35th International Chemistry Olympiad, Athens, Greece, 5-14 July 2003

Syllabus

Last revision: July 2002

1.The atom
1.1.Introduction
1.1.1.Counting of nucleons1
1.1.2.Isotopes1
1.2.The hydrogen atom
1.2.1.Concept of energy levels1
1.2.2.Shape of s-orbitals1
1.2.3.(7.5) Shape and orientation of p-orbitals1
1.2.4.(7.6) Shape and orientation of d-orbitals3
1.2.5.(7.3) Understanding the simplest Schrödinger equation3
1.2.6.(7.2) Square of the wave function and probability3
1.2.7.(7.4) Quantum numbers (n, l, ml)3
1.3.Radioactivity
1.3.1.Types of radioactivity1
1.3.2.Radioactive decay1
1.3.3.Nuclear reactions2
2.Chemical bonding
2.1.VSEPR - Simple molecular structures with
2.1.1.no more than four electron pairs about central atom1
2.1.2.with central atom exceeding the "octet rule"3
2.2.Delocalization and resonance3
2.3.Hybrid orbital theory3
2.4.Molecular orbital theory
2.4.1.(7.7) molecular orbital diagram (H2 molecule)3
2.4.2.(7.8) molecular orbital diagram (N2 and O2 molecules)3
2.4.3.(7.9) bond orders in O2, O2-, O2+3
2.4.4.(7.10) unpaired electrons and paramagnetism3
3.Chemical calculations
3.1.1.(1.6.1) Balancing equations1
3.1.2.(1.6.2) Stoichiometric calculations1
3.1.3.(1.6.3) Mass and volume relations (including density)1
3.1.4.(1.6.4) Empirical fomula1
3.1.5.(1.6.5) Avogadro's number1
3.1.6.(1.6.6) Concentration calculations1
4.Periodic trends
4.1.Electron configuration
4.1.1.(1.1.4) Pauli exclusion principle1
4.1.2.(1.1.5) Hund's Rule1
4.1.3.(1.1.1) Main group elements1
4.1.4.(1.1.2) Transition metal elements1
4.1.5.(1.1.3) Lanthanide and actinide metals3
4.2.(1.2.1) Electronegativity1
4.3.(1.2.2) Electron affinity2
4.4.(1.2.3) First ionization energy1
4.5.(1.2.4) Atomic size1
4.6.(1.2.5) Ion size1
4.7.(1.2.6) Highest oxidation number1
5.Inorganic Chemistry
5.1.Introduction
5.1.1.Trends in physical properties of elements (Main groups)
5.1.1.1.(1.3.1) melting point1
5.1.1.2.(1.3.2) boiling point1
5.1.1.3.(1.3.3) metal character1
5.1.1.4.(1.3.4) magnetic properties3
5.1.1.5.(1.3.7) electrical conductivity2
5.1.2.(1.5.1) Oxidation number1
5.1.3.Nomenclature1
5.1.3.1. (1.5.2) main group compounds1
5.1.3.2.(1.5.3) transition metal compounds1
5.1.3.3.(1.5.4) simple metal complexes3
5.2.Groups 1 and 2
5.2.1.(1.9.2) Trend in reactivity of (heavy elements more reactive)1
5.2.2.Products of reaction with
5.2.2.1.(1.9.1.1) water1
5.2.2.2.halogens1
5.2.2.3.(1.9.9.3) oxygen2
5.2.3.Basicity of oxides1
5.2.4.(1.10.2) Properties of hydrides3
5.2.5.Other compounds, properties and oxidation states3
5.3.Groups 13 - 18 and Hydrogen
5.3.1.Binary molecular compounds of hydrogen
5.3.1.1.(1.10.1) Formulae1
5.3.1.2.(1.10.3) Acid-base properties of CH4, NH3, H2O, H2S1
5.3.1.3.Other properties3
5.3.2.Group 13
5.3.2.1.(1.10.14) The oxidation state of boron and aluminium in their oxides and chlorides is +31
