H2 REVISION PACKAGE FOR BT1 2012

SOLUTIONS TO INORGANIC CHEMISTRY QUESTIONS

MCQs Section A

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

C D B C D B B A C A A D C A C B A A D A

21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

D D C A B C D C A B D B B A B C A D B D

41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

A C C A C B C C C D C D C C B D C C B C

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80

D B C A C B D D C B C D D C B C C B B D

81 82 83 84 85 86 87 88 89 90 91 92

B A D B C A D C D D B C

MCQs Section B 1 2 3 4 5 6 7 8 9 10 B B B C C C B B B C 11 12 13 14 15 16 17 18 19 20 C A D A D B B A C B 21 22 23 24 25 A A D B B

Structured/Free-Response 1 (a) Sodium, magnesium and aluminium are metals. They have metallic structures consisting of a regular arrangement of cations in a sea of delocalised electrons which allows them to conduct electricity. Conductivity increases from sodium to aluminum due to an increase in the number of valence electrons. Silicon is a metalloid with a low conductivity. Phosphorous, sulphur, chlorine and argon are non-conductors of electricity because they are non-metals with no mobile electrons. (b) Na2O is an ionic oxide which is basic in nature. It has no reaction with NaOH but

reacts with HCl to form a salt. Na2O + 2 HCl 2 NaCl + H2O Due to the high charge density on Al3+ ion and the large extent of polarization in Al2O3 , Al2O3 is an ionic compound with covalent character. Hence it is amphoteric and can react with both HCl and NaOH. Al2O3 + HCl 2 AlCl3 + 3 H2O Al2O3 + 2 NaOH + 3 H2O 2 Na+ + 2 [Al(OH)4]SiO2 is a covalent oxide which is acidic in nature. Hence it has no reaction with HCl but only NaOH to form a salt. SiO2 + 2 NaOH Na2SiO3 + H2O (c) (i) (ii) Na2O2 + CO2 Na2CO3 + H2O

Total volume of CO2 exhaled = 8 x 600 = 4800 dm3 Amount of CO2 exhaled = 4800 / 24 Amount of Na2O2 needed = 200 mol Mass of Na2O2 needed per day = 200 x (23.1 x 2 + 16.0x 2) = 15 600 g = 200 mol

(a)

(ii)

Due to the high charge density of Al3+ ion, it undergoes hydrolysis readily in water to form a strongly acidic solution.

(iii)

AlCl3

+ 6 H2O [Al(H2O)5(OH)] Cl2 + HCl

PCl5 + 4 H2O H3PO4 + 5 HCl (b) (i) Mg or Al Only oxides of Mg, Al and Si are insoluble in water. However, only oxides of Mg and Al are able to react with acids. (ii) Add aqueous sodium hydroxide. Only Al2O3 will dissolve in aqueous NaOH to give a colourless solution. MgO will not dissolve. 3 (a) X: Na Y: Al

A neutral solution is formed which does not react with Na 2CO3 when the chloride of X is dissolved in water.

Vigorous reaction of X with water implies that X could be sodium. Na + H2O NaOH + H2 NaCl Na+ + ClFrom the reaction shown, the compound has undergone electrophilic substitution of the benzene ring, hence a halogen carrier is needed. Therefore, Y is Al. Al is unreactive towards water due to the layer of the protective oxide layer. (b) Si has a giant molecular structure, where Si and O atoms are bonded by strong covalent bonds. Large amount of energy is needed to break the covalent bonds, hence it has the highest melting point. P4, S8, Cl2 and Ar are non-polar, simple covalent molecules with weak van der waals forces existing between the molecules. Hence, little amount of energy is needed to overcome the weak van der Waals forces and so, they have low melting points. The strength of van der Waals forces depends on the number of electrons in the molecule. The greater the number of electrons, the more polarisable the molecule becomes, the stronger the van der waals forces. Since the number of electrons of S 8 is larger than P4, Cl2 and Ar, it has the highest melting point, followed by P 4, Cl2 and Ar. (c) SiO2 is insoluble in water because it has a giant covalent structure with strong covalent bonds. Na2O reacts with water to form an alkaline solution: Na2O + H2O 2 NaOH SiO2 is an acidic oxide which will react with the alkaline solution to form a salt and water: SiO2 + 2 NaOH Na2SiO3 + H2O 4 (a) Aluminium chloride has a simple molecular structure. Less energy is needed to overcome the weak van der Waals forces between the molecules. Chromium (III) chloride has a giant ionic structure with strong ionic bonding between the oppositely charged ions. Large amount of energy is needed to overcome the ionic bonding and hence, it has a much higher melting point. (b) Al3+ ions have high charge density due to its small size and high charge.

It polarizes the water molecule strongly, weakening the OH bond to form H+. Hence, it undergoes hydrolysis. [Al(H2O)6]3+ (c) (i) (ii) [Al(H2O)5(OH)]2+ + H+

Al2O3 is able to react with both acids and alkalis. Al2O3 + 6 H+ 2 Al3+ + 3 H2O Al2O3 + 2 OH- + 3 H2O 2 Al(OH)4 -

(a)

(i)

Both Na2O and Al2O3 have giant ionic structures with strong ionic bonds between the oppositely charged ions which require a lot of energy to break them resulting in high melting points. Al3+ ions have a higher charge and smaller ionic radius than Na +, hence the lattice energy for Al2O3 is higher than Na2O. This accounts for the higher melting point of Al2O3 than Na2O. SO3 has a simple molecular structure with weak van der Waals forces between the molecules. Small amount of energy is needed to break them resulting in a low melting point.

