A Level Module 5: Physical chemistry and transition elements

Done
5.1.1 How fast? R A G Revised

(a) Explanation and use of the terms: rate of reaction, order, overall order, rate constant, half-life, rate-
determining step.
(b) Deduction of:
(i) orders from experimental data
(ii) a rate equation from orders of the form: rate = k[A]m[B]n, where m and n are 0, 1 or 2
(c) Calculation of the rate constant, k, and related quantities, from a rate equation including
determination of units.
(d) From a concentration–time graph:
(i) deduction of the order (0 or 1) with respect to a reactant from the shape of the graph
(ii) calculation of reaction rates from the measurement of gradients (see also 3.2.2 b)
(e) From a concentration–time graph of a first order reaction, measurement of constant half-life, t 1/2

(f) For a first order reaction, determination of the rate constant, k, from the constant half-life, t 1/2, using
the relationship: k = ln 2/t1/2

(g) From a rate–concentration graph:

(i) deduction of the order (0, 1 or 2) with respect to a reactant from the shape of the graph,
(ii) determination of rate constant for a first order reaction from the gradient.

(h) The techniques and procedures used to investigate reaction rates by the initial rates method and by
continuous monitoring, including use of colorimetry (see also 3.2.2 e).

(i) For a multi-step reaction, prediction of,

(i) a rate equation that is consistent with the rate-determining step,
(ii) possible steps in a reaction mechanism from the rate equation and the balanced equation for
the overall reaction.

(j) A qualitative explanation of the effect of temperature change on the rate of a reaction and hence the
rate constant (see 3.2.2 f–g).
(k) The Arrhenius equation:
(i) the exponential relationship between the rate constant, k and temperature, T given by the
Arrhenius equation, k = Ae–Ea/RT,
(ii) determination of Ea and A graphically using: ln k = –Ea/RT + ln A derived from the Arrhenius
equation.

Done
5.1.2 How far? R A G Revised

(a) Use of the terms mole fraction and partial pressure.

(b) Calculation of quantities present at equilibrium, given appropriate data.

(c) The techniques and procedures used to determine quantities present at equilibrium.

(d) Expressions for Kc and Kp for homogeneous and heterogeneous equilibria (see also 3.2.3 f).

(e) Calculations of Kc and Kp, or related quantities, including determination of units (see also 3.2.3 f).
(f)
(i) The qualitative effect on equilibrium constants of changing temperature for exothermic and
endothermic reactions.
(ii) The constancy of equilibrium constants with changes in concentration, pressure or in the
presence of a catalyst.
(g) Explanation of how an equilibrium constant controls the position of equilibrium on changing
concentration, pressure and temperature.
(h) Application of the above principles in 5.1.2 How far? for Kc, Kp to other equilibrium constants, where
appropriate (see also 5.1.3 c etc.).

Done
5.1.3 Acids, bases and buffers R A G Revised

(a)
(i) A Brønsted–Lowry acid as a species that donates a proton and a Brønsted–Lowry base as a
species that accepts a proton (see also 2.1.4 Acids),
(ii) use of the term conjugate acid–base pairs,
(iii) monobasic, dibasic and tribasic acids.
(b) The role of H+ in the reactions of acids with metals and bases (including carbonates, metal oxides
and alkalis), using ionic equations (see also 2.1.4 c, 2.1.5 e).
(c)
(i) The acid dissociation constant, Ka, for the extent of acid dissociation (see also 2.1.4 b),
(ii) the relationship between Ka and pKa.
(d) Use of the expression for pH as:
pH = –log[H+]
[H+] = 10–pH

(e) Use of the expression for the ionic product of water, Kw.
(f) Calculations of pH, or related quantities, for:
(i) strong monobasic acids,
(ii) strong bases, using Kw.
(g) Calculations of pH, Ka or related quantities, for a weak monobasic acid using approximations.

(h) Limitations of using approximations to Ka related calculations for ‘stronger’ weak acids.

