AS Chemistry – Revision Notes

Unit 2 – Organic, Energetics, Kinetics and Equilibrium

Warren Rieutort-Louis

Topic 2.1 – Energetics I

 Enthalpy change and standard conditions:

o Enthalpy (H) is the heat content of a system. In a reaction this may increase
or decrease and produce an enthalpy change (H).
o Enthalpy Change (H) = Hproducts - Hreactants
o Enthalpy change is affected by pressure and temperature so standard
conditions are used for measurements.
 Pressure of 1 atmosphere
 Temperature of 25oC or 298K.

 Exothermic and Endothermic reactions:

o An exothermic reaction is one in which heat is given out. It results in a
temperature increase and a decrease of energy. H is given a negative sign.
o An endothermic reaction is one in which heat is taken in. It results in a
temperature decrease and an increase in energy. H is given a positive sign.

 Enthalpy definitions:
o Enthalpy of formation (Hf )
 Enthalpy of formation is the enthalpy change when 1 mole of a
substance is formed from its constituent elements in their standard
states under standard conditions.
 Enthalpy of formation of an element is 0.
o Enthalpy of combustion (Hc )
 Enthalpy of combustion is the enthalpy change when 1 mole of a
substance is burnt completely in excess oxygen under stand. conditions.
o Enthalpy of neutralisation (Hneut )
 Enthalpy of neutralisation is the enthalpy change when 1 mole of water
is formed by the neutralisation of hydrogen ions by hydroxide ions
under standard conditions.

 Enthalpy level diagrams:

o Enthalpy diagrams show the enthalpy change of reaction
o x-axis is the reaction pathway and y-axis is the enthalpy.

Endothermic
Exothermic reaction profile
reaction profile also showing EA
also showing EA

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  Spontaneous change and enthalpy changes:
o Exothermic reactions with a -ve enthalpy change often proceed spontaneously.
This means they start as soon as the reactants meet. This is in the direction of
greatest stability.
o Endothermic reactions with +ve enthalpy changes are often not spontaneous.
When reactants are mixed no change occurs.
o The sign of enthalpy change does not always indicate the direction of
spontaneous change because other factors affect events e.g. the speed of the
reaction.

 Hess’s Law
o The total enthalpy change for a chemical reaction is the same regardless of the
route taken for the reaction.

Route 1 = Route 2 + Route 3

o It is derived from the Law of Conservation of Energy, which states that energy
cannot be created nor destroyed.

Warren Rieutort-Louis
  Using bond enthalpy data
o Bond dissociation enthalpy
 Bond dissociation enthalpy is the enthalpy change when one mole of
bonds of a particular type in a particular environment is broken.
o The Average Bond Enthalpy is an average value of bond dissociation
enthalpies for a particular bond.
o These quantities can be combined to calculate enthalpies of reaction.

Example: Enthalpy change of formation of water:

Hf[H2O(l)] + 2x [O-H] = [H-H] + ½x[O=O]

Hf[H2O(l)] = [H-H] +½x [O=O]- 2x [O-H]
Hf[H2O(l)] = 436kJmol-1 +½*498kJmol-1
-2*462kJmol-1

 Hf[H2O(l)] = -239kJmol-1

Topic 2.2 – Organic chemistry I (introduction, alkanes, alkenes,

haloalkanes and alcohols)

Organic chemistry is the study of carbon compounds. Carbon can catenate extensively i.e.
make chains. Bonding in organic compounds is almost always covalent. Carbon has a
covalency of 4.
 Homologous series
o Homologous series are groups of organic compounds that have the same
functional group, the same general formula, gradually changing physical
properties, similar chemical properties, and they always differ by CH2 every
time.
o Important homologous series with their own functional group include:
Alkanes, Alkenes, Halogenoalkanes, Alcohols…

 IUPAC Nomenclature
o There are two types of organic compounds:
 Aliphatic – has a functional group attached to an alkyl group.
 Aromatic – has a functional group attached to an aryl group
(containing benzene).
o The root name depends on the number of carbon atoms in the longest
chain. Branch names, and functional groups are also included.

Number of carbon atoms Root name Branch name (alkyl) Branch formula
1 meth- methyl -CH3
2 eth- ethyl -CH2CH3
3 prop- propyl -CH2CH2CH3

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 4 but- butyl
5 pent- pentyl
o To name an hydrocarbon from the displayed formula:
 Look for the longest carbon chain containing the functional group –
this gives the stem.
 Add the position of the functional group (lowest number) to the stem
(e.g. hex-2-ene).
 For any side-chains, write down the chain position (using the same
numbering as for the functional group) followed by a dash, followed by
the name (e.g. 2-ethyl…).
 For more than one of the same alkyl, use the di- and tri- prefixes (e.g.
2,3-dimethyl…).
 If in a ring, use cyclo-
o To draw a hydrocarbon from the name:
 a. Draw the longest carbon chain– number it from the right.
 b. Add the functional group (if any) in the correct position.
 c. Add the side-chains in the correct positions.
 d. Fill in the rest of the bonds with hydrogens.
o Functional Groups:
 A functional group is defined as groups of atoms that give the
compound its characteristic properties i.e. chemical and physical.

