Chapter 10 Organic Chemistry

Key Definitions:
Hydrocarbon: A compound containing only carbon and hydrogen.

Saturated: Compounds which contain only single bonds. (alkanes)

Unsaturated: Compounds which contain double or triple bonds. (alkenes, alkynes)

Empirical Formula: The simplest whole number ratio of the elements present in a
compound.

Molecular Formula: The total number of atoms of each element present in a

molecule of the compound. An integer multiple of the empirical formula.

Structural Formula: Representation of the molecule showing how the atoms are
bonded to each other.

Full Structural Formula: Shows every bond and

atom. Sometimes angles are applied.

Condensed Structural Formula: Omits bonds

where they can be assumed. Groups atoms together.
Contain the minimum information needed to describe
the molecule non-ambiguously.

Skeletal Formula: (not used in exams)

Functional Group: The atom or group of atoms in a molecule that gives it its
characteristic chemical properties. The reactive part of a molecule.

Homologous Series: A series of compounds that have the same functional group.
Each member differs from the next by a common structural unit. (usually —CH2—)

Features of members in a Homologous Series:

1. Successive members differ by a —CH2— group.
2. Same general formula.
3. Show a gradation in physical properties.
4. Similar chemical properties.
Structural Isomers: Compounds with the same molecular formula but different
structural formula (arrangement of atoms).

Free Radicals: Species (atoms or group of atoms) with an unpaired electron and are
vey reactive because of this unpaired electron.

Substitution Reaction: One atom or group is replaced by another atom or group.

Addition Reaction: Two reactants combine to form a single product.

Condensation Reaction: Two reactants join together and in the process a small
molecule such as H2O, HCl, NH3 is lost.

Electrophile: A positively charged ion or the positive end of a dipole that is attracted
to regions of high electron density and accepts a pair of electrons to form a covalent
bond.
δ+
EG: NO2+, H+, Br

Nucleophile: A molecule that has a lone pair of electrons or a negatively charged ion.
It is attracted to a relatively highly positively charged region in a molecule and
donates a lone pair of electrons to form a covalent bond.
EG: Cl-, OH-, NH3

Aliphatics: Compounds which do not contain a benzene ring.

Arenes: Compounds which contain a benzene ring.

Homolytic Fission: When a covalent bond breaks by splitting the shared pair of
electrons between the products and produce two free radicals with an unpaired
electron respectively.

Heterolytic Fission: When a covalent bond breaks with both the shared electrons
going to one of the products and produce two oppositely charged ions.
Alkanes: No functional group (alkyl). General formula: CnH2n+2.

Alkene: Functional group: C=C (alkenyl). General formula: CnH2n.

Alcohol: Functional group: —OH (hydroxyl). General formula: CnH2n+2O
Functional Groups:

Note: R is the abbreviation of alkyl or some exact details of

the hydrocarbon. !

The benzene ring. Molecules which contain a benzene ring

are aromatic compounds.
The IUPAC naming system:

1. Naming alkanes.
(i) Find the longest continues carbon chain in the molecule.

(ii) Choose the appropriate prefix corresponding to the number of carbon

atoms in the longest continuous carbon chain and add the ending ‘ane’ to
indicate an alkane:

(iii) Look for substituent groups (alkyl groups).

(iv) Number the positions of the substituent groups using the combination that
has the lowest individual numbers.

(v) Choose the appropriate prefix to indicate the number of each substituent
present.

(vi) Arrange the names of substituent groups in alphabetical order. (ignoring the
prefix used in step v)
Examples:

2. Naming alkenes and alkynes:

(i) alk-x-ene, where x indicates the position of the double bond.

(ii) alk-x-yne, where x indicates the position of the triple bond.

3. Naming halogenoalkanes (amines):

x-haloaklkane, where x indicates the position of the halogen atom.

halo-: fluoro-, chloro-, bromo-, iodo-…(amino-)

4. Naming alcohols:

alkan-x-nol, where x indicates the position of —OH.

5. Naming ethers:

The shorter group and the oxygen together are an alkoxy group and is named as a
substituent on the main chain.

-oxy: Choose the appropriate prefix corresponding to the number of carbon atoms in
the substituent.
6. Naming aldehydes, ketones and carboxylic acids:

aldehydes: based upon alkanal. Same as alkanes.

ketones: alkan-x-one, where x indicates the position of O=.

carboxylic acids: based upon alkaloid acid. Same as alkanes.
7. Naming esters:

ester = reaction of alcohol + carboxylic acid

[ alcohol — -yl ] + [ carboxylic acid — -anoate ]
Trends in Physical Properties:

1. Increasing b.p. with increasing carbon number: 


Increased instantaneous induced dipoles causing stronger London dispersion
forces between the molecules as their molecular size increases.

2. Lower b.p for branched-chain isomers than straight-chain isomers:

Branched-chain isomers have less contact with each other than their straight-
chain isomers, and so have weaker intermolecular forces and so lower b.p.

3. Trends in b.p. for different functional groups: Intermolecular forces.

3-D Model of Organic Molecules:

Primary, Secondary and Tertiary Compounds:

Primary: Attached to the functional group and also to at least 2 hydrogen atoms.

Primary alcohol: (carbon)

Primary amine: (nitrogen)

Primary halogenoalkanes: (carbon)

Secondary: Attached to the functional group and also to 1 hydrogen atom and 2 alkyl
groups.

