CHEMISTRY UPPER 6

ORGANIC CHEMISTRY
CHAPTER 7 : CARBOXYLIC ACID
& ITS DERIVATIVES
7.1 Nomenclature

Organic acid containing one or more carboxyl (COOH) groups as
functioning group

Carboxylic acid has the general formula of CnH2n+1COOH or sometimes

CnH2nO2.

The naming of carboxylic acid end with –oic acid.

Methanoic Ethanoic Propanoic Butanoic Pentanoic Hexanoic

Name
acid acid acid acid acid acid

Structure HCOOH CH3COOH C2H5COOH C3H7COOH C4H9COOH C5H11COOH

7.1.1 Naming carboxylic acid

1. Find the longest chain that attached to –COOH and name them
accordingly. The C in COOH is C1.
2. Identify the group that attached to the parent chain and name them
accordingly
3. Give the numbering of the group that attached accordingly
2-methylbutanoic acid 6-chloro- 2-ethyl-3-methylpentanoic 3-hydroxy-3-
4,4-dimethylhexanoic acid acid methylpentanoic acid

3,5-dibromobenzoic acid 2-phenylbutanoic acid But-2-enedioic acid

Propanedioic acid
or malonic acid

3-methylbutanoic acid 3-ethyl-3- 2,3,4- Pentandioic acid

methylpentanoic acid trimetylpentanoic acid
HOOCCH2CH2CH2COOH

Practice : Draw all isomers for carboxylic acid with formula C3H7COOH
6.2 Physical properties
(A) Boiling point – The trend of the boiling points of may be caused by many
factors
a) Factors of the number of carbon atom
HCOOH CH3COOH C2H5COOH C3H7COOH

Boiling point increase

Explanation : When going down to homologous series, the boiling point increase.
This is due to the increase in relative molecular mass, which increase the weak Van
Der Waals forces causing boiling point increase.
 Boiling point of different functioning group

propanol Chloroethane
Compound CH3COOH Butane (C4H10)
(C3H7OH) (C2H5Cl)
RMM 60 60 58 64.5
Boiling
78 117 4.4 21
point (oC)
Explanation : Ethanoic acid has the highest boiling point among these organic
compound as it form dimer among itself using 2 hydrogen bonds. Propanol which has
same molecular mass, contain only 1 hydrogen bond, has a lower boiling point.
Chloroethane has higher boiling point compare to butane as it is a polar molecules
which form permanent dipole while butane is a non-polar molecules which form
induced dipole.

Solubility of Carboxylic Acid

HCOOH CH3COOH C2H5COOH C3H7COOH C4H9COOH

Solubility decrease
Explanation : methanoic, ethanoic and propanoic acid are completely miscible in water
as they can form hydrogen bond with water. However, the LONGER the ALKYL
GROUPS ATTACHED, molecule become MORE HYDROPHOBIC. As a result,
HYDROGEN BOND BECOME LESS SIGNIFICANT and cause the solubility decrease.
(C) Acidity of carboxylic acid

Carboxylic acid is considerably weak acid since it has a small pKa value. It
undergoes partial dissociation

[ RCOO − ][ H 3O + ]
Ka = pK a = − lg K a
[ RCOOH ]

Name Methanoic acid Ethanoic acid Propanoic acid

Structure HCOOH CH3COOH C2H5COOH
pKa 3.75 4.76 4.90

Name Benzoic acid 2-chloro-ethanoic acid 2-methyl ethanoic acid

Structure C6H5COOH CH2(Cl)COOH CH2(CH3) COOH
pKa 4.19 4.42 4.86

Carboxylic acid is generally a stronger weak acid than alcohol, since the
charge delocatisation at carboxylate ion makes the ion formed become
more stable as it formed resonance structure due to mesomeric effect,
hence increase the stability of carboxylate ion which result the
equilibrium favour to right position (favour to position of donate proton)

Similar to alcohol, carboxylic attached to an alkyl has lower acidity

compare to carboxylic acid attached to a phenyl. This is due to alkyl is
an electron donating group, while a phenyl is an electron withdrawing
group
 Carboxylic acid Explanation

Carboxylic acid dissociate in water according to the equation

R-COOH + H2O R-COO- + H3O+
Alkyl group, which is an electron donating group, donate electron to O and
caused the electron density of O in R–OH increase. As a result, O is more
readily to accept proton.
Acidity decrease in the order, where
Methanoic acid > Ethanoic acid > Propanoic acid
This is due to, longer the alkyl chain, stronger the electron donating effect,
equilibrium favours more to left.

