Chemistry – Paper 4
Life-saving notes
1. Relative acidities of ethanol, phenol, carboxylic acids, and water
Carboxylic acid > Phenol > Water > Alcohol
In acids, the electron-withdrawing C=O group further weakens
the O-H bond in the acid. They delocalize the negative charge on
the -COO- ion, making it less likely to bond with an H+ ion.
In phenol, since the negative charge is delocalized with the
benzene ring, the charge density is reduced, so H+ ions aren’t
strongly attracted to it.
In ethanol, the electron-donating ethyl group increases the
charge density on the oxygen atom, making it a weaker acid (its
more ready to accept an H+ ion)
2. Relative ease of hydrolysis
Acyl bromides > Acyl chlorides > Alkyl chlorides > Aryl chlorides
Br has larger atomic radius - minimal orbital overlap making C-Br
bond weaker.
Acyl halides > Alkyl halides as carbon in C-Cl & C-Br bond is
electron-deficient and attached to electron-withdrawing C=O
group. Easier to break.
C-Cl bond in alkyl halide is strengthened by electron-donating
alkyl group - harder to break.
In aryl chlorides, lone pair on Cl atom delocalises with pi benzene
ring, so C-Cl ring is stronger.
3. Relative basicities
Diethylamine > Ethylamine > Ethanamide
Basicity linked to availability of lone pair on N atom & ability to
accept H+ ion.
Electron-donating ethyl groups increase electron density on N,
making it more available to accept H+. Diethylamine has one
more donating group; therefore, higher density.
Ethanamide has C=O group which delocalises lone pair of N,
reducing charge density and ability to accept H+ ion.
When a system is in equilibrium, and reactant moles = product moles, the
value of ΔG is 0. There is no free energy change.
In electrochemical cells, the electrode being reduced is the cathode and
will have a positive charge. The electrode being oxidized is the anode and
will have a negative charge. Electrons flow from negative to positive
terminals.
Transition elements have variable oxidation states as their d and s sub-
shells are similar in energy.
If temperature increases, value of rate constant increases.
Enantiomers are stereoisomers that are non-superimposable mirror
images.
Producing two enantiomers provides a lower yield of the desired molecule.
If a solvent used for thin-layer chromatography (TLC) does not cause the
tested ink to move as further as with an initial solvent, it is because the
ink is less soluble in the new solvent.
In TLC, stationary phase solvents can include SiO2 and Al2O3.
When a less polar solvent is used in partition coefficient, least-polar
species will be more soluble in least-polar solvents as stronger id-id forces
would form than compared to a polar and non-polar species and solvent.
Transition elements behave as catalysts as they have variable oxidation
states and their empty d orbitals can form dative bonds with ligands.
Colored transition element complexes always have empty d orbitals; the
d-d transitions when electrons get excited are possible as a result,
emitting visible energy.
Complexes are colored as they have two sets of d-orbitals with different
energy. Excited electrons jump to higher level and energy from visible
regions is absorbed. Energy not absorbed is complementary to color seen.
Colorless complexes have full d-orbitals, so no electrons can be excited
The isoelectric point is the pH value at which there is no overall charge on
a particular amino acid in its aqueous solution.
A reaction has zero order kinetics when the reactant amount is large and
the catalyst is small, as all active sites on catalyst surface are occupied.
A conjugate acid-base pair is a pair of species in a reaction where one
species donates a proton (acid) to a second species which accepts it
(base).
Only -COOH and -NO2 groups direct joining groups to 3 and 5 (meta)
positions. Rest groups direct joining groups to 2, 4, 6 (ortho & para)
positions.
In benzene, all carbons are sp2 hybridized. The structure is a hexagonal
planar ring with a C-C-C bond of 120. Partial p orbital overlap of electrons
on carbon atoms creates a delocalized benzene ring.
Solubilities of group 2 compounds depend on ΔH latt and Hhyd values.
Bromine water cannot react with benzene ring. Aromatic compounds
maintain a highly stable delocalized ring of bonding electrons intact.
Addition reactions would disrupt the ‘aromatic stabilization’, so only
substitution reactions work.
Polyamides and polyesters are biodegradable as they undergo hydrolysis.
A racemic mixture is a mixture containing equal amounts of a pair of
enantiomers.
The best ways to produce pure enantiomers is by using enzymes or using
chiral catalysts.
Retention factor is the ratio of the distances of the specific component and
the solvent front.
Retention time is the time taken for a compound to travel through a
chromatography column in gas-liquid chromatography.
In acid hydrolysis, amides are reduced to carboxylic acids and primary
amines. In alkali hydrolysis, amides are reduced to a carboxylate salt and
an amine.
