UN

NESCO-NIGGERIA TECCHNICAL &

VOCATIOONAL EDUCCATION
REVIITALISATIION PROJE
ECT-PHASE II

NATIIONAL
L DIPLO
OMA IN
I
S
SCIENC
CE LAB BORATORY TECH
HNOLO
OGY

O GANIC
ORG C CH
HEMIISTR
RY I
COURSE CODE:
C STC 1221
YEAR I-- SE MESTER 2

T
THEORY

Version 1:
1 Decemberr 2008

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TABLE OF CONTENTS THEORY STC 121 ORGANIC CHEMISTRY

Week 1………………………………………………………………………………………………………………5
1.0 understanding the classification of organic compounds
1.1 Meaning of organic compound
1.2 Classification of organic compound
1.3 Functional and examples
1.4 Electro magnetic radiation

Week 2………………………………………………………………………………………………………………10
2.0 understanding bonding, reactions and application of Aliphatic hydrocarbons
2.1 Alkanes
2.2 Nomencleture of alkanes
2.3 Industrial uses of alkanes
2.4 Hybridization in alkanes
2.5 Alkenes

Week 3………………………………………………………………………………………………………………13
2.6 structural differences between alkenes and alkanes
2.7 uses of alkenes

Week 4………………………………………………………………………………………………………………15
2.8 Hybridization in alkenes
2.9 Test for unsaturation
2.10 Alkynes
2.11 Uses alkynes

Week 5………………………………………………………………………………………………………………17
3.0 Alkanols
3.1 Nomenclture
3.2 methods of preparation
3.3 physical properties
3.4 Reaction of alcohols
3.5 Types of alcohols

Week 6………………………………………………………………………………………………………………21
3.6 Dehydration
3.7 Classification
3.8 Industrial preparation of ethanol by fermentation
3.9 Effects of alcohols

Week 7………………………………………………………………………………………………………………24

4.0 Halo Alkanes

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 4.1 Nomenclature
4.2 Physical properties
4.3 SNI Reactions
4.4 Uses of Halo alkanes

Week 8………………………………………………………………………………………………………………27
5.0 ALDEHYDES
5.1 Methods of preparation
5.2 Nocleophillic Addition reactions
5.3 Uses of Aldehydes

Week 9………………………………………………………………………………………………………………30
6.0 KETONES
6.1 Methods of preparations
6.2 Reactions of Ketones
6.3 Uses of Ketones

Week 10……………………………………………………………………………………………………………33
7.0 CARBOXYLIC ACIDS
7.1 Introduction
7.2 Methods of preparation

Week 11……………………………………………………………………………………………………………35
7.3 Reaction of carboxylic acid
7.4 Uses of carboxylic acids

Week 12……………………………………………………………………………………………………………37
8.0 ESTERS
8.1 Nomenclature
8.2 Methods of preparation

Week 13……………………………………………………………………………………………………………37
8.3 Reaction of esters
8.4 Mechanisms
8.5 Uses of esters

Weeks 14……………………………………………………………………………………………………………40
9.0 Petroluem rifining
9.1 Origin of petroluem
9.2 Fractions obtained from fractional distillation

WEEK 15……………………………………………………………………………………………………………40
9.3 DISTILLATION
9.4 Vaccum distillation

3
9.5 Fractional distillation
9.6 Solvent extraction
9.7 Cracking

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1.0 WEEK 1

1.1 The Meaning of the term “Organic”

At the beginning of modern chemistry the pioneer chemists were engaged with two activities:
• Isolation and characterization of compounds from natural sources

• Duplication of the isolated compounds in the laboratory

In isolating compounds from nature the pioneer chemists considered both living and non-living
things. For example they isolated and characterized urea (from human urine), formic acid (from
ants), sucrose (from sugar cane plant), etc. From mineral sources they obtained common salt,
sodium nitrate, sodium sulphate, etc.. Having isolated and characterized a compound, they
proceeded to duplicate, i.e., make the compound using the paraphernalia of the chemistry
laboratory. In all cases of compounds isolated from mineral sources, they succeeded in their
duplication attempts. However, in the case of compounds obtained from living things they were
unsuccessful in their duplication attempts, and for this reason they put forward a theory to
explain this inability. According to this theory the bodies of living things contain a certain vital
force which enables them to make compounds. By inference therefore since the paraphernalia of
the chemistry laboratory lacks this vital force, this explains the inability of the pioneer chemist to
make compounds obtained from living things in the laboratory. This theory is known as the vital
force theory. As the pioneer chemists continued with their activities the number of known
compounds increased tremendously and the need for a simplification of the study of naturally-
obtained compounds arose. The pioneer chemists solved this problem by classifying the known
compounds. They used, as a basis for classification, the source of the compound. They therefore
classified all the naturally-known compounds int two classes:

• Organic compounds: These are compounds obtained from living things, the word
“organic” meaning life.
• Inorganic compounds: These are compounds obtained from mineral sources.

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According to the pioneer chemist therefore organic chemistry is the chemistry of compounds
obtained from living things.

With time every human problem is finally overtaken by a solution. Around the middle of the
nineteenth century, a German chemist, Frederick Wohler, succeeded in making urea in the
laboratory. This success shook the foundation of the vital force theory. Subsequently, other
chemists succeeded in making compounds from living things in the laboratory. For instance
Kolbe, another chemist, succeeded in making acetic acid from its elements, carbon, hydrogen
and oxygen. With these preparations the foundations of the vital force theory finally crumbled
and it became abandoned. Organic compounds were then realized to be just like their inorganic
counterparts.

Even though the vital force theory is abandoned, the term “organic” is retained but with a
different meaning. All compounds that were originally classified as organic have one
constitutional character in common and that is the presence of the element carbon. This
constitutional character is the basis for the modern definition of organic chemistry. Today
organic chemistry is defined as the chemistry of carbon compounds regardless of whether the
compound is obtained from living thing or not. There are however, certain exceptions to this
definition. Simple oxides of carbon along with the metallic carbonates and hydrogencarbonates
are not classified as organic.

