Carboxylic Acids and Derivatives

Tuesday 31 October 2023
AQA – Carboxylic Acids

and Derivatives
What the spec says

Carboxylic acids and esters Acylation
The structures of: The structures of:
• carboxylic acids • acid anhydrides
• acyl chlorides
• esters.
• amides.
Carboxylic acids are weak acids but will liberate CO2 from carbonates. The nucleophilic addition–elimination reactions of water, alcohols,
Carboxylic acids and alcohols react, in the presence of an acid ammonia and primary amines with acyl chlorides and acid
catalyst, to give esters. anhydrides.
The industrial advantages of ethanoic anhydride over ethanoyl
Common uses of esters (eg in solvents, plasticisers, perfumes and
food flavourings). chloride in the manufacture of the drug aspirin.
Students should be able to outline the mechanism of nucleophilic
Vegetable oils and animal fats are esters of propane-1,2,3-triol
(glycerol). addition–elimination reactions of acyl chlorides with water,
alcohols, ammonia and primary amines.
Esters can be hydrolysed in acid or alkaline conditions to form
alcohols and carboxylic acids or salts of carboxylic acids.
Preparation of:
• a pure organic solid and test of its purity
Vegetable oils and animal fats can be hydrolysed in alkaline • a pure organic liquid.
conditions to give soap (salts of long-chain carboxylic acids) and
glycerol.
Biodiesel is a mixture of methyl esters of long-chain carboxylic acids.
Biodiesel is produced by reacting vegetable oils with methanol in the
presence of a catalyst.
Carboxylic Acids
Carboxylic Acids have the carboxyl (–COOH) functional group which
contains both a carbonyl group (C=O) and a hydroxyl group (O-H)
Carboxylic acids are named by When naming carboxylic acids The carboxyl group
finding the longest carbon chain the carbon on the carboxyl will always be at the
then adding ‘–oic acid’ on the end. group is always carbon 1. end of the molecule.
O
H H H H C
O O
C OH
H C C Cl C C C
OH OH
H H OH H
ethanoic acid benzoic acid
Carboxylic Acids
Carboxylic Acids are weak acids and react with carbonates to form carbon
dioxide.
Carboxylic acids are weak acids As they are acids they react with carbonates (CO32-)
which means they dissociate
to form a salt, carbon dioxide gas and water.
partially to form a H+ ion and a
carboxylate ion.
Here is the reaction between ethanoic acid and sodium
O O carbonate
R C
OH
⇌ R C
O-
+ H+
2CH3COOH(aq) + Na2CO3(s)  2CH3COONa(aq) + H2O(l) + CO2(g)
carboxylate ion Here is the reaction between ethanoic acid and sodium
hydrogen carbonate
Equilibrium lies to the left as it CH3COOH(aq) + NaHCO3(s)  CH3COONa(aq) + H2O(l) + CO2(g)
dissociates poorly
Formation of esters (esterification)

