STC 121: Organic Chemistry

DR. TALEAT ADEWALE A. TELLA

08/02/2024 STC 121: Organic Chemistry Dr. Taleat A. A. Tella 1

  Organic chemistry is the study of compounds containing carbon
INTRODUCTION with the exception of simple compounds e.g. carbonates (CO32-),
carbon dioxide (CO2) and carbon monoxide (CO).
 Carbon formed the most important element in any organic
compounds because of its ability to catenate.
 Catenations is the joining of atoms of the same element to one
another to form a long chain of compounds.
 Carbon atom has the highest catenation property and hence the
reason for being critical to any organic compound. Other elements
with catenation property include Sulphur (S8), Oxygen (O3),
Phosphorous (P4), Nitrogen (N2) etc.

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 Electronic
 Carbon nucleon is 126C, a nucleon is the representation of atom of
configuration of an element with its atomic symbol, with its atomic number as
Carbon subscript and mass number as super subscript.
 The electronic configuration of carbon atom is thus 1S2, 2S2, 3S2
(ground state configuration) indicating that carbon is divalent with
at the ground state.
 The configuration of carbon at excited state is: 1S2, 2S1 2p3
indicating that carbon is tetravalent.
 Carbon hardly uses its divalent configuration to form compounds
and when such compounds are formed at all, they are highly
unstable e.g carbon(II)oxide (CO), carbon(II)chloride (CCl2).

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 Hybridization
 The simplest organic molecule is methane CH 4.
 The ground electronic state of carbon suggests it should form 2 bonds as
there are two unpaired electrons.

 Promotion of one of the two 2s electrons increases energy but the formation
of four bonds causes a four-fold decrease.
 This mixing of an s orbital and three p orbitals to produce four hybrid
orbitals is called sp3 hybridization

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  ALL tetrahedral carbon and nitrogen atoms in organic chemistry are
Hybridization sp3 hybridized.
 ALL trigonal carbons such as those found in double bonds are sp 2
hybridized.

 The unused p orbital on each carbon overlaps to form the π part of

the double bond, e.g. ethene.

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  ALL linear carbons such as those found in triple bonds are sp
Hybridization hybridized. The unused p orbitals on each carbon overlap to form
the π parts of the triple bond, e.g. ethyne

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 Electronic
 Carbon nucleon is 126C, a nucleon is the representation of atom of
configuration of an element with its atomic symbol, with its atomic number as
Carbon subscript and mass number as super subscript.
 The electronic configuration of carbon atom is thus 1S2, 2S2, 3S2
(ground state configuration) indicating that carbon is tetravalent
with at the ground state.
 The configuration of carbon at excited state is: 1S2, 2S1 2p3
indicating that carbon is tetravalent.
 Carbon hardly uses its tetravalent configuration to form compounds
and when such compounds are formed at all, they are highly
unstable e.g carbon(II)oxide (CO), carbon(II)chloride (CCl2).

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 Covalent Bonds

 Carbon formed most of its compounds using covalent bonds.

 Covalent bonds are formed by sharing of electrons between the
atoms.
 The simplest organic compounds is methane (CH4) form through
covalent bonds between carbon atom and four hydrogen atoms.
 All the four C-H bonds are of equal strength as a result for
hybridization of orbitals.

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HYBRIDIZATIO
N
 Hybridization is the mixing of orbitals to form new orbitals
(hybridized orbitals) with different characteristics different from
their parent orbitals.
 The hybridization between carbon and hydrogen can be SP3, SP2 or
SP and each of these hybridized orbitals characterized each
homologous series of compounds (hydrocarbons).
 The homologous series of hydrocarbons are the alkanes, alkenes
and alkynes.

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  Hydrocarbons are compounds made up of carbon and hydrogen
HYDROCARBONS ONLY. They are a family of compounds containing only hydrogen
and carbon. There are two main classes:
Aliphatic and Aromatic
 Within the aliphatic class there are both saturated and unsaturated
hydrocarbons.
 They include the Alkanes, Alkenes and Alkynes characterized by
SP3, SP2 and SP hybridization respectively.
 A homologous series of saturated compounds with general
molecular formula CnH2n+2 (where n is an integer).
 methane CH4, ethane C2H6, propane C3H8, butane C4H10, pentane
C5H12, hexane C6H14, heptane C7H16, octane C8H18, nonane C9H20,
decane C10H22, etc.

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  Homologous series: a series of compounds in which each
successive compound differs from the previous one by a CH 2 unit.
Homologous  At n = 4 it becomes possible to arrange the carbon skeleton
series differently i.e. it becomes possible for structural isomers to exist.
The result is termed branching of the C-C backbone.
 How does this affect a physical property such as the boiling point?

 As branching increases, the strength of the van der Waals

interactions between molecules decreases, resulting in the lowering
of boiling points.