Varieties of Carbon Compounds

CLASSIFICATION OF ORGANIC COMPOUND

• Draw attention to the fact the number of compounds formed by the element carbon alone
is much larger than those formed by all the elements put together.
• Use the following points to explain the above difference:
1. Catenation
Here attention should be drawn to the fact that the chains formed by carbon can either be open
(aliphatic) or closed (cyclic). Attention should also be drawn to the fact that besides carbon and
hydrogen the more common elements encountered among organic compounds include: Oxygen,
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nitrogen, sulphur, the halogens, phosphorus and some metals. Emphasis should be made of the
involvement of these elements in bonding with carbon and hydrogen in organic compounds.
2. Multiple bond formation
Here draw attention to the different types of bonds formed by carbon..These include carbon-
carbon single, double and triple bonds. Mention the distinction between saturated and
unsaturated compounds.
3. Ring formation
Here illustrate the different types of rings formed by carbon: Three-membered, four-membered,
etc. Draw attention of the involvement of other elements such as nitrogen, oxygen and sulphur in
ring formation to produce heterocyclic compounds.

• Classify organic compounds into aliphatic and cyclic. Further classify cyclic compounds
into carbocyclic and heterocyclic. Carbocyclic compounds can be further classified as
alicyclic and benzenoid.

Organic compounds contain carbon and hydrogen and sometimes other elements such as oxygen

nitrogen, sulphur, etc. The bonding in organic compounds is predominantly covalent. The

numerous organic compounds can be grouped into a comparatively small number of series or

families of compounds known as Homo.logous series. Homologous series are define as series

of a family of organic compounds which follows a regular structural pattern, in which each

successive member differ in its molecular formular by a – CH2 – group.

Members of homologous series includes, alkane, alkenes, alkanols, carboxylic acids etc.

Members of homogenous series have the following properties.

(i) They have general molecular formula. All members have a general molecular

formular i.e CH2n + 2 for alkane, Cn H2n for alkenes etc.

(ii) They have difference of CH2 group between successive members

7
 (iii) They have gradation in their physical state properties. The physical properties of the

members change gradually as the number of carbon atom per molecule increases.

(iv) Members of homologous show similar chemical properties

(v) Members of homologous series have the same general methods of preparation.

FUNCTIONAL GROUP

Functional groups are groups of atom or bond common to a series or family of compounds and

which govern the principal chemical properties of the series. Below are some major

classification of organic compounds by functional group

Homologous series Functional group Structure

Alkenes C C C C
Alkynes
C C C C
Alkanols
OH OH
Ethers
O O
Amine
NH2 R NH2
Aldehydes
CHO
Ketones C =O
Esthers
COOR
Nitriles

Carboxylic acids COOH

C =N
Phenols
AROH
Amide

CONH

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ELECTROMAGNETIC RADIATION (I.M.R)

Electromagnetic radiation is the source of the energy that a molecule absorbs in NMR, IR, UV –

VIS spectroscopy. Electromagnetic radiation, of which infra-red (IR) is but one example is used

principally to reveals the presence or absence of key functional group within a molecule.

Wavelength

X -ray Visible Micro wave Radio

Grammes Ultra violet
frequency
rays

Electromagnetic radiation

Frequency
The absorption of a photos of infra – red radiation exicites a molecule from it lowest , or ground

vibration state to a higher one. These vibrations include stretching and bending modes. In using

infra – red spectrotroscopy for structure determination, peaks in the range 16000 – 4000cm are

usually emphasised because this is the region in which the vibrations characteristics of particular

functional group are found. The region. It is here that the pattern of peak varies most from

compound to compound.

Infra-Red Absorption Frequencies of some Common Functional Group

Structural units Frequency cm-1

Alkanol – OH 3200 – 3600

Carboxylic acid – COOH 2500 – 3600

Amides – CONH2 1680 – 1700

Esters - COOR 1730 – 1750

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 WEEK 2
UNDERSTANDING BONDING, REACTION AND APPLICATION OF

HYDROCARBON

ALKANES

Alkanes are aliphatic hydrocarbons, they form a homologous series of saturated hydrocarbon

and represented by general molecular formular ,CnH2n+2. The major sources of alkanes are crude

oil and natural gas.

NOMENCLETURE OF ALKANES

Below are the rules used for alkane nomenclecture in accordance with I.U.P.A.C systems of

naming;

(i) Establish the parent hydrocarbon by counting the longest continuous carbon chain, name

the parent compound by ending with –ane.

(ii) Name the attached group(s) or substituent’s. If there are several substituent’s, separate

the no by putting comma, and the number from the word by hyphen (-).

(iii) If the substituent’s are identical, use prefix, di, tri, tetra penta etc.

(iv) When there are two or more substituent’s present in a compound, the substituent are cited

in alphabetical order, for e.g ethyl substituent should be cited before methyl substituent.

(v) Numbering of the parent hydrocarbon should begin from the end of the carbon chain that

is closet to where there is highest branching such that the least possible numbers are

assigned to substituent consider, the following examples;

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CH3CH2CH2CH2CH2CH2CH3
n – heptanes

CH3
CH3CH2CH2CH2CH2
2 – methyl pentane

CH3CH2CH2CH2CH2CH3
CH2CH3
3 – ethyl hexane

CH3CH CH C CH3
Br CH3

3 – Bromo – 2, 2, 4 – Trimethyl pentane

CH3CH2CCHCH2CH3
CH3CH3

3, 3, 4 – trimethyl hexane

INDUSTRIAL USES OF ALKANES

(i) Methane is mainly used as a fuel, either by itself or mixed with other gases

(ii) Methane is used in making carbon black, hydrogen gas etc

(iii) Some alkanes are also used as solvents and in the manufacture of other chemicals

(iv) Solid alkane have variety of uses e.g Vaseline is a mixture paraffin wax

(a solid alkane) and oil.