(ii)

Na2O dissolves readily in water to give a strongly alkaline solution of pH 13 (or 14). Na2O + H2O 2 NaOH Al2O3 is insoluble in water due to its extremely high lattice energy. SO3 dissolves readily in water to give a strongly acidic solution with pH 1 or 2. SO3 + H2O H2SO4

(b)

Mr of AgCl = 143.5 No. of moles of AgCl precipitated = 0.574 / 143.5 Mr of Si2OCl6 = 285.2 No. of moles of Cl in Si2OCl6 = (0.2 / 285.2) x 6 Mr of Si3O2Cl8 = 400.3 No. of moles of Cl in Si3O2Cl8 = (0.2 / 400.3) x 8 = 4.00 x 10-3 mol = 4.21 x 10-3 mol = 4.00 x 10-3 mol

Since the number of moles of Cl in AgCl = No. of moles of Cl in Si3O2Cl8 therefore, the identity of the oxochloride = Si3O2Cl8 6 (a) Most d-block compounds are coloured due to the splitting of the d-orbitals in the metal ion. When they are bonded to ligands, the 3d orbitals undergo splitting, resulting in 2 groups of non-degenerate orbitals. This is called the d-d splitting. By absorption of energy, electrons can be promoted from a lower energy d-orbital to a higher energy d-orbital. This is called the d-d transition. The light not absorbed is thus seen as the colour of the complex. Sc and zinc compounds are colourless because such d-d transitions cannot occur in ions with empty d-orbitals or completely filled d-orbitals. (b) Copper(II) sulphate salts dissolve in water to give a blue colour solution, which is attributed to [Cu(H2O)6]2+ (aq) CuSO4 (s) +aq [Cu(H2O)6]2+ (aq) + SO42- (aq) Blue solution When dilute aqueous NH3 is gradually added, a blue precipitate of Cu(OH) 2 is first formed. NH3 + H2O NH4+ + OH-

[Cu(H2O)6]2+(aq) + 2OH-(aq) Cu(OH)2(s) + 6H2O blue solution blue precipitate When excess aqueous NH3 is added, the precipitate dissolves to give a deep blue solution, due to the formation of the soluble complex ion, [Cu(NH3)]2+. Cu(OH)2 + 4NH3 + 2H2O [Cu(NH3)4(H2O)2]2+ + 2OHdeep blue solution

NH3 is a stronger ligand than H2O, so it displaces water from [Cu(H2O)6]2+ to form [Cu(NH3)4(H2O)2]2+. Overall reaction: (c) [Cu(H2O)6]2+ + 4NH3 blue solution [Cu(NH3)4(H2O)2]2+ + 4H2O deep blue solution

The uncatalysed reaction is slow due to high activation energy since 2 negatively ions S2O82- and I- are involved and they repel each other The Co3+ acts as a homogenous catalyst in this redox reaction of I - and S2O82-. The catalysed pathway involves two steps: Step 1: 2Co3+ + 2I- 2Co2+ + I2

Reduction: Co3+ + e Co2+ Oxidation: 2 I- I2 + 2 e Ecell= 1.82 + (-0.54) = + 1.28 V

Ered = +1.82 V Eoxd = - 0.54 V

Step 2: 2Co2+ + S2O82- 2Co3+ + 2SO42Reduction: S2O82- + 2e 2SO42Ered = +2.01 V 2+ 3+ Oxidation: Co Co + e Eoxd = -1.82 V Ecell = 2.01 + (-1.82) = +0.19V Overall: S2O82- + 2I- 2SO42- + I2 Both steps in the catalysed reaction involve the interaction of oppositely charged ions, which attract one another strongly; hence the activation energy is lower and enhances the rate of reaction. 7 Ti 4+ : [Ar]3d0 and Ti 3+ : [Ar] 3d1

Ti3+ has one d electron. In [Ti(H2O)6]3+, the presence of the H2O ligands causes the 3d orbitals to split into 2 different energy levels which are close in energy. When energy from light is absorbed, the d electron can be promoted from the lower energy to higher energy dorbital. The light energy not absorbed will be seen as the colour of the complex. Ti4+ has no d electron and d-d transition cannot occur. Hence, it appears colourless. 8 (a) Transition elements are able to exhibit a variety of oxidation states because of the close similarity in energy of the 4s and 3d electrons. Hence, transition metals are able to lose all of the electrons in the 3d and 4s subshells. (b) No. of moles of KMnO4 used = (20.0 / 1000) x 0.100 = 2.00 x 10-3 mol =1.00 x 10-2 mol

No. of moles of electrons gained by MnO4- = 2.00 x 10-3 x 5 Mole ratio of VOClx : electrons 0.01 : 1.00 x 10-2 1: 1 Hence, the oxidation number of vanadium increases by 1. Therefore, the original oxidation state of V in VOClx = +4 x=2

(a)

In the complex, the degenerate 3d orbitals are split into 2 sets of different energy levels, separated by a small energy gap. Electrons absorb energy from light and are promoted from a lower to a higher energy 3d orbitals. The wavelength of light not absorbed will be seen as the colour of the complex.

