CARBOXYLIC ACIDS (ALKANOIC ACIDS)

Occurrence and General Molecular Formula of Alkanoic Acids

I The general molecular formula for monocarboxylic acid is C nH2n +1COOH where n starts from 0. The
functional group is –COOH.

II General properties of monocarboxylic acid

0-3 carbon atom monoic carboxylacid are colourless liquid with sharp odour of vinegar.

4-8 carbon atom have unpleasant odour while others are colourless and odourless.

Ii There is a regular increase in b.p and viscosity as the relative molecular mass increases.

Iii Among the isomeric alkanoic acids b.p decreases as the branching increases. This is due decrease in
the surface area and intermolecular attraction as the branching increases.

Iv The b.p of an alkanoic acid is much more higher than the corresponding alkanol.

Iii Natural sources of alkanoic acids

Aliphatic carboxylic acids occur in nature as free acids or in the form of fats and oils. The pain and
irritation expirencedfrom the stings of ants, bees or wasps are due to the injection of methanoic acid into
the blood stream.

Other occurences are ethanoic acid from vinegar, buthanoic acid from human sweat.,citric acid from
lemon,palmitic acid from palm fruits,lactic acid from sour milk e.t.c

Lab methods of preparing alkanoic acid

I. The oxidation of primary alkanoic
II. The hydrolysis of alkenoate in acid media
III. The distillation of an hydrons sodium ethanoic with con H2 SO4.

Lab. Preparation of Ethanoic acid

The oxidation of ethanoic of ethanol
The suitable oxidizing agents are KM nO4 and KzCr2O7.

Procedure
Add 30cm3 of H2SO4 to 20cm3 of water. Stir continually and allow to cool. The dissolve 70g of K2Cr2O7
in it and place in around bottomed flask.
Mix 40cm3 of ethanol with 20cm3 of water, place in dropping funnel and set the apparatus as shown. The
teacher unfolds the chant illustrating the preparation of ethanol and continue:

The mixture (acidified K2CrO7 and ethanol) is refluxed as the ethanol is being added from the dropping
funnel. When all the ethanol has added (100cm3), the mixture is refluxed
CH3 CH2OH + [0] CH3-CHO + H20
CH3-CHO + 2OJ CH3COOH
NB
Apparatus must be all glass because hot CH3COOH vapors attacks wooden / rubber cork.
HCL cannot be used because it is too volatile.
The oxidizing agent is required in excess of the ethanol for complete oxidation

Industrially, ethanoic acid is prepared from ethyne using mercury II tetraoxosulphate vi as catalyst.
The chemistry of Alkanoic Acids

The functional group (--COOH), The carboxy group is responsible for the high reactivity of alkanoic
acids. Using ethanoic acid as a typical carboxylic acid, the following are some of the reactions.

As an acid: it slightly lionizes in water to give hydroxonium

CH3COOH + H2O --------- CH3COO- + H3O+

b. it libertate hydrogen from strongly electropositive metals.

C. it neutralizes a base

CH3COOH + 2Na 2CH3COONa + H

CH3COOH + NaOH CH3COONa + H2O

I Esterification Reaction: This is a reaction of carboxy acid with an alkanol in the presence of cone.
H2SO4 as catalyst to produce ester and water only. The reaction is reversible and accompanied with a
fruity or fragment small of the ester formal.

CH3COOH –CH3 CH2OH ========== CH3COOC H2CH3 + H2O

Ethyl ethanoate
(i) Esterification (ii) Alkaline hydyolysis

Ii Reduction of Alkanoic acid: Alkanoic acids can be reduced to primary alkanols using lithium
tetrahydride aluminate

LiAlH4 as reducing agents to supply hydrogen.

CH3COOH + 4 [H] CH3CH2OH + H2O

Uses Ethanoic Acids

Ethanoic acid is an important organic solvent

It is used in food industry as vinegar for preserving and flavoring food. It is also used in coagulating
rubber latex.

