REACTION KINETICS
aA+bB cC+dD
rate = k[A] [B]y
x
The constant k depends on the reaction and the temperature, not depend on
the concentrations of substances
Order indicates how many A and B participate in the rate-determining
(slowest) step.
The half-life (t1/2) of a reactant is the time taken for the initial concentration
of a reactant to fall by half.
Those molecules having energy above a certain minimum value will react
when they collide. This minimum energy value is called the activation
energy. The activation energy can be thought of as an energy barrier to the
progress of the reaction.
THERMOCHEMISTRY
ΔH = ΔH products - ΔH reactants
An exothermic enthalpy change: negative value, as energy is lost to
the surroundings.
ΔH = -xkJmol-1
An endothermic enthalpy change: positive value, as the energy is
gained by the system from the surroundings.
ΔH = + ykJmol-1.
GROUP II
Reactivity
extra shielding from inner shells and increase in distance from the nucleus=>
Ionisation energy decreases=> easy to lose electrons
Thermal stability of carbonates and nitrates
Carbonates
The thermal stability of Group II carbonates increases as we descend
the group. BeCO3 decomposing most easily.
MCO3(s) → MO(s) + CO2(g)
The larger the anion the easier the distortion=> polarising ability of
the M2+ ion decreases down the group.
The greater the distortion caused by the polarising ion the less stable
the compound is to heat. This means that beryllium carbonate
decomposes at a lower temperature to the rest of the group.
Nitrates
ionic radius increases=> the polarising power of the M2+ decreases =>
The thermal stability of the nitrates increases
ORGANIC CHEMISTRY
ALKANES
Physical properties
1. At room temperature and pressure:
• C1 - C4 are gases
• C5 - C15 are liquids
• C16 - are solids.
2. each molecule is identical in terms of types of atom and bonds
present, only mass increases
=> no. of carbon atoms in increases, the boiling points rise
3. Compounds with branched chains have boiling points < straight
chain compound.
4. 'even' carbon molecules pack tighter together=> van der Waal's
forces > in 'odd' carbon molecules => elting point increases with the
no. of carbon atoms However, when plotted on a graph, two curves are
obtained that
5. non-polar => immiscible in water and other polar solvents. CH4 is
the most soluble.
Chemical properties
1. Combustion (room temperature, sunlight or U.V. light)
Mechanism: Free radical substitution
There are 3 stages:
a) Initiation:
Light or heat will cause a few chlorine molecules to split homolytically
into chlorine radicals having unpaired electrons.
Cl:Cl(g) → 2Clo(g) (chlorine radical)
b) Propagation:
The radicals are very reactive and will react with the first particle they
meet - most probably a methane molecule because the formation of a
H-Cl bond is more exothermic than the formation of a C-Cl bond.
• i) Clo(g) + CH4(g) → oCH3(g) + HCl(g) (formation of a methyl radical is
more likely)
Or:
• Clo(g) + CH4(g) → CH3Cl(g) + Ho(g)
c) Termination:
Some reactions occur in which atoms or radicals combine together to
produce a molecule without a new radical being formed:
• Clo(g) + Clo(g) → Cl2(g)
• o
CH3(g) + Clo(g) → CH3Cl(g)
• o
CH2Cl(g) + Clo(g) → CH2Cl3(g)
ALKENES
1. Physical properties
Increased molecular mass=>Gases at room temperature, then liquids,
finally solids=>increasing Van der Waal's forces=> decrease in volatility.
Covalent, physical properties (i.e. almost insoluble in water, soluble in
organic solvents)
General Formula: CnH2n
2. Chemical properties
Addition of Bromine
Mechanism:
ARENES
General formula: CnH2n+1OH
Examples: CH3OH - methanol, C2H5OH - ethanol.
Isomerism
For example: C3H7OH
Stereoisomers of butan-2-ol exist (i.e. two optical isomers) form due to the
presence of an asymmetrical carbon atom - one carbon which has attached to
it four different groups.
Chemical properties
Primary and secondary but not tertiary alcohols can be easily oxidised. Most
alcohols also undergo elimination (dehydration) and substitution reactions.
