CHEMISTRY

HIGHER 2 (Syllabus 9746) CONTENTS

Page

INTRODUCTION AIMS ASSESSMENT OBJECTIVES SCHEME OF ASSESSMENT ADDITIONAL INFORMATION SUBJECT CONTENT QUALITATIVE ANALYSIS NOTES SUMMARY OF KEY QUANTITIES AND UNITS MATHEMATICAL REQUIREMENTS GLOSSARY OF TERMS DATA BOOKLET PERIODIC TABLE TEXTBOOKS

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INTRODUCTION
Candidates will be assumed to have knowledge and understanding of Chemistry at O level, as a single subject or as part of a balanced science course. This syllabus is designed to place less emphasis on factual material and greater emphasis on the understanding and application of scientific concepts and principles. This approach has been adopted in recognition of the need for students to develop skills that will be of long term value in an increasingly technological world rather than focusing on large quantities of factual material which may have only short term relevance. Experimental work is an important component and should underpin the teaching and learning of Chemistry.

AIMS
These are not listed in order of priority. Many of these Aims are reflected in the Assessment Objectives which follow; others are not readily assessed. The aims are to 1. provide, through well designed studies of experimental and practical chemistry, a worthwhile educational experience for all students, whether or not they go on to study science beyond this level and, in particular, to enable them to acquire sufficient understanding and knowledge to 1.1 1.2 1.3 2. become confident citizens in a technological world, able to take or develop an informed interest in matters of scientific import; recognise the usefulness, and limitations, of scientific method and to appreciate its applicability in other disciplines and in everyday life; be suitably prepared for employment and/or further studies beyond A level.

develop abilities and skills that 2.1 2.2 2.3 2.4 2.5 are relevant to the study and practice of science; are useful in everyday life; encourage efficient and safe practice; encourage the presentation of information and ideas appropriate for different audiences and purposes; develop self motivation and the ability to work in a sustained fashion.

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3.

develop attitudes relevant to science such as 3.1 3.2 3.3 3.4 3.5 3.6 accuracy and precision; objectivity; integrity; enquiry; initiative; insight.

4. 5.

stimulate interest in, and care for, the environment. promote an awareness that 5.1 5.2 5.3 5.4 the study and practice of science are co-operative and cumulative activities, and are subject to social, economic, technological, ethical and cultural influences and limitations; the applications of science may be both beneficial and detrimental to the individual, the community and the environment; science transcends national boundaries and that the language of science, correctly and rigorously applied, is universal; the use of information technology is important for communication, as an aid to experiments and as a tool for interpretation of experimental and theoretical results.

ASSESSMENT OBJECTIVES
The assessment objectives listed below reflect those parts of the Aims which will be assessed. A Knowledge with understanding

Students should be able to demonstrate knowledge with understanding in relation to: 1. 2. 3. 4. 5. scientific phenomena, facts, laws, definitions, concepts, theories; scientific vocabulary, terminology, conventions (including symbols, quantities and units); scientific instruments and apparatus, including techniques of operation and aspects of safety; scientific quantities and their determination; scientific and technological applications with their social, economic and environmental implications.

The Syllabus Content defines the factual knowledge that candidates may be required to recall and explain. Questions testing these objectives will often begin with one of the following words: define, state, describe, explain or outline. (See the Glossary of Terms.)

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Handling, applying and evaluating information

Students should be able in words or by using symbolic, graphical and numerical forms of presentation to: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. locate, select, organise and present information from a variety of sources; handle information, distinguishing the relevant from the extraneous; manipulate numerical and other data and translate information from one form to another; analyse and evaluate information so as to identify patterns, report trends and conclusions, and draw inferences; present reasoned explanations for phenomena, patterns and relationships; construct arguments to support hypotheses or to justify a course of action; apply knowledge, including principles, to novel situations; evaluate information and hypotheses; demonstrate an awareness of the limitations of Chemistry theories and models; bring together knowledge, principles and concepts from different areas of chemistry, and apply them in a particular context; use chemical skills in contexts which bring together different areas of the subject.

These assessment objectives cannot be precisely specified in the Syllabus Content because questions testing such skills may be based on information which is unfamiliar to the candidate. In answering such questions, candidates are required to use principles and concepts that are within the syllabus and apply them in a logical, reasoned or deductive manner to a novel situation. Questions testing these objectives will often begin with one of the following words: predict, suggest, construct, calculate or determine. (See the Glossary of Terms.) C Experimental skills and investigations

Students should be able to: 1. 2. 3. 4. 5. devise and plan investigations, select techniques, apparatus and materials; use techniques, apparatus and materials safely and effectively; make and record observations, measurements and estimates; interpret and evaluate observations and experimental data; evaluate methods and suggest possible improvements.

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SCHEME OF ASSESSMENT
All candidates are required to enter for Papers 1, 2, 3 and 4. Paper 1 2 3 4 Type of Paper Multiple Choice Structured Questions Free Response Questions School-based Science Practical Assessment (SPA) Duration 1h 1 h 30 min 2h Marks 40 60 80 64 Weighting (%) 20.0 25.0 35.0 20.0

Paper 1 (1 h)(40marks) Forty multiple choice questions, all compulsory. Thirty items will be of the direct choice type and ten of the multiple completion type. All questions will include 4 responses. Paper 2 (1 h 30 min)(60 marks) A variable number of structured questions plus one or two data-based questions, all compulsory. Answered on the question paper. The data-based question(s) constitute(s) 1520 marks for this paper. The data-based question(s) provide(s) good opportunity to test higher order thinking skills such as handling, applying, and evaluating information. Some questions will also require candidates to integrate knowledge and understanding from different areas and topics of the chemistry syllabus. Paper 3 (2 h)(80 marks) Candidates will be required to answer a total of four out of five questions. Each question will carry 20 marks. All the questions will require candidates to integrate knowledge and understanding from different areas and topics of the chemistry syllabus. Paper 4 (64 marks) The School-based Science Practical Assessment (SPA) will take place over an appropriate period that the candidates are offering the subject. The assessment of science practical skills is grouped into four skill areas: Skill A Planning Skill B Implementing Skill C Analysing Skill D Evaluating Each assessment carries a maximum of 8 marks. Each candidate is to be assessed only once for Skill A and only twice for each Skill B, C and D.

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To maintain an equal weighting for each skill, a maximum sum total of 64 will be computed as follows: Skill A B C D No. of assessments 1 2 2 2 Total for SPA Weight 2 1 1 1 Sub-total = No. of assessments x Marks x Weight 1 x 8 x 2 = 16 marks 2 x 8 x 1 = 16 marks 2 x 8 x 1 = 16 marks 2 x 8 x 1 = 16 marks 64 marks

Please refer to the SPA Information Booklet for more detailed information on the conduct of SPA.

Marks allocated to assessment objectives and syllabus areas

In demonstrating what they know, understand and can do, candidates will be expected, within the theory papers (other than the multiple-choice paper), to use a form of communication appropriate to the context of the question. Theory Papers Assessment Objectives A B Knowledge with understanding Handling, applying and evaluating information Weighting 40% 60% Assessment Components Papers 1, 2, 3 Papers 1, 2, 3

The proportion of marks allocated to Physical, Inorganic and Organic Chemistry in Papers 1, 2 and 3 will be in the approximate ratio 5:2:5. School-based Science Practical Assessment The school-based Science Practical Assessment (SPA) will be conducted to assess appropriate aspects of objectives C1 to C5. Disallowed Subject Combinations Candidates may not simultaneously offer Chemistry at H1 and H2.

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ADDITIONAL INFORMATION
Data Booklet A Data Booklet is available for use in the theory papers. The booklet is reprinted at the end of this syllabus document. Nomenclature Students will be expected to be familiar with the nomenclature used in the syllabus. The proposals in "Signs, Symbols and Systematics" (The Association for Science Education Companion to 16-19 Science, 2000) will generally be adopted although the traditional names sulfate, sulfite, nitrate, nitrite, sulfurous and nitrous acids will be used in question papers. Sulfur (and all compounds of sulfur) will be spelt with f (not with ph) in question papers, however students can use either spelling in their answers. Grading Conditions Candidates results are based on the aggregation of their marks in the various papers, i.e. there are no hurdle conditions under which a prescribed level of performance in an individual paper prevents the award of an A level result.