Reacting alcohols with carboxylic acids and acid anhydrides can be used to
make esters which have the –COO– group.
An ester is produced when O H+ O H
R
we react a carboxylic acid R C + ⇌ R C +
with an alcohol and O H O H
O H O R
sulfuric acid catalyst. Carboxylic Acid Alcohol Ester Water
O
R C O
An ester is also produced R Mineral O
O + wool soaked R C
when an acid anhydride O H R
in ethanol C +
reacts with an alcohol. R C O H
O R
(more on this later on) O
Acid anhydride Alcohol Ester Carboxylic acid
Esters
Esters are named in 2 sections, the first bit is named from the alcohol used
and the second bit is named from the carboxylic acid
Example 1 - Reacting ethanol with propanoic acid
This part of the ester is
H H This part of the ester is
formed from the
carboxylic acid. We
O H H formed from the
remove ‘–oic acid’ and H C C C alcohol and is the alkyl
replace with ‘-oate’ In O C C H group. In this example
H H this is ‘ethyl’ and is
this example this is
H H named FIRST when
‘propanoate’ and is
naming an ester.
named SECOND when
naming an ester. The full name is ethyl propanoate
Esters
Esters are named in 2 sections, the first bit is named from the alcohol used
and the second bit is named from the carboxylic acid
Example 2 - Reacting ethanol with 2-methylpropanoic acid
This part of the ester is When we name esters
formed from the H H with alkyl branches we
carboxylic acid. In this
O H H number from the
example this is ‘2- H C C C carbons in the C-O-C
3 2 1 O C C H part.
methylpropanoate’ as 1 2
H CH3 This part of the ester is
it sits on the 2nd H H
carbon. formed from the
alcohol. In this example
The full name is ethyl 2-methylpropanoate this is ‘ethyl’
C Harris - Allery Chemistry
Esters
Esters are used commercially and in industrial processes.
Solvents Plasticisers
Perfumes and food Esters are used to make
Esters are polar so other
flavorings plastics more flexible
polar compounds will
Some esters have sweet during the polymerisation
dissolve readily in esters.
smells such as pear process. They can leach out
They also have low boiling
drops. This make them of the plastic over time and
points and evaporate easily.
ideal in fragrances and the plastic does become
This makes them valuable in
food products. brittle.
making glues.
Ester Hydrolysis
Esters can be hydrolysed (split using water) however it can be sped up
using an acid (acid hydrolysis) and a base (base hydrolysis).
ACID HYDROLYSIS
Here we use dilute acid to split an ester We can use sulfuric or hydrochloric acid
into a carboxylic acid and an alcohol. and the reaction is conducted under reflux
H H H H
O H H O
H+
H C C + H O C C H
O C C H
+ H2O ⇌ H C C
H O H
H H H
H H
The addition of more water shifts
equilibrium right, more product produced
Ester Hydrolysis
Esters can be hydrolysed (split using water) however it can be sped up
using an acid (acid hydrolysis) and a base (base hydrolysis).
BASE HYDROLYSIS
Here we use dilute base to split an ester We can use sodium hydroxide and the
into a carboxylate ion and an alcohol. reaction is conducted under reflux
H H H H
O H H O
H C C + H O C C H
O C C H
+ OH- ⇌ H C C
H O-
H H H
H H
Fats and Oils

When we react glycerol (alcohol) and fatty acids (carboxylic acid) we
produce an ester which makes fats and oils.
Glycerol (propane-1,2,3-triol) is reacted with long chain fatty acids which can be
saturated (with no double bonds) and unsaturated (with at least 1 double bond)
H Glycerol Saturated fatty acid O

Unsaturated fatty
H C OH acids can have C OH
more than 1
H C OH double bond.
These are called Unsaturated fatty acid
polyunsaturated
O
H C OH
fatty acids.
C OH
H
Fats and Oils

Oil is an ester and an example is shown below. Vegetable oils
Notice the ester links in the blue box. They have unsaturated hydrocarbon chains
that are not straight which means the
H O Oil ester chains can’t pack together closely and
hence have lower van der waals forces.
H C O C They have lower melting points and are
O liquids at room temperature.
H C O C
O
H C O C
H
Fats and Oils

Fat is an ester and an example is shown below. Animal Fats
Notice the ester links in the blue box. They have saturated hydrocarbon chains
that are straight and more uniform than
H O Fat ester oils which means the chains can pack
together closely and hence have much
H C O C higher van der waals forces. They have
O higher melting points and are solids at
room temperature.
H C O C
O
H C O C
H
Soap
Animal fats and vegetable oils can be hydrolysed by heating them with
sodium hydroxide. The product is……. SOAP!
The example below uses an animal fat to make soap
H O Fat Sodium H Glycerol Soap