5.3.2.2.The acid-base properties of aluminium oxide/hydroxide2
5.3.2.3.Reaction of boron(III) oxide with water3
5.3.2.4.Reaction of boron(III) chloride with water3
5.3.2.5.Other compounds, properties and oxidation states3
5.3.3.Group 14
5.3.3.1.(1.10.14) The oxidation state of Si in its chloride and oxide is +41
5.3.3.2.(1.10.16) The +2 and +4 oxidation states of carbon tin and lead, the acid-base and redox properties of the oxides and chlorides2
5.3.3.3.Other compounds, properties and oxidation states3
5.3.4.Group 15
5.3.4.1.(1.10.17) Phosphorus(+5) oxide and chloride, and their reaction with water2
5.3.4.2.Phosphorus(+3) oxide and chloride, and their reaction with water2
5.3.4.3.Oxides of nitrogen
a(1.10.4) Reaction of NO to form NO21
b(1.10.5) Dimerization of NO21
c(1.10.6) Reaction of NO2 with water1
5.3.4.4.Redox properties of
a(1.10.8) HNO3 and nitrates1
b(1.10.9 and 7) HNO2 and NH2NH23
5.3.4.5.(1.10.16) Bi(+5) and Bi(+3)3
5.3.4.6.Other compounds, properties and oxidation states3
5.3.5.Group 16
5.3.5.1.(1.10.14) The +4 and +6 oxidation states of sulfur, reaction of their oxides with water, properties of their acids1
5.3.5.2.(1.10.12) Reaction of thiosulfate anion with I23
5.3.5.3.Other compounds, properties and oxidation states3
5.3.6.Group 17 (Halogens)
5.3.6.1.(1.10.19) Reactivity and oxidant strength decreases from F2 to I21
5.3.6.2.Acid-base properties of the hydrogen halides1
5.3.6.3.(1.10.14) The oxidation state of fluorine in its compounds is -11
5.3.6.4.(1.10.14) The -1, +1, +3, +5, +7 oxidation states of chlorine1
5.3.6.5.Mononuclear oxoanions of chlorine2
5.3.6.6.(1.10.18) Reactions of halogens with water3
5.3.6.7.(1.10.14) Reaction of Cl2O and Cl2O7 with water3
5.3.6.8.Other compounds, properties and oxidation states3
5.3.7.(1.12.3) Group 183
5.4.Transition elements
5.4.1.(1.11.1) Common oxidation states of common transition metals1
Cr(+2), Cr(+3) Mn(+2), Mn(+4), Mn(+7) Ag(+1)
Fe(+2), Fe(+3) Co(+2) Zn(+2)
Hg(+1), Hg(+2) Cu(+1), Cu(+2) Ni(+2)
5.4.2. (1.11.2) Colours of ions listed above in aqueous solution2
5.4.3.(1.11.4) Insolubility of Ag, Hg and Cu don't in HCl2
5.4.4.(1.11.5) M2+ arising by dissolution of the other metals in HCl2
5.4.5.(1.11.7) Cr(OH)3 and Zn(OH)2 are amphoteric and the other +2 oxides/hydroxides of the metals listed above are basic2
5.4.6.(1.11.8) MnO4- and Cr2O72- are strong oxidants in acid solution1
5.4.7.(1.11.9) pH dependence of products of MnO4- acting as oxidant2
5.4.8.(1.11.10??) Interconversion between CrO42- and Cr2O72-3
5.4.9.Other compounds, properties and oxidation states3
5.5.(1.12.2) Lanthanides and actinides3
5.6.Coordination chemistry including stereochemistry
5.6.1.(6.2) Definition of coordination number1
5.6.2.(6.1) Writing equations for complexation reactions given all formulae1
5.6.3.Formulae of common complex ions
5.6.3.1.Ag(NH3)2+1