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SUBJECT CONTENT
PHYSICAL CHEMISTRY
1. ATOMS, MOLECULES AND STOICHIOMETRY

Content Relative masses of atoms and molecules The mole, the Avogadro constant The calculation of empirical and molecular formulae Reacting masses and volumes (of solutions and gases)

Learning Outcomes [the term relative formula mass or Mr will be used for ionic compounds] Candidates should be able to: (a) (b) (c) (d) (e) (f) (g) define the terms relative atomic, isotopic, molecular and formula mass, based on the 12C scale define the term mole in terms of the Avogadro constant calculate the relative atomic mass of an element given the relative abundances of its isotopes define the terms empirical and molecular formula calculate empirical and molecular formulae using combustion data or composition by mass write and/or construct balanced equations perform calculations, including use of the mole concept, involving: (i) (ii) (iii) (h) 2. reacting masses (from formulae and equations) volumes of gases (e.g. in the burning of hydrocarbons) volumes and concentrations of solutions

deduce stoichiometric relationships from calculations such as those in (g) ATOMIC STRUCTURE

Content The nucleus of the atom: neutrons and protons, isotopes, proton and nucleon numbers Electrons: electronic energy levels, ionisation energies, atomic orbitals, extranuclear structure

Learning Outcomes Candidates should be able to: (a) (b) identify and describe protons, neutrons and electrons in terms of their relative charges and relative masses deduce the behaviour of beams of protons, neutrons and electrons in both electric and magnetic fields

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(c) (d) (e)

describe the distribution of mass and charges within an atom deduce the numbers of protons, neutrons and electrons present in both atoms and ions given proton and nucleon numbers (and charge) (i) (ii) describe the contribution of protons and neutrons to atomic nuclei in terms of proton number and nucleon number distinguish between isotopes on the basis of different numbers of neutrons present

(f) (g) (h) (i)

describe the number and relative energies of the s, p and d orbitals for the principal quantum numbers 1, 2 and 3 and also the 4s and 4p orbitals describe the shapes of s and p orbitals state the electronic configuration of atoms and ions given the proton number (and charge) (i) (ii) explain the factors influencing the ionisation energies of elements (see the Data Booklet) explain the trends in ionisation energies across a period and down a Group of the Periodic Table (see also Section 9)

(j) (k)

deduce the electronic configurations of elements from successive ionisation energy data interpret successive ionisation energy data of an element in terms of the position of that element within the Periodic Table CHEMICAL BONDING

3.

Content Ionic (electrovalent) bonding Covalent bonding and co-ordinate (dative covalent) bonding (i) The shapes of simple molecules (ii) Bond energies, bond lengths and bond polarities Intermolecular forces, including hydrogen bonding Metallic bonding Bonding and physical properties The solid state

Learning Outcomes Candidates should be able to: (a) (b) describe ionic (electrovalent) bonding, as in sodium chloride and magnesium oxide, including the use of dot-and-cross diagrams describe, including the use of dot-and-cross diagrams, (i) (ii) covalent bonding, as in hydrogen; oxygen; nitrogen; chlorine; hydrogen chloride; carbon dioxide; methane; ethene co-ordinate (dative covalent) bonding, as in formation of the ammonium ion and in the Al2Cl6 molecule.

(c)

explain the shapes of, and bond angles in, molecules such as BF3 (trigonal planar); CO2 (linear); CH4 (tetrahedral); NH3 (trigonal pyramidal); H2O (non-linear); SF6 (octahedral) by using the Valence Shell Electron Pair Repulsion theory

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(d) (e) (f) (g) (h)

describe covalent bonding in terms of orbital overlap, giving and bonds (see also Section 10.1) predict the shapes of, and bond angles in, molecules analogous to those specified in (c) describe hydrogen bonding, using ammonia and water as examples of molecules containing -NH and -OH groups explain the terms bond energy, bond length and bond polarity and use them to compare the reactivities of covalent bonds describe intermolecular forces (van der Waals forces), based on permanent and induced dipoles, as in CHCl3(l); Br2(l) and the liquid noble gases describe metallic bonding in terms of a lattice of positive ions surrounded by mobile electrons describe, interpret and/or predict the effect of different types of bonding (ionic bonding; covalent bonding; hydrogen bonding; other intermolecular interactions; metallic bonding) on the physical properties of substances deduce the type of bonding present from given information show understanding of chemical reactions in terms of energy transfers associated with the breaking and making of chemical bonds describe, in simple terms, the lattice structure of a crystalline solid which is: (i) (ii) (iii) (iv) (v) ionic, as in sodium chloride, magnesium oxide simple molecular, as in iodine giant molecular, as in graphite; diamond hydrogen-bonded, as in ice metallic, as in copper

(i) (j)

(k) (l) (m)

[the concept of the unit cell is not required] (n) (o) (p) 4. outline the importance of hydrogen bonding to the physical properties of substances, including ice and water suggest from quoted physical data the type of structure and bonding present in a substance recognise that materials are a finite resource and the importance of recycling processes THE GASEOUS STATE

Content Ideal gas behaviour and deviations from it pV = nRT and its use in determining a value for Mr

Learning Outcomes Candidates should be able to: (a) state the basic assumptions of the kinetic theory as applied to an ideal gas

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(b)

explain qualitatively in terms of intermolecular forces and molecular size: (i) (ii) the conditions necessary for a gas to approach ideal behaviour the limitations of ideality at very high pressures and very low temperatures

(c)

state and use the general gas equation pV = nRT in calculations, including the determination of Mr CHEMICAL ENERGETICS

5.

Content Enthalpy changes: H, of formation; combustion; hydration; solution; neutralisation; atomisation; bond energy; lattice energy; electron affinity Hess Law, including Born-Haber cycles Entropy and Free Energy

Learning Outcomes Candidates should be able to: (a) explain that some chemical reactions are accompanied by energy changes, principally in the form of heat energy; the energy changes can be exothermic (H negative) or endothermic (H positive) explain and use the terms: (i) enthalpy change of reaction and standard conditions, with particular reference to: formation; combustion; hydration; solution; neutralisation; atomisation bond energy (H positive, i.e. bond breaking) lattice energy (H negative, i.e. gaseous ions to solid lattice)

(b)

(ii) (iii) (c)

calculate enthalpy changes from appropriate experimental results, including the use of the relationship heat change = mcT

(d) (e)

explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a lattice energy apply Hess Law to construct simple energy cycles, e.g. Born-Haber cycle, and carry out calculations involving such cycles and relevant energy terms (including ionisation energy and electron affinity), with particular reference to: (i) (ii) (iii) determining enthalpy changes that cannot be found by direct experiment, e.g. an enthalpy change of formation from enthalpy changes of combustion the formation of a simple ionic solid and of its aqueous solution average bond energies

(f) (g)

construct and interpret a reaction pathway diagram, in terms of the enthalpy change of the reaction and of the activation energy explain and use the term entropy

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(h)

discuss the effects on the entropy of a chemical system by the following: (i) (ii) (iii) (iv) change in temperature change in phase change in the number of particles (especially for gaseous systems) mixing of particles

[quantitative treatment is not required] (i) (j) predict whether the entropy change for a given process or reaction is positive or negative define standard Gibbs free energy change of reaction by means of the equation G = H TS calculate G for a reaction using the equation G = H

(k)

TS

[the calculation of standard entropy change, S , for a reaction using standard entropies, S , is not required] (l) (m) state whether a reaction or process will be spontaneous by using the sign of G predict the effect of temperature change on the spontaneity of a reaction, given standard enthalpy and entropy changes ELECTROCHEMISTRY

6.