(b)

No. of moles of KMnO4 = (19.60 / 1000) x 0.02 No. of moles of Fe = no. of moles of Fe2+ = (3.92 x 10-4) x 5 = 1.96 x 10-3 mol

= 3.92 x 10-4 mol

Percentage of iron in the meteorite = [(1.96 x 10-3 x 55.8) / 0.20] x 100% = 54.7 % 10 (a) Due to the close proximity in energies of the 4s and 3d orbitals, transition metals can exhibit variable oxidation states by losing different number of electrons in the 3d and 4s orbitals. (b) In the presence of ligands, the degenerate 3d orbitals in copper (II) ions are split into 2 sets with different energies with a small energy gap between them. When a d-electron from the lower energy group is promoted to the higher energy group (d-d transition), light energy is absorbed. The light energy not absorbed will be seen as the colour of the complex. 11 (a) (i) Across the period from Na to Cl, nuclear charge increases; but increase in shielding effect is negligible as electron is added to the same quantum shell; Hence, the effective nuclear charge increases OR the electrostatic forces of attraction between the nucleus and the outermost/ valence electrons increases across the period. (ii) Therefore, the atomic radius decreases across the period from Na to Cl.

Na+ has one electron less than Na or Na+ has one quantum shell less than Na. Nuclear charge remains the same. The electrostatic forces of attraction between the nucleus and the remaining electrons are greater for Na+.

(b)

(i)

(ii)

The anionic radii of P3, S2 and Cl are larger than their respective atoms. This is due to electrons are being added to the same valence shell, resulting in greater inter-electronic repulsions between the valence electrons. Across the period from P3, S2 and Cl, the anionic radii decrease. The nuclear charge increases across the period with negligible increase in shielding effect resulting in the corresponding increase in the effective nuclear charge OR electrostatic forces of attraction between the nucleus and the valence electrons.

12

(a)

(i)

Al2O3 has a giant ionic lattice structure with strong ionic bonds / high lattice energy / partial covalent character, hence it is insoluble. SiO2 has a giant molecular structure with strong covalent bonds requiring large amounts of energy to break, hence it is insoluble.

(ii)

AlCl3 dissolves to give [Al(H2O)6]3+(aq) which undergoes hydrolysis due to the high charge density on Al3+: [Al(H2O)6]3+ [Al(H2O)5(OH)]2+ + H+ OR 2AlCl3 + 6H2O Al2O3 + 6HCl OR AlCl3 + 3H2O Al(OH)3 + 3HCl SiCl4 hydrolyses in water to give HCl, a strong acid / H+ is produced: SiCl4 + 2H2O SiO2 + 4HCl

OR SiCl4 + 4H2O Si(OH)4 + 4HCl 13 (i) (ii) AB(CO3)2 AO + BO + 2CO2 Assume: AB(CO3)2 AO(s) + BO (aq) + 2CO2 0.057 (0.275-0.057) x

Masses given: 0.400

Therefore, x = 0.400 0.275 = 0.125 g (iii) Soln: Let Ar of A be a and that of B be b AB(CO3)2 AO(s) + BO (aq) + 2CO2 Mass/g: 0.400 0.057 0.218 0.125 Determining amts and using mol ratios Amt of CO2 = 0.125/44 = 0.00284 mol Amt of AO = 0.057/(a + 16) = 0.00284/2 mol Giving a = 24.1, Giving b = 137.5, 14 (a) Therefore A is Mg Therefore B is Ba Amt of BO = 0.218/(b + 16) = 0.00284/2 MOL

The alkaline earth metals exhibit +2 oxidation state in their compounds because they have 2 valence electrons which are lost to achieve stable octet. They do not exhibit +1 oxidation state due to the low lattice energy of the compounds formed. +3 oxidation state is also not favorable due to the very high 3rd ionization energy required to remove the third electron from the inner quantum shell.

15

(a)

(i) (ii)

CaCO3(s) CaO(s) + CO2(g) From Data Booklet: Zn2+ : 0.074 nm; Ca2+ : 0.099 nm

Since Zn2+ has a larger cationic radius than Ca2+, the charge density of Zn2+ is larger and it has a higher polarizing power than Ca 2+. This leads to a greater distortion of CO32- electron cloud, thus there is greater weakening of bonds in CO32-. thermal stability of ZnCO3 < CaCO3. (iii) O O C O

16

(b)

(i) Bond Energy

1

HCl (kJmol ) 431

HBr 336

HI 229

ease of breaking the HX bond: HCl < HBr < HI thermal stability: HCl > HBr > HI (ii) 17 (b) (i) Hydrogen bonding exist between HF molecules x=3 2ICl3 + 6I- 4I2 + 6Cl18 (a)

19

(a)

Iodine oxidises thiosulfate to tetrathionate resulting in a change of average oxidation number from +2 to +2.5: I2 + 2S2O32 2I + S4O62

Chlorine oxidises thiosulfate to sulfate(VI) resulting in a change of average oxidation number from +2 to +6: 4Cl2 + S2O32 + 5H2O 8Cl + 2SO42 +10H+

Since chlorine is able to increase the oxidation state of S in thiosulfate more greatly than iodine, chlorine has higher oxidising power than iodine.

