NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! 1991 AL Chemistry paper I marking scheme 1.

(a) Markownikoff rule s The answer must involve the addition of acid and explain and show the correct direction of addition.

Acid; could be HI, HCl, H 2SO4, H3O+, HX but not HNO3 mark Mechanism: Correct use of arrows or H + in the first step mark Intermediate Carbonium ion (draw or write) mark Correct product mark

If wrong product e.g. but use of HX (max. mark) The mechanism is Electrophilic Addition Polymerization reaction: Reagents: can be radical R or ion either cationic polymerization (e.g. above using an acid) [OUT] or anionic polymerization - using a base e.g. KNH 2 mark [OUT] Mechanism: Correct intermediate or arrows or indicate chain initiation, propagation and termination. 1 mark Direction of addition is not important. Product: must clearly show a polymer mark Radical e.g.

Cationic e.g. [OUT] Anionic e.g. [OUT]

(b) (i) In F, the double bond is strongly polarized, no such polarization. OR

due to the electronegativity of oxygen. In E there is

The oxygen has a tendency to acquire electrons leading to in which the carbon is electron deficient. (1 mark) Hydroxylamine with N having lone electron pair is electron rich and takes part in nucleophilic addition at C. OR

(This properties of NH 2OH must be shown in some way) 1 mark Product is Me-CH=NOH (no mark for Me-CHOH-NHOH) 1 mark There are many ways to answer this question: For all the 3 marks, answer MUST explain WHY polarization difference is responsible for the difference in reactivity - answer MUST include the fact that NH2OH reacts as nucleophile or by nucleophilic addition. (ii)

1991-AL-CHEM PI - 1

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!!

(c)

(d)

There are many ways to answer this questions. Basic mark awards: Nucleophile I- [1m] Transition state [1m] Products showing substitution [1m] (e)

2. (a)(i) cathode: 2H+ + O 2 + 2eanode: H2 2H+ + 2e-

H2O

1991-AL-CHEM PI - 2

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! overall: H2 + O2 H2O 2 marks wrong coefficient - reverse labelling of cathode and anode reaction - wrong species in each reaction - wrong direction of reaction (e.g. if a single arrow) -
+ (ii) [H ] will shift equilibrium of 2H+ + O 2 + 2e- d H2O to right, and shift equilibrium of H2 d 2H+ + 2e- to left. mark each

(iii)

voltage reading increase 1 mark pressure in O2 and H2 chamber increase or [O 2] and [H2] increase mark equilibrium of H2 + O2 H2O is shifted to right and favours the discharge of battery mark

(b)(i) temp. will shift the equilibrium to the left for system X and system Y. 1 mark (ii) pressure will shift the equilibrium to the left for system X and system Y. 1 mark (iii) temp. will increase the rate of reaction of both systems, 1 mark the % increase in rate will be large for system X 1 mark (iv) different reaction paths or different reaction mechanisms is involved with the catalyst added. 2 marks (c)

1 mark for correct final answer (0.315 - 0.324) 2 marks for intermediate answers (partial pressure, partial volume, no. of mole), equations and method. (d)(i)

1 mark (ii) Outside syllabus. (iii) In CsCl, the ions are held together by strong coulombic forces and cannot be easily displaced. Because of lack of mobility of ions, conductivity is low. In iron, the iron atoms occupy the BCC sites and electrons are delocalized. Conductivity is high because electrons can move. 1 mark 3. (a) NaH(s) is an ionic compound and its reducing properties is due to the hydride anion which can undergo the reaction, H- H2 + e-, i.e. releasing electrons in an overall redox reaction. 1 mark HCl(g) does not undergo such reaction to release electron. mark HCl(g) is acidic because it is a proton donor in the presence of a base. e.g. HCl(g) + H2O(l) H3O+ (aq) + Cl-(aq). 1 mark NaH(s) is not acidic because it is not a proton donor. mark 1991-AL-CHEM PI - 3

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! (b)(i) ZnCl(s) + 4H2O(l) [Zn(OH2)4] (aq) + 2Cl (aq) 2+ + + [Zn(OH2)4] (aq) + H2O(l) [Zn(OH2)3(OH)] (aq) + H3O or ZnCl2 + H2O Zn(OH)Cl + HCl 1 mark (ii) NaHCO3(s) Na+(aq) + HCO3-(aq) HCO3 (aq) + H2O(l) H2CO3(aq) + OH (aq) 1 mark (c) NaOCl and KClO3 mark each both are strong oxidizing agents 1 mark (d) (i)
2+ -

1 mark (ii)

1 mark (e)