Content Redox processes: electron transfer and changes in oxidation number (oxidation state) Electrode potentials (i) Standard electrode (redox) potentials, E ; the redox series (ii) Standard cell potentials, E cell , and their uses (iii) Batteries and fuel cells Electrolysis (i) Factors affecting the amount of substance liberated during electrolysis (ii) The Faraday constant; the Avogadro constant; their relationship (iii) Industrial uses of electrolysis

Learning Outcomes Candidates should be able to: (a) (b) describe and explain redox processes in terms of electron transfer and/or of changes in oxidation number (oxidation state) define the terms: (i) (ii) (c) standard electrode (redox) potential standard cell potential

describe the standard hydrogen electrode

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(d)

describe methods used to measure the standard electrode potentials of: (i) (ii) metals or non-metals in contact with their ions in aqueous solution ions of the same element in different oxidation states

(e) (f)

calculate a standard cell potential by combining two standard electrode potentials use standard cell potentials to: (i) (ii) explain/deduce the direction of electron flow from a simple cell predict the feasibility of a reaction

(g) (h) (i) (j)

understand the limitations in the use of standard cell potentials to predict the feasibility of a reaction construct redox equations using the relevant half-equations (see also Section 9.4) predict qualitatively how the value of an electrode potential varies with the concentration of the aqueous ion state the possible advantages of developing other types of cell, e.g. the H2/O2 fuel cell and improved batteries (as in electric vehicles) in terms of smaller size, lower mass and higher voltage state the relationship, F = Le, between the Faraday constant, the Avogadro constant and the charge on the electron predict the identity of the substance liberated during electrolysis from the state of electrolyte (molten or aqueous), position in the redox series (electrode potential) and concentration calculate: (i) (ii) the quantity of charge passed during electrolysis the mass and/or volume of substance liberated during electrolysis, including those in the electrolysis of H2SO4(aq); Na2SO4(aq)

(k) (l) (m)

(n)

explain, in terms of the electrode reactions, the industrial processes of: (i) (ii) the anodising of aluminium the electrolytic purification of copper

[technical details are not required] 7. EQUILIBRIA

Content Chemical equilibria: reversible reactions; dynamic equilibrium (i) Factors affecting chemical equilibria (ii) Equilibrium constants (iii) The Haber process

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Ionic equilibria (i) Brnsted-Lowry theory of acids and bases (ii) Acid dissociation constants, Ka and the use of pKa (iii) Base dissociation constants, Kb and the use of pKb (iv) The ionic product of water, Kw (v) pH: choice of pH indicators (vi) Buffer solutions (vii) Solubility product; the common ion effect

Learning Outcomes Candidates should be able to: (a) (b) (c) (d) explain, in terms of rates of the forward and reverse reactions, what is meant by a reversible reaction and dynamic equilibrium state Le Chateliers Principle and apply it to deduce qualitatively (from appropriate information) the effects of changes in concentration, pressure or temperature, on a system at equilibrium deduce whether changes in concentration, pressure or temperature or the presence of a catalyst affect the value of the equilibrium constant for a reaction deduce expressions for equilibrium constants in terms of concentrations, Kc, and partial pressures, Kp [treatment of the relationship between Kp and Kc is not required] (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) calculate the values of equilibrium constants in terms of concentrations or partial pressures from appropriate data calculate the quantities present at equilibrium, given appropriate data (such calculations will not require the solving of quadratic equations) describe and explain the conditions used in the Haber process, as an example of the importance of an understanding of chemical equilibrium in the chemical industry show understanding of, and apply the Brnsted-Lowry theory of acids and bases, including the concept of conjugate acids and conjugate bases explain qualitatively the differences in behaviour between strong and weak acids and bases in terms of the extent of dissociation explain the terms pH; Ka; pKa; Kb; pKb; Kw and apply them in calculations, including the relationship Kw = KaKb calculate [H+(aq)] and pH values for strong acids, weak monobasic (monoprotic) acids, strong bases, and weak monoacidic bases explain the choice of suitable indicators for acid-base titrations, given appropriate data describe the changes in pH during acid-base titrations and explain these changes in terms of the strengths of the acids and bases (i) (ii) (o) explain how buffer solutions control pH describe and explain their uses, including the role of H2CO3/HCO3- in controlling pH in blood

calculate the pH of buffer solutions, given appropriate data

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(p) (q) (r) 8.

show understanding of, and apply, the concept of solubility product, Ksp calculate Ksp from concentrations and vice versa show understanding of the common ion effect REACTION KINETICS

Content Simple rate equations; orders of reaction; rate constants Concept of activation energy Effect of concentration, temperature, and catalysts on reaction rate Homogeneous and heterogeneous catalysis Enzymes as biological catalysts

Learning Outcomes Candidates should be able to: (a) (b) explain and use the terms: rate of reaction; rate equation; order of reaction; rate constant; halflife of a reaction; rate-determining step; activation energy; catalysis construct and use rate equations of the form rate = k[A]m[B]n (limited to simple cases of singlestep reactions and of multi-step processes with a rate-determining step, for which m and n are 0, 1 or 2), including: (i) (ii) (iii) (iv) (v) deducing the order of a reaction by the initial rates method justifying, for zero- and first-order reactions, the order of reaction from concentration-time graphs verifying that a suggested reaction mechanism is consistent with the observed kinetics predicting the order that would result from a given reaction mechanism calculating an initial rate using concentration data

[integrated forms of rate equations are not required] (c) (i) (ii) (d) (e) (f) (g) (h) show understanding that the half-life of a first-order reaction is independent of concentration use the half-life of a first-order reaction in calculations

calculate a rate constant using the initial rates method devise a suitable experimental technique for studying the rate of a reaction, from given information explain qualitatively, in terms of collisions, the effect of concentration changes on the rate of a reaction show understanding, including reference to the Boltzmann distribution, of what is meant by the term activation energy explain qualitatively, in terms both of the Boltzmann distribution and of collision frequency, the effect of temperature change on a rate constant (and, hence, on the rate) of a reaction

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(i)

(i) (ii)

explain that, in the presence of a catalyst, a reaction has a different mechanism, i.e. one of lower activation energy, giving a larger rate constant interpret this catalytic effect on a rate constant in terms of the Boltzmann distribution

(j)

outline the different modes of action of homogeneous and heterogeneous catalysis, including: (i) (ii) (iii) (iv) the Haber process the catalytic removal of oxides of nitrogen in the exhaust gases from car engines (see also Section 10.2) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur dioxide catalytic role of Fe2+ in the I-/S2O82- reaction

(k) (l)

describe enzymes as biological catalysts which may have specific activity explain the relationship between substrate concentration and the rate of an enzyme-catalysed reaction in biochemical systems INORGANIC CHEMISTRY

9.

Preamble It is intended that the study should: be concerned primarily with aspects of selected ranges of elements and their compounds; be based on a study of the patterns: across the third period of the Periodic Table in the two Groups II and VII; introduce, with examples, the transition elements and their compounds; apply unifying themes to inorganic chemistry, such as atomic structure (Section 2), chemical bonding (Section 3), redox (Section 6), the reactions of ions, acid-base behaviour, precipitation (Section 7) and complexing behaviour (Section 9.4), where appropriate; include: the representation of reactions by means of balanced equations (molecular and/or ionic equations, together with state symbols); the interpretation of redox reactions in terms of changes in oxidation state of the species involved; the prediction of the feasibility of reactions from E values; the interpretation of chemical reactions in terms of ionic equilibria; the interpretation of chemical reactions in terms of the formation of complex ions.

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9.1

THE PERIODIC TABLE: CHEMICAL PERIODICITY

Content Periodicity of physical properties of the elements: variation with proton number across the third period (sodium to argon) of: (i) atomic radius and ionic radius (ii) melting point (iii) electrical conductivity (iv) ionisation energy Periodicity of chemical properties of the elements in the third period (i) Reaction of the elements with oxygen and chlorine (ii) Variation in oxidation number of the oxides (sodium to sulfur only) and of the chlorides (sodium to phosphorus only) (iii) Reactions of these oxides and chlorides with water (iv) Acid/base behaviour of these oxides and the corresponding hydroxides

Learning Outcomes Candidates should, for the third period (sodium to argon), be able to: (a) (b) (c) (d) (e) describe qualitatively (and indicate the periodicity in) the variations in atomic radius, ionic radius, melting point and electrical conductivity of the elements (see the Data Booklet) explain qualitatively the variation in atomic radius and ionic radius interpret the variation in melting point and in electrical conductivity in terms of the presence of simple molecular, giant molecular or metallic bonding in the elements explain the variation in first ionisation energy describe the reactions, if any, of the elements with oxygen (to give Na2O; MgO; Al2O3; P4O6; P4O10; SO2; SO3), and chlorine (to give NaCl; MgCl2; AlCl3; SiCl4; PCl3; PCl5) state and explain the variation in oxidation number of the oxides and chlorides describe the reactions of the oxides with water [treatment of peroxides and superoxides is not required] (h) (i) (j) (k) describe and explain the acid/base behaviour of oxides and hydroxides, including, where relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and acids describe and explain the reactions of the chlorides with water interpret the variations and trends in (f), (g), (h), and (i) in terms of bonding and electronegativity suggest the types of chemical bonding present in chlorides and oxides from observations of their chemical and physical properties

