2006 STPM Chemistry Papers 1 and 2

Time: 1h 45 min There are fifty questions in this paper. Answer all questions. Marks will not be deducted for wrong answers. Section A Four suggested answers labelled A, B, C, and D are given for each question. Choose one correct answer. 1.
12 6

C and C atoms are isotopes of carbon.

6

14

Which of the following is the same for the isotopes? A Stability B Nuclear charge C Nucleon number D Relative isotopic mass 2. The values of Ka of several substances are given in the following table. Substance HCOOH CH3COOH OH COOH Ka/ mol dm3 1.7 10
4

C CH3SH molecule is bigger than CH3OH molecule. D The electronegativity of oxygen is higher than that of sulphur. 4. The table below shows the sizes and charges of six ions. Ion U V W X Y Z Radius/nm 0.181 0.135 0.151 0.169 0.182 0.065 Charge +1 +2 +2 1 1 2

1.8 105 1.3 1010 6.5 105

Which of the following is the strongest base? A HCOO B CH3COO C D O COO

Which of the following represents the correct ascending order of lattice energy? A UX < UY < WZ C UY < UX < WZ B UX < WZ < VY D VY < UX < WZ 5. Which of the following is not required in the calculation of the lattice energy of calcium oxide using the Born-Haber cycle? A Enthalpy of hydration B Enthalpy of ionisation C Enthalpy of atomisation D Electron affinity 6. The kinetic data for the reaction A + 2B C at a certain temperature is shown in the following table.
1 Majlis Peperiksaan Malaysia 2006

3. The boiling points of CH3 OH and CH3SH are 64.5 C and 5.8 C respectively. What is the cause of the difference in the boiling points? A The OH bond is stronger than the SH bond. B Hydrogen bonds exist between CH3OH molecules.

2006 STPM Chemistry Papers 1 and 2

Initial Initial rate of concentration Experiment reaction [A]0 [B]0 1 a b r 2 2a b 4r 3 a 2b r What is the rate of the reaction? A k[A]2 C k[A][B]2 2 B k[B] D k[A]2[B] 7. The reaction in the preparation of sulphur trioxide is shown below. 2SO2(g) + O2(g) 2SO3(g); H = 197 kJ Sulphur dioxide and oxygen are passed over a heated vanadium(V) oxide catalyst. Which of the following may increase the formation of sulphur trioxide? A Reduction in pressure B Decrease in temperature C Addition of a promoter to the catalyst D Increase in the volume of the container 8. MX, MY and MZ are sparingly soluble salts. When aqueous MNO3 is added dropwise to an aqueous solution containing X , Y and Z ions, MX is precipitated. When aqueous NaZ is added to a small amount of MY precipitate, MY dissolves and MZ is precipitated. The sequence of MX, MY and MZ according to the descending order of their solubility products is A MX, MY, MZ C MY, MZ, MX B MX, MZ, MY D MZ, MY, MX 9. Compounds have either ionic or covalent bonds or both. Which of the following statements is not true of ionic bonds? A They involve the transfer of one or more electrons from s, p or d orbitals. B The strength of ionic bonds is proportional to the size of the ions. C They involve ions with stable electronic configurations. D They result in the formation of solid compounds. 10. Phosphorus pentachloride decomposes according to the equation PCl5(g) PCl3(g) + Cl2(g).
2

When 1.3 102 mol PCl5 is heated at 727 C in a 1 dm3 flask, the total pressure formed is 150 kPa. What is the partial pressure of chlorine in the flask? [R = 8.31 J K1 mol1] A 29 kPa C 42 kPa B 32 kPa D 73 kPa 11. Which of the following statements is true of the Periodic Table? A It is built based on the nucleon number. B The elements are divided into five blocks. C There are eight groups in the Periodic Table. D There are seven periods in the Periodic Table. 12. The graph below shows the variation of the concentrations of the gases X, Y and Z at T C for the reaction
X(g) + Y(g) Z(g); H = positive

Concentration/ mol dm3

X Y Z

5 7

10 Time/min

Which of the following statements is true of the above reaction? A The equilibrium constant Kc can be calculated at 7 minutes. B The equilibrium constant Kc at 5 minutes is the same as that at 10 minutes. C The changes of the concentrations of X, Y and Z at 7 to 10 minutes are due to the increase in the pressure of the system. D The changes of the concentrations of X, Y and Z at 7 to 10 minutes are due to the increase in the temperature of the system. 13. A 2.0 dm3 stoppered flask at T C contains 0.50 mol of SO2, 0.010 mol of O2 and 4.6 mol of SO3 at equilibrium. Calculate Kc for the following equilibrium at T C. 2SO2(g) + O2(g) 2SO3(g)

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2006 STPM Chemistry Papers 1 and 2

A B C D

5.9 9.2 8.5 1.7

105 dm3 mol1 102 dm3 mol1 103 dm3 mol1 104 dm3 mol1

14. Mercury and diaphragm cells are used in industrial processes for the electrolysis of brine. Which of the following is not the product of the two processes? A Sodium metal B Sodium hydroxide solution C Chlorine gas D Hydrogen gas 15. Buffer solutions are very important to chemical and biological systems. Calculate the pH of a buffer solution formed by mixing 100 cm3 of 0.050 mol dm3 ethanoic acid and 50 cm3 of 0.20 mol dm3 sodium ethanoate. [Ka for ethanoic acid is 1.7 105 mol dm3.] A 4.1 C 5.1 B 4.5 D 5.4 16. Which of the following species has the most number of unpaired electrons? A 7N2 C 12Mg+ B 8O D 21Sc 17. Which of the following statements is true of Grignard reagents? A They are sources of halogens. B Their Lewis structures are RMgX :. C Their reactions involve homolysis of the RMg bond. D They are formed from reactions between haloalkanes and magnesium metal in anhydrous alcohols. 18. The respective electrolytes of three electrolytic cells are aqueous sodium hydroxide, concentrated aqueous sodium chloride and aqueous silver nitrate. Each cell has carbon electrodes connected in series. What is the ratio of the number of moles of hydrogen gas in the first cell, chlorine gas in the second cell and oxygen gas in the third cell when an electric current flows through the three cells? A 1:1:0 C 1:1:2 B 1:1:1 D 2:2:1
3