(f) [Cu(H2O)6] (aq) + 2NH3(aq) [Cu(H2O)4] + Cu(OH)2(s) + 2NH4 (aq) or Cu(OH)2(s) 1 mark [Cu(H2O)4]2+ + Cu(OH)2(s) + excess NH3(aq) [Cu(NH3)4]2+ 1 mark When NH3(aq) is added slowly, at first insoluble pale blue basic salt or hydroxide is formed, but these dissolve readily in excess NH 3(aq) to give deep blue solution containing tetraaminecopper(II) ion. 1 mark (g) I. II. III. 2CrO4 (aq) + 2H (aq) H2O(l) + Cr2O7 (aq) 1 mark 2+ 2+ 5C2O4 (aq) + 2MnO4 (aq) + 16H (aq) 2Mn (aq) + 10CO2(g) + 8H2O(l) 1mark 2+ + 4+ Sn + H2O2(aq) + 2H (aq) Sn (aq) + 2H2O(l) 1 mark
2+ 2-

2+

2+

(h) NH4NO3(s) is unstable and readily/easily decomposes to give large volumes of gaseous products (N 2O and H2O) and is therefore explosive. 1 mark No smoking because N2O is a supporter of combustion at elevated temperature 1 mark 4.(a) For NaNO3(s), add conc. H2SO4 and heat / add conc. H2SO4 + Cu and heat to give brown fumes of NO2 having no action on fluorescein (C20H12O5 yellowish to red in colour) impregnated paper. Add freshly prepared FeSO4 and conc. H2SO4 slowly / dropwise to give brown ring at the liquid junction. For NaBr(s), add conc. H2SO4 to give acid vapour of HBr which gives white fumes with NH 3 and reddish brown vapours of Br2 which turns fluorescein impregnated paper red. 1991-AL-CHEM PI - 4

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! or Add acidified AgNO3 solution to give pale yellow ppt which is slightly / partially / sparingly soluble in excess NH3 or which darkens in colour on exposure to sunlight. or Add HOCl solution to give orange-red colour of bromine. When the solution is shaken with CS2 / CHCl3 / CCl4, the Br2 dissolves in the organic solvent leaving a colourless aqueous layer. mark for each point (b)(i) CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l) Ca(s) + 2HCl(aq) CaCl2(aq) + H2(g) 2 marks (missing or incorrect physical state - ; wrong coefficient - ; inappropriate acid e.g. H 2SO4 and HNO3 - ) Calorimeter (beaker or plastic cup, stirrer, temperature bath, insulation, electric heater) mark thermometer or thermocouple mark measuring cylinder, burette or pipette mark balance mark

(ii)

(iii) Ca(s) + C(s) + 3/2O2(g) CaCO3(s) Side reactions: 2Ca(s) + O 2(g) 2CaO(s); C(s) + O2(g) CO2(g) 2 marks for any one explanation: - extent of reaction cannot be controlled - side reactions - directly combustion of Ca can be violent - cannot react or cannot react to form CaCO 3 (1 mark only) 5.(a)(i) The reaction mixture would contain X, Y, HCl and Sn which need to be separated. 1 mark Firstly remove Sn by filtration and Y by extraction with ether. 1 mark Followed by basification with NaOH of the aqueous layer and extraction with ether 1 mark (Instead of ether extraction, distillation / steam distillation may be used.) Evaporation of ether gives X. mark (ii) relative molecular mass of X, C 7H9N = 107 relative molecular mass of Y, C 7H7NO2 = 137

2 marks (b)

1991-AL-CHEM PI - 5

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! Chemistry essay marking scheme 1991 - IC(1) (A) Chemical knowledge: max. 10m [Core marks: each point 1m. max. 6m] 1. Chemical bonding is a rearrangement of electrons between two atoms leading to a state of lower energy. 2. Ionic bond: - transfer of electrons from one atom to another resulting in two types of ions with opposite charges (positive & negative) held together (or illustration by "dot & cross" diagrams). 3. Covalent bond: - formed by the sharing of electrons / overlapping of atomic orbitals between two atoms (or illustration by "dot & cross" diagrams) 4. Pure ionic and covalent bonds are only two extreme cases of a range of intermediate possibilities / there is no 100% pure covalent bond. 5. Dative (covalent) bond: - one which has the bond pair coming from a particular atom (or illustration by suitable diagrams). 6. Metallic bond: - an ordered array of positive ions surrounded by a sea of electrons / electrostatic attraction between positive cores and delocalized electrons (or illustrated by diagrams). [Optional marks: each point 1/2m, max. 4m] 1. Strength of (covalent) bond depends on - size of atom (bond strength increases for smaller atoms) - no. of valence electrons involved in the bond / bonded electrons (larger no. of e-s strengthens the bond) 2. Ionic bond - pointing out which types of elements have high tendency to form ionic bonds (elements with great electronegativity difference, etc.) - formation of ions is to acquire a noble gas structure (octet) - electrostatic attraction between +ve and -ve ions - deviation from ideal ionic bond due to polarization of ions or as illustrated by difference in the values of calculated and measured lattice energies for some compound such as ZnS & AgCl. 3. Covalent bond - multiple bonds or suitable examples - delocalization of electrons / resonance - how polar covalent bonds may arise - giant covalent structure versus discrete molecules - formation from elements of similar electronegativities 4. Dative bond - a special type of covalent bond - suitable example (e.g. H 3N AlCl3) (B) Organization: Max. 6m e.g. - no contradictory concepts - no irrelevant materials - ordered sequence in the essay in general: 6 - 5 (if knowledge > 7) 4 - 3 average 2 - 1 weak (C) Presentation: max. 4m e.g. - proper English - suitable examples - suitable illustrations - headings & sections 1991 - IC (2) Nitrogen A. OXIDES 1. Types: N 2O, NO, NO2, N2O4, N2O5 [1/2m + 1/2m] 2. Formation: [1/2m + 1/2m] e.g. NH4NO3 N2O + H2O 3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO 1991-AL-CHEM PI - 6