SP3 HYBRIDIZATION IN ALKANES

Hybridization is a process of mixing orbitals of different energy level by excitation in order to

produce orbitals that of the same energy level or degenerate. SP3 hybridization involves mixing

of one s- orbitals and 3 – p – orbitals to hybrid orbitals. Methane as a members of alkane

undergo sp3 hydrization.

CH4 – methane

C = 1S2 2S2 2P2

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 Ground state
At excited level

H H

3
Hydrogen atoms are SP
H HHybridizatio
attached n
to the vacant orbitals

The mixing of one – s– orbitals and 3 – p aorbitals methane is known as Sp3 hybridization.

ALKANES Alkenes are homologous series of unsaturated hydrocarbon and are represented by

a general molecular formula Cn H2n.

SP2 HYBRIDIZATION IN
2 ALKENES
1S 2S2 2P2
Ethene shows sp2 hybridization. The one s – orbital combine with 2 – 2p – orbitals in the bonding to produce hybrid orbitals of

the same energy level CH2 = CH2.

C = 1S2 2S2 2P2

At ground
level

At exerted
level
These electronics are not involved
H H H
2
S P hybridization in the bonding
C = 1S2 2S2 2P2
For 1 –
carbon atom 1S2 2S2 2P2
At ground
h
level

At exercited
level
H
For 1 – H H
carbon atom H

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 WEEK 3
There are two major structural differences between alkenes and alkanes. First,
alkanes have a tetrahedral geometry (∼109.50) around each C-atom, whereas the
double-bonded C- atoms in alkenes are trigonal planar (∼1200C)

Second, the C-C bond allows rotation of bonded groups, so the atoms in an alkane
continually change their relative positions, in contrast, the π bond of the c = c bond
restricts relation, which fixes the relative position of the atoms bonded to it. This
rotational restriction leads to another type of stereoisomerism. Geometric isomers
also called cis-trans isomers and diastereomers) have different orientations of
groups around a double bond. The example below shows the two geometric
isomers of 2-butene. one isomer, cis-2-butene has the CH3groups on the same sides
whearaeas the other isomer has them on opposition sides of the c = c bond. This
type of geometric isomerism is also called cis-trans isomerism. Like all isomers,
the geometric isomers have different properties.

H H
Cis-2-Butene Density = 0.621g/m
| |
C = C Bpt = 3.70C
CH3 CH3

CH H
Trans -2-Butene Density = 0.604g/ml
| |
C = C Bpt = 0.90C
H CH3
The most characteristics chcteristic reaction of an alkene is addition reaction, in
which atoms supplied by the reactant form δ -bonds to the two atoms joined by the
double. In the process, the π-bond is lost. An example is halogenations, addition
of HBr to propene, etc.

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CH2 = CH2 + Cl2 CH2cl - CH2CL
H H H H +

C =C + CL – Cl C C Cl-

H H H Cl H

H Cl H + H Cl

C - C H C C H

H H Cl H
1,2-D1 Chloromethane
Also, addition of HBr to propane to form 2-bromopropane for the following
mechanism.

CH3 - CH = CH2 + HBr CH3 - CHBr - CH3

USES OF ALKENES
• Alkene are used in the production of polymers
• Alkene are used in the production of oxyacetylene flame
• Alkene are used in the production of polysterene
• Alkene are used in the production of polyethylene

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 WEEK 4
In the formation of carbon-carbon triple bonds, -C= C-, only two of the valence
electrons are hybridized to form sp-orbital, leaving two p-orbital unaffected.

IS 2s 2P
Carbon atom 1 7 7 7

excited state Sp hybridized unaffected by

hybridization

The simplest hydrocarbon containing triple bond, ethyne (acetylene), is a linear

molecule. The carbon and hydrogen atoms are attached by –bonds which are
formed by the overlapping of the sp-orbitals of the hydrogen atoms. One of the
carbon bonds is a δ-bond which results from overlapping of the other sp orbital of
each carbon. The remaining two carbon-carbon bonds are both π bonds which are
formed as a result of the overlapping of adjacent p-orbitals. The ethyne molecule
is virtually encased by clouds of negatively charged electrons.

TEST FOR UNSATURATION

ALKENES: When few drops of 1% KMn04 solution made alkaline with Na2C03
are added to aqueous solution of an unknown compound and the purple colour of
the KMn04 is discharged, the compound is unsaturated.

Unsaturation in a compound is also confirmed by its decolourization of bromine.

Alkynes are distinguished from alkenes by slow decolorization process of KMn04
and bromine.

15
ALKYNES: Alkynes, (those with acidic hydrogen) forms alkynide with silver
nitrate (grey precipitate) and copper (1) chloride (reddish-brown precipitate) in
liquid ammonia. This reaction is not given by alkenes and alkanes.

USES OF ALKYNES
• Alkynes are used in the production of oxyacetylene flame.
• They are used in the production of vinyl chloride
• They are used in the production of vinyl polymers.

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 WEEK 5
ALKANOLS
Alphatic monohydric alcohols are mono hydroxyl derivatives of alkanes and have
a general formular CnH2n+1H or simply ROH. -0H is simply identified as their
functional group. They may be classified as primary (10) secondary (20) or tertiary
(30) according to the nature of the carbon atom to which the hydroxyl group (-0H)
is attached.

CH30H, CH3 CH2 OH , CH3 – CH2 – CH

|0 |
CH3 Propane -2-01
|
CH – C – CH 20
|
0H
30

NOMENCLATURE
The I.UPAC system is generally adopted for most alcohols, although common
names, which are afforded by stating the name of the appropriate alkyl group
followed by the word “alcohol” are still sometimes used for the simpler
compounds, e.g. methyl alcohol, benzyl alcohol, etc.

