UNIT : CHEMISTRY II

NAME : OKOTH NESTER.

REG. NO : ENE211-0035/2022.

DEPARTMENT : ELECTRICAL AND ELECTRONICS

ENGINEERING.

SCHOOL : ELECTRICAL,ELECTRONICS,AND INFORMATION

ENGINEERING

LECTURE : DR. ONDITI.

DATE : 23\02\2023.

TOPIC : CARBOXYLIC ACIDS

 EXPERIMENT 1: REACTIONS OF CARBOXYLIC ACIDS.

OBJECTIVES OF THE EXPERIMENT

1. To find out how carboxylic acid reacts with other reagents such as;
 Sodium hydrogen carbonate
 Concentrated sulphuric (iv) acid
 Iron (iii) chloride solution
 Ammonical silver nitrate

INTRODUCTION
A carboxylic acid is an inorganic compound containing carboxylic functional group. They may occur
naturally or synthetically manufactured by humans. They have a general formula of R-COOH, Where
COOH denotes the carboxylic group. Upon deprotonating, carboxylic acids yield a carboxylate anion with
the general formula R-COO–, which can form a variety of useful salts such as soaps. This type of organic
compounds can be obtained by different routes, some carboxylic acids, such as citric acid, lactic acid or
fumaric acid are produced by fermentation, and most of these types of carboxylic acids are applied in
the food industry

In this carboxyl group, there exists a carbon which shares a double bond with an oxygen atom and a
single bond with a hydroxyl group.

The first four carboxylic acids derived from alkanes are methanoic acid (HCOOH), ethanoic acid
(CH3COOH), propanoic acid (C2H5COOH), and butanoic acid (C3H7COOH).

Physical properties

Carboxylic acids are higher boiling liquids than aldehydes, ketones and even alcohols of comparable
molecular masses.

Aliphatic carboxylic acids up to nine carbon atoms are colorless liquids at room temperature with
unpleasant odors. The higher acids are wax like solids and are practically odorless due to their low
volatility.

The solubility decreases with increasing number of carbon atoms. Higher carboxylic acids are practically
insoluble in water due to the increased hydrophobic interaction of hydrocarbon part.

Benzoic acid, the simplest aromatic carboxylic acid is nearly insoluble in cold water.

Carboxylic acids are also soluble in less polar organic solvents like benzene, ether, alcohol, chloroform,
etc.

Carboxylic acid molecules are polar due to the presence of two electronegative oxygen atoms.
They also participate in hydrogen bonding due to the presence of the carbonyl group (C=O) and the
hydroxyl group.

When placed in non-polar solvents, these compounds form dimers via hydrogen bonding between the
hydroxyl group of one carboxylic acid and the carbonyl group of the other.

The solubility of compounds containing the carboxyl functional group in water depends on the size of
the compound. The smaller the compound (the shorter the R group), the higher the solubility.The
boiling point of a carboxylic acid is generally higher than that of water.

These compounds have the ability to donate protons and are therefore Bronsted-Lowry acids.They
generally have a strong sour smell. However, their esters have pleasant odours and are therefore used
in perfumes.A carboxylic acid can be reduced to an alcohol by treating it with hydrogen to cause a
hydrogenation reaction.Upon reaction with alcohols, these compounds yield esters.

Carboxylic acids are defined as weak acids, meaning that in a neutral aqueous solution, they do not fully
dissociate to create H+ cations. Hydrogen bonds are formed between the individual molecules of the
acid and water molecules. That’s why They partially ionise to give H+ and RCOO−. Therefore they are
called weak acidsCompared with mineral acids such as hydrochloric, perchloric, nitric, and sulphuric
acids, the carboxylic acids, CH3 (CH2) nCO2H, are weak. The extent of dissociation in aqueous solution is
relatively small, the acidity constants, K ,

Even though the carboxylic acids are weak acids, they are many orders of magnitude stronger than the
corresponding alcohols, CH3(CH2)nCH2OH . Thus the Ka of ethanoic acid, CH2CO2H , is 1011 times
larger than that of ethanol, CH3CH2OH .

The acidity of the carboxyl group arises, at least in part, from the polar nature of the carbonyl group, the
polarity of which can be ascribed to contributions of the structure

Acidity (Reactions with metals and alkalies): Carboxylic acids dissociate in water to give resonance
stabilized carboxylate anions and hydronium ion.

Formation of anhydride: Carboxylic acids on heating with mineral acids such as H2SO4 or with P2O5 give
corresponding anhydride.

Esterification: Carboxylic acids are esterified with alcohols or phenols in the presence of a mineral acid
such as concentrated H2SO4 or HCl gas as a catalyst.

Reactions with PCl5, PCl3 and SOCl2: The hydroxyl group of carboxylic acids, behaves like that of
alcohols and is easily replaced by chlorine atom on treating with PCl5, PCl3 and SOCl2.

Thionyl chloride (SOCl2) is preferred because the other two products are gaseous and escape the
reaction mixture making the purification of the products easier.

Reaction with ammonia: Carboxylic acids react with ammonia to give ammonium salt which on further
heating at high temperature give amides. For example:

Reduction: Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride or better with
diborane.
Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium salts are
heated with soda lime (NaOH and CaO in the ratio of 3 : 1). The reaction is known as decarboxylation.

Halogenation: Carboxylic acids having an α-hydrogen are halogenated at the α-position on treatment
with chlorine or bromine in the presence of small amount of red phosphorus to give α-halo carboxylic
acids. The reaction is known as Hell-Volhard-Zelinsky reaction.

