389

ANSWERS
PAPER 1
2+ Number of neutrons in 56 26Fe is 56 26 = 30 55 Number of neutrons in 25Mn7+ is 55 25 = 30 2. C Number of moles of aspirin 18.0 g = 180 g mol1 = 0.1 Number of carbon atoms = 0.1 9 6.02 1023 = 5.42 1023 nO2 pO 3. B = 2 ntotal ptotal 0.187 3.0 atm = ntotal 3.3 atm ntotal = 0.2057 nO2 + nhalothane = ntotal 0.187 + nhalothane = 0.2057 nhalothane = 0.2057 0.187 = 0.0187 Mass of halothane = 0.0187 197.4 g mol1 = 3.7 g 4. A When copper is heated with a Bunsen ame, the electrons absorb a specic amount of energy and are excited to a higher energy level. At this level, the electrons are not stable. When the electrons fall back to a lower energy level, they release energy in the form of greenish blue light. 5. B Electronic conguration of 52 24Y is 1s2 2s2 2p6 3s2 3p6 3d 5 4s1 not 1s2 2s2 2p6 3s2 3p6 3d 4 4s2 because a half-lled d orbital gives extra stability. 6. D Ca2+, K+ and Cl have the same number of electrons but Ca2+ has 20 protons, K+ has 19 protons and Cl has 17 protons. So Ca2+ has the greatest effective nuclear charge and its electrons are pulled the closest to the nucleus, causing Ca2+ to have the smallest ionic radius. 7. D Ionisation energy increases across the period because of increasing effective nuclear charge and decreasing atomic radius. More energy is needed to remove the outermost electrons when going across Period 3 from left to right. 8. B CH4, BCl3 and PCl5 are symmetrical so m = 0. The structure of SF4 is

1. B

9.

10.

11. 12.

The dipole moments of the two SF bonds that extend above and below the plane of the triangle cancel each other out but the dipole moments of the other two SF bonds do not cancel each other. A When an anion is small in size, it has a very high electron density. This makes the electrostatic force strong and the bonding in the compound tends to be electrovalent bonding. D Formal charge = Number of valence e (number of bonding e) number of lone pair e Formal charge on Cl atom = 7 (6) 2 = +2 Formal charge on O atom = 6 (2) 6 = 1 C D At constant volume, when a non-reacting gas (such as a noble gas) is added to a system at equilibrium, the total number of moles as well as total pressure will increase. However, the partial pressures of the constituent gases will not change, so the equilibrium position will not change. PCl3(g) + Cl2(g) PCl5(g) n = 1 2 (1 mol product 2 mol reactant) Kc = 26 Kp = Kc(RT)n Kp = 26(RT)1 26 = RT H2(g) + I2(g) 2HI(g) [H2] = [I2] = [HI] = 1.75 103 M [HI]2 Qc = [H2] [I2] (1.75 103 M)2 = (1.75 103 M)(1.75 103 M) =1 Qc = 1 Kc= 50.2 Qc < Kc The forward reaction is favoured until equilibrium is established. Therefore, [HI] is increased when the system establishes equilibrium. 2HBr(g) H2(g) + Br2(g) Kp = 3.3 105 1 1 HBr(g) H (g) + Br2(g) 2 2 2
1 1

