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TOPIC 10: ORGANIC CHEMISTRY

10.1 Fundamentals of organic chemistry

Syllabus:
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Understandings:

A homologous series is a series of compounds of the same family, with the same general formula,
which differ from each other by a common structural unit:

Homologous series (HS):

• Classified families of organic compounds with certain common features

Common feature Additional info
Successive members differ by -CH2- group Molecular mass increases by fixed amount
going up a series

Have same general formula e.g. alkanes - CnH2n+2

Show gradation in physical properties (e.g. Due to successively longer C chains from added
boiling point, density, viscosity) -CH2- groups

Have similar chemical properties Due to the same functional group (FG)
e.g. carboxylic acids have a -COOH group which
gives them acidic properties

Solubility:

• Alcohols with smaller hydrocarbon chains are more water-soluble as there are less non-polar
sections decreasing attraction between the alcohol and polar water molecules
Trend in boiling point:

• Boiling point increases with increasing C number due to increased instantaneous induced
dipoles
• Larger molecular size causes stronger LDF
• However, increase is steeper near beginning as influence of increased chain length is
proportionately greater for smaller molecules

• FGs affect volatility due to the different polarities and intermolecular forces
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Functional groups are the reactive parts of molecules:

Functional groups = sites of reactivity

Saturated compounds contain single bonds only and unsaturated compounds contain double or triple
bonds.

Saturated compounds = only single bonds

Unsaturated compounds = contain double or triple bonds

Structural formulas can be represented in full and condensed format. Construction of 3-D models
(real or virtual) of organic molecules:

Structural formula:

• Represents molecule, showing how atoms are bonded to each other

Type of structural formula Definition Example
Full Shows every bond and atom

Condensed Omits bonds where assumed, e.g. CH3CH3

and groups atoms together

Stereochemical Shows relative positions of

atoms in 3D
Solid – comes forward
Hashed – sticks behind

Structural isomers are compounds with the same molecular formula but different arrangements of
atoms.

Structural isomers:

• Same molecular but different arrangements of atoms

• Each is a distinct compound with unique properties
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• Includes molecules with different functional groups in different classes

o e.g. C2H6O could be an alcohol or an ether
• More isomers exist for larger molecules
• A different type of structural isomers occurs when the C-C double/triple bond is found in
different positions
Structural isomers for alkanes:

Number of carbons Number of structural isomers

1 1
2 1
3 1
4 2
5 3
6 5
7 9
8 18
Structural isomers for alkenes/alkynes:

• Ethene and propene have 1 structural isomer

• Butene has 3 structural isomers
• Pentene - 5
• Ethyne and propyne have 1 structural isomer
• Butyne has 2 structural isomers
• Pentyne – 3
Structural isomers for alcohols:

• Ethanol – 2 (methyl ether + ethanol)

• Propanol – 2
• Butanol – 4
• Pentanol - 11

Application of IUPAC rules in the nomenclature of straight-chain and branched- chain isomers:

IUPAC system:

• Three possible parts, usually written as a single word

o Prefix – position, number, and name of substituents
o Stem – number of C atoms in longest chain
o Suffix – class of compound (determined by FG)

1. Identify longest continuous carbon chain

2. Identify FG
o Number between dashes before the ending shows its position by referring to the C
atom to which it is attached
o Chains are numbered starting at the end to give the smallest number to the group
o E.g. propan-2-ol, but-1-ene
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3. Identify side chain/substituent groups

o Number followed by dash before name gives its position by referring to the C atom
to which it is attached
o Chains are numbered to give the smallest number to the group
o With multiple same substituents, use the prefixes di/tri/tetra before the name and
put commas between the numbers, in the order of the C atom to which they are
attached
o If there are more than one group on the same atom, give them in alphabetical order
o E.g. 1,2-dicholoropropane, 1-chloro-2-methylpropane, 2-bromo-2-chloropropane
Amines (-NH2):

• Can appear as both a possible suffix and prefix

• Usually takes the suffix when it is the only FG
• Takes prefix with multiple functional groups (e.g. in amino acids)

Identification of primary, secondary and tertiary carbon atoms in halogenoalkanes and alcohols and
primary, secondary and tertiary nitrogen atoms in amines.