(f) (g)

In addition, candidates should be able to: (l) (m) predict the characteristic properties of an element in a given Group by using knowledge of chemical periodicity deduce the nature, possible position in the Periodic Table, and identity of unknown elements from given information of physical and chemical properties

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9.2

GROUP II

Content Similarities and trends in the properties of the Group II metals magnesium to barium and their compounds

Learning Outcomes Candidates should be able to: (a) (b) (c) (d) describe the reactions of the elements with oxygen and water describe the behaviour of the oxides with water interpret and explain qualitatively the trend in the thermal stability of the nitrates in terms of the charge density of the cation and the polarisability of the large anion interpret, and make predictions from, the trends in physical and chemical properties of the elements and their compounds GROUP VII

9.3

Content The similarities and trends in the physical and chemical properties of chlorine, bromine and iodine (i) Characteristic physical properties (ii) The relative reactivity of the elements as oxidising agents (iii) Some reactions of the halide ions (iv) The reactions of chlorine with aqueous sodium hydroxide

Learning Outcomes Candidates should be able to: (a) (b) (c) (d) (e) describe the trends in volatility and colour of chlorine, bromine and iodine analyse the volatility of the elements in terms of van der Waals forces describe and deduce from E values the relative reactivity of the elements as oxidising agents

describe and explain the reactions of the elements with hydrogen (i) (ii) describe and explain the relative thermal stabilities of the hydrides, interpret these relative stabilities in terms of bond energies

(f)

describe and explain the reactions of halide ions with: (i) (ii) aqueous silver ions followed by aqueous ammonia, concentrated sulfuric acid

(g)

describe and analyse in terms of changes of oxidation number the reaction of chlorine with cold, and with hot, aqueous sodium hydroxide

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9.4

AN INTRODUCTION TO THE CHEMISTRY OF TRANSITION ELEMENTS

Content General physical and characteristic chemical properties of the first set of transition elements, titanium to copper Colour of complexes

Learning Outcomes Candidates should be able to: (a) (b) (c) (d) explain what is meant by a transition element, in terms of d-block elements forming one or more stable ions with incomplete d orbitals state the electronic configuration of a first row transition element and of its ions state that the atomic radii, ionic radii and first ionisation energies of the transition elements are relatively invariant contrast, qualitatively, the melting point; density; atomic radius; ionic radius; first ionisation energy and conductivity of the transition elements with those of calcium as a typical s-block element describe the tendency of transition elements to have variable oxidation states predict from a given electronic configuration, the likely oxidation states of a transition element describe and explain the use of Fe3+/Fe2+, MnO4 /Mn2+ and Cr2O72 /Cr3+ as examples of redox systems (see also Section 6) (i) explain the reactions of transition elements with ligands to form complexes, including the complexes of copper(II) ions with water and ammonia describe the formation, and state the colour of, these complexes values, the likelihood of redox reactions
-

(e) (f) (g)

(h)

(ii) (i) (j) (k) (l)

predict, using E

explain qualitatively that ligand exchange may occur, including CO/O2 in haemoglobin explain how some transition elements and/or their compounds can act as catalysts (see also 8(j)) explain, in terms of d orbital splitting, why transition element complexes are usually coloured

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10.

ORGANIC CHEMISTRY

Preamble Although there are features of organic chemistry topics that are distinctive, it is intended that appropriate cross-references with other sections/topics in the syllabus should be made. In their study of organic chemistry, candidates may wish to group the organic reactions in terms of the mechanisms in the syllabus where possible. Candidates may wish to compare and contrast the different mechanisms. When describing preparative reactions, candidates will be expected to quote the reagents, e.g. aqueous NaOH, the essential practical conditions, e.g. reflux, and the identity of each of the major products. Detailed knowledge of practical procedures is not required: however, candidates may be expected to suggest (from their knowledge of the reagents, essential conditions and products) what steps may be needed to purify/extract a required product from the reaction mixture. In equations for organic redox reactions, the symbols [O] and [H] are acceptable. 10.1 INTRODUCTORY TOPICS In each of the sections below, 10.1 to 10.7, candidates will be expected to be able to predict the reaction products of a given compound in reactions that are chemically similar to those specified. Content Molecular, structural and empirical formulae Functional groups and the naming of organic compounds Characteristic organic reactions Shapes of organic molecules; and bonds Isomerism: structural; geometrical; optical

Structural formulae In candidates answers, an acceptable response to a request for a structural formula will be to give the minimal detail, using conventional groups, for an unambiguous structure, e.g. CH3CH2CH2OH for propan-1-ol, not C3H7OH. Displayed formulae A displayed formula should show both the relative placing of atoms and the number of bonds between them, e.g.

H H C H C

O O H

for ethanoic acid.

Skeletal formulae A skeletal formula is a simplified representation of an organic formula. It is derived from the structural formula by removing hydrogen atoms (and their associated bonds) and carbon atoms from alkyl chains, leaving just the carbon-carbon bonds in the carbon skeleton and the associated functional groups. Skeletal or partial-skeletal representations may be used in question papers and are acceptable in candidates answers where they are unambiguous.

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The skeletal formula for butan-2-ol and a partial-skeletal formula for cholesterol are shown below.

The

convention for representing the aromatic ring is preferred.

Optical Isomers When drawing a pair of optical isomers, candidates should indicate the three-dimensional structures according to the convention used in the example below.

CH 3 C HO H CO2H
mirror plane
Learning Outcomes Candidates should be able to: (a)

CH 3 H C CO2H OH

interpret, and use the nomenclature, general formulae and displayed formulae of the following classes of compound: (i) (ii) (iii) (iv) (v) (vi) alkanes, alkenes and arenes halogenoalkanes and halogenoarenes alcohols (including primary, secondary and tertiary) and phenols aldehydes and ketones carboxylic acids, acyl chlorides and esters amines, amides, amino acids and nitriles

(b)

interpret, and use the following terminology associated with organic reactions: (i) (ii) (iii) functional group homolytic and heterolytic fission free radical, initiation, propagation, termination

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9746 H2 CHEMISTRY (2009)

(iv) (v) (vi)

nucleophile, electrophile addition, substitution, elimination, hydrolysis oxidation and reduction

[in equations for organic redox reactions, the symbols [O] and [H] are acceptable] (c) (d) describe sp3 hybridisation, as in ethane molecule, sp2 hybridisation, as in ethene and benzene molecules, and sp hybridisation, as in ethyne molecule explain the shapes of, and bond angles in, the ethane, ethene, benzene, and ethyne molecules in relation to and carbon-carbon bonds predict the shapes of, and bond angles in, molecules analogous to those specified in (d) describe structural isomerism describe geometrical isomerism in alkenes, and explain its origin in terms of restricted rotation due to the presence of bonds [use of E, Z nomenclature is not required] (h) (i) (j) (k) (l) (m) (n) explain what is meant by a chiral centre deduce whether a given molecule is optically active based on the presence or absence of chiral centres and/or a plane of symmetry recognise that optical isomers have identical physical properties except in the direction in which they rotate plane-polarised light recognise that optical isomers have identical chemical properties except in their interactions with another chiral molecule recognise that different stereoisomers exhibit different biological properties, for example in drug action deduce the possible isomers for an organic molecule of known molecular formula identify chiral centres and/or geometrical isomerism in a molecule of given structural formula

(e) (f) (g)

10.2 HYDROCARBONS Content Alkanes (exemplified by ethane) (i) Free-radical reactions Alkenes (exemplified by ethene) (i) Addition and oxidation reactions Arenes (exemplified by benzene and methylbenzene) (i) Influence of delocalised electrons on structure and properties (ii) Substitution reactions with electrophiles (iii) Oxidation of side-chain Hydrocarbons as fuels

21

9746 H2 CHEMISTRY (2009)

Learning Outcomes Candidates should be able to: (a) (b) recognise the general unreactivity of alkanes, including towards polar reagents describe the chemistry of alkanes as exemplified by the following reactions of ethane: (i) (ii) (c) (d) combustion substitution by chlorine and by bromine

describe the mechanism of free-radical substitution at methyl groups with particular reference to the initiation, propagation and termination reactions describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene: (i) (ii) (iii) addition of hydrogen, steam, hydrogen halides and halogens oxidation by cold, dilute manganate(VII) ions to form the diol oxidation by hot, concentrated manganate(VII) ions leading to the rupture of the carbonto-carbon double bond in order to determine the position of alkene linkages in larger molecules