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! Cu + 4HNO3 Cu(NO3)2 + 2H2O + 2NO2 4HNO3 + P4O10 2N2O5 + 4HPO3 3. Structure: [1/2m + 1/2m]

4. Properties: [1/2m + 1/2m] a. Neutral oxides (N 2O, NO) b. Acidic oxides 2NO2 + H2O --> HNO2 + HNO3 c. Oxidizing action of NO 2 (with example) 5. Social relevance: a. Uses: N2O as anaethetics (not common now) [1/2m] b. Pollution: acidic oxides of nitrogen cause acid rain / affect human respiratory function [1/2m] B. OXOACIDS 1. Types: (H2N2O2), HNO2, HNO3 [1/2m + 1/2m] 2. Preparation: [1m] Nitric(V) acid from ammonia (must have some description / equation related to the process) 3. Structure [1/2m]

4. Properties: [1/2m x 3] a. Acid - reactions of H + b. Oxidizing action (with suitable example) e.g. 4HNO3 + C 2H2O + 4NO2 + CO2 c. Reducing action (with suitable example) + 2+ e.g. 5NO2 + 6H 2MnO4 5NO3 + 2Mn + 3H2O d. HNO3 as a nitrating agent (with example) 5. Uses: [1/2m + 1/2m] HNO3 in making nitrogenous fertilizers / explosives. Sulphur A. OXIDES 1. Types: (S2O), SO2, SO3 [1/2m + 1/2m] 2. Formation: [1/2m + 1/2m] e.g. S + O2 SO2 2SO2 + O2 2SO3 S2O is produced by passing a glow discharge through SO 2 3. Structure: [1/2m + 1/2m]

4. Properties: [1/2m + 1/2m] a. Acidic oxides SO2 + H2O H2SO3 SO3 + H2O H2SO4 b. Reducing action of SO 2 (with example) 5. Social relevance: a. Uses: SO2 for making H2SO4 b. Pollution: oxides of sulphur cause acid rain / affect human respiratory function [1/2m] B. OXOACIDS 1991-AL-CHEM PI - 7

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! 1. Types: H 2SO3, H2SO4, H2S2O3, H2S2O6.H2S2O7, H2S2O8 2. Preparation: [2m] Sulphuric(VI) acid by contact process (must have some description / equations related to the process) 3. Structure: [1/2m]

4. Properties: [1/2m x 3] + a. Acid - reaction of H b. Oxidizing action (with suitable example) e.g. 2H2SO4 + Cu CuSO4 + SO2 + 2H2O c. Reducing action (with suitable example) e.g. 5SO32- + 6H+ + 2MnO4- 2Mn2+ + 5SO42- + 3H2O d. H2SO4 as a sulphonating agent (with example) e. Dehydrating property of H2SO4 (with example) 5. Uses: [1/2m + 1/2m] H2SO4 in making fertilizers/dyes/white paint pigments/etc. Organization (6 marks) Good 5-6 Average 3-4 Poor 1-2 Presentation (4 marks) 4 2-3 1

1991 IC(3) GENERAL GUIDANCE The most important point about awarding marks for the essay is that all the following points are merely rough guidelines. After allocating marks REASSESS THE MARK WITH AN IMPRESSION MARK. This is the most important mark. ORGANIZATION [(6M) NORMAL] - [(5M) if exceptionally good C.K.] I suggest that you look out for and mark the following points: - Is the essay organized logically? - This should take the form of sub-headings or paragraphs. The following are expected - Defining the types of stereoisomerism - Their origins - of each type - Properties of each type of stereoisomerism - chemical & physical - Other relevant chemistry, e.g. the synthesis of each type ... (4m) Errors in chemistry and logic showing disorganization These can take several forms: errors in structures errors in concepts errors in arrows/reactions, etc. If no errors .................................(2m) Note also that a student who can hardly write anything, can't get the full 6 marks! The 6 marks assumes a full essay, so marking accordingly Proportionately w.r.t. Chem. Knowledge, as shown below: Max. 6 marks with C.K. 10/10 Max. 3 marks with C.K. 5/10 MARKING OF ORGANIZATION IS TO BE BY DEDUCTION FROM THE MAXIMUM PRESENTATION [(4M) NORMAL] Scripts with very little useful material can't hope to get the full 4 marks, therefore award proportionately - suggest: for Chem. Knowledge 8 - 10 award up to 4 6 - 7 max. is 3 4 - 5 max. is 2 etc. The presentation mark to be awarded for "ability to express clearly" - this is measured by - EQUATIONS / DIAGRAMS (1.5m) which should adequately describe the headings 1991-AL-CHEM PI - 8