Benzoic acid dissociate in water according to the equation

C6H5–COOH + H2O C6H5–COO- + H3O+
The phenyl group is an electron-withdrawing group, which withdrawn the
electron density from partially negative charge, δ−, from O making O less
readily to accept proton. As a result, O is more readily to donate proton
which makes equilibrium favour more to right.
Benzoic acid

Since CH3 is an electron donating group to benzene ring, it will increase the
electron density in benzene ring, hence increase the polarity of -O-H bond in
the benzene ring. As a result, H is harder to dissociate, hence caused the
equilibrium to shift slightly to the left, decreasing the acidity of benzoic acid
p-methylbenzoic acid
 Effect of the distance
of electron
withdrawing group
toward acidity of
butanoic acid
Due to inductive effects operate through π bonds and are dependent on distance, the effect of
halogen substitution decreases as the substituent moves farther from the carboxyl. Thus, 2-
chlorobutanoic acid has pKa = 2.86, 3-chlorobutanoic acid has pKa = 4.05, and 4-chlorobutanoic
acid has pKa = 4.52.

Effect of the number of

substituent toward
acidity of ethanoic acid

-Cl act as electron withdrawing group in carboxylic acid. Note that as the number of -Cl
increased, the acidity increased. This can be explained in term of the increment of negative
inductive effect caused by -Cl, which further stabilise the conjugate base formed. As a result,
equilibrium shift to right, increased the acidity.
7.3 Chemical Properties of Carboxylic acid
7.3.1 Preparation of carboxylic acid
Name of Reagent used and
Equation
reaction condition

Acidified KMnO4 or
Oxidation of
acidified K2Cr2O7 +
10 alcohol
heat Propan-1-ol propanoic acid

Acidified KMnO4 or
Oxidation of
acidified K2Cr2O7 +
aldehyde
heat Propanal propanoic acid

Dilute sulphuric
Hydrolysis of
acid H2SO4 + H2O
nitrile
under reflux
2-methylbutylnitrile 2-methylbutanoic acid

Hydrolysis of Dilute HCl / NaOH

ester with heat
7.3.2 Chemical reaction of carboxylic acid

Reagent
Name of
used and Equation
reaction
condition

Alkali, NaOH
or Na2O
Properties
of an acid
-----------
Reaction
Sodium, Na
with alkali,
metal and
metal
carbonate
Sodium
carbonate,
Na2CO3
 Name of Reagent used
Equation
reaction and condition
Alcohol
catalysed by
Esterification
concentrated
sulphuric acid

Phosphorous
pentachloride(P
Formation of Cl5)
acyl chloride @
Thionyl chloride
(SOCl2)

Lithium
Reduction –
aluminium
Formation of
hydride ; LiAlH4
alcohol
with dry ether
(1) Reaction of acid-base : Formation of salts
A. Reaction with base (metal hydroxide and metal oxide)

Like all acid, when carboxylic acid reacts with base, it will form salt and

water
Carboxylic Acid Base Salt Water

CH3COOH NaOH CH3COO–Na+ H2O

CH3CH2COOH K2O CH3CH2COO–K+ H2O

CH3CH2CH2COOH Mg(OH)2 Mg(CH3CH2CH2COO)2 H2O

B. Reaction with metal

When acid react with metal, a colourless gas liberated. This gas will give

“pop” sound when burning splinter is put close to the gas liberated,
indicating ………… gas hydrogen
is released.
Hydroge
Carboxylic Acid Metal Salt
n

CH3COOH Zn Zn(CH3COO)2 H2

CH3CH2COOH Mg Mg(CH3CH2COO)2 H2
C. Reaction with metal carbonate

When acid react with metal carbonate solution, an effervescence is

observed and a colourless released and gas turned lime water chalky,
indicating ………..……… carbongas
dioxide
is released.
Carbon
Carboxylic Acid Metal carbonate Salt Water
dioxide

CH3CH(CH3)COOH K2CO3 CH(CH3)2COO–K+ CO2 H2O

CH3CH2COOH ZnCO3 Zn(CH3CH2COO)2 CO2 H2O

(2) Esterification – Formation of ester

When alcohol reacts with carboxylic acid catalysed by concentrated
sulphuric acid, ester and water is formed. The –H is donated by alcohol
while –OH is given off by carboxylic acid

carboxylic acid alcohol ester

Carboxylic Acid Alcohol Name of ester :

