bond = cis
H H
On this sp2 carbon the On this sp2 carbon the
e.g 2-butene big group is CH i.e CH C C
3 3 big group is CH3
H3C CH3
is bigger than H
The two big groups
are on the same side
of the double bond = cis

Full name is cis-2-butene

2. The big groups are on different sides of the double bond = trans.
This big group is on the upper side
of the double bond
H
On this sp2 carbon the H3C On this sp2 carbon the
e.g 2-butene big group is CH i.e CH C C
3 3 big group is CH3
H CH3
is bigger than H
This big group is on the lower
side of the double bond
Full name is trans-2-butene

Unlike conformations of alkanes, geometric isomers of alkenes are not interchangeable

Without breaking of bonds. They are two distinct compounds with different physical
characteristics.
Cycloalkenes
CH3

H3C H3C
Cyclopentene Cyclohexene 1-Methylcyclopentene 1,3-Dimethylcyclopentene

The sp2 carbons are always numbered 1 and 2 for simple cycloalkenes. If one of sp2 carbons
has a substituent, it is numbered 1
 REACTIONS OF ALKENES
Reactions of alkenes with halides
Halides add to alkenes to give 1,2-dihaloalkanes. The decolouration of the red bromine when it
reacts with alkenes is used as a test of the presence of a carbon-carbon double bond in an
unknown sample.
Br
H2C CHCH3 + Br2 H2C CHCH3
Addition reaction
Br
Red in colour colourless

Mechanism of the addition reaction of halides to alkenes

Step 1
Br Br
H2C CHCH3 + Br Br Slow
H2C CHCH3 + H2C CHCH3 + Br
Stability of carbocations
Secondary Primary
3o>2o>1o>>CH3+
carbocation Carbocation
More stable

Step 2
Br Br
H2C CHCH3 + Br Fast
H2C CHCH3
Br
 Addition of asymmetric reagents to alkenes (H2O and HX)
a) Reaction of H2O with alkenes
Water reacts with alkenes in the presence of catalytic amount of acid to give alcohols.
Remember: Alcohols are organic compounds with an –OH functional group attached to an sp3
carbon atom.
Catalyst
OH OH Naming alcohols
H2SO4 The –e ending of alkanes is
H2C CHCH3 + H2O H3C CHCH3 + H2C CH2CH3
2-propanol 1-propanol
replaced by -ol.
secondary alcohol Primary alcohol The IUPAC rules apply.
major product Minor product

Mechanism of the reaction of H2O with alkenes

Step 1 Slow
H2C CHCH3 + H H3C CHCH3 + H2C CH2CH3 Markovnikov’s Rule
More stable Less stable
From the
carbocation carbocation
catalyst

Step 2
Fast
Fast Reproduced in this step
H3C CHCH3 + H2O H3C CHCH3 H3C CHCH3 + H hence the acid is used in
O OH catalytic amount
H H
 Structures and nomenclature of alcohols and ethers
Alcohols are derivatives of H2O (water) in which one of the hydrogen atoms is replaced by an
alkyl chain
-OH water R
H3-OH methanol (Methyl alcohol) R C OH
H3CH2OH ethanol (primary (1o) Alcohol) R sp3 carbon
H3CH2CH2OH 1-propanol (primary (1o) alcohol) Where R = H or alkyl chain
H3CH(OH)CH3 2-propanol (secondary (2o) alcohol)
Classification of alcohols
1o alcohol = -OH attached to a Carbon that in turn is attached to only one other carbon
2o alcohol = -OH attached to a carbon that in is attached to only two other carbons
Tertiary (3o) alcohol = -OH attached to a carbon that is attached to three other carbons
Names of alcohols are derived from alkane names by replacing the –e ending with -ol
Ethers are derivatives of water in which the two hydrogen atoms are replaced by alkyl chains.
Names of ethers will be discussed in CHE232.
Examples of ethers
CH3-O-CH3 R R
CH3-O-CH2CH3 O
CH3CH2-O-CH2CH3 Where R = alkyl chains
CH3-O-CH2CH2CH3
CH3-O-CH(CH3)2
Reaction of alkenes with Bronsteid acids (HX)
Bronsteid acids react with alkenes to give haloalkanes. The reaction proceed to give
Markovnikov’s product as the major isomer.
Cl Cl
Example H2C CHCH3 + HX CH3CHCH3 + CH2CH2CH3
2-chloropropane 1-chloropropane

