Part 3 - Teaching Scheme

NAS
Part 3 – Teaching Scheme

Introduction
The tables in this section contain data that is intended to help teachers/lecturers incorporate practical
work, practical assessment and key skill teaching and assessment into teaching schemes. It also
indicates where the specification content is located in the new student books.
Specification
This is the Edxecel AS and A Level GCE Chemistry specification as it is laid out in the specification
document.
Notes and cross links to student books
This material seeks to amplify the specification. It also includes the location, in bold, of content from
the student texts that matches the specification. The book, chapter and major heading are provided
for reference.
References are made in the section to the following texts:
The Essential Chemistry Industry, published by CIEC, University of York, York,
YO10 5DD, ISBN 1 85342 577X
Fats and Oils, published by Unilever, Education Liaison, UK National Management, Unilever House,
London EC4P 4BQ
Experiments/resources
The material in this column covers suggestions for practical experiments that might be included in a
laboratory course in chemistry. There are many examples of overlap within the suggestions. These are
intended as a resource of ideas from which teachers might choose, not a list of what must be covered.
The material is based on two sources:
Chemistry in Context Laboratory Manual and Study Guide, 3rd Edition, referred to in the table as
C in C, published by Nelson, ISBN 0 17 448 2310
Classic Chemistry Demonstrations, published by the Royal Society of Chemistry.
The Laboratory of the Government Chemist (LGC) has produced an excellent aid to teaching good
quantitative technique, sources of error and analysis of error:
Basic Laboratory Skills: A training pack for laboratory techniques, ISBN 0 948 926 14 7
It has a large number of exercises plus a CD-ROM that can be used to teach students laboratory
techniques. Further details are available from the Office of Reference Materials, LGC,
Queen’s Road, Teddington, TW11 0LY
Practical assessment opportunities

These are exercises that can be found in the Exemplar Coursework Assessment Materials produced by
Edexcel and available from the Assessment Leader Chemistry. Within the material, there are many
examples of overlap. The ideas are intended as a resource from which teachers might choose, not a
list of what needs to be covered.
Key skills mapping

The specification gives a detailed analysis of the areas where evidence for the assessment of specific
key skills could be collected. The details provided make suggestions in more detail about materials or
ideas that might be used to produce the evidence. There are far more examples than could possibly
be needed by any one centre.
SATIS 16-19 is a series of 100 exercises that is produced by The Association for Science Education and
is available from the Publications Department, ASE, College Lane, Hatfield, Herts AL10 9AA.
NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Unit 5 – Transition Metals, Quantitative Kinetics and Applied Organic Chemistry
Topic 5.1 Redox equilibria

Specification Notes and cross links to student books Experiments/resources Practical assessment
opportunities
Candidates should be able to: The basis of this unit is the use of redox potentials C in C” Laboratory Manual and Edexcel exemplar
(a) relate changes in oxidation number to to explain and predict the feasibility of reactions Study Guide, 3rd Edition material experiment
reaction stoichiometry based on data from data books. Practical Number 5 A test tube “Redox reactions”.
(b) understand the procedures and principles (a) p 1 More about oxidation numbers study of redox reactions (if not Edexcel exemplar
involved in the use of potassium (b) p 18 Titrations used in Unit 2) material experiment
manganate(VII) to estimate reducing agents (c) There is no requirement for students to carry “Determination of the
and potassium iodide and sodium out experiments to measure cell potentials, number of moles of water
thiosulphate to estimate oxidising agents nor is there a requirement to be able to draw of crystallization in one
(c) recall the definition of standard electrode cell diagrams or calculate cell potentials. mole of ethanedioic acid”.
potential (standard reduction potential) and Details of the standard hydrogen electrode or
understand the need for a standard electrode its operation are not required.
(d) predict the likely direction of spontaneous (d)/(e) This is seen as an application of data.
change of redox reactions, using standard (c) p 9 Standard electrode potentials
electrode potential data, and understand why (d) p 10 Reduction potentials and the feasibility
these predictions may not be borne out of reactions
in practice (e) p 14 Disproportionation
(e) understand disproportionation reactions in (f) p 19 Corrosion
terms of standard electrode potentials (g) The recall of specific storage cells will not
(f) understand the applications of electrode be required.
potentials in connection with corrosion and (g) p 17 Practical cells and batteries
to the solution of problems caused
by corrosion
(g) understand the application of electrode
potential to the construction of simple
storage cells.

Topic 5.1 (continued)
Key skills mapping
Students could be asked to:
• gather information on the various types of storage cells and produce a paper on the advantages and disadvantages of the various types of storage cell: C3.2
• present an illustrated talk for non-specialists on the application of electrode potentials to the solution of corrosion problems: C3.1.
C in C Section 2 – Rust: this exercise involves many aspects of the rusting of iron and its prevention. It could provide some material for an assessment in C3.2.
C in C Section 2 – Fuel and Fuel Cells: this involves a discussion of fuels and energy and could form the basis for assessment of C3.2.

Topic 5.2 Transition metal chemistry

opportunities
Candidates should be able to: (a)–(b) p24 Electronic structures and variable Classic Chemistry Edexcel exemplar
(a) derive the electronic configurations of the d oxidation numbers Demonstrations Experiments 1, material experiment
block elements (Sc to Zn), and their simple 20, 52, 92 and 93 provide ideas “Inorganic observation
ions, from their position in the Periodic Table for simple demonstrations of the exercise – II”.
(b) recall the transition metals as d block properties of transition metals Edexcel exemplar
elements forming one or more stable ions and their compounds. material experiment
which have incompletely filled d orbitals “Inorganic observation
Candidates should be able to recall appropriate exercise – II”.
parts of the chemistry of chromium, iron and
copper to illustrate the properties of transition
elements described in (c), (d) and (e)
(c) recall the characteristic properties of the
(c) (i)–(iii) p26 Formation of complex ions
transition elements, such as
(i) the formation of coloured aqueous, and
other complex ions
(ii) the formation of a range of compounds in (d) Stereoisomerism in such complex ions will
which they are present in different stable not be tested.
oxidation states Students should understand that the bonding
(d) understand the nature of the bonding in between the ligand and the metal ion is dative
complex ions, including the aquo-ions, their covalent and this causes a splitting of the d orbitals C in C Laboratory Manual and
shape and the cause of their colour Colour should be related to a simple transfer of Study Guide, 3rd Edition
(e) understand simple ligand exchange processes electrons between d orbitals. Practical Numbers 12 and 13
(f) recall the formation of hydroxide precipitates (f) The concepts of deprotonation and ligand Complex formation and
on the addition of aqueous solutions of exchange should be applied to these competition for cations and
sodium hydroxide or ammonia, and that reactions. Knowledge of the colours of the Determination of the formulae
some hydroxide precipitates react with an precipitates is expected. of complex ions

excess of strong alkali, and some react with
an excess of ammonia; limited to Cr3+, Mn2+,
Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+; recall (d)–(e) p26 Formation of complexions.
the oxidation states of vanadium (+2, +3, (f) p29 The action of alkali on aqua complexes.
+4, +5) in its compounds, and the formulae (g) This includes recall of the colours of the
of the metal ions, oxo anions and oxo cations various oxidation states of vanadium in
of the element in these oxidation states aqueous solution.
(g) describe reactions for the interconversion (g) p31 Vanadium C in C Laboratory Manual and
of the oxidation states of vanadium in Study Guide, 3rd Edition
aqueous solution Practical Number 22
(h) recall that transition elements and their (h) p33 catalytic activity and the transitions metals The oxidation states of
compounds are important catalysts in vanadium and manganese
industrial catalytic processes, and that their Practical Number 22 Copper
catalytic activity is often associated with the
variable oxidation states of the elements
(i) recall examples of catalytic action by
vanadium, iron and nickel and/or their
compounds.
Key skills mapping

• produce a paper summarizing the reactions of transition metal ions with sodium and ammonium hydroxide: C3.2
• produce a document to explain in non-technical language the reasons for colour in transition metal ions: C3.3.
Steel SATIS 16–19 Number 40 ASE

Students review the uses of steels, assemble a flow diagram for the BOS steel making process, interpret data and calculate the energy changes involved: C3.3.
The Laboratory of the Government Chemist has produced a package that contains material that could be used for key skills assessment. The package, called Contaminated
Land Study, involves analysis of data, decision making, calculations and role-play. It could be used to assess N3.1, N3.3, C3.1b and C3.2.

Topic 5.3 Organic chemistry III

opportunities
(a) Structure of benzene and reactions of (a) Benzene is chosen as the exemplar for C in C Laboratory Manual and Edexcel exemplar
aromatic compounds electrophilic substitution in aromatic systems Study Guide, 3rd Edition material experiment
Candidates should be able to use the concepts of to remove the need for students to become Practical Number 34 (part) Nitration of methyl
the different types of covalent bond, and bond involved in discussion about the orientation Amines benzoate”.
enthalpy to explain the structure and stability of of substitution.
the benzene ring. (a) p36 Structure of benzene
Candidates should be able to recall, in terms of (a) (i) p43 Nitration
reagents and general reaction conditions, the (a) (ii) p44 Side-chain oxidation
reaction of: (a) (iii) p45 Phenols
(i) benzene with a nitrating mixture, (a) (iv) p47 Amines
bromine, chloroalkanes or acid chlorides (a) (iv) p48 Amines and nitrous acid
in the presence of anhydrous aluminium
chloride
(ii) aromatic compounds with carbon-
containing side chains with alkaline
potassium manganate(VII) solution
resulting in the oxidation of the
side chains
(iii) phenol with sodium hydroxide, bromine
and acid chlorides
(iv) reduction of aromatic nitro compounds
to amines using tin/concentrated
hydrochloric acid
(v) phenylamine with nitrous acid; and the
subsequent coupling reaction of
benzenediazonium ions with phenol.

(b) Reaction mechanisms (b) Students should be able to illustrate each of C in C Laboratory Manual and
The convention of ) to represent movement of the reaction types with specific examples Study Guide, 3rd Edition
an electron pair will be expected. Candidates and be able to write an equation for the Practical Number 29
should be able to recall the following reaction reaction chosen. Nucleophilic substitution
mechanisms together with reagents and general Students should understand that the reaction of a reactions of halogenoalkanes
conditions for the reactions shown and apply molecule with a free radical will generate another
them to simple allied reactions. free radical and that reaction between free radicals
(i) homolytic, free radical substitution provides a termination reaction.
(alkanes with chlorine) Students should be encouraged to use the )
(ii) homolytic, free radical addition convention to represent the movement of a
(polymerisation of ethene) single electron from a pair of electrons in
(iii) heterolytic, electrophilic addition radical reactions.
(symmetrical and unsymmetrical alkenes Explanations of the orientation of addition should
with halogens and hydrogen halides) be in the context of the relative stability of the
(iv) heterolytic, electrophilic substitution intermediate carbocation.
(benzene with a nitrating mixture, with (b) (iv) The generation of the electrophile, e.g.
bromine and with chloroalkane and NO2+ must be shown as part of the
acid chlorides) mechanism.
(v) heterolytic, nucleophilic substitution The orientation of substituents in
(halogenoalkanes with hydroxide ions benzene derivatives will not be
and cyanide ions) SN1 and SN2. examined.
(vi) heterolytic, nucleophilic addition (b) (i) p52 Chlorination of methane.
(carbonyl compounds with (b) (ii) p52 Homolytic polymerisation.
hydrogen cyanide). (b) (iii) p53 Addition reactions.
(b) (iv) p55 Substitution in the aromatic
nucleus..
(b) (v) p58 Heterolytic nucleophilic substitution.
(b) (vi) p60 Nucleophilic reactions at the
carbonyl group.
Key skills mapping

Students could be asked to produce:
• an illustrated talk on the history and development of the understanding of the structure of benzene: C3.2, C3.3.
• summarise the evidence that leads to an understanding of the mechanism of a nucleophilic substitution reaction: C3.2.
The Trouble with Free Radicals SATIS 16–19 Number 12 ASE
The unit involves data analysis and problem solving. The activities allow students to apply their knowledge of halogenoalkanes and free radical reactions:
C3.1a.

Topic 5.4 Chemical kinetics II

opportunities
Candidates should be able to: (a) p62 Rates, orders and rate constants. C in C Laboratory Manual and Edexcel exemplar
(a) recall that rates of reaction may be expressed Study Guide, 3rd Edition material experiment “To
by empirical rate equations of the form: Practical Number 15 investigate the rate of
rate = k[A]m[B]n, where m and n are 0, 1 Determination of the order of a reaction between iodine
or 2 reaction and propanone in acid
(b) define the terms rate constant and order of (b) The concept of molecularity is not expected. Practical Number 16 Using solution”.
reaction and understand that these are (b) p63 Units of the rate constant. colorimetry to find the order of Edexcel exemplar
experimentally determined the reaction between bromine material experiment
(c) deduce rate equations from given (c) p63 Orders of reaction from initial rate and methanoic acid “Kinetics of the reaction
experimental, initial rate data measurement. Practical Number 17 between manganate(VII)
(d) recall that reactions with a large activation (c) The concept of molecularity is not expected. Determination of the activation ions and ethanedioate
energy will have a small rate constant (d) Students will be expected to be familiar with energy for the reaction between ions in solution”.
(e) understand that many reactions take place in the Arrhenius equation but not to recall it. bromide and bromate(V) ions Edexcel exemplar
several steps, one of which will be the rate (d)–(g) p65 Multi-stage reactions. material experiment
determining step “Kinetics of the reaction
(f) understand that it is sometimes possible to between manganate(VII)
deduce information regarding the mechanism ions and ethanedioate
of a chemical reaction from kinetic data (h) The selection will be based on evidence given ions at different
(g) understand that many reactions proceed in the question. Thus, the choice of a gas temperatures”.
through a transition state syringe to measure evolved gas would be Edexcel exemplar
(h) select and describe a suitable experimental based upon information that a gas was material experiment
technique for following a given reaction produced in the reaction. It is not intended “Determination of the
(i) present and interpret the results of kinetic that methods be a matter of recall. activation energy of a
measurements in graphical form (j) A knowledge of radioactive decay is not reaction”.
(j) define the term “half-life” and recall that this expected nor are decay products.
is constant for any given first order reaction. (h)–(j) p66 Measuring rates of reaction.

Key skills mapping
• collate data and use it to predict the rate equation for the reaction between propanone and iodine, providing an opportunity to assess N3.2.

