TOPIC 9

CARBOXYLIC ACID &

IT’S DERIVATIVES

R
LECTURE NOTES
CHEMISTRY
SK025
BY NURNASUHA HASHIM
@nurnasuhashim
 10.1 INTRODUCTION
10.2 NOMENCLATURE

10.1 Introduction
Structure of Carboxylic Acids:
O
General Formula:CnH2nO2
Functional group: carboxyl R C OH

10.2 Nomenclature
Step 1:
Find the longest parent carbon chain containing the Carboxyl group.
Step 2:
Name the compound as alkane, drop ‘e’ in alkane and add ‘oic acid’

O
a) IUPAC name : methanoic acid
Common name : Formic acid
methanoic acid
b) IUPAC name : ethanoic acid
HC OH
Common name : Acetic acid
O
c) IUPAC name : propanoic acid
Common name : Propionic acid H3C C OH ethanoic acid

d) IUPAC name : butanoic acid

Common name : Butyric acid
O
H2 propanoic acid
e) IUPAC name : pentanoic acid
Common name :Valeric acid H3C C C OH

O
H2 H2 H2
H3C C C C C OH
pentanoic acid

@nurnasuhashim
 10.2
NOMENCLATURE

More Examples

a)
H3
C O
H
HC C C
H3C C C OH
H H2 O
a)
5-methyl-3-hexenoic acid
OH
b)
cyclopentanecarboxylic acid
H2 O
C C OH b)
H3C C H C
H2 OH
O
2-cyclohexylpentanoic acid

• A cyclic carboxylic acid is named as cycloalkanecarboxylic acid.

• The C atom which is attached to —COOH is numbered as C1
3,3-dimethylcyclohexanecarboxylic ac
O c) O
a)

OH OH

cyclopentanecarboxylic acid cyclopentenecarboxylic acid

O
b)

OH

3,3-dimethylcyclohexanecarboxylic acid
c) O

OH
@nurnasuhashim
 10.2
NOMENCLATURE

• If there are two COOH groups, the compound will be named as ‘alkanedioic acid’

H O HH
C
H2
2 2 HC
2 OH
HO CC CC C OH
C CH C
O H2 2 O
O O
pentanedioic acid
pentanedioic acid
• If there are more than one functional groups, -COOH takes priority over the others
OH
OH
NH OH O
NH2 2OH O
5-amino-3-hydroxyhexanoic acid
5-amino-3-hydroxyhexanoic acid

10.3
Physical
properties
A. Boiling Point
The BP of carboxylic acid is higher than alcohol, ketone/aldehyde (with similar
Mr):
H O
Compound Formula Mr b. pt. (°C) O C R
ethanoic acid CH3COOH 60 118
1-propanol C3H7OH 60 97 R C O
propanal C2H5CHO 58 49
O H
BP of carboxylic acid is the highest is because:
a.It exist as a stable dimer that form intermolecular Hydrogen bond
Dimerisation of carboxylic acid
b. The geometry of the carboxyl groups allows for the formation of stronger hydrogen bonds per
molecule
c. More energy is needed to overcome the IMF

Exercise 1
Arrange ethanoic acid, butane and propanol in ascending order of boiling point.
Explain.

Solution
•Both ethanoic acid and butanol can form hydrogen bonding
•BUT, ethanoic acid has the highest bp due to the ability of the compound to form dimer
•Thus, ethanoic acid form stronger H-bonds
•More energy needed to overcome strong intermolecular forces between molecules

@nurnasuhashim
 10.3
Physical
properties
Exercise 2
Arrange ethanoic acid, propanoic acid and pentanoic acid in ascending order of boiling point. Explain.

Solution
All compounds has carboxyl group – CANNOT USE DIMER AS YOUR ANSWER
•Pentanoic acid has higher bp compared to the others
•It has the highest molecular weight, thus molecular size
•The greater the molecular size, the stronger the Van Der Waals forces
•More energy needed to overcome the intermolecular forces

B. Solubility in Water
Carboxylic acids are soluble in water due to the formation of hydrogen bonding between the water
molecules and carboxylic acid molecules
•Carboxylic acids having < 5C are soluble in water
•Carboxylic acids having > 5C are insoluble in water because the non-polar alkyl portion is too large to
dissolve in water
•Aromatic carboxylic acids are insoluble in water due to the huge aromatic ring
(hydrophobic area)

Exercise 3
Compare the solubility of the carboxylic acids with molecular formula C5H10O2.

