Functional Groups

Chapter 11 Essential Chemistry

1
 Alcohols functional group

Alcohols contain the –OH functional group. This is

known as the alcohol or hydroxyl group.

The hydroxyl group is reactive and determines the

chemical properties of the molecule.

2
 Uses of alcohols
• Drinks-The "alcohol" in alcoholic drinks is simply
ethanol. methanol is poisonous, industrial
methylated spirits are unfit to drink.
• As a fuel-Ethanol burns to give carbon dioxide and
water and can be used as a fuel in its own right, or in
mixtures with petrol (gasoline). "Gasohol" is a petrol
/ ethanol mixture containing about 10 - 20%
ethanol.
• As a solvent-Ethanol is widely used as a solvent. It is
relatively safe, and can be used to dissolve many
organic compounds which are insoluble in water. It is
used, for example, in many perfumes and cosmetics.3
 Classification of Alcohols
• An alcohol can be classified as a:
• Primary alcohol (also referred to as 1o alcohol)
• Secondary alcohol (also referred to as
2o alcohol)
• Tertiary alcohol (also referred to as 3o alcohol)
• Classification of an alcohol depends on the
location of the OH (hydroxyl or hydroxyl)
functional group:
4
 Primary Alcohols
• In a primary (1°) alcohol, the carbon atom that
carries the -OH group is only attached to one
alkyl group. Some examples of primary
alcohols are shown below:

5
 Secondary Alcohols
• In a secondary (2°) alcohol, the carbon atom
with the -OH group attached is joined directly
to two alkyl groups, which may be the same or
different. Examples include the following:

6
 Tertiary Alcohols
In a tertiary (3°) alcohol, the carbon atom holding the -OH group is attached
directly to three alkyl groups, which may be any combination of the same or
different groups. Examples of tertiary alcohols are given below:

7
Examples of Primary, secondary and
tertiary alcohols

8
 Alcohols Properties

The oxygen in the hydroxyl group is highly

electronegative so creates a strong polar bond
within the functional group.

The hydroxyl group can form hydrogen bonds

with other polar groups, raising the melting and
boiling points.

They can also form hydrogen bonds to water,

increasing solubility in water. Solubility
decreases as chain length increases.
9
 Physical properties
• The lower members of alcohols are colourless,
volatile liquids with a characteristic alcoholic
smell and burning taste whereas higher
alcohols are odourless and tasteless.
• Higher alcohols having 12 or more carbon
atoms are colourless waxy solids.

10
 Physical Properties
• Trend- boiling point increases as number of C-
atoms increases.
• Boiling point of any given alcohol is higher than
its parent hydrocarbon. Why?? Due to hydrogen
bonding.
• Alcohol and the parent hydrocarbon both show
an increase in B.P. as molecular mass increases,
this is due increased dispersion forces.

11
 Solubility in water
• The first three members are completely miscible with water.
The solubility rapidly decreases with increase in molecular
mass. The higher members are almost insoluble in water but
are soluble in organic solvents like benzene, ether etc.

• The solubility of lower alcohols is due to the existence of

hydrogen bonds between water and polar -OH group of alcohol
molecules.
• The -OH group in alcohols contain a hydrogen bonded to an
electronegative oxygen atom. Thus they form hydrogen bonds
with water molecules. 12
 Solubility in water
• Trend- Solubility in water decreases as number of C-atoms
increases.

• The solubility of alcohols in water decreases with increase in

molecular mass because the increase in molecular mass, the non
polar alkyl group becomes predominant and masks the effect of
polar -OH group.
• In addition, among the isomeric alcohols, the solubility increases
with branching of chain. As the surface area of the non-polar part
13
in the molecule decreases, the solubility increases.
 Preparation of alcohols

Ethanol (primary alcohol) is commonly prepared

through fermentation of simple sugars in the
presence of yeast.

Hydration (addition of water) of an alkene will also

produce an alcohol. The final molecule chain length
depends upon the reactant alkene.

14
 Reactions of alcohols

Alcohols, like all hydrocarbons, will undergo

combustion in air to form carbon dioxide, water and
energy.

An alcohol can have water removed chemically

(dehydration) by heating in the presence of a
concentrated acid.

15
 Reactions of alcohols

When alcohols react with sodium they form an ion

called an alkoxide where the hydrogen ion is
removed from the hydroxyl group leaving the
hydrocarbon with an O– ion. Hydrogen gas also
forms.