(i) A buffer solution as a system that minimises pH changes on addition of small amounts of an acid or a
base.
(j) Formation of a buffer solution from:
(i) a weak acid and a salt of the weak acid, e.g. CH3COOH/CH3COONa,
(ii) excess of a weak acid and a strong alkali, e.g. excess CH3COOH/NaOH.
(k) Explanation of the role of the conjugate acid–base pair in an acid buffer solution, e.g.
CH3COOH/CH3COO–, in the control of pH.
(l) Calculation of the pH of a buffer solution, from the Ka value of a weak acid and the equilibrium
concentrations of the conjugate acid–base pair; calculations of related quantities.
(m) Explanation of the control of blood pH by the carbonic acid–hydrogencarbonate buffer system.
(n) pH titration curves for combinations of strong and weak acids with strong and weak bases,
including:
(o) The techniques and procedures used when measuring pH with a pH meter.

Done
5.2.1 Lattice enthalpy R A G Revised

(a) Explanation of the term lattice enthalpy (formation of 1 mol of ionic lattice from gaseous ions, ∆ LEH)
and use as a measure of the strength of ionic bonding in a giant ionic lattice (see also 2.2.2 b–c).
(b) Use of the lattice enthalpy of a simple ionic solid (e.g. NaCl, MgCl2) and relevant energy terms for:
(i) the construction of Born–Haber cycles,
(ii) related calculations.
(c) Explanation and use of the terms:
(i) enthalpy change of solution (dissolving of 1 mol of solute, ∆solH),
(iii) enthalpy change of hydration (dissolving of 1 mol of gaseous ions in water, ∆hydH).
(d) Use of the enthalpy change of solution of a simple ionic solid (e.g. NaCl, MgCl 2) and relevant energy
terms (enthalpy change of hydration and lattice enthalpy) for:
(i) the construction of enthalpy cycles,
(ii) related calculations.
(e) Qualitative explanation of the effect of ionic charge and ionic radius on the exothermic value of a
lattice enthalpy and enthalpy change of hydration.

Done
5.2.2 Enthalpy and entropy R A G Revised

(a) Explanation that entropy is a measure of the dispersal of energy in a system which is greater, the
more disordered a system.
(b) Explanation of the difference in magnitude of the entropy of a system:
(i) of solids, liquids and gases,
(ii) for a reaction in which there is a change in the number of gaseous molecules.
(c) Calculation of the entropy change of a system, ∆S, and related quantities for a reaction given the
entropies of the reactants and products.
(d) Explanation that the feasibility of a process depends upon the entropy change and temperature in
the system, T∆S, and the enthalpy change of the system, ∆H.
(e) Explanation, and related calculations, of the free energy change, ∆G, as: ∆G = ∆H – T∆S (the Gibbs’
equation) and that a process is feasible when ∆G has a negative value.
(f) The limitations of predictions made by ∆G about feasibility, in terms of kinetics.

Done
5.2.3 Redox and electrode potentials R A G Revised

(a) Explanation and use of the terms oxidising agent and reducing agent (see also 2.1.5 Redox).
(b) Construction of redox equations using half equations and oxidation numbers.

(c) Interpretation and prediction of reactions involving electron transfer.

(d) The techniques and procedures used when carrying out redox titrations including those involving
Fe2+/MnO4– and I2/S2O32− (see also 2.1.5 e–f).
(e) Structured and non-structured titration calculations, based on experimental results of redox
titrations involving:
(i) Fe2+/MnO4– and I2/S2O32−
(ii) non-familiar redox systems.
(f) Use of the term standard electrode (redox) potential, EѲ including its measurement using a hydrogen
electrode.
(g) The techniques and procedures used for the measurement of cell potentials of:
(i) metals or non-metals in contact with their ions in aqueous solution,
(ii) ions of the same element in different oxidation states in contact with a Pt electrode.
(h) Calculation of a standard cell potential by combining two standard electrode potentials.
(i) Prediction of the feasibility of a reaction using standard cell potentials and the limitations of such
predictions in terms of kinetics and concentration.
(j) Application of principles of electrode potentials to modern storage cells.
(k) Explanation that a fuel cell uses the energy from the reaction of a fuel with oxygen to create a
voltage and the changes that take place at each electrode.