Solution a) b)
•All the molecules have the same number of carbon
OH OH
•But, the size of hyrophobic area is different
•____ has the smallest hydrophobic area O O
•Thus, it is most soluble in water

c) d)
OH OH

O O
C. Solubility in Non-Polar solvent
Carboxylic acids are soluble in non polar solvent such as benzene due to the van Der
Waals forces between the benzene and alkyl group of carboxylic acids

D. The acidity of carboxylic acid

Acidity : how easy your H+ to be released
: how stable your ion produces
Measurement of ACIDITY:
•The stronger the acid, the easier for it to releases hydrogen ions to the water
molecules

@nurnasuhashim
 10.3
Physical
properties
Resonance effect
Carboxylic acid is relatively weak acid, however, it is STRONGER when compared to phenol and alcohol

Electron delocalisation of Phenoxide ion:

O- O O O

electron are delocalised into the benzene ring

O O-
Electron delocalisation of Carboxylate ion:

C C
R O- R O
electron are delocalised onto 2 oxygen
atom, which is electronegative atom
@nurnasuhashim
 10.3
Physical
properties
Inductive effect
(A) ELECTRON WITHDRAWING GROUP (EWG)
An electron withdrawing group that attached to a carboxylate ion will decrease the density of negative charge,
thus stabilises the carboxylate ion
•Examples of EWG: Halogen @ Electronegative atoms
•EWG decrease the electron density of –OH
•Thus the O-H bond becomes weaker and H+ can be easily transferred
O
•Electron-withdrawing group increase the acidity of carboxylic acid
EWG C O
(B) ELECTRON DONATING GROUP (EDG)
An electron donating group, will destabilises the carboxylate ion and decrease acidity
O
EDG C O
Exercise 4
Compare the acidity of CH3CHClCOOH and CH3CH2COOH

Solution:
•The inductive effect of Cl is an electron withdrawing group, which decrease electron density of –OH
•Thus the O-H bond becomes weaker and H+ can be easily donated
• CH3CHClCOOH is to be more acidic

Exercise 5
Compare acidity of :
CH3CHF-COOH and CH3CHCl-COOH

Solution:
•Both F and Cl are electron withdrawing group
•The electronegativity of F >Cl
•The electron density of –OH in CH3CHF-COOH is decrease thus the –OH bond is weaker than in
CH3CHCl-COOH
•Therefore, H+ is easily donated
•Acidity : CH3CHF-COOH > CH3CHCl-COOH

Exercise 6
Compare the acidity of: CH3C(Cl)2-COOH and CH3CHCl-COOH

Solution
•CH3C(Cl)2-COOH contains two Cl atoms that make the bond of –OH weaker than CH3CHCl-COOH
(with only one Cl atom)
•Thus, H+ is easily donated
•Acidity : CH3C(Cl)2-COOH higher CH3CHCl-COOH

@nurnasuhashim
 10.3
Physical
properties
Inductive effect
Exercise 7
Compare the acidity of:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH

Solution
•The distance between Cl atom and carboxyl group in CH3CH2CHCl-COOH is closer compare to in
CH2ClCH2CH2-COOH
•The –OH bond in CH3CH2CH(Cl)COOH is weaker than in CH2ClCH2CH2-COOH
•so H+ is easily donated
Acidity : CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH

Exercise 8
Compare the acidity of: CH3COOH and CH3CH2COOH

Solution
•R is an electron donating group
•The size of –R group in CH3CH2COOH is bigger than in CH3COOH, so CH3CH2- is a stronger EDG than
CH3-.
•The electron density of –OH in CH3CH2COOH increase
•H+ is dif cult to be donated

Try Yourself
Draw the structure of the following compounds and arrange them in the order of increasing acidity. Explain.
a) Benzoic acid
b) 2-methylbutanoic acid
c) m-methoxyphenol
d) 2,3-dichloropropanoic acid