13. C

14. B

15. B

[pH2]2 [pBr2]2 Kp = pHBr = Kp

F

= 3.3 105 Kp = 5.74 103

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According to the BrnstedLowry theory, an acid is a proton donor and a base is a proton acceptor. HCO3 acts as a proton donor in the reaction HCO3(aq) + OH(aq) H2O(l) + CO32(aq) 17. D NH4Cl and NH3 form a basic buffer. 50 cm3 of 0.1 M NaOH and 50 cm3 of 0.1 M CH3COOH will completely neutralise each other. The HCOONa/HCOOH and CH3COONa/ CH3COOH mixtures form acidic buffers. [conjugate base] pH = log Ka + log [weak acid] For HCOONa/HCOOH, 0.05 pH = log 1.8 104 + log 0.05 = 3.74 (not between pH 4.65.0) For CH3COONa/CH3COOH, 0.05 pH = log 1.8 105 + log 0.05 = 4.74 (between pH 4.65.0) 18. A Mg(OH)2 is a base which easily dissolves in a solution of ammonium chloride (acidic salt) because the ammonium ion, NH4+ acts as an acid. Mg(OH)2 is insoluble in a solution of sodium chloride because sodium chloride is a neutral salt. 19. D Let x = molar solubility of Ag2CO3 Ag2CO3 2Ag+ + CO32 2x x Ksp = [Ag+]2 [CO32] 8.1 1012 = (2x)2x 8.1 1012 = 4x3 x = 1.27 104 M Solubility in g L1 = 1.27 104 mol L1 275.8 g mol1 = 3.5 102 g L1 20. A Element V: IE2 IE1 = 1820 580 = 1240 kJ mol1 IE3 IE2 = 2730 1820 = 910 kJ mol1 IE4 IE3 = 11 600 2730 = 8870 kJ mol1 Element X: IE2 IE1 = 2400 800 = 1600 kJ mol1 IE3 IE2 = 3700 2400 = 1300 kJ mol1 IE4 IE3 = 25 000 3700 = 21 300 kJ mol1 For both V and X, there is a large difference between the 3rd and 4th ionisation energies, showing that a large increase of energy is needed to remove the 4th electron. This means that the rst three electrons are in the outermost shell while the 4th electron is in an inner shell. 21. C The N atom acts as a proton acceptor only in reaction 3. 22. D The intermolecular forces in naphthalene are weak van der Waals forces. Covalent bonds are not involved in the melting process of naphthalene. 16. C 23. D 24. B 25. A The structure of CO2 is O=C=O. The structure of CO is CO. The bond dipoles in CO2 cancel out each other so CO2 is non-polar (I correct). Triple bonds are shorter and stronger than double bonds (II and III incorrect). 26. A CaCO3(s) CaO(s) + CO2(g) There are no gaseous reactants on the left side of the equation while there is one mole of gaseous product (CO2) on the right side of the equation. Therefore, a decrease in pressure will shift the equilibrium towards the right in order to increase the pressure by producing more CO2 gas. 27. A For Ca(OH)2, ionic product Q1 = [Ca2+] [OH]2 = x(2x)2 = 4x 3 For Mg(OH)2, Q2 = [Mg2+] [OH]2 = x(2x)2 = 4x3 For Ni(OH)2, Q3 = [Ni2+] [OH]2 = x(2x)2 = 4x3 Q1 = Q2 = Q3 = 4x3 = 4(1 104)3 = 4 1012 M3 Ksp of Ca(OH)2 = 6.5 106 M3 Ksp of Mg(OH)2 = 7.1 1012 M3 Ksp of Ni(OH)2 = 6.0 1016 M3 As the ionic product for Ni(OH)2 is larger than the Ksp value, Ni(OH)2 will precipitate. 28. A HCl reacts with NH3 to form NH4Cl. At X, both NH3 and NH4Cl are present so the mixture is a buffer solution. At Y and Z, all the NH3 has been completely neutralised by HCl. 29. C From the diagram, at pressures lower than 5.2 atm, solid Z does not melt but sublimes. 30. B S S O O O O O H O C O

O H C

PAPER 2
Section A
1. (a) (i) Molar mass of BaSO4 = 137.3 + 32.1 + 4(16.0) = 233.4 g mol1 Number of moles of SO42 = Number of moles of BaSO4 0.298 g = 233.4 g mol1 = 1.277 103 mol

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Mass of SO42 = 1.277 103 mol 96.1 g mol1 = 0.123 g Mass of SO42 (ii) Percentage of SO42 = 100% Mass of sample 0.123 g 100% 0.205 g = 60.0% 12 (b) Mass of carbon = 1.530 g 44 = 0.4173 g 2 Mass of hydrogen = 0.470 g 18 = 0.0522 g Mass of oxygen = (0.497 0.4173 0.0522) g = 0.0275 g = Element Number of moles Mole ratio C 0.4173 12 = 0.0348 0.0348 1.72 103 = 20.2 H 0.0522 1 = 0.0522 0.0522 1.72 103 = 30.3 O 0.0275 16 = 1.72 103 1.72 103 1.72 103 =1 Number of moles of NH3 4 = 0.555 5 = 0.444 mol Number of moles of NO 6 = 0.555 5 = 0.666 mol Vask = 15.0 L Task = 25 + 273 = 298 K nRT p= V (0.444 0.0821 298) pNH3 = 15.0 = 0.724 atm (0.666 0.0821 298) pNO = 15.0 = 1.086 atm (iii) Total pressure of products = 0.724 atm + 1.086 atm = 1.810 atm (b) (i) C (ii) A (iii) 120 oC (iv) A (v) 60 oC 3. (a) Energy released when one electron falls to a lower energy level 185 103 J 6.02 1023 = 3.07 1019 J hc E = hc = E 6.63 1034 J s 3.00 108 m s1 = 3.07 1019 J = 6.4788 107 m = 647.88 nm (b) E = (3.50 1018 2.00 1018) J = 1.50 1018 J = hc 6.63 1034 J s 3.00 108 m s1 1.50 1018 J = = 1.33 107 m = 133 nm (c) (i) 1s2 2s2 2p6 3s2 3p6 3d 5 4s 2 4p2 (ii) Wavelength of the second line of Balmers series is given by E = 1 1 1 = RH 2 2 n1 n2 1 1 = 1.09 107 2 2 2 4 = 2.0438 106 m1 = 4.89 107 m = 489 nm