Ester

Nitro
R - NO2

Acid
Chloride

Alkyne
R–CC-R

 Structural isomerism:
o Isomers are molecules that have the same molecular formula, but have a
different arrangement of the atoms in space. This does not include any
different arrangements, which are simply due to the molecule rotating as a
whole, or rotating about particular bonds.
o There are 3 types of structural isomers:
 Chain Isomers:

Warren Rieutort-Louis
 This is when the carbon chain can be arranged in different ways
with side chains, i.e. making the carbon skeleton different:
 Positional Isomers:
 This is when the functional groups are in different positions
 Functional Group isomers:
 This is when the compounds belong
to different homologous series but
have the same molecular formula:

 Geometric (stereo) isomerism:

o In stereoisomerism, the atoms making up the isomers are joined up in the
same order, but still manage to have a different spatial arrangement.
o Geometric isomers exist for some compounds with C=C double bonds in their
molecules. No rotation is possible around the double bond so different
compounds result if atoms or groups are in positions on the same side or
opposite sides of a double bond.
o For a substance to have g. i. the carbons must have different substituents.
o The rotation around the double bond is not possible because the pi bond would
have to be broken (sp2 hybridization) and this requires too much energy

o In one, the two chlorine atoms are locked on opposite sides of the double bond.
This is known as the trans isomer. (trans : from latin meaning "across" - as in
transatlantic).
o In the other, the two chlorine atoms are locked on the same side of the double
bond. This is know as the cis isomer. (cis : from latin meaning "on this side")

 Classifying reactions:
These are reactions in which
one atom in a molecule is e.g. substitution reaction between
replaced by another atom or methane and chlorine in the presence of
Free-radical group of atoms. A C-H bond is UV light
broken and the H is replaced by CH4 + Cl2  CH3Cl + HCl
something else.
Electrophilic Electrophilic addition happens With Hydrogen Halides
addition in many of the reactions of
alkenes.

With Halogens:

C2H4 + Cl2 ---> CH2ClCH2Cl

In alkenes, there is a pi bond
which is open to attack because

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 they are controlled less by the
nuclei. Electrophiles are
strongly attracted to the exposed
electrons in this pi bond.

An addition reaction is a The double bond breaks, and a bromine

reaction in which two atom becomes attached to each carbon.
molecules join together to The bromine loses its original red-
make a bigger one. The main brown colour to give a colourless liquid
molecule is attacked by an
electrophile.
Nucleophilic substitution
happens in many reactions of
halogenoalkanes.

They involve breaking the

carbon-halogen bond so depend
on its strength. The harder it is
to break, the slower the rate of
reaction
All the carbon-halogen bonds
are polar (except with I but it
can easily be polarised) because
Nucleophilic the halogens have greater E.N. CH3CH2Br + OH- 
substitution values. This leaves the halogen CH3CH2OH + Br-
slightly negative ( -) and the
carbon slightly positive ( +)

The carbon-fluorine bond is

very strong (stronger than C-H)
and isn't easily broken. In the
other halogenoalkanes, the
bonds get weaker as you go
from chlorine to bromine to
iodine
Rates of reaction:
R-Cl < R-Br < R-I
A reaction in which the elements
of a simple molecule like HBr,
H2O etc. are removed from the Dehydration of alcohols
Elimination organic compound and not CH3CH2OH  C2H4 + H2O
replaced by anything else. This
usually forms double bonds.
A reaction in which water
(catalysed by aqueous acid or
alkali) either forms a new CH3CH2Br + H2O 
Hydrolysis compound or splits an existing CH3CH2OH + HBr
organic molecule into two
compounds.

Warren Rieutort-Louis
 These involve a reaction with
Reduction of an aldehyde
Reduction hydrogen. A compound gains
CH3CHO + 2[H]  CH3CH2OH
hydrogen.
These reactions involve the loss
of hydrogen or the gain of Oxidation of an alcohol
Oxidation oxygen. An oxidising agent like CH3CH2OH + 2[O] 
acidified potassium dichromate CH3COOH + H2O
(VI) is used
These reactions involve the
joining of small molecules
called monomers to make large
molecules called polymers. A
Polymerisation large number (n) of monomer
molecules in involved and a
long polymer molecule is
formed.

o Free radicals are atoms or groups of atoms, which have a single unpaired
electron and are formed if a bond splits evenly leaving each atom with one
unpaired electron (e.g. Cl)
 Homolytic fission: a bond breaks evenly leaving each atom with one
unpaired electron i.e. free radicals.
o An electrophile is something that is attracted to an electron-rich region in
other molecules. It must be itself positive or partly positive. They could be
cations or electron-deficient atoms.
 The electrophile is normally the slightly positive ( +) end of
a molecule like hydrogen bromide
o A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
 Nucleophiles are either negative ions, or else have a strongly - charge
somewhere on a molecule: e.g. hydroxide ions, cyanide ions, water and
ammonia.

Warren Rieutort-Louis