achem6
ALKANES

general MF: CnH2n+2 (n > 0)
functional group: none (all C atoms sp3-hybridsed > saturated)
isomerism: structural- > 3 C atoms, optical- > 6 C atoms

Physical properties
-1-4 C atoms: gases, 4-17 C atoms: liquids, > 17 C atoms: gas
-mp, bp & densities ^ as Mr ^
-non-polar organic cpds, insoluble in water, soluble in organic solvents

Chemical properties
-chemically inert, don't react w/ (oxidizing / reducing agents / alkali / acid) under normal lab conditions
-typical reactions: combustion + substitution

Combustion
alkanes: hydrocarbons(H/C), in excess O2 > CO2 + H2O (incomplete combustion: O2 limited > CO + C soot)
CnH2n+2 + [(3n+1)/2] O2 (g) > n CO2 (g) + (n+1) H2O (l: rtp / g: >100°C)

Combustion of petrol in car engine
gasoline (5-12 C) + air (78% N, 21% O, 1% rare gases) > air + fuel mixture > (combustion) >
products:
  -non-pollutants: CO2(g) + N2(g) + rare gases + H2O(g)
  -pollutants: CO(g) + NO2(g) + unburnt petrol + PbBr2(s- leaded petrol only)

leaded petrol unleaded petrol
anti-knocking agent:
TEL:tetraethyl lead- Pb(CH2CH3)4
TEL provides ethyl free radicals which react w/ alkanes in petrol > branched molecules which can burn more completely (lower bp) > prevents "knocking of engine" caused by preignition of residual petrol Pb(CH2CH3)4 > Pb + 4CH3CH2
Pb can react w/ O2 at high temp of engine > PbO(s), 1,2-dibromoehtane added to petrol > provide Br to react w/ Pb > PbBr2 which is more volatile > vapour instead of solid
anti-knocking agent:
MTBE: methyltertiarybutyl ether- CH3OC(CH3)3
MTBE provides methyl free radical & tertiary butyl free radical(2-methylpropyl free radical) which react w/ alkanes in petrol > branched molecules > prevents "knocking of engine"
combustion products
non-pollutants: CO2 (g), N2(g), H2O(l), rare gases
pollutants: CO(g), NO2(g), H/C unused, PbBr2(from leaded petrol- 'poisons' catalytic activity of catalysts > catalytic converter useless)
combustion products
non-pollutants: CO2 (g), N2(g), H2O(l), rare gases
pollutants: CO(g), NO2(g), H/C unused(l)
pollutants > rhodium-platinum catalyst in catalytic converter > non-pollutants
 -2CO(g)+ 2NO2(g) > 2CO2 (g) + N2(g)
 -H/C(l) + N2(g) > CO2(g) + H2O(l) + N2(g)

Substitution (photochemical reaction)-H atom replaced by Cl/Br atom, occurs only in sunlight / UV rays
-Chlorination of methane:
reagent: Cl2(g), conditions: room temp, sunlight/UV light, equation: CH4+Cl2 >(UV light/sunlight)> CH3Cl + HCl
if excess Cl2 > di-, tri-, tetra- substituted products formed (CHCl2,CHCl3,CCl4)
--Mechanism: occurs through free radical (FR) substitution involving a 3 step-chain reaction
Chain initiation step: Cl2(g): homolytic fission > Cl FR (Cl FR = Cl atoms) [Cl-Cl >(UV)> 2Cl•]
Chain propagation step: FR reacts w/ molecule > product + new FR (FR produced continues reaction)
[CH4 + Cl• > CH3• + HCl => CH3• + Cl2 > CH3Cl + Cl•]
Chain termination step: 2 FR react > molecule w/ no FR > finally no more FR > reaction stops
[CH3• + CH3• > CH3CH3, Cl• + Cl• > Cl2,
-bromination: same conditions as chlorination, observation: if excess org cpd used: reddish brown Br2 (l) disappears (product = colourless)
Sources of alkanes: Crude oil (petroleum)
crude oil: mixture of alkanes of diff bp > allows separation by fractional distillation (in fractionating towers)

Fraction C atoms BP (°C) Uses
petroleum gases 1 - 4 -160 - ~0.5 fuel: cooking gas
light petroleum 5 - 6 20 - 60 solvent
light naptha 6 - 7 60 - 100 solvent
gasoline (petrol) 5 - 12 40 - 200 fuel: car
kerosene 12 - 18 175 - 325 fuel: aircrafts
gas oil (diesel) 18 - 25 275 - 400 fuel: diesel engine
lubricating oil 20 - 40 non-volatile lubricating machine
paraffin wax 25 - 40 solid polishing waxes
bitumen (asphalt) > 30 solid road surfacing + prevent roof leakage

Catalytic cracking
cracking: larger org molecules broken down > smaller org molecules using temp, pressure + catalyst
large alkane molecule > smaller alkane molecule + alkene
C12H26 >(N2O3 catalyst, 400°C, 10 atm)> C8H18 + C4H8
larger fractions (gas oil) > more useful fraction (gasoline)

Catalytic reforming
converts straight-chained alkanes into aromatic HC (w/ benzene ring) using cyclisation & dehydrogenation
Cyclisation: alkanes of straight C chain converted to aliphatic cyclic cpd(ring cpd)
hexane >(Pt catalyst, 500°C, 10-15atm)> cyclohexane + H2 gas
Dehydrogenation: 6 H atoms removed from cyclohexane > benzene cpd + 3H2


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