GCE Chemistry for exams from June 2014 onwards (version 1.

5)

3.5 Unit 5 CHEM5 Energetics, Redox and Inorganic Chemistry

Candidates should

3.5.1 Thermodynamics
Enthalpy change (DH) be able to define and apply the terms enthalpy of formation,
ionisation enthalpy, enthalpy of atomisation of an element
and of a compound, bond dissociation enthalpy, electron
affinity, lattice enthalpy (defined as either lattice dissociation
or lattice formation), enthalpy of hydration and enthalpy of
solution
be able to construct Born–Haber cycles to calculate lattice
enthalpies from experimental data. Be able to compare
lattice enthalpies from Born–Haber cycles with those from
calculations based on a perfect ionic model to provide
evidence for covalent character in ionic compounds
be able to calculate enthalpies of solution for ionic
compounds from lattice enthalpies and enthalpies of
3
hydration
be able to use mean bond enthalpies to calculate an
approximate value of DH for other reactions
be able to explain why values from mean bond enthalpy
calculations differ from those determined from enthalpy
cycles
Free-energy change (DG) and understand that DH, whilst important, is not sufficient to
entropy change (DS) explain spontaneous change (e.g. spontaneous endothermic
reactions)
understand that the concept of increasing disorder (entropy
change DS) accounts for the above deficiency, illustrated
by physical change (e.g. melting, evaporation) and
chemical change (e.g. dissolution, evolution of CO2 from
hydrogencarbonates with acid)
be able to calculate entropy changes from absolute entropy
values
understand that the balance between entropy and enthalpy
determines the feasibility of a reaction; know that this is
given by the relationship
DG = DH – TDS (derivation not required).
be able to use this equation to determine how DG varies
with temperature
be able to use this relationship to determine the temperature
at which a reaction is feasible

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 GCE Chemistry for exams from June 2014 onwards (version 1.5)

3.5.2 Periodicity
Study of the reactions of be able to describe trends in the reactions of the elements
Period 3 elements Na – Ar to with water, limited to Na and Mg
illustrate periodic trends be able to describe the trends in the reactions of the
elements
Na, Mg, Al, Si, P and S with oxygen, limited to the formation
of Na2O, MgO, Al2O3, SiO2, P4O10 and SO2.
A survey of the acid base be able to explain the link between the physical properties
properties of the oxides of of the highest oxides of the elements Na – S in terms of their
Period 3 elements structure and bonding
be able to describe the reactions of the oxides of the
elements
Na – S with water, limited to Na2O, MgO, Al2O3, SiO2,
P4O10, SO2 and SO3
know the change in pH of the resulting solutions across the
3 Period
be able to explain the trends in these properties in terms of
the type of bonding present
be able to write equations for the reactions which occur
between these oxides and given simple acids and bases
3.5.3 Redox Equilibria
Redox equations be able to apply the electron transfer model of redox,
including oxidation states and half equations to d block
elements
Electrode potentials know the IUPAC convention for writing half-equations for
electrode reactions
know and be able to use the conventional representation of
cells
understand how cells are used to measure electrode
potentials by reference to the standard hydrogen electrode
know the importance of the conditions when measuring the
electrode potential, E (Nernst equation not required)
know that standard electrode potential, E , refers to
conditions of 298 K, 100 kPa and 1.00 mol dm−3 solution of
ions
Electrochemical series know that standard electrode potentials can be listed as an
electrochemical series
be able to use E values to predict the direction of simple
redox reactions and to calculate the e.m.f. of a cell
Electrochemical cells appreciate that electrochemical cells can be used as a
commercial source of electrical energy
appreciate that cells can be non-rechargeable (irreversible),
rechargeable and fuel cells
be able to use given electrode data to deduce the reactions
occurring in non-rechargeable and rechargeable cells and to
deduce the e.m.f. of a cell
understand the electrode reactions of a hydrogen-oxygen
fuel cell and appreciate that a fuel cell does not need to be
electrically recharged
appreciate the benefits and risks to society associated with
the use of these cells

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 GCE Chemistry for exams from June 2014 onwards (version 1.5)

