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Federal university of health sciences, azare
CHEM 102 (GENERAL CHEMISTRY II)
{2 Unit}

Introduction to organic chemistry

bY
M.s mukhtar
 IUPAC Nomenclature and functional group classes of organic compounds; Homologous
series, functional groups, Isolation and purification of organic compounds

Organic chemistry: is the branch of chemistry which deals with the study of compounds of carbon
with hydrogen (hydrocarbons), and their derivatives
Organic compounds: are compounds containing carbon, hydrogen essentially and oxygen,
nitrogen, Sulphur, phosphorus, halogens with their derivatives. For example ethyl alcohol, sugar,
starch are organic compounds.
Origin of organic compounds: Carbon compounds are of two types: inorganic and organic. The
compounds that have a mineral origin fall under the category of inorganic compounds. The
compounds having plant or animal origin are classified as organic compounds. Lavoisier showed
that nearly all compounds of plant origin are composed of carbon, hydrogen and oxygen. While
those of animal origin also had other substances like nitrogen, sulphur or phosphorus. In spite of
the fact that organic compounds were originally derived from living sources, today, most of these
compounds can be synthesized.
Organic compounds were found to contain mainly hydrogen and carbon. Therefore, organic
chemistry is defined as the study of hydrocarbons and their derivatives.
Application of Organic Compounds in Daily Life

Foods [starch, sugar, fats, vitamins, proteins]

Fuels [wood, coal, alcohol, petrol]
Household and commercial articles [paper, soap, cosmetics, oils, paints]
Textile fabrics [cotton, wool, silk, linen, rayon, nylon]
Drugs and disinfectants [penicillin, quinine, aspirin, sulpha drugs]
Poisons [opium, strychnine]
Perfumes [vanillin, camphor]
Explosives [nitroglycerine, dynamite, picric acid, TNT]
Dyes [indigo, congo red, malachite green]
War gases [mustard gas, chloropicrin, lewisite]
 What makes carbon so special
A carbon atom has a total of six electrons occupying the first two shells, i.e., the K-shell has two
electrons and the L-shell has four electrons. This distribution indicates that in the outermost shell
there are one completely filled 's' orbital and two half-filled 'p' orbitals, showing carbon to be a divalent
atom. But in actuality, carbon displays “tetravalency” in the combined state. Therefore, a carbon atom
has four valence electrons. It could gain four electrons to form C4- anion or lose four electrons to form
C4+ cation. Both these conditions would take carbon far away from achieving stability by the octect
rule. To overcome this problem carbon undergoes bonding by sharing its valence electrons. This
allows it to be covalently bonded to one, two, three or four carbon atoms or atoms of other elements
or groups of atoms. Let us see how carbon forms the single, double and triple bonds in the following
examples
Methane molecule (single bond)
Carbon Dioxide Molecule (double bond)

Acetylene Molecule (triple bond)

Why are there so many carbon containing compounds

The property of self-linking with atoms of the same element is termed “Catenation”. Carbon
has a unique property of linking itself to other carbon atoms to give open chain or/and cyclic
structures. Catenation is favored by atoms where atom to atom covalent bond is quite strong.
In carbon, C-C bond energy is very high (347.3 kJ mol-1) causing catenation. Further, the carbon
atom due to its tetravalency, can be bonded to two, three or four carbon atoms by forming
single and multiple bonds. Therefore, chains of carbon atoms may be linear, branched or cyclic.
For example,
Functional groups and homologous series
Functional groups: are atoms or group of atoms which determine the chemical
behavior of an organic compound. When an atom or group of atoms bonded to a
carbon atom in the chain or ring of an organic compound, shown some characteristic
properties of their own, they are termed as a functional group.
All the compounds having a particular functional group behave alike. For example all
compounds containing -OH (hydroxyl) group undergo similar reactions.
Examples of functional groups are double bond, triple bond others include –cl-, -Br-, -
NH2,-
C OO H , -
C HO ,-
C O NH 2etc .

The functional group present in the following molecules are encircled.

Why functional group is important
Functional groups are important in chemistry
because they are the portion of a molecule
that is capable of characteristic reactions.
They, therefore, determine the properties
and chemistry of many organic compounds.
It serves as aid In classifying organic
compounds In to classes(family)
It serves as basis for nomenclature (name g )
of organic compounds
A molecule that possesses more-than one
Functional groups are said to be poly-
functional.
 Homologous series
A homologous series (homos is Greek word meaning “the same as”) is a group of organic compounds in
which each member is differ from the next member by -CH2 (14 units atom) group. The member of a
homologous series is called “homologs”
A homologous series is a family of organic compounds containing a particular characteristic group and
exhibiting similar properties. For example, the compounds given below belong to the alcohol family.
CH3
O
Hme
t
hy
l
al
c
oh
ol
(
me
th
a
n
o
l
)C
H
,C
3H
C
2H
O
2H
pr
o
p
yl
a
lc
o
ho
l
(
1-
p
ro
p
an
o
l
)
C
,H
3C
H
.
C
2H
.
C
2H
O
2H
bu
t
y
l
al
c
oh
ol
(
1-
bu
t
an
ol
)
Characteristics of a Homologous Series
All members of a homologous series exhibit some common characteristics. They are:
All the members of a homologous series can be represented by a common general formula, as they have the
same functional group. For example, alkanes can be represented by the formula Cn
H
2n
+2
.

CH4
(
Me
th
a
n
e
)
CH
2
5(
E
th
a
n
e
)C
H
3
8(
Pr
o
p
an
e
)C
H
4
1
0(
Bu
t
a
n
e)
Each member of a homologous series has a common difference of -CH2
f
ro
mt
h
e
ne
x
th
i
g
he
ro
r
l
o
we
r
mem ber
.
Common general methods of preparation exist for all members of the series.
All members exhibit similar chemical behavior.
An increase in molecular mass of members within a homologous series show a similar regular gradation of
the physical properties, such as, physical state, melting and boiling points etc.
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CHM 102: (Prof. Adeogun Section)

The chemistry of carbon atom and bonding

Introduction

Carbon is a very important non-metallic element, it is the sixth most abundant element in the
universe and can exist in the free state or in the form of its compounds. It is the major chemical
constituent of most organic matter. Carbon is the second most common element in the human
body after oxygen. Carbon is present in coal, oil and natural gas.
The main natural sources of carbon and its compound which are industrially important are coal,
petroleum and natural gas which contribute to our national economy in a big way. Carbon also
occurs in a numbers of minerals. When kerosene oil lamp burns it produces black soot which
contains carbon particles, also when some materials like wood, paper are burnt, a black residue is
left which contains carbon.
Carbon atoms can form compounds by combining with other carbon atoms as well as atoms of
other elements. Carbon has the unique property of forming long chains of carbon atoms. These
long chains serve as a backbone on which various groups can attach to give a large variety of
compounds. These compounds have a variety of structures, properties and uses in our life.

The Chemistry of carbon atom

Carbon is abundant in the universe (i.e. in Sun, planets, and atmosphere of the Earth). In the
rocks, it is present as carbonate rocks i.e. limestone, dolomite, marble etc. It is also a major
constituent of fossil fuels such as coal, petroleum and natural gas. It is present in the form of its
compounds in all living organisms. Some such compounds are carbohydrates, proteins, fats etc.
In combination with oxygen, it occurs as carbon monoxide and carbon dioxide. Our atmosphere
also contains some pollutants arising from these carbon compounds.
There are three naturally occurring isotopes of carbon – 12C, 13C, 14C, Carbon-14, (14C) is a
radioactive and its half life is 5730 years. It is used in radio carbon-dating to determine the age of
formerly living things.
The electronic configuration of carbon is (2,4 i.e. 1s2 2s22p2) The structure of Carbon atom
revealed that there are 4 electrons in the second shell, in order to complete its octet, carbon
requires four more electrons. But due to unfavorable energy considerations, it cannot gain four
electrons by ion formation and hence attain the electronic configuration of neon. Due to the same
reason, it is also not possible for carbon to lose these four electrons and attain the noble gas
configuration of helium. However, it can form covalent bonds by sharing these four electrons.
It can form four covalent bonds, i.e. it is tetravalent in nature. It has a valency of four, thus, the
sharing of four more electrons from other atoms completes the octetof carbon atom and it attains
the stability by forming four covalent bonds.
Carbon can form bonds with atoms of other elements such as hydrogen (H), nitrogen (N),
oxygen (O), sulphur (S) and halogens etc. It also has the property of self combination i.e. bond
formation with the other carbon atoms. Thus, carbon can form long chains of carbon atoms. This
unique property of forming long chains is known as catenation.
The carbon-carbon covalent bond is strong in nature, long carbon chains can act as a backbone to
which various groups can attach and give a large number of compounds. The total number of
compounds formed by carbon exceeds the total number of compounds formed by all other
elements of the periodic table.
In addition to the single covalent bonds, carbon can also form multiple bonds, i.e. double or
triple bonds with other carbon, oxygen or nitrogen atoms to give a large variety of compounds.
The number of compounds formed is so large that a separate branch of chemistry, called organic
chemistry, is devoted to the study of these compounds.

