ALCOHOLS MASTERDOC:
- Contains an OH functional group
- General formula is CnH2n+1OH
Physical properties in water:
- It can hydrogen bond to water as the oxygen is more
electronegative, so is partially negatively charged and due to the
water’s polarity, the hydrogen is partially positively charged-
causing attraction and therefore hydrogen bonding
- However, the hydrocarbon chain itself is non polar as the c-h
bonds are held together by VDW forces
- This means that short chain molecules are soluble in water, due
to the predominance of the hydrogen bonding
- Therefore the longer the chain, the more insoluble it becomes in
water
Boiling points:
- Relatively low volatility
- Generally higher melting and boiling points than their alkane
equivalents due to the existing hydrogen bonding
- The polarity of the OH group allows alcohol molecules to bond to
each other
Shape of alcohols:
- With a tetrahedral shape, this means that the H-C-H bond have a
109.5 bonding angle because the four bonding pairs of electrons
repel each other to a position of minimum repulsion
- C-O-H bonding angle is 104.5 because of the two bonding and
lone pair of electrons repelling each other to a position of
minimal repulsion
Classification of alcohols:
- Primary alcohols: The carbon atom bonded to the OH group is
bonded to only one other alkyl group
- Secondary alcohols: The carbon atom bonded to the OH group
is bonded to two alkyl groups
- Tertiary alcohols: The carbon atom bonded to the OH group is
bonded to three alkyl groups
Oxidation of primary alcohols:
- Acidified orange potassium dichromate/ K2Cr2O7 is used as the
agent that cause the alcohols to oxidise
- It is required in the acidic form as it itself needs to be reduced,
needing the H+ ions provided by the acidic medium
- When the alcohol is oxidized, the solution turns from orange to
green (Cr3+)
- This, alongside Tollens or Fehling solution, can be represented
by (O)
- Primary alcohols distill to produce aldehydes, which can further
be oxidized to become carboxylic acids
- 1) After being added to the oxidizing agent, the solution is
warmed
- 2) Due to having a lower boiling point than the alcohol, the
aldehyde product can be distilled off as soon as it its formed
- 3) However, if it remains in reflux with the excess oxidizing
agent, the aldehyde products will be oxidised into a carboxylic
acid
Oxidation of secondary alcohols:
- Required the additional reagent of dilute sulfuric acid (H2SO4)
- Requires hot conditions and to be under reflux
- Produces a ketone rather than an aldehyde due to the functional
group only having one hydrogen on the carbon attached to the
alcohol and so once this is removed, there are no hydrogens left
for oxidation into a carboxylic acid
Further notes on the oxidation of alcohols:
- Tertiary alcohols are unable to oxidise due to the carbon atom
that is attached to the OH group having no hydrogens to be
removed in the first place
- Reflux: Used for heating organic reaction mixtures over a
sustained period, as the condenser prevents vapours from
escaping and instead turns them back into liquids
- The end of the reflux condenser should NEVER be sealed or
else this will cause a build up of pressure that will likely make the
container explode
Fermentation:
- The required temperature is as such because the enzymes
involved in this process may denature or refuse to function if the
conditions are not optimum
- Performed in the absence of air as if it were present in the
reaction, extra unwanted reactions may occur and ethanoic acid
(vinegar) will be produced instead
- Unlike the hydration of ethene, the reaction uses renewable
sources
- The production uses low level technology and cheap equipment,
maximising profits in industry
- A batch process, meaning its’ production efficiency is limited and
is unable to continuously be produced; also high production
costs are required to keep the reaction at optimum conditions
- The ethanol further needs to be purified by fractional distillation
- Sugar required for the source of glucose, takes up land that
could be used for food crops
Hydration of ethene:
- The reactant is obtained through crude oil being fractionally
distilled and thermally cracked by a zeolite catalyst
- Occurs at a faster rate than fermentation (about a two week
process), whilst also managing to produce a product that
requires less purification
- A continuous process, meaning the production is overall more
efficient and profits can be maximised by industry as less
manpower is required for the process
- However, the initial costs for equipment are quite high and the
mechanical components are quite complex
- Ethene is a non renewable resource, meaning in addition to
depleting natural resources, it will drive up costs as it increases
in scarcity
- The continuous effort required for pumps to maintain a high
pressure means that energy costs are high
Electrophilic addition reaction involved in this process:
-The acid catalyst is key in this process as it provides the partially
positively charged h+ ion that the electron rich double bond becomes
attracted to; this is something the water cannot do due to its poor
performance as an electrophile
-A primary carbocation is formed, which the negatively charged water
molecule attacks and subsequently forms a protonated alcohol
-One of water’s hydrogen ions are lost to regenerate the acid catalyst
and to form a more stable product
Dehydration of alcohols (elimination reaction):
- Requires concentrated sulfuric or phosphoric acids and a
temperature of around 170*c
- Oxygen’s lone pair, as a result of its’ deprotonation, attacks the
acid’s H+ ion and reforms the protonated alcohol once again
- The reformation of water also makes it a good leaving group, as
due to its’ stability and neutrality it is more easily removable
- Subsequently, the acidic base removes the remaining H+ on the
carbon and a pi bond/ double carbon bond is formed instead
- Allows addition polymers to be produced from fermentation
without the involvement of a non renewable resources such as
crude oil- which are involved in oxidation
Bioethanol as a biofuel:
- Ethanol specifically produced from fermentation can act as a
biofuel because of its’ derivation from renewable biomass
sources
- Can also be considered a carbon neutral resource as any CO2
given off when the biofuel is burnt, would have been extracted
via photosynthesis as the plant grew- therefore there would be
no net CO2 emissions into the atmosphere
- However, this consideration does not take into account the
energy required to irrigate the plants, process the fuel and purify
the ethanol from the reaction mixture if it needs to be