(b)

(i) (ii)

NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g) Hydrogen iodide formed is oxidised by conc H 2SO4 to iodine since HI is easily oxidised.

(iii) 20 (a)

Concentrated phosphoric(V) acid.

Any two properties: Fe has a higher melting/boiling point than Al. Fe has stronger metallic bonds as both the 3d and 4s electrons can be used in metallic bonding due to their proximity in energies, hence more energy is required to overcome the stronger bonds. Fe has a greater density than Al. Fe has a greater atomic mass but its atomic radius is smaller. Hence atomic volume is smaller. Since density = mass/volume, density of Fe is greater than Al. Fe has better conductivity than Al as both the 3d and 4s electrons are available in the mobile sea of electrons due to the proximity in energy of 3d and 4s orbitals. Fe is harder than Al due to stronger metallic bonding in Fe as Fe can use both its 3d and 4s electrons for metallic bonding due to the proximity in energy of 3d and 4s electrons.

(b)

26 26

Fe

1s2 2s2 2p6 3s2 3p6 3d6 4s2

13

13

Al

1s2 2s2 2p6 3s2 3p1

Fe3+ 1s2 2s2 2p6 3s2 3p6 3d5

Al3+

1s2 2s2 2p6

Although Fe has one more quantum shell than Al and higher nuclear charge, the increase in shielding effect due to the d electrons is proportionately less than the increase in nuclear charge, hence Fe experiences higher effective nuclear charge and is smaller. Fe3+ has one more quantum shell than Al3+ and the additional shielding is due to s and p electrons which are more effective in shielding compared to d electrons. 21 (a) Fe(H2O)63+ = Fe(H2O)5(OH)2+ + H+

(b)

(i) (ii)

1s22s22p63s23p63d10 Colourless because Cu+ does not have unfilled/ partially filled d-orbital

22

(a)

(b)

23

(i) (ii) (iii)

K2Cr2O7 + 2 HBr

2 KCrO3Br + H2O

No, oxidation no. of Cr doesnt change, remains at +6 Eocell = +1.33 (+1.07) = +0.26 V >0 Products should be Cr3+(aq) and Br2(l)

(iv)

Reaction didnt take place at standard condition. OR The reaction in step I took place under cooled conditions.

(v) (vi)

AgBr Cr is reduced from +6 (orange solution of Cr 2O72-) to +3 Cr3+ (deep green solution)

24

25

26

(a)

X = Mg Y = Ca or Sr or Ba Reason: Reducing power increases down the group.

(b) (c)

High melting point of MgO (i) SiO2 does not dissolve in water. pH 7 Na2O dissolves readily in water to give a colourless solution. Na2O + H2O 2NaOH

pH 13-14 CaO dissolves sparingly in water. CaO + H2O pH 9-12 (ii) The basic metal oxide will react / undergo neutralisation with the acidic SO2. OR Acid-base reaction (d) (i) Br2 has a smaller electron cloud size than I2. electron cloud of Br2 is less polarisable weaker Van der Waals forces between the molecules More energy is required to overcome the interaction between I 2 molecules, leading to a higher boiling point. (ii) Cl- has one more electron; hence its p/e ratio is smaller attraction of the nucleus for the outer electrons is weaker. Therefore it has a bigger radius. OR electron-electron repulsion (e) Disproportionation 3Cl2(g) + 6OH-(aq) 5Cl-(aq) + ClO3-(aq) + 3H2O(l) Smell of Cl2 disappears OR greenish-yellow/pale green/green colour of Cl2 disappears (hard to observe) 27 Li+ is much smaller than Cs+ Charge density of Li+ is higher than that of Cs+ I3- is polarized to a greater extent by Li+ CsI3 is more stable than LiI3. 28 (i) F : [Fe(CN)6]4G : [Fe(CN)6]3(ii) Ligands are molecules or ions that possess at least one lone pair electrons that can form dative covalent bonds to the central metal ion. Transition elements have strong tendency to form complexes as their cations Ca(OH)2

are small and highly charged. Central metal ion have empty low-lying 3d orbitals to accommodate the lone pair electrons from the ligands. (iii) (iv) Fe3[Fe(CN)6]2 / Fe4[Fe(CN)6]3 Hexadentate ligand EDTA can form a very stable complex with Fe 2+, thus removing the catalytic effect of Fe2+ 29 (a) (i) SiO2 is insoluble in water due to the high bond dissociation energy needed to break the strong SiO covalent bonds. SiCl4 (l) + 4H2O (l) Si(OH)4 (s) + (ii) Green Red 30 (i) (ii) (iii) Co(OH)2 [Co(NH3)6]2+ [Co(NH3)6]3+ Oxidation by O2(g) in the air (iv) 31 (i) 2Co3+ + 2I- 2Co2+ + I2 G is hydrogen peroxide BaO2 + 2H2O Ba(OH)2 + H2O2 Hydrogen peroxide which in acidified condition, acts as a reducing agent to reduce MnO4- ions to Mn2+ ions. (ii) Ca2+ being the smaller cation than Ba 2+, has greater charge density and has better ability to polarise/distort the large electron cloud of the nitrate ion. As a result, one N-O bond is weakened and the nitrate ion is more easily decomposed to form an oxide anion. Conversely, Ba 2+ ions are large and have the lower charge density, resulting in poorer polarising power. Thus, the Ba 2+ cation does not have the ability to distort the electron cloud of the nitrate ions. Hence, Ba(NO3)2 is more stable to heating than Ca(NO3)2 . 4HCl (aq)