Allotropes of Carbon
Allotropes are different forms of the same element in the same physical state. Carbon occurs
freely in nature (i.e. not combined with any other element) in three allotropic forms. Though,
earlier only two allotropic forms i.e. graphite and diamond were known. Another allotropic
forms of carbon had been recently discovered, these are graphene and fullerene.

Diamond: Diamonds are formed inside the earth under the conditions of high temperature (about
1500oC) and high pressure (about 70,000 atmospheres). South Africa is the leading producer of
natural diamonds. In Nigeria, diamonds has been reported to be found in Mambila Village
Kastina State. In a diamond crystal, each carbon atom is linked to four other carbon atoms by
covalent bonds in a tetrahedral fashion. This result in a three dimensional arrangement as shown
in below:

The three-dimensional network of covalently bonded carbon atoms provides a rigid structure to
diamonds. This rigidity makes diamond a very hard substance. It is, in fact, the hardest natural
substance known. The only other substance harder than diamond is silicon carbide which is also
known as carborandum but note that diamond is a natural substance whereas carborandum is a
synthetic one.

Structure of Diamond
Diamonds are basically colourless. However, some impurities impart colour to them. The density
of diamond is high, (3.51 g/cm3) with high melting point of 3500 oC in vacuum, since large
amount of heat energy is required to break the three-dimensional network of covalent bonds.
Since all the four electrons are covalently bonded and there are no free electrons in diamond,
hence it does not conduct electricity. But diamond is a good conductor of heat. Its thermal
conductivity is five times that of copper. Thus, it can easily dissipate the heat energy released by
friction when it is used as an abrasive.
Because of its above-mentioned properties, diamond has the following uses:
i. It is used in cutting and grinding of other hard materials.
ii. It is also employed in instruments used for cutting of glass and drilling of rocks.
iii. It is used in jewellery. Beautiful ornaments are made with diamonds. The high refractive
index of diamond (2.5) makes it very brilliant when it is properly cut and polished.

Synthetic Diamonds: Because of their importance diamonds worth millions of dollars are
synthesized. In 1950’s diamonds were synthesized by the scientist at General Electric in New
York. They heated graphite to 1500 oC in the presence of a metal such as nickel and iron under a
pressure of 50000 to 65000 atmospheres. Most of the diamonds so produced are used as
abrasives and for making diamond coated cutting tools used for drilling. Most synthetic
diamonds lack the size and clarity of natural diamonds and are generally not used in jewellery.
Gem quality diamonds can be produced but they are costly.

Graphite: In contrast to diamond, graphite is soft, black and slippery solid. It has a metallic
luster. It is also a good conductor of electricity and heat. Both graphite and diamond contain only
carbon atoms, then why do they exhibit such different properties? We can find an answer to this
question if we look at the structure of graphite as given below.

In contrasts to diamond, that has a three-dimensional tetrahedral arrangement of carbon atoms,

graphite contains layers of carbon atoms. In each layer, a particular carbon atom is linked to
three other carbon atoms in a trigonal planar arrangement with a bond angle of 120 o. Thus, three
electrons of carbon are covalently bonded to the other three carbon atoms. The fourth electron,
which does not participate in bonding, is free. These electrons of various carbon atoms are free to
move along between the layers and hence are able to conduct electricity.

The bonding between these layers of carbon atoms is weak. Hence, these layers can slide one
over the other. This property makes graphite a good solid lubricant. The density of graphite is
less than that of diamond. It has a value of 2.2g/cm3 and the melting point of graphite (in
vacuum) is about 3700 oC. Graphite can be converted to diamond by applying very higher
atmospheric pressure and temperature.
 Structure of Graphite

Because of the above properties, graphite has the following uses:

i. It is used as a dry lubricant for moving machine parts which operate at a high temperature
and where other ordinary oil lubricants cannot be used.
ii. It is used for making electrodes in dry cells and in electric arcs.
iii. It is used for making pencil leads. Because of its soft nature and layered structure, it
leaves black marks on paper. Hence, it is used for writing as leads in pencils.
iv. It is used for making containers which are used for melting metals.

Graphene: This is a one-atom-thick planar sheet of graphite. It is the thinnest and lightest
material known. It is a mono layer of Carbon atoms packed into a honeycomb crystal structure,
the sheets are one atom thick 2-dimensional layers of sp2 – bonded carbon. The carbon atoms in
graphene are arranged in Hexagonal structure with two atoms per unit cell. The Carbon – Carbon
bond length in Graphene is 1.42 nm. Graphene was experimentally extracted from 3-dimensional
Graphite in 2004. Graphene transparent and can be bent, stacked, or rolled. It is harder than
diamond and it conducts electricity better than copper.

Structure of Graphene

Fullerenes: Fullerenes were discovered in 1985 by Robert F. Curl, Harold W. Kroto and Richard
E. Smalley. Fullerenes have closed structures like a football. A typical fullerene, named as
buckminsterfullerene has 60 carbon atoms. Its structure is shown below:
 Structure of Fullerenes

Fullerenes are formed when vaporized carbon condenses in an atmosphere of an inert gas. The
discovery of fullerenes has opened up a new field in Chemistry. Fullerenes of various other sizes
are being synthesized and their properties and uses are being studied. It is hoped that these
materials would find uses as superconducting materials, new catalysts, polymers etc.

Carbon nanotubes are cylindrical fullerenes. These tubes of carbon are usually only a few
nanometres wide, but they can range from less than a micrometer to several millimeters in
length. They often have closed ends, but can be open-ended as well. Their unique molecular
structure results in extraordinary macroscopic properties, including high tensile strength,
high electrical conductivity, high ductility, high heat conductivity, and relative chemical
inactivity. One proposed use of carbon nanotubes is in paper batteries, developed in 2007 by
researchers at Rensselaer Polytechnic Institute. Another highly speculative proposed use in the
field of space technologies is to produce high-tensile carbon cables required by a space elevator.

Carbon nanotubes

In addition to the above allotropic forms, carbon also exists in three microcrystalline or
amorphous forms of graphite. They are charcoal, coke and carbon black.
Chemistry of Carbohydrates, Proteins and Lipids

Carbohydrates
The term carbohydrate is applied to a large number of relatively heterogeneous compounds.
They are the most abundant biomolecules on earth. The name carbohydrate (hydrate of carbon)
is derived from the fact that the first compound of this group which was studied had an empirical
formula Cx(H2O)y . They are commonly called ‘sugars’ and are ‘polyhydroxy compounds’ of
aldelydes and ketones.

Classification of Carbohydrates
The commonly described classification is given below.

Monosaccharides
These are simple sugars which cannot be hydrolyzed. They have an empirical formula (CH 2O)n
where n = 3 or some large number. Monosaccharides are either aldoses (aldehydic group) or
ketoses (ketonic group). Common examples are glyceraldehyde, glucose, fructose, etc. Sugars
with five carbon atoms (pentoses) or six carbon atoms (hexoses) are more stable as cyclic
structures than as open chain structures. Glucose and fructose are very common examples of
hexoses, both of which have molecular formula, C 6H12O6.

Glucose also called dextrose, grape sugar or blood sugar, occurs natuarlly in both combined and
free states. In the free state, it is present in most sweet fruits and in honey. Small quantities of
glucose are also present in human blood and urine. In the combined state it forms a major
component of many disaccharides and polysaccharides. It is the source of energy in our body.
Fructose is also found in combined and free states.It is used as a sweetening agent in
confectionery and as a substitute of cane sugar. Other examples of monosaccarides are galactose
and mannose.

Disaccharides or Oligosaccharides
The oligosaccharides are formed when two to nine monosaccharide units combine by the loss of
water molecules. This results in the formation of a glycosidic linkage. For example; sucrose
which is a common table sugar, is a disaccharide of glucose and fructose.