Topic 5.5 Organic chemistry IV – synoptic topics

opportunities
(a) Organic analysis (a) (i) p74 Summary of tests Students will be expected to Edexcel exemplar
Candidates should be able to: (a) (ii) p71 Before the spectoscopic revolution describe tests to distinguish material experiment
(i) Describe practical tests or a combination (a) (iii) Students will be given tables of data as between primary, secondary “Organic observation
of tests to confirm the presence of the appropriate. and tertiary alcohols. exercise – I”.
functional groups: Students will not be expected to recall The halogeno group may be Edexcel exemplar
double bond, chloro, bromo, iodo, specific spectra patterns and/or wave identified by simple alkaline material experiment
primary, secondary and tertiary alcohols, numbers, but may be required to inspect hydrolysis, subsequent “Organic observation
carbonyl, aldehyde, acid, secondary given spectra and tables of data to draw acidification and testing with exercise – II”.
carbonyl and hydroxy groups conclusions. aqueous silver nitrate. Edexcel exemplar
(ii) interpret physical data and chemical (a) (iii) (a) p83 Mass spectroscopy Other groups may be identified material experiment
information, including information (a) (iii) (b) p76 Infrared spectrocopy by reactions of the candidate’s “Organic observation
relating to derivatives where appropriate, (a) (iii) (c) p98 M.m.r. spectroscopy choice but the reactions of the exercise – III”.
to arrive at the structural formula of a (a) (iii) (d) p103 Ultra violet and visible spectra common reagents: bromine Edexcel exemplar
compound (b) (i) p111 Choice of starting material and solution, phosphorus material experiment
(iii)(a) interpret simple fragmentation route pentachloride, 2,4-dinitrophenyl- “Boiling points and
patterns from a mass spectrometer hydrazine solution, Fehling’s composition”.
(b) interpret simple infrared spectra solution, alkaline ammoniacal Edexcel exemplar
(c) interpret simple low resolution silver nitrate, sodium or material experiment
nuclear magnetic resonance spectra potassium hydrogen carbonate, “Investigation of an
(d) interpret simple ultraviolet/visible iodine in the presence of alkali unknown acid”.
spectra. (or potassium iodide and
(b) Organic synthesis sodium chlorate(I)) solution will
Candidates should be able to: be expected to be known.
(i) propose practicable pathways for the C in C Laboratory Manual and
synthesis of organic molecules Study Guide, 3rd Edition
Practical Number 35 Polymers

(ii) propose suitable apparatus, conditions (a) (iii) (c) This is limited to proton magnetic (c) (ii) The Essential
and safety precautions for carrying out resonance. Chemistry Industry
organic syntheses, given suitable Students will not be expected to describe the “Fertilizers”
information theory or the apparatus connected with the (c) (iii) The Essential
(iii) demonstrate familiarity with a range production of uv/visible, infrared or nuclear Chemistry Industry
of practical techniques used in magnetic resonance spectra. “Edible fats and oils”
organic chemistry (b) (iii) Mixing, boiling under reflux, fractional (c) (iii) Fats and Oils. Unilever
(iv) demonstrate an understanding of the distillation, filtration under reduced The Essential
principles of fractional distillation in pressure (filter pump and Buchner Chemistry Industry
terms of the graphs of boiling point funnel), recrystallisation, melting Polymers:
against composition. temperature and boiling temperature, “Poly(ethene)”
(c) Applied organic chemistry and heating by a variety of sources. “Poly(phenylethene)”
Candidates should be able to appreciate the (b) (iv) Students will not be expected to recall “Poly(chloroethene)”
importance of organic compounds in experimental procedures for obtaining “Poly(tetrafluoro-
pharmaceuticals, agricultural products and graphs of boiling point against ethene)”
materials. Questions will be confined to the composition. The Essential
following aspects: Knowledge of systems that form azotropes will not Chemistry Industry
(i) changes to the relative lipid/water be expected. “Polyesters”
solubility of pharmaceuticals by (b) (ii) p116 Practical synthetic techniques “Polyamides”
introduction of non-polar side-chains or (b) (iii) p116 Practical synthetic techniques
ionic groups (b) (iv) p119 Fractional distillation
(ii) the use of organic compounds such as (c) (i) p122 Pharmaceuticals
urea as sources of nitrogen in (c) (ii) p125 Nitrogenous fertilisers
agriculture and their advantages (c) (iii) This is to include flavourings, margarine,
compared with inorganic compounds soaps, and essential oils. Oils and fats are to be
containing nitrogen considered from the point of view of saturation.
(iii)the use of esters, oils and fats (iv) This should include reference to the
(iv) properties and uses of addition polymers difficulties involved in the disposal
of ethene, propene, chloroethene, of polymers.
tetrafluoroethene and phenylethene, and (c) (iii) p127 Esters, oils and fats
of the condensation polymers (polyesters (c) (iv) p130 Polystyrene
and polyamides).
Key skills mapping

This section could provide many opportunities for key skills assessments.
• take part in a discussion of the uses of the various types of spectra in analysis: C3.1

• produce talks, papers or posters, or take part in discussions on the use of organic chemicals in pharmaceuticals or agriculture: C3.1, C3.2, C3.3.
• take part in a discussion on the problems associated with the disposal of polymers: C3.1.
• produce a poster on the advantages/problems associated with the use of fertilizers: C3.2, C3.3.
C in C Section 2 – The Vanilla Counterfeiters: this involves some calculations based on isotopic abundance, analysis and application of organic reaction chemistry. It could
form the basis for a discussion on possible means to solve the problem of counterfeiters: C3.1a.
Accident or Arson SATIS 16–19 Number 41 ASE
Students are asked to weigh evidence, assesses reliability, draw conclusions and present a case to justify their findings. In the more specialist parts of the unit students
interpret gas chromatograms and explain the rationale of the practical techniques used: C 3.2.
Polyurethanes SATIS 16–19 Number 64 ASE
Students are asked to imagine that they are working in the public relations department of a firm which manufactures and supplies basic materials for producing
polyurethanes. They are asked to prepare a question-and-answer leaflet to put across the importance of these materials to a diverse audience with the help of the information
in the unit and a video: C3.3.
The Perfume Industry SATIS 16–19 Numbers 67 and 68 ASE
Students’ activities can include a survey into the uses of perfumes, planning and carrying out a practical investigation, making models of the molecules of perfume
constituents and discussing the reasons why manufacturers choose to add perfumes to the formulations of many domestic products.
Students make models of molecules, interpret the volatility of organic compounds in terms of intermolecular forces and work out the structure of the two constituents of a
perfume with the help of infrared, NMR and mass spectra: C3.2.
Almost all the topics in this section provide opportunities for discussion and presentation of talks, or posters as tests of Communication.

Summary of Key Skills Requirements
Communications
C3.1a Contribute to a group discussion about a complex subject.
C3.1b Make a presentation about a complex subject, using at least one image to illustrate complex points.
C3.2 Read and synthesize information from two extended documents about a complex subject. One of these documents should include one image.
C3.3 Write two different types of document about complex subjects. One piece of writing should be an extended document and include at least one image.
Suggested candidate evidence:
(i) Tutor observation records, (ii) preparatory notes audio/video tapes, (iii) notes based on documents read, (iv) essays, (v) reports on practical work, investigations or
work experience.
Information Technology
IT3.1 Plan and use different sources to search for, and select, information required for two different purposes.
IT3.2 Explore, develop, and exchange information and derive new information to meet two different purposes.
IT3.3 Present information from different sources for two different purposes and audiences. Your work must include at least one example of text, one example of
images and one example of numbers.
(i) Tutor observation records, (ii) preparatory plans, (iii) printouts with annotations, (iv) draft documents.
Application of Number
N3.1 Plan and interpret information from two different types of sources, including a large data set.
N3.2 Carry out multi-stage calculations to do with (a) amounts and sizes; (b) scales and proportion; (c) handling statistics; (d) rearranging and using formulae.
Candidates should work with a large data set on at least one occasion.
N3.3 Interpret results of calculations, present findings and justify methods. Candidates must use at least one graph, one chart and one diagram.
(i) Tutor observation records, (ii) reports on practical work, investigations or work experience, (iii) printouts with annotations.

Summary of Key Skills Requirements (continued)
Working with Others
WO3.1 Plan the activity with others, agreeing objectives, responsibilities and working arrangements.
WO3.2 Work towards achieving the agreed objectives, seeking to establish and maintain co-operative working relationships in meeting your responsibilities.
WO3.3 Review the activity with others against the agreed objectives and agree ways of enhancing collaborative work.
(i) Tutor observation records, (ii) preparatory plans, (iii) records of process and progress made, (iv) evaluative reports.
Managing Ones Own Learning

LP3.1 Agree targets and plan how these will be met, using support from appropriate others.
LP3.2 Use your plan, seeking feedback and support from relevant sources to help meet your targets, and use different ways of learning to meet new demands.
LP3.3 Review progress establishing evidence of achievements, and agree action for improving performance.
(i) Tutor records, (ii) annotated action plans, (iii) records of discussions, (iv) learning log, (v) work produced.
Problem Solving
PS3.1 Recognize, explore and describe the problem, and agree the standards for its solution.
PS3.2 Generate and compare at least two options which could be used to solve the problem, and justify the option that is taken forward.
PS3.3 Plan and implement at least one option for solving the problem, and review progress towards its solution.
PS3.4 Agree and apply methods to check whether the problem has been solved, describe the results and review the approach taken.
(i) Description of the problem, (ii) tutor observation records and agreement of standards and approaches, (iii) annotated action plan, (iv) reports on practical work, (v)
records of discussions, (vi) records of reviews.

Part 6 – Answers
Unit 5 – Transition Metals, Quantitative Kinetics
and Applied Organic Chemistry
Answers to Marginal Questions
The marginal questions are there to make you think about the material you are studying. They are
not necessarily confined to the Edexcel specification as their purpose is not to assess your
performance. The answers given below are not “specimen answers”; such answers should be
confined to the question asked! The answers offered sometimes contain explanatory material,
examples, extensions, and even further suggestions of questions “to make you think”.
page 1
Q: What is the oxidation number of nitrogen in NO2, NH3, N2, NH4+, NH4+(aq), NO3–?
A: NO2 +4; NH3 –3; N2 0; NH4+ –3; NH4+(aq) –3, NO3– +5
page 2
Q: A sample of cast iron of mass 0.500 g was converted to an acidified solution of iron(II) sulphate.
This solution required 17.1 cm3 of 0.100 mol dm–3 potassium manganate(VII) for complete
oxidation. Find the percentage of iron in the sample.
A: You may either have the equation:
5Fe2+ + MnO4– + 8H+ → 5Fe3+ + Mn2+ + 4H2O
or, you may note that the increase in the oxidation number of iron (from +2 to +3) is 1 whilst the
decrease in the oxidation number of manganese (from +7 to +2) is 5 hence:
5Fe2+ ≡ MnO4–
However you arrive at the information, 5 moles of iron(II) are oxidised by 1 mole of
manganate(VII).
Amount of MnO4– = 17.1 × 0.100 = 1.71 × 10–3 mol
1000
Amount of iron(II) = 5 × 1.71 × 10–3 mol = 8.55 × 10–3 mol
Mass of iron in sample = 8.55 × 10–3 × 56 = 0.4788 g
Percentage of iron in cast iron = 0.4788 × 100 = 95.8 (3 significant figures)
0.500
You should realise that such a conclusion assumes that nothing else in the cast iron (i.e. in the 4.2%
of “rubbish”) will dissolve in acid to give an ion which will reduce manganate(VII). The question
also simply states that the iron is converted to iron(II) sulphate and errors could arise depending
on the method and what it is required to show. If you want to know the percentage of the free
metal iron, then any iron(II) sulphide, a common impurity in cast iron, would dissolve in acid to
give iron(II) ions, Fe2+(aq) and hydrogen sulphide. Both of these would reduce manganate(VII),
increasing the apparent percentage of “free” iron. The hydrogen sulphide could be “boiled off ” but
the iron(II) ions would remain. This would not matter if you were interested in the percentage of
iron “in all forms”, but then, traces of iron(III) oxide, Fe2O3, another common impurity (e.g. as
rust), would give iron(III) ions, Fe3+ (aq), which would not affect the manganate(VII) unless the
solution was reduced with zinc before the titration.
page 4
Q: Deduce an equation for the oxidation of Sn2+ to Sn4+ using acidified MnO4– which is reduced
to Mn2+.
A: Using the half-equation method:

Sn2+ – 2e– → Sn4+
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O

Part 6 – Answers
We must multiply the first equation by 5 and the second by 2 in order to make the number of
electrons transferred the same (10e–):
5Sn2+ – 10e– → 5Sn4+
2MnO4– + 16H+ + 10e– → 2Mn2+ + 8H2O
We can then add the two equations, eliminating the electrons:

5Sn2+ + 2MnO4– + 16H+ → 5Sn4+ + 2Mn2+ + 8H2O
Then, if necessary, we can add the state equations. In this case there is no change of state to which
we wish to draw attention (a precipitate or evolved gas) and if we wish to use the equation for a
calculation of quantities the state symbols would be a useless ornament:
5Sn2+(aq) + 2MnO4–(aq) + 16H+(aq) → 5Sn4+(aq) + 2Mn2+(aq) + 8H2O(l)
page 12
Q: If the Daniell cell, Zn(s)|Zn2+(aq) Cu2+(aq)|Cu(s) , is set up under standard conditions and
an opposing potential greater than 1.10 V is applied to the terminals of the cell, what changes
would you expect.
A: The e.m.f. of the cell is 1.10 V, Zn negative. (As written, by convention, the e.m.f. has the sign of the
right hand electrode, in this case copper, i.e. E = + 1.10 V) If a more negative potential is applied
to the Zn, electrons will flow in and reduce the Zn2+ ions to Zn. They will come from the Cu
electrode where Cu will be oxidised to Cu2+.
The overall change will therefore be:

Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s)
which is the opposite of normal experience.
page 13
Q: State a practical objection to the use of the (standard) hydrogen electrode.
A: The most obvious objection is that there must be a continuous flow of hydrogen. Not only must this
be adjustable to 1 atmosphere pressure, but the effluent hydrogen must be disposed of safely. Also,
the platinum electrode has to be prepared (beforehand) by alternately making it the cathode and
anode in the electrolysis of an acid. This is because the surface has to be activated.
page 15
Q: Find and use appropriate electrode potentials to show whether disproportionation will occur in
the following cases under standard conditions:
(a) VO2+ → VO2+ and V3+
(b) MnO2 → MnO4– and Mn2+
A: The first example is a particularly difficult one because we say (and tend to think) “vee-oh-two-plus”
for two of the species. This makes it very confusing!
(a) VO2+ → VO2+ and V3+

+4 +5 +3
We must find the electrode potentials for the two (half) equations in which (i) VO2+
is reduced to V3+ (ii) VO2+ is produced by reduction of VO2+:
VO2+ + 2H+ + e– → V3+ + H2O E = +0.34 V
VO2+ + 2H+ + e– → VO2+ + H2O E = +1.00 V

Part 6 – Answers
E for the first equation is positive and this process will therefore absorb electrons, going forward.
The more negative E value of the second equation means that it will provide electrons but it can
only do this by reversing:
VO2+ + 2H+ + e– → VO2+ + H2O (absorbs electrons)
V3+ + H2O → VO2+ + 2H+ + e– (provides electrons)
Adding the two half equations:

VO2+ + V3+ → 2VO2+
This shows that disproportionation is not favoured.
(b) MnO2 → MnO4– and Mn2+

+4 +7 +2
We must find the electrode potentials for the two half equations (reductions) in which
(i) MnO2 is reduced to Mn2+ and (ii) MnO2 is produced by reduction of MnO4–:
MnO2 + 4H+ + 2e– → Mn2+ + 2H2O E = 1.23 V
MnO4– + 4H+ + 3e– → MnO2 + 2H2O E = 1.70 V
The (lower) reaction with the more positive electrode potential absorbs electrons (goes forward)
and the half reaction with the more negative (less positive) electrode provides the electrons (by
going backwards). In order to write a (properly balanced) equation for the favoured direction of
reaction, we must also multiply the upper half equation by 3 and the lower one by 2:
3Mn2+ + 6H2O → 3MnO2 + 12H+ + 6e–
2MnO4– + 8H+ + 6e– → 2MnO2 + 4H2O
Adding these gives the equation showing the likely direction of the disproportionation reaction:
2MnO4– + 3Mn2+ + 2H2O → 5MnO2 + 4H+
This again shows that disproportionation is not favoured and the reverse is likely. You have answered
the question without the use of state symbols; in an examination you might like to add them. The fact
that manganese(IV) oxide is an insoluble solid only helps to drive the reaction in the unfavourable
direction here but the formation of an insoluble solid might affect some other reactions:
2MnO4– (aq) + 3Mn2+ (aq) + 2H2O (l) → 5MnO2 (s) + 4H+(aq)
Q: Write an ionic equation for the disproportionation of Sn2+(aq) into tin and Sn4+(aq). Use
electrode potentials to predict whether it is likely to happen.
A: The equation for the disproportionation is:
2Sn2+(aq) [ Sn4+(aq) + Sn(s)
The two electrode potentials required will be those associated with the two half equations in which
(i) Sn2+ is reduced (to Sn) and (ii) Sn2+ is formed by reduction (of Sn4+):
Sn2+(aq) + 2e– [ Sn(s) E = –0.14 V

Sn4+(aq) + 2e– [ Sn2+(aq) E = +0.15 V
The second equation has the more positive electrode potential and will thus be the electron
absorber, i.e. it will go forwards as written:
Sn4+(aq) + 2e– [ Sn2+(aq)

Part 6 – Answers
The first equation (with the more negative electrode potential) will provide the electrons and, in
order to do this, it will have to be written in reverse:
Sn(s) [ Sn2+(aq) + 2e–
Our prediction is that the likely direction of change in the disproportionation reaction is:
Sn4+(aq) + Sn(s) [ 2Sn2+(aq)
Disproportionation will not occur.
page 17
Q: How would you represent a cell with zinc and silver electrodes?
A: Since both zinc and silver have only one stable oxidation state in ionic form, there is little ambiguity
in the terms “zinc electrode” or “silver electrode”. The relevant ions are Zn2+(aq) and Ag+(aq). You
could represent the cell either as:
Zn(s)|Zn2+(aq) Ag+(aq)|Ag(s)
or as
Ag(s)|Ag+(aq) Zn2+(aq)|Zn(s)
The difference between the two is that in the first, the e.m.f. would be positive and in the second it
would be negative. The arrangement in which the cell has a positive e.m.f., by convention the sign
of the right hand electrode, would show the direction of change to be:
Zn(s) → Zn2+(aq) and Ag+(aq) → Ag(s)
Q: How would you expect the e.m.f. of a Daniell cell to alter (qualitatively) if 0.1 mol dm–3 ZnSO4
and 2.0 mol dm–3 CuSO4 were used (in the same cell) instead of 1.0 mol dm–3 solutions?
A: Increasing the concentration of the positive ion (or oxidised form) in each electrode or half cell
makes the e.m.f. more positive. The greater concentration of copper(II) ions would increase the
already positive electrode potential of the copper half cell. The lower concentration of Zn2+ ions
would make the negative electrode potential of the zinc half cell even more negative (i.e. less
positive). The difference between the electrode potentials would thus be greater than before (on
both counts) and the magnitude of the cell e.m.f. would increase.
page 18
Q: A quantity of sodium ethanedioate was weighed out and dissolved in water to make 250 cm3 of
solution. A 25.0 cm3 portion was acidified with dilute sulphuric acid, warmed to 60 °C, and
titrated with 0.0200 mol dm–3 potassium manganate(VII) solution; 27.3 cm3 was required for
complete oxidation. How much sodium ethanedioate was originally weighed out, assuming it to
have been pure.
A: The equation (omitting unnecessary state symbols is):
2MnO4– + 5C2O42– + 16H+ → 2Mn2+ + 10CO2 + 8H2O
Amount of manganate(VII) in titre = 27.3 × 0.0200 = 5.46 × 10–4 mol