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  1. Find the longest carbon chain in the molecule. This will give
NOMENCLATURE you the base of the name:
No of C atoms Name
1 Methane
2 Ethane
3 Propane
4 Butane
5 Pentane
Hexane
6 Heptane
7 Oct-ne
8 Nonane
9 Decane
10

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PINCIPAL 2. Determine the principle functional group and its position.

FUNCTIONAL principal
GROUP functional
group formula
ending
becomes
alkane C-C -ane
alkene C=C -ene
alkyne C≡C -yne
alcohol -OH -anol
aldehyde -CH=O -anal
ketone >C=O -anone
carboxylic acid -COOH -anoic acid

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  Position is indicated, where necessary, by numbering the
carbons in the main chain.
 Position need not be indicated for alkanes, as they have
no functional group, and aldehydes and acids, as they
are terminal functional groups.
 Positioning numbers are flanked by dash signs.
 Multiple positions for a given functional group are
separated by commas and indicated by the prefixes di,
tri, tetra, penta, hexa, hepta, octa , nona and deca.

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08/02/2024 STC 121: Organic Chemistry Dr. Taleat A. A. Tella 15
Occurrence
 Natural gas is principally methane CH 4 ,Petroleum oil - mixture up to
ca. n = 40
 Separation of crude oil is achieved by fractional distillation. This
forms the basis of the petroleum refinery and petrochemical
industries.
 Relatively, alkane chemistry is very limited.
 Their main use is as fuels for combustion or oxidation.
 Methane domestic gas supply
 Propane LPG (liquid propane gas)
 Butane camping stove gas
 Octane petrol

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combustion or
oxidation  Complete combustion yields carbon dioxide and water. Incomplete
Reaction. combustion is dangerous as it produces carbon monoxide. Always
provide a good supply of air to any process in which a hydrocarbon
is being burned.
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l)
2C2H6(g) + 5O2(g) 4CO(g) + 6H 2O(l)
 Chemically this is more accurately described as oxidation. Both
reactions produce energy in the form of heat and are said to be
exothermic.

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  Quantitative elemental analysis indicates the elements that make up
Empirical and a compound and in what proportions.
Molecular  The percentage of each element present in a compound is
determined by total combustion.
Formulae  C, H, S and N burn to give CO2, H2O, SO2 and NO2. The quantities
of these gases may readily be measured and this leads to
information that can be used to calculate the % composition and
hence empirical and molecular formulae.
 One mole of a substance is 6.02 x 1023 particles of that substance.
This huge value is termed Avogadro’s number.
 One mole of any substance has a mass equal to the relative
molecular mass (RMM) of that substance in grams.
 Relative molecular mass is the sum of the relative atomic masses
(RAMs) of the constituent elements in the compound.

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  Relative molecular mass is the sum of the relative atomic masses (RAMs)
Calculations of of the constituent elements in the compound. e.g. for ethanol C2H5OH
Relative RMM = (2 x 12.010 g mol-1) + (6 x 1.006 g mol-1) + (15.999 g mol-1) =
46.057 g mol-1
Molecular mass  If 0.152 g of an organic compound X containing only C, H and O produces:
and Empirical 0.223 g of CO2 0.091 g of H2O upon total combustion. Calculate the
Formula empirical formula of the compound X.
Solution:
First consider the CO2: RMMCO2 = 12.010 g mol-1 + 2 x 15.999 g mol-1 =
44.008 g mol-1
It implies that 0.223 g of CO2 gave = 0.223 g / 44.008 g mol-1 = 5.07 x 10-3
mol
hence, the mass of C in 5.07 x 10-3 mol of CO2 is: 5.07 x 10-3 mol x 12.010
g mol-1 = 0.061 g Percentage of C in X = x 100 = 40.1%

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  Consider the H2O: RMM = 2 x 1.0 g mol-1 + 16.0 g mol-1 = 18.0 g mol-1

Hence, 0.091 g of H2O = 0.091 g / 18.011 g mol-1 = 5.05 x 10-3 mol

Thus, 5.05 x 10-3 mol of H2O were produced from 1.01 x 10-2 mol of H
The mass of C = 1.01 x 10-2 mol x 1.006 g mol-1 = 0.010 g
% C in X = x 100 = 6.7 %
Consider the Oxygen:
The percentage of oxygen in X = 100 % – (40.1 + 6.7) % = 53.2%
 Mass % are used to calculate mole % which yield the empirical formula or
simplest ratio of the elements present.
C H O
Relative %mass 40.1 6.7 53.2
divide by RAM 12.010 1.006 15.999
relative %mole 3.3 6.6 3.3
divide by smallest 1 2 1

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  This gives the ratio 1:2:1 and the empirical formula CH2O. The
molecular formula could be any multiple of the empirical formula
e.g. C2H4O2, or C3H6O3 since these would all have the same
percentage mass ratios.
 5.05 x 10-3 mol of C means 5.05 x 10-3 mol of X in 0.152 g
 RMM of X = 0.152 g / 5.05 x 10-3 g mol-1 = 30.10 g mol-1
 The molecular formula is also CH2O and X is actually methanal or
formaldehyde.