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! - ENGLISH (2.5m) Look out for the following: - Essays must not be in note form - Repeated minor errors in English (-1m) - Repeated occasions when MEANING IS LOST due to poor choice of words or incorrect words being used or ambiguous statements - Insufficient use of English .... no English - no marks Note: This is not a neatness mark. RULE: final mark = 2 x CK marks CHEMCIAL KNOWLEDGE [(10M) NORMAL] - [(12M) for exceptionally good CK] (i) If exceptionally good, more than 10 marks can be awarded a 'bonus' of 2 can be given with less expected for organisation and presentation. (ii) Award marks to any relevant material even if not included in marking scheme - use your discretion and judgment (Discuss examples at markers meeting) A good essay beginning with an INTRODUCTION defining stereoisomerism, and putting it into perspective with respect to other types of isomerism. This is not really CK and is part of the Organisation mark. A GOOD ESSAY WILL CONTAIN A VARIETY OF INFORAMATION THEREFORE DO NOT GIVE TOO MANY MARKS FOR PARTICULAR ASPECT THERE ARE MANY RELEVANT TYPES OF INFORMATION WHICH IS EXPECTED WHILST THIS ESSAY IS OBVIOUSLY DIVIDED INTO TWO MORE OR LESS EQUALLING DEMANDING PARTS VIZ.: GEOMETRICAL AND OPTICAL ISOMERISM. WE SHOULD NOT NECESSARILY AWARD 5 MARKS TO EACH PART. SINCE BOTH PARTS ARE EXPECTED TO BE INCLUDED. ANY STUDENT WRITING ON ONLY ONE PART SHOULD BE HEAVILY PENALIZED. I SUGGEST A MAX. 6M FOR EACH OF THESE 2 MAIN DIVISIONS. Most candidates seem to have more CK for optical than geometrical isomerism. Therefore in most cases it would be highly appropriate to mark these out of a maximum of 6 and 4 respectively. GENERAL RULE FOR MARKS: 1/2m for RELEVANT STATEMENT WITH BACKUP EVIDENCE (a) For the case of ALKENES CORE MARKS (3.5m) 2 Geometrical isomerism: due to restricted rotation of the double bond formed by sp hybridization [1/2m] Defining of cis and trans or E/Z (using priority rule based on atomic number - not expected) [1/2m] Diagram, correctly labelled for cis & trans

Chemical properties: (max. 1m) (more than a one line statement expected, as well as example(s)) chemical properties - similar but not identical. chemical reactions can also be expected The reactions are electrophilic addition and can be exemplified with addition of HX, Br2 etc. Physical properties: (max. 1m) (more than a one line statement is expected - answer should include an example.) Physical properties - different, e.g. m.p., solubility, if R & R' are non-chiral, the isomers are optically inactive For above 2 properties a good answer should include a generalized statement and not a statement referring to ONE example. e.g. from a reaction such as anhydride formation (from cis-butenedioic acid), the answer should also state that all chemical reactions WILL show some differences between isomers. Marks of up to 5 (or even 6) can be made from further chemical reactions 1991-AL-CHEM PI - 9

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! - Separation by b.p. or by crystallization - Preparation of geometrical isomers: alkene synthesis e.g. dehydration of alcohols, aldol condensation, etc. (b) For saturated carbon CORE MARKS (3.5m) Optical isomerism Due to sp3 tetrahedral arrangement of bonds, 4 different groups can give rise to non-identical isomers.

Nomenclature: (+), (-), d, l etc. Chemistry: They have identical chemical reactions (with achiral reagents) Reactions are not very important as a result. More than one line statement is expected. All physical properties are identical except reaction to plane polarized light, one + other -. FURTHER MARKS (UP TO 2.5m) EXPECTED FROM: (1) Further examples not involving a single chiral C e.g. optical activity due to restricted rotation,

(2) Separation: by hand picking crystals or forming a diastereoisomer (different physical properties, e.g. solubility) (3) Preparation: an example, e.g. Strecker synthesis

(4) A discussion on DIASTERISOMERISM with examples and properties MESO-ISOMERISM with examples and properties (5) Conformation of molecules: This is stereoisomerism which is dynamic and/or depends on stability. Whilst not expected in an answer. It IS stereoisomerism in its widest sense and deserves a max. of 1 mark if in some detail e.g. example with diagrams of say boat/chair forms, and properties; or eclipsed/staggered conformers which obviously have some free rotation. It would seem that assessing the right mark is difficult especially "what is worth 3.5 core marks." The principle of overall impression assessment helped by such questions as: - in the case of say 50% mark for CK: "do we expect 2 times the amount of material present in the script?" for example, is not working too well. I suggest that we use a system of ticks ON for EVERY CORRECT FACT OR PIECE OF INFORMATION - AND EACH PAIR OF TICKS IS 1/2 MARK particularly for making the CORE PART. This is in line with the rule of 1/2 mark for statement + backup evidence. Example: Thus a tick for each of: geometrical isomerism; cis; trans; diagram of cis; diagram of trans; a definition of cis/trans; these compounds have restricted rotation; present in alkenes; different physical properties; reaction of cis-dioic acid to form anhydride (at least two facts would probably be given and thus 2 ticks); comment on trans-dioic acid (maybe 2 ticks). Also for: Optical isomerism; non-superimposable; 4 different groups on a carbon atom; definition of chiral centre; 1991-AL-CHEM PI - 10