1000
from the equation 1 mol MnO4– oxidises 2.5 mol of ethanedioate
Amount of ethanedioate in 25.0 cm3 solution = 2.5 × 5.47 × 10–4 = 1.368 × 10–3 mol

Part 6 – Answers
Only 25.0 cm3 of the original 250 cm3 of solution were used in the titre, hence
Amount of sodium ethanedioate = 1.368 × 10–2 mol

Mr(Na2O4C2) = 134
Mass of sodium ethanedioate weighed out = 1.368 × 10–2 × 134 = 1.83 g
page 19
Q: A sample of sodium sulphite of mass 1.80 g was dissolved in water and made up to 250 cm3.
25.0 cm3 portions of this solution were acidified with dilute sulphuric acid and titrated with
0.0200 mol dm–3 potassium manganate(VII) solution. 26.2 cm3 was required for oxidation. Find
the percentage purity of the sodium sulphite.
The equation is not an easy one. It can be avoided if you consider the changes in oxidation number.
The sulphite (SO32–) is being oxidised to sulphate (SO42-) and the oxidation number of the sulphur
changes from +4 to +6; change = +2. The manganate(VII) is being reduced to Mn2+ with a
change in oxidation number from +7 to +2; change = –5. Thus 5 mol of sulphite is oxidised by
2 mol of manganate(VII).
We reach the same conclusion by writing the equation. If we ignore the work on oxidation numbers
that we have just done, and write two half equations, notice that we have to add H2O to the
sulphite in order to convert it into sulphate:
SO32– + H2O – 2e– → SO42– + 2H+
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
Then, adding 5× the first to 2× the second (to eliminate the electrons)
2MnO4– + 5SO32– + 6H+ → 2Mn2+ + 5SO42– + 3H2O
5SO32– ≡ 2MnO4–
Amount of MnO42– in titre = 26.2 × 0.0200 = 5.24 × 10–4 mol

1000
Amount of sulphite in 25.0 cm3 soln = 2.5 × 5.24 × 10–4 = 1.31 × 10–3 mol
Mr (Na2SO3) = 126
Mass of sodium sulphite used originally = 10 × 126 × 1.31 × 10–3 g = 1.65 g
Percentage of sodium sulphite in sample = 1.65 × 100 = 91.7

1.80
page 21
Q: Why is the corrosion of iron pier supports often worst in the region between high and low tide
levels?
A: In addition to iron, air and water are required for rusting. The process is accelerated by the
presence of carbon dioxide and electrolytes. The region between high and low tide is the only one
which gets a regular supply of water (and electrolytes) at high tide, and a regular supply of air (with
carbon dioxide) at low tide.

Part 6 – Answers
page 29
Q: Why are scandium(III) compounds colourless?
A: Sc has the structure [Ar] 3d1 4s2. Its only simple cation, Sc3+ , has the [Ar] structure. For an ion
to be coloured it must normally have an incomplete d sub-shell and be complexed. Whilst
scandium(III) compounds form aqua complexes they have no electrons in d-orbitals and they are
thus colourless.
Q: Suppose you have solutions of an iron(II) salt and an iron(III) salt, containing [Fe(H2O)6 ]2+ and
[Fe(H2O)6 ]3+, of equal concentration. Which would be more acidic and why?
A: Acidity, in each complex cation, is caused by the generation of the species H3O+ from H2O in the
water by deprotonation of H2O in the complex. The driving force is the positive field exerted on the
complex H2O by the central metal ion; this helps the heterolytic fission of the O−H bond, leaving a
negative charge on the oxygen atom (attached to the positive ion). As the central positive field in the
iron(III) complex is larger than that in the iron(II) complex, the iron(III) complex will be more acidic.
page 30
Q: Suggest how, using either sodium hydroxide solution or ammonia solution as appropriate, you
could separate the ions in aqueous solutions of (a) Zn2+ and Cu2+, (b) Fe2+ and Cr3+.
A: (a) Both zinc and copper(II) ions form soluble ammine complexes, therefore aqueous ammonia
would not separate them. On addition of sodium hydroxide solution, both form hydroxide
precipitates, however, that of zinc is sufficiently acidic to dissolve in excess sodium hydroxide to
give a zincate solution. (Both metal ions exist as hexaaqua complexes and the processes of
precipitation and redissolving are simply successive stages of deprotonation.) A suitable method
would be (i) add excess aqueous sodium hydroxide, (ii) filter off (or centrifuge), and wash the
precipitated copper(II) hydroxide, (iii) redissolve the precipitate in a suitable acid to regenerate
the Cu2+ solution, (iv) acidify the filtrate with a suitable acid to regenerate the Zn2+ solution.
(b) Although, in theory, it is possible to separate these two using aqueous ammonia, in practice it
would not be easy because of the amount of ammonia solution required to form a solution of
the chromium(III) ammine complex. Once again, the use of excess sodium hydroxide appears
to offer the better separation. The iron(II) solution would form a precipitate of iron(II)
hydroxide (basic) whereas the initially formed chromium(III) hydroxide (amphoteric) would
dissolve in excess of the alkali to give a (green) chromite(III) solution. The practical method
would be essentially the same as that in part (a). A further complication, in this example, is the
rapid tendency of iron(II) to be oxidised by air to the iron(III) state; in practice it would be
almost impossible, without working in an inert atmosphere or with the addition of a reducing
agent, to preserve the iron(II) entirely in this oxidation state using this method.
You will notice that no equations have been given for the above. That is because to do so
without comment would be misleading. In an examination, you would be expected to support
any such answer by equations. Thus the formation of iron(II) hydroxide on adding alkali could
be written:
Fe2+(aq) + 2OH–(aq) [ Fe(OH)2(s)
or, it could be written, more informatively, as:
[Fe(H2O)6]2+(aq) + 2OH–(aq) [ [Fe(H2O)4(OH)2](s) + 2H2O(l)
The former equation is obviously much easier than the latter, so which do you write in an
examination? In this context, either would be acceptable to an examiner, since you are merely
illustrating the formation of a precipitate, not justifying its formation. Nevertheless, the upper

Part 6 – Answers
equation has the disadvantage that it represents the precipitate by a misleading formula. If you had
been asked to show how a hydrated iron(II) ion reacts with aqueous alkalis, however, the second
equation is preferred.
page 31
Q: Justify the view that vanadium is a transition metal, giving examples of the characteristic
properties you would expect.
A: This must be a limited answer since all the characteristics of transition metals and their compounds
are not expected in the Edexcel specification. If you were answering this in a test paper, you should
note that “characteristic properties” are expected, not the electronic structure. Also, you should
note the number of marks available. It is unlikely that more than one mark would be given for
colour; if you mention colour of compounds, give two at the most (unless it is to justify some other
part of your answer), not a list of every coloured vanadium compound you can think of.
The formation of coloured compounds and variable oxidation state are perhaps best dealt with
together in answering a question of this kind. Thus, a solution of ammonium vanadate (itself
colourless) which has been acidified, is orange. The addition of a sulphite reduces it from the +5
oxidation state to the +4 oxidation state, observed as a change of colour from orange to blue. On
the other hand the addition of zinc reduces it from the +5 to the +2 state, with the formation of a
violet solution. There is only need to quote one of these in the context of the question, but it
should be illustrated by an equation, e.g.
2VO2+(aq) + 3Zn(s) + 8H+(aq) → 2V2+(aq) + 3Zn2+(aq) + 4H2O(l)
(+5) (+2)
orange violet
Vanadium and its compounds have catalytic properties, again a property of transition elements
(though not limited to them). The best example is the use of vanadium(V) oxide as the catalyst in
the contact process for the oxidation of sulphur dioxide:
2SO2(g) + O2(g) [ 2SO3(g)
In view of the limited knowledge of vanadium chemistry expected, it would be difficult for you to
justify the claim that vanadium forms a wide range of complexes, again characteristic of d block
and transition metals. You would simply have to state that its cations did not normally exist in
simple form in solution, e.g. in the +5 state the ion is best represented as VO2+ not V5+. This is
probably where you would have to play the “examinations game”; as indicated earlier, if you saw
that 6 marks were allocated, it would probably mean that three characteristics and one illustration
of each, were expected. In that case you would not need to quote complex formation.
page 32
Q: Write half equations for the redox reactions of VO2+ shown.
A: The separate equations for the two half reactions are given below. The oxidation numbers are not
part of the equations but are included because they relate to the numbers of electrons added or
taken away:
VO2+ + 2H+ + e– → VO2+ + H2O
(+5) (+4)
SO32– + H2O → SO42– + 2H+ + 2e–
(+4) (+6)

Part 6 – Answers
If the equation for the total redox process is required (as given in the Unit 5 book) then the first of
these two equations has to be doubled throughout so that the numbers of electrons (or the changes
in oxidation number) are the same in both equations. Notice that in the oxidation of sulphite we
had to add water to the left hand side of the half equation. The two half equations can then be
added and the state symbols added, giving:
2VO2+(aq) + 2H+(aq) + SO32–(aq) → 2VO2+(aq) + H2O(l) + SO42–(aq)
The other oxidation half reaction has the equation:
Fe2+(aq) → Fe3+(aq) + e–
Had the question asked for the full equation it could have been obtained by adding this half
reaction to the equation above for the reduction of VO2+.
page 33
Q: Write equations to show (a) the reduction of iron(III) oxide to iron using carbon monoxide, (b)
the reduction of iron(III) oxide to iron using carbon. Both reactions occur in the blast furnace.
A: (a) Fe2O3(s) + 3CO(g) a 2Fe(s) + 3CO2(g)
(b) Fe2O3(s) + 3C(s) a 2Fe(l) + 3CO(g)
or
2 Fe2O3(s) + 3C(s) a 4Fe(l) + 3CO2(g)
What happens in the blast furnace depends on the position in the furnace and the temperature. In
the cooler upper parts the predominating reaction is (a) (and possibly reduction to FeO) – hence
the (s) state symbol after Fe. At temperatures where the carbon is a satisfactory reducing agent the
iron produced is more likely to be molten and the carbon is more likely to be oxidised to the
monoxide. The question was simply intended as an elementary exercise in balancing equations,
not as a study of the blast furnace.
Q: Write the equation for the oxidation of Fe2+(aq) to Fe3+(aq) using oxygen. The equation for the
reduction of oxygen is:
O2(g) + 4H+(aq) + 4e– → 2H2O(l)
A: Combining this with the equation for the oxidation of iron(II) (above) multiplied by 4:
4Fe2+ (aq) → 4Fe3+(aq) + 4e–
we have:
4Fe2+(aq) + 4H+(aq) + O2(g) → 4Fe3+(aq) + 2H2O(l)
This answers the marginal question but it must be treated with caution. It is correct – but is the
equation describing oxygen acting in acidic solution. In the absence of acid, the oxidising action of
oxygen is more correctly represented by a different equation with a different standard electrode
potential:
O2(g) + 2H2O(l) +4 e– → 4OH–(aq)
You may recollect that this is the one which we use when discussing rusting.
page 46
Q: Ka (phenol) = 10–10 mol dm–3. Write an expression for this and use it to calculate the pH of
0.10 mol dm–3 phenol.

Part 6 – Answers
A: C6H5OH(aq) [ C6H5O–(aq) + H+(aq)
Ka = [C6H5O–] [H+]
[C6H5OH]
Ignoring the small amount of H+(aq) from ionisation of the water:

[C6H5O–] = [H+]
[H+]2 = 10–10 (mol dm–3)
0.1
[H+]2 = 10–11 (mol2 dm–6)
[H+] = 10–5.5 mol dm–3
pH = 5.5
page 47
Q: Why is the acyl chloride:phenol ratio greater than 1 in the Schotten–Baumann reaction?
A: This reaction uses strongly alkaline conditions to activate the phenol and enhance its attack on the
acid chloride:
C6H5OH(aq) + OH–(aq) [ C6H5O–(aq) + H2O(l)
then, for example:

C6H5O–(aq) + C6H5COCl(l) → C6H5COOC6H5(s) + Cl–(aq)
Hydrolysis of the acyl halide, here benzoyl chloride, is accelerated in alkaline conditions and some
of this reactant is lost in the competitive reaction:
C6H5COCl(l) + 2OH–(aq) → C6H5COO–(aq) + Cl–(aq) + H2O(l)
It is therefore important to ensure that there is excess of the acyl chloride.
page 49
Q: Explain why this test cannot be used for the detection of a tertiary amine.
A: The test relies on the presence of the –NH2 group (attached to a benzene ring). This must be
oxidised to the –N2+ (diazonium) group before the coupling reaction will occur. The presence of
three organic substituents on the nitrogen atom, as in a tertiary amine e.g., C6H5N(CH3)2, makes it
impossible to oxidise with nitrous acid (and secondary amines are oxidised differently).
page 54
Q: Predict the number of and name the products when HCl is added to pent-2-ene.
CH3CH=CHCH2CH3 pent-2-ene
A: The hydrogen chloride molecule can add to the double bond, which is unsymmetrical, in two ways.
This gives rise to the products:
CH3CH2CHClCH2CH3 and CH3CHClCH2CH2CH3
3-chloropentane 2-chloropentane
The situation is more complicated if we go beyond structural isomerism and look at the possibility
of stereoisomerism. 2-Chloropentane has a chiral centre – the second carbon atom has four
different substituents, H, Cl, CH3 and C3H7. In consequence, it has two optical isomers
(enantiomers); in the reaction above neither is preferred and we should have equal amounts of
each, a “racemic mixture”.