Primary carbon/nitrogen atoms:

• Attached to FG and at least 2 H atoms

• i.e. only attached to 1 other C atom
Secondary:

• Attached to FG, 1 H, and 2 alkyl groups

• i.e. attached to 2 other C atoms
Tertiary:

• Attached to FG and 3 alkyl groups (no H atoms)

• i.e. attached to 3 other C atoms
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Benzene is an aromatic, unsaturated hydrocarbon:

Arenes:

• Class of compounds derived from benzene (C6H6)

• Forms special branch of organic compounds called the aromatics with distinct properties
• Contains phenyl functional group (C6H5-)

• Properties come from the parent arene molecule, benzene

Unsaturation:

• 1:1 ratio of C to H indicates high degree of unsaturation

• However, it does not show characteristic structures of highly unsaturated molecules
o It has no isomers
o It is reluctant to undergo addition reactions

Discussion of the structure of benzene using physical and chemical evidence:

1865 model of benzene:

• Suggested cyclic arrangement of C with alternating single and double bonds

• e.g. 1,3,5-cyclohexatriene

• The symmetry of this model explains some of its properties

o E.g. has no isomers
• However, could not explain its atypical reactivity considering its unsaturation
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Development of the current model:

• Current model was developed through data provided by technological advances

Evidence Explanation
X-ray crystallography Provided info about bond length
The benzene bond length and strength was in-
between a C single and double bond

Enthalpy of hydrogenation Benzene has a value between the

hydrogenation of a cyclic molecule with 1 and 2
double bonds
Its enthalpy is 152kJ/mol lower than the
predicted value for 1,3,5-cyclohexatriene
(known as its resonance energy)

Structure of benzene:

• Cyclic structure
• Framework of single bonds attaches each C to a C on either side, and a H atom
• Each C forms 3 single bonds with 120o bond angles, forming a planar shape
• Leaves 1 electron on each C, which are delocalised through all 6 C atoms
• Delocalisation produces symmetrical ‘cloud’ of electron charge above and below the plane
of the ring
• The delocalisation minimises repulsion between electrons
• Creates very stable arrangement, lowering its internal energy
• The electrons are free to move and change positions, so double bonds can shift
• Usually depicted as a ring inside a hexagon, to denote the delocalised electrons

• This model explains most observed properties of benzene

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Property
Bond lengths are between single and double bonds
Enthalpy of hydrogenation (adding H2) is lower than
molecules with 3 C double bonds
Reluctant to undergo addition reactions
More likely to undergo substitution reactions
Only one isomer exists
High boiling point (compared to similarly sized
hydrocarbons)
High melting point
Insoluble in water
Explanation
Each bond contains a share of 3 electrons between
the bonded atoms
Delocalisation minimises repulsion to stabilise
structure and lower internal energy
Addition would disrupt delocalised cloud, so is not
energetically favourable (products would be of
higher energy than reactants)
Substitution reactions preserve the stable ring
structure
Symmetrical molecule with no alternating single and
double bonds
Thus, all adjacent positions in the ring are equal
Delocalised electrons allow temporary dipoles to be
easily set up
Small and symmetrical, allowing it to pack efficiently
and optimise their intermolecular forces
Benzene is quite large compared to water
Would require energy to break existing H-bonds and
relatively strong vdW forces between benzene
molecules
Can only create weak vdW forces with water, so
would not be energetically profitable
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Identification of different classes: alkanes, alkenes, alkynes, halogenoalkanes, alcohols, ethers,

aldehydes, ketones, esters, carboxylic acids, amines, amides, nitriles and arenes. Identification of
typical functional groups in molecules eg phenyl, hydroxyl, carbonyl, carboxyl, carboxamide,
aldehyde, ester, ether, amine, nitrile, alkyl, alkenyl and alkynyl:
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10.2 Functional group chemistry

Syllabus:
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Understandings:

Alkanes:

Alkanes have low reactivity and undergo free-radical substitution reactions:

Alkanes have low reactivity:

• Saturated – only contains very strong single C-C and C-H bonds
• Only react in presence of strong energy
• Thus, are stable in most conditions and can be safely stored/transported/compressed
• The C-C and C-H bonds are also characteristically non-polar
• Will not be susceptible to attack by most common reactants
• Thus, alkanes are generally of low reactivity
Combustion reactions:

• Combustion reactions are highly exothermic

• Release lots of energy in forming double bonds in CO2 and the bonds in H2O
• Alkanes are widely used as fuels – they release significant amounts of energy when burnt
o E.g. in internal combustion engines and household heating
• Alkanes burn in the presence of excess oxygen to produce CO2 and H2O
• Supply of oxygen influences extent of oxidation
• From complete to incomplete combustion:
o C3H8 (g) + 5O2 (g) --> 3CO2 (g) + 4H2O (g)
o 2C3H8 (g) + 7O2 (g) --> 3CO (g) + H2O (g)
o C3H8 (g) + 2O2 --> 3C (g) + 4H2O (g)
• Other hydrocarbons (e.g. alkenes, alkynes, arenes) similarly undergo complete or
incomplete combustion, depending on oxygen availability
• However, as C:H ratio increases with unsaturation, this increases the smokiness of the flame
due to the unburned carbon

Bromine water can be used to distinguish between alkenes and alkanes:

Substitution reactions of alkanes (halogenation):

• Main reaction of alkanes (saturated molecules)

• Occurs when another reactant replaces a H atom, like a halogen
• E.g. methane (CH4) reacts with chlorine to produce chloromethane and hydrogen

• The reaction requires UV light energy to break down the covalent bond in Cl2
o Does not take place in the dark
• This splits it into Cl free radicals, each with an unpaired electron
• Once formed, these radicals start a chain reaction where a mixture of products is formed
• Can be described as a sequence of steps called the reaction mechanism
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1. Initiation:

• Occurs in presence of UV light

• Known as photochemical homolytic fission
• Bond between Cl is broken, splitting shared pair of electrons between the two atoms
• The two products have equal assignment of electrons from the bond

2. Propagation:

• Uses and produces free radicals

• Many possible propagation steps, all which allow the reaction to continue
• Thus, often called a chain reaction

3. Termination:

• Removes free radicals from the mixture

• Causes them to react and pair up electrons together
• Many possible termination steps
• The reaction may contain mono and di-substituted halogenoalkanes, HCl, and larger alkanes

• A similar reaction occurs with other alkanes and with bromine

• Bromine water that reacts with an alkane in UV light changes from brown to colourless
• This can distinguish between alkanes and alkenes
• Alkenes do not require light to cause the colour change
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Alkenes:

Alkenes are more reactive than alkanes and undergo addition reactions:

Alkenes:

• General formula CnH2n

• Are unsaturated with a C=C double bond
• The C atoms forming double bonds have a trigonal planar shape (120o angles)
• The double bond is the site of reactivity, so alkenes are more reactive than alkanes
• The bond is relatively easily broken, creating 2 new bonding positions on the C atoms
• Enables alkenes to undergo addition reactions and form a range of saturated products
• Used as the starting materials in the manufacture of many industrially important chemicals

Addition of hydrogen (hydrogenation):

• Hydrogen reacts with alkenes to form alkanes

• Requires the presence of nickel catalyst at around 150oC
• No UV light is required due to the higher reactivity of alkenes

• This is used in the margarine industry to convert oils with unsaturated hydrocarbon chains
into more saturated compounds
• This gives them higher melting points, so they will be solid at room temperature
• However, there are health concerns over trans-fats produced by partial hydrogenation

Addition of halogens:

• Halogens react with alkenes to form dihalogeno compounds

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• The halogen atom attaches to each of the 2 C atoms at the double bond
• This happens quickly at room temperature
• It is accompanied by a loss of colour in the reacting halogen

Addition of hydrogen halides:

• Hydrogen halides (e.g. HCl, HBr) react with alkenes to form halogenoalkanes
• All hydrogen halides can react, but by reactivity: HI > HBr > HCl
o Due to the decreasing strength of the hydrogen-halide bond down Group 7
o Thus, HI has the weakest bond and reacts the most readily
• This takes place rapidly in solution at room temperature

Addition of water (hydration):

