HYDROXY

COMPOUND
-by zm
Learning outcomes
 Production of
Alcohols
• Alcohols are compounds that contain at least one hydroxy (-OH) group

• The general formula of alcohols is CnH2n+1OH

• Alcohols can be prepared by a wide range of chemical reactions

Electrophilic addition of alkenes

• When hot steam is reacted with an alkene, using concentrated phosphoric(V)

acid (H3PO4)as a catalyst, electrophilic addition takes place to form an alcohol
.
Oxidation of alkenes

• Cold, dilute KMnO4 is a mild oxidising agent and oxidises alkenes

• The C-C double bond is not fully broken and a diol is formed

• A diol is a compound with two hydroxy, -OH, groups

Nucleophilic substitution of halogenoalkanes

• The halide atom in halogenoalkanes can be substituted when heated

with aqueous NaOH in a nucleophilic substitution reaction
Reduction of aldehyde & ketones
• Aldehydes and ketones can be reduced by reducing agents such as NaBH 4 or LiAlH4

• Aldehydes are reduced to primary alcohols

• The carbon attached to the hydroxy group is bonded to one other alkyl group

• Ketones are reduced to secondary alcohols

• The carbon attached to the hydroxy group is bonded to two other alkyl groups
Reduction of carboxylic acids

• Similarly, carboxylic acids are reduced by NaBH 4 or LiAlH4 to primary alcohols

• Carboxylic acids can also be reduced by H 2 using a nickel catalyst and heat
Hydrolysis of ester
• Esters are made by a condensation reaction between an alcohol and a carboxylic acid

• When an ester is heated with dilute acid or alkali, hydrolysis will take place and the
carboxylic acid and alcohol will be reformed
 Free Writing
Type something here.

Exam Tip
The symbol [O] is
used to represent
oxygen provided by
an oxidising agent.
 Reactions of
Alcohols
Alcohols are reactive molecules which undergo a wide range of reactions

Combustion of alcohols

• Alcohols react with oxygen in the air when ignited and undergo complete combustion to
form carbon dioxide and water

Alcohol + oxygen → carbon dioxide + water

Substitution of alcohols

• In the substitution of alcohols, a hydroxy group (-OH) is replaced by a

halogen to form an halogenoalkane

• The substitution of the alcohol group for a halogen can be achieved by

reacting the alcohol with:

• HX (rather than using HBr, KBr is reacted with H2SO4 or H3PO4 to make HBr
that will then react with the alcohol)
• PCl3 and heat
• PCl5 at room temperature
• SOCl2
Reaction with Na

• When an alcohol reacts with a reactive metal such as sodium (Na), the
oxygen-hydrogen bond in the hydroxy group breaks
• Though the reaction is less vigorous than sodium reacting with water,
hydrogen gas is given off and a basic compound (alkoxide) is formed
• If the excess ethanol is evaporated off after the reaction a white
crystalline solid of sodium alkoxide is left

Alcohol + sodium → sodium alkoxide + hydrogen

• The longer the hydrocarbon chain in the alcohol, the less vigorous the
reaction becomes
Oxidation of alcohols

• Primary alcohols can be oxidised to form aldehydes which can undergo further oxidation to form carboxylic acids

• Secondary alcohols can be oxidised to form ketones only

• Tertiary alcohols do not undergo oxidation

• The oxidising agents of alcohols include acidified K2Cr2O7 or acidified KMnO4

• Acidified potassium dichromate(VI), K2Cr2O7, is an orange oxidising agent

• Acidified means that that the potassium dichromate(VI) is in a solution of dilute acid (such as dilute sulfuric acid)

• For potassium dichromate(VI) to act as an oxidising agent, it itself needs to be reduced

• This reduction requires hydrogen (H+) ions which are provided by the acidic medium

• When alcohols are oxidised the orange dichromate ions (Cr2O72-) are reduced to green Cr3+ ions
•Acidified potassium manganate(VII), KMnO4, is a purple oxidising agent

•As with acidified K2Cr2O7 the potassium manganate(VII) is in an acidic medium to allow reduction
of potassium manganate(VII) to take place

•When alcohols are oxidised, the purple manganate ions (MnO4-) are reduced to colourless Mn2+
ions

•Warm primary alcohol is added to the oxidising agent

•The formed aldehyde has a lower boiling point than the alcohol reactant so it can be distilled off as
soon as it forms

•If the aldehyde is not distilled off, further refluxing with excess oxidising agent will oxidise it to a
carboxylic acid

•Since ketones cannot be further oxidised, the ketone product does not need to be distilled off straight
away after it has been formed
Oxidation of ethanol
by acidified K2Cr2O7
to form an aldehyde
by distillation and
carboxylic acid by
refluxing
Oxidation of propan-2-ol by acidified K2Cr2O7 to form a ketone by distillation
Dehydration of alcohols

