SECTION B- ARC TUTORS CHEMISTRY CRASH COURSE

Sources of Hydrocarbon Compounds

Although how they were produced is not completely understood, petroleum and natural gas
were most likely formed from the remains of marine organisms that lived approximately 500
million years ago. Petroleum is a thick, dark liquid composed mostly of compounds called
hydrocarbons that contain carbon and hydrogen only. (Carbon is unique among elements in the
extent to which it can bond to itself to form chains of various lengths.)
The table which follows gives the formulae and names for several common hydrocarbons.
Natural gas, usually associated with petroleum deposits, consists mostly of methane, but it also
contains significant amounts of ethane, propane, and butane. The composition of petroleum
varies somewhat, but it consists mostly of hydrocarbons having chains that contain from 5 to
more than 25 carbons. To be used efficiently, the petroleum must be separated into fractions
by boiling. The lighter molecules (having the lowest boiling points) can be boiled off, leaving
the heavier ones behind.

Bonding Properties of carbon

The exitence of millions or organic compounds is prmarily due to the unique bonding
properties of the carbon atom.
1) Carbon atoms can form single, double or triple bonds with other carbon atoms and with
atoms of other elements.
 Single bonds: C-C, C-H, C-O, C-N, C-X, C-S
 Double bonds: C=C, C=O, C=N
 Triple bonds: 𝐶 ≡ 𝐶, 𝐶 ≡ 𝑁,
2) Crabon atoms bond to one another and to other atoms to form compounds containing
both rings and chains. The rings may be branched or straight. The ability of the taoms
of an element to form l,ong chains is known as catenation.
NB: X stands for any halogen atom, F, Cl, Br or I
Straight (unbranched) chain compounds.
Straight-chain molecules ae unbranched.
 Branched chain compounds
Look at the structures below. These are all exmaples of branched-chain compounds, Each
compound has a main chain that contains five carbon atoms.

1) Structure 1: this molecule has one branch, which is on the second carbon of the main
chain.
2) Structure 2: There are two main branches on the same carbon atom of the main chain.
3) Structure 3: There are two branches on different carbons of the main chain.
NOTE THAT EVERY CARBON ATOM IN ALL THE COMPOUNDS HAS A TOTAL
OF FOUR BONDS.
Saturated and unsaturated compounds.
Saturated organic compounds contain only carbon to carbon single bonds in their structure.
Unsaturated organic compounds contain at least one carbon to carbon double bond or one
carbon to carbon triple bond in their structure.
Formulae of organic compounds
There are five types of formulae which can be used to describe and identify organic
compounds:
 molecular formula
 empirical formula
  full structured or displayed formula
 condensed strutural formula
 general formula
Full structural formula or displayed formula
The full structural formula or displayed formula of a compound shows how all the atoms in
one molecule of the compound are bonded to one another.
Note the following;
 all bonds in the molecule are shown when writing full structural formulae;
 full structural formulae are shown only in two dimensions- full structural formulae
are flat and do not indicate the actual shapes of the molecules, nor do they show how
the atoms are positioned in space relative to one another.
The figure below shows the full structural formulae of some organic compounds:

Condensed strutural formula

The condensed structural formula shows atoms in realtion to each other but omits the bonds.
When you are interpreting condnesed strutural formula, you need to remember that each
carbn atom always forms a total of four covalent bonds in organic compounds.

General formula
The general formula gives the numerical relationship between the number of carbon atoms
and the other types of atoma in one molecule of any of the compounds in the same
homologous series.
Homologous series
A homologous series is a group of organic compounds with the same general formula and
showing specific chracteristics.
We can classify similar organic compounds into well defined sets or groups known as
homologous series. The members of a homologous series are usually arranged in order of
increasing molecular mass. The characteristics of a homologous series are:
 All members of the series have the same general formula
 The molecular mass of each member of the homologous series differs from the
member positioned before or after it (its nearest neighbour) by a –CH2- unit, which
corresponds to a molecular mass of 14
 Members of a homologous series have similar chemical properties
 For a given homologous series, physical properties(e.g boiling point, density and
enthalpy of combustion), change in a regular way as the molecular mass or carbon
chain length of the compound increases.
 All members of aperticular homologous series may be prepared by the same genral
method.
The main homologous series and theor general formula are shown below:

Fuctional groups in organic compounds

The functional group is that atom or group of atoms that determines the specific chemical
properties of the organic compounds in a homologous series.
A functional group approach to the study of organic chemistry greatly reduces the number of
specific facts that have to be memorised. With this approach, the chemical properties of
organic compounds can be predicted from the fuctional groups they possess.
Naming organic compounds
Organic compounds are named using the IUPAC system of nomenclature. Before you can
name any compound you must know or be able to derive its molecular formula and the
homologous series to which it belongs.
 The molecular formula allows you to determine the total number of carbon atoms in
one molecule of the compound.
 The homologous series to which it belongs helps you to work out which functional
group the molecule contains.
Naming straight-chain alkanes and alkenes
The name of an alkane or alkene consists of two parts- the prefix and the suffix.
 The first part (the prefix) is related to the number of carbon atoms in the chain.
 The scond part (the suffix) is related to the functional group present. The functional
group for alkanes is –C-C- and the suffix is ‘ane’ and the functional group for alkenes
is –C=C- and the suffix is ‘ene’.
Naming straight-chain alkanols and alkanoic acids
Straight-chain alkanols and alkanoic acids are named as follows;
 use the name of the corresponding alkane with the same number of carbon atoms;
 remove the ‘-e’ from the end of the name of the alkane
 add the suffix ‘-ol’ for alkanols and the ‘-oic acid’ for alkanoic acids.


Naming branched-chain alkanes and alkenes

To name branched-chain compunds, you must first be familiar with the formulae and names
of the akyl group. Alkyl groups are represented by the symbol ‘R’ and have a genral formula
of 𝐶𝑛 𝐻2𝑛+1. Alkyl groups cannot exist alone. They are usually linked to a hydrogen atom, as
in the alkanes, or to some functional group, such as –O-H in alkanols ane –COOH in alkanoic
acids. The formula R-H will therefore represent an alkane, R-O-H is an alkanol and R-COOH
is an alkanoic acid.
The formula of each akyl group is derived by inserting the value ‘n’ into the general formula.
The name of each akyl group is based on the prefix for the number of carbon atoms in the
group and the suffix ‘-yl’ is added.

Now look at the stages needed to name the following branched-chain compound:
Step 1: Establish the homologous series to which the compounds belongs.
 Based on its molecular formula, 𝐶6 𝐻14 , the compound is an alkane. The name will
end in ‘-ane’/
Step 2: Note the number of carbon atoms in the longest (main) chain.
 There are five carbon atoms in the longest chain. The prefix will be ‘pent’
Step 3: Identify and name the alkyl group that branches off the main chain in the compound.
 The branch has the formula ‘CH3’. The name of the branch is ‘methyl’.
Step 4: Assign numbers to the carbon atoms in the longest chain so that the branch has the
lowest possible number.

 The position of the methyl branch is carbon 2, of we count from the right-hand side of
the diagram. We need to use ‘2’ in the name of the compound (rather than 4).
Step 5 Form the name from the parts obtained in steps 1 to 4.
 The name of the branched-chain compound is 2-methylpentane.
Naming organic compounds with more than one functional group
So far, we have discussed compounds with only one functional group. However, organic
compounds may have more than one functional group, and these groups may be the same or
different.
To name such compounds, we need to indicate;
  the types or types of functional groups
 the number of functional groups
 the positions of the functional groups that the compound contains.
We will now work out names for these compounds:

 Count the number of carbon atoms to get the main part of the name. Compound H has
two carbon atoms, so its name is based on ethane. Compound I has 6 carbon atoms, so
its name is based on hexane.
 Both molecules contain the same functional group which is a hydroxyl group, so we
need to have ‘ol’ in the names of the compounds.
 The compounds are diols because there are two alkanol functional groups.
 We need to use numbers to indicate the positions of the functional group in the two
molecules. The numbers we need are ‘1,2’ for H and ‘1,6’ for I.
H is called ethane-1,2 diol. I is called hexane-1,6-diol.
Sometimes molecules contain two or more different functional groups. Here are two
examples:

Structural formulae and isomerism

Isomers are compounds which have the same molecular formula but different structural
formulae. We use structural formulae rather than molecular formulae when naming
compounds because there are examples of two or more organic compounds having the same
molecular formula but a different arrangement of their atoms.
As you study the different homologous series, you will see that isomers can belong to the
same homologous series or to different homologous series. isomers foubd within a
homologous series will show differences in physical properties, but similar chemical
properties. Isomers from different homologous series will show different physical and
chemical properties.
THE HYDROCARBONS: ALKANES AND ALKENES
Alkanes
Alkanes are saturated hydrocarbons. We can use the general formula 𝐶𝑛 𝐻2𝑛+2 to determine
the molecular formula for the first five members of the alkane series.

Alkanes can be gases, liquids or solids at room temperature. Alkanes may be used to show
that the physical properties change in a regular way for a given homologous series. For
example, boiling point, density and enthalpy of combustion all increase with an increase in
molecular mass or length of the carbon chain. The figure below shows that an almost linear
relationship exists between the boiling point of the alkanes and the number of carbon atoms
in the chain.