The IUPAC names are afforded by dropping the ending ‘one’ of the corresponding
alkane and replacing it with the suffix ‘OL’. The position of the hydroxyl group in
the iron chain is specified by inserting the appropriate number between the stem of
the name and the ‘-01’.

CH3
|
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 CH3CH2CH20H CH3CH CH3 CH3 – C – CH3
| |
Propane – 1 – 0l 0H OH
Propane – 2- 0l 2-methyl-propan-2-0l

METHODS OF PREPARATION
Methods of preparing monohydric alkanols includes:-
1. Hydration of alkenes
2. fermentation of carbohydrates either from cane sugar or starch
3. catalytic polymerization of alkene
4. reduction of carbonyl compounds
5. hydrolysis of alkyl halides
6. adol condensation
7. hydrolysis of esters.

PHYSICAL PROPERTIES
1. Simple alcohols (lower members of the family) are liquid at room
temperature. They have burning taste, characteristics smell and are
generally volatile and colourless.
2. The hydrophilic nature of the -OH group makes the alkanols to be very
soluble in water. They are generally soluble in organic solvents. Their
solubility in water decreases as their molecular weight increases.
3. The simple alkanols have low melting points
4. They have higher boiling points than their corresponding alkanes.

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REACTIONS OF ALCOHOLS

1) Esterification: When excess alkanol is heated under reflux with anhydrous

organic acid in the present of a little conc H2S04 or dry Hcl )as a catalyst),
the corresponding ester is formed:
R – 0H + R1COOH R1COOR + H20

2. Oxidation: Primary and secondary alkanols are easily oxidized by dilute

solution of acidified Knan04 or K2Cr207 or dilute HN03. A strong oxidant
and vigorous conditions are required for the oxidation of tertiary alkanols.
10 RCH20H [0] RCHO [0] RCOOH

CH3CH20H [0] CH3CH0 [0] CH3COOH

-H20

20 R2CH0H [0] R2 C = O [0] RCOOH

H20

3. Alkoxide Formation
Treatment of alkanol with sodium, potassium or calcium metal produces the
corresponding alkoxide hydrogen gas is evolved.
2ROH + 2Na 2R0Na+ + H2
sodium
alkoxide

2 C2H50H + 2Na C2H50Na+ + H2

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Types of Alcohol

Kind Manufacture Uses

Methyl (wood By destructive distillation of wood. Also by Solvent for fats, oils, resins, nitrocellulose.
alcohol, synthesis from hydrogen and carbon Manufacture of dyes, formaldehyde, antifreeze
methanol) monoxide under high pressure. solutions, special fuels, plastics.
Ethyl (grain By fermentation of sugar, starch, or waste Solvent for products such as lacquers, paints,
alcohol, sulfite liquor. Synthesis from ethylene or varnishes, glues, pharmaceuticals, explosives. Also as
ethanol) acetylene. Direct hydration of ethylene. 'building block' in making high-molecular-weight
chemicals.
Isopropyl By hydration of propylene from cracked Solvent for oils, gums, alkaloids, resins. Making
(isopropanol) gases. Also as by-product of certain acetone, soap, antiseptic solutions.
fermentation processes.
Normal propyl As a coproduct of air oxidation of propane Solvent for lacquers, resins, coatings, films, waxes.
and butane mixtures. Also as brake fluid, in manufacture of propionic acid,
plasticizers.
Butyl (n- By fermentation of starch or sugar. Also by Solvent for nitrocellulose, ethyl cellulose, lacquer,
butanol) synthesis, using ethyl alcohol or acetylene. urea-formaldehyde, urea-melamine plastics. Diluent of
hydraulic fluids, extractant of drugs.
Isobutyl By synthesis from carbon monoxide and Solvent for castor-oil-base brake fluids. Substitute for
hydrogen at high pressure, then distillation n-butyl alcohol in making urea resins.
from products formed.
Secondary butyl By hydration of 1-butane, formed in In making other chemicals such as methyl ethyl
petroleum cracking. ketone. Solvent in nitrocellulose lacquers. Production
of brake fluids, special greases.
Tertiary butyl By hydration of isobutylene, derived from In perfume making. As wetting agent in detergents.
petroleum cracking. Solvent for drugs and cleaning compounds.
Amyl (pentyl) By fractional distillation of fusel oil, a Solvent for many natural and synthetic resins. Diluting
coproduct of ethyl alcohol manufacture by brake fluids, printing inks, lacquers. In medicinal
fermentation. products.
Ethylene glycol By oxidation of ethylene to glycol. Also by Deicing fluid, antifreeze, brake fluid. In production of
hydrogenation of methyl glycolate made explosives. Solvent for stains, oils, resins, enamels,
from formaldehyde and methanol. inks, dyes.
Diethylene As coproduct in manufacture of ethylene Solvent for dyes, resins. Antileak agent. In gas drying.
glycol glycol. Softening agent in adhesive printing inks.
Triethylene Coproduct in manufacture of ethylene Air disinfectant and dehumidifier. Production of resins,
glycol glycol. plasticizers.
Glycerol From treatment of fats in soapmaking. In alkyd resins, explosives, cellophane. Tobacco
(glycerin; Synthetically, from propylene. By humectant.
1-, 2-, 3- fermentation.
propanetriol)
Pentaerythritol By condensation of acetaldehyde and In synthetic resins. As tetranitrate in explosives. Also
formaldehyde. as drug for treatment of heart disease.
Sorbitol By reduction of sugar, usually corn sugar, In foods, pharmaceuticals, in chemical manufacture.
with hydrogen. Conditioning agent in paper, textiles, glue, cosmetics.
Source of alcohol in resin manufacture.
Cyclohexanol By catalytic hydrogenation of phenol. By Intermediate in making chemicals used in nylon
catalytic air oxidation of cyclohexane. manufacture. Stabilizer and homogenizer of soaps,
synthetic detergents. Solvent.
Phenylethyl By synthesis from benzene and ethylene Principally in perfumes.
oxide.
Microsoft ® Encarta ® 2007. © 1993-2006 Microsoft Corporation. All rights reserved.