(e) (f)

describe the mechanism of electrophilic addition in alkenes, using bromine/ethene as an example describe the chemistry of arenes as exemplified by the following reactions of benzene and methylbenzene: (i) (ii) (iii) substitution reactions with chlorine and with bromine nitration oxidation of the side-chain to give a carboxylic acid describe the mechanism of electrophilic substitution in arenes, using the mono-nitration of benzene as an example describe the effect of the delocalisation of electrons in arenes in such reactions

(g)

(i) (ii)

(h) (i) (j)

predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction conditions apply the knowledge of positions of substitution in the electrophilic substitution reactions of mono-substituted arenes recognise the environmental consequences of carbon monoxide, oxides of nitrogen and unburnt hydrocarbons arising from the internal combustion engine and of their catalytic removal

22

9746 H2 CHEMISTRY (2009)

10.3 HALOGEN DERIVATIVES Content Halogenoalkanes and halogenoarenes (i) Nucleophilic substitution (ii) Elimination Relative strength of the C-Hal bond

Learning Outcomes Candidates should be able to: (a) recall the chemistry of halogenoalkanes as exemplified by (i) (ii) (b) (c) (d) (e) the following nucleophilic substitution reactions of bromoethane: hydrolysis; formation of nitriles; formation of primary amines by reaction with ammonia the elimination of hydrogen bromide from 2-bromopropane

describe the mechanism of nucleophilic substitution in halogenoalkanes interpret the different reactivities of halogenoalkanes and chlorobenzene with particular reference to hydrolysis and to the relative strengths of the C-Hal bonds explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative chemical inertness recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone layer [the mechanistic details of how CFCs deplete the ozone layer are not required]

10.4 HYDROXY COMPOUNDS Content Alcohols (exemplified by ethanol) (i) Formation of halogenoalkanes (ii) Reaction with sodium; oxidation; dehydration (iii) The tri-iodomethane test Phenol (i) Its acidity; reaction with sodium (ii) Nitration of, and bromination of, the aromatic ring

Learning Outcomes Candidates should be able to: (a) recall the chemistry of alcohols, exemplified by ethanol: (i) (ii) (iii) (iv) (v) combustion substitution to give halogenoalkanes reaction with sodium oxidation to carbonyl compounds and carboxylic acids dehydration to alkenes

23

9746 H2 CHEMISTRY (2009)

(b)

(i) (ii)

classify hydroxy compounds into primary, secondary and tertiary alcohols suggest characteristic distinguishing reactions, e.g. mild oxidation

(c)

deduce the presence of a CH3CH(OH) group in an alcohol from its reaction with alkaline aqueous iodine to form tri-iodomethane recall the chemistry of phenol, as exemplified by the following reactions: (i) (ii) (iii) with bases with sodium nitration of, and bromination of, the aromatic ring

(d)

(e)

explain the relative acidities of water, phenol and ethanol

10.5 CARBONYL COMPOUNDS Content Aldehydes (exemplified by ethanal) (i) Oxidation to carboxylic acid (ii) Reaction with hydrogen cyanide (iii) Characteristic tests for aldehydes Ketones (exemplified by propanone and phenylethanone) (i) Reaction with hydrogen cyanide (ii) Characteristic tests for ketones

Learning Outcomes Candidates should be able to: (a) (b) (c) (d) describe the formation of aldehydes and ketones from, and their reduction to, primary and secondary alcohols respectively describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with aldehydes and ketones describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to detect the presence of carbonyl compounds deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the results of simple tests (i.e. Fehlings and Tollens reagents; ease of oxidation) describe the reaction of CH3CO compounds with alkaline aqueous iodine to give tri-iodomethane

(e)

24

9746 H2 CHEMISTRY (2009)

10.6 CARBOXYLIC ACIDS AND DERIVATIVES Content Carboxylic acids (exemplified by ethanoic acid and benzoic acid) (i) Formation from primary alcohols and nitriles (ii) Salt, ester and acyl chloride formation Acyl chlorides (exemplified by ethanoyl chloride) (i) Ease of hydrolysis compared with alkyl and aryl chlorides (ii) Reaction with alcohols, phenols and primary amines Esters (exemplified by ethyl ethanoate and phenyl benzoate) (i) Formation from carboxylic acids and from acyl chlorides (ii) Hydrolysis (under acidic and under basic conditions)

Learning Outcomes Candidates should be able to: (a) (b) describe the formation of carboxylic acids from alcohols, aldehydes and nitriles describe the reactions of carboxylic acids in the formation of (i) (ii) (iii) (c) (d) (e) (f) (g) (h) salts esters on reaction with alcohols, using ethyl ethanoate as an example acyl chlorides, using ethanoyl chloride as an example

explain the acidity of carboxylic acids and of chlorine-substituted ethanoic acids in terms of their structures describe the hydrolysis of acyl chlorides describe the reactions of acyl chlorides with alcohols, phenols and primary amines explain the relative ease of hydrolysis of acyl chlorides, alkyl chlorides and aryl chlorides describe the formation of esters from acyl chlorides, using phenyl benzoate as an example describe the acid and base hydrolyses of esters

10.7 NITROGEN COMPOUNDS Content Primary amines (exemplified by ethylamine and phenylamine) (i) Their formation (ii) Salt formation (iii) Other reactions of phenylamine Amides (exemplified by ethanamide) (i) Their formation from acyl chlorides (ii) Their hydrolysis Amino acids (exemplified by aminoethanoic acid) (i) Their acid and base properties (ii) Zwitterion formation Proteins (i) Protein structure: primary; secondary; tertiary; quaternary structures (ii) The hydrolysis of proteins (iii) Denaturation of proteins

25

9746 H2 CHEMISTRY (2009)

Learning Outcomes Candidates should be able to: (a) describe the formation of ethylamine (by nitrile reduction see also Section 10.3) and of phenylamine (by the reduction of nitrobenzene) explain the basicity of amines explain the relative basicities of ammonia, ethylamine and phenylamine in terms of their structures describe the reaction of phenylamine with aqueous bromine describe the formation of amides from the reaction between RNH2 and R'COCl describe amide hydrolysis on treatment with aqueous alkali or acid describe the acid/base properties of amino acids and the formation of zwitterions describe the formation of peptide (amide) bonds between amino acids and, hence, explain protein formation list the major functions of proteins in the body describe the hydrolysis of proteins explain the term primary structure of proteins recognise that the twenty amino acids that make up all the proteins in the body are -amino acids with the general formula RCH(NH2)CO2H, and be able to interpret the properties of -amino acids in terms of the nature of the R group describe the secondary structure of proteins: -helix and -pleated sheet and the stabilisation of these structures by hydrogen bonding state the importance of the tertiary protein structure and explain the stabilisation of the tertiary structure with regard to the R groups in the amino acid residues (ionic linkages, disulfide bridges, hydrogen bonds and van der Waals forces) describe (i) (ii) (p) (q) the quaternary structure of proteins the protein components of haemoglobin

(b) (c)

(d) (e) (f) (g) (h) (i) (j) (k) (l)

(m) (n)

(o)

explain denaturation of proteins by heavy metal ions, extremes of temperature and pH changes apply the knowledge of the loss and formation of secondary and tertiary structures to interpret common everyday phenomena

26

9746 H2 CHEMISTRY (2009)

QUALITATIVE ANALYSIS NOTES

[Key: ppt. = precipitate; sol. = soluble; insol = insoluble; xs = excess.] 1 Reactions of aqueous cations cation aluminium, Al3+(aq) ammonium, NH4+(aq) barium, Ba2+(aq) calcium, Ca2+(aq) chromium(III), Cr3+(aq) copper(II), Cu2+(aq), iron(II), Fe2+(aq) iron(III), Fe3+(aq) lead(II), Pb2+(aq) magnesium, Mg2+(aq) manganese(II), Mn2+(aq) zinc, Zn2+(aq) reaction with NaOH(aq) white ppt. soluble in excess ammonia produced on heating no ppt. (if reagents are pure) white. ppt. with high [Ca2+(aq)] grey-green ppt. soluble in excess giving dark green solution pale blue ppt. insoluble in excess green ppt. insoluble in excess red-brown ppt. insoluble in excess white ppt. soluble in excess white ppt. insoluble in excess off-white ppt. insoluble in excess white ppt. soluble in excess NH3(aq) white ppt. insoluble in excess

no ppt. no ppt. grey-green ppt. insoluble in excess blue ppt. soluble in excess giving dark blue solution green ppt. insoluble in excess red-brown ppt. insoluble in excess white ppt. insoluble in excess white ppt. insoluble in excess off-white ppt. insoluble in excess white ppt. soluble in excess

[Lead(II) ions can be distinguished from aluminium ions by the insolubility of lead(II) chloride.]