5.6.3.2.Ag(S2O3)22-3
5.6.3.3.FeSCN2+3
5.6.3.4.Cu(NH3)42+1
5.6.3.5.Other complex ions3
5.6.4.(6.5) Ligand field theory (eg and t2g terms, high and low spin)3
5.6.5.Stereochemistry
5.6.5.1.(6.7) cis and trans3
5.6.5.2.enantiomers3
5.7.Selected industrial processes
5.7.1.(1.12.1) Preparation of H2SO41
5.7.2.(1.12.1) Preparation of NH31
5.7.3.(1.12.1) Preparation of Na2CO32
5.7.4.(1.12.1) Preparation of Cl2 and NaOH2
5.7.5.Preparation of HNO32
6.Physical chemistry
6.1.Gases
6.1.1.(2.7.1) Ideal gas law1
6.1.2.(2.7.2) van der Waal's gas law3
6.1.3.(2.7.3) definition of partial pressure2
6.1.4.Dalton's Law3
6.2.Thermodynamics
6.2.1.First Law
6.2.1.1.(2.5.1) Concept of system and surroundings2
6.2.1.2.(2.5.2) Energy, heat and work2
6.2.2.Enthalpy
6.2.2.1.(2.5.3) Relationship between internal energy and enthalpy3
6.2.2.2.(2.5.4) Definition of heat capacity2
6.2.2.3.(2.5.5) Difference between Cp and Cv (ideal gas only)3
6.2.2.4.(2.5.6) That enthalpy is a state property (Hess's Law)2
6.2.2.5.(2.5.7) Born-Haber cycle for ionic compounds3
6.2.2.6.(2.5.9) Use of standard formation enthalpies2
6.2.2.7.(2.5.10) Enthalpies of solution and solvation3
6.2.2.8.(2.5.11) Bond enthalpies (definition and use)2
6.2.3.Second Law (Entropy and Free Energy)
6.2.3.1.(2.6.1) Entropy definition (dq/T)3
6.2.3.2.(2.6.2) Entropy and disorder2
6.2.3.3.(2.6.3) Entropy definition (S = k ln W)3
6.2.3.4.(2.6.4) Free energy definition (DG = DH - TDS)3
6.2.3.5.(2.6.5) Using DG to predict direction of natural change3
6.2.3.6.(2.1.5) Relationship of DG0 and equilibrium constant K3
6.3.Equilibrium
6.3.1.Acid-base
6.3.1.1.(2.2.1) Arrhenius definitions of acids and bases1
6.3.1.2.(2.2.2) Brønsted-Lowry definitions,1
6.3.1.3.(2.2.2) conjugate acids and bases1
6.3.1.4.(2.2.3) pH definition1
6.3.1.5.(2.2.4) Kw definition1
6.3.1.6.(2.2.5) Ka as a measure of acid and base strength1
6.3.1.7.(2.2.6) Acidity or basicity of ions1
6.3.1.8.(2.2.9) Calculation of pH from pKa(weak acid)1
6.3.1.9.(5.4) Calculation of pH of a simple buffer solution2
6.3.2.Gas phase
6.3.2.1.(2.1.4) Equilibrium constant in partial pressures3
6.3.2.2.(2.1.3) Relating Kp and Kc3
6.3.3.Solubility
6.3.3.1.(2.2.7) Solubility constant (product) definition (Ks)2
6.3.3.2.(2.2.8) Calculation of solubility in water from Ks2
6.3.4.Compleximetric
6.3.4.1.(6.4) Complex formation constant (definition)3
6.3.4.2.Problems involving compleximetric equilibria3
6.3.4.3.(7.12) Lewis acids and bases3
6.3.4.4.(7.13) Hard and soft Lewis acids and bases3
6.3.5.Phase
6.3.5.1.(2.7.4) Temperature dependence of vapour pressure3
6.3.5.2.(2.7.5) Clausius-Clapeyron equation3
6.3.5.3.Single component phase diagrams
a(2.7.6) triple point3
b(2.7.7) critical point)3
6.3.5.4.liquid-vapour system
a(2.7.9) ideal and nonideal systems3
b(2.7.8) diagram3
c(2.7.9) use in fractional distillation3