19. The vapour pressures of pure liquids X and Y at 25 C are 48 kPa and 36 kPa respectively. The total vapour pressure of a mixture of the two liquids with a 0.30 mole fraction of X at the same temperature is 39.6 kPa. Which of the following statements is true of the mixture? A The mixture shows a negative deviation from Raoults law. B Fractional distillation of the mixture yields Y as the distillate. C The vapour pressure of Y in the mixture at 25 C is 10.8 kPa. D The strengths of intermolecular forces of X and Y are about the same. 20. A Ziegler-Natta catalyst is used to produce high density polyethene because the titanium(IV) ion in the catalyst A has empty d orbital B has a low activation energy C has many valence electrons D can change its oxidation states 21. Transition elements have variable oxidation states in complex ions. What are the correct oxidation states of iron in the following complex ions? A B C D [Fe(en)2(SCN)2]+ +2 +2 +3 +3 [Fe(EDTA)]2 +2 +3 +2 +3

22. Astatine is an element in Group 17 of the Periodic Table. What are the expected properties of astatine at 25 C? Colour A B C D Black Black Violet Violet Physical state Solid Solid Solid Liquid Oxidising power Weak Strong Strong Weak

23. Which of the following chlorides fumes in moist air? A PbCl2 C CCl4 B SnCl2 D PbCl4
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2006 STPM Chemistry Papers 1 and 2

24. The sequence of reactions for an oxide, X, is shown in the scheme below. Fe2+(aq) X + NaOH(aq) Y(aq) Yellow solution X could be A MgO C SiO2 B Al2O3 D Cl2O7 25. Aqueous sodium chloride, concentrated aqueous ammonia and aqueous potassium iodide are added sequentially to aqueous silver nitrate in a test tube. Which of the following graphs represents the height of the precipitate formed after the addition of each of the reagents? A C
Height of the precipitate Height of the precipitate

29. An hydroxy compound has the following properties. I It is optically active. II It undergoes dehydration to form a compound without isomer. III It forms a yellow precipitate when heated with alkaline iodine solution. The compound could be A CH3CH2OH B CH3CH2CH(OH)CH3 C HOCHCH3 D HOCHCH3 | CH2

B
Height of the precipitate

NaCI NH3 KI

D
Height of the precipitate

NaCI NH3 KI

30. The suitable reagent used to differentiate benzene from 2-hexene is A Cl2 C H2SO4 B HBr D KMnO4 31. Which of the following reaction schemes can be used for the preparation of benzoic acid? Conc.H2SO4 CH3Cl A Intermediate Product Conc.HNO3 AlCl3 B CH3COCl AlCl3 Cl2 Fe CH3Cl AlCl3 Intermediate Excess H2 Ni 1. KCN Intermediate 2. H3O+ 1. KMnO4, OH, 2. H3O+ Product Product

NaCI NH3 KI

NaCI NH3 KI

26. The photochemical smog is a type of air pollution. The gas which causes the pollution is A O3 C NO2 B NO D SO2 27. The reactions in the manufacture of nitric acid by the Ostwald process are as follows: 4NH3 + 5O2 4NO + 6H2O 2NO + O2 2NO2 3NO2 + H2O 2HNO3 + NO What is the theoretical percentage yield of nitric acid obtained from 1 mol of NH3? A 24% C 50% B 31% D 67% 28. When water is added to a compound X, a vigorous reaction occurs which evolves white fumes of hydrogen chloride. What is the chemical formula of X? A CH3COCl C CH3NH3+Cl B CH3CH2Cl D CH2ClCH2OH
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Intermediate

Product

32. Which of the following best explains the function of OH ion as a nucleophile? A It is alkaline. B It is negatively charged. C It has lone pair electrons. D It has a highly electronegative oxygen atom.

2006 STPM Chemistry Papers 1 and 2

33. Which of the following compounds can form condensation homopolymers? A CH2 = CHCl B CH2 = C(CH3)COOCH3 C H2NCH2CH2CH2CH2NH2 D H2NCH2CH2CH2CH2COOH 34. The structural formula of a compound is as follows. CH3C = CHCH2CH2C = CHCHO | | CH3 CH3 What is its IUPAC name? A 2, 6-Dimethyl-2, 6-octadienal B 2, 6-Dimethyl-3, 7-octadienal C 3, 7-Dimethyl-2, 6-octadienal D 3, 7-Dimethyl-3, 7-octadienal 35. Which of the following could not be used to differentiate between CH3CHO and CH3COCH3? A Tollens reagent B Fehlings solution C Iodoform test D Mass spectrometry 36. A compound X with the molecular formula C8H8Cl2 produces a compound Y after it is refluxed with alcoholic sodium hydroxide. Compound Y which is produced from 1.75 g of compound X can absorb 210 cm3 of hydrogen gas at 25 C and 1.1 105 Pa. Which of the following is the structural formula of X? [Relative molecular mass of X is 175; molar gas constant is 8.31 J K1 mol1] H H A C H H | | | | Cl CCH CCH | | | | H Cl C1 C1 B Cl H | | CCH | | Cl H D Cl C1 H H | | CCH | | H H

37. Hydrocarbons undergo various reactions. One of the reactions involving 3, 3-dimethyloctane is shown below. X 3, 3-Dimethyloctane Products X could be A 450 C, Al2O3/SiO2 B H2SO4(conc.), 180 C C NaOH(aq), reflux D KCN(aq)/ ethanol, reflux 38. A weak acid X with molecular formula C6H6O reacts with sodium metal and aqueous sodium hydroxide. When a mixture of X and hydrogen gas is passed over platinum, A a tertiary alcohol is formed B substitution reaction occurs C the product has the molecular formula C6H12O D the product is in the same homologous series as X 39. The repeating unit of a polymer is shown below H H H CH3 H H | | | | | | CCCCCC | | | | H H H Which of the following statements is not true of the polymer? A It is elastic. B It is thermally stable. C It can be vulcanised. D Its monomers are CH2 = C(CH3)CH=CH2. 40. Glycine (2-aminoethanoic acid) is an optically inactive amino acid. Which of the following compounds is formed not because of the acid-base property of glycine? A H2NCH2COONa B CH3OOCCH2NH2 C HOOCCH2NH3Cl D HOOCCH2NH3OOCCH3
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CH=CH2 and

2006 STPM Chemistry Papers 1 and 2

Section B For each of the questions in this section, one or more of the three numbered statements 1 and 3 may be correct. The responses A to D should be selected on the basis of the following. A 1 only is correct. B 1 and 2 only are correct. C 2 and 3 only are correct. D 1, 2 and 3 are correct.