32

(i)

T: I2 U: Br2

(ii) (iii)

4Br2 + S2O32- + 5H2O 8 Br + 2SO42- + 10H+ Having the highest E= +1.36V, Cl2 is a strongly oxidizing, it is able to oxidise sulphur in +2 oxidation state in S2O32- to +6 oxidation state in SO42-. 4Cl2 + S2O32- + 5H2O 2SO42- + 10H+ + 8Cl-

Br2 is also quite oxidising, E=+1.07 V. It is able to oxidize S2O32- to SO42-. 4Br2 + S2O32- + 5H2O 2SO42- + 10H+ + 8 Br

Being less oxidizing (E=+0.54V), I2 is only able to oxidize sulphur in +2 oxidation state in S2O32- to + 2.5 oxidation state in S4O62-. I2 + 2S2O32- S4O62- + 2IThis trend is supported by the decreasing oxidising power down the group as illustrated by E0 values. (iv) 33 (i) Aqueous iron(II) sulfate, followed by aqueous sodium hydroxide Transition metal ions have empty 3d orbitals, thus they can act as Lewis acids (electron pair acceptors) and form dative bonds with ligands to form complexes. (ii) Copper (II) salts dissolve in water to give a blue colour solution, which is due to the complex ion [Cu(H2O)6]2+. When dilute aqueous NH3 is gradually added, a blue precipitate of Cu(OH)2 is first formed. NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) [Cu(H2O)6]2+(aq) + 2OH-(aq) Cu(OH)2(s) + 6H2O (l) blue solution blue precipitate When excess aqueous NH3 is added, the precipitate dissolves to give a deep blue solution due to the formation of the soluble complex ion, [Cu(NH3)]2+. Cu(OH)2(s) + 4NH3(aq) + 2H2O(l) [Cu(NH3)4(H2O)2]2+(aq) + 2OH-(aq) deep blue solution NH3 is a stronger ligand than H2O and so, displaces water from [Cu(H2O)6]2+ to form [Cu(NH3)4(H2O)2]2+, which is deep blue in colour. Overall reaction:

[Cu(H2O)6]2+(aq) + 4NH3(aq)
blue solution Cu(OH)2(s) CuO(s) + H2O(l) 34 (i) A = Na NaO and NaCl are giant ionic solids . Na2O (s) + H2O (l) 2NaOH (aq) NaCI (s) Na+ (aq) + CI- (aq) (ii) B=P P4O10 (s) + 6H2O (l) 4H3PO4 (aq) Or P4O6 (s) + 6H2O (l) 4H3PO3 (aq)

[Cu(NH3)4(H2O)2]2+(aq) + 4 H2O(l)
deep blue solution

On heating, the precipitate forms copper(II) oxide.

PCI3 (l) + 3H2O (l) H3PO3 (aq) + 3HCI (aq) Or PCI5 (l) + 4H2O (l) H3PO4 (aq) + 5HCI (aq) (iii) C= Si SiO2 has giant molecular structure with strong covalent bonds between atoms, thus insoluble in water. 35 Solubility of Li2O is lower than that of BaO. Therefore, the basicity of Li2O is also lower than that of BaO. 36 (a) (i) X is Na/ Mg W is Si (ii) (b) SiCl4 + 2H2O SiO2 + 4HCl

To 2 separate samples of the powder, add in dilute HCl and dilute NaOH respectively. If the powder dissolves in both dilute HC l and dilute NaOH to form colourless solution, it is Al2O3. If the powder dissolves only in dilute HCl to form colourless solution, it is MgO. If the powder does not dissolve in both dilute HCl and dilute NaOH, it is SiO2.

37

(a)

(i)

To increase the yield of PCl5 since reaction is exothermic. To cool the exothermic reaction for safety.

(ii)

PCl5 will react/hydrolyse in water to give an acidic solution. PCl5(s) + H2O(l) POCl3(aq) + 2HCl(aq) OR PCl5(s) + 4H2O(l) H3PO4(aq) + 5HCl(aq)

(b)

A white precipitate of AgCl is obtained when sodium chloride is mixed with silver nitrate. Precipitate dissolves in aqueous ammonia to give a colourless solution of Ag(NH3)2+. Ag+(aq) + Cl(aq) AgCl(s) Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq) When NH3 is added, the formation of the complex ion decreases the concentration of Ag+, causing equilibrium position of the equilibrium AgCl Ag+ + Cl to shift to the right such that ionic product < Ksp(AgCl).