Done
5.3.1 Transition elements R A G Revised

(a) The electron configuration of atoms and ions of the d-block elements of Period 4 (Sc–Zn), given the
atomic number and charge (see also 2.2.1 d).
(b) The elements Ti–Cu as transition elements i.e. d-block elements that have an ion with an incomplete
d-sub-shell.
(c) Illustration, using at least two transition elements, of:
(i) the existence of more than one oxidation state for each element in its compounds (see also
5.3.1 k),
(ii) the formation of coloured ions (see also 5.3.1 h, j–k),
(iii) the catalytic behaviour of the elements and their compounds and their importance in the
manufacture of chemicals by industry (see 3.2.2 d).
(d) Explanation and use of the term ligand in terms of coordinate (dative covalent) bonding to a metal
ion or metal, including bidentate ligands.
(e) Use of the terms complex ion and coordination number and examples of complexes with:
(i) six-fold coordination with an octahedral shape,
(ii) four-fold coordination with either a planar or tetrahedral shape (see also 2.2.2 g–h).
(f) Types of stereoisomerism shown by complexes, including those associated with bidentate and
multidentate ligands:
(i) cis–trans isomerism e.g. Pt(NH3)2Cl2 (see also 4.1.3 c–d),
(ii) optical isomerism e.g. [Ni(NH2CH2CH2NH2)3]2+ (see also 6.2.2 c).
(g) Use of cis-platin as an anti-cancer drug and its action by binding to DNA preventing cell division.
(h) Ligand substitution reactions and the accompanying colour changes in the formation of:
(i) [Cu(NH3)4(H2O)2]2+ and [CuCl4]2– from [Cu(H2O)6]2+
(ii) [Cr(NH3)6]3+ from [Cr(H2O)6]3+ (see also 5.3.1 j)
(i) Explanation of the biochemical importance of iron in haemoglobin, including ligand substitution
involving O2 and CO.
(j) Reactions, including ionic equations, and the accompanying colour changes of aqueous Cu 2+, Fe2+,
Fe3+, Mn2+ and Cr3+ with aqueous sodium hydroxide and aqueous ammonia, including:
(i) precipitation reactions,
(ii) complex formation with excess aqueous sodium hydroxide and aqueous ammonia.
(k) Redox reactions and accompanying colour changes for:
(i) interconversions between Fe2+ and Fe3+
(ii) interconversions between Cr3+ and Cr2O72-
(iii) reduction of Cu2+ to Cu+ and disproportionation of Cu+ to Cu2+ and Cu
(l) Interpretation and prediction of unfamiliar reactions including ligand substitution, precipitation,
redox.

Done
5.3.2 Qualitative analysis R A G Revised

(a) Qualitative analysis of ions on a test-tube scale: processes and techniques needed to identify the
following ions in an unknown compound:
(i) anions: CO32–, Cl–, Br–, I–, SO42– (see 3.1.4 a),
(ii) cations: NH4+; Cu2+, Fe2+, Fe3+, Mn2+, Cr3+ (see 3.1.4 a, 5.3.1 j).

A Level Module 6: Organic chemistry and analysis

 Done
6.1.1 Aromatic compounds R A G Revised

(a) The comparison of the Kekulé model of benzene with the subsequent delocalised models for
benzene in terms of p-orbital overlap forming a delocalised π-system.
(b) The experimental evidence for a delocalised, rather than Kekulé, model for benzene in terms of
bond lengths, enthalpy change of hydrogenation and resistance to reaction (see also 6.1.1 f).
(c) Use of IUPAC rules of nomenclature for systematically naming substituted aromatic compounds.
(d) The electrophilic substitution of aromatic compounds with:
(i) concentrated nitric acid in the presence of concentrated sulfuric acid,
(ii) a halogen in the presence of a halogen carrier,
(iii) a haloalkane or acyl chloride in the presence of a halogen carrier (Friedel–Crafts reaction) and
its importance to synthesis by formation of a C–C bond to an aromatic ring (see also 6.2.4 d).
(e) The mechanism of electrophilic substitution in arenes for nitration and halogenation (see also 4.1.1
h–i).
(f) The explanation of the relative resistance to bromination of benzene, compared with alkenes, in
terms of the delocalised electron density of the π-system in benzene compared with the localised
electron density of the π-bond in alkenes (see also 4.1.3 a, 6.1.1 a).
(g) The interpretation of unfamiliar electrophilic substitution reactions of aromatic compounds,
including prediction of mechanisms.
(h) The weak acidity of phenols shown by the neutralisation reaction with NaOH but absence of
reaction with carbonates (see also 5.1.3 b).
(i) The electrophilic substitution reactions of phenol:
(i) with bromine to form 2,4,6-tribromophenol,
(ii) with dilute nitric acid to form a mixture of 2-nitrophenol and 4-nitrophenol.
(j) The relative ease of electrophilic substitution of phenol compared with benzene, in terms of electron
pair donation to the π-system from an oxygen p-orbital in phenol (see also 4.1.3 a).
(k) the 2- and 4-directing effect of electron donating groups (OH, NH2) and the 3-directing effect of
electron-withdrawing groups (NO2) in electrophilic substitution of aromatic compounds.
(l) The prediction of substitution products of aromatic compounds by directing effects and the
importance to organic synthesis (see also 6.2.5 Organic Synthesis).
 Done
6.1.2 Carbonyl compounds R A G Revised