1 The forward reaction is endothermic. 2 At high pressures, the amount of Z in the equilibrium mixture increases. 3 At high temperatures, the amount of Z in the equilibrium mixture increases. 44. The Boltzmann distribution curves at temperatures T1 and T2 are shown below.
Fraction of molecules T2 Ea T1

41. The energy-level diagram for a hydrogen atom shows several electronic transitions with frequencies f1, f2, f3, f4 and f5.
n= n=4 n=3 Energy f4 f5 n=2

Energy

At 1 2 3

temperature T1, the activation energy is lower more molecules have lower energy the total number of molecules remains constant

f1

f2

f3

n=1

Which of the following statements is/are true of the above diagram? 1 f1 represents the convergence limit of the Lyman series. 2 f1, f2 and f3 represent lines in the Lyman series. 3 f4 and f5 are used to calculate the difference between the energy levels of n = 3 and n = 4. 42. The element X has a proton number 25. Which of the following statements is/are true of X? 1 The metal X has a high density. 2 X forms coloured complex ions. 3 The highest oxidation number of X in its ion is +7. 43. The graph below shows the effect of temperature T on the equilibrium constant, Kp, for the reaction X(g) + Y(g) Z(g).

45. Silicon is a semiconductor. The electrical conductivity of silicon can be increased by 1 doping with boron 2 doping with phosphorus 3 increasing the temperature 46. The charge density of beryllium ion is similar to that of aluminium ion. Which of the following statements is/are true? 1 Beryllium oxide is basic. 2 Beryllium chloride is covalent. 3 Aqueous beryllium chloride is acidic. 47. Which of the following reactions occur(s) in a catalytic converter? 1 2CO(g) + O2(g) 2CO2(g) 2 2NO(g) + 2CO(g) N2(g) + 2CO2(g) 3 2C8H18(g) + 25O2(g) 16CO2(g) + 18H2O(g) 48. Which of the following compounds is/are the major product(s) when p-methylphenol reacts with aqueous bromine? 1 2 3 OH OH OH Br Br CH3
6

Kp

1 T

Which of the following conclusions about the graph is/are correct?

Majlis Peperiksaan Malaysia 2006

CH3

Br

Br

CH3

Br

2006 STPM Chemistry Papers 1 and 2

49. The structural formula of 4-(aminomethyl) aniline is H2N CH2NH2.

This compound can be prepared by 1 the reduction of O2N C N by hydrogen with a nickel catalyst 2 the heating of a mixture of concentrated ammonia and Cl CH2Cl Cl

50. Most simple esters give the odours of fruits and flowers. Which of the following statements is/are true of the ester CH=CHCOOCH2CH3? 1 It reacts with LiAlH 4 to form CH2CH2CH2OH and CH3CH2OH. 2 It undergoes saponification to form CH=CHCOONa+ and CH3CH2OH. 3 It reacts with aqueous bromine to form CHCHCOOCH2CH3. | | OH Br

3 the addition of CH3NH2 to H2N with an iron powder catalyst

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2006 STPM Chemistry Papers 1 and 2

Time: 2h 30 min Answer all questions in Section A. Write your answers in the spaces provided. All working should be shown. For numerical answers, units should be quoted wherever they are appropriate. Answer any four questions in Section B. Write your answers on the answer sheets provided. Begin each answer on a fresh sheet of paper and arrange your answers in numerical order. Tie your answer sheets to this question paper. Answers may be written in either English or Malay. A Data Booklet and graph paper are provided. Section A [40 marks] Answer all questions in this section. 1. (a) X is an element in Period 4 of the Periodic Table. The stable oxides of X are XO, X2O3 and X3O4. An aqueous solution of X3+ is yellow. X can conduct electricity in the solid and molten states. (i) What is X?
[1 mark]

(ii) Explain the electrical conductivity of X.

[1 mark]

(iii) Compare the electrical conductivity of X with that of potassium. Explain your answer.

[2 marks]

(b) The following diagram shows the Born-Haber cycle for the formation of X2O3 from its elements under standard conditions. 2X3+(g) + 3O2(g) 2X3+(g) + 3O(g) Energy 2X(g) + 3O(g) 2X(s) + 3O(g) 3 O (g) 2X(s) + 2 2 X2O3(s)
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H5 = +1950.0 kJ H4 H3 = +831.0 kJ H2 = +742.5 kJ H1 = 1117.1 kJ

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H6 = Lattice energy

2006 STPM Chemistry Papers 1 and 2

(i) Write an equation for the atomisation of oxygen.

[1 mark]

(ii) Calculate the enthalpy change of atomisation for oxygen.

(iii) By referring to the Data Booklet, calculate H4.

[1 mark]

[2 marks]

(iv) Compare the lattice energy of X2O3 with that of XO. Explain your answer.

[2 marks]

2. (a) Chemists of ancient times prepared phosphorus, P, from urine. (i) Write the electronic configuration of the phosphorus atom.
[1 mark]

(ii) Draw the shape of one orbital containing the valence electrons of the phosphorus atom.