Conversely, hydrolysis of an oligosaccharide by water in the presence of an acid or by enzymes

yields two or more monosaccharide units. Among the most common disaccharides are sucrose,
lactose and maltose. Of these, sucrose occurs in sugar cane, sugar beet, pineapple, apricot,
mango, almond, coffee and honey. Lactose (milk sugar) occurs in the milk of all animals. It does
not occur in plants.

Trisaccharides, which yield three monosaccharide molecules on hydrolysis, have molecular

formula, C18H32O16 for example raffinose. In general, the mono-saccharides and oligosaccharides
are crystalline solids soluble in water and sweet to taste. They are collectively known as ‘sugars’.

Polysaccharides
The polysaccharides are carbohydrates of high molecular mass which yield many
monosaccharide molecules on hydrolysis. Examples are, starch and cellulose, both of which have
molecular formula, (C6H10O5)n. The polysaccharides are amorphous solids, insoluble in water
and tasteless and are called ‘non-sugars’. Polysaccharides perform two principal functions in
animals and plants. They are used as energy storage compounds and for building structural
elements of cells. Plants store glucose as starch and animals store glucose in the form of a highly
branched polymer known as glycogen. Glycogen is stored in the liver and muscles.
Starch
Starch is the most important source of carbohydrates in human diet. The chief commercial
sources of starch are wheat, rice, maize, potatoes and barley. Starch is a polymer of a-D-glucose.
Starch is not a pure compound. It is a mixture of two polysaccharides, amylose and amylopectin
which can be separated from one another.
Amylose is soluble in water and gives a deep blue colour with iodine while amylopectin is
insoluble and gives no colour. Natural starch consists of 10 to 20% amylose and 80 to 90%
amylopectin. It is used in coating and sizing of paper to improve the writing qualities. It is also
used in laundering and in the manufacture of glucose and ethyl alcohol.

Cellulose
By far, the most abundant structural polysaccharide is cellulose. Some 100 billion tons of
cellulose are produced each year by plants. For example, cotton is 99% cellulose and the woody
parts of trees are generally more than 50% cellulose. It is a polymer of β-D-glucose. It is present
mainly in the plant kindom but also occurs in some marine animals. It is an unbranched polymer
consisting of a large number (up to 2500) of glucose residues joined
to each other through β -1—>4 linkages.

Glycogen
It occurs mainly in the liver and muscles where it represents the main storage polysaccharide in
the same way as starch functions in plant cells. Glycogen is therefore also called ‘animal starch’.
Its structure closely resembles with that of amylopectin having 1 4 and 1 6 glycosidic linkages.
Human glycogen is a much more branched molecule than amylopectin. On hydrolysis it yields
glucose units.
Proteins
Proteins are extremely complicated molecules of living things. They are the nitrogeneous
compounds made up of a variable number of amino acids. The human body probably contains at
least 10,000 different kinds of proteins. The name protein is derived from the Greek word
proteios meaning of prime importance. Proteins are present in all living organisms and without
proteins life would not be possible. They are present in muscles, skin, hair and other tissues that
make up the bulk of the body’s non-bony structure.

All proteins contain the elements carbon, hydrogen, oxygen and nitrogen. They may also contain
phosphorus and traces of other elements like iron, copper, iodine, manganese, sulphur and zinc.
Proteins are very high molecular weight macromolecules. All proteins yield amino acids upon
complete hydrolysis. Thus proteins may be defined as the high molecular weight organic
materials, which upon complete hydrolysis, yield amino acids.

Classfication of Proteins
Based on the physico-chemical properties, proteins may be classified into three types:

Simple Proteins
These proteins on hydrolysis yield only amino acids or their derivatives. For example, albumins,
globulins, legumin, collagen, etc. Globulins are insoluble in water but soluble in dilute salt
solutions. They are found in animals, e.g; lactoglobulin is found in muscles and also in plants.
Legumin and collagen proteins are present in the connective tissues throughout the body. They
are the most abundant proteins in the animal kingdom forming some 25 to 35% of body protein.

Compound or Conjugated Proteins

In these molecules the protein is attached or conjugated to some non- protein groups which are
called prosthetic groups. For example; phospho-proteins are conjugated with phosphoric acid,
lipoproteins are conjugated with lipid substances like lecithin, cholesterol and fatty acids.

Derived Proteins
This class of protein includes substances which are derived from simple and conjugated proteins.
For example, proteoses enzymes, peptones, oligopeptides, polypeptides, etc. Based on their
functions, proteins may also be classified as regulatory or hormonal proteins, structural proteins,
transport proteins, genetic proteins, etc.

Structure of Proteins
The majority of proteins are compact, highly convoluted molecules with the position of each
atom relative to the others determined with great precision. To describe the structure of a protein
in an organism it is necessary to specify the three- dimensional shape that the polypeptide chain
assumes. Proteins assume at least three levels of structural organization.
 (i) Primary structure
(ii) Secondary structure
(iii)Tertiary structures
Some proteins also possesses a fourth structure called the quaternary structure.
The sequence of the amino acids combined in a peptide chain is referred to as the primary
structure.

The secondary structure of a protein is a regular coiling or zigzagging of polypeptide chains

caused by hydrogen bonding between NH and C = O groups of amino acids near each other in
the chains. The three dimensional twisting and folding of the polypeptide chain results in the
tertiary structure of proteins.

Denaturation of Proteins
The structure of proteins can be disrupted easily by heat, change in pH and under strongly
oxidizing or reducing conditions. Under such conditions the proteins undergo denaturation. The
most familiar example of denaturation is the change that takes place in albumin, the principal
component of egg white, when it is cooked. In this particular case the change is irreversible.

Importance of Proteins
1. Proteins take an essential part in the formation of protoplasm which is the essence of all
forms of life.
2. Nucleoproteins which are complexes of proteins with nucleic acids serve as carriers of
heredity from one generation to the other.
3. Enzymes which are biological catalysts are protein in nature. Without them life is not
possible.
4. Many proteins have specialized functions. Haemoglobin acts as a carrier of O 2. Some
proteins act as hormones which have regulatory functions, for example; insulin, thyroxine
etc.

Industrially proteins have great importance. We are familiar with the use of leather made by
tanning of hides. This is essentially a precipitation of the proteins with tannic acid. Gelatin is
obtained by heating bones, skin and tendons in water. It is used in bakery goods. Caesein is
another protein used in the manufacture of buttons and buckles.
Lipids
Lipids (Greek, lipos means fat) are naturally occurring organic compounds of animals and plants
origin which are soluble in organic solvents and belong to a very heterogeneous group of
substances. Lipids have the following characteristics:
1. They are insoluble in water and soluble in non-polar solvents e.g. ether, chloroform and
benzene, etc.
2. Their primary building blocks are fatty acids, glycerol and sterols.
3. They are utilized by the living organisms.

Fats and oils are the most important lipids found in nature. They are one of the three major “food
factors” needed for human body, the other two being proteins and carbohydrates. Fats and oils
are widely distributed in various type of foods and are of great nutritional value. Not only the
edible fats and oils occupy a place of pride in human diet but they also find use as raw materials
for the manufacture of soaps and detergents, paints, varnishes, polishes, cosmetics, printing inks
and pharmaceuticals.

Sources of Fats and Oils

Fats and oils come from a variety of natural sources like animals, plants and marine organisms.
Animal fats are located particularly in adipose tissue cells. Butter and ghee are a special type of
animal fats which are made form milk. Vegetable oils are chiefly present in seeds and nuts of
plants. Marine oils are obtained form sea animals like salmons and whales etc.

Structure and Composition of Fats and Oils

Animal and vegetable fats and oils have similar chemical structures. They are triesters formed
from glycerol and long chain acids called fatty acids. A triester of glycerol is called a triglyceride
or glyceride. The degree of unsaturation of the constituent fatty acid determines whether a
triglyceride will be a solid or a liquid. The glycerides in which long- chain saturated acid
components predominate tend to be solid or semi-solid and are termed as fats. On the other hand,
oils are glycerol esters which contain higher proportion of unsaturated fatty acid components.

The melting points of mixed glycerides would depend on the extent of unsaturated fatty acid
components in the molecule. The poly unsaturated glycerides therefore have very low meting
points and are liquids (oils). Chemically common oils and fats are the mixture of saturated and
unsaturated triglycerides, present in various ratios.