20
 WEEK 6
Dehydration: On heating with acid catalyst (e.g. Al2, 03, S, 02, H2S04), alcohols
which have hydrogen atom attached to the adjacent carbon atom undergo
elimination of water to form alkenes. The reaction occurs least readily with
primary alcohols and with competition from ether formation
CH3CH20H AI203 CH2= CH2
3750C

MECHANISM
It involves protonation of the alcohol followed by the loss of water molecule to
form a carbonation. The process is terminated by the removal of a proton from the
carbonation by hydrogen sulphate ion.

CH3CH2 0 H H+ - 0S03 0H CH3CH2 - 0H2 -H20

CH2 – CH2 HS04 CH2 = CH2+ H2S04

When tetraoxosulphate (vi) acid is not the dehydrating agent, the protons comes
from the acid catalyst used.

CH3CH2 0 H H+ - CH3 CH2 -0H2 - 0H2 CH2 CH2 CH2 = CH2 = CH2

CLASSIFICATION
Monohydric alcohols are that contain one hydroxyl group. Compounds containing
more than one hydroxyl group are described as polyhydric alcohols they may be
classified as primary, secondary or tertiary alcohols according to the nature of the
carbon atom to which the hydroxyl group is attached.

21
Primary and secondary alcohols are reality oxidized to aldelredes and ketones
respectively. Aldehydes may be further oxidized to carboxylic acids. Tertiary
alcohols are comparatively stable to oxidation and are not oxidized at all in neutral
or alkaline medium.

INDUSTRIAL PREPARATION OF ETHANOL BY

FERMENTATION

(a) Fermentation of carbohydrates: Fermentation is a process whereby a

complex organic molecules are broken down into simple one through the
action of enzymes (organic catalyst). The source of carbonyl may be sugar
or starch.

(b) From Starch: The starchy sources e.g. potatoes are ground and steamed
to release the required to which malt is added and allowed to stand for about
1hr of 600C. malt contains the enzyme, diastase that acts on the starch by
hydrolyzing it to maltose.

Daltase
2(C6 H10 05 )n + n H 20 n C12 H22 011
maltose

The enzyme maltose which is contained in yeast hydrolyses the maltose to

glucose

Maltase
C12 H12 06 + H20 C6 H12 06
Glucose

22
Another enzyme, zymase also contained in yeast finally converts the glucose into
ethanol with the evolution of carbon (IV) oxide.

C6H1206 Zymase 2CH2CH20H + C02

ethanol

Effects of Alcohol

Blood Alcohol Concentration (%) Effects

0.02 Mild alteration of feelings, slight intensification of moods.
0.05 Feelings of relaxation, giddiness, lowered inhibitions. Judgment and motor skills are both slightly impaired.
0.08 Muscle coordination and reaction time impaired. Face, hands, arms, and legs may tingle and then feel numb.
Legally intoxicated in Canada and some U.S. states.
0.10 Clumsiness, uncoordinated behavior. Impairment of mental abilities, judgment, and memory. Legally
intoxicated in most U.S. states.
0.15 Irresponsible behavior, euphoria. Some difficulty standing, walking, and talking.
0.20 Motor and emotional control centers measurably affected. Slurred speech, staggering, loss of balance, and
double vision can all be present.
0.40 Drinker is usually unconscious.
0.45 Respiration slows and can stop altogether.
0.50 Death can result.
Source: National Safety Council and California Department of Alcohol and Drug Programs

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 WEEK 7
HALO ALKANES
Halo alkanes are halogen derivatives of alkanes. Mono halo derivatives (alkyl
halides) have a general molecular formular, CnH2n+1X or simply R-X, where R
represents an alkyl group.

e.g. CH3Cl – Chloro methane (methyl chloride)

CH3CH2 Br – Poromo ethane (ethyl poromide)

CH3

CHI 2-iodo propane

CH3

They may be classified as primary (I0), secondary (20) or tertiary (30) according to
the nature of the carbon atom to which the halogen is attached.

CH3
|
CH3 - C - Cl 2-Chloro -2-methyl propane
| (Tert –Butyl Chloride)
CH3

NOMENCLATURE
According to the IU PAC System, an alkyl halide is named as a derivative of an
alkane. The name of the halogen is added to that of the parent alkane as one word.
The position of the halogen is indicated with a number.
CH3 CH2 CH2 Br CH3 CH2 CH CH3
1-bromo propane Cl

24
 2- chloro butane

When two halogen atoms are attached to a hydrocarbon, the compounds are named
a dihalogen derivatives of the parent hydrocarbon. The positions of the halogen
atoms are indicated by numbers. The names of the halogens and any other
substituent present are arranged alphabetically.
Br Cl CH Br
| | | |
CH2 CH CH2 CH2
1,5-di bromo-2-chloro-3-methyl pentane

Cl Cl
| |
CH3 CH2 CH CH2 CH2 CHCH3
2,5-dichloro hexane

PHYSICAL PROPERTIES

i) Boiling Point: The boiling point of an alkyl halide is higher than that of
an alkane with the same number of carton atoms e.g. boiling point CH3CH2
for is higher than CH3 CH3 . Boiling point of the alkyl halide increases with
increase in the molecular mass of the halogen e.g. boiling point.
CH3CH2I>CH3CH2Cl>CH3CH2F
ii) Solubility: alkyl halides are insoluble in water due to their inability to form
hydrogen bonds. They are however, soluble in organic solvents of low
polarity like benzene, ether, chloroform etc.