(a) Oxidation of aldehydes using Cr2O72–/H+ (i.e. K2Cr2O7/H2SO4) to form carboxylic acids.
(b) Nucleophilic addition reactions of carbonyl compounds with:
(i) NaBH4 to form alcohols,
(ii) HCN [i.e. NaCN(aq)/H+(aq)], to form hydroxynitriles (see also 6.2.4 b).
(c) the mechanism for nucleophilic addition reactions of aldehydes and ketones with NaBH 4 and HCN.
(d) Use of 2,4-dinitrophenylhydrazine to:
(i) detect the presence of a carbonyl group in an organic compound,
(ii) identify a carbonyl compound from the melting point of the derivative.
(e) use of Tollens’ reagent (ammoniacal silver nitrate) to:
(i) detect the presence of an aldehyde group,
(ii) distinguish between aldehydes and ketones, explained in terms of the oxidation of aldehydes
to carboxylic acids with reduction of silver ions to silver.

Done
6.1.3 Carboxylic acids and esters R A G Revised

(a) Explanation of the water solubility of carboxylic acids in terms of hydrogen bonding.
(b) Reactions in aqueous conditions of carboxylic acids with metals and bases (including carbonates,
metal oxides and alkalis).
(c) Esterification of:
(i) carboxylic acids with alcohols in the presence of an acid catalyst (e.g. concentrated H 2SO4),
(ii) acid anhydrides with alcohols.
(d) Hydrolysis of esters:
(i) in hot aqueous acid to form carboxylic acids and alcohols,
(ii) in hot aqueous alkali to form carboxylate salts and alcohols.
(e) The formation of acyl chlorides from carboxylic acids using SOCl2.
(f) Use of acyl chlorides in synthesis in formation of esters, carboxylic acids and primary and secondary
amides.

Done
6.2.1 Amines R A G Revised

(a) The basicity of amines in terms of proton acceptance by the nitrogen lone pair and the reactions of
amines with dilute acids, e.g. HCl (aq), to form salts.
(b) The preparation of:
(i) aliphatic amines by substitution of haloalkanes with excess ethanolic ammonia and amines,
(ii) aromatic amines by reduction of nitroarenes using tin and concentrated hydrochloric acid.

Done
6.2.2 Amino acids, amides and chirality R A G Revised

(a) The general formula for an α-amino acid as RCH(NH2)COOH and the following reactions of amino
acids:
(i) reaction of the carboxylic acid group with alkalis and in the formation of esters (see also 6.1.3
c),
(ii) reaction of the amine group with acids.
(b) Structures of primary and secondary amides (see also 6.1.3 f, 6.2.3 a–b).
(c) Optical isomerism (an example of stereoisomerism, in terms of non-superimposable mirror images
about a chiral centre) (see also 4.1.3 c–d).
(d) Identification of chiral centres in a molecule of any organic compound.

