IB

SL Chemistry DB = data booklet section

Topic 10: Organic Chemistry

10.1 Fundamentals of Organic Chemistry

Homologous Series
Homologous series:
• Contain the same functional group
• Have the same general formula
• Differ by a CH2 group
• Have similar chemical properties

Boiling point
Higher boiling points are a result of:
• A larger molar mass, meaning stronger London forces.
• Polar functional groups have stronger dipole-dipole IMF.
• Functional groups with hydrogen bonding IMF have stronger intermolecular
forces.

Branched chain isomers have less surface contact between molecules than straight
chain isomers, so have weaker intermolecular forces and consequently, lower boiling
points.

Formulae
A structural formula displays all atoms and bonds between atoms.

A condensed structural formula is a structural formula with bonds between atoms
omitted.

In a skeletal formula atoms are omitted (but bonds are shown). Carbon atoms are
assumed to be at the intersections and ends of bonds. Hydrogen atoms alone are not
shown.






A 3-D formulae uses solid wedges to represent bonds coming towards the
viewer and striped wedges to represent bonds directed away from the
viewer.

Structural isomers are compounds with the same molecular formula but
different structural formula.
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Classes / Functional Groups
Functional groups are the reactive parts of molecules.

Saturated compounds contain single bond only. Each carbon atom is bonded to as many
hydrogen atoms as possible.

Unsaturated compounds contain at least one double / triple bond. Each carbon atom is not
bonded to as many hydrogen atoms as possible

Functional Group Formula

alkyl –CH2–CH2–

alkenyl –CH=CH–

alkynyl –C≡C–

hydroxyl

ether R–O–R'

aldehyde R–CHO

carbonyl

carboxyl

ester

amine R–NH2

carboxamide

nitrile R–CN

phenyl


 IB SL Chemistry DB = data booklet section

Functional
Class Name Description Formula General Formula
Groups
alkanes -ane saturated hydrocarbon alkyl –CH2–CH2– CnH2n+2
unsaturated hydrocarbon (at least
alkenes -ene
one double bond)
alkenyl –CH=CH– CnH2n
unsaturated hydrocarbon (at least
alkynes -yne
one triple bond)
alkynyl –C≡C– CnH2n− 2
chloro-
halogenalkanes bromo- halogen–carbon bond R–X
iodo-, etc.
hydroxyl–carbon bond (alcohols
alcohols -ol are polar because of the hydroxyl hydroxyl –C–OH CnH2n+1OH
group)
alkoxy- oxygen atom links two hydrocarbon
ethers ether
methoxy- chains

aldehydes -al carbonyl bond on terminal carbon aldehyde CnH2n+1CHO

carbonyl bond on non-terminal

ketones -one ketone CnH2n+1COCxH2x+1
carbon

esters -oate ether + ketone ester

carboxyl–carbon bond (the H
-anoic
carboxylic acids dissociates making the compound carboxyl CnH2n+1COOH
acid
acidic)


-amine
amines amine–carbon bond amine
amino-

amides -amide amine–carbonyl bond carboxamide

nitriles -nitrile nitrogen–carbon triple bond nitrile –C≡N
phenyl group (cyclic hexagonal
-benzene
arenes structure with 6 carbons and 5 phenyl
phenyl-
hydrogens)

*R & R’ represent hydrocarbon chains
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Benzene
Aromatic hydrocarbons (arenes) contain a benzene ring (phenyl group).

Benzene (C6H6) is an aromatic, unsaturated hydrocarbon.

Each carbon atomic is bonded to two other carbon atoms and one
hydrogen atom, so has one delocalised electron. The delocalised
electrons occupy rings above and below the benzene plane
(represented by a circle inside the benzene hexagon).

Physical evidence
• All carbon-carbon bond lengths and strengths in benzene are identical (we would expect
the double bonds to be shorter than the single bonds, DB.10, DB.11).

Chemical evidence
• If benzene contains three double bonds, it should readily undergo addition reactions,
but it actually undergoes substitution reactions instead.
• The enthalpy change of the hydrogenation of benzene is lower than expected.

The evidence suggests that the carbon-carbon bonds in benzene are neither single nor double,
but are intermediate between a single and double bond.