Combustion
All alcohols can be oxidised =>CO2 + H2O
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H20(l)
Substitution to give haloalkanes
C2H5OH(l) + HBr(aq) → C2H5Br(aq) + H2O(l)
Mechanism:
In the above mechanism, the lone pair on the oxygen atom of the ethanol
accepts a proton from the HBr. In doing this, a covalent bond is formed
between the oxygen and the proton.
The intermediate formed in the reaction then loses a molecule of water and
the Br- then attacks to carbonium ion to form the product.
Reaction with sodium
2R-OH + 2Na → 2RO-Na+ + H2 (sodium alkoxide + hydrogen)
Oxidation to carbonyl compounds and carboxylic acid.
Oidising agent is acid. K2Cr2O7 which turns from orange to green (Cr3+). The
reactions involve the loss of the hydroxyl hydrogen together with a hydrogen
atom from the adjacent alkyl group.
With primary alcohols, the initial aldehyde => oxidised further to a
carboxylic acid, if heat or excess oxidising agent is used, but ketones cannot
be readily oxidised (involves breaking C-C bond).
Tertiary alcohols have no hydrogen atom on the alkyl group adjacent to the
hydroxyl group =>nnot be easily oxidised.
Primary alcohols → Aldehydes → Carboxylic acid
Secondary alcohols → Ketones
Tertiary alcohols resist oxidation
Dehydration of alcohols to form alkenes
This dehydration is achieved by passing ethanol vapour over hot alumina. In
the lab, conc. H2SO4 is used.
C2H5OH(g) → C2H4(g) + H2O(g)
C2H5OH(l) + H+(aq) C2H4(g) + H20(l) + H+(aq)
Formation of esters
Alcohols react with acids to form esters.
These reactions are both slow and reversible.
CARBOXYLIC ACIDS
1. Physical properties
All carboxylic acids are highly associated with H-bonding=> gaseous acids
exist at room temperature nd their miscibility in water.
The Carboxylic GroupThis group contains both a carbonyl (C=O) group
and a hydroxyl group (O-H).Both bonds in isolation, are quite strongly polar
(C=O and O-H).
2. Chemical properties
Acidity: weak acids. In solution the equation is:
The loss of the proton is enhanced by the electronegativity of the adjacent
oxygen, and the charge separation in the C=O. The latter produces a
slight+ve charge on the carbon which pulls the bonding electrons in O-H to
itself:
In the alcohol the inductive effect of the electronegativeoxygen in the O-
H bond=> less tendency for H+ to be [Link] acid equilibrium is
encouraged to move to the right
i.e. cloud extends on O-C-O;
1. Ethanoic acid is less acidic than methanoic acid due to the inductiveeffect
of the CH3 group.
2. Introduction of a electronegative Cl atom produces an increasein acidity
due to the electron withdrawing power of Cl.
[Link], with an NO2 group. This also produces a greateracidity, i.e.
4. With CH3CH2CH2COOH: inductiveeffect of CH3 group reduced as it is
transmitted through 2 CH2groups.
Methods of preparation and manufacture
a) By oxidation of primary alcohols or aldehydes
b) By hydrolysis of nitriles
This hydrolysis can be brought about both in acids and alkaline [Link]
acid solution, using dilute sulphuric acid:
2CH3CN(aq) + H2SO4(aq) + H2O(l)
2CH3COOH(aq) + (NH4)2SO4(aq)
Chemical reactions
a) Formation of saltsCarboxylic acids will react with bases and
carbonates to form salts:
b) Formation of EstersCarboxylic acids react with alcohols to form esters,
the H atom of the carboxylgroup is replaced by an alkyl group.
CH3COOH(aq) + C2H5OH(aq)CH3COOC2H5(aq)
Concentrated H2SO4 is often used as it catalyses thereaction and removes
the water. This removal of water drives the equilibriumtowards the right.
b) Formation of Acyl Chlorides
These can be prepared by the reaction of sulphur oxide dichloride
SOCl2,phosphorus pentachloride (PCl5) or phosphorous trichloride
(PCl3)on the acid.
Acyl chloride
Hydrolysis of acyl chloridesAcyl chlorides react with water, often
violently, to give the correspondingcarboxylic acids and hydrogen
chloride.
The mechanism is a simple variation of the general addition-
elimination reaction.
Reactions of Acyl ChloridesAcyl chlorides react with nucleophiles,
the Cl atom being replaced by othergroups.