Alkyl carboxylate

Carboxylate ion Alkyl

 Carboxylic Acid Alcohol Ester Water

CH3COOH CH3CH2OH H2O

CH3CH(CH3)COOH CH3CH2CH2OH H2O

CH3C(CH3)2COOH CH3CH(CH3)OH H2O

H2O
(3)Formation of acyl chloride

When carboxylic acid is reacted with a chlorine-rich compound such as
phosphorous pentachloride (PCl5) or thionyl chloride (SOCl2), an acyl chloride is
formed. A white fume of hydrogen chloride is given off as side product.

The reaction take place is a nucleophilic substitution reaction.

Chlorine Side Hydrogen

Carboxylic acid Acyl chloride
Compound product chloride

CH3CH2COOH PCl5 CH3CH2COCl + POCl3 + HCl

CH3CH(CH3)COOH SOCl2 CH3CH(CH3)COCl + SO2 + HCl

CH3CH(CH3)CH2COOH HCl CH3CH(CH3)CH2COCl + H 2O

PCl5 + POCl3 + HCl

(4) Reduction of carboxylic acid : Formation of alcohol

Using strong reducing agent such as lithium tetrahydridoluminate (LiAlH4),
carboxylic acid is readily to reduce to become alcohol.

Reagent : Lithium tetrahydridoaluminate (LiAlH4) under dry ether
dry ether
CH3CH2COOH + LiAlH4   → CH3CH2CH2OH + H2O

CH3CH(CH3)COOH + LiAlH4 dry

 ether

→ CH3CH(CH3)CH2OH + H2O

CH3C(CH3)2COOH + LiAlH4 dry

 ether

→ C(CH3)3CH2OH + H2O

+ LiAlH4 dry
 ether

→
7.3.3 Simple test for carboxylic acid
Differentiate Chemical test Observation & Equation
Positive test : Carboxylic acid
Sodium Effervescence occurs. Gas released turn lime water
carbonate, chalky indicating carbon dioxide is released.
Na2CO3 Eq. : R–COOH + Na2CO3 
R–COO-Na+ + CO2 + H2O
Carboxylic Positive test : Carboxylic acid
acid with Dark red solution is obtained when FeCl3 is added to
other carboxylic acid.
organic Equation :
compound Iron (III) CH3COO- + FeCl3  Fe(CH3COO)3 + 3 Cl-
chloride, FeCl3 red solution
When boiled, the red solution turns to brown
precipitate.
Fe(CH3COO)3 + 2 H2O 
Fe(CH3COO)(OH)2 + 2 CH3COOH
brown precipitate
7.4 Methanoic acid (Common name : formic acid)

Methanoic acid is the first member of carboxylic acid homologous series. Not only
it shows the similar properties of carboxylic acid as proposed earlier, it also
possessed other special properties.

This special properties is due to the of having 2 functioning group at the same
molecule where
Functioning Functioning as
as aldehyde carboxylic acid

Methanoic acid is a strong reducing agent, unlike other carboxylic acid. It is easily
oxidised to form carbon dioxide as shown in the following reaction (can also be its
salt like HCOONa)
Reaction with Observation, Equation and explanation

Observation : White precipitate is 1st formed and eventually turn to

silver
Silver nitrate,
AgNO3
Equation : HCOONa + AgNO3 
HCOOAg (white ppt) + NaNO3
2 HCOOAg  2 Ag (silver) + CO2
Due to the presence of aldehyde as functioning group, it give
positive test to
Tollen reagent (silver complex)
Tollen’s Test
Observation : a silver mirror is observed
Equation : HCOOH + Ag2O 
2 Ag (silver mirror) + CO2 + H2O

Methanoic acid reduce mercury (II) chloride to mercury (I) chloride

(white ppt)
Mercury (II) Equation : HCOOH + 2 HgCl2  Hg2Cl2 + CO2 + 2 HCl
chloride, HgCl2 Under excess methanoic acid, a black precipitate of mercury is
observed
Equation : HCOOH + Hg2Cl2  CO2 + 2 HCl + 2 Hg
Reaction with Observation, Equation and explanation