In this reaction, the ethanol acts like an acid,

donating its hydrogen ion.

16
 Redox in Organic chemistry
• Normally: Oxidation is a loss of electrons;
Reduction is a gain of electrons.
• But in organic terms:
• Oxidation: loss of H2; addition of O or O2;
addition of X2 (halogens).
• Reduction: addition of H2 or H- ; loss of O or
O2; loss of X2. (Neither an oxidation nor
reduction: Addition or loss of H+ , H2O, HX).
17
 Oxidation of Alcohols
• In the lab controlled oxidation of alcohol is
used to synthesise other organic compounds
like aldehydes, ketone and carboxylic acids.

• This achieved by using oxidising agents like

acidified KMnO4 (aq), K2Cr2O7(aq)

18
 Oxidation of 1° Alcohols
• Primary alcohols will oxidise when in the
presence of a strong oxidising agent such as
acidified permanganate ions (MnO4–) or
acidified dichromate ions (Cr2O72–).

• They oxidise to form an aldehyde, which is

then further oxidised to a carboxylic acid.
• [O] = oxidation has occurred.

19
 Partial oxidation of Primary
Alcohols
• It difficult to achieve because there is a strong
tendency for aldehydes to oxidised to carboxylic acids.
• Partial oxidation is favoured by using excess alcohol
and a weak oxidising agent like K2Cr2O7 (aq), and distil
off the aldehyde as soon as it forms.
• The excess of the alcohol means that there isn't
enough oxidising agent present to carry out the
second stage. Removing the aldehyde as soon as it is
formed means that it doesn't hang around waiting to
be oxidised anyway!
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21
 Question?
• Write down the half oxidation and reduction
reaction, and the full redox reaction of
propan-1-ol using acidified potassium
permanganate KMnO4 and potassium
dichromate K2Cr2O7.

22
• Reduction reaction-

• CH3CH2CH2OH  CH3CH2CHO +2H+ + 2e- (*5)

Oxidation reaction
• Full redox reaction-

23
24
Complete Oxidation of Primary Alcohol

Overall reaction-

25
Complete oxidation of primary alcohol
1. Excess of oxidising agents like KMnO4 and Kr2Cr2O7

26
 Oxidation of Secondary alcohols

Secondary alcohols oxidise to form ketones. There

is no further oxidation of a ketone.

Tertiary alcohols do not oxidise.

This reaction can be used to distinguish a tertiary

alcohol from a primary/secondary alcohol as the
oxidising agents show a distinct colour change
when a reaction occurs. For example, dichromate
ions (orange) form chromium ions (green).

27
Oxidation of secondary alcohols

28
Examples

29
Reduction summary of oxidising agents

30
• Polarity and Boiling Point:
• The polarity of the molecules determines the
forces of attraction between the molecules in
the liquid state. Polar molecules are attracted
by the opposite charge effect (the positive end
of one molecule is attracted to the negative end
of another molecule. Molecules have different
degrees of polarity as determined by the
functional group present.
• Principle: The greater the forces of attraction
the higher the boiling point or the greater the
polarity the higher the boiling point.
31
 Aldehydes and ketones
• Aldehydes and ketones as carbonyl
compounds A carbon with a double bond to
an oxygen atom is a carbonyl group.
• Aldehydes and ketones are simple
compounds which contain a carbonyl group -
a carbon-oxygen double bond. >C=O
• In aldehydes, the carbonyl group has a
hydrogen atom attached to it

32
 Aldehyde/ketone group Nomenclature

In the aldehyde the carbonyl is terminal (at the end

of the chain). In the ketone the carbonyl is on a
carbon in the middle of the chain.

33
 Naming aldehydes and ketones

1 Locate the longest carbon chain that contains

the carbonyl group.
2 Delete the ‘e’ from the alkane and add ‘al’ for
an aldehyde and ‘one’ for a ketone.
3 Number the carbons in the chain so the
carbonyl group has the smallest number, the
aldehyde will always be a 1 so does not need to be
allocated a number. Number the ketone according
to position: 2-butanone
4 Name any alkyl side chains according to
position and length: 3-methyl-2-butanone

34
 Aldehydes and Ketones
• Bonding and reactivity
• Bonding in the carbonyl group
• Oxygen is far more electronegative than carbon
and so has a strong tendency to pull electrons
in a carbon-oxygen bond towards itself. One of
the two pairs of electrons that make up a
carbon-oxygen double bond is even more easily
pulled towards the oxygen. That makes the
carbon-oxygen double bond very highly polar.