Classification
Lipids are classified as:
1. Simple Lipids: These are esters of fatty acids with glycerol. For example, common fats
and oils.
2. Compound Lipids: These contain radicals in addition to fatty acids and alcohol and
include glycerol phospholipids, sphingolipids, lipoproteins and lipopolysaccharides.
3. Derived or Associated Lipids: They are the hydrolytic products of the above mentioned
compounds. Sterols, vitamin D and terpenes belong to this class of lipids.

Physical Properties:
1. Oils and fats may either be liquid or non-crystalline solids at room temperature.
2. When pure they are colourless, odourless and tasteless.
3. They are insoluble in water and readily soluble in organic solvents like diethyl ether,
acetone, carbon tetrachloride and carbon disulphide.
4. They readily form emulsions when agitated with H2O in the presence of soap or other
emulsifiers.
5. They are poor conductor of heat and electricity and therefore serve as excellent insulator
for the animal body.

Chemical Properties
1. Hydrolysis: Triglycerides are easily hydrolyzed by enzymes called lipases to fatty acids
and glycerol.

2. Saponification: It is the hydrolysis of a fat or an oil with an alkali to form soap (salt of
fatty acid) and glycerol.

3. Hardening of Oils: Unsaturated glycerides react with hydrogen in the presence of a metal
catalyst to give saturated glycerides. The result is the conversionof a liquid glyceride (an
oil) into a semi-solid glyceride (a fat).
This reaction is used commercially to harden vegetable oils for the production of vegetable ghee
or margarine. Hardened oils are also extensively used for making soaps and candles.

Saponification Number: It is defined as the number of milligrams of potassium hydroxide or

sodium hydroxide required to saponify one gram of the fat or oil. For example, one mole of
glycerol tripalmitate (mol. wt = 807) requires 168,000 mg of KOH for saponification. Therefore,
one gram of fat will require 168000/807 mg of KOH. Hence the saponification number of
glycerol tripalmitate is 208.

Rancidity of Fats or Oils: Fats or oils are liable to spoilage and give off an odour known as
rancidity. It is mainly caused by the hydrolytic or oxidative reactions which release foul smelling
aldelydes and fatty acids. Oils from sea animals which contain a relatively high proportion of
unsaturated acid chains deteriorate rapidly.

Iodine Number: The extent of unsaturation in a fat or an oil is expressed in terms of its iodine
number. It is defined as the number of grams of iodine which will add to 100 grams of a fat or an
oil The value of iodine number depends on the number of double bonds present in the acid
component of the glycerides. The glycerides with no double bonds have zero iodine number.

Acid Number
The acid number of a fat or an oil tells the amount of free fatty acids present in it. It is expressed
as the number of milligrams of potassium hydroxide required to neutralize one gram of fat.

Steroids

Steroids are naturally occurring lipids. Their parent nucleus has

perhydrocyclopentanophenanthrene component which consists of three six- membered rings (A,
B and C) and one five-membered ring (D). These rings are joined or fused to each other and have
a total of 17-C atoms Very small variations in the bonding of atoms in the ring and in the groups
attached to them give rise to compounds that are remarkably diverse in their biological functions.
Some of the natural occurring compounds belonging to steroids are cholesterol, ergosterol, male
and female sex hormones and the hormones of the adrenal cortex.
Cholesterol
It is the most abundant animal sterol and occurs in all animal tissues but only in a few higher
plants. Cholesterol is present both in the free as well as esterified form in the blood, animal
tissues, egg, yolk, various oils and fats and nerve tissues. Its increased quantities in blood makes
plaque like deposits in the arteries causing blood pressure and other heart diseases.

Ergosterol
It is the sterol of fungi and yeasts. When irradiated with ultraviolet rays, it is converted into
ergocalciferol or vitamin D2.

Phospholipids
Phospholipids are molecules of enormous biological importance. In the compounds, two of the
hydroxyl groups are esterified with fatty acids and third forms a link with phosphoric acid or a
derivative of phosphoric acid.

Importance of lipids
1. They are good source of energy and make the food more palatable.
2. They exert an insulating effect on the nervous tissues.
3. They are good energy reservoirs in the body.
4. Lipids are an integral part of cell protoplasm and cell membranes.
5. Some lipids act as precursors of very important physiological compounds.
For example, cholesterol is the precursor of steroid hormones.
Introductory to reaction mechanism and kinetics
In an organic reaction, the organic molecule (also referred as a substrate) reacts with an
appropriate attacking reagent and leads to the formation of one or more intermediate(s) and
finally product(s). The general reaction is depicted as follows:

Substrate is that reactant which supplies carbon to the new bond and the other reactant is called
reagent. If both the reactants supply carbon to the new bond then choice is arbitrary and in that
case the molecule on which attention is focused is called substrate. In such a reaction a covalent
bond between two carbon atoms or a carbon and some other atom is broken and a new bond is
formed.

A sequential account of each step, describing details of electron movement, energetics during
bond cleavage and bond formation, and the rates of transformation of reactants into products
(kinetics) is referred to as reaction mechanism. The knowledge of reaction mechanism helps in
understanding the reactivity of organic compounds and in planning strategy for their synthesis.

Fission of a Covalent Bond

A covalent bond can get cleaved either by: (i) heterolytic cleavage, or by (ii) hemolytic cleavage.

In heterolytic cleavage, the bond breaks in such a fashion that the shared pair of electrons
remains with one of the fragments. After heterolysis, one atom has a sextet electronic structure
and a positive charge and the other, a valence octet with at least one lone pair and a negative

charge. Thus, heterolytic cleavage of bromomethane will give C H 3 and Br– as shown below.

A species having a carbon atom possessing sextext of electrons and a positive charge is called a

carbocation (earlier called carbonium ion). The C H3 ion is known as a methyl cation or methyl
carbonium ion. Carbocations are classified as primary, secondary or tertiary depending on
whether one, two or three carbons are directly attached to the positively charged carbon. Some
other examples of carbocations are: CH3 C H 2 (ethyl cation, a primary carbocation), (CH3)2 C H
 

(isopropyl cation, a secondary carbocation), and (CH3)3 C (tert-butyl cation, a tertiary



carbocation).
Carbocations are highly unstable and reactive species. Alkyl groups directly attached to the
positively charged carbon stabilise the carbocations due to inductive and hyperconjugation
   
effects. The observed order of carbocation stability is: C H3 < CH3 C H2 < (CH3)2 C H < (CH3)3 C H3 .

In homolytic cleavage, one of the electrons of the shared pair in a covalent bond goes with each
of the bonded atoms. Thus, in homolytic cleavage, the movement of a single electron takes place
instead of an electron pair. The single electron movement is shown by ‘half-headed’ curved
arrow.

Such cleavage results in the formation of neutral species (atom or group) which contains an
unpaired electron. These species are called free radicals. Like carbocations and carbanions, free
radicals are also very reactive. A homolytic cleavage can be shown as:

Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical stability increases as
we proceed from primary to tertiary:

Organic reactions, which proceed by homolytic fission, are called free radical or homopolar or
nonpolar reactions.

Nucleophiles and Electrophiles

A reagent that brings an electron pair is called a nucleophile (Nu:) i.e., nucleus seeking and the
reaction is then called nucleophilic. A reagent that takes away an electron pair is called
electrophile (E+) i.e., electron seeking and the reaction is called electrophilic.

During a polar organic reaction, a nucleophile attacks an electrophilic centre of the substrate
which is that specific atom or part of the electrophile that is electron deficient. Similarly, the
electrophiles attack at nucleophilic centre, which is the electron-rich centre of the substrate.
Thus, the electrophiles receive electron pair from nucleophile when the two undergo bonding
interaction.

Some examples of nucleophiles are the negatively charged ions with lone pair of electrons such
as hydroxide (HO– ), cyanide (NC–) ions and carbanions (R 3C:–). Neutral molecules such as
H2O, R3N and R2NH etc., can also act as nucleophiles due to the presence of lone pair of

electrons. Examples of electrophiles include carbocations ( C H3 ) and neutral molecules having
functional groups like carbonyl group (>C=O) or alkyl halides (R3C-X, where X is a halogen
atom). The carbon atom in carbocations has sextet configuration; hence, it is electron deficient
and can receive a pair of electrons from the nucleophiles. In neutral molecules such as alkyl
halides, due to the polarity of the C-X bond a partial positive charge is generated on the carbon
atom and hence the carbon atom becomes an electrophilic centre at which a nucleophile can
attack.