Dehydration :
When heated with conc. H2SO4, methanoic acid dehydrated and
reaction with
produce carbon monoxide and water
conc.
sulphuric acid, conc. H SO4
Equation : HCOOH 2 → CO + H2O
H2SO4

Acidified As discussed earlier, when methanoic acid dissolved in KMnO4 /

potassium H+, the purple colour of potassium manganate (VII) is decolourised
manganate while carbon dioxide and water is formed
(VII).
KMnO4 / H+ Equation : HCOOH + KMnO4 / H+  CO2 + H2O

Unlike other carboxylic acid, when react with phosphorous

Phosphorous
pentachloride, it will not form acyl chloride
pentachloride,
PCl5
Equation : HCOOH + PCl5  CO + 2 HCl + POCl3
7.5 Ethanedioic acid, H2C2O4 (also known as oxalic acid)

The structure of ethanedioic acid can be described as

It dissolve in alcohol and water but not in organic solvent such as propanone or
ether.

It can be prepare by the following method :
Step 1 : heating sodium methanoate Step 2 : add with sulphuric acid

→ Na2C2O4 + H2SO4 ∆

→
2 HCOONa ∆ Na2C2O4 + H2
H2C2O4 + Na2SO4

Reaction with ethanedioic acid

Reaction with Observation, Equation and explanation

The purple colour of potassium manganate (VII) is reduced to Mn2+
Acidified potassium which is pink colour according to the equation
manganate (VII),
KMnO4 / H+ Equation : 5 C2O42- + 2 MnO4- + 16 H+  2 Mn2+ + 8 H2O + 10
CO2

Similar to methanoic acid, dehydration occur when added to conc.

Concentrated
H2SO4
sulphuric acid,
H2SO4
Equation : H2C2O4 + conc. H2SO4  CO2 + CO + H2O

White precipitate is observed when reacted

Calcium chloride,
CaCl2
Equation : Ca2+ + C2O42-  CaC2O4 (white precipitate)
7.6 Uses of Caboxylic acid

Methanoic acid and ethanoic acid is used in rubber industries to coagulate latex

Ethanoic acid is used as preservative and additive in food industries

Ethanoic acid is used to manufacture ethanoic anhydride

Ethanoic anhydride is used to manufacture aspirin

Benzoic acid is used as preservative. It is also used as an antibacterial and antifungal

agent

Calcium propanoate (react propanoic with calcium hydroxide) is used as preservative in
bread to prevent the growth of mold

Dicarboxylic acid is used mainly in manufacturing synthetic polymer such as nylon
7.7 Carboxylic Acid’s Derivatives

In this Chapter, we’re looking into organic compounds derived from carboxylic
acid. Examples of these compounds are
→ acyl chlorides → esters → amides
7.7.1 Physical properties of carboxylic acid derivatives

The boiling point of a few organic compounds are shown below
Name Molecular structure Molecular mass Boil point (0C)
Ethanoyl chloride CH3COCl 78 51
Ethyl methanoate CH3COOCH3 74 57
Butanal CH3CH2CH2COH 72 76
Butanone CH3COCH2CH3 72 80
Propanamide CH3CH2CONH2 73 213

Propanamide has the highest boiling point among these organic compound as it
contain 2 hydrogen bonds. Butanal and butanone are polar molecule which are held
by permanent dipole – permanent dipole, while ethanoyl chloride and ethyl
methanoate is non-polar which are held by temporary dipole – induced dipole.
7.8 Acyl chloride

Acyl chloride has the general formula of CnH2n+1COCl.

The ending of alkyl group attached to COCl = ~noyl chloride

Acyl chlorides are colourless liquids with pungent smell. They are very reactive
compound

CH3COCl Ethanoyl chloride

CH3CH2COCl Propanoyl chloride

CH3CH(CH3)COCl 2-methylpropanoyl chloride

C6H5COCl Benzoyl chloride
7.8.1 Chemical properties of acyl chlorides

Most of the reaction of acyl chlorides are acylation reaction, where the –Cl is
substitute out easily.

This is due to the negative inductive effect (–I) of the oxygen atom, which cause the
carbon atom become more positively partial charged. As a result, C–Cl carries a
much higher partially positive charge and become more reactive for nucleophilic
attack
 Reagent
Name of
used and Equation
reaction
condition

Hydrolysis Water
propanoyl chloride water propanoic acid

propanoyl chloride ethanol

Esterification Alcohol
ethyl propanoate

Formation of Ammonia of
amide amine
propanoyl chloride ammonia propylamide
(A) Hydrolysis of acyl chloride

Acyl chloride undergoes hydrolysis when react with water to form carboxylic acid.
A white fume of hydrogen chloride is released as side product of the reaction.