6.3.5.5.(2.7.11) Henry's Law3
6.3.5.6.(2.7.12) Raoult's Law3
6.3.5.7.(2.7.13) Deviation from Raoult's Law3
6.3.5.8.(2.7.14) Boiling point elevation3
6.3.5.9.(2.7.15) Freezing point depression3
6.3.5.10.(2.7.16) Osmotic pressure3
6.3.5.11.(2.7.17) Partition coefficient3
6.3.5.12.(2.7.18) Solvent extraction3
6.3.6.Multiple
6.3.6.1.(2.2.11) Calculation of pH for multiprotic acids3
6.3.6.2.(2.2.12) Calculation of pH for weak acid mixtures3
6.4.Electrochemistry
6.4.1.(2.3.1) Electromotive force (definition)1
6.4.2.(2.3.2) First kind electrodes1
6.4.3.(2.3.3) Standard electrode potential1
6.4.4.(2.3.4) Nernst equation3
6.4.5.(2.3.5) Second kind electrodes3
6.4.6.(2.3.6) Relationship between DG and electromotive force3
7.Chemical kinetics (Homogeneous reactions)
7.1.Introduction
7.1.1.(2.4.1) Factors affecting reaction rate1
7.1.2.(2.4.15) Reaction coordinates and the basic idea of a transition state1
7.2.Rate law
7.2.1.(2.4.2) Differential rate law2
7.2.2.(2.4.4) Concept of reaction order2
7.2.3.(2.4.3) Rate constant definition2
7.2.4.First order reactions
7.2.4.1.(2.4.5) Dependence of concentration on time3
7.2.4.2.(2.4.6) Concept of half life3
7.2.4.3.(2.4.7) Relationship between half life and rate constant3
7.2.4.4.(2.4.11) Calculation of first order rate constant from
aDifferential rate law3
bIntegrated rate law3
7.2.4.5.(2.4.12) Rate constant for second and third order reactions3
7.3.Reaction mechanisms
7.3.1.(2.4.9) Concept of molecularity3
7.3.2.(2.4.8) Rate-determining step3
7.3.3.(2.4.14) Basic concepts of collision theory3
7.3.4.(2.4.16) Opposing parallel and consecutive reactions3
7.3.5.Arrhenius's law
7.3.5.1.(2.4.10) Definition of activation energy3
7.3.5.2.(2.4.13) Calculation of activation energy3
8.Spectroscopy
8.1. UV/visible
8.1.1.(8.1.1) Identification of aromatic compound3
8.1.2.(8.1.2) Identification of chromophore3
8.1.3.(3.11.10) Dyes: colour vs structure3
8.1.4.(5.9) Beer's Law3
8.2.Infrared
8.2.1.(8.3.1) Interpretation using a table of frequencies3
8.2.2.(8.3.2) Recognition of hydrogen bonds3
8.3.x-Ray
8.3.1.(8.5.1) Bragg's Law3
8.3.2.Concept of
8.3.2.1.(8.5.3) coordination number3
8.3.2.2.(8.5.1) unit cell3
8.3.3.Solid structures
8.3.3.1.(8.5.5) NaCl3
8.3.3.2.(8.5.6) CsCl3
8.3.3.3.(8.5.7) metals3
8.4.NMR
8.4.1.General Concepts
8.4.1.1.(8.4.2.) chemical shift3
8.4.1.2.(8.4.2) spin-spin coupling and coupling constants3
8.4.1.3.integration3
8.4.2.(8.4.1) Interpretation of a simple 1H spectrum (like ethanol)3
8.4.3.(8.4.4) Identification of o- and p-disubstituted benzene3
8.4.4.(8.4.5 +) Interpretation of simple spectra of 13C (proton decoupled) and other spin ½ nuclei3
8.5.Mass spectrometry
8.5.1.1. (8.1.1) Recognition of molecular ion3
8.5.1.2.(8.1.2) Recognition of fragments with the help of a table3
8.5.1.3.(8.2.3) Recognition of typical isotope distribution3
9.Organic Chemistry