Mechanism of the reaction of alkenes with HX

The mechanism is comparable to that of the reaction of alkenes with water. The first step
Involves the reaction of alkene with H+ to give a carbocation and this is the rate-determining
Step. The second step which is fast involves the reaction of the carbocation with X - to give the
haloalkane.

slow
Step 1 H2C CHCH3 + H H3C CHCH3 + H2C CH2CH3 Markovnikov’s Rule
2o Carbocation 1o Carbocation
From HX
more stable. forms less stable
more readily

Cl Cl
Fast
Step 2 H3C CHCH3 + H2C CH2CH3 + Cl H3C CHCH3 + H2C CH2CH3
Major product Minor product
 ALKYNES
These are hydrocarbons with at least two sp hybridised carbons connected by a triple bond.

Naming alkynes
The names of alkynes have the ending –yne.

Number of carbon atoms Formula Name

1 N/A N/A
2 C 2H2 Ethyne
3 CH 3CCH propyne
Just like alkenes, alkynes with 4 or more carbon atoms exhibit positional isomerism.
e.g
Number of carbons Formula Name
4 CH 3CH2CCH 1-butyne
4 CH 3CCCH3 2-butyne
5 CH 3CH2CH2CCH 1-pentyne
5 CH 3CH2CCCH3 2-pentyne

IUPAC rules comparable to those for alkenes are followed to name branched alkynes.
 REACTIONS OF ALKYNES
Alkynes undergo many of the addition reactions that were described for alkenes. However,
Alkynes are less reactive than alkenes.
Reaction of alkynes with halides This reaction proceeds to give
Cl Cl
tetrahaloalkanes. It is impossible to
H3CC CH + 2Cl2 H3CC CH
stop the reaction at the alkene
Cl Cl
propyne halide 1,1,2,2-tetrachloropropane stage. (WHY?)

Addition reactions of alkynes with HX Alkynes react with HX to give

Cl dihaloalkanes. Markovnikov’s Rule
H3CC CH + 2HCl H3CC CH2 H3CC CH3 applies in these reactions and the
Cl Cl reactions can not be stopped at the
propyne 2,2-dichloropropane alkene stage. (WHY?)
Addition reactions of alkynes with H2O
Alkynes react with H2O in the presence of H2SO4 and HgSO4 to give ketones and aldehydes .
Markovnikov’s Rule applies in this reaction. Remember: Alkenes react with H2O in the presence
Of H2SO4 to give alcohols.
H3CC CH3 Propanone
H3CC CH2 O
H2SO4
H3CC CH + H2O OH Tautomerization Ketone
HgSO4 H3CHC CH propanal
propyne water H3CC CH
H O
H OH
Aldehyde
Enols (unstable)
 Structure and nomenclature of aldehydes and ketones
R
Aldehydes and ketones are distinguished by presence of O C
a carbonyl group R
Where at least one R = H (aldehydes)
R = alkyl chains (ketones

Aldehydes are terminal carbonyl compounds while ketones have their carbonyl group within a
chain.
Name group
methanal aldehyde
ethanal aldehyde
propanal aldehyde
Propanone ketone
HO butanal aldehyde
H3 Butanone ketone
H2CHO pentanal aldehyde
OCH3 2-pentanone ketone
H2CH3 3-pentanone ketone
Aldehyde: the –e ending of alkane name is replaced by –al
Ketone: the –e ending of alkane name is replaced by -one
 Structure and nomenclature of carboxylic acids and amines
O
Carboxylic acid is an organic compound with a Carbonyl hydroxyl group
carbon atom double bonded to the oxygen C
R OH
(carbonyl group) and also bonded to –OH R = hydrogen or alkyl group
(hydroxyl) group

ormula Name
CO2H Methanoic acid
H3CO2H Ethanoic acid
Replace the –ne ending of the
H3CH2CO2H propanoic acid
corresponding alkane with -oic
H3CH2CH2CO2H butanoic acid
CH3)2CH2CO2H 2-methylpropanoic acid
Amines are derivatives of ammonia where at least one hydrogen attached to nitrogen is
replaced by an alkyl chain. Nomenclature of amines will be discussed in CHE232.
H H
ula Classification N
N
ammonia
H H RH2C CH2R
ammonia o
2 amine
NH2 1o amine
)2NH 2o amine H CH2R
N N
)3N 3o amine RH2C H RH2C CH2R
o
1o amine 3 amine