Part 6 – Answers
page 55
Q: Predict the result of the addition of hydrogen iodide to 2-methylbut-2-ene
A: The first thing to do is write down the structure of 2-methylbut-2-ene
H3CC=CHCH3
|
CH3
Applying the Markownikov rule, the hydrogen atom will add on to carbon-3. Note that this is not an
explanation; if you are asked for an explanation then you will have to refer to the stability or ease
of formation of the relative carbocation (carbonium ion) – as on this page (Unit 5 p. 55). Here you
are merely asked to predict the product. Thus 2-methyl–2-iodobutane will be the main product
H3C CI CH2CH3
|
CH3
page 58
Q: Name C6H5CH(CH3)CHO
A: The presence of a functional group in the side chain makes it desirable to name
the compound as a derivative of the three-carbon chain.
It is therefore 2-phenylpropanal.
page 62
Q: The concentration of a compound X falls from 0.80 mol dm–3 to 0.72 mol dm–3 in 1 minute 20
seconds. Calculate the approximate rate. Why is it almost certainly approximate?
A: The best estimate of rate is (0.80 – 0.72) mol dm–3 = 1.0 × 10–3 mol dm–3 s–1
80 seconds
(You do not need to write “seconds” – it was done here to make the origin of the 80 more obvious).
It is almost certainly approximate; nearly all reactions become slower as they proceed because the
reactant concentrations are falling. If the rate is not constant, the figure is, at best, an average.
page 63
Q: When the initial concentration of X (see previous question) was 0.40 mol dm–3 the rate fell to
5 × 10–4 mol dm–3s–1. What is the order with respect to X?
A: The rate appears to have fallen to half its previous value when the initial concentration did likewise.
The reaction is thus of first order with respect to X.
page 71
Q: If Mr is about 420, why is a molecular formula of C27H47O impossible?
A: Carbon atoms normally have four covalent bonds (sometimes called a valency or covalency of 4),
hydrogen atoms have one and oxygen atoms two. Every covalent bond has two “ends” – two atoms
which it connects. Because of this, in a normal compound all these valencies must add up to an
even number. For carbon or oxygen, of course, it does not matter how many atoms you have, the
total is bound to be even, but for hydrogen or nitrogen (with a covalency of 3), an odd number of
atoms will give rise to an odd number of “ends”. Look at any compound containing hydrogen. If it
has an odd number of hydrogen atoms per molecule then it must have an odd number of some
other atom with an odd covalency. Ethanol C2H6O, ethanoic acid C2H4O, and benzene C6H6 have
even numbers of hydrogen atoms but bromoethane C2H5Br, iodobutane C4H9I or phenylamine
C7H7N, with odd numbers of hydrogen atoms per molecule must have Br, I or N to compensate.
No-one will ask you in an Edexcel examination to explain this, but it is a useful rule to bear in mind

Part 6 – Answers
when you write down the molecular formula of a compound as the answer to a question. Similarly,
if you find the empirical formula of a compound is CH3 then you know it must be (at least)
doubled to obtain the molecular formula. You might like to ponder, in this case, why it can only be
doubled and not multiplied by four to get an even number of hydrogen atoms.
page 72
Q: What would you use to oxidise X and what would you expect to get from the two possible
structures?
A: Hot alkaline potassium manganate(VII) would convert B and C (after acidification) into benzene-1,3-
dicarboxylic acid and benzene-1,2-dicarboxylic acid, respectively. These isomers of C6H4(COOH)2
could be distinguished by melting point or because the 1,2-diacid loses water on heating.
page 73
Q: What kind of isomers are I and J?
A: While it would be correct to say that these are stereoisomers, it would be better to be specific and
to state what kind of stereoisomerism is shown. In this case, it is geometrical isomerism, caused by
the lack of free rotation about the axis of the double bond.
page 81
Q: How would you distinguish between A, B, C and D by chemical tests alone?
A: Compound A is a cyclic ether; you know nothing about these and would therefore have to apply
positive tests for the other three. In fact, ethers of this type are remarkably unreactive.
Compound B is the only one with a C=C double bond. Firstly all four compounds are shaken with
bromine solution (since the product is not important it doesn’t matter whether you use aqueous
bromine or an organic solution). The only one which will decolourise the bromine rapidly is the
alkene, B.
The remaining three compounds are shaken with 2,4-dinitrophenylhydrazine reagent. Two will
give orange precipitates, only the ether, A, will not react.
C and D are warmed with iodine solution, the mixture is cooled and aqueous sodium hydroxide is
carefully added until the iodine colour is (effectively) removed. D is a methyl ketone and will give
a yellow precipitate of iodoform, CHI3; C will show no change.
Why did the marginal question not include E in the list of compounds to be distinguished by
chemical test? You might like to decide how you would cope if E had been pentanal.
page 94
Q: Assign an ion to the peak at m/z = 181.
A: The molecular ion at m/z = 216 contains the common isotope of chlorine 35Cl (by definition). The
ion at m/z = 181 is the result of the loss of a fragment of (relative) mass (216 – 181) = 35. This can
only be the chlorine atom. The fragment is thus
C6H5COC6H4+.
Q: Why must the fragment at m/z = 51 be a ring fragment?

A: We do not have a complete spectrum to enable recognition of the typical fragmentation pattern of
a benzene ring, nevertheless it can be simply argued that this must be a ring fragment. The
fragment cannot contain a benzene ring, its relative mass would have to exceed 72 if every
hydrogen atom and substituent had been stripped off. If we assume that the structure of the
compound is one of the isomers envisaged, the remaining fragments which do not contain a ring
can only be CO (with perhaps an additional hydrogen atom or two) and Cl (with perhaps an

Part 6 – Answers
additional hydrogen atom), with masses 28, 35 or 37 plus 1 or 2. These are too small for a mass
of 51. The only other possibility is a ring fragment.
You are reminded that the prediction of NMR absorption spectra is a higher level “skill” than is
required by the Edexcel syllabus which only requires the reverse process, interpretation of a given
spectrum. Marginal questions are there to make you think about the topic in depth. You might like
to see how many of the points, in the predictions given below, that you can predict.
page 101
Q: Predict the NMR spectrum of pentan-2-one.
A: CH3CH2CH2COCH3
a b c d e
The two methyl groups, a and e are in different environments. e is next to an electron-withdrawing
carbonyl group and would absorb well downfield relative to a. We might expect two absorption
peaks of area 3 units: a should absorb at about δ = 0.9 to 1.0 ppm (it is too far from the C=O group
to show much effect) and, [not required by Edexcel] it should be a triplet because of the effect of
the protons on the group b; e, by reference to figure 5.26, should absorb at about δ = 2.1 to 2.2
ppm and, [not required by Edexcel] the peak should be sharp because there are no neighbouring
protons.
The methylene groups, b and c, should give rise to two peaks of area 2 units. That due to b would
absorb a little downfield of the methyl group a, perhaps at δ = 1.5 ppm (slightly influenced by the
C=O group) and [not required by Edexcel] on a good machine might be resolved into a sextuplet.
That due to c would be very close to the methyl group absorption of e, but perhaps a little further
downfield (–CH2– rather than CH3–), say 2.3 to 2.4 ppm. It should be clearly distinguishable from
the methyl absorption, however, [not required by Edexcel] because it would be a low “fat” peak – a
triplet as a result of coupling with the protons of b.
page 102
Q: Predict the NMR spectra of (i) 2-iodopropane (ii) 2-chlorobutane.
A: (i) CH3CHICH3
a b c
The two methyl groups, marked a and c, are identical and will, therefore, form one peak. In each case,
there is only one hydrogen atom on the next carbon atom b and the peak will be a doublet [not
required for Edexcel]. The position will be slightly downfield from CH3 in an alkane because of the
electron-withdrawing effect of the neighbouring iodine atom. Perhaps δ would be nearer 1.5 ppm.
The methynyl CH (marked b) would be moved well downfield from its normal value of δ = 1.5
ppm as there is an iodine atom on the same carbon atom. Looking at figure 5.26 we might expect a
value of about δ = 4 ppm. Because this proton has six protons on the two methyl groups next to it,
we might expect it to be a heptuplet (assuming the machine could resolve it – again, this is not
required for the Edexcel specification).
The ratio of the areas of the two absorption peaks should be 6:1.
(b) CH3CHClCH2–CH3
a b c d
The two methyl groups (a and d) are in very different environments; carbon-1, a, has an electron-
withdrawing group (Cl) on the next carbon atom, whereas carbon-4, d, has the chlorine atom

Part 6 – Answers
further away. Protons on carbon-1, a, would absorb downfield from the spectrum of a simple alkane
methyl group (δ = 1.0 ppm ), perhaps at δ = 1.5 ppm. Those on carbon-4, d, would be only
slightly affected and might absorb at δ = 1.0 to 1.2 ppm. As carbon-1, a, has only one neighbouring
hydrogen atom, the peak would be a doublet, but carbon-4, d, should give rise to a triplet [not
required by Edexcel].
The methylene group, c, is next to the C−Cl and its absorption would move downfield to a point
about 0.2 ppm beyond the methyl group a. a and c would be similarly affected by the chlorine
atom. The methyl and methylene protons would move down the field together. The peak would be
a quintuplet if resolved.
Finally, the C−H (methynyl) group, b, would be most affected by the chlorine atom and its
absorption might be expected to occur at about δ = 4 ppm (see figure 5.25 Unit 5). The small peak
would be a sextuplet if resolved.
Therefore, we would expect a spectrum with four peaks at about δ = 1(d, triplet), δ = about 1.5
(a, doublet), δ = about 1.7 or 1.8 (c, quintuplet) and δ = 4 or a little more (b, sextuplet) of area
ratio 3:3:2:1.
Such information is probably best represented by means of a table, the rows and columns of which
will depend on the information you wish to give (or you could use a labelled sketch). It is unlikely
that you will be asked to predict a spectrum in an Edexcel test as the specification is concerned
with the interpretation of NMR spectra. If you can predict them, however, you can certainly
interpret them. It is only fair to point out to students (of other examination boards) that, strictly,
the two hydrogen atoms on carbon-3 (c) should be considered separately. This is for reasons well
outside the Edexcel specification; often protons of this type absorb (fortuitously) at the same
frequency or field strength.
A simple exercise, after you have read this answer, might be to download the 1H- NMR spectrum of
2-chloro-, bromo- or iodobutane and see if you can interpret it. A suitable source is www.aist.go.jp.
This internet source has an advantage, if you “get stuck”, because it identifies the protons
responsible for particular absorption peaks for you.
page 103
Q: Predict the NMR spectrum of methyl ethanoate.
A: CH3COOCH3
a b
The two methyl groups will both absorb well downfield of the simple alkane methyl proton
absorption. Methyl group a is connected to carbon, but b is connected to oxygen. Bear in mind
that both C=O and O are involved. Looking at figure 5.26, δ values of perhaps 2 to 2.5 for a and 3.5
to 4 ppm for b seem likely. The peaks should be of equal area. Neither methyl group has a
neighbouring C−H proton and thus the peaks will be sharp singlets [not required for Edexcel].
page 105
Q: How would you intensify the colour of a copper(II) salt solution in order to make it suitable for
colorimetry?
A: The easiest method would be to add an excess of (concentrated) aqueous ammonia to give the
deep blue tetraammine complex:
[Cu(H2O)6]2+(aq) + 4NH3(aq) [ [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
pale blue aqua complex intense deep blue ammine complex

Part 6 – Answers
page 111
Q: An expensive material, A, is to be converted into B. Route 1 is one step with 45% yield. Route 2 is
two steps, each with 60% yield. Which is better?
A: Using route 2, at the end of the first step, the yield is 0.6 of theoretical. At the end of the second step
it is 0.6 of this, i.e. 0.6 × 0.6 = 0.36 or 36% of theoretical. Route 1, with a 45% yield is thus better.
page 112
Q: What products would be formed if you used (i) butan-2-ol at the start instead of propan-2-ol, (ii)
ethylmagnesium bromide as the Grignard reagent, (iii) both of these?
A: (i) Butan-2-one and 2-methylbutan-2-ol
(ii) Propanone (as before) and 2-methylbutan-2-ol
(iii) Butan-2-one and 3-methylpentan-3-ol
Note: It is correct to call butan-2-one simply butanone as there is no ambiguity.
page 114
Q: How would you convert 1-bromopropane into 2-bromopropane?
A: Treatment with boiling ethanolic potassium hydroxide would convert 1-bromopropane into propene.
Addition of hydrogen bromide would then give 2-bromopropane. There are two important
competing reactions. In the first reaction propan-1-ol is an alternative product; the conditions are
chosen to favour elimination over substitution. In the second reaction 1-bromopropane will be
formed to some extent though the 2-bromopropane is favoured (Markownikov):
KOH(ethanolic) HBr
CH3CH2CH2Br → CH3CH=CH2 → CH3CHBrCH3
Q: How would you convert propan-2-ol into (i) 2,3-dimethylbutan-2-ol, (ii) propene?
A: (i) Looking at the structure of 2,3-dimethylbutan-2-ol

OH
|
CH3 CH C CH3
| |
CH3 CH3
gives an indication of how this problem might be solved. There are two 3-carbon units joined at the
“middle” and one “middle” carbon has a hydroxyl group. Joining two groups and being left with
–OH at the joining point is often achieved by Grignard attack on a carbonyl (C=O) group. The
carbonyl compound, propanone, can easily be made by boiling the propan-2-ol with dilute
sulphuric acid and potassium dichromate(VI):
K2Cr2O7/H2SO4
CH3CHOHCH3 → CH3COCH3
The Grignard reagent can be made in two steps. First the propan-2-ol can be converted to the
corresponding bromocompound by heating with potassium bromide and concentrated sulphuric acid:
KBr/H2SO4
CH3CHOHCH3 → CH3CHBrCH3

Part 6 – Answers
then the purified and dried 2-bromopropane is treated with magnesium in dry ethoxyethane (ether):
CH3CHBrCH3 + Mg → CH3CHMgBrCH3
The Grignard reagent is then mixed with propanone in situ, that is to say, without isolating it from
the reaction mixture. Acidification with hydrochloric acid will break down the complex giving the
desired product.
(ii) Propan-2-ol can be dehydrated simply by heating with concentrated sulphuric acid:
CH3CHOHCH3 → CH3CH=CH2
Q: Which important method of increasing carbon content is missing from figure 7.5?
A: The Friedel–Crafts reactions
page 115
Q: What does the carbon atom of the methyl group become in the haloform reaction?
A: The appropriate trihalomethane, e.g. iodoform CHI3
Q: How would you convert phenylethanone into (i) benzoic acid, (ii) phenylamine,
(iii) 2,4,6-tribromophenol (in that order)?
A: Use the reaction schemes below:
COCH3 CO2H CO2–NH4+
1. KMnO4/OH–(aq) 2. NH3
H+(aq)
Heat
OH NH2 CONH2
4. HCl(aq)/NaNO2 3. NaOH(aq)/Br2
5. Br2
OH
Br Br
Br
1. Boil under reflux with excess aqueous alkaline potassium manganate(VII) then acidify with
hydrochloric acid (and “remove” excess manganate and manganese(IV) oxide with sodium
sulphite which converts them to soluble manganese salts). Benzoic acid will be precipitated.
2. Add excess aqueous ammonia to give ammonium benzoate, evaporate to dryness and heat to
give benzamide.
3. Treatment of benzamide with aqueous sodium hydroxide and bromine (Hofmann reaction) will
give phenylamine. (This would be most tedious to isolate but don’t worry about this in such
theoretical questions about preparative reaction schemes).

Part 6 – Answers
4. Treatment of the aqueous solution in hydrochloric acid with sodium nitrite gives phenol.
Probably best done below 5 °C to give the intermediate diazonium salt, C6H5N2+Cl– , followed by
boiling to decompose this to phenol. The yield would be miserable, with much chlorobenzene,
but again, in these theoretical schemes this does not matter.
5. Addition of bromine to aqueous phenol would precipitate 2,4,6-tribromophenol almost

quantitatively.
page 116
Q: If only the diacid shown were available, how could you make the diamine from it?
A: Treatment of the diacid, or its aqueous solution, with ammonia or ammonium carbonate, would
give the diammonium salt. This would be dehydrated by heating to give the diamide. Treatment
with bromine and alkali (Hofmann degradation) would give the diamine:
NH3 Heat NaOH/Br2
HO2C(CH2)CO2H → NH4O2C(CH2)CO2NH4 → H2NCO(CH2)4CONH2 → H2N(CH2)4NH2
page 118
Q: Why is it helpful, when purifying by recrystallisation, if an impurity is much less or much more
soluble than the desired compound in the chosen solvent?
A: Very insoluble impurities will be filtered from the hot solution. Very soluble ones will remain in the
filtrate when it cools. This is not the basis of the method of recrystallisation, which depends
primarily on the difference in solubility at high and low temperature of the substances to be
purified.
page 126
Q: What ion, present in ammonium sulphate, causes its aqueous solution to be acidic? Explain your
answer.
A: The ammonium ion. It is the protonated form of a weak base, ammonia, and reacts with (the vast
excess of) water to give the acid H3O+:
NH4+(aq) + H2O(l) [ NH3(aq) + H3O+(l)
Q: During the second half of the 20th century Israel developed an extensive agricultural industry.
River water (and artesian water) containing minute amounts of dissolved minerals, has been
used for irrigation. Recently, in such areas, crop yields have fallen. Suggest why.
A: The very high temperatures and long periods of hot sunshine cause extremely high rates of
evaporation. The accumulated residues of salts in the soil have an adverse effect on the ability of
plants to take up water because the irrigation water tends to dissolve the salt residues and its
osmotic pressure is significant.

Part 6 – Answers
Answers to End-of-Chapter Questions

These answers are not “model answers” in the sense that they “fit” the question perfectly. They contain
hints about answering questions and occasionally additional relevant material. Thus, if a question asks
for a “use of sulphuric acid”, it would be most misleading here to answer “as the electrolyte in car
batteries”; this would undoubtedly score the necessary mark in an examination but a “mark scheme”
would contain a range of examples. The answers below fall somewhere in between these situations.
Chapter 1
1 (a) (i) NO3– (ii) NO2– (iii) ClO– (iv) ClO3– (v) AlO2– or AlO33–
(b) 3 ClO– → 2 Cl– + ClO3–
3 (+1) 2 (–1) (+5)
2 (i) H2 + S → H2S
(0) (0) 2(+1),(–2)
H oxidised [0 → +1]; S reduced [0 → –2]
(ii) 2 Al + 3 Cl2 → Al2Cl6
(0) (0) 2(+3),6(-1)
Al oxidised [0 → +3]; Cl reduced [0 → –1]
(iii) 2 OF2 → O2 + 2 F2
(+2),2(–1) (0) (0)
O reduced [+2 → 0]; F oxidised [–1 → 0]
This example is worth special attention. Firstly we usually find that oxygen is reduced – but
not when the oxygen is going from the combined state to the elemental state. The usual
examples where oxygen is reduced are when it forms an oxide
e.g. 2 Mg + O2 → 2 MgO. Fluorine is never oxidised; never, that is, when we refer to a
reaction of the uncombined element fluorine. Here, however, the fluorine is in the form of a
fluoride undergoing thermal decomposition. You must be extremely careful when answering
questions that it is clear whether you refer to the free or combined element e.g. by giving an
equation to show the direction of change (as here) or specifying fluoride and fluorine, or, best
of all, by doing both.
(iv) This reaction is offered as an exercise for discussion. If we apply the ordinary rules for
calculating oxidation number of an ion i.e. sum of oxidation numbers = charge on ion, then
the oxidation number of sulphur in S2O32– is (+2):
S + SO32– → S2O32–
(0) (+4),3(–2) 2(+2),3(–2)
However, the oxidation number of one of the two atoms of sulphur may not be the same as
that of the other.
You are familiar with a few simple compounds where a combined element has more than one
oxidation number. An example is ammonium nitrate, (NH4)+(NO3)–, in which the first
nitrogen atom has an oxidation number of (+3) but the second has an oxidation number of
(+5). Just as, in ammonium nitrate, the mean oxidation number of nitrogen (a rather pointless
application merely included to illustrate the idea) is (+4), so the mean oxidation number of
sulphur in thiosulphates is (+2). It would be most unwise to claim that the elemental sulphur
had been oxidised from (0) to (+2) whereas that of the combined sulphur had been reduced
from (+4) to (+2).

