Halogenoalkanes

Substitution & Elimination Reactions of Halogenoalkanes

 Halogenoalkanes are much more reactive than alkanes due to the presence
of the electronegative halogens
o The halogen-carbon bond is polar causing the carbon to carry a partial
positive and the halogen a partial negative charge
 A nucleophilic substitution reaction is one in which a nucleophile attacks a
carbon atom which carries a partial positive charge
o An atom that has a partial negative charge is replaced by the
nucleophile
 In an elimination reaction of halogenoalkanes, a halogen halide
is eliminated to form an alkene

Hydrolysis

 Halogenoalkanes can be broken down under reflux by water to form

an alcohol
o The breakdown of a substance by water is also called hydrolysis
 The reaction is classified as a nucleophilic substitution reaction as a water
molecule in the silver nitrate solution acts as a nucleophile and replaces the
halogen
o Eg. bromoethane reacts with aqueous silver nitrate solution to form
ethanol
  This reaction is similar to the nucleophilic substitution reaction of
halogenoalkanes with aqueous alkali, however the hydrolysis with water is
much slower than with the OH- ion
o The hydroxide ion is a better nucleophile than water as it carries a full
formal negative charge
o In water, the oxygen atom only carries a partial negative charge

The halogenoalkanes have different rates of hydrolysis, so this reaction can

be used as a test to identify halogens in a halogenoalkane by measuring how
long it takes for the test tubes containing the halogenoalkane and aqueous
silver nitrate solutions to become opaque

Formation of nitriles

 The nucleophile in this reaction is the cyanide, CN- ion

 Ethanolic solution of potassium cyanide (KCN in ethanol)
is heated under reflux with the halogenoalkane
 The product is a nitrile
o Eg. bromoethane reacts with ethanolic potassium cyanide when heated
under reflux to form propanenitrile

 The nucleophilic substitution of halogenoalkanes with KCN adds

an extra carbon atom to the carbon chain
 This reaction can therefore be used by chemists to make a compound with
one more carbon atom than the best available organic starting material
Formation of primary amines by reaction with ammonia

 The nucleophile in this reaction is the ammonia, NH3 molecule

 Ethanolic solution of excess ammonia (NH3 in ethanol) is heated under
pressure with the halogenoalkane
 The product is a primary amine
o Eg. bromoethane reacts with excess ethanolic ammonia when heated
under pressure to form ethylamine


  Halogenoalkanes: SN1 & SN2 Mechanisms

In nucleophilic substitution reactions involving halogenoalkanes, the halogen atom

is replaced by a nucleophile

 These reactions can occur in two different ways (known

as SN2 and SN1 reactions) depending on the structure of the halogenoalkane
involved

SN2 reactions

 In primary halogenoalkanes, the carbon that is attached to the halogen is

bonded to one alkyl group
 These halogenoalkanes undergo nucleophilic substitution by
an SN2 mechanism
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘2’ means that the rate of the reaction (which is determined by the
slowest step of the reaction) depends on the concentration of both the
halogenoalkane and the nucleophile ions
SN1 reactions

 In tertiary halogenoalkanes the carbon that is attached to the halogen is

bonded to three alkyl groups
 These halogenoalkanes undergo nucleophilic substitution by
an SN1 mechanism
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘1’ means that the rate of the reaction (which is determined by the
slowest step of the reaction) depends on the concentration of only one
reagent, the halogenoalkane
Carbocation

 In the SN1 mechanism, a tertiary carbocation is formed

 This is not the case for SN2 mechanisms as a primary carbocation would have
been formed which is much less stable than tertiary carbocation.
 This has to do with the positive inductive effect of the alkyl groups attached
to the carbon which is bonded to the halogen atom
o The alkyl groups push electron density towards the positively charged
carbon, reducing the charge density
o In tertiary carbocations, there are three alkyl groups stabilising the
carbocation whereas in primary carbocations there is only one alkyl
group
 o This is why tertiary carbocations are much more stable than primary
ones

Relative strength of the C–Hal

Reactivity of Halogenoalkanes
 The halogenoalkanes have different rates of substitution reactions
 Since substitution reactions involve breaking the carbon-halogen bond
the bond energies can be used to explain their different reactivities

Halogenoalkane Bond Energy Table


The formation of the pale yellow silver iodide is the fastest
(fastest nucleophilic substitution reaction) whereas the formation of the
silver fluoride is the slowest (slowest nucleophilic substitution reaction)
 This confirms that fluoroalkanes are the least reactive and iodoalkanes are the
most reactive halogenoalkanes
Fluoroalkanes & Flurohalogenoalkanes
Uses of Fluoroalkanes & Fluorohalogenoalkanes
 Fluoroalkanes and fluorohalogenoalkanes are chemically inert
 The amount of energy required to break the halogen-carbon bond is so high that
fluoroalkanes and fluorohalogenoalkanes are very unreactive

Fluorohalogenoalkanes

 The most common fluorohalogenoalkanes are chlorofluorocarbons (CFCs)

 These compounds contain carbon atoms with chlorine and fluorine atoms attached to
them
o Eg. CCl3F and CCl2F
 CFCs have many uses due to their chemical inertness as they are non-
flammable and non-toxic
o They are used as refrigerators
o Propellants for aerosols
o As solvents for dry cleaning

Fluoroalkanes
  Hydrofluorocarbons (HFCs) are compounds that contain a carbon attached to
hydrogen and fluorine atoms only
o Eg. CH2F-CF3
 As with CFCs, HFCs are chemically inert and are therefore used for a wide range of
purposes

Fluorohalogenoalkanes & the Ozone Layer

 The most common example of Fluorohalogenoalkanes
is chlorofluorocarbons (CFCs)
 Though chlorofluorocarbons (CFCs) have many beneficial uses, they also have
devastating effects on the ozone layer:
o CFCs absorb a lot of UV radiation in the upper atmosphere
o The CFCs are then broken down by the UV light causing the formation of
chlorine radicals
o These radicals react with ozone and break down the ozone layer
 This is why hydrofluorocarbons (HFCs) are often used as an alternative to CFCs
 As these compounds don’t contain any chlorine atoms, they will not have adverse
effects on the ozone layer
Reactions of Alcohols
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

Compl
ete combustion of alcohols to produce carbon dioxide and 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:
o HX (rather than using HBr, KBr is reacted with H 2SO4 or H3PO4 to make
HBr that will then react with the alcohol)
o PCl3 and heat
o PCl5 at room temperature
o 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
o 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
o Acidified means that that the potassium dichromate(VI) is in a solution
of dilute acid (such as dilute sulfuric acid)
o For potassium dichromate(VI) to act as an oxidising agent, it itself
needs to be reduced
o This reduction requires hydrogen (H +) ions which are provided by the
acidic medium
 When alcohols are oxidised the orange dichromate ions (Cr 2O7 )
2-

are reduced to green Cr3+ ions

 Acidified potassium manganate(VII), KMnO4, is a purple oxidising agent
o 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 (MnO 4-)
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
Dehydration of alcohols
  Alcohols can also undergo dehydration to form alkenes
o Dehydration is a reaction in which a water molecule is removed from a
larger molecule
o 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

Exam Tip
The first part of an ester’s name comes from the alcohol, whereas the second
part comes from

`````````````

cc lassifying and Testing for Alcohols

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)