(c)

NaAt(s) + H2SO4(l) HAt(g) + NaHSO4(s) 2HAt(g) + H2SO4(l) At2(g) + SO2(g) + 2H2O(l) 8HAt(g) + H2SO4(l) 4At2(g) + H2S(g) + 4H2O(l)

38

(d)

(i)

E is MgCO3 F is CO2 G is Mg(NO3)2.6H2O or Mg(NO3)2. xH2O

(ii)

MgCO3 MgO + CO2 MgCO3 + 2HNO3 Mg(NO3)2 + H2O + CO2 2Mg(NO3)2. xH2O 2MgO + 4NO2 + O2 + xH2O

(iii)

Mg2+

has

smaller

radius

than

Ba2+. polarising

Mg2+ has a higher charge density than Ba2+ and hence stronger power to polarise the electron cloud of the large NO3 anion. 39 (a) (ii)

In the presence of water, AlCl3 undergoes hydrolysis to form an acidic solution of pH 3. AlCl3 (s) + aq [Al(H2O)6]3+ (aq) + 3Cl (aq) [Al(H2O)5(OH)]2+ (aq) + H3O+ (aq)

[Al(H2O)6]3+ (aq) + H2O (l)

The acidic nature of the solution is due to the relatively small but highly charged

Al3+ ion which polarizes the surrounding water molecules to give up H+ ions. (iii) SiCl4 (l) + 4H2O (l) Si(OH)4 (s) + PCl5 (s) + 4H2O (l) 40 (a) (i)
conc. H2SO4

4HCl (aq) 5HCl (aq)

H3PO4 (aq) +

dehydration of alcohol to form alkene:

H2C CH2 + conc. H2SO4 H2O

CH3CH2OH

OR esterification: RCO 2H + R'OH

RCO2R' + H2O

nitration of benzene:
NO2 + conc. HNO3 conc. H2SO4 + H2O

RCO2H + R'OH OR esterification:

conc. H2SO4

RCO2R' + H2O

CH =CH2 + H2O OR hydration2of alkene:

conc. H2SO4

CH3CH2OH

(ii) (b) (i) (ii)

H2SO4 (l) + NaBr (s) HBr (g) + NaHSO4 (aq) H2SO4 (l) + 2HBr (g) Br2 (g) + SO2 (g) + 2H2O (l)
Tetrachloromethane / hexane (or any other non-polar organic solvent) The halide is iodide. 2I(aq) + Cl2(g) 2Cl(aq) + I2(aq)

41

(a)

(i)

A: [Cr(H2O)6]3+ B: [Cr(H2O)6]2+ C: Cr(OH)3 or Cr(H2O)3(OH)3 D: CrO42 or Na2CrO4

(ii)

E:

3+

H2 N N H2

H2N Cr H2N NH2 NH2

(iii)

Cr3+ has a high charge density. Hence [Cr(H 2O)6]3+ can undergo hydrolysis in water to produce H+ ions, forming CO2 with carbonate ions.

(iv) (b)

Ligand exchange

Cr3+ has d3 electronic configuration. In an octahedral ligand field, the 6 NH3 ligands will split the five degenerate 3d orbitals into 2 groups of different energy levels. The difference in the two energy levels, E, falls within the visible region of the electromagnetic spectrum. An electron in a lower d orbital energy level can absorb radiation in the visible spectrum and be promoted into the higher d orbital energy level. This dd electron transition gives rise to the colour as the complement of the absorbed colour.

42

(i)

Both Cl2 and I2 exist as diatomic molecules and have dispersion forces existing between molecules. I, being lower down in the group than C l, has a bigger electron cloud size and hence, stronger dispersion forces. Therefore I2 is less volatile than Cl2.

(ii)

4Cl2 (aq) + S2O32 (aq) + 5H2O (l) 8Cl (aq) + 2SO42 (aq) + 10H+ (aq) I 2 (aq) + 2S2O32 (aq) 2I (aq) + S4O62 (aq)

Cl2 + 2e 2Cl I2 + 2e 2I 36

E / V +1 +0.54

ECl2/Cl is more positive than EI2/I, indicating that Cl2 is a stronger oxidizing agent than I2. Hence, Cl2 can oxidize S2O32 to SO42 while I2 can only oxidize S2O32 to S4O62. 43
Melting point /oC

(a)

M.p. /oC

Na

Mg

Al

Si

SP

Si

Cl

Ar

High melting point from Na to Al as they exist as giant metallic structures with strong metallic bonds of increasing strengths due to smaller cationic radius and increased number of delocalized electrons. Very high melting point for Si as it exists as a giant covalent structure with an extensive network of strong covalent bonds. These strong bonds require a lot of energy to break before melting can occur. Low melting point from P to Ar as they exist as simple molecular structures, consisting of discrete molecules with weak dispersions forces between the molecules. Melting point decreases from S8 > P4 > Cl2 > Ar because the size of the electron clouds decreases from S8 > P4 > Cl2 > Ar, such that dispersion forces are weaker. (b) Mg(OH)2 is basic, and reacts only with acids: Mg(OH)2(s) + 2HCl (aq) MgCl2(aq) + 2H2O(l) Be(OH)2 is amphoteric, and reacts with both acids and bases:

Be(OH)2(s) + 2HCl (aq) BeCl2(aq) + 2H2O(l) Be(OH)2(s) + 2NaOH(aq) Na2Be(OH)4(aq) 44 (a) (i) A = [Fe(H2O)6]2+ B = [Fe(H2O)6]3+ (ii) X = K2Cr2O7 or KMnO4 or Cl2 or H2O2 (or in words) Y = potassium thiocyanate or KSCN (or NH4CN) (iii)

(b)

(i)

This is due to the presence of partially-filled 3d subshells that can accept electrons from lone pairs or form temporary bonds with reactant molecules during adsorption, thus weakening the bonds in the reactant molecules and lowering the activation energy of the reaction.