Nomenclature
Identify the longest continuous carbon chain in the molecule to get the stem name:
Number of carbon atoms in longest chain Stem name
1 meth
2 eth
3 prop
4 but
5 pent
6 hex

Identify side chains and use them as a prefix to the stem name:
Name of side chains condensed structural formula
methyl –CH3
ethyl –CH2CH3
propyl –CH2CH2CH3
butyl –CH2CH2CH2CH3

If there is more than one substituent group use the prefixes: di, tri, tetra

If a molecule contains several different side chains, list them in alphabetical order.


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To identify the position of the side chains / functional groups:
• Assign a number, referring to the carbon atom in the stem.
• The carbon atoms in the carbon chain are numbered starting from the end,
which will give the side chain / functional group the lowest number.
• Place the number in front of the prefix for side chains / between the stem name
and suffix for functional groups.

Classification of organic compounds
Alcohols and halogenalkanes
Alcohols and halogenalkanes are classified based on the number of carbon atoms
bonded to the carbon atom that is directly bonded to the functional group.

Primary alcohol / halogenalkane – the functional group is bonded to a carbon that is
only bonded to one other carbon.

Secondary alcohol / halogenalkane – the functional group is bonded to a carbon that is
bonded to two other carbons.

Tertiary alcohol / halogenalkane – the functional group is bonded to a carbon that is
bonded to three other carbons.

Amines
Amines are classified based on the number of alkyl groups that are bonded to the
nitrogen atom of the amine group.

Primary amine – one alkyl group is bonded to the nitrogen.

Seconday amine – one alkyl group is bonded to the nitrogen.

Tertiary amine – one alkyl group is bonded to the nitrogen.














IB SL Chemistry DB = data booklet section

10.2 Functional Group Chemistry

Alkanes
Alkanes have low reactivity:
• The carbon-hydrogen bonds are non-polar.
• The carbon-carbon and carbon-hydrogen bonds are strong covalent bonds so
must be supplied with enough energy to overcome the energy barrier (activation
energy) and react.

Combustion reactions
Alkanes burn in oxygen in exothermic reactions. The amount of oxygen available
determined the type of combustion undergone by alkanes:

Complete combustion – burning in excess oxygen. Carbon dioxide and water are
produced.

alkane + excess oxygen à carbon dioxide + water

Incomplete combustion – oxygen supply is limited. Carbon monoxide and water or
carbon (soot) and water are produced.

alkane + limited oxygen à carbon monoxide + water OR carbon + water

Substitution reactions
Alkanes undergo free radical substitution reactions with halogens in the presence of UV
light. A halogenalkane and a hydrogen halide are produced:

Free radical substitution mechanism:














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Initiation
• Homolytic bond fission occurs when a covalent bond breaks evenly with each
atom taking one electron from the pair. This results in the formation of free
radicals.
• UV radiation has sufficient energy to break the covalent bond between two
halogen atoms.
• The individual halogen atoms have unpaired electrons – they are very reactive
free radicals.

Propagation
• A halogen free radical reacts with a molecule of the alkane producing a hydrogen
halide and an alkane free radical.
• The alkane free radical reacts with a halogen molecule to produce a
halogenalkane and another halogen free radical.

Termination
• Two free radicals combine with each other.

Alkenes
Alkenes are more reactive than alkanes due to the presence of a carbon=carbon double
bond.

Addition reactions
Alkenes undergo addition reactions due to the presence of a carbon=carbon double
bond – two smaller molecules combine to form a larger molecule.

Hydrogenation
Gaseous hydrogen is added across the carbon=carbon double bond. An alkane is
produced.

Conditions:
• High pressure
• High temperature
• Nickel catalyst

Hydration
Alkenes react with steam in the presence of a (H2SO4) or phosphoric acid (H3PO4)
catalyst to produce alcohol.

Halogenation
Alkenes react with halogens to produce dihalogenalkanes. The reaction takes place
readily at room temperature and is indicated by the decolourisation of the reacting
halogen (turns colourless).
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The reaction is used as a test to distinguish between saturated alkanes and saturated
alkenes:
• Bromine is added to both samples
• The brown colour of bromine is decolorised by the alkene.
• The mixture of bromine and alkane show no colour change.

Alkenes also react with hydrogen halides to produce halogenalkanes.

Addition polymerisation
Individual alkene molecules (monomers) can bond together to form long chains
(polymers).





n represents the number of repeating units – the section of the polymer chain whose
repetition would produce the complete polymer chain, except for the end groups.

