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Curve is initially quite steep, as for small molecules, the addition of an extra
carbon has a proportionally larger effect on the molar mass (eg, from CH4 to C2H6
there is an increase of 97.5%) & hence on the strength of the van der Waals’ forces
As the length of the carbon chain increases, the percentage change in molar
masses becomes progressively smaller (there is a 10.9% increase in molar mass
from C9H20 to C10H22, hence the curve flattens
The trend is the same for other physical properties, such as density & viscosity for
the same reasons
Empirical, molecular, structural
(condensed & full) formulae
Using ethane, C2H6, as an example
Empirical formula: simplest whole number ratio of atoms e.g. CH3
Molecular formula: actual number of atoms of each type present in a
molecule e.g. C2H6
Full structural formula: show the relative positioning of all the
atoms in a molecule & the bonds between them
3 types:
1) Chain isomerism
2) Position isomerism
3) Functional group isomerism
Chain isomerism
Different arrangement of the carbon skeleton
For example butane & methylpropane are chain
isomers of each other
Have similar chemical properties but different
physical ones; the branched isomer has a lower
melting/boiling point than the straight-chained one
H H H H H CH3 H
H C C C C H H C C C H
H H H H H H H
butane methylpropane
Position Isomerism
Have functional group placed at a different position
along the carbon skeleton
E.g. 1-bromopropane & 2-bromopropane
Has similar physical & chemical properties
Br H H H Br H
H H C C C H
H C C C
H H H H H H
1-bromopropane 2-bromopropane
Functional group Isomerism
The molecules have different functional groups (hence
different chemical properties)
E.g. ethanol & methoxymethane all have the same
molecular formula of C2H6O, however ethanol is an
alcohol while methoxymethane is an ether
ethanol methoxymethane
Naming organic compounds
International Union of Pure & Applied Chemistry (IUPAC) devised
nomenclature method
It is irregular for up to 4 carbon atoms, just have the prefixes meth-, eth-,
prop-, but-
From 5 carbon atoms & above the naming becomes systematic, like
those of geometrical shapes, e.g. pent- (pentagon), hex- (hexagon), hep-
(heptagon), oct- (octagon) etc
The name of any organic compound is usually made up of 3 parts: prefix
(substituents), stem (number of carbon atoms in main chain) & suffix
(homologous series of main carbon chain)
e.g. methylpropane
methyl- CH3 substituent
prop- 3 carbon atoms in main chain
-ane- belongs to the alkane homologous series
Monkeys
Eat
Peeled
Bananas
Counting to Ten in Organic
01 = meth Mother
02 = eth Enjoys
03 = prop Peanut
04 = but BUTter
05 = pent PENTagon
06 = hex HEXagon or HEX nut
07 = hept HEPTember (Roman sept is Greek hept)
08 = oct OCTober
09 = non NONember (Roman nov is Greek
non)
10 = dec DECember
Naming side chains
If there are alkyl groups (R groups) attached in isomers,
the prefix for the alkyl groups must be used
Prefix Name of Name of Alkyl Structure of
alkane group alkyl group
Meth- Methane Methyl CH3-
Eth- Ethane Ethyl CH3CH2-
Prop- Propane Propyl CH3CH2CH2-
But- Butane Butyl CH3CH2CH2C
H2-
Pent- Pentane Pentyl CH3CH2CH2C
H2CH2-
Hex- Hexane Hexyl CH3CH2CH2C
H2CH2CH2-
Steps in naming alkanes- step 1
For the molecule CH3CH(CH3)CH(CH3)CH3
H
H C H
H H H H
H C C C C C H
H H H H
H C H
H C H
H
2 methyl
groups
Hence green is
2 methyl correct
groups
Using the green
numbering gives the
lower substituent
number of 3,3- 3 4 5 6
dimethylhexane
4 3 2 1
H
H C H
H H H H
H C C C C C H
H H H H
H C H
H C H
H
Methylpropane
methylbutane
dimethylpropane
IUPAC common
IUPAC: 2,3,5,4,6-Pentahydroxyhexanal IUPAC: 3-carboxy-3-hydroxypentanedioic acid
Common: citric acid
Common: glucose
Alkene isomers
Have the general formula CnH2n
Have the C=C functional group within the chain
Simplest alkene is ethene, C2H4
If molecule is longer than 3 carbon chains, the
double bond can be in more than 1 position
ethene propene
Naming alkene isomers
Same 1st 4 steps as alkanes except the name
(suffix) ends in -ene instead of -ane
Step 5- The position of the double bond C=C is
shown by inserting the numb er of the carbon
atom at which C=C starts
E.g. for the isomers of C4H8
CH3CH2CH=CH2 is but-1-ene
CH3CH=CHCH3 is but-2-ene
CH2=C(CH3)2 is 2-methylprop-1-ene
Practice problem
What is the name of the following alkenes:
1) CH3CH=CHCH2CH2CH3
2) CH3CH2CH(CH3)CH=CH2
3) CH2=C(CH3)CH2CH=CH2
Answer:
1) hex-2-ene
2) 3-methylpent-1-ene
3) 2-methylpent-1,4-diene
Naming alcohols (ROH)
Always end in –ol
Simplest is methanol
Like alkenes, the position of the –OH group must be specified after
ethanol
e.g.