• Converts the alkene into an alcohol

• Takes place in heat with steam, and a catalyst of concentrated H2SO4
• Involves an intermediate, where H+ and HSO4- ions are added across the double bond
• This is quickly followed by hydrolysis, with replacement of the HSO4- by OH- and reformation
of the H2SO4
• This reaction has industrial significance as ethanol is a very important solvent, and is
manufactured on a large scale
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Polymers: Addition polymers consist of a wide range of monomers and form the basis of the plastics
industry

Polymerisation of alkenes:

• Alkenes readily undergo addition reactions by breaking their double bond

• They can be joined together to produce long chains called addition polymers
• The alkene used is the monomer, and determines the properties of the polymer
• Polymers are a major product of the organic chemical industry (e.g. many plastics)
• Their structures are shown using a repeating unit with open bonds on each end
• It is put in a bracket with subscript n, which denotes the number of repeating units
Ethene polymerises to form poly(ethene)/polythene:

Propene polymerises to form poly(propene)/polypropylene:

Other common addition polymers include poly(chloroethene)/PVC and poly(tetrafluoroethene)

or PFTE, marketed as Teflon:

Alcohols:

Alcohols undergo nucleophilic substitution reactions with acids (also called esterification or
condensation) and some undergo oxidation reactions:

Alcohols:

• General formula CnH2n+1OH

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• -OH FG is polar, which increases their relative solubility in water

• The most common alcohol is ethanol, which is soluble in water in all proportions
Combustion of alcohols:

• Alcohols also undergo combustion reactions, releasing significant amounts of energy

• Thus, they are an important fuel
o E.g. used in alcohol burners
• Like hydrocarbons, when oxygen is limited they will produce CO instead of CO2
• The amount of energy released per mole increases going up the HS, mainly due to the
increasing number of CO2 molecules produced
• E.g. comparing the burning of methanol vs pentanol

Oxidation of alcohols:

• Combustion involves the complete oxidation of the alcohol molecules

• They can also react with oxidising agents, which selectively oxidise the C attached to the -OH
• This keeps the carbon skeleton of the molecule intact
• Thus, alcohols can be oxidised into other important organic compounds
• The products of these reactions often depend on if they are primary/secondary/tertiary
• Various oxidising agents are used
• Acidified potassium dichromate(VI) is commonly used
o Is bright orange due to Cr(VI) but is reduced to the green Cr(III) as the alcohol is
oxidised
• +[O] is sometimes used when writing the reactions to show the oxidising agent

Oxidisation of primary alcohols:

• Occurs in a two-step reaction, which requires heat

• First forms an aldehyde
• This, under prolonged conditions, is oxidised further to carboxylic acid
o E.g. when a bottle of wine is left exposed to air, bacteria slowly oxidise the ethanol
to ethanoic acid, which gives the smell of vinegar
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• The acidified oxidising agent can be:

Oxidising agent Starts as Ends as
Acidified potassium dichromate Orange Cr(VI) Green Cr(III)
Acidified potassium Purple MnO4- Colourless Mn2+
permanganate
• The reaction can be stopped after the first step to obtain the aldehyde product
o Distillation is used to remove it from the reaction mixture
o This is possible as aldehydes lack H-bonds and have lower boiling points than
alcohols or carboxylic acids
• To obtain carboxylic acid, the aldehyde is left in prolonged contact with the oxidising agent
o This is achieved most efficiently using apparatus for reflux
Oxidation of secondary alcohols:

• Secondary alcohols are oxidised to ketones, by a similar process of oxidation

• This requires an acidified oxidising agent, heat, and apparatus for reflux

Oxidation of tertiary alcohols:

• Tertiary alcohols are not readily oxidised under comparable conditions

• It would require breaking the carbon skeleton, which requires significantly more energy
• Thus, no colour change would be seen in the potassium dichromate(VI) oxidising agent when
reacted with a tertiary alcohol
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Esterification of alcohols:

• Alcohols react with carboxylic acids to form esters

• Occurs in a condensation (equilibrium) reaction which also produces water

• For example, ethanoic acid reacts with ethanol, catalysed by concentrated H2SO4

• The ester can be separated by distillation as it has the lowest boiling point of the
components
• They have distinct smells, which can be detected if the reaction mixture is poured into a
beaker of water
• Unlike carboxylic acids or alcohols, esters lack free -OH groups, so they cannot form H-bonds
• Thus, they are quite insoluble and form a layer on the surface
• Other esterification reactions include:
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Halogenoalkanes:

Halogenoalkanes are more reactive than alkanes:

Halogenoalkanes:

• General formula is CnH2n+1X (where X = halogen)

• Contain an atom of F/Cl/Br/I bonded to the C skeleton of a molecule
• They are saturated like alkanes, so their reactions involve substitution
• Unlike alkanes, they possess a polar bond, which makes them more reactive
• The reactivity is mainly due to the electron-deficient C atom

A nucleophile is an electron-rich species containing a lone pair that it donates to an electron-deficient

carbon:

Nucleophiles:

• Reactants that are electron-rich

• Have a lone pair of electrons and may carry a negative charge
• Thus, they are attracted to positive charges
Electrophiles:

• Reactants that are electron-deficient

• Have vacant orbitals which can accept electron pairs
• Thus, they are attracted to negative charges
They can undergo (nucleophilic) substitution reactions:

Nucleophilic substitution reactions:

• Halogenoalkanes are polar as the more electronegative halogen atom exerts a stronger pull
on the shared electron in the bond to C
• Thus, the halogen gains a partial negative charge
• The C gains a partial positive charge and is said to be electron-deficient
• An electron-rich species (e.g. OH-) attacks the electron-deficient C atom
• This leads to substitution of the halogen functional group by the nucleophile
• E.g. halogenoalkanes react with alkalis like NaOH to form alcohols
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• Requires dilute, aqueous, and warm conditions

• Reactions like these mean that halogenoalkanes can be converted into many other classes of
compounds
• Thus, they are very useful intermediates in organic synthetic pathways

Benzene:

Benzene does not readily undergo addition reactions but does undergo electrophilic substitution
reactions:

Benzene:

• Delocalised electrons in benzene gives it a special stability

• This means addition reactions are generally unfavourable
• Instead, substitution reactions occur more readily
• Some H atoms are replaced by an incoming group
• This leads to products which conserve the aromatic ring
• The delocalised electron ring is the site of reactivity

Electrophilic substitution reactions:

• Electrophiles are attracted to the electron-rich benzene ring

• This leads to electrophilic substitution
• E.g. benzene reacts with the nitronium ion, NO2+, derived from nitric acid HNO3
• This requires concentrated H2SO4 and 50oC heat
• It forms nitrobenzene
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• Benzene also reacts with halogens

• E.g. with AlCl3 in dry ether
• It forms chlorobenzene

Summary:

Reactants Products Required conditions Other

Alkane + oxygen Carbon dioxide + water Combustion
Alkane + halogen Halogenoalkane UV light Halogenation
(substitution)
Free radical mechanism
Alkene + hydrogen Alkanes Ni catalyst Hydrogenation
150oC (addition)
Changes bromine from
brown to colourless
without UV
Alkene + halogens Dihalogeno compounds Loss of colour of halogen
Alkene + hydrogen Halogenoalkane HI is strongest
halide
Alkene + water Alcohol Conc. H2SO4 Hydration (addition)
In heat with steam Involves intermediate
stage where H is
replaced by OSO3H
Alkene + alkene Polymer Addition reactions
(addition polymers)
Alcohol + oxygen Carbon dioxide + water More release of energy
Primary alcohol → Aldehyde → carboxylic Oxidising agent e.g. Acidified potassium
aldehyde acid Heat dichromate - Orange
Distillation for aldehyde Cr(VI) to green Cr(III)
Reflux for carboxylic acid acidified potassium
permanganate – purple
MnO4- to colourless Mn2+
Secondary alcohol Ketone Oxidising agent Same oxidising agents
Heat
Reflux
Tertiary alcohols No reaction Would require breaking
C skeleton
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Alcohols + carboxylic Esters + water Conc. H2SO4 Condensation reaction

acids Equilibrium reaction
Halogenoalkanes + Alcohol + salt Nucleophilic substitution
nucleophile e.g. OH-
Benzene + electrophile Halogen benzene Conc. H2SO4 and 50oC Electrophilic substitution
with nitric acid (HNO3)
Dry ether and AlCl3 with
Cl2