METHODS OF PREPARATION
Methods of preparation of halo alkanes include:

25
- Direct halogenetion of hydrocarbon e.g. chlorine in methane to yield chloro
methane.

- Chloro ethane can be prepared from ethanol and hydrochloric acid using zinc
chloride as a catalyst.

- Halo alkanes can be prepared by saturating the alcohol with dry hydrogen
chloride.

SNI REACTIONS
SNI stands for substitution nucleophilic unimolarcular. It is a reaction pathway in
which an alkyl halide undergoes nucleophilic substitution. First, ionizes (a slow
and rate determining step) to yield a planar carbonium ion intermediate. This is
followed by a rapid attack of the carbonium ion by the nucleophile.
q -+ q -+
Step 1: R-X R-------X Slow R+ +X-

Step II: R++Nu Fast R-Nu. In SNI reaction rate depends only on the
concentration of the alkyl halide.

USES OF HALO ALKANES

1. In the production of organometallic compound of the most electropositive
elements.

2. Magnesium, reacts with alkyl and aryl halides to form Grignard reagents.

3. Used in the formation of Retormatku reagent.

26
 WEEK 8
ALDEHYDES
Aldehydes and Ketones are referred to as carbonyl compounds as they both contain
the carbonyl compounds as they both contain the carbonyl C=0 functional group.
The function group of aldehydes -CHO and its general molecular formular is
CnH2n0. It is structurally represented as
R
C=0
|
H

The simplest members of Aldehydes includes ethanol, methanol and propanal.

H CH CH
C=0 , C=0 CH
H H C=0
Methane Ethanol H
Propanal

METHODS OF PREPARATION
Laboratory methods
1) Oxidation of primary alcohol
2) Ozonisation of olefins
3) Hydration of terminal alkynes, etc.

Industrial methods
1) Catalytic oxidation toluene
2) Catalytic dehydrogenation of primary alcohols

27
 3) Wacker process.

Oxidation of Primary alcohols

When primary alcohol is reacted with acidic aqueous K2Cr207 or Cr03 in pyridine,
primary alcohols are oxides to alkanal.
Q
R – CH20H K2Cr207 R-C-H + H20
H2S04 alkanol

Further oxidation produces alkanoic acid

Or
CH30H + ½02 Ag HCHO + H20
560-6500C

NUCLEOPHILIC ADDITION REACTIONS

Nucleophilic addition to the carbonyl group is the most important type of
Aldehydes reaction. Typical nucleophilc reagents which give an addition reaction
only are water, alcohols, ammonia, sodium hydrogen sulphate and cyanide ions.

a) With Water: Water reacts more especially with aldehyde to form a

gem-diol which is generally unstable.

CH3 C CH3 H+ H20 OH

+ +
Q Q
C=0 C–0 CH3C – C – H
H H OH 0H

28
Uses of aldehydes
• In the manufacture of synthetic drugs and dyes
• In the preparation of ethanioc acid
• In the manufacture of antiseptic

29
 WEEK 9
KETONES
Ketones are referred to as carbonyl compound as they contain
C = 0. The functional group is –RCO i.e.
R
C=0
R
They have general molecular formula CnH2n0. Simple ketone includes propanone,
methane, butanone, etc.

H |
H- C
|
H C=0 Propane

H–C–H
|
H H
| H
|
H–C C
| |
H H C=0 Butanone
|
H -C–H
|
H

Methods of Preparation
Methods of preparation includes:-
1) By Friedal-craft acylation reaction.
2) Dehydrogenation of secondary alcohols

30
 3) Oxidation of secondary alcohols
4) Decarboxylation of carboxylic acid

Oxidation of Secondary Alcohols

Ketones are prepared by the controlled oxidation of secondary alcohols with milder
oxidizible agents such as acidified solution of potassium dichromate.
(CH3)2 CHOH [0] K2Cr207 (CH3)2 CO + H20
Warm Propanone

REACTION OF KETONES
i) Condensation: This is elimination of water molecules from condensation
reaction of ketone with derivatives of ammonia e.g.

R R
C = 0 + H2NOH warm C = NOH + H20

C C
H3 H3

ii) Oxidation: Ketones are not readily oxidized but on treatment with powerful
oxidants with heating brings about necessary cleavage of the comparatively
stronger alkyl carbon-carbonyl carbon singe bond to give two carboxylic
acids.

R
|
C=0 Hot acid RCOOH + RCOOH
| KMn04
R

31
3) Nucleophilic Addition: Alcohol reacts with ketones in the presence of
acidic catalyst to form hemiketals
CH3 OH
| |
C = 0 + CH3OH CH3 – C – OCH3
| |
CH3 CH3
2-melhoxy propane-2-01
(hemiketal, unstable)

Uses
a) In the manufacture of useful compounds such as chloroform, iodoform,
drugs, etc.
b) Propanone (acetane) is used as
- Solvents for paints, celluloid, nitrocellulose
- A substitute for ethanol in perfumery
- A solvent for ethyne gas in storage cylinders.

32
 WEEK 10
REACTION OF CARBOXYLIC ACIDS

1) ESTERIFICATION: This is a reaction where carboxylic acids react with

alcohols to form esters in the presence of strong acid catalyst.

+
RCOOH + ROH H RCOOR + H20
Ester

2) REDUCTION TO PRIMARY ALCOHOLS

Carboxylic acids are very difficult to reduce but can be reduced by lithium
tetrahydroaluminate (III) and diborane from intermediate compounds with
the acids which liberate the alcohol on hydrolysis.