Structural formulae and isomerism

The atoms in compounds for example with a molecular formula of C4H10 can be arranged in
two ways either as

or as:
Both these structural formulae correspond to a molecular formula of C4H10. This means that
the two compounds are isomers. Isomers differ in their structure. They cannot be converted to
one another by turning the molecule or by rotation about the carbon-carbon bonds.
The physical properties of isomers such as butane and 2-methylpropane differ. However,
their chemical properties are very similar because the two compounds contain the same
functional groups.
Chemical Properties of the Alkanes
Members of the alkane homologous series have similar chemical properties.
1) Combustion
If ignited, alkanes burn in an excess of air (or an excess of oxygen) to produce carbon
dioxide, water and heat. The reaction is described as a complete combustion reaction.
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) + heat
However, if the supply of air or oxygen is insufficient, the alkane molecules are not
completely oxidised to carbon dioxide and water. Other products such as carbon monoxide
and carbon, and even hydrogen, might be formed. Note that the reaction is exothermic.
2) Reaction of alkanes with halogen
Alkanes undergo substitution reactions with the halogens (especially chlorine) in the presence
of bright light, usually sunlight,(A substitution reaction is a reaction that replaces one or more
hydrogen atoms in a saturated compound by some other atom or group of atoms). The
substitution reaction gives a mixture of organic products and hydrogen chloride gas as shown
in the following equations.
You can show that substitution is taking place by reacting the HCl(g) produced with
concentrated ammonia. Dense white fumes of ammonium chloride will be formed:
HCl (g) + NH3(g) → NH4Cl(s)
The organic products are known as halogenoalkanes. The number of hydrogen atoms
replaced in the reaction depends on the relative quantities of alkane and halogen used.

Uses of alkanes and their derivatives.

Alkanes
Alkanes are used mainly as fuels- examples are LPG and natural gas. This is because alkanes
produce a lot of heat when they burn. In technical terms, we say that their heat of combustion,
∆𝐻𝑐 , is large. Other properties of a good fuel are:
 they ignite easily but not spontaneously under normal conditions
 they burn well, but not explosively
 they have low smoke and ash content
 they are inexpensive
 they are safe to use
 they are easy to use and transport
Halogenoalkanes
Some halogenoalkanes are
 solvents-examples are tetrachloromethane and trichloromethane
 Anaesthetics. Halothane for example, is a halogenoalkane which is widely used in
hospitals. It contains the atoms bromine and fluorine as well as chlorine.
Chloromethane is used for local anaesthesia by spraying on the skin.
 Pesticides. Halogenated hydrocarbons are also very widely used as pesticides.
Alkenes
The alkenes form another homologous series of general formula 𝐶𝑛 𝐻2𝑛 . Alkenes are
unsaturated hydrocarbons. Every alkene molecule must contain at least one carbon to carbon
double bond. The carbon to carbon double bond is the functional group of the alkenes.

Structural formula of alkenes

Only 1 structure can be drawn for alkenes containing two or three carbon atoms:
When you study these three strutures, you should notice the following:
 The straight chain structures have the double bond in two different positions. The third
isomer is a branched chain compound.
 When naming alkenes, the position of the double bond in the molecule must be
indicated.
The position of the double bond is given by the lower number of the two carbon atoms that
are linked by the double bond.
Reactions of alkenes
Combustion of alkenes
Alkenes, like alkanes, burn in a plentiful supply of oxygen to produce carbon dioxide and
steam. Again the reaction is highly exothermic;
C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l) + heat
However, alkenes are not used as fuels because:
 they burn with a smoky flame (this is in contrast to alkanes which burns with a clean
blue flame)
 they are prized starting materials for making other valuable organic compounds such
as polymers
Addition reactions of alkenes
The typical reactions of the alkenes are addition reactions. (Addition reactions are those in
which an unsaturated compound reacts with a given reagent to form a saturated compound as
the only product. The reagent adds across the double bond).
Reaction with hydrogen
Hydrogen adds to alkenes in the presence of finely divided nickel, which serves as a catalyst.
This reaction, which results in the formation of alkanes is commonly described as
hydrogenation.

Note that the hydrogen molecule is added across the double bond. One hydrogen atom is
added to each of the carbon atoms linked by the double bond. Hydrogenation reactions with
unsaturated alkene-type molecules are carried out in industry.
The hydration of alkenes to produce alkanols
Hydration is the addition of a water molecule across a double bond in an unsaturated
molecule.

The direct hydration of ethene is used to produce ethanol commercially. Ethene is

compressed to about 70 atm, mixed with water and passed through a furnace. The heated
mixture is then passed over a phosphoric(V) acid catalyst at a temperature of 300𝑜 𝐶. Ethanol
is formed and the mixture of gases, ethanol vapor plus uncombined ethene and steam are
condensed and drawn off. Unreacted ethene can then be recycled. The process is shown
below:

Difference between alkanes and alkenes

The difference between alkanes and alkenes are based on the fact that:
 alkanes are saturated compounds so they undergo substitution reactions
 alkenes are unsaturated compounds, so they undergo addition reactions
Alkenes can therefore be told apart from alkanes by testing for the presence of unsaturation.
Alkenes rapidly decolourise an acidified solution of potassium manganate( VII), MnO4-
/H+(aq). The acidified potassium manganate(VII) reagent has no effect on alkanes.
Uses of alkenes
The figure below summarizes the major uses of a typical alkene, ethene. It is one of the major
building blocks of the chemical industry.

