CHE102
General Chemistry II Notes
Lecturers: Prof Masesane 237/218
Carbon in the periodic table
CLASSES OF HYDROCARBONS
Alkanes
cycloalkanes
Arenes
Alkynes
(Aromatic)
Alkenes
cycloalkenes
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
BUT The electronic configuration of C is 1S22S22p2 and has only 2 unpaired
electrons and one
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
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
Each hybrid orbital has 25% s-character and 75% p-
character and is said to be ‘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
Tetrahedral carbon and H-C-H bond
angles are all 109.5o
Carbon-Carbon bonds
Consider Ethane One sp3 orbital of one carbon overlaps an sp3 of the
other carbon to form the C-C bond. The remaining 3
sp3 orbitals of each carbon overlaps with the s-orbitals
of hydrogens to form C-H bonds
Orbital description of formation of C-C double bonds
Consider ethene Each carbon atom is bonded to three atoms. To achieve
this, three hybridised orbitals are required. This can be
achieved by hybridisation of one s-orbital and two p-
orbitals to give three sp2 hybridised orbitals and one unhybridized 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
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 ethyne 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.
Ethyne adopts a linear shape with H-C-C
angle of 180o
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 CH4 Methane
2 CH3CH3 Ethane
3 CH3CH2CH3 Propane
4 CH3CH2CH2CH3 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.
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
2. Number the longest continuous chain from the end nearest to a substituent.
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.
4. Suppose the longest continuous chain has two or more substituents, these are arranged
In alphabetic order in the name.
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.
• A carbon attached to one other carbon is
classified as a primary carbon
• A carbon attached to two other carbons is
classified as a secondary carbon
• A carbon attached to three other carbons is
classified as a tertiary carbon
• A carbon attached to four other carbons is
classified as quaternary carbon
NAMING CYCLOALKANES
For cyclic alkanes the preffix cyclo- is added to the alkane name
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.
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
Examples of monohalogenation of alkenes
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
The mechanism of this reaction is as follows;
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 CH2CH2 Ethene
3 CH2CHCH3 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.
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
2. The big groups are on different sides of the double bond = trans.
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
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.
Addition reaction
Mechanism of the addition reaction of halides to alkenes
Step 1
Stability of carbocations
3o>2o>1o>>CH3+
Step 2
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.
Naming alcohols
The –e ending of alkanes is
replaced by -ol.
The IUPAC rules apply.
Mechanism of the reaction of H2O with alkenes
Step 1
Markovnikov’s Rule
Step 2
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
H-OH water
CH3-OH methanol (Methyl alcohol)
CH3CH2OH ethanol (primary (1o) Alcohol)
CH3CH2CH2OH 1-propanol (primary (1o) alcohol)
CH3CH(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
CH3-O-CH2CH3
CH3CH2-O-CH2CH3
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.
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.
Markovnikov’s Rule
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 C2H2 Ethyne
3 CH3CCH propyne
Just like alkenes, alkynes with 4 or more carbon atoms exhibit positional isomerism.
e.g
Number of carbons Formula Name
4 CH3CH2CCH 1-butyne
4 CH3CCCH3 2-butyne
5 CH3CH2CH2CCH 1-pentyne
5 CH3CH2CCCH3 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
tetrahaloalkanes. It is impossible to
stop the reaction at the alkene
stage. (WHY?)
Addition reactions of alkynes with HX Alkynes react with HX to give
dihaloalkanes. Markovnikov’s Rule
applies in these reactions and the
reactions can not be stopped at the
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.
Propanone
propanal
Enols (unstable)
Structure and nomenclature of aldehydes and ketones
Aldehydes and ketones are distinguished by presence of
a carbonyl group
Aldehydes are terminal carbonyl compounds while ketones have their carbonyl group within a
chain.
Formula Name group
CH2O methanal aldehyde
CH3CHO ethanal aldehyde
CH3CH2CHO propanal aldehyde
CH3COCH3 Propanone ketone
CH3CH2CH2CHO butanal aldehyde
CH3CH2COCH3 Butanone ketone
CH3CH2CH2CH2CHO pentanal aldehyde
CH3CH2CH2COCH3 2-pentanone ketone
CH3CH2COCH2CH3 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
Carboxylic acid is an organic compound with a
carbon atom double bonded to the oxygen
(carbonyl group) and also bonded to –OH
(hydroxyl) group
Formula Name
HCO2H Methanoic acid
CH3CO2H Ethanoic acid
CH3CH2CO2H propanoic acid Replace the –ne ending of the
CH3CH2CH2CO2H butanoic acid corresponding alkane with -oic
(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.
Formula Classification
NH3 ammonia
RCH2NH2 1o amine
(RCH2)2NH 2o amine
(RCH2)3N 3o amine