Hydroxide (sodium
H C O C (CH2)16CH3 H C OH
O salt)
H C O C (CH2)16CH3 + 3NaOH  H C OH + 3CH (CH ) COO-Na+
3 2 16
O
H C O (CH2)16CH3 H C OH
C
H H
Biodiesel
Vegetable oils can be converted into biodiesel by reacting oils with
methanol and a potassium hydroxide as a catalyst.
Biodiesel is a mixture of fatty acids made from methyl esters and can be made from
rapeseed oil
H O Oil Methanol H Glycerol Methyl ester
H C O C R H C OH O
O KOH
H C O C R + 3CH3OH  H C OH + 3 H3C O C R
O
H C O R H C OH
C
H H
Acyl Chlorides
Acyl Chlorides (aka Acid Chlorides) have the functional group -COCl which
contains the acyl group (COCl).
Acyl chlorides are named by finding When naming acyl chlorides The acyl group will
the longest carbon chain then the carbon on the acyl group always be at the end
adding ‘–oyl chloride’ on the end. is always carbon 1. of the molecule.
H H H CH3
O O
H C C HO C C C C
Cl Cl
H H OH H
ethanoyl chloride 3,4-dihydroxy-2-methylbutanoyl chloride
Acyl Chlorides
Acyl Chlorides react with water, ammonia, alcohol and primary amines. In
each reaction the Cl is substituted for either an oxygen or nitrogen
REACTION WITH WATER PRODUCES CARBOXYLIC ACIDS
H H
O O
H C C + H2O  H C C + HCl
Cl OH
H H This is a vigorous
reaction and white misty
ethanoyl chloride ethanoic acid fumes of hydrogen
chloride gas is produced
Acyl Chlorides
REACTION WITH AMMONIA PRODUCES AMIDES
H H
O O
H C C + NH3  H C C + HCl
Cl NH2
ethanoyl chloride ethanamide fumes of hydrogen
Acyl Chlorides
REACTION WITH ALCOHOL PRODUCES ESTERS
H H
O O
H C C + CH3OH  H C C + HCl
Cl OCH3
ethanoyl chloride methyl ethanoate fumes of hydrogen
Acyl Chlorides
REACTION WITH PRIMARY AMINES PRODUCES N-SUBSTITUTED AMIDES
H H
O O
H C C + CH3NH2  H C C + HCl
Cl NHCH3
ethanoyl chloride N-methyl ethanamide reaction and white misty
fumes of hydrogen
Acid Anhydrides
Acid anhydrides is a molecule made from 2 carboxylic acids that are the
same.
O
Acid anhydrides are named by H3C C
naming knowing the carboxylic acid O
it is made from and removing ‘-acid’ H3C C
and adding ‘–anhydride’ on the end. O
ethanoic anhydride
Acid Anhydrides
Acid Anhydrides react with water, ammonia, alcohol and primary amines.
Very similar to acyl chloride reactions except they are less vigorous.
REACTION WITH WATER PRODUCES CARBOXYLIC ACIDS
O H H
H3C C O O
O + H2O  H C C + H C C
H3C C OH OH
O H H
ethanoic anhydride ethanoic acid
Acid Anhydrides
REACTION WITH AMMONIA PRODUCES AMIDES
O H H
H3C C O O
O + NH3  H C C + H C C
H3C C NH2 OH
O H H
ethanoic anhydride ethanamide
Acid Anhydrides
REACTION WITH ALCOHOL PRODUCES ESTERS
O H H
H3C C O O
O + CH3OH  H C C + H C C
H3C C OCH3 OH
O H H
ethanoic anhydride methyl ethanoate
Acid Anhydrides
REACTION WITH PRIMARY AMINES PRODUCES N-SUBSTITUTED AMIDES
O H H
H3C C O O
O + CH3NH2  H C C + H C C
H3C C NHCH3 OH
O H H
ethanoic anhydride N-methyl ethanamide
Nucleophilic Addition-Elimination
Acid chlorides have a strong δ+ on the carbon which is susceptible to attack from
nucleophiles
They have a strong δ+ as the oxygen and chlorine atoms are electronegative and draw electrons towards
themselves.
In this example we look at the mechanism for ethanol reacting with propanoyl chloride.
H H δ- A pair of electrons from the double H H Cl Electrons from