Crude oil to gasoline and ethene

Crude oil is a natural source of hydrocarbons. Fractional distillation is used to separate the
constituents of crude oil. On an industrial scale, the fractionating column consists of
perforated horizontal trays on which the rising vapour condenses and is then vaporised later
by more rising vapor. Thus each tray functions both as a condenser and a boiling flask.
The components (fractions) of petroleum ranges from volatile liquids used as gasoline
(boiling at 50𝑂 𝐶 to 20𝑜 𝐶) and kerosene (boiling at 175𝑂 𝐶 to 325𝑜 𝐶) to the heavier fractions
that are used as diesel fuel (boiling point above 275𝑂 𝐶). The residue that remains behind
after fractional distillation of heavy oil is asphalt, which is used for surfacing highways.The
composition of crude oil from different sources varies considerably. Components which are
in lesser demand can be changed into more useful ones by two important processes: Cracking
and Reforming.
Cracking
Cracking is the process by which hydrocarbons in the heavier fractions produced by the
distillation of crude oil are broken down to lower molecular mass hydrocarbons.The figure
below shows how a molecule such as decane (C10H22) may be cracked. Cracking may be
achieved by heat alone or by a combination of heat and a catalyst. Heat makes the
hydrocarbon molecules vibrate to such an extent that the carbon to carbon bonds break at
certain points.

Reforming
The process of reforming is similar to cracking- straight chain hydrocarbons are broken up
and then reassembled into branched-chain hydrocarbons. In reforming, low grade gasoline
(with a low octane rating) is converted to high grade gasoline (with a high octane rating.
The Alkanols
The reactions of alkanols
Ethanol and the other alkanols undergo a number of reactions based on the presence of the
hydroxyl (-OH) functional group.
Reactions with more reactive metals
Highly reactive metals, such as sodium, lithium and calcium, react with low molecular mass
alkanols, such as methanol, ethanol and propanol. These reactions give hydrogen gas and
salts of the alkanols called alkoxides. The equation for the reaction of ethanol with sodium
metal is:
2Na(s) + 2CH3CH2OH(l) → 2CH3CH2O-Na+(s) +H2(g)
This reaction is similar to that of sodium and water, but it is less vigorous. We can think of
ethanol as having the same functional group as water.
Oxidation of alkanols
Powerful oxidising agents such as acidified potassium dichromate(VI) or acidified potassium
manganate(VII) convert alkanols to organic acids. In these reactions, an intermediate alkanal
or aldehyde is formed:

During this reaction, the reaction mixture changes colour from purple to colourless. The same
reactions take place with potassium dichromate(VI), but the colour change is from orange to
green.
Dehydration of alkanols to alkenes
Dehydration is a chemical reaction in which a molecule of water is removed from one
molecule of a compound to form a new compound. Alkanols react with dehydrating agents,
such as concentrated sulphuric acid or anhydrous aluminium oxide, to form alkenes. The
reaction is described as a dehydration. The water lost across two adjacent carbon atoms in the
alkanol. This results in the formation of a double bond between the two carbon atoms.

Dehydration can be achieved by:

 Heating the ethanol with excess concentrated sulphuric acid at a temperature of
170𝑂 𝐶.
 Passing ethanol vapour over activated alumina (Al2O3) heated to 450𝑂 𝐶.
Conversion of alkanols to esters
Another reaction of alkanols is their conversion to esters.

This reaction is commonly called a ‘condensation’ reaction.

Combustion of alkanols
The combustion of alkanols is a highly exothermic reaction: hence the use of alkanols,
especially methanol and ethanol as fuels. Ethanol burns with a blue flame to yield carbon
dioxide and water.
2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O(g) + heat
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g) + heat
These equations represent the complete combustion of the alkanols. In an insufficient supply
of oxygen, carbon monoxide, carbon and even hydrogen may be formed.
Properties and uses of alkanols
Like water, ethanol is a polar covalent compound. However, when compared with water, it
has a higher molar mass and higher heat of combustion, but lower melting point and boiling
points. The boiling point of water is 100𝑂 𝐶, whereas the b.p of ethanol is 78𝑂 𝐶. This
suggests that the intermolecular forces are weaker in ethanol than in water. Ethanol is
therefore a more volatile liquid than water.
These properties make ethanol useful as:
 a solvent
 fuel
  germicide
 antifreeze
Production of Rum
Anaerobic fermentation is the conversion of sugars to smaller molecules like carbon dioxide
and ethanol. It takes place in the absence of oxygen. Ethanol, the main ingredient in many
alcoholic drinks such as beer, wine and rum is obtained by the anaerobic respiration of
grapes, sugar, molasses and other carbohydrate materials. In the Caribbean, molasses, which
is a by-product of cane sugar manufacture, is frequently used in fermentation.
The fermentation process can be summarized as follows:

Yeasts are unicellular fungi and are the source of the enzymes which are necessary for
fermentation. Yeast cells grow rapidly and bud freely if sucrose, water, specific nitrogen
sources, vitamins and mineral salts are present. The figure below summarizes the stages in
the manufacture of rum from molasses. The final distillation can be controlled to obtain
ethanol for either industrial purposes (99.6% ethanol) or rum(40% ethanol).