Hydrolysis occur vigorously as the –Cl is readily to leave the group. Examples of
reaction

Acyl chloride Water Carboxylic acid HCl

CH3COCl + H2O CH3COOH HCl

CH3CH(CH3)COCl + H2O CH3CH(CH3)COOH HCl

+ H2O HCl
(B) Formation of ester

Acyl choride react with alcohol / phenol at room temperature to form ester. Unlike
carboxylic acid, which required an acidic medium, acyl chloride does not require
an acidic medium.

Similar to the hydrolysis of acyl chloride, a white fume of hydrogen chloride is
released.
Acyl chloride Alcohol Ester HCl

CH3COCl CH3CH2OH CH3COOCH2CH3 HCl

CH3CH2CH2COCl CH3CH2CH2OH CH3CH2CH2COOCH2CH2CH3 HCl

CH3C(CH3)2COCl CH3OH CH3C(CH3)2COOCH3 HCl

When phenol react with benzoyl chloride, NaOH is used.

HCl
(C) Formation of amide

Acyl chloride form amides when reacted with ammonia, primary and secondary
amine
Ammonia /
Acyl chloride Amide HCl
amine

CH3CH2COCl NH3 CH3CH2CONH2 HCl

CH3COCl CH3CH2NH2 CH3CONHCH2CH3 HCl

CH3CH2CH2COCl CH3NH(CH3) CH3CH2CH2CON(CH3)2 HCl

7.9 Ester

Esters are the functional isomerism of carboxylic acid. Similar to carboxylic acid, it
has the general formula of CnH2nO2. In naming ester, the alkyl attached to alcohol
is named where the carboxylic acid is named as its anion. Examples

Methyl propanoate

Ethyl butanoate

Propyl benzoate

Phenyl benzoate

Lower esters are colourless liquid with pleasant fruity odour. Larger esters are
colourless solid.

Small ester such as methyl methanoate or ethyl methanoate is soluble in water.
Most of the esters are insoluble in water but soluble in organic solvent.
7.9.1 Preparation of ester

Name of Reagent used

Equation
reaction and condition

Esterification Alcohol
by carboxylic catalysed by
acid with concentrated
alcohol sulphuric acid

Esterification
by acyl propanoyl chloride ethanol
Alcohol
chloride with
alcohol
ethyl propanoate
7.9.2 Chemical reaction of ester
Name of Reagent used
Equation
reaction and condition

Diluted acidic
solution

Hydrolysis
of ester
Sodium
hydroxide
(NaOH)
Name of Reagent used
Equation
reaction and condition

Reaction ethyl propanoate ammonia

Concentrated
with
NH3
ammonia

propylamide ethanol

Lithium
Reduction tetrahydrido- ethyl propanoate
of ester aluminate
(LiAlH4)
propan-1-ol ethanol
(A) Hydrolysis of ester

Hydrolysis of ester is a reverse reaction of esterification. When ester is
dissolved in diluted acidic solution, it will form back carboxylic acid and
ester.
Ester Water Carboxylic acid Alcohol

+ H2O/ CH3CH2CH2COOH
H+ CH3CH2CH2OH

CH3CH(CH3)CH2COOH
+ H2O/
H+ CH3CH2CH2OH

+ H2O/ CH3CH2COOH
H+ CH3CH(OH)CH3

When ester is hydrolysed under alkaline condition, metal salt is formed
together with alcohol

Example ; when ethyl propanoate is hydrolysed under alkaline condition.

When sodium propanoate is react using acid such as sulphuric acid, the
carboxylic acid formed back.
(B)Formation of amide : reaction with ammonia

Ammonia is a weaker nucleophile compare to hydroxide ion. So, to
effectively react with ester, concentrated ammonia is mixed with ester and
heated. The products are an amide and alcohol
Ester Ammonia Amide Alcohol

+ NH3 CH3CH2CONH2 CH3CH2OH

+ NH3 CH3OH

+ NH3 CH3CH2CONH2
(C) Reduction of ester

When reduced using strong reducing agent such as LiAlH4, ester will formed
alcohol as products
Ester LiAlH4 Alcohol Alcohol

LiAlH4 /
H+ CH3CH2CH2OH CH3CH2OH

LiAlH4 /
H+ CH3OH

LiAlH4 /
H+
CH3CH2CH2OH
7.9.3 Natural ester (Lipid) – Fats and Oils

Lipids are organic substance found in living organisms, which is insoluble in water.