3.5.4 Transition Metals

General properties of know that transition metal characteristics of elements
transition metals Ti – Cu arise from an incomplete d sub-level in atoms or ions
know that these characteristics include complex formation,
formation of coloured ions, variable oxidation state and
catalytic activity
Complex formation be able to define the term ligand
know that co-ordinate bonding is involved in complex
formation
understand that a complex is a central metal ion surrounded
by ligands
know the meaning of co-ordination number
understand that ligands can be unidentate (e.g. H2O, NH3
and Cl− )
or bidentate (e.g. NH2CH2CH2NH2 and C2O42–)
or multidentate (e.g. EDTA4– )
3
know that haem is an iron(II) complex with a multidentate
ligand
Shapes of complex ions know that transition metal ions commonly form octahedral
complexes with small ligands (e.g. H2O and NH3)
know that transition metal ions commonly form tetrahedral
complexes with larger ligands (e.g. Cl− )
know that square planar complexes are also formed, e.g.
cisplatin
know that Ag+ commonly forms the linear
complex [Ag(NH3)2]+ as used in Tollens’ reagent
Formation of coloured ions know that transition metal ions can be identified by their
colour, limited to the complexes in this unit
know that colour changes arise from changes in oxidation
state, co-ordination number and ligand
know that colour arises from electronic transitions from the
ground state to excited states: DE = hν
appreciate that this absorption of visible light is used in
spectrometry to determine the concentration of coloured
ions
Variable oxidation states know that transition elements show variable oxidation states
know that Cr3+ and Cr2+ are formed by
reduction of Cr2O72– by zinc in acid solution
know the redox titration of Fe2+ with MnO4–
and Cr2O72– in acid solution
be able to perform calculations for this titration and for
others when the reductant and its oxidation product are
given
know the oxidation of Co2+ by air in ammoniacal solution
know the oxidation in alkaline solution of Co2+
and Cr3+ by H2O2

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 GCE Chemistry for exams from June 2014 onwards (version 1.5)

Catalysis know that transition metals and their compounds can act as
heterogeneous and homogeneous catalysts
Heterogeneous know that a heterogeneous catalyst is in a different phase
from the reactants and that the reaction occurs at the
surface
understand the use of a support medium to maximise the
surface area and minimise the cost (e.g. Rh on a ceramic
support in catalytic converters)
understand how V2O5 acts as a catalyst in the Contact
Process
know that a Cr2O3 catalyst is used in the manufacture of
methanol from carbon monoxide and hydrogen
know that Fe is used as a catalyst in the Haber Process
know that catalysts can become poisoned by impurities
and consequently have reduced efficiency; know that this
has a cost implication (e.g. poisoning by sulfur in the Haber
3 Process and by lead in catalytic converters in cars)
Homogeneous know that when catalysts and reactants are in the same
phase, the reaction proceeds through an intermediate
species (e.g. the reaction between I − and S2O82– catalysed
by Fe2+ and autocatalysis by
Mn2+ in reactions of C2O42– with MnO4–).
Other applications of understand the importance of variable oxidation states in
transition metal complexes catalysis; both heterogeneous and homogeneous catalysts
understand that Fe(II) in haemoglobin enables oxygen to be
transported in the blood, and why CO is toxic
know that the Pt(II) complex cisplatin is used as an
anticancer drug
appreciate the benefits and risks associated with this drug
understand that [Ag(NH3)2]+ is used in Tollens’ reagent to
distinguish between aldehydes and ketones
3.5.5 Reactions of Inorganic Compounds in Aqueous Solution
Lewis acids and bases know the definitions of a Lewis acid and Lewis base;
understand the importance of lone pair electrons in
co-ordinate bond formation
Metal-aqua ions know that metal–aqua ions are formed in
aqueous solution:
[M(H2O)6]2+, limited to M = Fe, Co and Cu
[M(H2O)6]3+, limited to M = Al, Cr and Fe
Acidity or hydrolysis understand the equilibria
reactions [M(H2O)6]2+ + H2O M(H2O)5(OH)]+ + H3O+
and
[M(H2O)6]3+ + H2O [M(H2O)5(OH)]2+ + H3O+ to show
generation of acidic solutions with M3+, and
very weakly acidic solutions with M2+

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 GCE Chemistry for exams from June 2014 onwards (version 1.5)

understand that the acidity of [M(H2O)6]3+ is greater than

that of [M(H2O)6]2+ in terms of the (charge/size ratio) of the
metal ion
be able to describe and explain the simple test-tube
reactions of
M2+ (aq) ions, limited to M = Fe, Co and Cu,
and of M3+ (aq) ions,
limited to M = Al, Cr and Fe, with the bases
OH¯, NH3 and CO32–
know that MCO3 is formed but that M2(CO3)3 is not formed
know that some metal hydroxides show amphoteric
character by dissolving in both acids and bases
(e.g. hydroxides of Al3+ and Cr3+)
know the equilibrium reaction
2CrO42– + 2H+ Cr2O72–+ H2O
3
Substitution reactions understand that the ligands NH3 and H2O are
similar in size and are uncharged, and that ligand exchange
occurs without change of
co-ordination number
(e.g. Co2+ and Cr3+)
know that substitution may be incomplete (e.g. the
formation of
[Cu(NH3)4(H2O)2]2+)
understand that the Cl− ligand is larger than these
uncharged ligands and that ligand exchange can involve a
change of
co-ordination number
(e.g. Co2+ and Cu2+)
know that substitution of unidentate ligand with a bidentate
or a multidentate ligand leads to a more stable complex
understand this chelate effect in terms of a positive entropy
change in these reactions

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