35
 Physical Properties of aldehydes and ketones

The carbonyl group is highly polar because of the

electronegativity difference between the carbon
and oxygen atoms.

Dipole-dipole bonds form between molecules with

carbonyl groups giving higher melting and boiling
points than simple hydrocarbon molecules with
dispersion forces.

As the carbonyl group can also form bonds with

water, smaller aldehydes and ketones are water
soluble.
36
 Aldehydes physical properties
• Boiling points
• Methanal is a gas (boiling point -21°C), and
ethanal has a boiling point of +21°C. That
means that ethanal boils at close to room
temperature.
• The other aldehydes are liquids, with boiling
points rising as the molecules get bigger.
• The size of the boiling point is governed by the
strengths of the intermolecular forces.

37
 van der Waals & dipole-dipole attractions
• Both aldehydes and ketones are polar
molecules because of the presence of the
carbon-oxygen double bond. As well as the
dispersion forces, there will also be attractions
between the permanent dipoles on nearby
molecules.
• That means that the boiling points will be
higher than those of similarly sized
hydrocarbons - which only have dispersion
forces.
38
• It is interesting to compare three similarly sized
molecules. They have similar lengths, and similar
(although not identical) numbers of electrons.
molecule type boiling point (°C)
CH3CH2CH3 alkane -42

CH3CHO aldehyde +21

CH3CH2OH alcohol +78

Notice that the aldehyde (with dipole-dipole attractions as well as dispersion forces) has a
boiling point higher than the similarly sized alkane which only has dispersion forces.

However, the aldehyde's boiling point isn't as high as the alcohol's. In the
alcohol, there is hydrogen bonding as well as the other two kinds of
intermolecular attraction.
Although the aldehydes and ketones are highly polar molecules, they don't have
any hydrogen atoms attached directly to the oxygen, and so they can't hydrogen
bond with each other.
39
 Solubility in water

• The small aldehydes are freely soluble in

water but solubility falls with chain length. For
example, methanal, ethanal and the common
small aldehydes - are miscible with water in
all proportions.
• The reason for the solubility is that although
aldehydes can't hydrogen bond with
themselves, they can hydrogen bond with
water molecules.

40
 • One of the slightly positive hydrogen atoms in a water
molecule can be sufficiently attracted to one of the lone pairs
on the oxygen atom of an aldehyde for a hydrogen bond to be
formed.

There will be dispersion forces and dipole-dipole attractions between the aldehyde and
the water molecules.
Forming these attractions releases energy which helps to supply the energy needed to
separate the water molecules and aldehyde molecules from each other before they can
mix together.
As chain lengths increase, the hydrocarbon "tails" of the molecules start to get in the way.

By forcing themselves between water molecules, they break the relatively strong
hydrogen bonds between water molecules without replacing them by anything as good.
This makes the process energetically less profitable, and so solubility decreases.
41
42
 Properties of Ketones
• Dipole-dipole forces due to the presence of
carbonyl group.

• B.P. increases with chain length.

• Solubility decreases with increase chain.
• Eg- propanone is a liquid at room temperature,
soluble in water whereas hexane-3-one is
slightly soluble.
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44
45
 Summary of physical properties
• KETONES and ALDEHYDE: A comparison of the boiling points of
aldehyde and ketone with the corresponding alcohol shows that
the alcohol is more polar due to its ability to hydrogen bond.
Since ketones and aldehydes lack hydroxyl groups, they are
incapable of intermolecular hydrogen bonds. But due to the
presence of the oxygen, they can accept hydrogen bonds from
water molecules which account for the complete solubility of
low molecular weight compounds.
• On the other hand, their boiling points are considerable higher
than the ether or alkane, indicating the presence of weak
intermolecular dipole-dipole forces. The carbonyl group
("carbon double bond oxygen") is polar since oxygen is more
electronegative than carbon and forms a partially charged
dipole
46
 Carboxylic acids
• contain a -COOH group. Carboxyl group
(carbonyl + hydroxyl group)
• A carbon atom double bonded to an oxygen
atom is a carbonyl group.
• A hydrogen atom bonded to an oxygen atom is
a hydroxyl group .
• These compounds are higher in the polarity
with alcohols, because of hydrogen bonding
capabilities and the presence of two oxygen
atoms. 47
 Carboxylic acids

Carboxylic acids contain the carboxyl functional

group – COOH.