Types of Organic Reactions and Mechanisms

Organic reactions can be classified into the following categories:

(i) Substitution reactions: Involves removal of an atom or group of atoms from the central atom
(usually carbon). The displacement could be electrophilic (E): Ph + +NO2 → Ph-NO2 +H+ or
Nucleophilic (N) e.g. NC- + R-Cl → NCR + Cl- or Free Radical mechanism (R)
(halogenations of alkanes) Usually the displaced atom is hydrogen, group of atoms or any
other atom
(ii) Addition reactions: Adding an atom, molecule or ion to another molecule. It could be
initiated by electrophilic, nucleophilic or radical mechanism. The attack is usually on C-C
multiple bonds (E, R) e.g. H2C=CH2 +HF → H3C-CH2-F or by nucleophilic attack on C-O
bonds
(iii)Elimination reactions: This is opposite to addition reaction. It involves loss of hydrogen and
a loss of another atom or group of atoms to from an unsaturated bond H3C-CH2-F →
H2C=CH2 +HF
(iv) Rearrangement reactions: this involves rearrangement of the skeleton of a compound
(carbon compounds). It may sometimes involve rearrangement through an intermediate in a
chemical reaction. The rearrangement process may involve a cation, anion, radicals,
carbonium ions or other electron deficient species. Rearrangement is often accompanied by
addition or elimination reaction. Me3C-C=O(Me)→Me2C(OH)-C(Me2)OH in acidic
medium (H+)

Factors that Affects a chemical Reaction

There are many factors that affect a chemical reaction, these include: (i) type of bonds (single,
multiple, conjugated, polarized etc.) (ii) availability of electrons (electron density), (iii)
resonance, (iv) steric effect, (v) reagent type (electron donating or withdrawing, nucleophilic,
electrophilic, carbonium etc)

Stereochemistry
The branch of chemistry which deals with three dimensional structure of molecule and their
effect on physical and chemical properties is known as stereochemistry. It focuses on
stereoisomers and spans the entire spectrum of organic, inorganic, biological, physical and
especially supramolecular chemistry.
The phenomenon of existence of two or more compounds possessing the same molecular
formula but different properties is known as isomerism. Such compounds are called as isomers.
The following flow chart shows different types of isomerism

Structural Isomerism Compounds having the same molecular formula but different structures
(manners in which atoms are linked) are classified as structural isomers. Some typical examples
of different types of structural isomerism are given below:

(i) Chain isomerism: When two or more compounds have similar molecular formula but
different carbon skeletons, these are referred to as chain isomers and the phenomenon is
termed as chain isomerism. For example, C5H12 represents three compounds:

(ii) Position isomerism: When two or more compounds differ in the position of substituent
atom or functional group on the carbon skeleton, they are called position isomers and this
phenomenon is termed as position isomerism. For example, the molecular formula
C3H8O represents two alcohols:

(iii) Functional group isomerism: Two or more compounds having the same molecular
formula but different functional groups are called functional isomers and this
phenomenon is termed as functional group isomerism. For example, the molecular
formula C3H6O represents an aldehyde and a ketone:
(iv) Metamerism: It arises due to different alkyl chains on either side of the functional group
in the molecule. For example, C4H10O represents methoxypropane (CH3OC3H7) and
ethoxyethane (C2H5OC2H5).

Stereoisomerism
The compounds that have the same constitution and sequence of covalent bonds but differ in
relative positions of their atoms or groups in space are called stereoisomers. This special type of
isomerism is called as stereoisomerism and can be classified as follows:

Enantiomers:
Stereoisomers which are non superimposable mirror images of each other are called enantiomers.
Chirality is necessary and sufficient condition for existence of enantiomers. These always exist
as discrete pairs or mirror image.

Two isomers of lactic acid

Diastereomers:
Stereoisomers that are not mirror images of each other are called diastereomers.

Geomatrical Isomers:
Geometrical isomers
They occur as a result of restricted rotation about a carbon-carbon bond. This is also called cis-
trans isomerism. This isomerism exhibited by variety of compounds such as compound ontaining
double bond C=C, C=N, N=N, compound containing cyclic structure or compound containing
restricted rotation due to steric hindrance.

Conformational isomers:
Conformational isomers are the isomers that can be converted into one another by rotation
around a single bond. Example: eclipsed, gauche and anti butane are all conformational isomers
of one another.(eclipsed means that identical groups are all directly in line with one another,
gauche means that identical groups are 60 degree from one another and anti means that identical
groups are 180 degree from one another.
 HYBRIDIZATION

BY
DR. M. B. FUGU
DEPARMENT OF CHEMISTRY

FEDRAL UNIVERSITY OF HEALTH SCIENCES

AZARE
 Hybridization
❖ Intermixing of atomic orbitals of equal or
slightly different energies in the formation
of new set of orbitals with equivalent
energies and shape is known as
hybridization.

❖ The new orbital formed is called hybrid

orbital which is suitable for the qualitative
description of atomic bonding properties.
The sp hybrid atomic orbitals

❖ The sp hybrid atomic orbitals are

possible states of electron in an
atom, especially when it is bonded
to others. These electron states
have half 2s and half 2p characters
 The sp hybrid atomic orbitals
❖ For example, the
molecule H-Be-H is
formed due to the
overlapping of two
1s orbitals of 2 H
atoms and the two
sp hybridized
orbitals of Be.
Thus, the H-Be-H
molecule is linear.
The sp2 hybrid orbitals

❖ The energy states of the valence

electrons in atoms of the second
period are in the 2s and 2p orbitals.
If we mix two of the 2p orbitals with
a 2s orbital, we end up with three
sp2 hybridized orbitals. These three
orbitals lie on a plane, and they
point to the vertices of a equilateral
triangle as shown here.
 The sp2 hybrid orbitals

❖ When the central

atom makes use of
sp2 hybridized
orbitals, the
compound so
formed has a
trigonal shape.
BF3 is such a
molecule:
The sp3 hybrid orbitals
⚪ Mixing one s and all
three p atomic orbitals
produces a set of four
equivalent sp3 hybrid
atomic orbitals. The
four sp3 hybrid
orbitals points towards
the vertices of a
tetrahedron, as shown
here in this
photograph
The sp3 hybrid orbitals

❖ In the case of methane, the three

2p orbitals of the carbon atom are
combined with its 2s orbital to form
four new orbitals called "sp3" hybrid
orbitals.
⚪ .
 Hybridization Involving Multiple
Bonds

❖ Only a maximum of two electrons can

occupy any orbital whether it is an
atomic orbital or a molecular orbital
due to electron-electron repulsion.

❖ When we draw a double or a

triple-bond between two atoms, we
imply that either four or six electrons
are directly between these two atoms.
 Hybridization Involving Multiple
Bonds

❖ Since this is impossible, we must have

these extra electrons off to the side in
what we refer to as pi bonds.

❖ Therefore, all multiple bonds are

composed of two different kinds of
molecular bonds called pi-bonds and
sigma-bonds.
Hybridization Involving Multiple
Bonds

❖ The sigma-bond is defined as the

linear overlap of atomic orbitals
(hybrids except for hydrogen) in
which two electrons are directly
between the two bonded nuclei.
Hybridization Involving Multiple
Bonds

❖ Pi-bonds are defined as the parallel

overlap of p-orbitals. A double bond
has one sigma-bond and one
pi-bond. A triple bond thus consists
of a sigma-bond and two pi-bonds
with the pi-bonds in different planes
 GOMBE STATE UNIVERSITY
DEPARTMENT OF CHEMISTRY
CHEM 102 (Isolation and Purification of Organic Compounds)
Dr. Hamza Ahmed Pantami

Extraction: All techniques for isolation and purification of products use phase
equilibria: isolate the desired product into one phase that is in equilibrium with another
phase. The second phase ideally contains all other components of the mixture.
Equilibrium constants for distribution of materials between two phases are rarely either
infinite or zero, so partial separation of the components usually occurs .Phase equilibria
used for purification may involve gas-liquid, gas-solid, liquid-liquid, or liquid-solid
interfaces. Extraction procedures make use of phase equilibria at liquid-liquid and
liquid-solid interfaces.