9.1.Introduction
9.1.1.(3.1.1) Alkane naming (IUPAC)1
9.1.2.Trends in boiling points of
9.1.2.1.(3.1.3) alkanes with structure1
9.1.2.2.(3.7.1) alcohols vs ethers due to hydrogen-bonding1
9.1.3.(3.3.1, 3.4.1) Geometry at singly, doubly, and triply bonded carbon1
9.1.4.Identification of common functional groups1
9.1.5.Isomerism of alkenes
9.1.5.1.(3.3.2) cis-trans1
9.1.5.2.(3.3.2) E/Z3
9.1.6.Enantiomers
9.1.6.1.(3.10.3.14) Optical activity2
9.1.6.2.(3.10.3.14) R/S nomenclature3
9.2.Reactivity
9.2.1.Alkanes
9.2.1.1.reaction with halogens
a(3.1.4.1) products1
b(3.1.4.2) free radical mechanism (initiation, termination)2
9.2.1.2.Cycloalkanes
a(3.2.1) names2
b(3.2.2) Strain in small rings3
c(3.2.3) chair/boat conformations of cyclohexane3
9.2.2.Alkenes
9.2.2.1. (3.3.3.1) Products from Br2, HBr and H2O/H+1
9.2.2.2.(3.3.3.2) Markownikoff's rule2
9.2.2.3.(3.3.3.3) Mechanism involving carbocation intermediates3
9.2.2.4.(3.3.3.4) Relative stability of carbocations3
9.2.2.5.(3.3.3.5) 1,4 addition to dienes3
9.2.3.Alkynes
9.2.3.1.(3.4.2) Acidity relative to alkenes3
9.2.3.2.(3.4.3) Differences in chemical properties from alkenes
9.2.4.Benzene
9.2.4.1.(3.5.1) formula1
9.2.4.2.(3.5.2 and 3) stabilization by resonance1
9.2.4.3.electrophilic substitution (nitration, halogenation)
a(3.5.9) directing effect of first substituent3
b(3.5.8) effect of first substituent on reactivity3
c(3.5.10) explanation of substituent effects3
9.2.5.Halogen compounds
9.2.5.1.Nomenclature of monofunctional1
9.2.5.2.(3.6.1) Substitution reactions
agiving alcohols3
b(3.6.2) in which halogen is exchanged3
c(3.6.3) reactivity
iprimary vs secondary vs tertiary3
ii(3.6.6) aliphatic vs aromatic3
d (3.6.4) SN1 and SN2 mechanisms3
9.2.5.3.Elimination reactions2
9.2.5.4.(3.6.5) Competition of elimination and substitution2
9.2.6.Alcohols
9.2.6.1.Nomenclature of monofunctional1
9.2.6.2.(3.7.1) Comparison of acidity of alcohols and phenols2
9.2.6.3.(3.7.2) Dehydration to alkenes1
9.2.6.4.Esters with inorganic acid2
9.2.6.5.Oxidation reactions1
9.2.7.Adehydes and ketones
9.2.7.1.Nomenclature of monofunctional1
9.2.7.2.Oxidation of aldehydes1
9.2.7.3.Reduction to alcohols (LiAlH4, NaBH4)3
9.2.7.4.Keto/enol tautomerism3
9.2.7.5.Nucleophilic addition reactions with
aHCN3
bRNH2 (R = alkyl, HO, NH2)3
cenolate anions (aldol condensation)3
dalcohols to form acetals/ketals3
eGrignard reagents3
9.2.8.Carboxylic acids and their derivatives
9.2.8.1.Nomenclature of carboxylic acids and their derivatives (esters, acid halides, amides)2
9.2.8.2.Acidity strength related to inductive effects3
9.2.8.3.Preparation of carboxylic acids by hydrolysis of
aesters (including soaps)1
bamides2
cnitriles3
9.2.8.4.Reaction of carboxylic acids
awith alcohols to form esters1
bto form acid chlorides3
cto form anhydrides3
9.2.8.5.Reaction of acid chlorides to form amides3