The distillate is processed further. Some flavours are removed during the processing and the
raw spirit is matured in oak casks before it acquires the characteristics (Colour and taste) of
rum.
The effects of ethanol on the body
Some of the short-term effects of ethanol are:
 initial relaxation
 euphoria
 loss of inhibitions
  impaired coordination
 reflexes slow down
 mental processes slow down
 attitude changes
Ethanol is a toxic drug. A concentration of 4 parts per 1000 in the blood can lead to a deep
anaesthetic effect of even death. When someone consistently consumes more ethanol than the
body can break down, there is a significant rise in blood ethanol level, which leads, among
other things, to:
 impaired circulation
 accumulation of toxins
 excessive loss of fluids via urination
 problems of digestion, hence stomach problems
 Malfunction of organs such as the pancreas, liver and brain in the long term.
3 THE ALKANOIC ACIDS AND ESTERS
Alkanoic acids
Alkanoic acids are also known as carboxylic acids. Long-chain alkanoic acids, particularly
those found in plants and animals are known as fatty acids. Alkanoic acids and esters are
constituents both of naturally occurring substances and of manufactured products with
distinct flavours and odours.
Alkanoic acids can be represented by their general formula 𝐶𝑛 𝐻2𝑛+1 𝐶𝑂𝑂𝐻, which can be
shown more conveniently as R-COOH.
The –COOH group (carboxyl group) is the functional group in organic acids. The carboxyl
group gives this class of compounds:
 acidic properties
 relatively high boiling points
 solubility in water
Ethanoic acid
Ethanoic acid, CH3COOH, has the following structural formula:

Ethanoic acid is a typical representative of the homologous series of the alkanoic acids. It is
found on the average kitchen shelf as vinegar, which is a 5% solution of ethanoic acid.
Vinegar can be used as a preservatives in pickling and also other types of food preparations.
Ethanoic acid is easily recognised by its ‘sharp’ smell and sour taste.
Preparation of ethanoic acid
A sample of ethanoic acid can be prepared by refluxing a mixture of ethanol and acidified
potassium dichromate(VI) or acidified potassium manganate(VII). Then the product mixture
needs to be distilled. You need to collect the fraction which comes off with a boiling point
neat to 118𝑜 𝐶.
The reactions of alkanoic acids
The reactions of organic acids nay be summarised using ethanoic acid as example. Alkanoic
acids are weak monobasic acids. They are incompletely dissociated. The alkanoic acids show
the typical reactions of mineral acids but they react less vigorously because they are weak
acids, whereas the mineral acids are strong.
1) Reactions with metal
Metals high in the reactivity series react with organic acids to produce hydrogen gas and the
salt of the organic acid:

The reaction between reactive metals and organic acids is less vigorous than the
corresponding reactions with mineral acids.

The balanced equations indicate that ethanoic acid is a monobasic acid. Note that only one
hydrogen atom, that of the –COOH group of the acid, is ‘acidic’.
2) Reactions with metal oxides and hydroxides
The oxides and hydroxides of metals react with organic acids to form the salt of the acid and
water. This is a neutralisation reaction.

3) Reactions with carbonates and hydrogencarbonates

Carbonates and hydrogencarbonates react with organic acids to yield carbon dioxide, the salt
of the acid and water.

4) Reactions with alkanols

Organic acids react with alkanols to produce esters. This type of reaction is known as
condensation. (Condensation reactions take place by the elimination of a small molecule such
as water, ammonia or hydrogen chloride, between certain groups in organic compounds.
The mixture of the alkanoic acid, the alkanol and a few drops of concentrated sulphuric acid
should be heated in a water bath for a few minutes. The mixture then needs to be poured into
a concentrated solution of sodium chloride.
A water molecule is lost between the functional group of an alkanoic acid and the functional
group of an alkanol producing an ester. The removal of water between the two molecules is
made possible by the dehydrating property of the sulphuric acid in the mixture.

The names of ester are derived from both the alcohols and the organic acids from which they
are derived. Look at the following names and see if you can work out how the name of the
ester is produced.
Note that the ‘oate’ comes form the acid and the alkyl part come from the alcohol. Note,
however, that in writing the molecular formula or structural formula of the ester, the acid part
is normally written first. Look at the structure of ethyl propanoate and the link the two parts
of the name to the formula.