CH3CH2CH2OH is propan-1-ol
CH3CH(OH)CH3 is propan-2-ol
Answers
1)2-methylpentan-2-ol
2) propan-1,2,3-triol
Naming aldehydes (RCHO)
Always end in –al NOT (ol)!
Simplest is methanal
-CHO group is always at the end, so this carbon must be
carbon 1 so unnecessary to specify location
E.g.
2) HCOCH2
CH2CH3
Answer:
1)butanal
2)butanal
Naming ketone (RCOR’)
Always ends in suffix –one
Simplest is propanone (acetone)
The C=O (carbonyl) group can be inserted anywhere along the
hydrocarbon chain except at the end (why?)
After butanone, the position of the carbonyl group must be
shown
E.g pentan-2-one & pentan-3-one
propanone butanone
Practice problems- ketones
Name the following ketones:
1) CH3COCH2CH2CH2CH3
2) CH3CH2CH2COCH3
OC CH3
CH2CH2CH3
Answer:
1)hexan-2-one
2)pentan-2-one
3)pentan-2-one
Naming carboxylic acid (RCOOH)
End in –oic acid
Like aldehydes, COOH is always the terminal
group & hence this carbon is always carbon
number 1
Ethanoic (acetic)
Methanoic acid Propanoic acid
acid
Practice problems- carboxylic acids
Name the following carboxylic acids:
1) CH3CH2CH2CO2H
2)HOOCCH2CH2CH3
3) CH3CH2CH(CH3)CH2COOH
Answer:
1) butanoic acid
2)butanoic acid
3) 3-methylpentanoic acid
Naming Haloalkanes (RX)
Have the prefix halo- e.g fluoro-, chloro-, bromo-. Iodo-
Involve substituting a halogen atom into an alkane
Same numbering as alcohols & ketones
Numbers must be used after 2 carbon (from propane) atoms
E.g. CH3CHClCH3 is 2-chloropropane
CH3CH2CHClCH2CH2Br is 1-bromo-3-chloropentane
Use the prefixes, di-, tri-, tetra- is there are more than 1 of the
same type of halogen atom e.g.
Tetrachloromethane
chloromethane Trichloromethane
dichloromethane (chloroform)
(carbon tetrachloride)
Practice problems
Name the following haloalkanes:
1) CH3CH2FCHCH2CH3
2) CH3CH2CH2CH2CHBrCH3
Answers:
1) 3-fluoropentane
2)2-bromohexane
Further functional groups
Homologous Functional Structural
Prefix Suffix Example(s)
series group formulae
Methylamine CH3NH2
Amine R-NH2 Amino- -amine
CH3CH(N
2-aminobutane
H2)CH2CH3
Benzene C6H6
Aromatic
C6H5- phenyl- -benzene
compounds methylbenzene
C6H5CH3
Primary compounds
Primary carbon atom attached to a functional
group & also to at least 2 H atoms & 1 alkyl (R)
group e.g.
H H
R C OH CH3 C OH
H H
General ethanol
structure
Secondary compounds
Secondary carbon atom attached to a
functional group & just 1 H atoms but 2 alkyl
(R) group e.g.