• Alcohols can also undergo dehydration to form alkenes

• Dehydration is a reaction in which a water molecule is removed from a

larger molecule

• A dehydration reaction is a type of elimination reaction

• Alcohol vapour is passed over a hot catalyst of aluminium oxide (Al2O3)

powder OR pieces of porous pot or pumice as well as concentrated acid can
be used as catalysts
Dehydration of ethanol
using aluminium oxide
as a catalyst forms
ethene gas, which can
be collected over water
Esterification of Alcohols
• Esterification is a condensation reaction between a carboxylic acid and an alcohol to
form an ester and a water molecule

• For esterification to take place, the carboxylic acid and alcohol are heated under
reflux with a strong acid catalyst (such as H2SO4 or H3PO4)

Carboxylic acid + alcohol → ester + water

• The reaction is reversible so an equilibrium mixture can be established with all the
reactants and products

• Esters have sweet, fruity smells

Esterification of ethanol and ethanoic acid using a strong acid catalyst to
form ethyl ethanoate and water
Exam Tip
The first part of an ester’s name comes from the
alcohol, whereas the second part comes from the
carboxylic acid.So, if ethanol and propanoic acid react
together, this will make the ester ethyl propanoate.
 Classifying Alcohols
•Primary alcohols are alcohols in which the carbon atom bonded to the -
OH group is attached to one other carbon atom (or alkyl group)

•Secondary alcohols are alcohols in which the carbon atom bonded to the
-OH group is attached to two other carbon atoms (or alkyl groups)

•Tertiary alcohols are alcohols in which the carbon atom bonded to the -
OH group is attached to three other carbon atoms (or alkyl groups)
 Classifying
primary,
secondary and
tertiary alcohols
and alcohols with
more than one
alcohol group
•Only primary and secondary alcohols can get oxidised when mildly oxidised
with acidified K2Cr2O7

•Primary alcohols get mildly oxidised to aldehydes

•Secondary alcohols get mildly oxidized to ketones

•Tertiary alcohols do not undergo oxidation with acidified K 2Cr2O7

•Therefore, only the oxidation of primary and secondary alcohols will change the
colour of K2Cr2O7 solution as the orange Cr2O72- ions are reduced to green Cr3+ ions
Only propan-1-ol and propan-2-ol, which are primary and secondary alcohols
respectively, can get oxidised, turning the orange solution green; no colour
change is observed with 2-methyl-propan-2-ol, which is a tertiary alcohol
 Test for Alcohols
•Tri-iodomethane (also called iodoform) forms a yellow precipitate with methyl ketones

•Methyl ketones are compounds that have a CH 3CO-group

•Ethanal also contains a CH3CO- group and therefore also forms a yellow precipitate with iodoform

•The reagent is heated with an alkaline solution of iodine

•This reaction involves a halogenation and hydrolysis step

•In the halogenation step, all three H-atoms in the -CH3 (methyl) group are replaced for iodine atoms,
forming -CI3

•The intermediate compound is hydrolysed by alkaline solution to form a sodium salt (RCO2- Na+)
and a yellow precipitate of CHI3
The reaction of methyl ketones with iodoform results in the
formation of a yellow CHI3 precipitate
Iodoform & alcohols

• The position of a secondary alcohol can be deduced by reacting the compound

with alkaline I2

• If the -OH group is on the carbon atom next to a methyl group, it will firstly get
oxidised to CH3CH(OH)- by the alkaline solution

• This will result in the formation of a methyl ketone RCOCH 3

• The methyl ketone will then first get halogenated and then hydrolysed to form
the sodium salt and the yellow precipitate

• If no yellow precipitate is formed, then this means that the secondary alcohol is
not on a carbon next to a methyl group
The secondary
alcohol butan-2-ol
will firstly get
oxidised to the
methyl ketone
butanone which
will form a yellow
precipitate when
reacted with
alkaline I2
Alcohol Dissociation
• Alcohols have a low degree of dissociation

• This means, that when dissolved in water, alcohol molecules do not dissociate (split up) to a great
extent

ROH (aq) ⇄ RO- (aq) + H+ (aq)

Alcohol alkoxide ion

• The position of the equilibrium lies to the left, meaning that there are far more alcohol molecules than
RO- and H+ ions

• When water dissociates, the position of the equilibrium still lies to the left, but there are more H+ ions
compared to the dissociation of alcohols
H2O (l) ⇄ OH- (aq) + H+ (aq)
• As alcohols have a lower [H+ (aq)] in solution compared to water, alcohols are weaker acids than
water
The inductive effect in alcohols

• Electron-donating species such as alkyl groups push electrons into a covalent

bond and are said to have a positive inductive effect

• In alcohols, the oxygen atom in the alkoxide ion is bonded to an electron-

donating alkyl group

• This means that there is more electron density on the O - atom

• The alkoxide ion is, therefore, more likely to accept an H+ ion and form the
alcohol again
Alkyl groups in the alkoxide ion donate electron density
to the negatively charged oxygen, causing it to more
readily accept a proton and form the alcohol again
•When water dissociates, the hydroxide ion only has one other hydrogen atom
•There is no extra electron density on the oxygen which is less likely to accept an H+ ion
•Water is therefore a stronger acid than alcohols

Water is a stronger acid than alcohols as there are no electron-donating groups in

the hydroxide ion, causing the O- to be less likely to accept a proton and reform water
Thank you