Members of lipid include fats and oils, steroids, waxes and some vitamins.

Fatty acids are common name for long-chain carboxylic acid obtained from fats
and oils

They are natural esters formed from propan-1,2,3-triol (known as glycerol) and
long chain fatty acid.

+ 3 CH3(CH2)14COOH

There are 2 types of fatty acid which are known as saturated fatty acid and unsaturated
fatty acid.

Saturated fatty acid – all C–C are singly bonded to each other in the long carbon chain

Unsaturated fatty acid – contain at least 1 C=C within the long carbon chain. If there’s
only one C=C in the long carbon chain, it is known as monounsaturated fat. If there’s
more than one C=C, they are known as polyunsaturated fat.

In natural product of fats and oils contain mixture of saturated fatty acid and unsaturated
fatty acid

Monounsaturated
Fats / oil Saturated fat Polyunsaturated fat
fat
Palm oil 51% 10% 39%

Sunflower oil 11% 69% 20%

Olive oil 14% 9% 77%

Butter fat 66% 4% 30%

Lard 41% 12% 47%

Manufacture of soap

An important use of soap is in soap making. Soaps are sodium (Na) or potassium (K)
salts of long chain of fatty acids. Hydrolysis of fats / oils in aqueous NaOH ( known
as saponification) form glycerol& sodium carboxylate salt (soap).

The cleansing action of soap is due to the hydrophobic part of soap which dissolves
in grease easily and dirt are removed easily using the attraction forces between
cation and the negative head of soap.
Application of ester in industries

Used as food additive in food processing industries (taste enhancer, flavouring and
preservatives)

Solvent for drugs, antibiotics and cosmetic.

Use to produce cosmetic, perfume / cologne and air-freshener.

Polystyrene cement – use to bind to another type of surface in the cement

Polyester (terylene) – synthetic fibres in textiles industries.

Polystyrene (alkyd resin) – used in pain and surface coating

Unsaturated polyester are readily copolymerised to give thermosetting products. They
are used in the manufacture of glass fiber products for reinforcement in boat and
cars.
7.10 Amides

Amides are organic compound with the general formula of CnH2n+1CONH2.

Amides are formed by replacing hydroxyl (–OH) with amine (–NH2) group.

Naming of amide end with suffix “amide”. Examples of amides are

ethanamide

propanamide

butanamide

benzamide
20 amide

N-propylethanamide

N-phenylpropanamide

30 amide

N-ethyl-N-methylbutanamide

N,N-dimethylbenzamide
7.11 Preparation of amide
Name of Reagent used
Equation
reaction and condition

Acyl chloride
with ammonia
propanoyl chloride ammonia propylamide
Reaction
with amine

Acyl chloride Ethanoyl chloride propylamine

with amine

Heating
ammonium Ammonium
salt with salt with ester
ester
ammonia ethanamide
 Name of Reagent used
Equation
reaction and condition

Hydrolysis of Diluted HCl

amide under reflux ethanamide ethanoic acid

Distilled over
Dehydration phosphorous
of amide pentoxide,
P2O5 Propanamide propanitrile

Reaction
Nitrous acid, Propanamide nitrous acid
with nitrous
HNO2
acid, HNO2
propanoic acid
 Name of Reagent used
Equation
reaction and condition

Bromine in
Hoffmann sodium
propanamide
degradation hydroxide,
NaOH

ethylamine

Lithium
Reduction of tetrahydrido-
propanamide
amide aluminate,
LiAlH4

propylamine
(A) Hydrolysis of amide

Amide slowly hydrolysed by refluxing with dilute acid / alkali solution. In both
cases, the intermediate product is ammonium salt of carboxylic acid

Step 1 : Formation of ammonium salt

Step 2 : Formation of carboxylic acid

Under acidic
medium

Overall :
 Step 1 : Formation of ammonium salt

Step 2 : Formation of carboxylate salt

Under alkaline
medium
(way of
distinguish
between amine
and amide)
Overall :
(B) Dehydration of amide

When amides are distilled over P2O5, phosphorous pentoxide, nitriles are formed.
So P2O5 act as dehydrating agent. The H2 from NH2 and O from C=O are
withdrawn out and formed water.