Ring substitution: Aromatic carboxylic acids undergo electrophilic substitution reactions in which the
carboxyl group acts as a deactivating and meta-directing group. They however, do not undergo Friedel-
Crafts reaction.

Uses of Carboxylic Acids

Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries.

Ethanoic acid is used as solvent and as vinegar in food industry.

Hexanedioic acid is used in the manufacture of nylon-6, 6.

Esters of benzoic acid are used in perfumery. Sodium benzoate is used as a food preservative.

Higher fatty acids are used for the manufacture of soaps and detergents.

PROCEDURE
1. Place 2g of sodium hydrogen carbonate in a test tube. Methanoic acid was thereafter added.
The observations were made. The experiment was there after repeated using ethanoic acid or
acetic acid and results were recorded.
2. A neutral iron (iii) chloride solution was made by adding dilute ammonia (2M) solution to cm 3 of
iron (III) chloride solution until a precipitate appears. The original iron (III) chloride solution was
added until the precipitate just disappeared. 5 drops of methanoic acid was placed in a test
tube. Dilute ammonia (2M) solution was added until just its alkaline and it was boiled to
remove excess ammonia. 5 drops of neutral iron (III) chloride solution was added later. The
observations were made. The experiment was there after repeated using ethanoic acid or acetic
acid and results were recorded.
3. 1 ml of methanoic acid was placed into a test tube.1 cm 3 of concentrated sulphuric acid was
added and warmed. The gas evolved was thereafter tested with a lighted splint.
4. 0.5 ml of methanoic acid was placed into a test tube.1 cm 3 of dilute sulphuric (vi) was added and
was warmed gently.1 percent of potassium manganite(vii) was added drop wise and noted if
potassium manganite(VII) decolorizes. The experiment was there after repeated using ethanoic
acid or acetic acid and results were recorded.
5. Place 1cm3 of ammonical silver nitrate solution that was prepared .drops of methanoic acid were
added and the observations were noted. The experiment was there after repeated using
ethanoic acid or acetic acid and results were recorded.
 APPARATUS
1. Dry test tubes
2. Splints [Lit during the experiment]
3. Heat source[burner]

REAGENTS
 Solid sodium hydrogen carbonate
 Methanoic acid
 Neutral iron (iii) chloride solution
 Dilute ammonia solution
 Concentrated sulphuric (vi) acid
 Dilute sulphuric( vi) acid
 Potassium manganite(vii) solution
 Amonnical silver bromide

TABLE OF RESULTS

METANOIC ACID ETHANOIC ACID

1. Effervescence is produced. Effervescence is produced
A colorless solution is formed A colorless solution is formed

2 there is formation of a red brown solution

3 Effervescence of a colorless gas that extinguishes a lighted splint is produced
4 Acidified Potassium manganate(vII) decolorizes.
5.Formation of a white precipate No silver layer formed
Formation of a silver layer

DISCUSSION OF THE RESULTS AND POSSIBLE ERROR ANALYSIS.

1. Sodium hydrogen carbonate: RCOOH + NaHCO3 → RCOO-Na+ + CO2 + H2O.
Carboxylic acid also gives salt when subjected to reaction with metal carbonates. For
example, when acetic acid is subjected to reaction with sodium carbonate, the products
formed will be sodium acetate, carbon dioxide and water. The salt formed will be same as
that formed in reaction of acetic acid with simple metal.
2. Anhydrous iron (III) chloride reacts with pure carboxylic acids RCOOH [where R = C2H5, n-
C3H7, CH2Cl, CHCl2 and CCl3] at low temperature to yield Fe2Cl5 (OOCR)·nRCOOH [n = 3
 when R = C2H5 and n-C3H7 and n = 2 when R = CH2Cl, CHCl2 and CCl3] and
[Fe3O(OOCR)6(H2O)3][FeCl4] at about 70–80°C.
3. The presence of a strong acid (like sulfuric acid), carboxylic acids and alcohols will react in
an esterification reaction, producing an ester and water.
4. Potassium permanganate (KMnO4) is a very strong oxidant able to react with many
functional groups, such as secondary alcohols, 1, 2-diols, aldehydes, alkenes, oximes,
sulfides and thiols. Under controlled conditions, KMnO4 oxidizes primary alcohols to
carboxylic acids very efficiently.
5. Carboxylic acid reduces ammoniacal silver nitrate solution to silver, carbon dioxide. Adding
the ammonia to the silver nitrate solution makes the silver ion less susceptible to
reduction, which produces silver in a more controlled manner. The half-equations indicate
that ammonia forms a complex with the silver ion, which is more difficult to reduce than
the silver ion.

CONCLUSIONS.
1. Carboxylic acid reacts with sodium hydrogen carbonate, a colourless carbon (IV) oxide is
evolved with a brisk effervescence .A colourless solution of sodium acetate is also formed in the
process.
2.
3. Carboxylic acids ( Methanoic acid)when reacted with sulphuric (VI) acid and warmed, it
decomposes and evolve carbon monoxide which on exposure to air it is oxidized to carbon (VI)
oxide. The also produce esters in the process if alcohols are added.
4. The reduction properties of carboxylic acid can be demonstrated using;


REFERENCES.

1. Https//byjus.com.
2. Https//www.vedantu.com.
3. https.//Scribd information’s. Com.
4. Chemistry laboratory manual for first years notes.

5. https://en.m.wikipedia.org.

6. https://www.chemedx.org.