The functional group is always on the end of the

carbon chain.

48
 Naming carboxylic acids

1 Identify the longest carbon chain that

contains the carboxyl group.

2 Remove the ‘e’ of the alkane and add ‘oic

acid’. For example propane becomes
propanoic acid.

3 Number the carbons with the carboxyl group

allocated the 1 carbon.

4 Name and number any alkyl side chains.

49
 Properties of carboxylic acids

The carboxyl group can donate a hydrogen ion so

acts as an acid. It undergoes normal acid-base
reactions.
The carboxyl group contains a highly polar –OH
bond which allows this to happen.

50
 Properties of carboxylic acids

The polar carboxyl group can form hydrogen bonds

with other carboxyl groups so these molecules
have relatively high melting and boiling points.

The carboxyl group can also form hydrogen bonds

with water, so when the carbon chain is small
carboxylic acids are soluble. As the carbon chain
gets longer, the acids become less soluble and
insoluble.

51
 Trends in B.P.

B.P. increases as the chain

increases.
Hydrogen bonding in carboxylic
acid.

52
 Boiling points
• The boiling points of carboxylic acids of similar
size are higher still.
• For example:
propan-1-ol CH3CH2CH2OH

ethanoic acid CH3COOH

propan-1-ol CH3CH2CH2OH

These are chosen for comparison because

they have identical relative molecular
masses and almost the same number of
electrons (which affects van der Waals
dispersion forces).
53
 Solubility in water
• Small chain are soluble in polar solvents like
water and alcohols.
• Large chain are insoluble in water but soluble
in non polar solvents like benzene.
• Long chain carboxylic acids are known as fatty
acids. They are greasy to touch, insoluble in
water and found naturally in plants and
animals.

54
Saturated and unsaturated Fatty acids

55
Examples of long chain fatty acids

56
Chemical properties of Carboxylic acids

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58
59
60
 Reactions of carboxylic acids

React with active metals to produce a salt and

hydrogen gas:

React with a base in a neutralisation reaction to

form a salt and water:

61
 Reactions of carboxylic acids

If a metal carbonate is added then a salt and water

and carbon dioxide are produced:

Addition of an alcohol with specific conditions

produces an ester, another organic compound.

62
Esters-are chemicals with pleasant smells. They are used in perfumes, and
as solvents.

63
 Esters
• Esters are chemicals with pleasant smells. They
are used in perfumes, and as solvents.
• An ester is made from an alcohol and a carboxylic
acid.
• Esters have their own rules for naming.
• The first part of the name comes from the
alcohol, and it ends with the letters '-yl'.
• The second part of the name comes from the
carboxylic acid, and it ends with the letters '-oate'.
64
 What is an ester?

The ester functional group contains a carbon with a

double bond to an oxygen and a separate single
bond to another oxygen.

The group is in the middle of a carbon chain.

65
 Synthesizing esters

An alcohol and a carboxylic acid can be used to

synthesise an ester.

Natural esters form very slowly. To speed up the

reaction, the reaction is heated and a catalyst is
used. Concentrated sulfuric acid is commonly used
as the catalyst for this reaction.

This process is called esterification. A general

equation for this process is:

66
 Synthesizing esters

This reaction is an example of a condensation

reaction. A molecule of water is formed as well as
the ester.

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 Naming esters

Naming esters involves looking at the alcohol and

carboxylic acid from which it was formed.

The first part of the name describes the alkyl group

and comes from the alcohol it is formed from. This
is the carbon chain attached to the oxygen within
the chain. Example: ethyl, propyl

The second part is from the carboxylic acid. The

end of the acid name is changed from ‘oic acid’ to
‘oate’. Example: butanoate, heptanoate

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 Naming Examples

Name the following esters

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 Properties

The polar C=O and C-O bonds make the ester

group polar. They only form dipole–dipole bonds
between molecules.

Their melting and boiling points are higher than

hydrocarbons, but lower than alcohols or carboxylic
acids of similar size.

They do not form hydrogen bonds with water so

are not soluble in water. Many esters are soluble in
organic solvents.

70
 Polarity of Esters
• ESTER: The ester functional group has a similar
character to the ketone and aldehyde
functional group. The boiling point indicates
that it is the least polar of the three.

71
 Reactions – acid hydrolysis

Acid hydrolysis of an ester involves reversing the

formation reaction.