Extraction Procedures:

Solid-liquid extraction.
If the material to be extracted into the liquid is very soluble, simple stirring or shaking
of a suspension of the solid in the liquid, followed by gravity filtration to remove
insoluble impurities will suffice. If the material to be extracted is less soluble or is
trapped in an insoluble matrix a continuous extraction device such as a Soxhlet
extractor is used. This device boils the extraction liquid, condenses it so that it can come
into contact with the solid, and siphons the liquid back into the boiling flask. The
extraction process occurs continuously until boiling is ceased. Over time the extraction
solvent is enriched in the desired compound.

Solid-liquid extraction when solid is very soluble. Soxhlet extractor for less
soluble solid
Liquid-liquid extraction:
Used to separate a component from one liquid phase into another. For most extractions
one phase is an aqueous solution, and the other is an immiscible organic liquid. The
two phases are shaken together gently in a separatory funnel (down), allowed to
separate, and separated from each other by allowing the lower, more dense, phase to
drain through the stopcock into an Erlenmeyer flask. The less dense phase is usually
poured out through the top of the funnel to avoid contamination. Multiple extractions
can be performed by returning/leaving the phase to be extracted in the funnel for
additional extractions with the other solvent.

Liquid-liquid extraction using separatory funnel.

Common Extraction Solvents

Solvent Density (g/mL) Bp (°C)

CHCl3 1.49 61
CH2Cl2 1.34 40
ethyl acetate 0.90 77
toluene 0.87 110
diethyl ether 0.71 36
hexanes 0.67 68-70
petroleum ether 0.64 35-60

The solvent must be immiscible with water, inexpensive, low boiling to allow easy
removal from the desired product, and relatively non-toxic (all of these have some
health and safety issues). Hexanes and petroleum ether are hydrocarbon mixtures
composed mostly of hexane isomers and pentane isomers, respectively. All these
solvents except CH2Cl2 and CHCl3 are flammable.

An Example of an Acid-Base Extraction

A weak organic acid will be extracted into a basic aqueous buffer as its conjugate base,
a weak organic base would be extracted into an acidic aqueous buffer as its conjugate
acid.

Extraction of weak bases

The most common organic weak bases are amines. Aliphatic amines have conjugate
acids with pKas in the range of 9-12 depending on substituents on the alkyl group(s).
Arylamines have conjugate acids with substituent dependent pKas of about 4-6.

Both types of amines are converted into their cationic conjugate acids under acidic
conditions, so they can be extracted from organic solvents into aqueous organic acids.
Typically, a 1 M HCl solution would be used unless it was necessary to separate weak
bases of differing pKas. To obtain the neutral amine the acidic extract must be
neutralized to a pH > pKa of the conjugate acid. The amine can then be collected by
filtration or extraction from the aqueous solution into an organic solvent.

You will make use of acid-base extraction procedures to separate a mixture of

acetylsalicylic acid (aspirin), acetaminophen, and caffeine found in Extra Strength
Excedrin®.
Aspirin and acetaminophen are both weak acids, but they have very different pKas that
allow them to be separated from each other by using aqueous extraction solutions of
different pH (< 10 to remove aspirin, > 10 to remove acetaminophen.

Caffeine is a neutral organic compound at pH > 1, so it will remain in the original

organic solution of ethyl acetate (EtOAc) during the extractions.

MELTING POINT:
The physical properties of a compound, such as melting point and boiling point can
provide useful information which can help in the identification of a sample or to
establish its purity. These pages describe two common methods for determining
melting point using(i) a Meltemp apparatus and (ii) a Thiele tube set up.
The temperature at which a solid melt and becomes a liquid is the melting point. Since
this requires that the intermolecular forces that hold the solid together have to be
overcome, the temperature at which melting occurs will depend on the structure of the
molecule involved - an example of the relationship between structure and properties.
Hence, different compounds tend to have different melting points.
A pure, non-ionic, crystalline organic compound usually has a sharp and characteristic
melting point (usually 0.5-1.0 0C range). A mixture of very small amounts of miscible
impurities will produce a depression of the melting point and an increase in the melting
point range. Consequently, the melting point of a compound is a criterion for purity as
well as for identification.
The melting point of an organic solid can be determined by introducing a tiny amount
into a small capillary tube, attaching this to the stem of a thermometer centred in a
heating bath, heating the bath slowly, and observing the temperatures at which melting
begins and is complete. Pure samples usually have sharp melting points, for example
149.5-150 0C or 189-190 0C; impure samples of the same compounds melt at lower
temperatures and over a wider range, for example 145-148 0C or 186-189 0C. .
It is standard practice (in order to make the most effective use of time) to carry out a
rapid melting point determination initially (by heating rapidly) to establish an
approximate melting point and then carry out at least two further careful determinations
(by heating more gently, i.e. temperature changing only about 2 0C/min) until you
obtain two consistent values.
The general method is to the heat the sample indirectly by placing the prepared sample
(either packed in a glass capillary or on a glass cover slip) in or on a heated medium,
these days this is most commonly a heated metal block such as a Mel-Temp apparatus.
There are other designs such as the Fisher-Johns apparatus. A more basic, but just as
effective method is the Thiele tube method where the capillary is immersed in a heated
oil bath. Note that the Thiele tube system is also used for boiling point determination.

Packing a capillary for melting point determination

Thin-walled capillary melting point tubes are used to hold melting point samples. This
tube needs to be sealed at one end. To pack the tube, the open end is pressed gently into
a small amount of the sample of the crystalline material on a watch glass or weighing
paper. To transfer the crystals from the open end to the bottom of the tube, tap the
bottom gently on the bench top or scratch the top edge of the tube on a small file or a
coin with a milled edge. A densely packed column of crystals about 3 mm high in the
tube is all that is required. A packed capillary attached to a normal mercury
thermometer is shown down.

Thermometer. Tapping compound into the bottom of capillary tube.

A Mel-Temp apparatus equipped with a digital thermometer is shown below. The

diagram shows the apparatus with the heat shield removed to reveal the inside structure.
The apparatus uses capillary packed samples (see above). Insert the thermometer into
the thermometer well and the capillary into the channels located on the front of the
thermometer tube. The sample can be observed through the lens on the front of the
apparatus, the eye should be about 15cm from the lens.
Remember that a slow heating rate at the melting point is needed in order to get an
accurate measurement. Record the temperature on the thermometer when the sample
starts to melt and record the temperature again when all of the sample has melted (this
gives you the melting point range).

Mel-Temp Apparatus.

Thiele tube method.

The Thiele tube is a glass tube designed to contain heating oil and a thermometer to
which a capillary tube containing the sample is attached. The shape of the Thiele tube
allows for formation of convection currents in the oil when it is heated. These currents
maintain a fairly uniform temperature distribution throughout the oil in the tube. The
side arm of the tube is designed to generate these convection currents and thus transfer
the heat from the flame evenly and rapidly throughout the heating oil. The sample,
packed in a capillary tube is attached to the thermometer, and held by means of a rubber
band or a small slice of rubber tubing. It is important that this rubber band be above the
level of the oil (allowing for expansion of the oil on heating). Otherwise, the oil softens
the rubber and allows the capillary tubing to fall into the oil.
 Thiele tube method.

BOILING POINT DETERMINATION:

The physical properties of a compound, such as melting point and boiling point can
provide useful information which can help in the identification of a sample or to
establish its purity. Since the boiling point of an unknown sample under the same
conditions (e.g. same pressure) is a constant, a measured boiling point can be compared
to known values (e.g. literature value or the measured value of a known sample).

Micro-Boiling Point Determination

Micro reflux method
The sample liquid (approx. 0.5 mL) is introduced into a 150mm diameter test tube using
a Pasteur pipette and a small magnetic stirring bar is added. The test tube is placed in
the metal heating block cantered on a hot plate stirrer and carefully clamped in place.
The thermometer is clamped in a small piece of rubber tube and lowered into place
such that the bulb or tip of the thermometer is about 1 cm above the surface of the
liquid.
 Micro reflux method of determining boiling point.

Once the set-up is complete, turn on the stirrer to give gentle stirring of the liquid and
then start to heat. Look for the liquid to be boiling (bubbles) and just above the liquid,
the vapour condensing and running back into the boiling liquid (i.e. the liquid is
refluxing). This is often visible as a ring of liquid on the walls of the glass. The bulb or
tip of the thermometer needs to be at the level of this ring for accurate measurement.
Once the liquid is gently refluxing, the thermometer temperature reading should be
stable and correspond to the observed boiling point of the liquid sample. Make sure not
to boil the sample dry. Once the boiling point has been measured, stop heating the metal
block (but leave it stirring).
SEPARATION TECHNIQUES FOR MIXTURES.