O bond is then transferred to the oxygen. the C-Cl bond
H C C C δ+ H C C C O:- move to Cl and
the bond is
Cl δ- broken
H H H H +
Ethanol is a nucleophile O H
O: that attacks the δ+ on the
:
H3 C The pair of electrons on

acyl chloride. H3 C the oxygen move to re-
H make the double bond
Nucleophilic Addition-Elimination
Acid chlorides have a strong δ+ on the carbon which is susceptible to attack from
nucleophiles
They have a strong δ+ as the oxygen and chlorine atoms are electronegative and draw electrons towards
themselves.
In this example we look at the mechanism for ethanol reacting with propanoyl chloride.
H The electrons in the O-H bond

H H
O move to the oxygen. The positive H
charge is neutralised. O
H C C C
+
H C C C + HCl
H H O H O CH3
H H
This mechanism also
applies to other
Cl :- The chlorine that was removed in the
H3 C The ester methyl propanoate
nucleophiles NH3, previous step bonds with the and HCl is fomed
H2O and CH3NH2 hydrogen atom in the hydroxyl group
Aspirin
Aspirin is an ester is made by reacting ethanoic anhydride or ethanoyl
chloride and salicylic acid.
OH H3C C O
O O O
H3C C C O C O
O + OH  OH + H3C C
H3C C OH
O
ethanoic anhydride salicylic acid aspirin ethanoic acid
It is safer as it does not produce
Ethanoic anhydride is used It is safer as it less corrosive
harmful HCl gas
instead of ethanoyl chloride It is safer as it does not react
It is cheaper
in industry because….. vigorously with water
Reflux
Reflux is technique used when you want to heat volatile liquids
Reflux allows strong

The Liebig condenser has cold heating without losing
water running through the wall. volatile reactants and
When hot evaporating substances products. Volatile
hit the colder condenser they turn compounds evaporate
back into a liquid and return back and condense and fall
the round bottomed flask to react back into the flask.
further.
As we are using flammable liquids
heating is done via a water bath or
electric heater called a mantle. This
is safer than using a naked flame.
Source – Andrew - https://commons.wikimedia.org/wiki/File:Reflux_English.svg
Distillation
Distillation is used when we want to separate substances with different
boiling points
Gently heating a mixture will result in the Knowing the
compounds separating out in order of boiling point. boiling point of the
chemical you want
If your compound has a lower boiling point that your
to separate will
starting mixture you heat to the temperature of the
allow you to decide
boiling point of your compound you want to separate.
how you are going
Collect your product in the separate vessel.
to separate your
If your compound has a higher boiling point that your compound.
starting mixture you heat to the temperature of the
boiling point of your compound you want to separate.
Your compound will remain in the round bottomed flask.
Distillation is useful when you want to extract a chemical before it reacts any further.
Oxidising primary alcohols can produce aldehydes however if the aldehyde isn’t
removed as soon as it is formed it will oxidise to a carboxylic acid. Distillation is used
to remove the aldehyde
Source –All pictures - Pixabay
Redistillation and Separation

Redistillation is used when we want to purify volatile substances which can
be purified further using separation
We need to separate the useful organic product
from the impurities and distillation can help. Despite distillation being able to
Distillation separates chemical by boiling point. separate most impurities, further
separation and purification may
We can collect the be needed. A separation funnel
different substances can help and addition of a drying
by monitoring the agent afterwards can be used.
temperature they
boil at and collecting The method is found on the next
the different liquids slide
as they come out the
condenser.
Separation & purification

