ISOMERISM IN ALKANOIC ACIDS

Alkanoic acid with four or more Carbon atoms exhibit structural isomerism. For example two
alkanoic acid have the molecular formula C4H3O2
C - C –C-C-OH and C – C- C-OH
2-methlpropanoic acid.

NATURAL SOURCES OF CARBOXYLIC ACID

A few naturally occurring aliphatic carboxylic acids and their sources areas follows;

Censorphic acid Sources

Methanomic acid Ants and bees
Ethanoic acid Vinegar
Butanoic acid Butter
Hexanoic acid Fats of goat milk
Palmitic acid Vegetable, fats and oils
Stearic acid “ “
Citric acid Citrus juice (lemons)
Terranic acid Grape juice and sours

PHYSICAL PROPERTIES OF ALKANOIC ACID

i. Alkanoic acids with 1 to 3 carbon atoms are colourless liquid with sharp odours of
vinegar.
ii. Liquid alkanoic acids show a regular increase in boiling point and viscosity as the
relative molecular mass increases.
iii. Among the isomeric alkanoic acids, boiling point decreases as branching increase.
iv. Lower members of the series are miscible with water to give weaker acidic solutions.
Miscibility is due to the formation of hydrogen bonds between water molecules and
the carboxylic group.
v. They are miscible with (or soluble in) alkanols, propanoic acid esters.
vi. The boiling point of an alkanoic acids much higher than the corresponding alkanol
with the same number of carbon. For example propanoicacid boils at 141OC, while
propanol boils at 980C. the reason being that an alkanoic acid has more opportunities
of form intermolecular hydrogen bonding than alkanol. Hence, intermolecular
hydrogen bonding in alkanoic acids are more exterwaive and stronger than those in
the corresponding alkanols.
vii. Diners formation accounts for the rather high boiling points of the carbon acids.

CHEMICAL PROPERTIES OF ALKANOIC ACIDS (ACIDIC PPT)

The covalent bonds in carboxyl group are polar, thereby leading to the formation of partial
charges R- C
They are weakly acids.
(a). An alkanoic acid, being a weaker electrolyte, is only slightly ionized in water to give
hydroxonium ions, H3O+
RCOOH + H2O  RCOO- + H3O+
Carboxylite
Ions
(b). neutralization (Rx N with NaOH)
(i). RCOOH + NaOH RCOONa+ +H2O
(ii). Reaction fo propanoic acid with aqueous ammonia produces a solution of ammonium
propanoic
CH3CH2COOH(aq) + NH3(aq)  CH3CH2COONH4+
(c). Reaction with Carbonate and hydrogen Carbonate in both cases, a salt is formed together
with carbon(IV) oxide and water.
(i). 2CH3COOH +NaCO3  2CH3COONa + H2O +CO2
(ii). CH3COOH +NaHCO3 CH3COONa + H2O + CO2
(d). It attacks electropositive metals e.g. 2CH3COOH(aq) + Mg(s) (CH3COO)2Mg(s) +H2
2RCOOH + Zn  (RCOO)2Zn+ H2
(e). Esterification: A carboxy acid reacts wit an alcohol in the presence of Conc. H2S04 as a
catalyst to produce ester and water only e.g. CH3COOH(aq) + HOC2HS(l)  CHCOOC2H510 +
H2O(l).
USES OF ALKANOIC ACID
1. Ethanoic acid is used as a solvent in organic reactions and in acid base.
2. It is used in the consulation of rubber latex (3). It is used as an emulsion for paints and
adhesive
4. vinegar is used for preserving food
5. Benzoic acid is used in the manufacture of disinfectants. 6. It is also used as a constituent
of frier’s balsam/ applied to the skin to alleviate raghes, sin sores and itching.
 >>>>>>>>>>>>
2. Combustion in oxygen: Alkanric acids burn-oxygen to produce CO2 and water vapour
CH3COOH(l) +2O2 2CO2 + 2H2O(s).
3. Reduction fo alkanric acids when an alkanoic acid is treated with a reducing agent such
as Lialhy, the corresponding primary alkanoic is obtain e.g. CH3COOH(l) + 2(H) 
CH3CH2OH.
4. Reaction with phosphorus (v) chloride to produce hydrogen chloride gas and the
corresponding alkanoyl chloride (acid chloride) e..g CH3COOH + PCl5  CH3COCl +
POCl3(s) + HCL. This reaction is used to confirm the presence of hydroxyl group- OH in
organic compounds as in alkanols acids.
ALKANOATE
Source: Esters with high relative molecular masses are found in animal and vegetable fats and
oils, while simple ester are present in fruits of plants and are responsible for the natural sweet
smell of flowers.
Homologous Series: Esters are a group of organic compounds formed when an alkyl group, R’
replaces the ionizable hydrogen atom in a carboxylic acid, RCOOH to form RCOOR1.
They are usually written as R – C – OR1 or RCOOR1 where R1 may be a hydrogen atom or an
alkyl group. The functional group in an ester is the alkanoace group, written as –C –O-R1 or
COOR1, R- O-C- or R1COOC.
For Ester is formed from the reaction between a Carboxylic acid and alcohol using Conc. H2S04
as a catalyst. A water molecule is always eliminated.
R-COOH + H-O-R - RCOOR1 + H2O
(Acid) Alcohol Ester
The general formula for alkanorates is CnH2nO2; where n = 2,3,4 etc. the first member
corresponds to n= 2 and has a molecular formula C2H4O2, with a structural formula written as
HCOOCH3.
The second member corresponds to n =3, with the molecular formula C3H6O2. It is structure is
either 1 or 2 carbon for the acid or alkanol, which can be written as;
HCOOCH2CH3 or CH3COOCH3 respectively.
IUPAC NOMENCLATURE
The name of an alkanrate is obtained from the responding alkanol and alkanoic acid from where
it is formed. The alkanol port then linked to the acid portion RCOO-, named alkanoate. From the
name of an ester, it is very easy to name the alkanol and the alkanoic acid from where it has been
forms.