NOT FOR SELLING, SELLING FOR THIS IS STRICTLY PROHIBITED!!!! diagram of a chiral centre; diagram of its mirror image; mirror image; 3 correct formulae of diastereoisomers and meso form (3 ticks); definition of each (3 ticks) with Correct assignment; etc. CK MARK IS OBTAINED BY TOTAL NO OF TICKS DIVIDED BY 4 PLEASE NOTE THE FOLLOWING 1. Many answers have very poor diagrams of chiral C and mirror;

2. Stereoisomerism of N compounds (NOT carbon compound) worth 0 mark 3. m.p.'s of enatiomers are the same, but racemates are not the same as that of enantiomer - a small point but has appeared in some students' scripts 4. Cis and trans forms can be interconverted by UV light and by heating to a high temperature.

1991-AL-CHEM PI - 11

Not for selling, selling for this is strictly prohibited!!!! 1991 A-level chemistry paper II marking scheme 1.(a)(i) particle are bare helium nuclei with 2 positive charges and 4 units of mass. It can be stopped easily by a thin sheet of aluminium [2m] particle is fast moving electrons with 1 negative charge and negligible mass. It can be stopped by several millimeter of lead. [1m] (ii) (238 - 206) / 4 = 8 82 + 8(2) - 92 = 6 The decay constant k can be calculated from the half-life: 9 ln (2/1) = k(4.51 x 10 ) 9 -10 -1 k = ln 2 / 4.51 x 10 = 1.5369 x 10 year [1m] Let the amount of U in the mineral be x, since all Pb came from U, The amount of U at the beginning = amount of Pb + U at present = 0.231x + x = 1.231x [1m] The age of the mineral is equal to the time taken from I0 = 1.231x to I=x -10 ln (1.231x/x) = (1.5369 x 10 )t [1m] 9 t = 1.35 x 10 year [1m] (b)(i) We need to have: Na(s) + 1/2Cl2(g) NaCl(s) (ii) It is because ethanoic acid is a weak acid and is only slightly ionized [1m] and the difference is due to enthalpy change for ionization: + -1 CH3COOH(aq) CH3COO (aq) + H (aq) H = + 2.1 kJmol [1m] (iii The dissolving of a salt in water is a case of an enthalpy change accompanying a chemical process. The first process requires an input of energy to break the lattice (- lattice energy or - Lattice). The second process involves the release of energy when new bonds are made between ions and water (Hydration). In the case of NaCl, the first process is more exothermic than the second process OR the magnitude of lattice energy is larger than that of the enthalpy of hydration. [2m] (iii) 2.(a) CH4 < C2H6 < C2H5Cl [1m] Polarizability (ease of distortion of e cloud) increase with increasing size (or no. of e ) Cl > C > H [1m] C2H5Cl has one highly polarizable Cl atom and has a permanent dipole moment, while C2H6 is less polarizable than C2H5Cl and has no permanent dipole moment. Thus C2H5Cl is expected to have stronger intermolecular forces than C2H6, and a higher boiling point. [1m] The AX4 type, tetrahedral CH4 molecule has no permanent dipole moment, none of its atom has a very large polarizability, none of its atom has a very large polarizability, and it is expected to have the lowest boiling point. [1m] 2(b)(i) CrO4 + 4H2O + 3e Cr(OH)4 + 4OH .........(1) [1m] 22S2O3 + 10OH 2SO4 + 5H2O + 8e .........(2) [1m] Overall equation: by 8 x (1) + 3 x (2) 2228CrO4 + 3S2O3 + 17H2O 6SO4 + 8Cr(OH)4 + 2OH [1m] (ii) No. of moles of S2O320 = 0.2 x 40 x 10-3 22Since 3 moles of S2O3 = 8 moles of CrO4 [1m] 2-3 no. of moles of CrO4 = (0.2 x 40 x 10 ) x (8/3) -3 3 vol. of Na2CrO4 = (0.2 x 40 x 10 )(8/3)(1/0.50) = 0.04267 dm 3 = 42.67 cm [1m] (c)(i) Solution S: + Since MOH M + OH Initial 0.1 0 0 At eqm. 0.1 x x x -5 2 Kb = 2 x 10 = x / (0.10 - x) , assuming (0.1 - x) = 0.1 -5 0.5 -3 x = [(2 x 10 )(0.1)] = 1.414 x 10 M [1m] -3 pOH = - log [1.414 x 10 ] = 2.85 pH = 14 - 2.85 = 11.15 [1m] MOH Initial 0.1 At eqm. 0.1 x -5 Kb = 2 x 10 = (0.50 + x)x / (0.10 -x) -5 Assuming x << 0.10, 2 x 10 =(0.50/0.10)x M 0.5 0.5+x
+