Uses of alkanoic acids and esters

1) Alkanoic acids
The use of alkanoic acids as a preservative has already been mentioned. Ethanoic acid is also
used in the manufacture of plastics, in cellulose ethanoate, textiles and in a wide range of
pharmaceuticals.
2) Esters
Many esters occur naturally. Some of the low boiling point, short chain esters, for example
butyl ethanoate and pentyl ethanoate, are pleasant smelling. They are responsible for the
fragrances and flavours of flowers and fruits. Artificial essences or flavourings are usually
mixtures of esters dissolved in ethanol.
Esters with long carbon chains are commonly found in vegetable oils and animal fats. They
are widely used in food preparations and in making soap. Fats and oils are important
constituents of our diets. They are concentrated energy sources, they make food more
palatable and contain vitamin A,D and E.
Preparing Ethyl Ethanoate

When ethanol is refluxed with excess ethanoic acid, in the presence of sulphuric acid as a
catalyst, the ester ethyl ethanoate is formed. Ethyl ethanoate (b.p 77𝑂 𝐶) can be obtained from
the product mixture by distillation.
Hydrolysis of Esters
The ester linkage is formed by the elimination of water and can therefore be broken by the
addition of water. This process is known as hydrolysis. (Hydrolysis of an ester involves the
splitting of the ester linkage by the action of water to reform the alkanoic acid and the
alkanol)
The hydrolysis of esters proceeds very slowly and can be catalysed by refluxing the ester
either with dilute mineral acid (acid hydrolysis) or an excess of dilute alkali (alkaline
hydrolysis).
Acid hydrolysis of ethyl ethanoate forms ethanol and ethanoic acid, as shown in this
equation:
With alkaline hydrolysis, the alkanoic acid is formed first. The alkanoic acid is then
neutralized by the excess alkali, to form the sodium salt of the acid. The other product is the
alkanol.

Alkaline hydrolysis of simple esters is sometimes referred to as saponification. However, the

term is more appropriately applied to the process of soap manufacture. The process of
alkaline hydrolysis and the separation of the products of the reaction can be carried out in the
laboratory by heating the mixture of ester and alkali under reflux and separating the products
of the reaction by distillation.
4.0 SYNTHETIC POLYMERS
What are polymers?
The word polymer means many units. Polymers consists of long chain-like molecules which
are formed when several thousands of small molecules, known as ‘monomers’ combine
chemically.
What are monomers?
Monomers are small molecules which can be linked to form long-chain molecules with high
molar masses known as polymers. Monomers are considered to be the ‘building blocks’ of
polymers. There are two distinct types of polymers:
1) Unsaturated small molecules- examples are ethene and some of its derivatives such as
chloroethene and phenylethene.
2) Molecules containing two functional groups – examples are ethane-1,2-diol and 1,6-
diaminohexane. The two functional groups do not need to be the same.

The typical reaction of unsaturated molecules like the alkenes is an ADDITION reaction.
Unsaturated monomers will therefore bond by an addition reaction to form addition
polymers. The process by which the polymers are formed is addition polymerisation.
Many of the bi-functional molecules used as monomers contain two identical functional
groups. Such monomers rarely bond with each other, so two different bi-functional
monomers are used and they bond by condensation reactions. The polymer formed is a
condensation polymer and the process by which it is formed is condensation polymerisation.
Classifying Polymers
We can group polymers based on three sets of criteria
1) Classification based on source

2) Based on mode of polymerisation

i) Addition polymers: These type of polymers are formed by the repeated addition of
monomer molecules. The polymer is formed by polymerization of monomers with double or
triple bonds (unsaturated compounds).
ii) Condensation polymers- These polymers are formed by the combination of monomers,
with the elimination of small molecules like water, alcohol etc.
 3) Based on types of monomer used. Polymers are either homo-polymers or co-polymers.
Forming addition polymers
Addition polymerisation is generally achieved by subjecting the unsaturated monomers to
heat and pressure in the presence of a suitable catalyst. The sequence in the formation of
polyethene is shown below:

Where ∙ represents an unshared electron. Species B (which is highly reactive) then attacks
another carbon-carbon double bond, leading to the formation of species C.

Species C is itself reactive and will, in turn attack another ethene molecule, eventually
leading to the formation of the polymer.

The process of addition polymerisation can also be represented by using a general

representation of the monomer as shown:

Where X= H for ethene, X = Cl for chloroethene (vinyl chloride) and X = a benzene ring for
phenylethene (styrene).
Since there is no loss of material during addition polymerisation, the empirical formula of the
polymer is the same as that of the monomer.
Industrial preparation of polyethene and other addition polymers
Polyethene, a well-known polymer, exists in two forms:
1) Low density polyethene (LDPE)
2) High density polyethene (HDPE)

LDPE and HDPE are structurally different materials. This is because they have different
properties such as:
 the length of polymer chains
 the spacing between the chains
 the extent to which the chains are interlinked
The conditions of polymerisation can have an effect on the properties of the polymer.