Separation techniques are use to remove impurities that are dissolved in
water.
Separation
Add the products from distillation into a separating funnel
(shown to the left). Add water to dissolve soluble impurities an
create an aqueous solution.
After allowing the solution to settle, 2 layers will form
Top layer – Impure product
Bottom layer – Aqueous layer containing water soluble impurities
Source –All
Drain the aqueous layer off (remember to remove the stopper)
pictures -
Pixabay Purification
Add anhydrous CaCl2 (calcium chloride). This Take the impure product from the separating funnel and
is a dehydrating agent and will remove and add to a round bottomed flask.
aqueous substances still remaining.
INVERT the flask and leave for 20-30 Filter the solid drying agent to remove.
minutes.
Filtration
Filtration is used to separate solids from liquids.
A vacuum is used to help separate the liquid and solid
components thoroughly.
Buchner funnel
and filter paper.
Place a filter paper disc in the Buchner funnel and
dampen slightly to make a seal. Pour the reaction
Vacuum
mixture into the Buchner funnel with the vacuum line
on.
The vacuum creates a reduced pressure in the
flask and pulls the liquid through. The solid will be
left in the Buchner funnel.
Source –All pictures - Pixabay The solid can be recrystallised to purify further
Recrystallisation
Recrystallisation is a method to purify solids and the solvent chosen is very
important.
1. Add just enough hot solvent to allow the
2. Allow the solution to cool down
impure solid to dissolve. This will mean you have
slowly… crystals will start to form.
a saturated solution of your impure product.
4. Filter to get your solid purified 3. Your impurities will remain dissolved in
crystals. Wash with very cold solvent solution as there is a smaller quantity of them, it
and dry them off. takes a lot longer for them to crystallise.
CHOSE YOUR SOLVENT CAREFULLY!
You want your impure solid to dissolve fully in hot solvent but virtually insoluble when it is cold.
If not your substance won’t dissolve in hot solvent and you can’t filter the purified solid if it is
soluble in cold solvent.
Purity and Boiling Points

Measuring the boiling point of your substance can help to detect impurities.
We can determine the boiling point of the liquid by using

distillation set up to the left.
If we gently heat the sample we can measure the temperature at

which it distils using the thermometer in the equipment. This the
boiling point.
Then compare this boiling point against the data book value.
Be careful!
Your sample contains impurities if- Various organic compounds have the
Your boiling point is higher than what is recorded in the data book. same boiling points. Need to use other
Your sample boils over a range of temperatures. analytical techniques such as mass
spectrometry to spot impurities.
Purity and Melting Points

The purity of a compound can be determined by measuring the melting
point
1. Add a sample of the solid product into a
2. Slowly increase the temperature until
capillary tube and place into the heating
the substance starts to melt.
element of the melting point apparatus.
4. Compare the melting point against

data book values. 3. There is a
temperature range
5. If your substance contains from when the solid
impurities the melting point will be just starts to melt to
lower and the temperature range the when it fully melts.
substance melts at will be larger.
Source –https://commons.wikimedia.org/wiki/File:MEL-TEMP_melting_point_instrument.jpg

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Tuesday 31 October 2023

AQA – Carboxylic Acids

What the spec says

Formation of esters (esterification)

Fats and Oils

H Glycerol Saturated fatty acid O

Fats and Oils

Fats and Oils

H O Fat Sodium H Glycerol Soap

REACTION WITH WATER PRODUCES CARBOXYLIC ACIDS

REACTION WITH AMMONIA PRODUCES AMIDES

REACTION WITH ALCOHOL PRODUCES ESTERS

REACTION WITH PRIMARY AMINES PRODUCES N-SUBSTITUTED AMIDES

REACTION WITH WATER PRODUCES CARBOXYLIC ACIDS

REACTION WITH AMMONIA PRODUCES AMIDES

REACTION WITH ALCOHOL PRODUCES ESTERS

REACTION WITH PRIMARY AMINES PRODUCES N-SUBSTITUTED AMIDES

H H δ- A pair of electrons from the double H H Cl Electrons from

H3 C The pair of electrons on

H The electrons in the O-H bond

Reflux allows strong

Redistillation and Separation

Separation & purification

Purity and Boiling Points

We can determine the boiling point of the liquid by using

If we gently heat the sample we can measure the temperature at

Purity and Melting Points

4. Compare the melting point against

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