H H H
R C OH CH3 C OH CH3 C OH
R’ CH3 CH2CH3
H C* CH2CH2CH3
Cl
CH3 C* CH2CH3
Br
CH3 C* CH2CH3
Br
General reaction:
Alkane + halogen haloalkane + hydrogen halide
RH + X2 RX + HX
R= alkyl group X= halogen atom
Halogenation of alkanes -
mechanism
Substitution reaction (chlorine atoms replace hydrogen
atoms in the methane molecule)
Substitution reaction- a reaction where 1 atom or group
of atoms is replaced by another atom or functional group
Mechanism is free radical substitution
Degree of substitution hard to control, often mixture of
products formed e.g.
Ethane reacts with excess bromine to form a mixture of
dibromoethanes:
C2H6(g) + 2Br2(g) C2H4Br2(g) + 2HBr(g)
Free radicals
Species with unpaired electron e.g. Cl., Br.
Extremely reactive
Formed by the homolytic fission of a molecule:
Cl-Cl 2Cl. (produced by action of UV light)
Homolytic fission- the breaking of a covalent bond so
that 1 electron from the bond is left on each atom,
resulting in the formation of 2 free radicals
Free radical substitution
mechanism
• Is a substitution reaction as a halogen atom replaces a
hydrogen/alkyl group.
• 3 steps:
1) Initiation (net increase in radicals)
2)Propagation (chain reaction- amount of radicals stays
the same)
3) Termination (net decrease in radicals)
Mechanism in detail UV
Initiation: Cl-Cl(g) 2Cl.(g)
H H H H
ethene ethane
Hydrogenation of alkenes-exercise
Write the reactions for the hydrogenation of but-1-
ene & but-2-ene in the presence of a nickel catalyst &
high temperature.
saturated
unsaturated
Halogenation of alkenes
Alkene + Halogen Dihaloalkane
Addition reaction
Br Br
H H
+ Br2 H C C H
C C
H H H H
1,2-dibromoethane
ethene
Halogenation of alkenes 2
Alkene + Halogen Dihaloalkane
Cl Cl
H CH3
+ Cl2 H C C CH3
C C
H H H H
1,2-dichloropropane
propene
Reaction with hydrogen halides
Alkene + Hydrogen halide haloalkane
Addition reaction
Cl H
H H
+ HCl H C C H
C C
H H H H
ethene chloroethane
Reaction with hydrogen halides 2
Reactivity order HI>HBr>HCl
Weaker strength (longer length) of H-X bond as descending group 7
Br H
CH3 CH3
H H H H
but-2-ene 2-bromobutane
Hydration of alkenes
Reaction where a water molecule reacts with an unsaturated
compound in an addition reaction
Alkene + water alcohol
RC=CR + H2O ROH
In Industry:
H H H
H H3PO4
C C + H2O H C C OH
300C
60 atm
H H H H
ethene ethanol
Also addition reaction- H+ & HSO4- added across double bond
H H
H H
+ H2SO4 H C C OSO3H
C C
H H H H
H H
H H Note
sulphuric
Ethyl ethanol acid is
hydrogensulfate reformed-
hence it’s a
catalyst
Distinguishing between alkanes &
alkenes
Use halogenation addition reaction to distinguish between these 2
functional groups
Monomer Polymer
Ethene Poly(e)thene
Polymerisation
H CH3
H CH3
n C C C C
H H H H n
propene polypropene
H Cl
H Cl
n C C C C
H H H H n
Chloroethene Polychloroethene
(vinyl chloride) (PVC)
H C6H5
H C6H5
n C C C C
H H H H n
phenylethene Polyphenylethene
(styrene) (Polystyrene)
Ethene
(from cracking)
React with steam polymerise React with chlorine React with benzene
Chloroethene Phenylethene
ethanol
Poly(e)thene (vinyl chloride) (styrene)
polymerise polymerise
Polychoroethene Poly(phenylethene)
(PVC) (polystyrene)
Alcohols
General formula: CnH2n+1OH
Have polar hydroxyl (-OH) group
Soluble in water due to hydrogen bonding from
hydroxyl group
2 types of main reactions:
1) Combustion
2) Oxidation
Combustion of alcohols
Alcohol + oxygen carbon dioxide + water
ROH + O2 CO2 + H2O
Methanol: 2CH3OH(l) + 3O2(g) 2CO2(g) + 4H2O(l) small Hc
Ethanol: 2C2H5OH(l) + 7O2(g) 4CO2(g) + 6H2O(l) medium Hc
Propanol: 2C3H7OH(l) + 9O2(g) 6CO2(g) + 8H2O(l) large Hc
Alcohol Ratio
Alcohol CO2
Methanol 1 1
Ethanol 1 2
Propanol 1 3
Answer:
Hexanol as has higher molar mass.