An acid is added, the mixture is heated and the

ester splits to form an alcohol and carboxylic acid.

72
 Reactions – alkaline hydrolysis

The splitting or hydrolysis of an ester can also be

performed by adding a base and heating the
mixture.

73
 Fats and oils

Fats and oils are esters called triglycerides.

A triglyceride that is solid at room temperature is a fat,

while one that is a liquid at room temperature is an oil.

A triglyceride has three ester groups in the molecule

and is formed from the alcohol 1,2,3-propantriol
(commonly called glycerol) and three, long chain fatty
acids.

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Synthesis of Triglyceride

75
 Production of a fat/oil

A fatty acid undergoes an esterification with one of the

alcohol groups in glycerol.

76
 Hydrolysis of a fat/oil

Reversal of the formation reaction occurs when water is

added to the fat/oil.

77
Amines and Amides

78
 What is an amine?

Amines are based on the ammonia molecule and

contain the functional group –NH2.

The hydrogen atoms on an ammonia molecule are

replaced by alkyl groups to create amine molecules.

79
 Primary, secondary and tertiary amines

Amines are classified as primary, secondary or tertiary

based on the number of alkyl groups attached to the
nitrogen atom.

A primary amine (a) has one alkyl group, while a

secondary amine (b) has two alkyl groups.

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81
 Naming amines

1 Put the alkyl groups attached to the N atom into

alphabetical order. Use the alkyl name for all except the
final group.
2 Remove the ‘e’ from the last alkane name and
add ‘amine’. Example: ethylmethanamine
3 Use di- and tri- if there are multiple identical alkyl
groups.
4 Number the carbons, allocating the amine the
lowest possible number.
5 Name any other side chains as for naming
alkanes.

82
Practice naming

83
 Properties of amines

The –NH2 amine group is highly polar because of the

large electronegativity difference between nitrogen and
hydrogen.

This gives amines relatively high melting and boiling

points as it can form hydrogen bonds between
molecules.

Small primary and secondary amines are also soluble in

water due to formation of hydrogen bonds.

84
 Polarity of amines
• AMINE : The polarity of the amine nitrogen is
shown to be much less than the oxygen in
alcohol group. The nitrogen in the amine is
much less electronegative than oxygen in the
alcohol. Therefore, the dipole on N-H is much
weaker than the dipole on O-H

85
 Basicity of Amines
• A base is: a substance which combines with hydrogen
ions. This is the Bronsted-Lowry theory.
• an electron pair donor. This is the Lewis theory.
• Amines are bases due to the lone pair of electrons on
the nitrogen atom of amines. These react with water to
form hydroxyl ions.

Bases are those species that donate OH- ions (hydroxyl

ions). The more easily is the availability of the hydroxyl
ions; more is the basicity of the amine.
• Let us now, explore and diagnose the order of basicity
in amines.
86
87
 Reactions of amines

As amines are weak bases, they will participate in

neutralisation reactions with acids.

88
89
 Amides

An amide contains a functional group that is part

carboxylic acid C=O and part amine –NH.

90
 Naming amides

1 Change the ending of the carboxylic acid

name from ‘oic acid’ to ‘amide’. Example:
propanoic acid becomes propanamide

2 Alkyl groups bonded to the nitrogen atom

become N-alkyl. Example: N-
ethylpropanamide

91
 Preparation of an amide

Reaction of a carboxylic acid with an ammonium salt

producing a salt, water and carbon dioxide.

The products are heated to dehydrate the salt,

producing a primary amide.

92
 Preparation of an amide

Secondary amides are made when carboxylic acids and

amines react together, a water molecule is eliminated.
This is a condensation reaction.

93
 Properties of Amides
• The amide are the most polar. The reason is
that it can both hydrogen bond and accept
hydrogen bonds on both the oxygen and the
nitrogen.
• High boiling and melting point as compare to
carboxylic acids and alcohols.
• Soluble in water.
• Solids at room temp.

94
 Amide reactions
Hydrolysis of amides will result in formation of a
carboxylic acid and amine.

This will occur under both acid and base conditions:

Under acidic conditions, in the presence of heat and dilute acid

CH3-CO-NH2 + H2O+ HCl  CH3COOH + NH4Cl

Under alkaline conditions, in the presence of heat and sodium hydroxide

CH3-CO-NH2 + NaOH  CH3COONa + NH3

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