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9746 H2 CHEMISTRY (2009)

2 Reactions of anions ion carbonate, CO32chromate(VI), CrO42-(aq) chloride, Cl-(aq) bromide, Br-(aq) iodide, I-(aq) nitrate, NO3-(aq) nitrite, NO2-(aq) sulfate, SO42-(aq) sulfite, SO32-(aq) 3 Tests for gases gas ammonia, NH3 carbon dioxide, CO2 chlorine, Cl2 hydrogen, H2 oxygen, O2 sulfur dioxide, SO2 test and test result turns damp red litmus paper blue; gives a white ppt. with limewater (ppt. dissolves with excess CO2) bleaches damp litmus paper pops with a lighted splint relights a glowing splint turns aqueous acidified potassium dichromate(VI) from orange to green reaction CO2 liberated by dilute acids yellow solution turns orange with H+(aq); gives yellow ppt. with Ba2+(aq); gives bright yellow ppt. with Pb2+(aq) gives white ppt. with Ag+(aq) (soluble in NH3(aq)); gives white ppt. with Pb2+(aq) gives pale cream ppt. with Ag+(aq) (partially soluble in NH3(aq)); gives white ppt. with Pb2+(aq) gives yellow ppt. with Ag+(aq) (insoluble in NH3(aq)); gives yellow ppt. with Pb2+(aq) NH3 liberated on heating with OH-(aq) and Al foil NH3 liberated on heating with OH-(aq) and Al foil; NO liberated by dilute acids (colourless NO (pale) brown NO2 in air) gives white ppt. with Ba2+(aq) or with Pb2+(aq) (insoluble in excess dilute strong acids) SO2 liberated with dilute acids; gives white ppt. with Ba2+(aq) (soluble in dilute strong acids)

28

9746 H2 CHEMISTRY (2009)

SUMMARY OF KEY QUANTITIES AND UNITS

The list below is intended as a guide to the more important quantities which might be encountered in teaching and used in question papers. The list is not exhaustive. Quantity Base quantities mass length time electric current thermodynamic temperature amount of substance Other quantities temperature volume density pressure frequency wavelength speed of electromagnetic waves Planck constant electric potential difference electrode potential (standard) redox electromotive force molar gas constant half-life atomic mass atomic relative mass isotopic molecular mass relative molecular mass molar mass nucleon number proton number neutron number number of molecules number of molecules per unit volume Avogadro constant Faraday constant enthalpy change of reaction standard enthalpy change of reaction ionisation energy lattice energy bond energy electron affinity rate constant equilibrium constant acid dissociation constant base dissociation constant order of reaction mole fraction concentration partition coefficient ionic product, solubility product ionic product of water pH Usual symbols m l t I T n SI unit kg, g m s A K mol

, t V, v

p v, f c h V (E ) E E R T, t ma Ar m Mr M A Z N N n L F H H I k K, Kp, Kc Ka Kb n, m x c K K, Ksp, Kw pH

m3, dm3 kg m-3, g dm-3, g cm-3 Pa Hz m, mm, nm m s-1 Js V V V J K-1 mol-1 s kg

g g mol-1 m-3 mol-1 C mol-1 J, kJ J mol-1, kJ mol-1 kJ mol-1 kJ mol-1 kJ mol-1 kJ mol-1 as appropriate as appropriate mol dm-3 mol dm-3 mol dm-3 as appropriate mol2 dm-6

29

9746 H2 CHEMISTRY (2009)

MATHEMATICAL REQUIREMENTS
It is assumed that candidates will be competent in the techniques described below. Make calculations involving addition, subtraction, multiplication and division of quantities. Make approximate evaluations of numerical expressions. Express small fractions as percentages, and vice versa. Calculate an arithmetic mean. Transform decimal notation to power of ten notation (standard form). Use calculators to evaluate logarithms (for pH calculations), squares, square roots, and reciprocals. Change the subject of an equation. (Most such equations involve only the simpler operations but may include positive and negative indices and square roots.) Substitute physical quantities into an equation using consistent units so as to calculate one quantity. Check the dimensional consistency of such calculations, e.g. the units of a rate constant k. Solve simple algebraic equations. Comprehend and use the symbols/notations <, >, , /, , , x (or <x>). Test tabulated pairs of values for direct proportionality by a graphical method or by constancy of ratio. Select appropriate variables and scales for plotting a graph, especially to obtain a linear graph of the form y = mx + c. Determine and interpret the slope and intercept of a linear graph. Choose by inspection a straight line that will serve as the least bad linear model for a set of data presented graphically. Understand (i) the slope of a tangent to a curve as a measure of rate of change, (ii) the area below a curve where the area has physical significance, e.g. Boltzmann distribution curves. Comprehend how to handle numerical work so that significant figures are neither lost unnecessarily nor used beyond what is justified. Estimate orders of magnitude. Formulate simple algebraic equations as mathematical models, e.g. construct a rate equation, and identify failures of such models. Calculators Any calculator used must be on the Singapore Examinations and Assessment Board list of approved calculators.

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9746 H2 CHEMISTRY (2009)

GLOSSARY OF TERMS
It is hoped that the glossary (which is relevant only to science subjects) will prove helpful to candidates as a guide, i.e. it is neither exhaustive nor definitive. The glossary has been deliberately kept brief not only with respect to the number of terms included but also to the descriptions of their meanings. Candidates should appreciate that the meaning of a term must depend in part on its context. 1. 2. Define (the term(s)...) is intended literally, only a formal statement or equivalent paraphrase being required. What do you understand by/What is meant by (the term(s)...) normally implies that a definition should be given, together with some relevant comment on the significance or context of the term(s) concerned, especially where two or more terms are included in the question. The amount of supplementary comment intended should be interpreted in the light of the indicated mark value. State implies a concise answer with little or no supporting argument, e.g. a numerical answer that can be obtained by inspection. List requires a number of points, generally each of one word, with no elaboration. Where a given number of points is specified, this should not be exceeded. Explain may imply reasoning or some reference to theory, depending on the context. Describe requires candidates to state in words (using diagrams where appropriate) the main points of the topic. It is often used with reference either to particular phenomena or to particular experiments. In the former instance, the term usually implies that the answer should include reference to (visual) observations associated with the phenomena. In other contexts, describe and give an account of should be interpreted more generally, i.e. the candidate has greater discretion about the nature and the organisation of the material to be included in the answer. Describe and explain may be coupled in a similar way to state and explain. 7. 8. 9. Discuss requires candidates to give a critical account of the points involved in the topic. Outline implies brevity, i.e. restricting the answer to giving essentials. Predict implies that the candidate is not expected to produce the required answer by recall but by making a logical connection between other pieces of information. Such information may be wholly given in the question or may depend on answers extracted in an early part of the question. Deduce is used in a similar way as predict except that some supporting statement is required, e.g. reference to a law/principle, or the necessary reasoning is to be included in the answer. Comment is intended as an open-ended instruction, inviting candidates to recall or infer points of interest relevant to the context of the question, taking account of the number of marks available. Suggest is used in two main contexts, i.e. either to imply that there is no unique answer (e.g. in chemistry, two or more substances may satisfy the given conditions describing an unknown), or to imply that candidates are expected to apply their general knowledge to a novel situation, one that may be formally not in the syllabus. Find is a general term that may variously be interpreted as calculate, measure, determine etc. Calculate is used when a numerical answer is required. In general, working should be shown, especially where two or more steps are involved.

3. 4. 5. 6.

10. 11. 12.

13. 14.

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9746 H2 CHEMISTRY (2009)

15. 16.