9.2.8.6.Mechanism of esterification3
9.2.8.7.Multifunctional acids (hydroxyacids, ketoacids)3
9.2.8.8.Polycarboxylic acids3
9.2.9.Amines
9.2.9.1.Nomenclature
asimple amines1
brecognition of primary, secondary, tertiary1
9.2.9.2.Basicity
aAs a property of an amine1
bComparison of basicity of aliphatic and aromatic3
cComparison of basicity of amines and amides3
dPreparation of amines
ifrom halides3
iifrom aromatic nitro compounds3
iiifrom amides (by hydrolysis)3
9.2.9.3.Diazotization
aof aliphatic amines3
bof aromatic amines3
10.Polymers
10.1.Synthetic
10.1.1.Addition polymers
10.1.1.1.polystyrene2
10.1.1.2.polyethene1
10.1.1.3.chain mechanism of formation2
10.1.2.Condensation polymers
10.1.2.1.polyesters2
10.1.2.2.polyamides2
10.1.3.Silicones3
10.1.4.Concept of cross-linking and its affect on properties3
10.2.Natural
10.2.1.Silicates3
10.2.2.Rubber3
11.Biochemistry
11.1.Carbohydrates
11.1.1.Glucose and fructose
11.1.1.1.chain formulae1
11.1.1.2.Fischer projections2
11.1.1.3.Haworth formulae3
11.1.2.Difference between starch and cellulose2
11.1.3.Difference between a- and b- D glucose2
11.2.Fats
11.2.1.Structure of fats in relationship to properties2
11.2.2.Formula of glycerol1
11.3.Nitrogen-containing Compounds of Biological Importance
11.3.1.Amino acids
11.3.1.1.Ionic structure1
11.3.1.2.Isoelectric point3
11.3.1.3.20 amino acids (classification with structures provided)2
11.3.1.4.Separation by electrophoresis3
11.3.1.5.The peptide linkage1
11.3.2.Proteins
11.3.2.1.Primary structure1
11.3.2.2.-S-S- bridges3
11.3.2.3.Sequence analysis3
11.3.2.4.Secondary structure3
11.3.2.5.Details of a helix structure3
11.3.2.6.Tertiary structure3
11.3.2.7.Denaturation (change in pH, temperature, metals, ethanol)2
11.3.3.Nuclei Acids and Protein Synthesis
11.3.3.1.Pyrimidine and purine3
11.3.3.2.Nucleosides and nucleotides3
11.3.3.3.Formulae of pyrimidine and purine bases3
11.3.3.4.Difference between ribose and 2-deoxyribose3
11.3.3.5.Base combination CG and AT (hydrogen-bonding)3
11.3.3.6.Difference between DNA and RNA3
11.3.3.7.Difference between mRNA and tRNA3
11.4.Enzymes
11.4.1.1.General properties, active centers3
11.4.1.2.Nomenclature, kinetics, coenzymes, function of ATP3
12.Analytical chemistry
12.1.Titrations
12.1.1.acid-base
12.1.1.1.(5.2) Titration curve; pH (strong and weak acid)2
12.1.1.2.(5.1) Choice of indicators for acidimetry2
12.1.2.(5.3) Redox titration3
12.2.Qualitative analysis
12.2.1.Ions (Inorganic)
12.2.1.1.(5.5) Identification of Ag+, Ba2+, Cl-, SO42-2
12.2.1.2.Identification of other anions and cations3
12.2.2.Organic functional groups
12.2.2.1.(3.7.7) Lucas reagent (1°, 2°, 3° alcohols)3
12.2.2.2.(3.7.6) Iodoform reaction3
12.2.2.3.(3.11.4) Identification of primary, secondary, tertiary, quarternary amines in the laboratory3
12.3.(2.7.19) Chromatographic methods of separation3