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  Different arrangements of atoms for a given molecular formula are
often possible. Compounds with the same molecular formula but
different structural formula are called isomers.
Structural and Examples : C4H10 has CH3CH2CH2CH3 and CH3CHCH3CH3
Isomerism (structural
isomers)
Structural
Formulae
C2H6O had CH3CH2OH CH3OCH3 (Functional Isomers)
 Both exemplify isomerism. C4H10 is a molecular formula as it
shows constituent atoms. CH3HC2CH2CH3 is a structural formula
as it shows constituent atoms AND connectivities.

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  Stereoisomerism: It is also possible to arrange the atoms in
molecules with the same structural formulae such that they have
Stereoisomerism different spatial orientation. This is known as stereoisomerism.
 There are two distinct types of stereoisomer: geometric and optical.
 Geometric isomerism : It occurs in unsaturated compounds. It is
possible for single C-C bonds to rotate freely, however, double C=C
bonds cannot.
 Thus if the two carbon atoms of a C=C bond carry different groups,
it becomes possible to orientate these groups in two ways to create
geometric isomers.

cis-isomer trans-isomer
Geometric isomers have different physical and chemical properties

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 Optical  A carbon atom attached to four different groups (substituents) is
isomerism termed a chiral centre. Two different non-superimposable mirror
images are possible.
 These mirror images are called enantiomers. Enantiomers have
identical physical properties, except for the direction in which they
rotate the plane of plane polarized light.
 Enantiomers have identical physical properties, except for the
direction in which they rotate the plane of plane polarised light.
 Rotation to right termed dextro or d (+) and Rotation to left termed
laevo or l (-)
 Stereochemistry is crucially important to the pharmaceutical
industry.

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combustion or
oxidation  Complete combustion yields carbon dioxide and water. Incomplete
Reaction. combustion is dangerous as it produces carbon monoxide. Always
provide a good supply of air to any process in which a hydrocarbon
is being burned.
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l)
2C2H6(g) + 5O2(g) 4CO(g) + 6H 2O(l)
 Chemically this is more accurately described as oxidation. Both
reactions produce energy in the form of heat and are said to be
exothermic.

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  In the presence of a halogen and ultraviolet light a series of reactions take
Halogenation place:

(Substitution Initiation step: Cl2 2Cl*

Reactions) Cl· + CH4 CH3· + HCl

Propagation Step:

CH3· + Cl2 CH3Cl + Cl·

Cl· + CH3Cl CH2Cl· + HCl
CH2Cl· + Cl2 CH2Cl2 + Cl·
Cl· + CH2Cl2 CHCl2· + HCl
CHCl2· + Cl2 CHCl3 + Cl·
Cl· + CHCl3 CCl3· + HCl
CCl3· + Cl2 CCl4 + Cl·
Termination Step: Cl· + Cl· Cl2
CH3· + CH3· C2H6

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FREE RADICAL
MECHANISM
 The first step (Initiation) is hemolytic fission of the halogen to
produce (Free) halide radicals. This is termed the initiation step, .
 Radicals are extremely reactive species with single unpaired
electrons denoted ·.
 Radicals react with non-radical and radical species in propagation
and termination steps, [P] and [T] respectively.

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Cracking

 Cracking is the process of producing simple organic compounds

from the complex ones that are more useful and economically
beneficial.
 This is enormously important industrially. When the bonds in
longer chain alkanes are broken using heat in a process called
pyrolysis.
 This process produces smaller more useful hydrocarbon molecules.

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The Alkenes
 Alkene is a homologous series of unsaturated compounds with
general molecular formula CnH2n (where n is an integer greater than
1) that contain a functional group double bond (C = C).
 ethene C2H4, propene C3H6, butene C4H8, pentene C5H10, hexene
C6H12, heptene C7H14, octene C8H16, nonene C9H18, decene C10H20,
etc

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  Alkenes are defined by the presence of a C=C double bond. They
Preparation can be prepared in the laboratory via the dehydration of alcohols
by strong acid.
of Alkenes CH3CH2OH H+(aq) CH2=CH2 + H2O
* Alkenes are much more reactive than alkanes. Most of their
chemistry involves addition to the C=C double bond.
 Hydrogenation (Addition reaction): Addition of H2 to C=C in the
presence of a suitable catalyst e.g. Pd activated charcoal or Raney
Ni (treat nickel aluminum alloy with hot NaOH)
H2C=CH2 + H2 H3C-CH3
Note: Products of substitution reaction are always two while that of
addition reaction is always one.

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