It was pointed out what a mixture is. It was also pointed out that the constituents of a
mixture can be separated from one another by physical method. Therefore, the
techniques for separating mixtures are essentially physical. A mixture can be in solid
state, liquid state, or gaseous state. The physical methods of separating mixtures are:
Filtration, Decantation, Evaporation, crystallization, fractional crystallization, use of
separation funnel, Distillation, Fractional Distillation, Sublimation, Precipitation,
Magnetization, Chromatography, Sieving and use of centrifuge machine.

Filtration:

Filtration is used to separate insoluble solids from liquids or solutions. Suspensions can
also be filtered to remove solids. Drinking water is filtered to remove insoluble solids.
In this method filter paper is used. Filtration is used to separate chalk and water or sand
and water. The insoluble sand will remain on the filter paper as residue while water will
pass through the filter paper and is collected in the beaker as filtrate. Industrially,
filtration is employed in the purification of town water supply and in breweries. It is
also employed in a chemistry laboratory to separate a mixture of soluble and insoluble
substances. For example, a mixture of insoluble lead tetraoxosulphate (vi), (PbSO4) and
soluble zinc tetraoxosulphate (vi), (ZnSO4) can be separated by the process of filtration.
Decantation:

Separation of two immiscible liquids by decantation

This method is used to separate a mixture of solid and liquid where the solid settles at
the lower part of the test-tube and the liquid at the upper part. The upper liquid can then
be separated from the solid by carefully running out the upper liquid into another
container. This method can also be used in the separation of two immiscible liquid,
where the lighter liquid A floats on the denser liquid B in the same test tube. The
disadvantage of this method is that while pouring out the lighter upper liquid, the denser
lower liquid may run off.

Evaporation:

Apparatus for evaporation

This is a method used to separate a solid (solute) from a solvent. The solution is heated
to dryness. Evaporation involves the heating of a solution to remove the solvent from
the solid substance. A solution of common salt in water is called brine. Brine can be
heated to evaporate all the water molecules leaving only solid salt after evaporation.
Evaporation method is mainly used where the liquid component is not required.
Evaporation is one of the fast methods of separating mixtures but the product obtained
using this procedure may not be very pure. It is used where the components cannot be
decomposed by heat.
Crystallization:
This method is also used in the separation of solids from solutions. The knowledge of
the solubility of solids at various temperatures is very vital here. The use of this method
is dependent on the solubility of the component of the mixture at various temperatures.
The solid to be separated is first of all dissolved in a solvent in which the component to
be separated is very soluble at high temperatures and less soluble at lower temperatures.
The solid is then dissolved in minimum amount of the solvent at high temperature, and
the solution is allowed to cool. If the solid (solute) is in excess solvent, crystalline
substance (solid) is separated by concentrating the
solution by evaporation. As evaporation is going on, after a time, crystals will start to
appear at the edge of the solution. When the crystalline substance is observed, the
solution is poured into a crystallizing dish and allowed to cool. As the solution cools,
solid particles called crystals will begin to appear in the solution. At room temperature,
the crystals are obtained in the solution. The crystals can then be separated from the
solution by filtration. It is washed with distilled water and allowed to dry on the filter
paper.

Fractional Crystallization:

separating the various components of a mixture by varying the temperature

This method is used where there are more than one solute in a given solution. There
must be difference in the solubility of the solutes at different temperatures. As the boiled
solution is allowed to cool, the different crystals can be obtained at different
temperatures. For example, at a temperature of 78oC the less soluble component will
separate out of the solution (or it crystallizes) and at a temperature of about 42oC the
crystals of the more soluble component will crystallize. Thus by varying the
temperature, various fractions of the solute components can be separated.

Use of Separating Funnel:

Separating funnel can be used in separating two immiscible liquids. It can also be used
in separating a mixture of two different solids in which the components are soluble in
different immiscible solvents. For example, if solid A is soluble in solvent B, and solid
C is soluble in D but not in B, a mixture of solids A and C can be separation by
dissolving the solid mixture in the mixture of the two solvents in a separating funnel.
The content of the separating funnel is shaken very well and allowed to settle. The less
dense solution will then float on top of the denser solution. The control tap is then
opened and the denser solution enters into a conical flask. To avoid being contaminated
by the remains of the denser solution, the less dense solution is removed through the
upper opening of the funnel.

Using a separating funnel

Distillation:
Distillation consists of the two basic processes of boiling and condensation. For example
impure water can be purified by distillation because the impurities in water are solids
which are nonvolatile. The impure water is heated to make it boil. Its vapour is collected
and cooled. As it cools, the vapour condenses into pure distilled water. The non-volatile
impurities remain behind. This method is commonly used in separating solvents from
solutions especially when the solvent
is needed. It can be used in separating the more volatile (lower boiling point) from less
volatile substances. Pure water can be obtained from brine (common salt solution) by
distillation. Distillation can also be employed in separating mixture of liquids with
widely differing boiling points. The difference in the boiling points should be large so
that only the more volatile constituent will be present in the vapour above the boiling
point of the constituent, in the liquid mixture.

Liebig condenser is used to convert vapour to liquid while distillating. To enhance the
condensation of the vapour, cold water is continuously being introduced through an
inlet. The thermometer helps one to know when the component of the mixture has
distilled off. For example, if the boiling point of the component is 60oC at a temperature
of about 62 oC that component must have distilled off. The condensed steam is called
the distillate or condensate.

Fractional Distillation:
Fractional distillation technique is used in separating mixture of liquids with boiling
points that are close together.

Fractional distillation

Fractional distillation method is similar to the ordinary distillation described above

except that a fractionating column is fitted between the distilling flask and the
condenser. This process is used to separate two or more mixture of volatile liquids with
very close boiling points. A fractionating column is a tube with irregular interior. It is a
glass column packed with glass beads, which exposes a large cooling surface to
ascending vapours. On heating a mixture of, for example ethanol (boiling point 78 oC)
and water (boiling point 100 oC), the liquid mixture boils and its vapour rises into the
fractionating column. This vapour mixture contains a higher proportion of the more-
volatile ethanol than water. The vapour begins to condense in the fractionating column.
Water vapour condenses more easily than the ethanol vapour. The column is cooler at
the top than at the bottom. Thus the higher the vapour mixture rises in the column, the
richer it becomes in ethanol. Finally, at the top of the column, pure ethanol can be
collected.

Any liquid in the above experiment boiling at a higher temperature than 78 oC, will
condense and run back into the flask. In this way, only ethanol reaches the top of the
fractionating column as a vapour, and distils over into the receiver. At any particular
time, the thermometer indicates the boiling point of the distilling liquid. A rapid rise in
temperature, shows that the next constituent is beginning to distill off and should be
collected in another receiver flask.

Industrial Application of Distillation:

(a). Crude oil as obtained from the ground is not suitable for use. It is a mixture of many
liquids, which must be separated using fractional distillation method.
(b). Distillation is the major process used in the manufacture of spirits such as whisky,
gin, rum and brandy. It serves both to separate the spirit from the raw materials and also
to strengthen it (the distillate). The distillate or the condensed vapour will then contain
a higher percentage of alcohol than the original alcohol/water mixture.

Sublimation:
There are substances which when heated changes directly from solid state to gaseous
state without passing through the liquid state. Such substances are said to sublime and
the process or the phenomenon is known as sublimation. Examples of the substances
which sublime when heated are anhydrous aluminum chloride (AlCl3), anhydrous iron
(III) chloride (FeCl3), benzoic acid and iodine. A substance which sublimes can be
separated from other components of a
mixture by heating the mixture.
A mixture of sand and ammonium chloride can be separated as follows: The mixture is
placed in an evaporating dish or basin. An inverted filter funnel is placed on the dish as
shown in Fig11.9 above. The basin is put on a tripod and gauze and is heated gently. If
the funnel becomes hot, strips of filter paper, sparked in water is placed on it to cool it.
On heating, ammonium chloride vaporizes wall of the funnel. The sublimate can be
scraped off the funnel. Sublimate is a substance formed by sublimation.