CH3CH2CH2CO2H LiAlH4 CH3CH2CH2CH20H

Butanoic acid butanol

CH3CH2CH = CH CO2H LiAlH4 CH3CH2CH2CH20H

Pent-2-enoic acid pent-2-o1

3) HALOGENATION
Substitution of the hydrogen on the a-carbon (i.e. carbon to the carboxyl
group) with halogen occurs when chlorine is bubbles through boiling
ethanoic acid in the presence of either iodine or red phosphorus in sunlight
to yield chloroethanoic acid. Further substitutions occur until all the
hydrogens are replaced with halogens.

33
 CH3CO2H CL2/I2 or CH2CL2COOH CI2/I2 CCl3COOH
Cl/P, 1100C 1200C

NEUTRALISATION ;
INTRODUCTION

Acids and Bases, are two classes of chemical compounds that display generally opposite
characteristics. Acids taste sour, turn litmus (a pink dye derived from lichens) red, and often
react with some metals to produce hydrogen gas. Bases taste bitter, turn litmus blue, and feel
slippery. When aqueous (water) solutions of an acid and a base are combined, a neutralization
reaction occurs. This reaction is characteristically very rapid and generally produces water and a
salt. For example, sulfuric acid and sodium hydroxide, NaOH, yield water and sodium sulfate:

USES OF CARBOXYLIC ACIDS

1) They are important raw material in the manufacture of soap.

2) Ethanoic anhydride is used in the manufacture of Aspirin
3) Cellulose ethanoate is used
- In packaging
- In vanishes
- In the filter tips of cigarettes

34
 WEEK 11
REACTION OF CARBOXYLIC ACIDS

1) ESTERIFICATION: This is a reaction where carboxylic acids react with

alcohols to form esters in the presence of strong acid catalyst.

+
RCOOH + ROH H RCOOR + H20
Ester

2) REDUCTION TO PRIMARY ALCOHOLS

Carboxylic acids are very difficult to reduce but can be reduced by lithium
tetrahydroaluminate (III) and diborane from intermediate compounds with
the acids which liberate the alcohol on hydrolysis.

CH3CH2CH2CO2H LiAlH4 CH3CH2CH2CH20H

Butanoic acid butanol

CH3CH2CH = CH CO2H LiAlH4 CH3CH2CH2CH20H

Pent-2-enoic acid pent-2-o1

3) HALOGENATION
Substitution of the hydrogen on the a-carbon (i.e. carbon to the carboxyl
group) with halogen occurs when chlorine is bubbles through boiling
ethanoic acid in the presence of either iodine or red phosphorus in sunlight
to yield chloroethanoic acid. Further substitutions occur until all the
hydrogens are replaced with halogens.

35
 CH3CO2H CL2/I2 or CH2CL2COOH CI2/I2 CCl3COOH
Cl/P, 1100C 1200C

NEUTRALISATION ;
INTRODUCTION

Acids and Bases, two classes of chemical compounds that display generally opposite
characteristics. Acids taste sour, turn litmus (a pink dye derived from lichens) red, and often
react with some metals to produce hydrogen gas. Bases taste bitter, turn litmus blue, and feel
slippery. When aqueous (water) solutions of an acid and a base are combined, a neutralization
reaction occurs. This reaction is characteristically very rapid and generally produces water and a
salt. For example, sulfuric acid and sodium hydroxide, NaOH, yield water and sodium sulfate:

USES OF CARBOXYLIC ACIDS

4) They are important raw material in the manufacture of soap.

5) Ethanoic anhydride is used in the manufacture of Aspirin
6) Cellulose ethanoate is used
- In packaging
- In vanishes
- In the filter tips of cigarettes

36
 WEEK 12
ESTERS
Esters are organic compounds having –COOR as functional group and a general
molecular formula CnH2n+1COOR’ or RCOOR’. Examples includes ethyl ethanoate,
methyl propanoate etc.

NOMENCLATURE
Esters are named by taking the I.UPA.C name of the parent carboxylic acid and replacing
the ending “ic” with the suffix “ate” preceeding this with the name of the alkyl, cyclo
alkyl, or aryl group of the appropriate alcohol, cyclic alcohol or phenol.

Examples:
CH3COOCH3 CH3CH2CH2C00CH2CH3

METHODS OF PREPARATION
The majority of esters are produced/prepared by interaction of alcohol with carboxylic
acid, acryl chloride, or acid anhydride.

RCOOH + R’OH H+cat RCOOR’ + H20

RCOCl + ROH RCOOR + HCI

(RCO) 20 + ROH RCOOR + RCOOH

37
WEEK 13

REACTIONS
SAPONIFICATION REACTION
Esters are hydrolyzed to the parent acid and alcohol by both acidic and basic catalyst in
aqueous solution.
RCOOR + H20 H+or OH-cat RCOOH + ROH

The alkaline hydrolysis is referred to as saponification because it is a type of reaction

used in preparing soaps. Ordinary households soaps are thus made from natural fats and
oils of plant or animal origin. They are typically mixtures of the salts of C12 and higher
fatty acids and the by-product is glycerol.
Q
|
CH20 – C + 3Na0H CH2OH + RCOONa
R

Mechanism for Saponification

-
0 0 0
-
|| OH | ||
R– C R– C OR R–C
OR | |
OH+ O-H

+OR

0
||
R – C +R’OH
|
0

38
USES OF ESTERS
Esters have important medical uses. Ethyl nitrite is a diuretic and an antipyretic. Amyl nitrite is
used in the treatment of asthma and epileptic convulsions as an antispasmodic. Nitroglycerin and
amyl nitrite both cause blood-vessel dilation thereby lowering blood pressure. Ethyl
chaulmoograte has been used in the treatment of leprosy. Dimethyl sulfate (often used in organic
synthesis as a methylating agent) and diethyl sulfate are extremely dangerous in vapor form and
must be handled cautiously. .