(ii) Energy / kJ mol1

Ea (uncatalysed) N2 + H2 H Ea (catalysed)

NH3 Reaction progress Al2O3 + 6H+ 2Al3+ + 3H2O Al2O3 + 2OH + 3H2O 2[Al(OH)4]-

45

(a)

(i)

(b) (i) Ionic Radius

pH

Na S

Mg Cl

Al

Si

Na2O SO3

MgO

Al2O3

SiO2

P4O10

(ii)

Ionic Radius: There are two isoelectronic series in period 3. Within each series, an increasing number of protons results in increasingly stronger nuclear attraction experienced by the valence electrons. Valence electrons are pulled closer to nucleus, leading to a decreasing trend in ionic radius. Anionic series has a larger size than cationic series as the valence electrons are in a higher principal quantum shell, experience weaker nuclear attraction and are less tightly held. pH: Na2O and MgO are ionic oxides that dissolve completely in water to form

basic solution. Al2O3 and SiO2 are insoluble in water pH of solution is that of water. P4O10 and SO3 are covalent oxides that hydrolyse in water to give acidic solution. (c) 46 (a) (i) [Mg(H2O)6]2+ + H2O
x x x

[Mg(H2O)5(OH)]+ + H3O+

2+ Ca

x x

x O Ix

O x

(b)

(i)

Calcium iodate is white as the electronic transitions are between different principal quantum shells. In the presence of ligands, the degenerate d-orbitals of Fe ions undergo dsplitting. An electron in the lower energy d-orbital undergoes d-d transition by absorbing visible light.

(ii)

Fe has more protons than Ca, thus has a higher nuclear charge. The inner 3d electrons of Fe are poor shielding compared to the inner 3s and 3p electrons of Ca. Thus, the valence electrons of Fe experience greater attraction to the nucleus and require more energy to remove compared to Ca.

(c)

(i) (ii)

2 Ca(IO3)2 (s) 2 CaO (s) + 2 I2 (g) + 5 O2 (g) The charge density of the ions given by group. Hence, polarizing power of the ions decreases and the electron cloud of the iodate ion is polarized to a smaller extent. The iodine-oxygen bonds in the iodate ion becomes less weakened and more energy is required to break the bonds. Thus, thermal stability of the group II iodates increase.
charge decreases down the ionic radius

47

(b)

(i)

e- config of cation if Y : 1s2 2s2 2p6 3s2 3p6 3d9 Identity of X : NH3 or ammonia

(ii)

(Y represents Cu)

Cu(NO3)2 + 6H2O [Cu(H2O)6]2+ + 2NO3Blue [Cu(H2O)6]2+ + 2OH- Cu(OH)2(s) + 6H2O Light blue ppt. [Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O Excess dark blue filtrate White residue, insoluble in excess NH3 48 (b) (i) A nickel (II) sulphate solution contains [Ni(H2O)6]2+ ions. In the presence of H2O ligands, the 3d orbitals are split into two groups with a small energy gap between them. Electrons in the lower energy 3d orbital absorb energy as they move to a vacant and higher energy 3d orbital. The energy absorbed corresponds to some wavelengths of visible light. The unabsorbed complementary colours are then emitted. Such d-d electrons transitions are responsible for the colour of the compounds. (ii) The NH3 ligands split the d orbitals of the Ni2+ ion into two sets of slightly different energies to a different extent from that of the H2O ligands. (size gap is different) Hence, visible radiation of a different wavelength is absorbed and emitted for d-d transitions, giving rise to a different colour. (iii) A bidentate ligand has 2 groups with lone pairs of electrons and hence can form 2 dative bonds to the central metal atom/ion. Mg(H2O)62+ + 2OH- Mg(OH)2 + 6H2O

49

(c)

(i)

(ii)

(d)

(i)

(ii)

50

(a)

(i)

(ii)

51

(a)

(i)

CaCO3 CaCO3 + SO2 CaSO3 + CO2

(ii)

Mass of S in coal = 1 x 109 x

2.5 = 2.5 x 107kg = 2.5 x 1010 g 100

Amt of S = 2.5 x 1010 32.1 = 7.788 x 108 mol Amt of CaCO3 = Amt of S = 7.788 x 108 mol