Part 6 – Answers

Draw out the structure of the thiosulphate ion. It is just like the SO42– ion except that one of
the S=O groups has been replaced by S=S. If we assume that bonding two like atoms
together does not change their oxidation number (H–H, Cl–Cl, O=O etc), then the central S
is still bonded to three O atoms and the ion still carries two negative charges, thus the
oxidation number of S is still (+4). The outer S atom, which started life bonded to other S
atoms (probably) in S8 is still just bonded to sulphur and still has an oxidation number of (0)
(which confirms that it does not affect the oxidation number of the central S atom).
You must remember that oxidation numbers are simply a system, invented by chemists, to
help them with book-keeping exercises using oxidation, reduction and electron transfer. It
has its limitations and in the example given, the formation of the thiosulphate ion, it is best
limited to the idea of a mean oxidation number. The mean oxidation number of sulphur does
not change.
Most of the examples of oxoanions met with at A-level contain only a single atom other than
oxygen, hence the problem does not arise. In rare exceptions met at A-level, such as the
dichromate ion Cr2O72– (or the pyrophosphate ion P2O72–), the two Cr (or P) atoms are
linked via oxygen, not connected directly hence, again, the problem does not arise).
(v) H2O + SO3 → 2 H+ + SO42–
2(+1),(–2) (+6),3(–2) (+1) (+6),4(–2)
No change in oxidation states
(vi) H+ + SO42– → HSO4–
(+1) (+6),4(–2) (+1),(+6),4(–2)
No change in oxidation state
(vii) SO3 + H2SO4 → H2S2O7
(+6),3(–2) 2(+1),(+6),4(–2) 2(+1),2(+6),7(–2)
(viii) 2 CrO42– + 2 H+ → Cr2O72– + H2O
(+6),4(–2) (+1) 2(+6),7(–2) 2(+1),(–2)
3 (i) E°– (Pb2+|Pb) = –0.13 V; E°– (Cu2+|Cu) = +0.34 V

The lead system has the more negative electrode potential and provides electrons i.e., the
reduced form (Pb) is the reducing agent in the reaction with the copper system. The copper
system has the more positive electrode potential and absorbs electrons i.e., its oxidised form,
Cu2+, is the oxidising agent in the reaction with the lead system.
Yes. Metallic lead should reduce copper(II) sulphate. There are, however, problems
associated with the insolubility of the product, lead sulphate, resulting from the combination
of the lead ions produced by oxidation with the sulphate ions in solution. The reaction may
be stopped by the formation of an insoluble film of lead sulphate over the surface of the lead.
(ii) The only equation for the reduction of (acidified) nitrates in Fig 1.1 is
NO3–(aq) + 3H+(aq) + 2e– a HNO2(aq) + H2O(l), for which E°– = 0.94 V.
The electrode potential of the Cl2|Cl– system is +1.36 If a reaction is possible between these
two systems then the oxidised form of the one with the more positive electrode potential
(Cl2) will oxidise the reduced form of the system with more negative electrode potential
(HNO2). The reaction is thus the reverse of that suggested in the question.

Part 6 – Answers

You must bear in mind the Fig 1.1 gives only one potential for NO3–. There are many possible
reduction products and you could usefully consult a book of data to find whether any of
them have electrode potentials more positive than +1.36 V.
(iii) E°– (Cr2O72–|Cr3+) = + 1.33 V; E°– (MnO4–|MnO2) = +1.70 V
By the same arguments as above, dichromate(VI) (the oxidised form) is not a sufficiently
powerful oxidising agent to oxidise manganese(IV) oxide (here the reduced form) to
manganate(VII).
(iv) E°– (VO2+|V3+) = +0.34 V; E°– (Ag+|Ag) = +0.80 V
The system with more positive E°– will absorb electrons (converting its oxidised form, Ag+, to
its reduced form, Ag). If a reaction occurs, it will be the oxidation of V3+ to VO2+ by Ag+ not
the reduction in the question.
(v) In solving this, first you have to find, in Fig 1.1, the half-equation for the reduction from
V(+5), which could be VO2+ or VO3– , to V4+ which is likely to be VO2+. This corresponds to
E°– = +1.00 V. The half-equation for the reduction of Cl2 to Cl– shows E°– = +1.36 V. If these
systems react, the oxidised form of the one with the more positive electrode potential (Cl2)
will oxidise the reduced form (VO2+) of the system with the more negative potential. Yes, Cl2
should oxidise VO2+ to VO2+.
(vi) To decide if this disproportionation will occur, we must find two half-equations (reductions).
In one, V(+4) (LHS) is reduced to V(+3):
VO2+(aq) + 2H+(aq) + e– [ V3+(aq) + H2O(l)

for which Fig 1.1 give E°– = +0.34 V
In the other, V(+4) is the product of reduction (RHS) of V(+5)
VO2+(aq) + 2H+(aq) + e– [ VO2+(aq) + H2O(l)

for which E°– = +1.00 V
If these two systems are put together, the oxidised form (VO2+) of that with the more positive
E°– (+1.00 V) will oxidise the reduced form (V3+) of the more negative (E°– = +0.34 V). The
resulting equation is thus obtained by adding the second half equation (which goes forward)
to the reverse of the first (which is driven backward), giving:
VO2+(aq) + V3+(aq) [ 2 VO2+(aq)
Note that we did not need to multiply either equation by a simple number because the
number of electrons transferred was one in each case. Note also that the H+ and H2O cancel
out. Thus we can predict that VO2+ will not disproportionate in the way suggested.
4 Mg(s)|Mg2+(aq) || Ni2+(aq)|Ni(s)
e.m.f. = –0.25 – (–2.37) = +2.12 V with Ni +ve
Mg(s) + Ni2+(aq) → Mg2+(aq) + Ni(s)
To increase the e.m.f. the magnesium system (half-cell) must be replaced by a more negative one,
or the nickel system (half-cell) must be replaced by a more positive one.
E°– (Cu2+|Cu) = +0.34 V, is more positive than either, therefore it must replace the Nickel half-cell.
The new e.m.f. would be Erhs – Elhs = (+0.34) – (–2.37) V = 2.71 V with copper positive.

Part 6 – Answers

5 6 H+ + IO3– + 5 I– → 3 H2O + 3 I2
I2 + 2 S2O32– → 2 I– + S4O62–
6 H+ liberate 3 I2 which react with 6 S2O32–
amount of S2O32– in titre = 27.8/1000 × 0.100 mol = 2.78 × 10–3 mol
amount of H+ in 25.0 cm3 = 2.78 × 10–3 mol
concentration of HCl = 1000/25 × 2.78 × 10–3 mol dm–3 = 0.1112 mol dm–3
concentration of HCl = 0.111 mol dm–3
6 2 Cu2+ + 4 I– → 2 CuI + I2
I2 + 2 S2O32– → 2 I– + S4O62–
2 Cu2+ liberate (1) I2 which reacts with 2 S2O32–
amount of S2O32– in titre = 26.7/1000 × 0.100 mol = 2.67 × 10–3 mol
amount of Cu2+ in 25.0 cm3 = 2.67 × 10–3 mol
mass of Cu in 250 cm3 = 63.5 × 10 × 2.67 × 10–3 g = 1.70 g
%age of Cu in alloy = 1.70/2.83 × 100 = 59.9
Chapter 2
1 (a) The pale green Fe2+(aq) ion has been oxidised by the hydrogen peroxide to the brown
Fe3+(aq) ion. (Note that it would be misleading to use the formulae [Fe(H2O)6]2+ and
[Fe(H2O)6]3+ here because the latter is pale violet and is hydrolysed in aqueous solution to a
mixture of brown forms).
(b) The yellow salt, potassium chromate(VI), forms the orange dichromate(VI) ion in
acidic solution:
2CrO42–(aq) + 2H+(aq) S Cr2O72–(aq) + H2O(l)
This ion is reduced to green hydrated Cr3+(aq) ions by the sulphite ion (again, it is best not to
be specific about the exact nature of the ion – see also part (d))
Cr2O72–(aq) + 8H+(aq) + 3SO32–(aq) → 2Cr3+(aq) + 3SO42–(aq) + 4H2O(l)
(c) The pale blue Cu(H2O)62+ ion undergoes ligand displacement to form the deep blue
[Cu(NH3)4 (H2O)2]2+ with ammonia or the yellow [CuCl4]2– with chloride ions; the latter is
usually seen as green because it is in equilibrium with the pale blue hexaaquacopper(II) ion.
(d) The dissolution of the double salt initially gives rise to (unchanged) [Cr(H2O)6]3+ ions. These
undergo ligand displacement to give a variety of complexes which are green in colour, e.g.
[Cr(H2O)6]3+(aq) + SO42–(aq) S [Cr(H2O)4SO4]+(aq) + 2H2O(l)
2 (i) Co2+ 1s2 2s2 2p6 3s2 3p6 3d7 Co3+ 1s2 2s2 2p6 3s2 3p6 3d6
(ii) (Easiest here) the evolved oxygen would relight a glowing wooden splint.
(iii) The gain or loss of an electron by the Ca2+ ion would be energetically prohibitive.

Part 6 – Answers

(iv) The strict definition of a catalyst requires that it be in the same state when the reaction is
completed as it was at the start. The iron is in the +2 oxidation state at the start and in the
+3 oxidation state at the end; to this extent it does not satisfy the requirements. However, it
must be pointed out that many catalysts in common use are not recovered unchanged at the
end, e.g. the Ziegler Natta catalysts for ionic polymerisation of alkenes.
(v) You could pick any cation from the d block other than Zn2+ which cannot show variable non-
zero oxidation number. Manganese(II), Mn2+, would be a good choice because it shows a
wide range of oxidation states.
(vi) In alkaline conditions the two ions would be precipitated as their hydroxides or hydrated
oxides, e.g.
Co2+(aq) + 2OH–(aq) S Co(OH)2(s)
It is most likely that these species are the ones which change oxidation state.
3 (i) The silver ion, Ag+, has the (Kr) 4d10 structure. Silver ions are normally colourless because if all
the 4d orbitals are fully occupied, it would not matter if ligands separated them into two energy
groups since it would not be possible for an electron to transfer from one group to the other.
Oxidation to Ag2+ changes the ion structure to (Kr) 4d9. Under the influence of the pyridine
ligands the five d orbitals (which are highly directional) will split into slightly different energy
levels. The lowest energy levels will be filled and there will be a vacancy in one of the higher
orbitals. This means that an electron in a lower orbital can absorb energy and “jump” to a
higher level d orbital. The small difference in energy corresponds to quanta of electromagnetic
radiation in the visible region, hence the complex is coloured.
(ii) The pyridine ligands are likely to be linked to the central ion by dative bonds which use the
lone pair on the nitrogen atoms.
N N
Ag2+
N N
Chapter 3
1 (i) Treat (dry) benzene with bromine in the presence of clean iron wire.
(ii) Treat benzene with iodomethane in the presence of anhydrous aluminium chloride.
(iii) Boil the methylbenzene (formed in (ii)) with excess alkaline potassium manganate(VII), acidify,
render the mixture colourless by adding sodium sulphite (to reduce manganese(IV) oxide, etc
to soluble manganese salts), cool and filter off the precipitated benzoic acid.

Part 6 – Answers

(iv) Bubble chlorine through some of the methylbenzene made above under a floodlight (in a
fume cupboard) in a flask fitted with a condenser for reflux. It is usual to detach and weigh
the flask periodically because the best yield will be obtained when the correct theoretical
increase in mass has occurred. There will be some unchanged benzene and some
(dichloromethyl)benzene in the crude product.
(v) Heat a mixture of ethanol and the benzoic acid prepared in (iii) with a little concentrated
sulphuric acid (in a flask with a condenser fitted for reflux). Pour the mixture into water,
wash, dry and distil.
2 Using the steps suggested in the problem:

(i) Amount of Na2S2O3 in 5.0 cm3 = 5.0 × 0.100 × 10–3 mol = 5.0 × 10–4 mol
Amount of Br2 after reaction = 0.5 × 5.0 × 10–4 mol = 2.5 × 10–4 mol
(ii) Amount of Na2S2O3 in 45.0 cm3 = 45.0 × 0.100 × 10–3 mol = 45.0 × 10–4 mol
Amount of Br2 before reaction = –12 × 45.0 × 10–4 mol = 22.5 × 10–4 mol Br2
(iii) Amount of Br2 that reacted with phenol = (22.5 – 2.5) × 10–4 mol = 2.00 × 10–3 mol
(iv) Amount of phenol in 25.0 cm3 = 1/3 × 2.00 × 10–3 mol
(v) Original conc. of phenol = 1000/25 × 2/3 × 10–3 mol dm–3 = 2.67 × 10–2 mol dm–3
M(C6H5OH) = 94 g mol–1
Original concentration of phenol = 94 × 2.67 g dm–3 = 2.51 g dm–3
3 The first thing to do when solving a problem like this is draw a reaction scheme linking
the compounds:
NaOH aq
C9H11I → C9H12O  
 
A  B 
 

K2Cr2O7/NaOH
  KMnO4/NaOH
 
→
 
→ NaOH/I2
→
C9H10O C8H7O2Na + E C7H6O2
C D F
(i) The following points should then be obvious to you – not necessarily in this order:
(a) The low hydrogen:carbon ratios suggest aromatic compounds.
(b) Dichromate(VI) oxidation has removed 2H atoms per molecule and this suggests the
formation of a carbonyl compound from an alcohol – probably a ketone from a secondary
alcohol as no further oxidation is mentioned.
(c) Manganate(VII) oxidation converts side chains to COOH groups. As 6C atoms are required
for a benzene ring and F has only 7, there appears to be only one side chain.
(d) E, from the reagents used, appears to be iodoform, CHI3, which suggests that B is either a
methyl secondary alcohol or a methyl ketone – which, in the light of (b) means that it must
be a methyl secondary alcohol and C the corresponding ketone.
(e) A is simply the corresponding iodo compound.

Part 6 – Answers

From this it follows that the structures are:
A = C6H5CH2CHICH3
B = C6H5CH2CH(OH)CH3
C = C6H5CH2COCH3
D = C6H5CH2CO2– Na+
E = CHI3
F = C6H5CO2H
(ii) In order to show optical isomerism the structure must contain a chiral centre – most
commonly a carbon atom to which are attached four different groups – obviously, if you see
–CH2- or –CH3 you can rule such an atom out immediately.
A = C6H5CH2CHICH3  Only these two compound have such a chiral centre


B = C6H5CH2CH(OH)CH3  marked by the bold C atom
(iii) Loss of H2O from compound B can occur with the formation of a double bond on either side
of carbon-2 (the one with the –OH group). This can give rise to two structural isomers:
C6H5CH= CHCH3 and C6H5CH2CH= CH2
The first of these, 1-phenylprop-1-ene, can give rise to two stereoisomers, more particularly,
geometrical isomers, cis- and trans-1-phenylprop-1-ene, but the second, 3-phenylprop-1-ene,
cannot because both substituents on carbon-1 are the same.
C6H5 CH3 C6H5 H

C=C C=C
H H H CH3
cis-1-phenylprop-1-ene trans-1-phenylprop-1-ene
Chapter 4
1 The cyanide ion :N≡ C:– is a nucleophile; it has a lone pair of electrons capable of being shared to
form a covalent bond and it carries a negative charge. Alkenes are electron-rich centres and the
negative cyanide ion cannot therefore attack them. Carbonyl compounds have a π bond and a σ
bond, like alkenes, but the large difference in electronegativity between carbon and oxygen causes
the bond to be highly polarised, with the carbon atom positive. The cyanide ion can thus attack the
positive carbon and displace the shared electron pair of the π bond on to the oxygen atom (which
then forms a new single bond with a proton).
Molecular bromine :Br=Br: can act as an electrophile (despite the apparent wealth of unshared
electron pairs). This is because it is polarised on approach to a π system forming, in effect,
Brδ– ---- Brδ+, then the pair of electrons shared between the bromine atoms is used to form the
stable Br :– whilst the other bromine atom, relieved of its shared pair, can the form a bond with the
electons in the π orbital of the alkene.
(One might ask, if this is the case, why does not the Brδ+, on approach to the C=O system, form a
bond with the negative oxygen atom? The main reason is that the resulting O−Br bond, unlike the
(stable) C−Br which is formed in an alkene would lead to a thermodynamically unstable molecule.
The O−Br bond dissociation enthalpy, because of the similarity of electronegativity of C and Br
would be far too low.)