The nitrile formed can be later used to synthesis amine and carboxylic acid using
suitable reagent
Amide Reagent Nitrile Reagent Compound

P
2O 5
→  LiAlH
4 →

P2 O 5 H 2O , H +

→  
→

P
2O 5
→  LiAlH
4 →
(C) Reaction with nitrous acid, HNO2

Nitrous acid, HNO2, can be prepared by treating sodium nitrite, NaNO2, with
dilute HCl in cold
NaNO2 (aq) + HCl (aq) cold
→ HNO2 + NaCl

When nitrous acid, HNO2, react with amide, carboxylic acid, nitrogen and water is
produced
Amide Nitrous acid Carboxylic acid Side product

HNO2
+ H2O
+ N2

HNO2 + H2O
+ N2

HNO2
+ H2O
+ N2
(D) Hoffmann Degradation : Way of shortening chain.

The terms degradation mean reduce the number of carbon, an opposite of
forming nitrile to increase no of carbon in an organic compound.

The reagents used for Hoffmann degradation are bromine solution in sodium
hydroxide (Br2 in NaOH)

Bromine in
Amide Amine Side products
sodium hydroxide

+ Na2CO3
Br2 + 4 NaOH
CH3CH2NH2 + 2 NaBr
+ 2 H2O

Br2 + 4 NaOH
+ Na2CO3
CH3CH2CH2NH2 + 2 NaBr
+ 2 H2O
Br2 + 4 NaOH + Na2CO3
+ 2 NaBr
+ 2 H2O
(E)Reduction of amide

Amide can be reduced to become an amine using strong reducing agent
such as LiAlH4 (lithium tetrahydridoaluminate) under dry ether. The number
of carbon after reduction remains the same
Strong reducing Side
Amide Amine
agent products

LiAlH4 CH3CH2CH2NH2 + H2O

LiAlH4 CH3CH2CH2CH2NH2 + H2O

LiAlH4 + H2O
RCOOH + H2O  RCOO- + H3O+

Acidity increase from CH3COOH < CH2ClCOOH < CHCl2COOH

Cl is electorn withdrawing group / caused negative inductive effect / Greater
number of Cl will increase the inductive effect, causing more acidic [1]

[H3O+] = K a × c or [ H 3O + ] = 0 .0014 × 0 .100 pH = 1.9

pKa = - lg Ka ; pKa = 1.3

alkene / C=C

hydroxyl group / -OH

Aldehyde / -CHO
KMnO4 / H+ cold , dilute
oxidation

Chlorine gas under UV

NaOH reflux
 X
Effervescences occur, which turn lime water chalky
CH3COOH + NaHCO3  CH3COO-Na+ + H2O + CO3
Y
Silver mirror is observed
CH2(OH)CHO + 2Ag+ + 3OH-  CH2(OH)COO- + 2H2O + 2 Ag
Acidic trend increase from 1 < 2 < 3 [1]
This is due to, when number of Cl increase, the negative inductive effect increase
gradually[1], which increase the acidity

Acid 2 is stronger than Acid 4 [1]

This is due to, inductive effect is stronger if Cl is closer to the π-bond of COOH
group [1]

[H3O+] = K a × c or [ H 3 O + ] = 1 . 26 × 10 −5
× 0 . 010
pH = 3.5
ester

Dilute HCl under reflux

CH3OH catalysed by H2SO4 under reflux

CH2(Br)CH(Br)CH2(Br)
COOHCOCOOH
 890g of triglyceride produces 3 × 298 = 894 g of biodiesel [1]
∴ 500kg produces 500 × 894/890 = 502 kg biodiesel [1]

C17H35CO2CH3 + 27 ½ O2 → 19 CO2 + 19 H2O

Mass of CO2 produced = 10 × 44 × 19/298

= 28 kg.

• economic argument (NOT just “cheaper”) – e.g. oil will become increasingly more expensive
as it runs out
• ref to CO2 cycle (e.g. no net increase in CO2, i.e. “carbon neutral”) or less global warming (due
to a smaller carbon “footprint”)
• renewable/sustainable
• the effect of biofuel cultivation on world food prices