Formula IUPAC Name of Alkanoic acid Alkanol

Ester
1. HCOOCH3 Methanoic Methanol
2. CH3COOCH2CH3 Ethanoic acid Ethanol
Ethylethanonate
3. HCOOCH2CH3 Methanoic acid Esthanol
4. CH3CH2COOCH3 Proponoic acid Methanol
Methylproponate

Example
1. Write the general molecular formula for the alkanoate, and give the molecular and
empirical formulae of third homologous.
2. To which group does the compound with the following structure belong? HC-C-O-CH3
(alkanoate).
3. The alkanoate CH3CH2COOC2H5 is a product of the reaction between _ and _ (Propanoic
acid and ethanol).
4. Name the compounds which will react together to give CH3(CH2)3COOCH3).
5. (a). Write the structural formula propylmethanoate.
(b). Give the name of the compound ‘a’ above are interchanged.

ISOMERISIM IN ALKANOATES
STRUCTURAL ISOMERISM

Alkanoates with three or more carbon atoms exhibit structural isomerism. For example;
1. C3H6O2 presents two alkanoates.
2. C4H8O2 represent four alkanoate (i). Propylmethanate (ii) ethlethanate (iii).
methlpropanoate acid 1-methlyethl-methanoate HC-O-C-H-CH3.
Lab preparation of ethylethanoate (Ester)
Ester are generally prepared by the reaction between carbonxylic acid and an alcohol in the
presence of a numeral acid as a catalyst. The reaction is called esterification. The general form of
the reaction is R-COOH +H-O-R1 - RCOOR1 + H2O.
Acid alcohol ester water
Esterification is similar to neutralization. However, esterification reaction is reversible and acid
catelized.
 Preparation of ethlethanoate
Esthlethanoate can be prepared by efluxing a mixture of equimolar amount of ethanol and
ethanoic acid in the presence of Conc. H2SO4 at about 1500C. the resulting mixture is shaven
with conc. Sodium trio-oxocarbonate(iv) to remove the excess acid, and the mixture separated.
The organic larger is then place in a simple distillation apparatus and the fraction that distal at
about 800C is a mixture of ethlylethanoate and ethanol. Pure ethlethanoate is obtained by
shaking the mixture with a saturated solution of calcium chloride, to remove the ethanol and the
mixture separated by the use of a separating funnel.
The upper larger is dried over fused calcium chloride and fin-alhydrdistilled to obtain pure
ethlethanoate.
CH3COOH + HO-CH2-CH3 - - CH3COO-CH2CH3 +H2O
In the reaction, the conc. H2S04 acts as a catalyst as well as a dehydrating agent.
Physical properties of ethlethanoate
1. It is colourless with a characteristic fruity smell and boils at 77OC.
2. It is slightly higher than water and slightly miscible with it to give a neutral solution
3. It is miscible with organic solvents such as ethanol, benzene and ethanoic acid.
4. It is a none-electrolyte.
Chemical reaction of ethlethanoate
1. Acid hydrolysis: When a mixture of an alkanoate and water is refluxed in the presence of
con. H2S04 at about 1500C, the corresponding alkanol and alkanoic acid and obtained
g.e. CH3COOCH2CH3 +H2O -- - CH3COOH + CH3OH.
2. Alkaline Hydrolysis: When alkanoate ester is refluxed with aqueous NaOH or KOH, it is
hydrolyzed to give the salt of alkanoic acid and an alkanol.
RCOOR1 + NaOH  RCOONa + R1OH.

Unliked acid hydrolysis, alkaline hydrolysis of an ester is not reversible.

3. Reaction with Ammonia- Ammonolysis

When a mixture of an alkanoate an aqueous ammonia is refluxed, the corresponding
amide and alkanol are produced e.g.
CH3COOCH2CH3 + NH3  CH3CONH2 + CH3Cl +2OH.

Uses of alkyl alkanoate

1. Production of soaps
2. Used as flavouring agent
3. Used as plasticizers
4. They are also used as solvents
5. They are used for making perfumes/cosmetics.