Naming addition polymers

In general, addition polymers are named after their monomers by inserting the prefix ‘poly’
before the name of the monomer, Polyethene, for example, is formed from ethene and
polystyrene from the monomer styrene and so on.
Differences between monomer and polymers
Although addition monomers have the same empirical formula as the polymers which they
form, their properties are distinctly different. The table below compares the properties of
ethene and polyethene.

Condensation Polymerisation
Condensation polymerisation is essentially a method of joining monomers by eliminating
small molecules such as water. This is in contrast to addition polymerisation, as this only
produces the polymer. Condensation polymers do not have the same composition as the
monomers from which they are made.
Polyesters
Polyesters are polymers which contain many ester linkages. They are formed in condensation
reactions between di-acids and di-alcohols (usually called diols). Remember that a di-acid has
two organic acid (-COOH) groupings and that a di-alcohol contains two alcohol (-OH)
groupings. Here are examples of a di-acid (benzene-1,4-dicarboxylic acid, commonly called
teraphthalic acid) and di-alcohol (ethane-1,2-diol).

In the sequence below, a di-acid(E) and a di-alcohol (F) combine to form a further compound
(G), a simple ester that is capable of condensing on both ends.
Compound G has the following groups:
 an ester grouping
 an uncombined alcohol grouping
 an uncombined acid grouping
Compound G then undergoes further condensation reactions at both ends of the molecule to
form compound H.

Even more condensation reactions will eventually lead to a polyester of molecular mass
10000-20000.

Polyamides
Polyamides are polymers which contain many amide (peptide) groups. The carbon to
nitrogen bond within this group is called the amide (peptide) linkage.
Nylon is a typical polyamide. It can be prepared as shown in the following sequence.

Both these starting materials can be made from phenol, which is obtainable from the naptha
fraction of oil. When the di-acid(J) reacts with the diamine(K), then species L is formed:

Special L has an amide linkage, but it also contains two other functional groups. These two
functional groups are capable of further condensation to produce the polymer which is
represented by one repeat unit:

Naming condensation polymers

Condensation polymers are named after the functional group that is repeated along its chain.
5.0 Natural Polymers and Trigylcerides
Natural Polymers
Proteins – are natural condensation polymers.
The table below shows examples of proteins, their sources and functions.

Building blocks of proteins

A peptide bond is an amide linkage formed by condensation between the amino group of one
amino acid and the acid of one another. The main building blocks for proteins are the amino
acids. Amino acids contain two different functional groups, which are:
 the amino group, -NH2
 the aid group, -COOH
Both of these groups participate in condensation reactions leading to the formation of amide
linkages, which are called peptide linkages in proteins. This is similar to the reaction forming
amide linkages in synthetic polymers.
The general structure of an amino acid is:

In this structure, the side group R is different for different amino acids. Although over 80
amino acids are known, only 26 occur naturally in living systems. Twenty of these naturally
occurring amino acids are frequently combined in proteins.

Peptide Formation
When two amino acids are linked by a condensation reaction, a dipeptide is formed.

The different superscripts on R1 and R2 indicate different R groups and therefore different
amino acids. The carbon nitrogen single bond is the newly formed amide or peptide bond.
Note that the dipeptide still has functional groups at both ends, so that further condensation
reactions with other amino acids are possible, resulting in an increase in the length of the
peptide chain.
A polypeptide is formed when a large number of amino acids are linked. The term
polypeptide comes from the many –CONH- groups that occur at intervals along the polymer
chain. The figure below shows polypeptide formation.