39
 WEEK 14
PETROLEUM REFINING
Petroleum is a naturally occurring oil that consists chiefly of hydrocarbons with some
other elements, such as sulphur, oxygen and nitrogen. In 1ts unrefined form petroleum is
known as crude oil. Petroleum is believed to have been formed from the remains of
living organism that were deposited, together with rock particles and biochemical and
chemical precipitates, in shallow depressions, chiefly in marine conditions, under burial
and compaction the organic matter went through reservoirs beneath a layer of
impermeable rock. The petroleum often floats above a layer of water and is held under
pressure beneath a layer of natural gas.

Before it can be used it is separated by means of a separation technique. Fractional

distillation is largely employed for the separation.

The main fractions obtained after fractional distillation are:

i) Refinery or Natural Gas: A mixture of methane, ethane, butane and propane
used as a fuel and for making other organic chemicals.

ii) Gasoline: A mixture of hydrocarbons containing 5 to 8 carbon atoms boiling in

the range 40-1800C. It is used for motor fuels and for making other chemicals.

iii) Kerosine or Paraffin oil): A mixture of hydrocarbons having 11 or 12 carbon

atoms, boiling in the range 160- 2500C. Kerosene is a fuel for jet aircraft and for
oil fired domestic heating. It is also cracked to produce smaller hydrocarbons for
use in motor fuels.

40
(iv) Diesel il (or gas oil). A mixture of hydrocarbons having 11 or 12 carbons atoms,
boiling in the range 220-3500C. it is a fuel for diesel engines.

The residue is a mixture of higher hydro-carbons. The liquid components are obtained by
vacuum distillation and used in lubricating oils. The social components (paraffin wax)
are obtained by solvent extraction. The final residue is a black tar containing free carbon
(asphalt or bitumen).

VACCUM DISTILLATION
Distillation under reduced pressure. If the liquid to be distilled. The depression in the
boiling point of the substance distilled means that the temperature is lower, which may
prevent the substance from decomposition.
Another method of distilling substances at temperatures below their normal boiling
points is to partially evacuate the still. Thus, aniline may be distilled at 100° C
(212° F) by removing 93 percent of the air from the still. This method is as
effective as steam distillation, but somewhat more expensive. The greater the
degree of vacuum, the lower is the distillation temperature. If the distillation is
carried on in a practically perfect vacuum, the process is called molecular
distillation. This process is regularly used industrially for the purification of
vitamins and certain other unstable products. The substance is placed on a plate in
an evacuated space and heated. The condenser is a cold plate, placed as close to the
first as possible. Most of the material passes across the space between the two
plates, and therefore very little is lost.

41
WEEK 15

FRACTIONAL DISTILLATION
This is a separation technique employed in separation of fraction of crude oil. The
technique separates components of a mixture with close range of boiling points.
The apparatuses used are those used in the distillation plus a fractionating column.
Vapour from the liquid rises up the column. The vapour in the column has more
volatileComponents towards the top and less volatile components at the bottom.
Various fractions of the mixture can be drawn off at points on the column.
Industrially, fractional distillation, is performed in large towers containing many
perforated trays. The fractionating column most often used is the so-called bubble
tower, in which the plates are arranged horizontally a few centimeters apart and the
ascending vapors are forced to rise through bubble caps in each plate and then
bubble through the liquid. The plates are baffled so that the liquid flows from left
to right on one plate, then overflows onto the plate below, and there flows from
right to left. If the interaction between liquid and vapor is incomplete, or if frothing
and entrainment occur so that some of the liquid is carried up by the vapor to the
plate above, five actual plates might be required to do the work of four theoretical
plates, producing four redistillations. An inexpensive equivalent of a bubble tower
is the so-called packed column, in which the liquid flows down over a packing of
earthenware rings or bits of glass tubing

SOLVENT EXTRACTION
The process of separating one constituent from a mixture by dissolving it in a solvent in
which it is soluble but in which the other constituent of the mixture are not. Thus,
extraction is based on the different solubilities of chemical compounds in different
solvents. Substances can be extracted from solids or from liquids which may be either a
solution or a mixture that is difficult to separate into its components.
42
There are several methods of extraction.
a) Cold extraction with the use of water, aqueous solutions or organic solvents.
b) Hot extraction with the use of the same solvents
c) Extraction with the use of melted solid organic solvent.

Extraction can be carried out by using simple apparatus (beakers, seperatory funnel) or
more complex equipment (e.g. soxhlet apparatus.)

CRACKING
The process of breaking down chemical compounds by heat. The term is applied
particularly to the cracking of hydrocarbons in the kerosene fraction obtained from
petroleum refining to give smaller hydrocarbon molecules and alkenes. It is an important
process, both as . a source of branched-chain hydrocarbons suitable for gasoline and as a
source of ethane and other alkenes. Catalytic cracking is a similar process in which a
catalyst is used to lower the temperature required and to modify the products
obtained.Cracking has become greatly important in the petroleum-refinery industry as a
means of increasing the production of gasoline at the expense of the heavier, less
valuable products such as kerosene and fuel oil. The best-known catalytic processes,
which have largely replaced the former thermal processes, are the fixed-bed and the fluid-
catalytic processes that use alumina-silica gel powders as catalysts. In the fixed-bed
process, the oil is passed through a stationary bed of solid particles; in the fluid-catalytic
process, the particles are mobile and suspended in a current of oil vapors at 450° to 540°
C (about 850° to 1000° F) at a pressure of 2.4 atmospheres.In the modern oil refinery,
petroleum is first separated by fractional distillation. Most of the heavier fractions are
then usually cracked. The products of cracking contain about 50 percent gasoline, which
is often further treated by such processes as hydrogenation and hydroforming. The other
43
50 percent consist largely of lighter components, which may be polymerized or used for
alkylation in order to further increase the yield and improve the quality of the gasoline.
By combining all these processes, of which cracking is the most important, 100 liters
(about 106 qt) of crude oil can be made to yield slightly more than 100 liters of gasoline.
More than half the gasoline produced in the U.S. today is produced by the cracking
process.

44