Part 6 – Answers

2 (a) The essential nature of aluminium chloride, as a Friedel Crafts catalyst, is that it acts as a Lewis
acid. That is, it is an electron pair acceptor:
R−Cl: → AlCl3
Only by doing this can it generate the electrophile Rδ+ -- Cl --- AlCl3δ–
In hydrated aluminium chloride, the aluminium ion is surrounded by six water ligands and it
can no longer act as an electron pair acceptor.
(b) (i) Reaction of (dry) benzene with ethanoyl chloride in the presence of anhydrous
aluminium chloride:
C6H6 + CH3COCl → C6H5COCH3 + HCl
(ii) Replace ethanoyl chloride with benzoyl chloride in the above reaction:
C6H6 + C6H5COCl → C6H5COC6H5 + HCl
(iii) Replace ethanoyl chloride with 2-iodopropane in the same reaction:
C6H6 + CH3CHICH3 → C6H5CH(CH3)2 + HI
(c) Hydrolyse some of the iodomethane by boiling with aqueous sodium hydroxide:
CH3I + NaOH → CH3OH + NaI
Prepare methylbenzene by reaction of iodomethane and benzene in the presence of

anhydrous aluminium chloride, then oxidise the side chain by boiling with alkaline potassium
manganate(VII), finally prepare the ester by boiling the resulting benzoic acid with the
methanol prepared earlier in the presence of a little concentrated sulphuric acid:
CH3I/AlCl3 MnO4–/OH– CH3OH/H2SO4

C6H6 → C6H5CH3 → C6H5COOH → C6H5COOCH3
3 Summarising the information initially helps you to see the problem as a whole:
 C5H10



 X



unbranched

→
→
(C5H11Br) (C5H11Br)
A B
→
→
.............KOH(aq) .................
→C5H12O C5H12O

 C D




→
→


yellow  NaOH/I2
→
NaOH/I2 no reaction
precipitate
............ Cr2O72–/H+ ............... →

G 






C5H10O C5H10O 
→
E F

Part 6 – Answers

Because A and B were formed by addition their formulae must be as shown. C5H10 corresponds to
one double bond. A and B were formed by the alternative additions to an unsymmetrical alkene.
Since you are told that the alkene is unbranched, it must be a pentene. It can only be pent-1-ene
or pent-2-ene (pent-3-ene is the same as pent-2-ene).
C and D are the corresponding alcohols, formed by hydrolysis of the bromo compounds A and B.
Both molecules, on oxidation with excess of the oxidising agent, lose two hydrogen atoms and
gain no oxygen atoms. They must both form carbonyl compounds. If either had been a primary
alcohol, with excess of the oxidising agent, a carboxylic acid would have been formed – with
addition of an oxygen atom. The double bond in X cannot be in the 1-position.
Thus X is pent-2-ene: CH3CH=CHCH2CH3.
A and B must be 2- and 3-bromopentane and C and D the corresponding pentanols – but which
is which?
The yellow precipitate, from the reagents used, must be iodoform, CHI3. C is therefore the
methyl secondary alcohol, pentan-2-ol. D must therefore be pentan-3-ol. E and F are the
corresponding ketones.
X = pent-2-ene CH3CH =CHCH2CH3
A = 2-bromopentane CH3CHBrCH2CH2CH3
B = 3-bromopentane CH3CH2CHBrCH2CH3
C = pentan-2-ol CH3CH(OH)CH2CH2CH3
D = pentan-3-ol CH3CH2CH(OH)CH2CH3
E = pentan-2-one CH3COCH2CH2CH3
F = pentan-3-one CH3CH2COCH2CH3
G = triiodomethane (iodoform) CHI3
Stereoisomerism of both types occurs in these compounds. Lack of rotation about the C= C double
bond in A gives rise to the geometrical isomers:
H3C C2H5 H3C H

C=C C=C
H H H C2H5
cis-pent-2-ene trans-pent-2-ene
In compounds A and C, carbon-2 is a chiral centre (asymmetric). These two compounds both exist
in mirror-image forms or optical isomers (enantiomers).
Chapter 5
1 (a) (i) x
(ii) x – y (∆H is negative)
(b) On your diagram:
x should be smaller (the activation energy should be lower)
x – y should be the same (the enthalpy change should be the same)
The peak should be a double peak (showing the formation of an intermediate).

Part 6 – Answers
Uncatalysed
y
Energy
Catalysed
Reactants
∆H1
Products
Extent of reaction
(c) Still x – y.
(d) At this level it is sufficient to say that the activation energies of both the forward and reverse
reactions are lowered, hence the rates of both reactions are increased. (If the forward and
reverse activation energies are reduced by the same amount (as is clearly the case), then the
forward and reverse rates are reduced in the same proportion and the equilibrium constant
is unchanged. This is easily proved (using the Arrhenius equation) but is beyond the scope
of A level GCE.)
2 (a)
Number of molecules having a given energy E
Temperature T1 < T
Temperature T
Temperature T2 > T
Energy E
EAct
Population of molecules with E > EAct

at T at T1 < T at T2 > T

Part 6 – Answers

(b) The activation energy is the necessary energy of molecular impact required to bring about a
reaction. The temperature is irrelevant and the position on the graph would not change.
(c) The rate of reaction will be lower at the lower temperature and higher at the higher
temperature. The population of molecules having the necessary activation energy will be
reduced or increased in proportion to the area lying under the curve on the right hand side
(higher energy) of the activation energy line.
3 (a) The order (in the context of the question) is the power to which the concentration of a
reactant is raised in the rate expression for the reaction:
(b) Rate = k[CH3CSNH2][OH–]
You can, of course, represent the rate by –d[CH3CSNH2] , but there is little point if you are
not going to use it mathematically. dt
(c) It is obvious, by inspection, that if you double the concentration of hydroxide ions you will
double the rate of the reaction. At double the concentration, the number of collisions per
second (frequency of collision) is doubled hence the doubling of the rate.
(d) The reaction must occur (as usual) in several steps (i.e. be complex rather than simple). The
rate-determining step appears to involve the collision of one thioethanamide molecule with
one hydroxide ion.
4 (a) The table shows that initial rates of reaction were being compared using different initial
concentrations of reactant. Such mixtures are most easily prepared by mixing different
volumes of stock solutions. In order that the concentration in the mixture should be
proportional to the concentration in the stock solution, the total volume of the mixture must
be the same for each experiment. A total volume is chosen so that it will always exceed the
sum of the volumes of the stock solutions used; the difference, in each experiment, is made
up by adding solvent.
(b) Rate = k[BrO3–]a[Br –]b[H+]c where a, b and c are the individual orders.
In experiments A and B, the concentration of H+ alone is changed. It is doubled but the rate is
increased by a factor of four hence the order with respect to H+ is 2:
Rate B 600c
= = 4, hence 2c = 4 and c = 2
Rate A 300c
In experiments B and C, [BrO3–] alone is changed. Doubling the concentration doubles the
rate, hence the reaction is first order with respect to bromate ions.
In experiments B and D, only the bromide ion concentration changes. When it is halved, so is
the rate. Hence the reaction is first order with respect to Br –.
(c) –d[BrO3–]
= k[BrO3–].[Br –].[H+]2
dt
Replacing variables by their units:
mol dm–3 s–1 = {units of k} mol dm–3 . mol dm–3 . (mol dm–3)2 = {units of k} mol4 dm–12
Therefore {units of k} = mol–3 dm9 s
Chapter 6
1 (a) Cyclooctatetraene has only one proton environment – all the protons are in the situation
=CH–. The right hand spectrum, with a single absorption at about δ = 5.8 ppm, must be that
of cyclooctatetraene.

Part 6 – Answers

(b) All six hydrogen atoms have the same environment in cyclopropane. The spectrum should
therefore consist of one peak in low resolution. The exact position is hard to predict. Whilst a
proton in a normal alkane −CH2− chain might be expected to have a chemical shift in the
region of δ = 1.3 to 1.4 ppm, this is not a normal alkane chain. The natural tetrahedral angle
of sp3 hybrid orbitals is far from the 60° C−C−C angle of the molecule and δ is likely to be
very different.
2 The isomers of C4H9Cl are:
CH3CH2CH2CH2Cl CH3CH2CHClCH3 (CH3)2CHCH2Cl

1-chlorobutane – A 2-chlorobutane – B 1-chloro-2-methylpropane – C
(CH3)3CCl
2-chloro-2-methylpropane-D
The low resolution spectra should show peaks as follows:

A should have four peaks in the area ratio 3:2:2:2 – the protons from left to right in the above
formula should have progressively greater chemical shift. The CH3 protons would absorb at about
δ = 1.0 and the methylene (–CH2−) protons would have greater chemical shift the nearer they
were to the electron-withdrawing chlorine atom.
B should also have four peaks in the area ratio 3:3:2:1 in order of increasing chemical shift. The
two methyl groups are different distances from the Cl atom and the methylene would have a
greater chemical shift than the protons on the methyl group in the 1-position. Strictly, the two
hydrogen atoms on the CH2 group are not chemical shift equivalent – they look alike as far as the
A level GCE syllabus is concerned but they would not have exactly the same absorption frequency.
However, the difference is likely to be slight and may not show in low resolution.
In C, the two methyl groups are equivalent and this would cause a large absorption a little
downfield from the normal CH3 absorption (because of the proximity of the Cl atom). We should
expect three peaks with the area ratio 6:1:2 (in order of increasing δ).
D is delightfully simple. Three identical methyl groups would give rise to identical absorption by
nine protons. A single peak (even in high resolution) downfield from the usual value of about 1
ppm for δ.
The spectra provided can only be those of C and D, 1-chloro-2-methylpropane and 2-chloro-2-
methylpropane.
3 Ignoring the fine splitting, there are four “low resolution” peaks. The integrator curve shows that
the areas are in the ratio 3:2:1:2 in the order of increasing chemical shift (going downfield). The
suggestion is, therefore, that the peak of relative area 1 is caused by proton absorption in the –OH
group. It will be remembered that the position of this absorption can not be relied on – it could
be anywhere between δ = 0 and δ = 5 depending on the extent of hydrogen bonding. The other
peaks presumably represent CH3− and two –CH2− groups getting ever nearer to the –OH group as
the absorption goes downfield. The structure can only be that of CH3CH2CH2OH, propan-1-ol.
This is as far as you could be expected to go in the Edexcel examination.
There is more information to be obtained from the spectrum however, which might be vital in
finding the structure of a more complicated alcohol. The peak at δ = 1.0, of area 3, is clearly
caused by a (terminal) methyl group, but the fine splitting, a triplet, shows that it is next to a
–CH2− group. The two peaks of area 2 are clearly caused by –CH2− groups, but their immediate
environment is shown, not only by the increasing value of the chemical shift, but also by the fine
splitting. The one centred on δ = 1.6 is a sextuplet (6 little peaks) and must be situated between a
CH3− group and a –CH2− group, whereas that centred on δ = 3.6 is clearly next to the –OH,

Part 6 – Answers

taking into account the value of δ, and must also be next to a –CH2– because it is a triplet. The
peak at δ = 2.3, of area 1, shows no splitting, indicating one non-coupled proton. This is typical of
–OH absorption, whatever the neighbouring groups may be, unless the spectroscopist takes special
measures to ensure –OH proton coupling.
4 The positive iodoform test indicates the presence of CH3CO– or CH3CH(OH)–. The infrared
spectrum shows a peak at about 3650 cm–1, indicative of –OH (with minimal hydrogen bonding)
and no significant absorption at 1700 cm–1 (C=O). The group CH3CH(OH)– appears definite. A
molecular ion at m/z = 86 suggests that the rest of the molecule has a molar mass of 86 – 45 g
mol–1 = 41 g mol–1. This corresponds to C3H5–; a saturated unit would be C3H7–. The rather weak
absorption at about 1650 cm–1 may be caused by a C=C double bond. Treatment with ethanoyl
chloride would esterify the –OH group:
CH3COCl + ROH → ROCOCH3 + HCl
The spectrum of the product would no longer show the absorption at 3650 cm–1 but should show
new absorption caused by the carboxylic ester group, probably in the region of 1750 cm–1.
5 Let us look first at the infrared spectrum of N. The huge broad band centred on 3400 cm–1 is
clearly caused by an –OH group. The impressive absorption at 1750 cm–1 indicates the presence of
a carbonyl group (C=O). The two cannot form part of a carboxylic acid group –COOH because N is
neutral. In the mass spectrum, the largest value of m/z is 74. If this is the molecular ion peak,
bearing in mind that we already know of the presence of a CO and an OH (= 45 g mol–1), we have
(a tempting) 29 mass units still to explain. (I say tempting because we all tend to jump to the
conclusion that C2H5 is missing – so it may be but we know that C2H5COOH is not the structure).
The only isomers which preserve both the C=O and –OH groups are:
CH3CH(OH)CHO HOCH2CH2CHO and CH3COCH2OH

A B C
Whilst there are minor differences between the infrared absorption of an aldehyde and a ketone
you would not be expected to know about them. We must therefore look to the mass spectrum for
guidance. The base peak is always a good one to look at first. Here, at m/z = 43, it dwarfs the
others. The most obvious interpretation is that it is caused by the ion CH3CO+. This is only formed
in a simple way by the third isomer, C. The other two would probably form some of this ion by
migration of a proton in a fragment (B) or by loss of molecular hydrogen (A) – but it is likely that
the ion would not be so important relative to the rest. We can conclude that N has structure C and
is 2-oxopropan-1-ol.
6 L is clearly a carbonyl compound. Red precipitates with 2,4-dinitrophenylhydrazine indicate

increased absorption of light in the visible region, often caused by extension of the chromophore
by condensation with an unsaturated or aromatic aldehyde or ketone. (This is not very reliable.)
The mass spectrum shows a typically aromatic fragmentation with clusters of fragments having m/z
values grouped around 13n, i.e. (=CH–)n+. The molar mass is probably 120 g mol–1. We do not
know how many side chains there are, but let us begin by assuming that there is one only.
M(C6H5) = 77 g mol–1 and M(C=O) = 28 g mol–1; this leaves 15 for the rest of the molecule. The
base peak at m/z = 105 suggests the easy loss of the methyl group. If we had a methyl-substituted
benzaldehyde it is difficult to see why the loss of a methyl group from the ring should be so
favoured. Of the two possible side chains: –CH2CHO and –COCH3, loss of a methyl group alone
would be impossible from the aldehyde.
We must conclude that the compound L is phenylethanone, C6H5COCH3.