Measure implies that the quantity concerned can be directly obtained from a suitable measuring instrument, e.g. length, using a rule, or angle, using a protractor. Determine often implies that the quantity concerned cannot be measured directly but is obtained by calculation, substituting measured or known values of other quantities into a standard formula, e.g. relative molecular mass. Estimate implies a reasoned order of magnitude statement or calculation of the quantity concerned, making such simplifying assumptions as may be necessary about points of principle and about the values of quantities not otherwise included in the question. Sketch, when applied to graph work, implies that the shape and/or position of the curve need only be qualitatively correct, but candidates should be aware that, depending on the context, some quantitative aspects may be looked for, e.g. passing through the origin, having an intercept, asymptote or discontinuity at a particular value. In diagrams, sketch implies that a simple, freehand drawing is acceptable: nevertheless, care should be taken over proportions and the clear exposition of important details.

17.

18.

19. 20. 21. 22.

Construct is often used in relation to chemical equations where a candidate is expected to write a balanced equation, not by factual recall but by analogy or by using information in the question. Compare requires candidates to provide both the similarities and differences between things or concepts. Classify requires candidates to group things based on common characteristics. Recognise is often used to identify facts, characteristics or concepts that are critical (relevant/appropriate) to the understanding of a situation, event, process or phenomenon.

Special Note Units, significant figures. Candidates should be aware that misuse of units and/or significant figures, i.e. failure to quote units where necessary, the inclusion of units in quantities defined as ratios or quoting answers to an inappropriate number of significant figures, is liable to be penalised.

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9746 H2 CHEMISTRY (2009)

BLANK PAGE

33

9746 H2 CHEMISTRY (2009)

for
Chemistry

(Advanced Level)

for use in all papers for the H1, H2, H3 Chemistry syllabuses

34

9746 H2 CHEMISTRY (2009)

TABLES OF CHEMICAL DATA

Important values, constants and standards molar gas constant the Faraday constant the Avogadro constant the Planck constant speed of light in a vacuum rest mass of proton, 1H rest mass of neutron, 0 n rest mass of electron, electronic charge molar volume of gas
0 1

R F L h c mp mn me e

= 8.31 J K-1 mol-1 = 9.65 x 104 C mol-1 = 6.02 x 1023 mol-1 = 6.63 x 10-34 J s = 3.00 x 108 m s-1 = 1.67 x 10-27 kg = 1.67 x 10-27 kg = 9.11 x 10-31 kg = -1.60 x 10-19 C

Vm = 22.4 dm3 mol-1 at s.t.p. Vm = 24 dm3 mol-1 under room conditions (where s.t.p. is expressed as 101 kPa, approximately, and 273 K (0 C)) ionic product of water specific heat capacity of water Kw = 1.00 x 10-14 mol2 dm-6 (at 298 K [25 C]) = 4.18 kJ kg-1 K-1 (= 4.18 J g-1 K-1)

35

9746 H2 CHEMISTRY (2009)

Ionisation energies (1st, 2nd, 3rd and 4th) of selected elements, in kJ mol-1 Proton Number H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge Br Sr Sn I Ba Pb 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 35 38 50 53 56 82 First 1310 2370 519 900 799 1090 1400 1310 1680 2080 494 736 577 786 1060 1000 1260 1520 418 590 632 661 648 653 716 762 757 736 745 908 577 762 1140 548 707 1010 502 716 Second 5250 7300 1760 2420 2350 2860 3390 3370 3950 4560 1450 1820 1580 1900 2260 2300 2660 3070 1150 1240 1310 1370 1590 1510 1560 1640 1750 1960 1730 1980 1540 2080 1060 1410 1840 966 1450 Third 11800 14800 3660 4610 4590 5320 6040 6150 6940 7740 2740 3230 2920 3390 3850 3950 4600 4940 2390 2720 2870 2990 3250 2960 3230 3390 3350 3828 2960 3300 3460 4120 2940 2040 3390 3080 Fourth 21000 25000 6220 7480 7450 8410 9290 9540 10500 11600 4360 4960 4540 5150 5770 5860 6480 7110 4170 4600 4770 5190 5400 5100 5400 5690 5980 6190 4390 4850 5440 3930 4030 4080

36

9746 H2 CHEMISTRY (2009)

Bond energies (a) Diatomic molecules Bond HH DD NN O=O FF ClCl BrBr II HF HCl HBr HI (b) Polyatomic molecules Bond CC C=C CC C.C (benzene) CH CCl CBr CI CO C=O CN C=N CN NH NN N=N OH OO SiCl SiH SiO SiSi S Cl SH SS Energy/kJ mol-1 350 610 840 520 410 340 280 240 360 740 305 610 890 390 160 410 460 150 359 320 444 222 250 347 264 Energy/kJ mol-1 436 442 994 496 158 244 193 151 562 431 366 299

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9746 H2 CHEMISTRY (2009)

Standard electrode potential and redox potentials, E For ease of reference, two tabulations are given:

at 298 K (25 oC)

(a) an extended list in alphabetical order; (b) a shorter list in decreasing order of magnitude, i.e. a redox series. (a) E in alphabetical order Electrode reaction Ag + e Al
3+ 2+ + -

E /V Ag Al Ba 2Br Ca 2Cl Co Co Cr Cr Cr
2+ 3+ 2+ -

+0.80 -1.66 -2.90 +1.07 -2.87 +1.36 +1.64 -0.28 +1.82 -0.43 -0.91 -0.74 -0.41 +1.33 +0.52 +0.34
+

+ 3e + 2e

Ba

Br2 + 2e Cl2 + 2e 2HOCl + 2H + 2e Co

2+ +

Ca2+ + 2e-

Cl2 + 2H2O

+ 2e +e + 2e

Co [Co(NH3)6]

3+

2+

Co + 6NH3

Cr2+ + 2eCr3+ + 3eCr Cr2O723+

+e

+ 14H + 6e Cu + e Cu
2+ +

2Cr + 7H2O Cu Cu Cu 2F Fe Fe Fe
2+ 4-

+ 2e +e

Cu

2+

+0.15 -0.05 +2.87 -0.44 -0.04 +0.77 +0.36 -0.56 0.00 +0.54 -2.92 -3.04 -2.38 -1.18

[Cu(NH3)4]2+ + 2eF2 + 2e Fe Fe
2+ 3+ -

Cu + 4NH3
-

+ 2e + 3e +e

Fe

3+ 3-

[Fe(CN)6] + e 2H + 2e I2 + 2e K +e Li + e Mg
2+ + + +

[Fe(CN)6] H2 2I K Li Mg Mn Mn Mn
2+ 2+ -

Fe(OH)3 + e-

Fe(OH)2 + OH-

+ 2e +e

Mn2+ + 2eMn
3+ -

+1.49 + 2H2O +1.23 +0.56 +1.67 +1.52 +0.81 +0.94 +0.87 -2.71 -0.25

MnO2 + 4H + 2e

MnO4- + eMnO4- + 4H+ + 3eMnO4- + 8H+ + 5eNO3- + 2H+ + eNO3- + 3H+ + 2eNO3- + 10H+ + 8e+ Na + e
2+

MnO42MnO2 + 2H2O Mn
2+

+ 4H2O

NO2 + H2O HNO2 + H2O NH4+ + 3H2O Na Ni

Ni

+ 2e

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9746 H2 CHEMISTRY (2009)

[Ni(NH3)6]2+ + 2eH2O2 + 2H+ + 2eO2 + 4H+ + 4eO2 + 2H2O + 4e O2 + 2H + 2e 2H2O + 2e Pb

2+ + -

Ni + 6NH3 2H2O 2H2O 4OH

-

-0.51 +1.77 +1.23 +0.40 +0.68

H2O2 H2 + 2OH Pb Pb2+ Pb2+ + 2H2O SO2 + 2H2O 2SO422S2O32Sn Sn V V V

2+ 3+ 2+ -

-0.83 -0.13 +1.69 +1.47 +0.17 +2.01 +0.09 -0.14 +0.15 -1.20 -0.26

+ 2e

Pb4+ + 2ePbO2 + 4H+ + 2eSO42+ 4H + 2e S2O82-+ S4O62-+ 2+ Sn Sn

4+ + -

2e 2e

+ 2e + 2e +e

V2+ + 2eV VO
2+ 3+ + + + -

+ 2H + e + 2H + e + 4H + e Zn
2+

+ H2O
2+ 2+

+0.34 +1.00 +1.00 -0.76

VO2+ VO3-

VO VO Zn

+ H2O + 2H2O

+ 2e

All ionic states refer to aqueous ions but other state symbols have been omitted. (b) E in decreasing order of oxidising power

(see also the extended alphabetical list on the previous pages) Electrode reaction F2 + 2e H2O2 + 2H + 2e MnO4+ 8H + 5e
+ + -