OH 0 x

1991 AL CHEM PII page 1

Not for selling, selling for this is strictly prohibited!!!! -5 x = (2 x 10 ) / 5 -6 = 4 x 10 [1m] -6 pOH = - log [4 x 10 ] = 5.40 pH = 14 - 5.40 = 8.60 [1m] (ii)

Assuming NO vol. change due to addition of acid -5 (0.51 + x)(x) / (0.09 - x) = 2 x 10 -5 -6 x = (2 x 10 )(0.09/0.51) = 3.53 x 10 -6 pOH = - log (3.53 x 10 ) = 5.45 pH = 14 - 5.45 = 8.55 [3m] * Solution T can resist the change in pH to a greater extent than solution S, it is generally known as a buffer. [1m] 3.(a)(i) Taking natural logarithm on the given expression: ln k = ln A - Ea / RT [1m] ln (k2 / k1) = Ea / R (1 / T1 - 1 / T2) [1m] T1 = 273 + 370 = 643 K T2 = 273 + 470 = 743 K -2 -4 ln (4.05 x 10 / 3.91 x 10 ) = Ea / 8.31 ( 1 / 643 - 1 / 743) [1m] -1 Ea = 184.2 kJ mol [1m] (ii) T1 = 643 K; T2 = 273 + 450 = 723 K -4 5 ln (k723K / 3.91 x 10 ) = (1.842 x 10 / 8.31)(1 / 643 - 1 / 723) [1m] -2 -1 3 -1 k723K = 1.77 x 10 mol dm s [1m] (b)(i) If a volatile solute is added to a solvent, the total vapour pressure will be the sum of the partial pressures of the solute and the solvent. If the vapour pressure of the solute is higher than the vapour pressure of the solvent, the total vapour pressure is higher and vice versa. [3m] (ii) CH3OH(A) C2H5OH(B) RMM 32 46 No. of moles 32/(12+4+16)=1 184/(24+6+16) = 4 Mole fraction 1/(1+4) = 0.2 4/(1+4)=0.8 [1m] By Raoult's law PA = XAPA [1/2m] PB = XBPB [1/2m] PA = (0.2)(89.2) = 17.84 mmHg [1/2m] PB = (0.8)(44.6) = 35.68 mmHg [1/2m] Total vapour pressure = 17.84 + 35.68 = 53.542 mmHg [1/2m] composition of CH3OH in the vapour = 17.84/53.52 = 1/3 composition of C2H5OH in the vapour = 35.68/53.52 = 2/3 [1/2m] i.e. composition of CH3OH : C2H5OH in the vapour = (1/3) : (2/3) = 1 : 2 (c) 1s-orbital is spherical (NOT circular) [1m] the variation is exactly the same in any direction from the nucleus / there is no angular dependence / accept diagram (a)

The most probable distance of the electron from the nucleus of the H atom is equal to the Bohr's radius, a0. [1m] The electron density is zero at the nucleus and at infinite distance from the nucleus / accept diagram 1991 AL CHEM PII page 2

Not for selling, selling for this is strictly prohibited!!!! (b) [1m] 4.(a)(i) Elements in same group (having same no. of outermost shell electrons) have similar chemical properties. [1m] Properties recur after an interval (=period) [1m] OR Element's properties are periodic functions *1m of atomic number. *1m (ii)

Graphs show maxima for m.p. at Gp. IV [1m] or for b.p, at either Gp. III or Gp. IV *1m Graphs show decrease on descending Gp. III or IV [1/2m] Graphs show minima for Gp. V - VIII [1/2m] (iii)

For I.E.: [2m] Graph shows decrease for each group Graph shows 2,3,3 pattern 3 4 Explanation: 2p for N (p for 0 is not necessary) [1/2m] stability of half-filled subshell [1/2m] (b)(i) Example: NCl3 NCl3(l) + H2O(l) NH3(aq) + 3HOCl(aq)

Example: Cl2O Cl2O(g) + H2O(l) 2HOCl(aq)

1991 AL CHEM PII page 3

Not for selling, selling for this is strictly prohibited!!!!