[1 mark]

(iii) State one of the phosphorus atomic orbitals that are filled according to Hunds rule.
[1 mark]

(iv) In urine, the phosphorus element exists as phosphate ion, PO43. What is the shape of this ion?
[1 mark]

(b) Element X reacts with element Y to form compound Z. The electronegativity values of X and Y atoms are 1.0 and 3.5 respectively. (i) State the type of chemical bond in Z.
[1 mark] Majlis Peperiksaan Malaysia 2006

2006 STPM Chemistry Papers 1 and 2

(ii) The Lewis symbols for atoms X and Y are shown below.

Atom X

Atom Y

What is the chemical formula of Z?

[1 mark]

(iii) State two physical properties of Z.

[2 marks]

(iv) The decimal bond in Z is stronger than that in Na2O. State two factors that explain this difference.

[2 marks]

3. (a) The two common oxides of lead are lead(II) oxide and lead(IV) oxide. Lead(II) oxide dissolves readily in aqueous nitric acid. Lead(IV) oxide reacts with concentrated hydrochloric acid to form lead(II) chloride and chlorine. (i) Write a balanced equation for the reaction between lead(II) oxide and aqueous nitric acid.
[1 mark]

(ii) What is the property shown by lead(II) oxide in the reaction in (i)?
[1 mark]

(iii) Write a balanced equation for the reaction between lead(IV) oxide and concentrated hydrochloric acid.
[1 mark]

(iv) State a change in the oxidation number of lead in the reaction in (iii).
[1 mark]

(v) What is the property shown by lead(IV) oxide in this reaction.

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2006 STPM Chemistry Papers 1 and 2

(vi) State the relative stability of lead(II) and lead(IV) compounds.

[1 mark]

(b) The standard reduction potentials E for several half-cells at 25 C are as follows.

I2(aq) + 2e 2I (aq) + H2O2(l) + 2H (aq) + 2e 2H2O(l) 2 2 S4O6 (aq) + 2e 2S2O3 (aq)

E/V +0.54 +1.77 +0.09

(i) Arrange I2, H2O2 and S4O62 in ascending order of the tendency to be reduced in aqueous solutions.
[1 mark]

(ii) What would be observed if a few drops of acidified aqueous hydrogen peroxide are added to excess aqueous potassium iodide? Explain your answer.

[2 marks]

(iii) What would be observed if tetrachloromethane is added to the products of the reaction mixture in (ii) which is shaken?
[1 mark]

4. (a) The following scheme shows several chemical reactions of 4-nitroaniline. O2N NH2 NaNO2/HCl 0 5 C X

HCl (aq) OH Z Y OH

(i) Write the structural formulae of compounds X, Y and Z in the boxes provided above.
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2006 STPM Chemistry Papers 1 and 2

(ii) Write an equation for the formation of 4-nitroaniline from Z.

[1 mark]

(iii) Why is the formation of 4-nitroaniline from Z possible?

[1 mark]

(b) Aspartic acid is used in the preparation of aspartame, an artificial sweetener. The structure of aspartic acid is as follows. H OH | | O HNCC | | H CH2 | O C | OH (i) State the IUPAC name of aspartic acid.
[1 mark]

(ii) Draw the structures of the dipeptides formed from aspartic acid.

[2 marks]

(iii) Name the bond between the dipeptide molecules other than hydrogen bond.
[1 mark]

(iv) State one method of separating a mixture of aspartic acid and glycine.
[1 mark]

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2006 STPM Chemistry Papers 1 and 2

Section B [60 marks] Answer any four questions in this section. 5. (a) An element X is in Group 9 and Period 4 in the Periodic Table. (i) Discuss the application of the Aufbaus principle in the construction of the electronic configuration of X. [3 marks] (ii) Name one element which has almost the same radius as X. Give three reasons for your answer. [4 marks] (b) Peroxyacetyl nitrate (PAN) is an air pollutant formed in the photochemical smog. The concentration of PAN in a polluted air sample is analysed at 25 C. The results are given in the table below. Time/ min 0 10.0 6.6 20.0 5.3 30.0 4.2 40.0 3.5 50.0 2.8 60.0 2.1
[4 marks] [2 marks] [2 marks]

Concentration of PAN/ 1010 mol dm3 8.4

(i) Determine graphically the order of the decomposition of PAN at 25 C. (ii) Calculate the rate constant for the decomposition of PAN at 25 C. (iii) Predict the concentration of PAN in air at 25 C after 90 minutes.

6. (a) Pure nitric(V) acid is a colourless liquid which forms an azeotropic mixture with water. Aqueous nitric(V) acid shows a negative deviation from Raoults law. (i) Explain why aqueous nitric(V) acid shows a negative deviation. [2 marks] (ii) Sketch a boiling point-composition diagram for aqueous nitric(V) acid given that nitric(V) acid boils at 78.2 C and an azeotrope mixture containing 68.2% of nitric(V) acid by mass boils at 121 C and 101 kPa. [3 marks] (iii) State the changes which occur in the composition of the residual liquid and the distillate when a solution containing 80.0% of nitric(V) acid is continuously distilled.
[2 marks]

(iv) What is the volume of an azeotropic mixture of aqueous nitric(V) acid required to prepare 1 dm3 of a 2 mol dm3 solution of nitric(V) acid? [2 marks] 3 [An azeotropic mixture of aqueous nitric(V) acid has a density of 1.42 g cm at 101 kPa.] (b) (i) Using the relevant standard electrode potentials in the Data Booklet, determine whether the corrosion of titanium in an acidic condition is spontaneous. [4 marks] (ii) Explain why titanium is still used as an alloy to make the frames of racing bicycles and spectacles despite its large negative reduction potential. [2 marks] 7. (a) (i) Titanium occurs in nature as a mixture of five isotopes with percentage abundance as follows. Relative isotopic mass 46.0 47.0 48.0 49.0 50.0 % abundance 8.00 7.40 73.80 5.50 5.30
[1 mark] Majlis Peperiksaan Malaysia 2006

Name the method used to obtain the above data.