Part 6 – Answers

Notice how much more prominent is the peak at m/z = 43 than are the ring fragments around it.
This is confirmation of the structure as it is presumably caused by the ion CH3CO+. Additional
confirmation that we are dealing with a mono-substituted benzene is the important peak at m/z =
77 which we may attribute to the ion C6H5+.
7 B is clearly benzoic acid, C6H5COOH. A is a monosubstituted benzene derivative. With a molar

mass of 148 g mol–1, subtracting 77 for the benzene nucleus, the rest of the molecule has a molar
mass of 71 g mol–1. The base peak at m/z = 43 is almost certainly caused by CH3CO+ and this
group must be connected to the ring by a fragment of mass (71 – 43) = 28 g mol–1. We have only
two possibilities: C6H5CH2CH2COCH3 and C6H5CH(CH3)COCH3. The peak at m/z = 105 simply
mirrors the one at m/z = 43 and is caused by the fragment C6H5CH2CH2+ or C6H5CH(CH3)+. The
peak at m/z = 91 is important; it differs from the previous peak by 14 units: CH2. It is easy to see
how C6H5CH2CH2+ could lose a methylene group (CH2) but C6H5CH(CH3)+ would be expected
to lose 15 units (CH3). We conclude that the peak at m/z = 91 is caused by C6H5CH2CH2+ and
that A is C6H5CH2CH2COCH3, 4-phenyl-butan-2-one.
An additional general point about the spectrum is that is shows typical benzene ring fragmentation
patterns with clusters around m/z = 13n.
8 The NMR spectrum of C is not terribly helpful as a starting point. It shows two groups of protons;
the area ratio is 3:1 but CH3CH is not a viable molecule. Of course, if you are smart enough to
spot that it almost certainly has a double bond, in order to exist as geometrical isomers, you can
suggest that CH3CH is only half the molecule and that C is CH3CH=CHCH3. Let us examine the
mass spectrum of D. The molar mass appears to be 184 g mol–1. Subtracting 127 for an iodine
atom, we have 57 g mol–1 for the rest of the molecule. This corresponds to C4H9 and C4H9+ is
presumably responsible for the base peak. The molecule fragments to a C2H5+ ion at m/z = 29 but
not a CH3CH2CH2 fragment at m/z = 43. Instead the peak is at m/z = 41. This presumably reflects
the fact that the iodine atom is not in the 1-position.
At some stage you will have put the two lots of evidence together and arrive at the structure of the
two possible isomers which could be C:
H3C CH3 H3C H

C=C C=C
H H H CH3
cis-but-2-ene trans-but-2-ene
both of which with HI would give 2-iodobutane, D
CH3CH2CHICH3
Now the peak at m/z = 41 is more obvious. Loss of a CH3 fragment would give the ion CH3CH2CHI
which could easily lose a molecule of HI forming the ion CH3CH2C+ (or perhaps (CH3CH=CH)+).
9 The molecular ion is presumably that giving rise to the peak at m/z = 170. The fact that there is a
double peak, each of the same intensity at m/z = 170 and 172 suggests the presence of one atom of
bromine. The base peak, at m/z = 91 is a singlet and the difference of 79 (or 81) clearly represents
the loss of one bromine isotope (Br = 79 or 81); the ion CpHq+ has a molar mass of 91 g mol–1. At
the time the Unit book was written, it was not known if the lack of activity of halogen substituents
in the benzene ring would be in the specification. If you have not covered this, all that you can

Part 6 – Answers

conclude from the formation of the yellow precipitate (AgBr) is that you have a bromoalkane. For
the group CpHq to have a molar mass of 91 g mol–1 the only possibility is C7H7; p = 8 exceeds 91
without any hydrogen and p = 6 requires 19 H atoms which is impossible. The compound must
be aromatic and the bromine must be part of a side chain, i.e. must behave as
a halogenoalkane.
X is thus (bromomethyl)benzene, C6H5CH2Br, p = 7, q = 7 and r = 1. When asked for such a
structure in an exam it is better to draw out the benzene ring rather than use C6H5–.
10 See note in the answer to Q9. If a bromo compound does not give a reaction with ethanolic silver
nitrate then the bromine must be substituted in an aromatic ring. The molecular ion is almost
certainly one of the group centred on m/z = 250; the structure of the group, a triplet in the
intensity ratio 1:2:1, indicates the presence of two Br atoms. (Technically the molecular ion is the
one with the two Br–79 atoms at m/z = 248, a rather pedantic point). Subtracting 160 from 250
we are left with 90 for the rest of the molecule and, knowing that a benzene ring is present with
two bromine substitutents, C6H3 = 75 seems likely for what remains of the benzene ring. This
leaves 15 for the side chain(s) which can only be CH3– and there can only be one side chain. From
the evidence, you cannot say which of the isomers, shown below, truly represents F – though the
mass spectrum is, in fact, that of F1.
CH3 CH3 CH3

Br
Br Br Br Br
Br
F1 F2 F3
CH3 CH3 CH3

Br Br Br Br
Br
Br
F4 F5 F6
The double peak centred on m/z = 170 shows that only one bromine atom is now present and
represents the pair of ions CH3C6H379Br+ and CH3C6H381Br+ (with m/z = 169 and 171).
Chapter 7
1 (i) Addition of hydrogen bromide:
CH3CH=CH2 + HBr → CH3CHBrCH3

Part 6 – Answers

(ii) You could either boil the above product with aqueous sodium hydroxide to give propan-2-ol:
CH3CHBrCH3 + NaOH → CH3CH(OH)CH3 + NaBr
or the propene could be absorbed in concentrated sulphuric acid and the mixture could then
be boiled with water to give propan-2-ol.
The propan-2-ol could then be oxidised by boiling (under reflux) with excess acidified
sodium dichromate(VI) solution:
CH3CH(OH)CH3 – 2e– → CH3COCH3 + 2H+
Some general points about this answer. (a) The preparation of propan-2-ol using the
sulphuric acid method would be both cheaper and faster. (b) Examiners like you to give the
names of reagents “as seen on a bottle”, thus sodium or potassium dichromate rather than
just “dichromate” and you might even think it worth while to say “aqueous sodium
dichromate(VI) acidified with sulphuric acid” if you wanted to play really safe. Sodium
dichromate is often preferred to the potassium salt because it is more soluble in water or
aqueous organic mixtures, but it would not matter which you chose. Equations for oxidation
reactions in organic chemistry using dichromate and manganate need not normally be
balanced. You are expected to balance such equations in questions about transition metals
but not in organic chemistry. A half-way stage was used above by writing a half equation, you
could just put the reagents (or even [O]) over an arrow in most contexts.
(iii) Prepare the Grignard reagent from your 2-bromopropane by adding dry magnesium turnings
to a solution of the compound in dry “ether” (ethoxyethane). A trace of iodine helps:
(CH3)2CHBr + Mg → (CH3)2CHMgBr
Then add the propanone prepared in (ii) and decompose the complex by adding (dilute
hydrochloric) acid:
CH3
|
(CH3)2CHMgBr + CH3COCH3 → (CH3)2CHCCH3
|
OMgBr
CH3
|
→ (CH3)2CHCCH3
|
OH
2 (i) There is an easy (traditional) method of making phenol from benzene, as well as a relatively
simple modern industrial process. These, however, are not in your specification. You would
have to resort to making nitrobenzene by treatment of benzene with a mixture of concentrated
nitric and sulphuric acids (warming to complete the reaction). This could be reduced to
phenylamine by treatment with tin and concentrated hydrochloric acid. (Again heating to
complete the reaction, followed by a long and tedious purification beginning with the
neutralisation of the acid with sodium hydroxide.) Finally, the amine would treated with
hydrochloric acid and sodium nitrite to give phenol in rather poor yield; this is best done by
diazotisation below 5 °C followed by heating and another tedious isolation:
C6H6 → C6H5NO2 → C6H5NH2 → [C6H5N2+Cl–] → C6H5OH

Part 6 – Answers

(ii) This may be prepared by boiling methylbenzene with excess aqueous alkaline potassium
manganate(VII) then acidifying (and rendering the manganese(IV) oxide soluble by treatment
with sodium sulphite). The benzoic acid is precipitated:
C6H5CH3 → C6H5COOH
(iii) Phenyl esters cannot be made in the normal way using a carboxylic acid with concentrated
sulphuric acid as catalyst. It will first be necessary to convert the benzoic acid to benzoyl
chloride, e.g. by treatment with phosphorus(V) chloride:
C6H5COOH + PCl5 → C6H5COCl + POCl3 + HCl
The purified benzoyl chloride can be shaken with a solution of phenol in aqueous sodium
hydroxide (Schotten–Baumann conditions):
C6H5COCl + C6H5O–Na+ → C6H5COOC6H5 + NaCl
3 (i) The number of carbon atoms in the molecule has not changed and so all you need to do is
hydrogenate to remove the C= C double bond. Treatment of the molten acid with hydrogen
under moderate pressure with a powdered nickel or platinum catalyst would serve. It is often
sufficient to illustrate such a change by a partial equation such as:
Pt
–CH=CH– + H2 → –CH2CH2–
(ii) You would need to have an awfully good reason to carry out this conversion – such as an
unavoidable examination question! This long, expensive and tedious procedure to convert
one cheap natural product into another cheap natural product could only occur in the mind
of an examiner. It is conceivable that the oleic acid might have been labelled with deuterium
or carbon-14 at some point in its long chain, even so, the loss of material in so many steps
would probably be unacceptable. One way would be to hydrogenate the acid, as above, and
then use the product in the following sequence which would need to be repeated:
RCH2COOH → RCH2COONH4 → RCH2CONH2 → RCH2NH2 → RCH2OH → RCOOH

1 2 3 4 5
The reagents and or conditions for each step would be:
1 ammonia
2 heat
3 aqueous sodium hydroxide and bromine (Hofmann degradation)
4 hydrochloric acid and sodium nitrite (with abominable yield)
5 sodium dichromate(VI) and aqueous sulphuric acid (with heat in the final stages)
(iii) The key to answering this is to spot the position of the new double bonds in relation to the
original one. Treatment with bromine followed by heating with ethanolic potassium
hydroxide should synthesise the desired product:
–2HBr
–CH2CH=CHCH2– + Br2 → –CH2CHBrCHBrCH2 → –CH=CHCH=CH–

Part 6 – Answers

4 (i) Heat with concentrated sulphuric acid and pass the resulting butene back into concentrated
sulphuric acid; then boil the mixture with water. The sulphuric acid adds (according to the
Markownikov rule) leaving the hydrolysable hydrogen sulphate group on carbon-2. Oxidation
with hot excess acidified sodium dichromate(VI) would then give butanone:
CH3CH2CH2CH2OH → CH3CH2CH=CH2 → CH3CH2CHCH3 →

|
OSO3H
CH3CH2CHOHCH3 → CH3CH2COCH3
(ii) You can devise a long route via butanoic acid, ammonium butanoate, butanamide,
propylamine and propan-1-ol. A simple solution, as you have made butanone, is to perform
the iodoform reaction on this compound. Warm with aqueous sodium chlorate(I) and
potassium iodide (or more expensively use iodine and aqueous sodium hydroxide):
CH3CH2COCH3 → CH3CH2COONa (+CHI3) → CH3CH2COOH
(The iodoform could be filtered out and the mixture acidified to release the acid from its
sodium salt before distilling).
(iii) Oxidation of the (primary) butan-1-ol with excess hot aqueous acidified sodium
dichromate(VI) would give butanoic acid. This could then be esterified by boiling (under
reflux) with methanol and a little concentrated sulphuric acid:
CH3CH2CH2CH2OH → CH3CH2CH2COOH → CH3CH2CH2COOCH3
(iv) Treat butanoic acid (prepared above) with aqueous ammonia (or the aqueous acid with
ammonium carbonate). Isolate the ammonium butanoate (by evaporation) and heat to form
the amide. Hofmann degradation with aqueous sodium hydroxide and bromine would then
give propylamine:
CH3CH2CH2COOH → CH3CH2CH2COONH4 → CH3CH2CH2CONH2 →

CH3CH2CH2NH2
(v) If the name butene is given, it is understood that it means but-1-ene. The compound is
prepared in (i) above.
(vi) This question is a bit sneaky, coming as it does directly after butene! It probably led you into
thinking that there was a way of making 2-methylbutene directly from butene. Various
methods are possible. I suggest that you convert your methanol to the Grignard reagent,
methylmagnesium iodide and use it, with the butanone prepared above, to make
2-methylbutan-2-ol. Heating with concentrated sulphuric (or phosphoric) acid would
then eliminate water to give a mixture of two 2-methylbutenes:

Part 6 – Answers

CH3
|
CH3OH → CH3I → CH3MgI → CH3CCH2CH3
1 2 3 |
OMgI
CH3
|
→ CH3C(OH)CH2CH3
4


 5
→
H3C CH3 H CH3

C=C and C=C
H H H CH2CH3
2-methylbut-2-ene 2-methylbut-1-ene
Reagents and conditions:

1 iodine and moist red phosphorus (or hydriodic acid)
2 magnesium turnings in dry ether (with a little iodine as initiator)
3 add (dry) butanone
4 add dilute (aqueous hydrochloric) acid
5 action of hot concentrated phosphoric acid on the (purified and dried) 2-methyl-
butan-2-ol.
The mixture of methylbutenes would be very hard to separate. However, for reasons beyond
A level GCE, the 2-methylbut-1-ene would (greatly) predominate.

Part 6 – Answers
Unit 5 – Transition metals, Quantity of Kinetics
Mark Scheme for Past Questions from Edexcel A and AS Level Papers
You are reminded that this mark scheme does not contain model answers but is a guideline to indicate
minimum or essential content for which marks may be awarded. It does not benefit from editing in
hindsight to take account of changes in emphasis etc. but is the mark scheme employed at the time of
the examinations
1 (i) (Ar) 3d2 4s1 – the 3d electrons must be in separate cells [1]
(Ar) 3d1 [1] [2]
(ii) partially filled/incomplete d-orbital/sub-shell in ions/compounds [1]
if just “partially filled d-orbitals) then [0] [1]
[Total 3 marks]
2 (i) Fe3+ d5; Fe2+ d6 [1]

d5 more stable [1] [2]
(ii) concn FeSO4.7H2O 55.6 /278 = 0.2 mol dm–3 [1]
moles oxidised = 0.2 x 37.5/1000 = 7.5 x 10–3 mol Fe2+ [1]
moles R used = 25/1000 x 0.1 = 2.5 x 10–3 [1]
R:Fe2+ = 3:1 [1], 3 electron change
Fe(VI) [1]
(ratio based on their figures scores consequentially) [5]
(iii) K2FeO4 [1] consequential on (ii) within reason [1]
[Total 8 marks]
3 (a) colourless/pale green [1]

(b) to oxidise Fe2+ / change Fe2+ to Fe3+ [1]
(c) Fe(H2O)63+ [1] (allow Fe3+ [1/2] only) [1]
(d) (i) Fe(CN)63– [1]
(ii) octahedral [1] and diagram clearly 3-D [1]
(iii) to check all the Fe2+ changed to Fe3+ [1]
(iv) add more conc nitric acid [1] reheat [1] [6]
(e) ammonia in excess [1] Fe3+ all pptd [1] [2]
(f) (i) iron(III) hydroxide [1] not the formula
(ii) [Fe(H2O)6]3+(aq) + 3 OH–(aq) → [Fe(H2O)3(OH)3](s)
+ 3 H2O(l) [1]
allow Fe3+(aq) + 3 OH–(aq) → Fe(OH)3(s) [ 1/
2 ] only [2]
(g) 2 Fe(OH)3 → Fe2O3 + 3 H2O [1] or using hydrated form above [1]
(h) 112/160 x 0.245 [1] = 0.1715 g [1] [2]
(i) %Fe = 0.1715/1.2 x 100 [1] = 14.3 [1] [2]
[Total 18 marks]

Part 6 – Answers
4 (a) (i) Cr 3d5 4s1 – all unpaired [1]
Cr2+ 3d4 – all unpaired and
Cr3+ 3d3 – al unpaired [1]
(ii) 3d5 4s1 (not 3d4 4s2) [1] increased symmetry/ stability of half-filled d-orbital set [1] [4]
(b) (i) (+6) [1] calc based on [Mnx(O2–)4]2– [1]
(ii) forms ion with octet [1] which is most favourable of the configurations available [1]
(iii) ionisation energies rise comparatively slowly [1] higher ones are offset by
lattice/hydration/bond energies [1] [6]
(c) (i) diagram shows two curves [1]
same ∆H [1] (enthalpy of products lower than reactants)
catalysed curve lower [1]
two humps in catalysed reaction profile [1] (ie intermediate formation)
(ii) the catalysed reaction is between oppositely charged ions rather than similarly charged
ions in the uncatalysed [1]
(iii) variable oxidation state [1] [6]
[Total 16 marks]
5 (a) V 3d3 4s2 – 3d electrons must be in separate cells [1]

V2+ 3d3 [1]
if V incorrect but contains 4s electrons and these are lost allow second mark [2]
(b) (i) not all d-orbitals filled/incomplete d-orbitals [1]
(ii) dative (covalent)/co-ordinate [1] covalent [1]; if ionic or metallic given
with other types then [–1] [3]
(c) (i) NH4+ + OH– → NH3 + H2O [1]
(ii) copper(II) hydroxide (allow correct formula) [1]
(iii) [Cu(NH3)4]2+ or [Cu(NH3)4(H2O)2]2+ or [Cu(NH3)6]2+ [1]
(iv) +4, +3, +2 [3]…..if no signs [–1]…..if all signs negative [–2]
(accept V4+, V3+, V2+ but not if oxygen present) [5]
(d) 2 VO2 + 1
–2 O2 → V2O5 [1]
accept if +SO3 on both sides [1]
(e) (i) dioxovanadium(V) [1]
(ii) dichlorotetraammine chromium (III) or
tetraamminedichlorochromium(III) [1]
do not accept amino instead of ammine [2]
(f) correct diagram [1] octahedral/octahedron [1]
any orientation of ligands acceptable – bonds not required – ignore charge [2]
[Total 15 marks]
6 (a) electron loss [1] [1]