The polymers formed are saturated, but retain the suffix –ene. They have a prefix poly-.

Addition polymers form the basis of the plastics industry.

Alcohos
Combustion reactions
Alcohols burn in oxygen in exothermic reactions. In excess oxygen, they undergo
complete combustion, producing carbon dioxide and water. In limited oxygen, they
undergo incomplete combustion, producing carbon monoxide and water or carbon and
water.
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Oxidation
Alcohols undergo oxidation in the presence of suitable oxidising agents:
• Potassium manganite (VII) changes from purple to colourless as the manganite
(VII) ion is reduced (DB.24).
• Acidified potassium dichromate (VI) changes from orange to green as the
dichromate ion is reduced (DB.24).

Primary alcohols
The partial oxidation of a primary alcohol produces an aldehyde. The reaction is carried
out with excess alcohol. *[O] is used to represent the oxidising agent.

If the aldehyde is the desired product, is can be removed from the solution by
distillation. The boiling point of aldehyde is lower than that of alcohol and carboxylic
acid. The aldehyde evaporates and rises up the distillation column, passes through a
condenser and condenses back to a liquid in the flask.

The complete oxidation of a primary alcohol produces a carboxylic acid. The reaction is
carried out with excess oxidising agent and heat under reflux.

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If the carboxylic acid is the desired product, the alcohol is heated under reflux to allow
the alcohol and the oxidising agent to remain in contact. This enables complete
oxidation.












Secondary alcohols
The oxidation of a secondary alcohol produces a ketone. The reaction is carried out with
heat under reflux and a suitable oxidising agent (e.g. potassium dichromate (VI)).

Tertiary alcohols have no hydrogen atoms bonded to the carbon atom that is directly
bonded to the tertiary group, so they do not undergo oxidation reactions.

Esterification (condensation reactions)
Esters are formed in reactions between alcohols and carboxylic acids. Water is also
produced. The reaction is reversible and a strong acidic catalyst is used.

The name of the alcohol changes to the alkyl group (in table showing side chain names),
followed by the name of the carboxylic acid with its ending changed to –oate.

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Halogenalkanes
Halogenalkanes are more reactive than alkanes.

Nucleophiles are electron rich species with a lone pair of electrons that is attracted to
regions of positive charge. It donates the electron pair to an electron deficient carbon.

The carbon-halogen bond is polar. The carbon atom is a partial positive charge and is
electron deficient. Nucleophiles are attracted to the positive dipole on the carbon atom.

The carbon-halogen bond undergoes heterolytic bond fission – a bond breaks with one
atom in the bond taking both of the bonding electrons, resulting in the formation of
oppositely charged ions.

Nucleophilic substitution reaction
The hydroxide ion (OH–) from a stron alkali is the nucleophile and it replaced the
halogen atom in the halogenalkane, which is then converted into an alcohol. A salt is
also produced.

Benzene
Benzene does not readily undergo addition reactions because the ring structure would
be disrupted and the molecule would lose stability. Benzene undergoes substitution
reactions, which do not cause disruption of the ring structure.

Electrophiles are species that are electron deficient and have either a positive charge or
a partial positive charge, so they are attracted to regions of negative charge.

Electrophiles are attracted to regions of electron density, such as the delocalised ring of
electrons around benzene.

Electrophilic substitution reaction
Benzene reacts with the nitronium ion (NO2+):
• Electrophile: nitronium ion
• Product: nitrobenzene (C6H5NO2)
• Catalyst: concentrated sulfuric acid (H2SO4).

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Benzene reacts with halogens:
Benzene and chlorine
• Products: chlorobenzene (C6H5Cl) and hydrogen chloride (HCl)
• Catalyst: aluminium chloride (AlCl3).

Benzene and bromine

• Products: bromobenzene (C6H5Br) and hydrogen bromide (HBr)
• Catalyst: aluminium bromide (AlBr3).

Summary of organic chemistry reactions
Class Reactions
Combustion
Alkanes
Free radical substitution

Addition:
Hydrogenation
Alkenes Hydration
Halogenation
Addition polymerisation

Combustion
Alcohols Oxidation
Esterfication

Halogenalkanes Nucleophilic substitution

Benzene Electrophilic substitution