OR 2ClO2 + H2O HClO2 + HClO3 OR Cl2O6 + H2O HClO4 + HClO3 OR Cl2O7 + H2O 2HClO4

ClO3 is the same as Cl2O6, which is a solid ClO2 + ClO4 ClO2 + H2O stable in the dark

(sunlight) 6ClO2(g) + 3H2O(l) HCl(aq) + 5HClO3(aq) Other acceptable answers: + 2ClO2(g) + 3H2O(l) 2H3O (aq) + ClO2 (aq) + ClO3 (aq) + 4ClO2(g) + 6H2O(l) 4H3O (aq) + ClO (aq) + 3ClO3 (aq) + Cl2O6(g) + 3H2O(l) ClO3 (aq) + ClO4 (aq) + 2H3O (aq) For oxygen chlorides, accept disproportionation reaction for oxidation states 2,4,6 but -1 or 7 for Cl. For ClO2 accept balanced equation for: 6ClO2 + 3H2O HCl + 5HClO3 or ClO2 + H2O stable (hydrate) [in the dark] or 2ClO2 + H2O HClO2 + HClO3 Example: S2Cl2(l) 2S2Cl2 + 2H2O 3S(s) + SO2(aq) + 4HCl(aq)

any sensible description, e.g. open book structure OR SCl2, SCl4 (not SCl6),

For S2Cl2 + H2O S + SO2 (or SO3) don't need HCl For SCl4, reasonable answer to give SO2 For SCl2 + H2O HOCl + HSCl (or accept S + SO2 + HCl) [Formula: 3 x 1/2m = 1.5m equation: 3 x 1/2m = 1.5m, need not be balanced. Must write + H2O electronic structure: 3 x 1/2m = 1.5m, must show lone pair(s) on S, N or O shape: 3 x 1/2m = 1.5m draw and / or name.] (c)(i) We expect that the X-X bond energy decreases on descending the group because the distance between the nuclear protons and the bond-pair electrons increases, so the attractive force decreases. This is so for Cl2 and Br2. [1m] The F-F bond is weaker than that of Cl2 due to non-bonding electron repulsion between lone pairs on the 2 F atoms. [1m] (ii) Definition: Reaction in which a single species / substance is simultaneously oxidized and reduced. [1m] [do not accept "element" or "atom" instead of "species"] e.g. H2O + Cl2 HCl + HOCl [1m] 1991 AL CHEM PII page 4

Not for selling, selling for this is strictly prohibited!!!! Other examples might include: 4KClO3(s) 3KClO4(s) + KCl(s) + Cl2 + 2H2O Cl + H3O + HOCl 3Cl2 + 6OH 5Cl + ClO3 + 3H2O etc. 5.(a)(i) CO2 acidic [1/2m] SiO2 acidic not SiO [1/2m] SnO amphoteric [1/2m] or SnO2 amphoteric (1/2m) [Name or formula acceptable. Nature incorrect, 0m] 2+ + (ii) CO2 + H2O H2CO3 H + HCO3 2H + CO3 [1/2m] or Ca(OH)2 + CO2 CaCO3 + H2O etc. SiO2 + 2NaOH(aq) H2O + Na2SiO3 [1/2m] 2or SiO2 + 4HF SiF4 + 2H2O etc. (actually SiF6 ) H2O + SnO + NaOH NaSn(OH)3 [1/2m] SnO + 2HCl SnCl2 + H2O [1/2m] or SnO2 + 2H2O + 2NaOH Na2Sn(OH)6 But 4HCl + SnO2 SnCl4 +2H2O unless acid is = 10 M, then also complex ion formation: 2+ SnO2(s) + 4H3O (aq) + 6Cl (aq) SnCl6 (aq) + 6H2O(l) [For equation showing acidic/basic/amphoteric properties, no need to balance, accept any reasonable 24+ 2silicate. Accept Na2Sn(OH)4 or Si(OH)4 for SnO and SnO3 for SnO2, but not Sn for SnO2] (iii) GeO [1/2m] amphoteric [1m] or GeO2 amphoteric (mainly acidic) (b) Reason A: electronegativity difference [1m] nucleophilic attack by OH- only on Si [1m] Reason B: state any one of the X-O, X-H bond strengths activation energy higher for breaking C-H Reason C: C no 2d orbital, Si has 3d orbitals (or accept C has no d orbitals) Si can form activated complex [Any of the 3 reasons is acceptable. Answer must have fact (1 mark) then deduction (1 mark). If 2 facts from different reasons are mixed, then award only 1 mark.] Equation: SiH4 + (n+2)H2O SiO2.nH2O + 4H2 [1m] or SiH4 + 2H2O SiO2 + 4H2 2SiH4 + 2OH SiO3 + 4H2 SiH4 + 4H2O Si(OH)4 + 4H2 [eq. need not be balance, if missing H2: -1/2m] (c) As Hsoln = -HLE + HHE [1m] The more negative the Hsoln, the higher the solubility of the compound [1/2m] Small anions, e.g. OH , can attract manly water molecules, which leads to very exothermic hydration energy. The HHE of the compound will be less dependent on the cation. The Hsoln is mainly governed by the lattice energy. As the size of the cation increases down the group, the HLE is less exothermic for the case of Ba. The overall Hsoln will be more negative for the case of Ba(OH)2. 2For large anions, e.g. SO4 , the lattice energy of the compound is less dependent on the size of the cation because L.E. alpha 1/(interionic distance) and is therefore fairly constant down the group. The 2+ Hsoln is therefore governed by HHE. Due to the large size of Ba , the HHE is less exothermic. The overall Hsoln will be less negative for the case of BaSO4. The dominating factor in energy cycle for large/small anion [1m] Reason why LE or HE is dominating factor [1.5m] (e.g. Know how size of anion governs LE. Magnitude of hydration energy decreases more than that of LE, so Hsoln less exothermic on descending group.) + (d) Li more polarizing than Na+ [1m] because smaller, with same charge or higher charge density or break up C-O bond easier or change in LE from Li2CO3 to Li2O larger. [1m] Charge cloud of the oxy-anion is more distorted, causing the anion to break up to give O2 and CO2 [1m]