Secondary alcohol: (carbon)

Secondary amine: (nitrogen)

Secondary halogenoalkanes: (carbon)

Tertiary: Attached to the functional group and also to 3 alkyl groups and so has no
hydrogen atoms.

Tertiary alcohol: (carbon)

Tertiary amine: (nitrogen)

Tertiary halogenoalkanes: (carbon)

Benzene: An aromatic, unsaturated hydrocarbon.

Delocalized Structure
Special Stability of Benzene:
Delocalized ! π electron cloud in which electron density is concentrated in two
donut-shaped rings above and below the plane of the ring. Very stable arrangement
and lowers the internal energy of the molecule.

Evidence for the Delocalized Structure:

1. Carbon-carbon Bond Length: 


(i) All carbon-carbon bond lengths in benzene are equal. 

(ii)It is intermediate in length between single and double bonds.

2. Type of Reactivity:

(i) Benzene does not undergo addition reactions like other alkenes under
normal conditions. Addition reactions would involve the destruction of the
delocalized system and the loss of stability associated with it.

(ii) Benzene undergoes electrophilic substitution reactions:
3. Number of Isomers:

Kekulé benzene has 4 structural

isomers,
but ONLY 3 isomers have ever been
found for C6H4Cl2.

4. Thermochemical Data:

Existence of Resonance(Stabilization) Energy: 155 kJ mol-1. Delocalization

minimized the electron repulsions and gives benzene a more stable structure.
Reactions of Organic Compounds: Functional Group Chemistry

Alkanes:
Stable saturated hydrocarbon due to strong and non-polar C-C and C-H bonds,
which are energetically unfavorable to break and not attracted to polar molecules or
ions.

1. Combustion Reaction: Fuels.


(i) Complete combustion: Greenhouse gas and global warming.



(ii) Incomplete combustion.
! (a) 2CH 4 (g) + 3O2 (g) → 2CO(g) + 4H 2O(l) toxic gas CO
! (b) CH 4 (g) + O2 (g) → C(s) + 2H 2O(l) global dimming

2. Substitution Reaction: Halogenation. Decolorize bromine water under the

presence of UV light.
! CH 4 (g) + Cl2 (g) ⎯⎯⎯→ CH 3Cl(g) + HCl(l)
UV light

Reaction Mechanism (Steps):

(i) Initiation: Photochemical homolytic fission. Number of free radicals
increases.

(ii) Propagation: Number of free radicals stays constant. (many)

Chain reaction: One initial event causes a large

number of subsequent events.

(iii) Termination: Number of free radicals decreases.

Formation of other products: Due to many possible propagation and termination steps
which allow reaction to continue.
Alkenes:
Unstable unsaturated hydrocarbon due to the existence of C=C double bond. ! π
bonds are more easily broken.

Addition Reactions:

(i) Addition of Halogens.

CH 2CH 2 + Cl2 → C2 H 4Cl2

Distinguish between alkanes and alkenes: Bromine water without UV light.

Alkenes: Orange/Brown to colorless.
Alkanes: No color change.
(ii) Addition of Halogen Halides. HI reacts the most rapidly due to the lowest
bond strength in HCl, HBr and HI.

(iii) Addition of Hydrogen: Hydrogenation.

(iv) Addition of Water: Hydration.

(v) Addition Polymerization: Alkenes break their double bonds and joined
together.

Monomers: Alkenes use in the reaction. Its chemical nature determines

the nature of the polymer.

Addition Polymers: Long chains products of the reaction.

Repeating Units: Has open bonds at each end. Put in a bracket with n
as subscript to denote the number of repeating units.

PE

PVC(polyvinylchloride)

PTFE
Alcohols: —OH functional group

1. Combustion Reaction: Fuels.

(i) Complete combustion.
(ii) Incomplete combustion.

2. Oxidation Reaction.
Oxidizing agents: Denoted simply as ‘+ [O]’. Acidified potassium dichromate(VI)
K2Cr2O7 / H+ (orange Cr2O72- to green Cr3+) or Acidified potassium manganate(VII)
KMnO4 / H+. (purple MnO4- to colorless Mn2+)

(i) Primary alcohols: Aldehyde (partial oxidation) and Carboxylic acid

(complete oxidation).
 Separating alcohol and aldehyde: Distillation since aldehydes have
lower b.p.

Making carboxylic acid: Reflux apparatus. Leave the aldehyde with the
oxidizing agent for a prolonged period of time.

(ii) Secondary alcohols: Ketone.

 (iii) Tertiary alcohols: Resistant to oxidation: Breaking the carbon skeleton of
the molecule requires significantly more energy.

3. Esterification Reaction: With carboxylic acids. 


Can also be called Nucleophilic Substitution Reaction. Alcohols are
nucleophiles and substitutes —OH. 

Can also be called Condensation Reaction.

Halogenoalkanes:
More reactive than alkanes. Undergo Nucleophilic Substitution Reaction.

Cl is more electronegative than C and exerts a stronger pull

on the shared electron pair.
C: Electron-deficient. Defines reactivity.
Cl: Electron-rich. Nucleophile.

Nucleophiles are attracted to the electron-deficient C and substitute Cl.

Hydrolysis:
Benzene: Electrophilic Substitution Reaction.