Alcohols vs alkanes for fuels
In general, alkane hydrocarbons release more energy
upon combustion as they are in a more reduced state
(more hydrogen atoms attached)
Hence petrol (mainly octane) releases more energy than
ethanol upon combustion
However, alcohols have advantage of being able to be
produced from renewable sources e.g. fermentation
H H H O
H+/Cr2O72-
H C C OH H C C + H2O
[O] H
H H
NB 2H atoms removed hence H
oxidation
Ethanol C2H6O Ethanal C2H4O
Oxidation of alcohols-primary
alcohols- stage 2
CH3CHO + [O] CH3COOH
H O O
H
H C C H+/Cr2O72-
H C C
H OH
H [O]
H
ethanal Ethanoic acid
C2H4O C2H4O2
NB: 1 O atom added hence
oxidation
Oxidation of alcohols-primary alcohols-
controlling the degree of oxidation
How do we control the reaction so that the aldehyde is
formed instead of the carboxylic acid or vice versa?
If the aldehyde is the desired product:
Heat reaction mixture in excess alcohol with distillation
apparatus (to distill off aldehyde as it’s being formed)
If carboxylic acid is the desired product:
Heat reaction mixture under reflux for a longer period of
time with excess oxidizing agent(a vertical condenser to
ensure the aldehyde drops back into reaction vessel for
further oxidation to the carboxylic acid)
Distillation Reflux
Summary of oxidation of primary
alcohols
In general:
O O
H
H+/Cr2O72-
R C OH
H+/Cr2O72-
R C R C
[O] [O]
OH
H
H
Primary aldehyde Carboxylic acid
alcohol
Oxidation of secondary alcohols
Only 1 product formed (ketone) as there is only 1
oxidisable hydrogen attached to the secondary
carbon
e.g. with propan-2-ol:
CH3CH(OH)CH3 + [O] CH3COCH3 + H2O
H O
H+/Cr2O72-
CH3 C OH CH3 C CH3
[O]
R’
Secondary Ketone
alcohol
Oxidation of tertiary alcohols
Cannot be oxidised as there is no hydrogen atom
attached to the hydroxyl carbon.
E.g. for 2-methylpropan-2-ol
CH3
No oxidation
H /Cr2O
+ 2-
7
possible as no
CH3 C OH H atom on C
[O]
atom bonded to
No colour change
CH3 Cr2O72- stays orange alcohol group
Rate = k[CH3C(CH3)2Br(aq)]
Hence it’s unimolecular as only 1 species involved in rate determining step
SN1 mechanism
carbocation
Step 2: nucleophile attacks carbocation intermediate
Some definitions
Carbocation- an organic ion with a positive charge on
an electron-deficient carbon atom
Heterolytic fission- the breaking of a covalent bond so
that 1 of the atoms/groups takes both of the bonding
electrons & becomes negatively charged, leaving the
other atom/group positively charged
Compare with homolytic fission (met earlier during the
free radical mechanism of alkanes)
Homolytic fission- the breaking of a covalent bond so
that 1 electron from the bond is left on each atom,
resulting in the formation of 2 free radicals
Other factors which favour SN1
With tertiary haloalkanes, the carbocation
intermediate is stabilised by the positive inductive
effect of the 3 alkyl groups (alkyl groups are have
an electron-donating effect) which help to reduce
the positive charge on the positive carbon e.g.:
4 4 Carboxylic
alcohol aldehyde
acid
4 Key:
1- subsitution halogenation NB M1 & M2
ketone 2- addition halogenation mechanism
3- polymerisation
4- oxidation
required
Reaction pathway puzzles
How can butanone be synthesised using 2-
bromobutane as one of the starting materials?
Answer:
Reflux with NaOH(aq) Reflux with H+/Cr2O72-
Answer:
Conc. H2SO4/H2O Reflux with H+/Cr2O72-