(e) 1991 AL CHEM PII page 5

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bond pair electrons nearer to F than to H [1/2m] since F more electronegative [1/2m] bond-pair - bond-pair repulsion is smaller in NF3 than in NH3. [1m] 6.(a)(i) Definition: Element which has incomplete d electron-subshell when combined in compounds (or complete in case of Zn). [1m] OR incomplete d-electron subshell / orbitals (between s, p blocks only: 1/2m) (ii) Name (must be correct; NOT -ate for +ion) [1/2m] Formula [1/2m] Shape [1m] (iii) Small [1/2m], highly charged [1/2m] OR high charge density 4+ V ion polarizes [1/2m] H2O molecule so strongly that it attracts electrons shared between H and O:

[1/2m] 22+ 2+ (iv) (I) By mild reductants, e.g. H2S, SO2, Fe , oxalate (C2O4 ), Sn , I . [1m] Blue [1/2m] (ii) Zn/HCl [1m] Violet [1/2m] (b) Out of syllabus 7.(a)(i) The reddish brown bromine turns colourless. [1m] The reaction is a free-radical substitution. [1/2m] Depending on the amount of bromine, various (colourless) substitution products are obtained. CH3CH2CH2CH2CH3 + Br2 (hv) CH3CH2CH2CH2CH2Br + CH3CH2CH2CH2CHBr2 etc. [1m] (ii) The purple colour of KMnO4 turns to a brown suspension of MnO2. [1m] KMnO4 is reduced and alkene is oxidized [1/2m]

[1m] (iii) The reddish brown solution of bromine is decolourized. [1/2m] Tribromophenol appears as a white precipitate. [1/2m] The reaction is an electrophilic substitution. [1/2m]

(iv)

[1m] A silver mirror is formed [1m] on the surface of the test tube (or some silver powder is formed). Ag+ is reduced by hexanal to Ag metal and deposits on the glass surface. [1/2m]

[1m] (b)(i)

[1m each] Q: 3,3-dimethylbut-1-ene [1m] 1991 AL CHEM PII page 6

Not for selling, selling for this is strictly prohibited!!!! R: 1-ethoxy-3,3-dimethylbutene [1/2m] (ii) Out of syllabus 8. Any reasonable answers are acceptable. (a)

[3m] (b)

[4m] (c)

[4m] (d)

[3m] (e)

[3m] 9.(a)(i) Warm the compound with aqueous KOH, cool, acidify with nitric acid, add AgNO3 White ppt of AgCl formed for Ar-CH2Cl [2m] (ii) Add solution of sodium hydrogencarbonate solution to the compound. PhCOOH will react to give CO2 (effervescence observed)

[2m] (iii) Warm the compound with iodine & NaOH

will give yellow ppt. of iodoform, no ppt observed for

1991 AL CHEM PII page 7

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[2m] (iv) Warm the compound with acidified K2Cr2O7/NaCr2O7 The primary alcohol will turn the solution from orange [Cr(VI)] to green [Cr(III)]. No change in colour for the tertiary alcohol. Primary alcohol can easily be oxidized.

[2m] Or Add ZnCl2 in conc. HCl to compound. If turbidity is observed immediately, it is the tertiary alcohol. The primary alcohol solution remains clear. (b)(i)

J [O] CH3CH=CHCHO [O] CHO [O] CH2=C(CH3)CHO [O] CH2=CHCH2CHO

K CH3CH=CHCOOH COOH CH2H =C(CH3)COOH CH2=CHCH2COOH

1+1 (2) (2) (2)

Oxidation of J increase the number of oxygen atoms in product by one oxidation of aldehyde to carboxylic acid.

(ii) OH C3H7 * C CH3 PCl5 Cl C3H7 * C H PCl5 (CH3)2CH CH3 Cl * C H PCl5 C2H5 * C

HCl

(CH3)2CH

H OH * C CH3 H CH2OH * C

+
CH3 CH2Cl CH3

HCl

C2H5

HCl

H H * chiral centre L can exist as a pair of enantiomers chiral centre in L. [1m] L gives out HCl on reaction with PCl5 -OH group present. [1m] (iii)

CH3

1991 AL CHEM PII page 8

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Ozonolysis of M without changing the carbon number double bond forms part of a ring, i.e. cyclic alkene. [1m]

1991 AL CHEM PII page 9