E /V 2F
-

+2.87 +2.01 +1.77 +1.52 +1.47 +1.36 +1.33 +1.07 +0.81 +0.80 +0.77 +0.54 +0.40 +0.34 +0.17 +0.15 +0.09 0.00 -0.13 -0.14 -0.44 -0.76 39

S2O82-+ +

2e

2SO422H2O Mn Pb
2+

+ 4H2O + 2H2O

PbO2 + 4H + 2e

2+ -

Cl2 + 2eCr2O72- + 14H+ + 6eBr2 + 2e NO3+ 2H + e Ag + e Fe

3+ + + -

2Cl 2Br Ag Fe 2I-

2Cr3+ + 7H2O NO2 + H2O

2+

+e

I2 + 2eO2 + 2H2O + 4eCu SO422+ +

4OHCu SO2 + 2H2O Sn H2 Pb Sn Fe Zn

2+

+ 2e + 2e 2e

+ 4H + 2e Sn
4+

S4O62-+ +

2S2O32-

2H + 2e

Pb2+ + 2eSn2+ + 2eFe Zn

2+ 2+

+ 2e + 2e

9746 H2 CHEMISTRY (2009)

Mg2+ + 2eCa2+ + 2eK+ + e-

Mg Ca K

-2.38 -2.87 -2.92

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9746 H2 CHEMISTRY (2009)

Atomic and ionic radii (a) Period 3 metallic atomic/nm Na 0.186 Mg 0.160 Al 0.143 Si P S Cl Ar Be Mg Ca Sr Ba Ra C Si Ge Sn Pb F Cl Br I At 0.117 0.110 0.104 0.099 0.192 0.112 0.160 0.197 0.215 0.217 0.220 0.077 0.117 0.122 0.162 0.175 0.072 0.099 0.114 0.133 0.140 0.144 0.132 0.122 0.117 0.117 0.116 0.116 0.115 0.117 0.125 Be2+ Mg2+ Ca2+ Sr2+ Ba2+ Ra2+ 0.031 0.065 0.099 0.113 0.135 0.140 ionic/nm Na+ 0.095 Mg2+ 0.065 Al3+ 0.050 Si4+ P3S2Cl0.041 0.212 0.184 0.181

single covalent

van der Waals (b) Group II metallic

(c)

Group IV single covalent

Si4+ Ge2+ Sn2+ Pb2+ FClBrI-

0.041 0.093 0.112 0.120

metallic (d) Group VII single covalent

0.136 0.181 0.195 0.216

(e)

First row transition elements single covalent Sc Ti V Cr Mn Fe Co Ni Cu Zn

Sc3+ Ti2+ V3+ Cr3+ Mn2+ Fe2+ Fe3+ Co2+ Ni2+ Cu2+ Zn2+

0.081 0.090 0.074 0.069 0.080 0.076 0.064 0.078 0.078 0.069 0.074

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9746 H2 CHEMISTRY (2009)

Characteristic values for infra-red absorption (due to stretching vibrations in organic molecules).

Bond CCl CO C=C C=O CC CN OH CH OH NH OH 'hydrogen-bonded' in acids alkanes, alkenes, arenes 'hydrogen-bonded' in alcohols, phenols primary amines 'free' aldehydes, ketones, acids, esters alcohols, ethers, esters

Characteristic ranges Wavenumber (reciprocal wavelength) /cm-1 700 to 800 1000 to 1300 1610 to 1680 1680 to 1750 2070 to 2250 2200 to 2280 2500 to 3300 2840 to 3095 3230 to 3550 3350 to 3500 3580 to 3650

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9746 H2 CHEMISTRY (2009)

43

The Periodic Table of the Elements

Group I II
1.0

III H
hydrogen

IV

VI

VII

0
4.0

He
helium

Key
6.9 9.0 relative atomic mass

1 10.8 12.0 14.0 16.0 19.0

2 20.2

Li
lithium

Be
beryllium

atomic symbol
name

B
boron

C
carbon

N
nitrogen

O
oxygen

F
fluorine

Ne
neon

3 23.0

4 24.3

atomic number

5 27.0

6 28.1

7 31.0

8 32.1

9 35.5

10 39.9

Na
sodium

Mg
magnesium

Al
aluminium

Si
silicon

P
phosphorus

S
sulfur

Cl
chlorine

Ar
argon

11 39.1

12 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4

13 69.7

14 72.6

15 74.9

16 79.0

17 79.9

18 83.8

K
potassium

Ca
calcium

Sc
scandium

Ti
titanium

V
vanadium

Cr
chromium

Mn
manganese

Fe
iron

Co
cobalt

Ni
nickel

Cu
copper

Zn
zinc

Ga
gallium

Ge
germanium

As
arsenic

Se
selenium

Br
bromine

Kr
krypton

19 85.5

20 87.6

21 88.9

22 91.2

23 92.9

24 95.9

25

26 101

27 103

28 106

29 108

30 112

31 115

32 119

33 122

34 128

35 127

36 131

Rb
rubidium

Sr
strontium

Y
yttrium

Zr
zirconium

Nb
niobium

Mo
42 43 184

Tc
44 186

Ru
ruthenium

Rh
rhodium

Pd
palladium

Ag
silver

Cd
cadmium

In
indium

Sn
tin

Sb
antimony

Te
tellurium

I
iodine

Xe
xenon

44

molybdenum technetium

37 133

38 137

39 139

40 178

41 181

45 190 192

46 195

47 197

48 201

49 204

50 207

51 209

52

53

54

Cs
caesium

Ba
barium

La
lanthanum

Hf
hafnium

Ta
tantalum

W
tungsten

Re
rhenium

Os
osmium

Ir
iridium

Pt
platinum

Au
gold

Hg
mercury

Tl
thallium

Pb
lead

Bi
bismuth

Po
polonium

At
astatine

Rn
radon

55

56

57

* 72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Fr
francium

Ra
radium

Ac
actinium

Rf

Db

Sg
seaborgium

Bh
bohrium

Hs
hassium

Mt
meitnerium

Unu
ununnilium

Uuu
unununium

Uub
ununbium

Uuq
ununquadium

Uuh
ununhexium

Uuo
ununoctium

87

88

89

* rutherfordium dubnium * 104 105

106

107

108

109

110

111

112

114

116

118

140

141

144

150

152

157

159

163

165

167

169

173

175

lanthanides

Ce
*
cerium

Pr
59 60

Nd
61

Pm
promethium

Sm
samarium

Eu
europium

Gd
gadolinium

Tb
terbium

Dy
dysprosium

Ho
holmium

Er
erbium

Tm
thulium

Yb
ytterbium

Lu
lutetium

praseodymium neodymium

58

62

63

64

65

66

67

68

69

70

71

actinides *

Th
thorium

Pa
protactinium

U
uranium

Np
neptunium

Pu
plutonium

Am
americium

Cm
curium

Bk
berkelium

Cf
californium

Es
einsteinium

Fm
fermium

Md
mendelevium

No
nobelium

Lw
lawrencium

90

91

92

93

94

95

96

97

98

99

100

101

102

103

9746 H2 CHEMISTRY (2009)

TEXTBOOKS
Teachers may find reference to the following books helpful. Chemistry for Advanced Level by P. Cann & P. Hughes, published by John Murray A-Level Chemistry (4th Edition) by E. N. Ramsden, published by Nelson Thornes Understanding Chemistry for Advanced Level (3rd Edition), by T. Lister & J. Renshaw, published by Nelson Thornes Chemistry in Action (2nd Edition) by Michael Freemantle, published by Macmillan Press Advanced Chemistry through Diagrams by M. Lewis, published by Oxford University Press Chemistry in Context (5th Edition) by Hill & Holman, published by Nelson Thornes Chemistry in Context Laboratory Manual and Study Guide (5th Edition) by Hill & Holman, published by Nelson Thornes Experiments and Exercises in Basic Chemistry (5th Edition) by S. Murov & B. Stedjee, published by John Wiley Chemical Ideas (Salters Advanced Chemistry) by G. Burton, published by Heinemann ILPAC Advanced Practical Chemistry (2nd edition) by A. Lainchbury, J. Stephens, A. Thompson, published by John Murray These titles represent some of the texts available at the time of printing this booklet. Teachers are encouraged to choose texts for class use which they feel will be of interest to their students and will support their own teaching style. Many publishers are also producing videos and software appropriate for A-level Chemistry students.

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