13

2006 STPM Chemistry Papers 1 and 2

Deduce the atomic structure of each isotope and calculate the relative atomic mass of titanium. [4 marks] (ii) Pure titanium is obtained commercially in a two-stage process starting from rutile, TiO2. Rutile is reacted with chlorine gas and coke to yield liquid titanium(IV) chloride, TiCl4, which is then reduced by magnesium. Write the equations for the reactions involved. [2 marks] (iii) Titanium(IV) chloride is a covalent compound. State what would be observed when it is exposed to moist air. Name the reaction involved and state one use of this reaction. [3 marks] 2+ (b) A solution of [Cu(H2O)6] complex is blue but a solution of [CuCl2] complex is colourless. Explain these observations in terms of electronic configurations. [5 marks] 8. (a) The standard electrode potentials of sodium, magnesium and chlorine are -2.71 V, 2.38 V and +1.36 V respectively. Explain the differences in the oxidation-reduction properties of these elements based on their standard electrode potentials. [7 marks] (b) A mixture of 3 mol of magnesium oxide and 1 mol of iron(III) oxide is heated with an excess of aluminium powder. (i) Determine the standard enthalpy change and explain the observation of the reaction that occurs. [7 marks] [Standard enthalpy of formation/kJmol1: MgO = 602, Fe2O3 = 824, Al2O3 = 1670.] (ii) Give one example of the industrial usage of the reaction. [1 mark] 9. (a) An optically active alcohol X produces compound Y on dehydration. Y reacts with bromine in tetrachloromethane to produce compound Z which has the composition by mass: carbon, 22.2%; hydrogen, 3.7%; bromine, 74.1%. (i) Determine the empirical formula of Z. [2 marks] (ii) What is the most likely molecular formula of Z? Give one reason for your answer.
[2 marks]

(iii) Suggest, with reasons, the structural formulae of X, Y and Z. [5 marks] (b) 1-Chlorobutane, chlorobenzene and ethanoyl chloride can undergo hydrolysis under suitable conditions. (i) Write an equation for each hydrolysis. [3 marks] (ii) Compare the rates of hydrolysis of these chloro-compounds. [3 marks] 10. (a) Compounds R and S are two isomers with molecular formula C8H10O. R gives off white fumes with thionyl chloride and forms a yellow precipitate with alkaline aqueous iodine but S does not. S dissolves in aqueous potassium hydroxide but R does not. R is synthesised starting from bromobenzene whereas S from 4-ethylaniline. (i) Explain the above observations and write the structural formulae of R and S.
[5 marks]

(ii) Write equations for the reactions involved. [2 marks] (iii) Write equations for the synthesis of R. [3 marks] (b) State the reagents and reaction conditions for the synthesis of 2-hydroxybutanoic acid starting from 1-propanol. Write equations for the reactions involved. [5 marks]

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2006 STPM Chemistry Papers 1 and 2

PAPER 1 Section A 1. B Isotopes have the same proton numbers. Since protons are in the nucleus therefore the nuclear charges are the same. 2. C A weak acid will have a stronger conjugate base. Phenol is the weakest acid as it has the smallest Ka value so its conjugate base will be the strongest. O OH + H+ conjugate base 3. B H bonded to O, F, N can form hydrogen bonds between the molecules (eg CH3OH). CH3SH cannot form hydrogen bonds with other molecules, only weak van der Waals force exist between the molecules. Therefore the boiling point of CH3OH is higher than CH3SH. Q + Q 4. C Lattice energy is proportional to r+ + r The ionic compound which has a larger cation and anion charge and a smaller size will have a bigger value of lattice energy. 5. A Hhydration is not needed in the calculation of lattice energy using the Born-Haber cycle. The energies used are (i) atomisation energy, (ii) ionisation energy, (iii) enthalpy of formation and (iv) electron affinity. 6. A rate = k[A]m[B]n Exp. 2 4r k(2a)m(b)n = Exp.1 r k(a)m(b)n m=2 Exp. 3 r k(a)m (2b)n = Exp. 1 r k(a)m(b)n n=0 rate = k[A]2 7. B The reaction is exothermic. Decrease in temperature shifts the equilibrium to the right. Therefore, the yield of SO3 increases. 8. C MX is precipitated when MNO3 is added to X , Y , Z . This shows that MX has the lowest Ksp. MZ is precipitated and MY dissolves when NaZ is added to MY precipitate. Therefore, MZ has a lower Ksp compared to MY. 9. B The strength of ionic bond depends on the difference in electronegativity between the atoms rather than the sizes of the ions. The bigger the difference in electronegativity, the stronger the ionic bond. A stronger ionic bond is formed between a bigger 15

cation and a smaller anion (eg KF). A smaller cation and a bigger anion form a weaker ionic bond. The compound will be ionic with covalent characteristic (eg BeO). 10. C PV = nRT 150 103 1 103 = n 8.31 (273 + 727) n = 0.018 (total number of moles) PCl5 PCl3 + Cl2 Compound Initial mole Reacted Formed At equilibrium 0.013x PCl5 0.013 x x x x x PCl3 0 Cl2 0

Total number of moles = 0.013 x + x + x 0.018 = 0.013 + x x = 0.018 0.013 = 0.005 PCl = PT XCl (X Cl is mole fraction)
2 2 2

= 150 kPa x 0.005/0.018 = 42 kPa 11. D The Periodic Table is built based on proton number. The elements are divided to blocks s, p, d and f (4 blocks). There are 18 groups and 7 periods. 12. B Kc only changes with temperature. [SO3]2 13. D Kc = [SO2]2[O2] (4.6/2)2 = (0.50/2)2(0.010/2) = 1.7 x 104 14. A Sodium. In the mercury cell at the cathode Na/Hg amalgam is produced which upon treatment with water forms NaOH and hydrogen. In the diaphragm cell, at the cathode, hydrogen is produced. At the anode for both cells, chlorine gas is produced. 15. C M1V1 = M2V2 0.050 100 Concentration of acid, M2 = 150 = 0.033 0.20 50 Concentration of salt, M2 = 150 = 0.067 [salt] pH = log Ka + log [acid] 0.067 = log 1.7 105 + log 0.033 = 5.1 Oxford Fajar Sdn Bhd (008974T) 2007