When 50 or more amino acids have been condensed together, the polypeptide formed is
called a protein. Protein structures are very complicated. Insulin for example, has a molecular
formula of C254H377N65O75S6. Each protein is made from an arrangement of amino acids that
is different from every other proteins. Proteins have a very high relative molecular mass
ranging from 6000 to 100000. In living systems the process of condensing amino acids is
known as protein synthesis and this is guided by the DNA in the cells.
Hydrolysis of proteins
Hydrolysis of proteins is the splitting of the peptide bonds in a protein by the action of water
to form smaller peptides or individual amino acids. If all peptide bonds are broken the
hydrolysis is complete. If some bonds are broken, the hydrolysis is partial.
Our digestive system breaks down the proteins we eat into amino acids. For example,
enzymes in the stomach, such as pepsin and rennin catalyse the splitting of the peptide bonds
in proteins to release the amino acids. The hydrochloric acid in the stomach provides the
correct acidic medium for the reaction. Digestion of protein is a hydrolysis reaction.
Hydrolysis of proteins can be accomplished in the laboratory in the presence of acid or alkali.
The acid or alkali acts as the hydrolysing agent.
Acid hydrolysis of proteins
Treat the protein with concentrated hydrochloric acid at 𝟔𝟎𝑶 𝑪 for 24 hours or longer, in the
absence of oxygen
Alkaline hydrolysis of proteins
Treat the protein with concentrated sodium hydroxide for 6-8 hours. In the laboratory the
hydrolysis is complete and a mixture of amino acids is left. These amino acids can be
separated by chromatography.
In the body, the amino acids obtained from hydrolysis of proteins can then be used to
synthesize the many specialised proteins that are essential to health. While our bodies can
convert some amino acids into others which we need, it is not capable of making eight of the
naturally occurring amino acids. These eight essential amino acids are known as the essential
amino acids. We must eat food which can supply our requirements of these essential amnio
acids. Foods such as meat, milk, cereals and vegetables are important constituents of our
diets, because they supply these essential amino acids.
Tests for proteins and amino acids
You are aware that polymers and their monomers have very different properties. This
difference can be used to follow the hydrolysis of proteins. Before the hydrolysis, any tests
for the presence of free amino acids should be negative. At the end of the hydrolysis, tests for
the proteins should be negative.
Testing for amino acids
 Reagent: ninhydrin solution
 Procedure: add 1cm3 of ninhydrin to food or solution of amino acid. Boil for 1-2
minutes, then allow to cool.
 Results: a blue color indicates that amino acids (or proteins which contain a free amino
acid group) are present.
Testing for proteins
 Reagent: NaOH(aq) and copper sulphate(aq) (known as the biuret reagent).
 Procedure: add biuret reagent to food material in water and heat
 Results: a violet colour indicates the presence of proteins
Another test for Protein
 Intimately mix the food sample with soda lime (a mixture of sodium hydroxide and
calcium oxide)
 Place the mixture in a hard glass test-tube.
 Heat the mixture, placing a moist strip of red litmus at the mouth of the test-tube.
If the food contains proteins, ammonia gas will be given off, turning the red litmus paper
blue.
Polysaccharides
Polysaccharides are polymers that belong to a group of naturally occurring compounds
containing carbon, hydrogen and oxygen based on the formula Cx(H2O)y. The simplest
carbohydrates are the monosaccharides, which have a general formula of CnH2nOn. Some
examples of these simple sugars are glucose, fructose and galactose. These all contain six
carbon atoms and have the same molecular formula, C6H12O6 but they have different
structures and are therefore isomers. The figure below shows one way that the structure of
glucose can be shown:

Glucose molecules are the building blocks for the carbohydrate polymers. The condensation
of glucose molecules can occur in a stepwise manner forming disaccharides, trisaccharides,
and eventually more complex carbohydrates, the polysaccharides. Examples are shown
below.
Polysaccharide formation
Disaccharides and polysaccharides contain an ether linkage that is the C-O-C linkage. This
linkage is commonly called the ‘glycosidic’ linkage. Disaccharides have two reactive (end) –
OH groups. These reactive groups may undergo further condensation reactions to yield a
trisaccharides and eventually, the polysaccharides.

Hydrolysis of carbohydrates
The polymerisation of glucose molecules to form a polysaccharide such as starch is a
condensation reaction. Hydrolysis is the reverse of the condensation process. Starch
molecules, for example, are broken down partially to maltose or completely to glucose.
Testing for carbohydrates
Testing for starch
Reagent: iodine solution
Procedure: to a sample of starch (or food) and water, add a few drops of iodine solution.
Results: a blue-black colour develops if starch is present
Testing for a reducing sugar
Reagent: Benedict reagent or Fehling’s solution.
Procedure: to glucose or food or water, add Benedict reagent and heat.
Results: A series of colour changes are seen. Eventually an orange-red precipitate is obtained,
indicating the presence of reducing sugars.
Triglycerides
A triglyceride is a triester formed by the condensation reactions between a trihydroxyl
alcohol known as glycerol and three long-chain organic acids known as fatty acids. As
mentioned before, fats and oils are not polymers even though they are formed by the same
type of chemical reaction, condensation. Fats and oils are triglycerides.

The fatty acids used to form triglycerides may be:

 Saturated, such as palmitc acid (C15H31COOH) and stearic acid (C17H35COOH);
 Unsaturated, such as oleic acid (C17H33COOH) which has one double bond and
linoleic acid (C17H31COOH) which has two double bonds.
All of the fatty acids used to form fats are saturated, while oil contain at least one unsaturated
fatty acid.
Testing for fats
Procedure: smear food on paper. Allow to dry, then expose paper to light.
Results: a translucent area is evidence that food contains a fat
A more sophisticated test involves placing the food into a test-tube, and adding ethanol. The
test tube should be shaken if the food is a liquid. If the food is a solid, crush it with a glass
rod. Then add an equal volume of water to the test tube-tube containing the food and ethanol.
A cloudy dispersion indicates that fat was present in the food tested.
Hydrolysis of triglycerides
When fats are digested , glycerol and fatty acids are produced, as shown below;
With alkaline hydrolysis, the fatty acids are neutralised by the alkali to form soap. Soap is the
sodium salt of a fatty acid.