Part 6 – Answers
(b) coloured ions/compounds (not metals) [1] form complexes/complex ions [1] paramagnetic
ions/compounds [1] variable valency/oxidation state [1] catalytic activity [1] high
melting/boiling temperature/high density [1] not partly filled d-shells or just “paramagnetism”
max [3]
(c) Fe: one pair and four unpaired electrons in 3d cells, one pair in 4s [1]
Fe3+: five unpaired electrons in the 3d cells [1]
(numbers of electrons acceptable) half-filled d-sub-shell/orbitals in Fe3+ /paired electrons
in Fe2+ [1] [3]
(d) (i) A to B: deprotonation [1]
B to C: ligand exchange/transfer/complex (ion) formation [1]
(ii) Cu(OH)2 [1] accept up to four molecules of water in addition
(iii) [Cu(NH3)4]2+ [1] planar drawn [1] not tetrahedral or [Cu(NH3)4(H2O)2]2+ [1]
octahedral drawn [1] or [Cu(NH3)6]2+ [1] octahedral drawn [1]
allow any of 1 to 6 NH3 with 5 to 0 H2O to balance [5]
(e) (i) Cu2+ + 2 I– → CuI + 1
–2 I2 [1] or doubled; state symbols not required
(ii) mol Cu = 0.6 × 2.00/63.5 [1] γ 0.0189 mol thiosulphate [1]
volume = 0.0189 mol/ 1.00 mol dm–3 = 18.9 cm3 (or 19 cm3) [1]
mark consequentially on the equation in (i) [4]
[Total 16 marks]
7 (a) (i) Cr2O72–(aq) + 14 H+(aq) + 6 e → 2 Cr3+(aq) + 7 H2O(l) [1]

ignore state symbols
(ii) Cr2O72–(aq) + 14 H+(aq) + 6 Fe2+(aq) → 2 Cr3+(aq) + 7H2O(l) + 6 Fe3+(aq) [2]
if (a)(i) correct: [1] for correct species [1] for balance
if (a)(ii) incorrect: give [1] if correct balancing factor for electrons from (i)
transferred to (ii) eg if 3e in (i) then 3Fe2+ in (ii). [3]
(b) {use of titration data to get moles of Cr2O72–}
moles of Cr2O72–(aq) = 27.40 × 0.0220/1000 [1] = 6.03 × 10–4
{use of stoichiometry}
moles of Fe2+(Fe) = 6.03 × 10–4 x 6 [1] = 3.62 × 10–3
{moles to mass}
mass of Fe = 3.62 × 10–3 × 56 [1] = 0.203 g
{mass to percent}
%Fe = 0.203/0.204 × 100 [1] = 99.3% or 99.5%
penalise [–1] if answer not to 3 or 4 sig figs; correct answer only [1]; penalise [–1] for
mathematical error. [4]
[Total 7 marks]
8 (a) any correct example. Not C4H9CHO [1] [1]

(b) (i) Diagrams of cis- and trans [1] Restricted rotation about C=C [1]
Need to show evidence of cis-trans isomerism about the double bond.
The compound must be identifiable as Q. [2]

Part 6 – Answers
(ii) Rotates plane of polarisation or rotates light [1]
Evidence from the drawing that the molecules shown are three-dimensional [1] Mirror
image drawn non-superimposable [1]
[3]
(c)
C C C C C C
Br Br Br Br Br
–
:Br
(1) (1) carbocation
(1) arrow
1 mark for two correct arrows in initial attack stage. 1 mark for carbocation as show or as
bridged structure. 1 mark for attack by Br-.
There is no need to show the lone pair. Ignore the shape of the arrows. [3]
(d) (i) CH3CCH=CHCH3
=
O
[1] [1]
(ii) Tollen’s reagent or ammoniacal silver nitrate [1] no silver mirror or black ppt. [1]
OR Fehling’s Solution [1] no ppt [1]
OR Benedict’s Solution [1] no ppt [1].
2,4,DNPor Brady’s reagent [1] yellow or red or orange ppt [1] [4]
(e) Molar mass of pent -3-en-2-ol is 86 [1]
Combines with 254g iodine (because 1 double bond) [1]
∴iodine number = 254 × 3 [1]
86
A candidate who uses 127 in place of 254 can score 1 mark. [3]
[Total 17 Marks]
9 (a) (i) kinetics depends on species or molecules in rate-limiting step or slowest step [1];
NOT “order can only be found by experiment”; this depends on mechanism or some
recognition that a multistage process may be involved in the reaction [1] [2]
(ii) 1, 0, 1 [3]
(iii) Not involved in rate-limiting step [1] consequential on (ii) [1]
(iv) rate = k [CH3COCH3] [H+] [1] could show [I2]0 but this is not required
Answers to (iii) and (iv) consequential on answer to (ii), and must be consistent
throughout [1]
(b) (i) ∆H = D(I – I) + D(C – H) – D(C – I) – D(H – I)
= (+151) + (+413) – (+228) – (+298)
= +38 kJ mol–1 [1]
[2]

Part 6 – Answers
(ii)
(1)
(1)
iodopropane +HI
enthalpy
propanone
+
iodine (1) see notes below
Extent of reaction
Relative positions of products and reactants which need not be identified [1]
Correct profile uncatalysed [1] could show a transition state Correct profile catalysed
[1] must show intermediate [3]
[Total 12 Marks]
10 (a) (i) HCl(g) + H2O(l) → H3O+(aq) + Cl–(aq)
(substituted for HF – not in new specification) [1]
(b) (i) 2F2(g) + 2H2O(l) → 4H+(aq) + 4F–(aq)
+ O2(g)
accept 4HF(aq)
or a cell diagram in place of the equation [1] (Max 2)
Water oxidised or oxygen produced or water is
reducing agent [1]
Fluorine oxidises or fluorine is reduced [1]
Use of E° or calculation of emf or reference to this implied [1] [3]]
(ii) 2Cl2(g) + 2H2O(l) → 4H+(aq) + 4Cl – (aq) + O2(g) [1] [1]
(iii) reaction in (ii) occurs very slowly at room temp. [1]
reaction shown in equation occurs first and then the HClO
decomposes → H+ Cl– + O2 [1]
or for chlorine to disproportionate or oxidise itself this must be more energetically
favourable [1] than for chlorine to oxidise water [1]
or Rate of oxidation of water is slower [1] than rate of alternative [1]
or Rate of oxidation of water has higher activation energy [1] than the alternative [1]
or the EMF of this reaction must be more positive [1] than the EMF calculated
above [1] [2]
(c) (i) 3 ClO– → 2Cl– + ClO3– or 2 ClO– → Cl– + ClO2– or
4 ClO– → 3Cl– + ClO4– [1]
heat [1] [2]
(ii) O.N. of chlorine +1 → –1 +5 or –1 +3 or –1 + 7 consequential on the
equation in (i).

Part 6 – Answers
∴ simultaneous oxidation (+1 → +5) and reduction
(+1 → –1) of Cl in ClO– ion ∴ disproportionation [2]
Simple definition of disproportionation alone [1] [2]
(d) (i) potassium bromide [1]
Br–(aq) + Ag+(aq) → AgBr (s) [1] [2]
(ii) 2KBrO3 → 2KBr + 3O2 [1] [1]
(e) (i) IO3– is reduced and H2O2 is oxidised [1]
reduction: 2IO3– + 12H+ + 1Oe- Æ I2 + 6H2O [1]
oxidation : H2O2 Æ 2H+ + O2 + 2e_
or 5H2O2 Æ 10H+ + 5O2 + 10e_ [1]
(ii) yellow or orange or brown [1], not purple effervescence or bubbles [1] [2]
[Total 21 Marks]
O
B CH3CH2C
NH2 [1]
C CH3CH2CN or C2H5CN [1]
-NH2 (not name) [1]
or RNH2 [3]
(b) (i) LiAlH4 [1] or dry ether [1]
or any other suitable reducing agent and conditions
e.g. sodium and ethanol [1] heat [1]
or hydrogen [1] with Ni or Pt [1] [2]
(ii) bromine [1] but not bromine water
sodium hydroxide solution [1]
bromine plus alkali (1 only) [2]
(c) (i) CH3CH2CN + 2H2O + HCl → CH3CH2COOH + NH4Cl
I mark for correct organic product and 1 mark for remainder of equation
correct [2]
(ii) hydrolysis [1] [1]
(d) (i) lone pair [1] [1]
(ii) CH3CH2CH2NH2 + HCl → CH3CH2CH2NH3+Cl– [2]
1 mark for product and 1 mark for balancing [2]
(e) (i)
NH2 NH2+Cl–
+ HNO2 + HCl + 2 H2O
diazonium cation [1] remainder [1]

If cation is shown in full it must be correct [2]

Part 6 – Answers
(ii)
HO
N N
[1]
(iii) dyes, indicators, colours, pigments. [1] [1]
[Total 17 Marks]
12 (a) (i) linear axes correctly labelled [1] points and line plotted correctly [1]
Deduction of first order kinetics [2]
e.g. titre graph shows 2 t1/2 [1] leading to first order [1]
lg graph straight line leading to first order [2] [4]
(ii) experiment done with double conc (say) of halogenoalkane [1] observe change in rate;
if rate doubles then order with respect to halogenoalkane is first [1]
or
Experiment done with double OH- concentration and rate does not change [1] then first
order with respect to halogenoalkane [1]
Quality of language [1] [3]
(iii)
CH3 CH3 CH3
rds +
CH3 C Cl CH3 C + Cl– CH3 C OH
[1]
CH3 CH3 :OH– CH3
[1] [1] [1]
• identifies rds [1]

• first arrow from C-Cl bond to Cl [1]
• correct intermediate [1] charge may be outside [1]
• arrow from O NOT negative charge [1]
If SN2 max [2] marks for first two points [4]
(iv)
CH2
CH3 C
CH3 [1]
[2] methylpropene or [2] methylprop-1-ene or isobutene [1]
ethanolic solution or dissolved in ethanol or alcohol [1] [3]

Part 6 – Answers
(b) (i) +
(need to show that one hydrogen is
R O H datively bonded for full marks)
H (any mistake or omission –1 mark)
water is lost [1]

water much weaker nucleophile than Cl– or OH– [1] [4]
(ii) NaHCO3 removes residual acid [1]
H2O removes residual salts or other water-soluble components or inorganic materials
[1]
anhydrous CaSO4 removes water [1]
moles of alcohol = 25g = 0.34 mol
74gmol–1
1 mol halogenoalkane from 1 mol alcohol [1]
∴ theoretical yield = 0.34 mol × 92.5gmol–1
= 31.3g (31.25g) [1]
∴ % yield = 28 × 100 = 89.5% (89.6%) [1]
31.3
competing reactions or handling losses [1]
NOT experimental error
[nb 25/28 = 89.3% is wrong] [7]
[Total 25 Marks]
13 (a) (i) CH3Br [1] [1]

(ii) Ethoxyethane/ dry [1] ether [1] or ethoxyethane/ether [1] iodine
catalyst [1] [2]
(b) (i) H H H
O
H C C C C
H
H H H
or CH3CH2CHO but not C3H7CHO [1] [1]

(ii) H H H H H
H C C C C C H
H OH H H H
or formulae as above [1]

Part 6 – Answers
(c) (i) Iodoform / CHI3 [1] [1]
(ii) H H H
O–Na+
H C C C C
H
H H H H
[1]
(d) H H H H
H C C C C C H
H O H H H
[1]
(e) (i) m/e 86 CH3COCH2CH2CH3+ [1]
m/e 43 CH3CH2CH2+ [1] CH3CO+ [1]
(ii) Strong peak at about 1700 cm–1 [1] shows C=O [1] [5]
[Total 13 marks]
14 (a) Correct arrows involving C=C and H-Br [1]

Correct intermediate with positive charge [1]
Correct arrow from Br – towards carbon atom [1]
H H H H
CH3 C C H CH3 C C H CH3CHBrCH3

+
H Br :Br– H [3]
(b) (i) Reagent: magnesium [1]
dry ethoxyethane / ether [1]
iodine catalyst / warm under reflux (or at room temperature) [1]
[3]
(ii) Reagent: aqueous or dilute sodium hydroxide [1]
Conditions: boil / heat under reflux [1] [2]
(c) Reagent:carbon dioxide (solid) [1]
Reagent second stage: water or dilute named acid [1]
[2]
(d) H CH3
CH3 C C O C H
CH3
O CH3
(2) [2]
[Total 12 marks]

Part 6 – Answers
15 (a)
N N C C
H H O O (n)
[1]
Correct structure if linkage [1]
Some evidence of continuation of molecule [1] [2]
(b) Peak at A : C=O [1]

Peak at B : C- O [1]
Spectrum is that of benzene – 1,4- dicarboxylic acid [1] [3]
(c) (i) To prevent the volatile reactant / dimethyl benzene boiling off [1]
(ii) Because the diacid is soluble in hot water [1]
(iii) M.Pt not sharp
or different from / not consistent with / less than data book [1] [3]
(d) (i)
F H F H F H H F
C C C C
or C C C C
F H F H F H H F
(n) (n)
(or H...F...F...H on chain)
Correct repeating structure [1]
Some evidence of continuation of molecule [1] [2]
(ii) Kevlar : condensation [1]
PDFE : addition [1] [2]
(e) (i) more carbon dioxide per kJ of energy [1]
therefore more global warming/ more greenhouse gas produced [1] [2]
(ii) Some reference to need for special arrangements for filling tank /
dangerous in the event of a crash /more weight as gas tank
weighs more than petrol tank / more likely to leak because gas
under pressure [1] [1]
[Total 15 marks]
16 (a) There is restricted rotation about the C=C [1] owing to sideways overlap of p-orbitals [1]
a diagram could score the second mark [2]
(b) (i) HOOC COOH
H C C H
Br Br [1] [1]

Part 6 – Answers
(ii) O
H C
C
O
C
H H (2) [2]
O
(c) (i)
HOOC H
C C
[1]
H COOH
[1]
(ii) Carboxyl groups too far apart to allow elimination of water [1] [1]
(d) (i) lithium aluminium hydride(in dry ether) [1] [1]
(ii) add PCl5 [1]
white / steamy / misty fumes produced or valid test for acid gas [1] [2]
[Total 10 marks]

Part 3 - Teaching Scheme

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Part 3 – Teaching Scheme

Practical assessment opportunities

Key skills mapping

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Topic 5.1 Redox equilibria

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Topic 5.2 Transition metal chemistry

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Key skills mapping

Steel SATIS 16–19 Number 40 ASE

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Topic 5.3 Organic chemistry III

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Key skills mapping

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Topic 5.4 Chemical kinetics II

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Topic 5.5 Organic chemistry IV – synoptic topics

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Key skills mapping

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Managing Ones Own Learning

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

A: Using the half-equation method:

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

We can then add the two equations, eliminating the electrons:

The overall change will therefore be:

which is the opposite of normal experience.

(a) VO2+ → VO2+ and V3+

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Adding the two half equations:

This shows that disproportionation is not favoured.

(b) MnO2 → MnO4– and Mn2+

2Sn2+(aq) [ Sn4+(aq) + Sn(s)

Sn2+(aq) + 2e– [ Sn(s) E = –0.14 V

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Disproportionation will not occur.

Amount of manganate(VII) in titre = 27.3 × 0.0200 = 5.46 × 10–4 mol

from the equation 1 mol MnO4– oxidises 2.5 mol of ethanedioate

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Amount of sodium ethanedioate = 1.368 × 10–2 mol

Mass of sodium ethanedioate weighed out = 1.368 × 10–2 × 134 = 1.83 g

SO32– + H2O – 2e– → SO42– + 2H+

MnO4– + 8H+ + 5e– → Mn2+ + 4H2O

2MnO4– + 5SO32– + 6H+ → 2Mn2+ + 5SO42– + 3H2O

Amount of MnO42– in titre = 26.2 × 0.0200 = 5.24 × 10–4 mol

Mass of sodium sulphite used originally = 10 × 126 × 1.31 × 10–3 g = 1.65 g

Percentage of sodium sulphite in sample = 1.65 × 100 = 91.7

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

Fe2+(aq) + 2OH–(aq) [ Fe(OH)2(s)

or, it could be written, more informatively, as:

[Fe(H2O)6]2+(aq) + 2OH–(aq) [ [Fe(H2O)4(OH)2](s) + 2H2O(l)

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.

2VO2+(aq) + 2H+(aq) + SO32–(aq) → 2VO2+(aq) + H2O(l) + SO42–(aq)

The other oxidation half reaction has the equation:

NAS Chemistry Teachers’ Guide © 2000 Nelson Thornes Ltd.