Empirical formula of vitamin A = C20H30O (i) Number of moles in 40.0 cm3 of 2 M NaOH 2 40.0 = 1000 = 0.08 mol Number of moles in 60.0 cm3 of 0.5 M NaOH 0.5 60.0 = 1000 = 0.03 mol Molarity of the prepared solution (0.08 + 0.03) mol = 0.100 dm3 = 1.10 M (ii) H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l) Macid Vacid 1 = Mbase Vbase 2 Macid 40.0 1 = 1.10 50.0 2 1.10 50.0 Macid = 2 40.0 = 0.688 M 2. (a) (i) 5N2(g) + 6H2O(g) 4NH3(g) + 6NO(g) (ii) VN2 = 20.0 L T = 173 + 273 = 446 K 772 p= 760 = 1.016 atm Number of moles of N2: pV n= RT 1.016 20.0 = 0.0821 446 = 0.555 mol (c)

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(iii) Electrons in p orbitals have l = 1. Number of electrons in p orbitals in atom L at ground state = 12 (iv) 1s2 2s2 2p6 3s2 3p6 3d7 4. (a) The valence-shell electron-pair repulsion theory states that the electron pairs in molecules and polyatomic ions will orientate themselves to be as far apart as possible in order to minimise the repulsion between them. (b) (i) The phosphorus atom in PCl6 uses 6 hybrid orbitals to form bonds to 6 chlorine atoms. P atom in PCl6: 1s 2s 2p hybrid orbitals electron from negative charge (ii) sp3d2 hybrid orbitals (iii) Octahedral
CI CI P CI CI CI

CI

(c)

(i) Both NH3 and CH4 have weak van der Waals forces existing between the molecules. But NH3 is a polar molecule while CH4 is nonpolar. When molecules have similar relative molecular mass, the more polar molecule tends to have stronger intermolecular forces. In addition, hydrogen bonding exists between NH3 molecules. The hydrogen bond is stronger than van der Waals forces. Thus, NH3 has a much higher boiling point than CH4. (ii) Diamond has a giant covalent structure in which the carbon atoms are held together by strong covalent bonds while aluminium has metallic bonds formed between Al3+ and delocalised valence electrons. A lot of energy is needed to break the large amount of covalent bonds in the giant covalent structure of diamond. Therefore, even though diamond is a covalent molecule while aluminium is a metal, more energy is needed to melt diamond compared to aluminium.

nRT V 17.75 1 pCl2 = 0.0821 300 71 3 = 2.05 atm The calculated pressure (2.05 atm) is signicantly different from the observed pressure (1.6 atm). Therefore, Cl2 does not behave as an ideal gas under these conditions. (iii) Gases deviate from ideal behaviour at low temperatures and high pressures. Under these conditions, the intermolecular forces and the volume of the gas particles are not negligible. (b) The ionic radius decreases from Li+ to B3+ because the electrons are in the same shell (n = 1) but the effective nuclear charge is increasing. A large increase in ionic radius occurs from B3+ to N3 as the number of shells increases from one shell to two shells. The ionic radius decreases from N3 to F because the ions have the same number of electrons but the effective nuclear charge is increasing. All cations have smaller radius compared to anions in the same period because cations have one less shell since the valence electrons have been removed. 6. (a) SO2Cl2(g) SO2(g) + Cl2(g) H = positive Ways to increase chlorine production: (i) Increase the concentration of SO2Cl2. (ii) Remove SO2 or Cl2 from the reaction vessel as soon as they are formed. (iii) Increase the temperature. (iv) Reduce the pressure or increase the volume. (ii) p= (b) SO2Cl2(g) SO2(g) + Cl2(g) Initially (mol) 0.10 0 0 Change (mol) x +x +x At eqm (mol) 0.10 x x x Assume that the volume of the vessel is 1 dm3 and given that x = 0.08 M, at equilibrium, [SO2] = [Cl2] = x = 0.08 M [SO2Cl2] = 0.10 0.08 = 0.02 M [SO2][Cl2] Kc = [SO2Cl2] (0.08)2 = = 0.32 M 0.02 SO2Cl2(g) Initially (mol) 0.02 + 0.07 = 0.09 Change (mol) y At eqm (mol) 0.09 y [SO2][Cl2] Kc = [SO2Cl2] (0.08 + y)2 0.32 = 0.09 y SO2(g) + Cl2(g) 0.08 0.08 +y +y 0.08 + y 0.08 + y