Precipitation:

Precipitation is the formation of an insoluble solid by a reaction, which occurs in

solution. It is one of the separation techniques where chemical means is applied to
facilitate the ease of separation by physical means (filtration). For example, if silver ion
is to be removed from an aqueous solution of its salt (Silver trioxonitrate v), an aqueous
solution of another compound such as Zinc Chloride is added. This will help in
precipitating on insoluble silver compound such as silver chloride. The silver compound
can then be separated from the soluble compound in solution by filtration.

2AgNO3(aq) + ZnCl2(aq) Zn(NO3)2(aq) + 2AgCl white ppt.

This method uses the differences of solubilities of a solid in different miscible solvents.
For instance, iron (ii) tetraoxosulphate (vi) is soluble in water and insoluble in ethanol.
Addition of ethanol to an aqueous solution of iron(ii) tetraoxosulphate (vi) will
precipitate the pure solid. To obtain a high degree of purity, the solid can then be
recrystallised.

Magnetization:

Separations of Iron filings from common salt using a bar magnet.

This is a method used in the separation of mixture where one of the components of the
mixture is a magnetic material. In magnetization, any magnetic material in a mixture
can be separated by bringing a bar magnet very close or in contact with the mixture. The
magnetic material is attracted to the magnet. It attaches itself to the bar magnet. A
mixture of common salt and iron fillings can be separated by magnetization method.
(see Fig3.11 above.) A mixture of sulphur and iron filling can also be separated using
this method.

CHROMATOGRAPHY:

This method is used in separation of complex mixture. The complex mixture includes
coloured substances. In this method there is mobile phase, which can be a liquid or gas
while the fixed phase is a solid. Types of chromatographic techniques are:

i. Paper Chromatography
ii. Column chromatography
iii. Thin-layer chromatography
iv. Gas chromatography

Paper chromatography:

A complex mixture of ink in a black bic can be separated using paper chromatographic
method. A spot is made on an oblong strip of filter paper. The filter paper is mounted in
a split cork in a boiling tube dipping the bottom end of the filter paper in a liquid
(propanone or ethanol). The liquid moves or rises up the filter paper and dissolves the
substances in the mixture (black ink). As the liquid rises up the paper, it carries the
dissolved substances with it. Each substance is carried at a different speed so that the
liquid separates out the components in the mixture.
Chromatography is used mainly in the analysis of mixtures. a variant of paper
chromatographic method is this: If the solution containing the mixture to be separated
is spotted on the filter paper, the components of the mixture move at different speeds
and as a result become separated. The mixture may be placed on the filter paper, an
appropriate solvent (ethanol) is dropped on the mixture. The components of the mixture
then move with the solvent at various speeds and are thus separated.

Separating the colours of black ink by chromatography

Gas Chromatography:
GC is a term used to describe the separation technique used to analyse volatile and semi-
volatile substances in the gas phase. The components of a sample are vaporized in order
to separate the analytes by distributing the sample between two phases: a stationary
phase (solid or liquid) and a mobile phase (gas). The mobile phase is a chemically inert
gas that carries the sample through the heated column. The stationary phase is either a
solid adsorbent, in the case of gas solid chromatography, or a liquid on an inert support,
as it is in gas liquid chromatography (GLC). In GC, the interaction of the sample with
the mobile phase can be disregarded.

Some common parameters of a gas chromatogram.

GLC is the method most commonly used to separate organic compounds, while the
combination of GC and mass spectrometry (MS) is an invaluable tool in the
identification of molecules. In GLC, the liquid stationary phase is adsorbed onto a solid
inert packing or immobilized on the capillary tubing walls. In a capillary column, the
tubing walls are coated with the stationary phase or an adsorbent layer, which is capable
of supporting the liquid phase. The separation of the compounds is done by partitioning
between both the phases. The main parts of a gas chromatograph include a source of gas
as the mobile phase, an inlet to deliver sample to a column, the column where
separations occur, an oven as a thermostat for the column, a detector to register the
presence of a compound in the column effluent, and data system to record and display
the chromatogram. A typical gas chromatograph is presented in Figure 3.

High-Performance Liquid Chromatography:

High-performance liquid chromatography (HPLC) is an analytical technique used to
separate and quantify each component in a mixture that must be soluble in the liquid
phase. Compounds that cannot be volatilised or are thermolabile for GC analysis are the
main compounds analysed by HPLC. Today, compounds in trace concentrations as low
as parts per trillion [ppt] may be easily analysed. HPLC can be, and has been, applied
to samples such as pharmaceuticals, food, cosmetics, environmental matrices, forensic
samples, and industrial chemicals. HPLC can be used in both qualitative and
quantitative applications (compound identification and quantification). There are two
main types of HPLC: normal phase HPLC (NP-HPLC) and reverse phase HPLC (RP-
HPLC). If the stationary phase is more polar than the mobile phase, the separation is
named as normal phase, while if the stationary phase is less polar than the mobile phase,
the separation is considered as reverse phase. NP-HPLC is only rarely used now, while
almost all HPLC separations are performed in reverse phase. In RP-HPLC, the retention
time of a compound increases as its polarity decreases. The key to an effective and
efficient separation is to combine the best separation between polar and nonpolar
components in the least retention time possible without losses in resolution. The goal is
for all the compounds to elute in the shortest time possible, but ensuring the best
separation of each individual peak. Typical columns for normal phase separation are
alumina or silica. For RP-HPLC, typical columns are composed of alkyl, aliphatic or
phenyl bonded phases. RP-HPLC is only ineffective for a few separation types. For
instance, it cannot separate inorganic ions (which are separated by ion chromatography)
and other highly hydrophobic compounds. Aside from these few exceptions, RP-LC can
be used for the separation of almost all other compound varieties, such as aromatic
hydrocarbons, amines, sugars, lipids, pharmaceutically active compounds, amino acids,
peptides, proteins and also other molecules of biological origin. HPLC has been used
for medical (e.g. detecting vitamin D levels in blood serum), legal (e.g. detecting
performance enhancement drugs in urine), research (e.g. separating the components of
a complex biological sample or of similar synthetic chemicals from each other) and
manufacturing (e.g. during the production process of pharmaceutical and biological
products) purposes. Figure 4 shows a schematic representation of the basic instrumental
components of a liquid chromatograph. The solvent inlet supplies the mobile phase,
which is then pumped through the inline solvent filter and passed through the injection
valve where it is mixed with the sample for injection. It then passes through another
filter and then through the column where the sample will be separated into its
components.

The detector detects the separated bands that correspond to the analytes and a computer
will record and process this information. The effluent goes through a backpressure filter
and then to waste. The analyte retention time will vary depending on the interaction
between the molecules being analysed and the stationary phase and the solvent, or
solvents used. As the sample passes through the column, it partitions between the two
phases at different rates, primarily due to different polarities of the analytes. Analytes
that have the least amount of interaction with the stationary phase or the most amount
of interaction with the mobile phase will exit the column faster.
Use of Centrifuge Machine:

Separation of solid from liquid using a centrifuge machine

This method is used to separate solid from liquid when the volume of the mixture is
small. The mixture of solid and liquid is poured into a test tube and the test tube is placed
inside the bucket of the centrifuge machine. As the centrifuge machine is put on, it
moves the bucket and its content at a very great speed in a circular form. After sometime,
the solid particles are thrown to the bottom of the test tubes while the liquid is on top.
The top liquid can now be decanted from the solid.

Sieving:
This method is used in separating mixture in solid state. Separation using this method
is dependent on the particle size of the solids and the size of the openings in the sieve.
The following mixtures can be separated by sieving:

i. Mixture of sand and beans

ii. Mixture of sand and stone
iii. Mixture of soya-beans and stone.

A sieve

Criteria for Purity:

After the separation of mixture, one may wish to know if the separated substances are
actually pure. To find this out, one has to determine some physical constants of the
separated substances like:

i. Melting points of solids

ii. Boiling points of liquids
iii. Refractive index or the relative density of both solids and liquids.
After finding these out, he has to compare the results with scientifically determined
values. If any of the constants determined is the same with scientifically determined
value, the substance is pure but if any of the constants determined differs from the
established value, then the substance is not pure.

Exercises:

1. Write out ten physical methods of separating mixture.

2. What are the industrial application of filtration as a separation technique?
3. What are the main difference between the following Separation techniques?
i. Crystallization and fractional crystallization.
ii. Distillation and fractional distillation
4. Define these terms:
i. Sublimation
ii. Evaporation
iii. Precipitation
5. Briefly describe how a complex mixture of black ink can be separated in your
chemistry laboratory.