2006 STPM Chemistry Papers 1 and 2

16. B

N2 has 1s22s22p5 has 1 unpaired electron. 2 2 4 8O has 1s 2s 2p has 2 unpaired electrons. + 2 2 6 1 12Mg has 1s 2s 2p 3s has 1 unpaired electron. 2 2 6 2 6 1 2 21Sc has 1s 2s 2p 3s 3p 3d 4s has 1 unpaired electron.
7

Eg: N2 + O2 2NO exhaust gas NO is oxidised by air to NO2 which causes smog: 2NO + O2 2NO2 27. D 4 mol NH3 = 4 mol NO Therefore, 1 mol NH3 = 1 mol NO = 1 mol NO2 3 mol NO2 = 2 mol HNO3 Therefore, 3 mol NH3 = 2 mol HNO3 1 mol NH3 = 2/3 mol HNO3 = 2/3 100 = 67% 28. A X must be acid chloride as only acid chloride, when reacted with water, will form white fumes of hydrogen chloride.

17. B Grignard reagent is used to prepare alcohols by reacting it with carbonyl groups. It is prepared by reacting a haloalkane with magnesium in dry ether. 18. D 2H2O + 2e 2Cl 2H2O H2 + 2OH Cl2 + 2e O2 + 4e + 4H+ H2 No. of moles of e Ratio 2 2 Cl2 2 2 O2 4 1

29. C optically active the carbon atom has 4 different groups forms yellow precipitate with iodine solution, therefore alcohol must have H | COH group | CH3

19. D Raoults Law: PA = XA PAo (XA is mole fraction of A in the miscible liquid mixture, PAo is the pure vapour pressure of A) PX = XX PXo = 0.30 48 = 14.4 kPa PY = XY PYo = 0.70 36 = 25.2 kPa PT = PX + PY = 14.4 + 25.2 = 39.6 kPa Since the calculated pressure using Raoults law is the same as the given pressure, the mixture is an ideal mixture. Therefore, the strengths of intermolecular forces of X and Y are the same. 20. A Titanium ion should be able to form bonds with the alkene. Therefore, it must have empty d orbitals. 21. C [Fex(en)2(SCN)2]+ x + 2(0) + 2(1) = +1 x = +3 [Fey (EDTA)]2 y + (4) = 2 y = 2 + 4 = +2 en has 0 charge SCN has 1 charge

OH | H2O CCH3 CH = CH2 | H optically active can react with alkaline iodine C atom solution to form yellow precipitate 30. D 2-hexene contains a C=C bond which decolourises KMnO4 solution. Benzene does not react with KMnO4. 31. D Alkylbenzene can be oxidised to benzoic acid by KMnO4/H+.

EDTA has 4 charge

CH2CI AICI3

CH3

KMnO4 H3O+

COOH

22. A Iodine is black, solid and has weak oxidising power. Since astatine is below iodine, astatine has similar properties. 23. D PbCl4 undergoes hydrolysis as it has d orbitals. 24. D Both Al2O3 (amphoteric oxide) and Cl2O7 (acidic oxide) react with NaOH(aq). However, Cl2O7 reacts with NaOH to form ClO4(aq) which oxidises Fe2+(aq), green solution, to Fe3+(aq), yellow solution. 25. A When NaCl is added to AgNO3, AgCl forms as a precipitate which dissolves in ammonia. When KI is added, AgI is formed as AgI has a smaller Ksp. The AgI precipitate formed is more than AgCl. 26. C Photochemical smog is formed by the reaction between hydrocarbons (automobile exhaust) and nitrogen dioxide (NO2) in the presence of sunlight. Oxford Fajar Sdn Bhd (008974T) 2007 16

32. C A nucleophile is an ion or molecule which has a pair of electrons which can be donated. 33. D For a condensation homopolymer, the monomer has 2 different functional groups at both ends which can react to eliminate small molecules such as water or HCl. Example: HO-(CH2)n-COOH or H2N-(CH2)n-COOH 34. C Numbering must start from the aldehyde group CH3C(CH3)=CHCH2CH2C(CH3)=CHCHO
8 7 6 5 4 3 2 1

3,7-dimethyl-2,6-octadienal 35. C Carbonyl groups which have CH3 gives a positive | CO iodoform test. The only aldehyde which gives a positive test is ethanal, CH3CHO.

2006 STPM Chemistry Papers 1 and 2

36. C X undergoes elimination reaction with alcoholic sodium hydroxide, forming Y which is an unsaturated hydrocarbon since it absorbs hydrogen gas. Therefore X must be a haloalkane. PV=nRT 1.1 105 x 210 106 = n x 8.31 298 23.1 n = 8.31 298 n = 0.00933 Y absorbs 0.00933 mol H2 No. of moles of X = 1.75/175 = 0.01 0.01 moles of X forms Y which absorbs 0.00933 moles hydrogen. 1 mole of X forms Y which absorbs approximately 1 mole of hydrogen therefore Y must have 1 double bond. H H | | NaOH/ethanol CCH | | H CI X Y CH=CH2 + HCI H2 CH2CH3

The difference in the energy between the two gives the energy difference between n=3 and n=4. 42. D X: [18Ar]3d54s2. X is in block d. Hence it has high density, forms coloured compounds and the highest oxidation number is +7 where all the valence electrons, 3d54s2, is removed.
25