@nurnasuhashim
fi
 10.4
Preparation
PREPARATION
Carboxylic acids
A. Oxidation of primary alcohol and aldehyde-Recap chapter hydroxy and carbonyl
compounds

B. Oxidation of alkyl benzene-Recap chapter benzene and it’s derivatives

C. Hydrolysis of Nitrile
1o haloalkane can be used to produce carboxylic acid:

D. Carbonation of grignard reagent-Recap chapter haloalkane

10.5
CHEMICAL CHEMICAL PROPERTIES
PROPERTIES
Carboxylic acids
A. NEUTRALISATION
Carboxylic acids are acidic, it can react with base such as NaOH (aq) or KOH to give metal carboxylate salts:

O O
C OH C O-Na+

NaOH H2O

Other base: Na2CO3/NaHCO3

O O
Na2CO3
H3C C O-Na+ H2O CO2
H3C C OH
O
Na2HCO3 H3C C O-Na+ H2O CO2

@nurnasuhashim
 10.5
CHEMICAL CHEMICAL PROPERTIES
PROPERTIES
Carboxylic acids
b. Reaction with electropositive metal
Carboxylic acid react with metal to form carboxylate salt:

O O
C OH C O-Na+

Na 1/2 H2

O O
Mg 2 Mg 2+
H3C C O -
H3C C OH

C. Formation of acid chloride

a) O O
H SOCl2 H
H3C C C OH H3C C C Cl HCl SO2
C C
H3 H3

b) O O
H PCl5 H
H3C C C OH H3C C C Cl HCl POCl3
C C
H3 H3

c) O O
H PCl3 H
H3C C C OH H3C C C Cl HCl H3PO3
C C
H3 H3

@nurnasuhashim
 10.5
CHEMICAL CHEMICAL PROPERTIES
PROPERTIES
Carboxylic acids
d. Esterification
Carboxylic acids react with alcohols in the presence of mineral acid catalyst to produce esters

O H3O+ O
H3C C OH HO C CH3 H3C C O C CH3 H2O
H2 H2

E. Formation of acid anhydride

2 carboxylic acids can react together to form acid anhydride:
O O O O
P2O5
H3C C OH HO C CH3 H3C C O C CH3 H2O

Acyl chloride can also react with carboxylic acid (in pyridine) to produce acid anhydride:
O O O O
H3C C OH Cl C CH3 H3C C O C CH3 HCl

f. Formation of amide
Reaction of carboxylic acids with an ammonia or amine will give amide:
a) O O
H3C C OH NH3 H3C C NH2 H2O
ammonia

O O
b) H
H3C C OH H2N CH3 H3C C N CH3 H2O
primary
amine
O O CH3
c)
H3C C OH CH3 H3C C N CH3 H2O
HN CH3
secondary
amine

@nurnasuhashim
 10.5
CHEMICAL CHEMICAL PROPERTIES
PROPERTIES
Carboxylic acids
g. Reduction of methanoic acid WITH KMnO4
On treating formic acid with strong oxidising agents like KMnO4 and dichromates, it gets
oxidized to CO2 and water
O KMnO4, H
+

CO2 H2O Mn2+

H C OH
observation:
purple colour decolourise

g. Reduction of methanoic acid WITH Tollens’ reagent

O Ag(NH3)2+, OH-
H C OH CO2 H2O Ag
observation:
silver mirror precipitate formed

@nurnasuhashim
 10.5
CHEMICAL CHEMICAL PROPERTIES
PROPERTIES
Carboxylic acids
g. Reduction of methanoic acid WITH KMnO4
On treating formic acid with strong oxidising agents like KMnO4 and dichromates, it gets
oxidized to CO2 and water
O KMnO4, H
+

CO2 H2O Mn2+

H C OH
observation:
purple colour decolourise

g. Reduction of methanoic acid WITH Tollens’ reagent

O Ag(NH3)2+, OH-
H C OH CO2 H2O Ag
observation:
silver mirror precipitate formed

@nurnasuhashim