(c)

Section B
5. (a) (i) An ideal gas is a gas which obeys the gas laws and the ideal gas equation pV = nRT. An ideal gas has negligible intermolecular forces and the volume of the gas particles is negligible.

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y2 + 0.48y 0.0224 = 0 y = 0.0428 M Concentration at the new equilibrium: [SO2Cl2] = 0.09 0.0428 = 0.05 M [Cl2] = 0.08 + 0.0428 = 0.12 M A weak acid is an acid which dissociates only partially in water to give hydronium ions. HOCl + H2O OCl + H3O+ HOCl + H2O OCl + H3O+ Initially (M) 0.375 0 0 Change (M) x +x +x At eqm (M) 0.375 x x x + [H O ][OCl ] Ka = 3 [HOCl] x2 3.2 108 = 0.375 x x = 1.095 104 pH = log [H3O+] = log (1.095 104) pH = 3.96 HOCl(aq) + NaOH(aq) NaOCl(aq) + H2O(l) (i) Number of moles of NaOH added MV 0.15 1.15 = = 1.725 104 = 1000 1000 (ii) The contribution of HOCl to the concentration of OCl is very small, so all the OCl present can be assumed to be from the NaOCl formed on addition of NaOH. Total volume of solution = 21.15 cm3 1000 1.725 104 [OCl] = 21.15 = 8.156 103 M Number of moles of HOCl initially 20.00 = 0.375 1000 = 7.5 103 Number of moles of HOCl remaining after reaction with NaOH = 7.5 103 1.725 104 = 7.3275 103 1000 7.3275 103 [HOCl] = 21.15 = 0.346 M [H3O+] [OCl] Ka = [HOCl] [H O+] (8.156 103) 8 3.2 10 = 3 0.346 [H3O+] = 1.36 106 M (iii) pH = log 1.36 106 = 5.87 Kw (iv) [OH] = [H3O+] 1.0 1014 = 1.36 106 = 7.35 109 M (f)
e Mg e
2+

e Mg e Mg2+
2+

e Mg e Mg2+
2+

e Mg e Mg2+
2+

e Mg2+ e Mg
2+

e Mg e
2+

e Mg e Mg2+ e
2+

e Mg e Mg2+
2+

7. (a) (b) (c)

e Mg2+

e Mg2+ e

(d) (e)

The valence electrons of the metal atoms are delocalised. Metallic bonding is due to the electrostatic attraction between the metal cations and the delocalised valence electrons. Mg atoms have 2 valence electrons each which are delocalised to form Mg2+ ions and a sea of electrons. The electrical conductivity of the metal is due to the presence of the mobile valence electrons which can move freely throughout the metal. 8. (a) (i) No change because there are no reactants or products in the gaseous phase. (ii) The concentration of HSO4 will increase because the equilibrium will shift to the left to counteract the decrease in the concentration of H+. (iii) The concentration of HSO4 will increase because the equilibrium will shift to the left to counteract the increase in the amount of H2SO4. (iv) Barium ions and bisulphate ions combine to form a solid. As a result, the concentration of bisulphate ion will be reduced and the equilibrium will shift to the left. Thus, the concentration of hydrogen ions will increase. (v) The equation given can be rewritten as: H3O+(aq) + HSO4(aq) H2SO4(aq) + H2O(l) The addition of water will shift the equilibrium to the left. (b) (i) The vapour pressure of a liquid is the pressure exerted by the vapour above the surface of the liquid, measured when the vapour is in equilibrium with the liquid, that is, when the rate of condensation equals the rate of vaporisation. (ii) When the molecules at the liquid surface receive heat from the surroundings, the kinetic energy of the molecules at the surface increases. The molecules at the surface gain enough kinetic energy to overcome the intermolecular forces of attraction and escape into the vapour phase.