Cl

Z(g) H = (+)ve 43. D X(g) + Y(g) According to Le Chateliers Principle an increase in temperature shifts the equilibrium to the side where the increase in heat is absorbed. The graph shows that Kp is higher with an increase in temperature (1/T 0). Therefore the reaction is endothermic as the equilibrium shifts to the right as the Kp becomes higher with the increase in temperature. Thus the amount of Z increases. According to Le Chateliers Principle an increase in pressure shifts the equilibrium to the side where the increase in the pressure is absorbed (to the side with less number of moles). Since the right side has less number of moles (1 mole) compared to the left (2 moles), therefore the increase in pressure shifts the equilibrium to the right forming more Z. 44. C T1 is of lower temperature, hence more molecules have lower energy. The activation energy for T1 and T2 are the same as activation energy does not depend on temperature. The number of molecules for T1 and T2 are the same. 45. D Doping (adding of impurities) increases the electrical conductivity of silicon. The impurities can be from Group 13, for example boron which has one valence electron less compared to silicon which is in Group 14. This type of semiconductor is known as p-type semiconductor. The impurities can be from Group 15 which has an extra valence electron compared to Si, for example phosphorus which has an extra electron compared to silicon. This is known as n-type semiconductor. Since silicon is a semiconductor, its electrical conductivity can be increased by increasing the temperature. 46. C Beryllium and aluminium have diagonal relationship and also Be2+ and Al3+ have similar charge density. Hence the properties of beryllium is similar to aluminium. 47. D A catalytic converter converts the toxic gases, CO, NO and unburned hydrocarbons from the exhaust of vehicles to non-toxic gases such as carbon dioxide and nitrogen. 48. A OH p-methylphenol CH3 OH is a stronger electron donor than CH3 , therefore it determines the position of the entering electrophile, 17 Oxford Fajar Sdn Bhd (008974T) 2007

A and B form triple bonds and D does not undergo elimination reaction. 37. A Hydrocarbons undergo free radical and catalytic cracking reactions. 38. C X is a phenol since it reacts with sodium hydroxide and sodium and also a weak acid. OH H2/Pt OH C6H12O 39. B The polymer is a addition copolymer. Its monomers are H H | | + CH2=C(CH3)CH=CH2 C C | | H Since the polymer has a double bond, it is elastic and can be vulcanised. It is not thermally stable. 40. B Glycine, NH2CH2COOH, has a base and acid group. The acid group reacts with NaOH forming structure A. The base group can react with HCl forming structure C. The base group can also react with CH3COOH forming structure D. B is formed when the acid group reacts with alcohol forming an ester by the condensation process. PAPER 1 Section B 41. C Convergence limit is from n=1 to n=. f4 can be used to calculate the energy difference between n=3 and n=2 and f5 to calculate the energy difference between n=4 and n=2 by using the equation E=hf.

2006 STPM Chemistry Papers 1 and 2

bromine. Bromine can enter the positions 2, 4, 6 relative to OH. Since position 4 is occupied by CH3, therefore bromine takes up positions 2 and 6 relative to OH. 49. A The reduction of nitrobenzene forms aniline and the reduction of nitrile, CN forms primary amine. 50. C LiAlH4 reduces ester to alcohol but it does not reduce the double bond to alkane. O , Saponification breaks the ester bond, | C O forming the salt COONa+ and alcohol. Aqueous bromine reacts with the double bond forming, OH Br | | CC PAPER 2 Section A 1. (a) (i) Fe (ii) X has free-moving (or mobile, or delocalised) electrons (iii) X has a higher electrical conductivity than potassium because X has more valence electrons (or delocalised 3d and 4s electrons). 1 O (g) (i) 2 2 O(g) O2N

(vi) Lead(II) is more stable (b) (i) S4O62 < I2 < H2O2 (ii) A brown solution is formed as I is oxidised to I2. (iii) A purple solution will be formed in the CCl4 layer. (i) X O2N or O2N or O2N Y O2N N=N N+ = NCI or N2CI N = N+ OH or O2N O2N N= N+CI N2+

4. (a)

or Z O2N (ii)

O2N

N=N OH NH3CI or O2N NH3+

(b)

(ii) +742.5 / 3 = + 247.5 kJ mol1 (iii) H4 = 2(1st IE + 2nd IE + 3rd IE) = 2(762 + 1560 + 2960) = + 10 564 kJ (iv) Lattice energy of X2O3 is higher than that of XO because the cationic charge of X in X2O3 is higher and the ionic radius of X3+ is smaller than that of X2+. 2. (a) (i) 1s2 2s2 2p6 3s2 3p3 (ii) 3px (iii) 2p or 3p (iv) Tetrahedron/tetrahedral (b) (i) Ionic bond (ii) XY or X 2+Y 2 (iii) High melting / boiling point, conducts electricity in molten or aqueous state, colourless / white, soluble in water / insoluble in organic solvent (Any two of the physical properties above) (iv) Size of X 2+ is smaller than Na+ and the charge of X 2+ is higher than Na+. (i) (ii) (iii) (iv) (v) PbO(s) + 2HNO3(aq) Basic property PbO2(s) + 4HCl(l) +4 to +2 Oxidising agent Pb(NO3)2(aq) + H2O(l) PbCl2(s) + Cl2(g) + 2H2O(l)

NH3+CI + NaOH (iii) Z is acidic (b)

O2N

NH2 + NaCI + H2O

(i) 2-aminobutane-1, 4-dioic acid (ii)

H H O H H | | || | | HNCCNCCOOH | | CH2 CH2 | | COOH COOH

(iii) Ionic bond (iv) Chromatography / electrophoresis PAPER 2 Section B 5. (a)

H H | | HNCCOOH | CH2 H | | CNCCOOH || | | O H CH2 | COOH

3. (a)

(i) X: 1s2 2s2 2p6 3s2 3p6 4s2 3d7 Aufbaus principle: electrons occupy orbitals with the lowest energy level first Energy levels: 1s < 2s < 2p < 3s < 3p < 4s < 3d (ii) Nickel or iron Electrons are filled into 3d orbitals. Hence, effective nuclear charge remains almost

Oxford Fajar Sdn Bhd (008974T) 2007

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2006 STPM Chemistry Papers 1 and 2

constant because the increase in nuclear charge and the screening effect cancels each other. (b) 0 20.9 21.0 21.1 In[PAN] (i) 20 40 60 80 100 time/min or t'1/2
=

(b)