Ethanoic acid is used in making compounds like ethyl ethanoate (vinyl acetate ) which is used in vinyl
resins, ethanoic anhydride which is used in aspirin ,cellulose acetate which is used in packing, in vanishes
in filter tips of cigarettes as well as in manufacture of synthetic fibers like rayon and artificial silk.
ALKANOATES

Sources of Alkanoates:

Animal and vegetable fats and oils are esters with high relative molecular masses, simples esters are
present is fruits of palnts and are responsible for the natural sweet smell of flowers and flavours of fruits.

Ethylethanoate has the flavor of pineapple

Penthylethanoate has the flavor of banana

Octyl Ethanoate has that of the orange

General Molecular formula

General Molecular formula for alkanoates (esters) is Cn H2nO2 where n = 2, 3, 4 etc. The formula is
represent as R COOR1. R1 repalces the tonisable H atoms of the Carboxylic and R is the allyl group of the
alkanol. The functional group is =COOR 1 when the two altyl group ends R and R 1 are Saturated the esters
are simply allcanoates.

NAMING OF ALKANOATES:

In the systematic name, the alkanol portion R1 is first named as alkyl followed by the acid portion RCOO-
named as ackanoates.
C2H5OH + CH3COOH CH3COOC2H5 + H2O

Ethanol ethanoic acid Ethyl ethanoate

PREPARATION OF ETHYLETHANOATE IN THE LAB.

Enthyl ethanoate is prepared by the esterification between glacial acid and ethanoate is prepared by the
esterification between glacial etharoic acid and ethanol in the presence of Conc. H2 SO4.
Prodcure: Add about 10 drops of conc. H2SO4 to about 2. Cm3 of glacial ethanoic acid in a dry test tube.
Mix well and add 4 cm3 of ethanol and mix again. Warm the mixture in a water both for about 25
minutes. Pour into a beaker partially filled with sodium or calcium chloride solution, the ethyl ethanoate
floats on the mixture as oil globules.

C2H5OH + CH3COOH CH3COOC2H5 + H2O

REACTIONS OF ALKANOIC ACIDS

Alkanoates are generally unreactive and undergo few reaction.

I Hydrolysis ; This is a reverse of esterification producing its component acid and ethanol. Ethyl
ethanoate can be hydrolysed by water into its component acid and alkanol again. The reaction is
extremely slow but is catalyzed by H+ or OH- i.e a dil. acid or alkali.

CH3COOC2H5 + H2O ====== CH3COOH + C2H5OH

If an alkali is used as a catalyst, the carboxylic acid reacts to immediately to produce the sodium salt of
the acid.
CH3COOC2H5 + NaOH ====== CH3COONa + C2H5OH

Ii Akaline hydrolysis is not reversible and lead to the formation of soap.

Iii Ammonolysis; Ethyl ethanoate reacts with aqueous ammonia to produce a mixture of ethanamide and
ethanol.
Uses of Esters.

Esters are used mainly as solvent for cellulos nitrate and quick drying substances .

They are also used in perfumes and cosmetics and as artificial flavouring for food.

ASSIGNMENT

1. Ethanoic acid reacts with both sodium hydroxide ethanol. Using equations compare the two
reactions and classify their products.