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9. (a) (i) The Lewis structure of I3 can be written as follows: Hydrogen chloride is a polar molecule, thus dipoledipole forces exist between its molecules. However, HCl cannot form hydrogen bonds and dipoledipole forces are not as strong as hydrogen bonds. Thus, the boiling point of HCl is lower than that of ammonia. Carbon dioxide is a non-polar molecule with weak London forces. However, CO2 is a bigger molecule than HCl. If the only intermolecular forces are van der Waals forces and the molecules are signicantly different in size, the molecule with the larger size will have stronger intermolecular forces. Therefore, CO2 has a slightly higher boiling point than HCl. (c) Assume x mol of BaSO4 is dissolved per dm3 of Ba(NO3)2. BaSO4(s) Initially (M) At equilibrium (M) Ba2+(aq) + SO42(aq) 0.010 0 0.010 + x x

[I I I]

There are 5 electron pairs around the central atom so the orientation of the electron pairs is trigonal bipyramidal. Lone pairs exert greater repulsion than bond pairs, so the three lone pairs occupy the equatorial positions to minimise repulsion. The bond pairs are located above and below the plane.

I
Therefore, I3 has a linear shape. (ii) sp3d hybrid orbitals (iii) 10. (a)
I

Ksp = [Ba2+][SO42] 1.1 1010 = (0.010 + x)x Assume x << 0.010 0.010 + x = 0.010 1.1 1010 = (0.010)x x = 1.1 108 The molar solubility of BaSO4 in 0.010 mol dm3 Ba(NO3)2 is 1.1 108 mol dm3. Al Period 3 13 p Si 3 14 p

Group Block

sp3d hybrid orbitals

Conguration of valence electrons of I: I 5s 5p 5d (ground state): I 5s 5p 5d (excited state): hybridisation I (hybridised: state)

sp3d hybrid orbitals (b) Ammonia is a polar molecule so dipoledipole forces exist between its molecules. In addition, ammonia can also form strong hydrogen bonds between molecules. Hence its boiling point is the highest.

(b) (i) Al and Si are in the same period (Period 3). Moving across the period from Al to Si, the proton number increases and the effective nuclear charge increases. So the valence electrons in Si are more strongly attracted by the nucleus and are pulled closer to the nucleus compared with the valence electrons in Al. Thus, the atomic radius of Si is smaller than that of Al. (ii) The first ionisation energy of Si is greater than Al. This is because the valence electrons in Si are held more tightly by the nucleus since Si has smaller atomic radius and greater effective nuclear charge. More energy is required to remove a valence electron from Si compared to Al. (iii) Al has a high melting point because it is a metal and thus has metallic bonding. However, Si has a giant covalent structure. Each Si atom is bonded to four other Si atoms by covalent bonds in tetrahedral arrangement. A lot of energy is required to break the strong covalent bonds between

395
the Si atoms in the giant covalent structure. Thus, the melting point of Si is even higher than that of Al. (c) The fourth electron. This is because the fourth electron is being removed from an inner shell (2p) which experiences stronger nuclear attractions. [CH3COO] (d) pH = pKa + log [CH3COOH] [CH3COO] 4.74 = log 1.75 105 + log [CH3COOH] [CH3COO] = 0.017 log [CH3COOH] [CH3COO ] = 0.962 ..(1) [CH3COOH] HCl + CH3COONa CH3COOH + NaCl Let the concentration of HCl added = x [CH3COOH] = concentration of CH3COOH formed after the addition of HCl = concentration of HCl added =x [CH3COO] = concentration of CH3COO left after reaction with HCl [CH3COO]initial = 0.1 M [CH3COO] after reaction with HCl = 0.1 x [CH3COO] 0.1 x = x [CH3COOH] = 0.962 1.962x = 0.1 0.1 x= 1.962 = 0.0510 M Number of moles of HCl 500 = 0.0510 1000 = 0.0255 mol Mass of HCl = 0.0255 36.5 = 0.931 g