[PAN]x10 10 mol dm3

t "1/2 time/min 7. (a)

(i) O2 + 4H + 4e 2H2O E = +1.23 V 2+ 2Ti 2Ti + 4e E = +1.63 V 2Ti2+ + 2H2O E = +1.23 + O2 + 4H+ + 2Ti (+1.63) V = +2.86 V The positive E value shows that the reaction is spontaneous. (ii) It is light (or it has low density). The presence of the TiO2 layer protects the underlying Ti from corrosion.
+

t'1/2 t "1/2 First order reaction time x 10

10

0 8.4

10.0 6.6

20.0 5.3

30.0 4.2

40.0 3.5

50.0 2.8

60.0 2.1

(i) Mass spectroscopy No. of protons = 22 No. of neutrons = 24, 25, 26, 27 and 28 respectively

In

20.9 21.1 21.4 21.6 21.8 22.0 22.3

Ar =
100

(46.0 8.00) + (47.0 7.40) + (48.0 73.80) + (49.0 x 5.50) + (50.0 5.30)

= 47.9
(ii) TiO2 + 2Cl2 + C TiCl4 + CO2 TiCl4 + 2Mg Ti + 2MgCl2 (iii) White fumes of HCl are produced due to the hydrolysis of TiCl4 Uses: Smoke grenades / smoke bombs (b) Cu+ : 3d10 Cu2+: 3d9 Splitting of 3d orbitals occurs in Cu2+ ion. In Cu2+ there is a d-d transition or an electron from a low 3d level absorbs energy and jumps to a higher 3d level. In Cu+ there is no d-d transition. 8. (a) The negative values of E show that sodium and magnesium are reducing agents. Na Na+ + e E = 2.71 V 2+ Mg Mg + 2e E = 2.38 V Sodium is a stronger reducing agent than magnesium. Therefore, E of sodium is less than E of magnesium. The positive E value shows that chlorine is an oxidising agent. Cl2 + 2e 2Cl E = +1.36 V (b) (i) 3MgO + 2Al 3 x (-602) 0 3Mg + Al2O3 0 1670

(ii) k = ln 2 / t1/2 or 0.693 / 30.0 = 0.0231 min1 or 3.85 x 104 s1 (iii) [PAN]90 = 1.05 x 1010 mol dm3 6. (a) (i) Interaction between pure nitric acid with water is stronger than the interaction between pure nitric(V) acid molecules and between pure water molecules. Consequently, vapour pressure is lower than expected according to Raoults Law for ideal solution. (ii) va
121 100 Boiling point/C
vapo ur
po ur

liquid

liquid

78.2

100 % composition of HNO3

68.2%

(iii) The distillate is pure or 100% nitric(V) acid, the concentration of nitric(V) acid in the residual liquid will continue to decrease until an azeotropic mixture of 68.2% nitric(V) acid is reached. (iv) Mr of HNO3 = 63 1 dm3 of 2 mol dm3 HNO3 contains 2 mol (2 63 g) of HNO3. 100 g of azeotropic mixture contains 68.2 g of HNO3. Mass of azeotropic mixture that contains (2 63 g) of HNO3 (2 63) 100 = 68.2 Mass (2 63) 100 Density = 1.42 = = Volume 68.2 Volume Volume = (2 63.0 100) / (1.42 68.2) = 130 cm3 19

H = (1670) 3(602) = +136 kJ Fe2O3 + 2Al 824 0 2Fe + Al2O3 0 1670

H = (1670) (824) = 846 kJ Observation: Molten metal is formed. Explanation: The aluminium does not react with magnesium oxide because magnesium is more reactive than aluminium and the reaction is endothermic. Aluminium reacts with ferum(III) oxide because aluminium is Oxford Fajar Sdn Bhd (008974T) 2007

2006 STPM Chemistry Papers 1 and 2

more reactive than ferum and the reaction is exothermic. (ii) Welding 9. (a) (i) Element Percentage No. of moles Ratio C 22.2 22.2/12 = 1.85 1.85/0.93 =2 H 3.7 3.7/1 = 3.7 3.7/0.93 =4 Br 74.1 74.1/80 = 0.93 0.93/0.93 =1

R has CH3CH(OH) group because a yellow precipitate is formed with alkaline aqueous iodine. S contains phenol group because it dissolves in KOH. R is S is HO (ii) CH(OH)CH3 CH2CH3

CH(OH)CH3 + SOCl2 CHClCH3 + SO2 + HCl CH(OH)CH3 + I2 + OH CHI3 + (iodoform) COO

Empirical formula: C2H4Br (ii) C4H8Br2 When addition reaction occurs, two bromine atoms are added to a double bond to form a dihaloalkane (dibromoalkane). (iii) Y is alkene or Y has double bond after dehydration. X has chiral C atom because it is optically active. X is CH3CH(OH)CH2CH3. Y is CH3CH=CHCH3. Z is CH3CHBrCHBrCH3. (b) (i) CH2ClCH2CH2CH3 + OH CH2(OH)CH2CH2CH3 Cl + OH CH3COCl + H2O (ii) reflux (iii)

HO KO

CH2CH3 + KOH CH2CH3 + H2O Br + Mg dry, ether MgBr CH3 COMgBr H CH3 COH H

MgBr + CH3CHO O

200 atm, 300 C cold

CH3COOH + HCl

Cl < CH2ClCH2CH2CH3 < CH3COCl Cl is least reactive because of delocalised electrons in the benzene ring (or because of overlapping of p orbital of Cl atom with C atom of benzene ring). CH3COCl is most reactive because C=O is an electron-withdrawing group.

CH3 H+ (aq) COMgBr +H2O H (b) CH3CH2CH2OH

Cu CH3CH2CHO or NaCN/H+ CH3CH2CHO + HCN CH3CH2CH(OH)CN

10. (a)

(i) R is an alcohol because it gives off white fumes with thionyl chloride.

CH3CH2CH(OH)CN + H+ + 2H2O CH3CH2CH(OH)COOH

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