2. Write the structural formula of the following esters

(i). ethylethanoate (ii) propyle methanoate

3. Briefly describe how you can prepare ethyl metanoate with appropriate equation

PETROLEUM
ORIGIN & EXPLORATION
) Petroleum is a mixture of gases, liquid and solid. Alkanes, alkene, cycloalkane, aromatic and
others.
Petroleum and natural gases are formed from remains of marine algae and animals which settle
on the sea beds.
ii) World prospects of crude oil.
Crude oil is discovered in Nigeria in 1956 at oloibri, Afam, Abata, Bomu, Owaza, Egbema and
Ughelli kokori ole zone, all in Niger delta.
3/5th of the world oil reserves are in Asia (middle East) including China and Indonesia. Russia
has the next largest oil reserve. Other world reserves are U.S.A, Canada, Venezuela and
Australia including Northern and western Africa.
(iii) Separation techniques in oil company.
To justify the true value of crude oil, it must be refined.
Refining of crude oil proceeds in three stages - separation, conversion and purification.
Separation of crude oil uses the technique of fractional distillation. Fractional distillation takes
place in a tall steel tower (fractionating tower).
The teacher unfolds the chart to describe.
It uses the differences in b.ps of fractions to split the mixtures. The fractions are petroleum gases,
petroleum ether and ligroin, petrol / gasoline, kerosene, gas oil and diesel, lubricating oil,
bitumen and other residues.
iv) Uses of fractions
(a) Gases: the liquified petroleum gas (LGP) containing methane, ethane, propane and
butane are supplied in cylinders under pressure. They are used as fuel for domestic and
industrial purposes.
(b) Gasoline (petrol): is used mainly as fuel for car engines.
(c) Kerosene: is predominantly used as fuel for jet, aircraft and as domestic fuel for lightning
and cooking.
(d) Diesel is predominantly used as fuel for diesel engine. It is also used to heat furnaces in
industry.
(e) Lubricating oil are used as lubricants for machinery.
(f) Bitumen: it is used to make roads, Airport, Runways and Water proof materials such as
roofing felts

CONVERSION AND PETROCHEMICALS

CRACKING & REFORMING
1. CONVERSION: The fractions obtained from crude oil ranges from those with one carbon
atom to those with more than sixty carbon atoms. Only the low molecular mass and low
boiling fractions are useful as fuel and raw materials for chemical industries. The conversion
of high molecular and high boiling fractions is the major task of company as the demand of
the later is high.
2. CRACKING AND REFORMING:
Cracking involves breaking down high fractions of petroleum to lower fractions. Cracking can be
thermal or catalytic. In thermal cracking, less volatile fractions are heated to a very high
temperature (above 1000 c)

Long chain alkane is converted into smaller chain alkane, alkene, and hydrogen.
Catalytic cracking involves the use of catalysts to reduce the temperature e.g. Silica alumina
(finely divided).
Thermal cracking is not very efficient because there is a poor control over cracking pattern to
yield alkanes of desirable chain length. In catalytic, it is more controllable and yields more
petrol of greater quality.

Cracking is employed to increase the quantity of petrol.

Reforming: Reforming is aimed at improving the quality of petrol. Linear alkane is converted to
branch chain or cyclic hydrocarbon. Oxides of silicon, aluminum and platinum are usually
employed. Reforming is employed to increase the quality of petrol.

Octane number and octane rating:

The term octane number is used to rate the grade of petrol (gasoline). The octane number is
based on the proportion of n-heptane number and 2,2,4- trimethylpentane in petrol.
The octane number of 2, 2, 4 -trimethylpentane is set at 100 while that of n-heptane is zero “0”,
A 50:50 mixture gives petrol grade of 50. The percentage of 2,2, 4 -trimethylpentane in the
mixture determine the octane number of petrol.
Petrochemicals
3. Petrochemicals: petrochemicals are substances obtained as by product of petroleum. They
are often called value added products because after processing their market can go up
thirteen times that of the original petroleum petrochemicals include:
a. Natural gas usually found together with crude oil mainly methane. Others are
propane & butane which can easily liquify under pressure and sold as bottled gas.
b. Alkanes: ethane and propane obtained from cracking of petroleum can be made into
polyethene, nylon, ethanol etc.
c. Aromatic compounds: benzene, toluene and xylene obtained from crude oil can be
processed to give synthetic fibers (nylon, plastic, detergents, insecticides).
d. Synthetic gas: synthetic gas be source of Co₂, H₂, S and H₂SO₄.
The economic importance of petrochemicals cannot be overemphasized. After processing their market
value are much higher than their original petroleum. Besides they serve as the starting/raw material for
the production of many products

ASSIGNMENT:

Read up fats and oils.