Done
6.2.3 Polyesters and polyamides R A G Revised

(a) Condensation polymerisation to form:
(i) polyesters,
(ii) polyamides.
(b) The acid and base hydrolysis of:
(i) the ester groups in polyesters,
(ii) the amide groups in polyamides.
(c) Prediction from addition and condensation polymerisation of:
(i) the repeat unit from a given monomer(s),
(ii) the monomer(s) required for a given section of a polymer molecule,
(iii) the type of polymerisation.

Done
6.2.4 Carbon–carbon bond formation R A G Revised

(a) The use of C–C bond formation in synthesis to increase the length of a carbon chain (see also 6.1.1
d, 6.1.2 b)
(b) Formative of C-C≡N by reaction of:
(i) haloalkanes with CN– and ethanol, including nucleophilic substitution mechanism (see also
4.2.2 c),
(ii) carbonyl compounds with HCN, including nucleophilic addition mechanism (see also 6.1.2 b–
c).
(c) Reaction of nitriles from (b):
(i) by reduction (e.g. with H2/Ni) to form amines,
(ii) by acid hydrolysis to form carboxylic acids.
(d) Formation of a substituted aromatic C–C by alkylation (using a haloalkane) and acylation (using an
acyl chloride) in the presence of a halogen carrier (Friedel–Crafts reaction) (see also 6.1.1 d).

Done
6.2.5 Organic synthesis R A G Revised

(a) The techniques and procedures used for the preparation and purification of organic solids involving
use of a range of techniques (see also 4.2.3 a) including:
(i) organic preparation,
 use of Quickfit apparatus,
 distillation and heating under reflux,
(ii) purification of an organic solid,
 filtration under reduced pressure,
 recrystallisation,
 measurement of melting points.

(b) For an organic molecule containing several functional groups:

(i) identification of individual functional groups,
(ii) prediction of properties and reactions.
(c) Multi-stage synthetic routes for preparing organic compounds.

Done
6.3.1 Chromatography and qualitative analysis R A G Revised

(a) Interpretation of one-way TLC chromatograms in terms of Rf values.
(b) Interpretation of gas chromatograms in terms of:
(i) retention times,
(ii) the amounts and proportions of the components in a mixture.
(c) Qualitative analysis of organic functional groups on a test-tube scale; processes and techniques
needed to identify the following functional groups in an unknown compound:
(i) alkenes by reaction with bromine (see also 4.1.3 f),
(ii) haloalkanes by reaction with aqueous silver nitrate in ethanol (see also 4.2.2 a),
(iii) phenols by weak acidity but no reaction with CO32– (see also 6.1.1 h),
(iv) carbonyl compounds by reaction with 2,4 DNP (see also 6.1.2 d),
(v) aldehydes by reaction with Tollens’ reagent (see also 6.1.2 e),
(vi) primary and secondary alcohols and aldehydes by reaction with acidified dichromate (see also
4.2.1 c, 6.1.2a),
(vii) carboxylic acids by reaction with CO32– (see also 6.1.3 b).

Done
6.3.2 Spectroscopy R A G Revised

(a) Analysis of a carbon-13 NMR spectrum of an organic molecule to make predictions about:
(i) the number of carbon environments in the molecule,
(ii) the different types of carbon environment present, from chemical shift values,
(iii) possible structures for the molecule.
(b) Analysis of a high resolution proton NMR spectrum of an organic molecule to make predictions
about:
(i) the number of proton environments in the molecule,
(ii) the different types of proton environment present, from chemical shift values,
(iii) the relative numbers of each type of proton present from relative peak areas, using
integration traces or ratio numbers, when required,
(iv) the number of non-equivalent protons adjacent to a given proton from the spin spin splitting
pattern, using the n + 1 rule,
(v) possible structures for the molecule.
(c) Prediction of a carbon-13 or proton NMR spectrum for a given molecule.

(d)
(i) The use of tetramethylsilane, TMS, as the standard for chemical shift measurements,
(ii) the need for deuterated solvents, e.g. CDCl3, when running an NMR spectrum,
(iii) the identification of O–H and N–H protons by proton exchange using D2O.
(e) Deduction of the structures of organic compounds from different analytical data including:
(i) elemental analysis (see also 2.1.3 c),
(ii) mass spectra (see also 4.2.4 f–g),
(iii) IR spectra (see also 4.2.4 d–e),
(iv) NMR spectra.