Mass of CaCO3 = 7.788 x 108 x 100.1 = 7.80 x 1010 g (b) Solution F is calcium chloride solution which is effectively neutral. For BeCl2, it becomes the aqua complex, [Be(H2O)4]Cl2 upon contact with water. The small, highly polarising Be2+ weakens the OH bonds of the water molecules in its surrounding sphere of coordination and results in the release of H+ (or H3O+) ions in solution, thus giving rise to an acidic solution. BeCl2(s) + 4H2O(l) [Be(H2O)4]2+(aq) + 2Cl (aq) [Be(H2O)4]2+(aq) + H2O(l) (c) (i) CaCO3 CaO + CO2 Amt of CaO = 1.00/100.1 x 56.1 = 0.560 g (ii) Mass/ g 1.00 [Be(OH)(H2O)3]+(aq) + H3O+(aq)

Decomposition curve of CaCO3

0 (iii) From Data Booklet ion Ionic radius Mg2+ 0.065

Decomposition curve of MgCO3 time

Ca2+ 0.099

The thermal stability depends on the charge density of the cation. The greater the charge density, the thermally less stable the carbonate. Since charge density and hence polarsing power of Mg 2+ is higher than that of Ca2+, the distortion of the electron cloud of the carbonate anion, thus weakening effect of the carbonoxygen bonds in the magnesium carbonate occurs to a greater extent. Hence MgCO3 is more unstable than CaCO 3 and should decompose to MgO

and CO2 at a faster rate (since its decomposition temperature is lower than that of CaCO3.) The mass of MgO obtained is 0.478 g, lower than x (i.e. 0.560 g) 52 (a) From data booklet, atomic size: F 0.072 nm ; Cl: 0.099 nm ; Br : 0.114 nm ; I : 0.133 nm As size of halogen atom increases down the group, the bond length of H X increases/effectiveness of overlap of orbitals decreases. Bond energy of H X decreases and ease of decomposition of HX increases. Or From data booklet: Bond energy values: H F : 562 kJ mol-1; H Cl : 431 kJ mol-1 ; Br : 366 kJ mol-1 and H I : 299 kJ mol-1 As the bond energy of H X decreases down the group, the ease of decomposition of HX increases. The bond energy decreases down the group as the atomic size of halogen atoms increases and H X bond length increases. (b) (i) (ii) 2 HBr + H2SO4 SO2 + Br2 + 2H2O HI is a stronger reducing agent than HBr It is able to reduce S from oxidation state +6 (in H2SO4) to -2 (in H2S). HBr is only able to reduce S to +4 oxidation state (in SO2) 53 Since the oxide of Y can react with both NaOH and HCl, it is an amphoteric oxide. Among the possible elements, only the oxide of aluminium is amphoteric in nature: Compound Y is Al. Al2O3 (s) + 6HCl (aq) 2AlCl3 (aq) + 3H2O (l) 2NaAl (OH)4 (aq)

Al2O3 (s) + 2NaOH (aq) + 3H2O (l) reacts with the NaOH. AlCl3 (s) + aq [Al(H2O)6]3+ (aq) + H2O (l)

In the presence of water, AlCl3 undergoes hydrolysis to form an acidic solution, which [Al(H2O)6]3+ (aq) + 3Cl (aq) [Al(H2O)5(OH)]2+ (aq ) + H3O+ (aq)

Phosphorus chloride and phosphorus oxide will react with water but silicon oxide is insoluble in water. Compound Z is P.

PCl3(l) +3H2O(l) H3PO3 (aq)+3HCl (aq) or PCl5 (s)+ 4H2O(l) H3PO4(aq) + 4HCl (aq) P4O6 (s) + 6H2O (l) 4H3PO3 (aq) or P4O10 (s) + 6H2O (l) 4H3PO4 (aq) 54 (i) (ii) 2Ba(NO3)2 2BaO + 4NO2 + O2 The temperature of the thermal decomposition increases down the group. This is because down the group, the size of the cations increase hence polarizing power of cations decrease ability of cations to distort the large anion decrease

nitrates are more stable to heat (iii) L.E is proportionate to ionic charge but inversely proportionate to ionic radius or L.E. Ionic

q+q r+ + r
size of nitrate ion bigger than that of chloride

- Hence, LE for barium nitrate is SMALLER than barium chloride. 55 (a) (i) MgO has a giant ionic lattice structure large amount of energy is needed to overcome the strong ionic bonds OR electrostatic forces of attraction between oppositely charged ions. has a high boiling point

P4O6 has a simple molecular structure small amount of energy is needed to overcome the weak intermolecular Van der Waals forces of attraction

 (ii) (iii)

has a low boiling point

Al2O3 (s) + 6HCl (aq) 2AlCl3(aq) + 3H2O (l) SO2 (g) + 2NaOH (aq) Na2SO3 (aq) + H2O (l) Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH)4] (aq)

(iv)

Al2O3 behaves as an amphoteric oxide or Al2O3 is able to react with both acid and base

(b)

(i) (ii)

Mg(NO3)2(s) MgO(s) + 2NO2 (g)+ O2 (g) Down the group, Ionic radius of cation: Mg2+ < Sr2+. Charge density of cation: Mg2+ >Sr2+ / decreases Polarising power of cation: Mg2+ > Sr2+ / decreases or Polarising effect on NO3- anion: Mg2+ > Sr2+ / decreases Mg(NO3)2 is less stable than Sr(NO3)2, hence it decomposes at a lower temperature Thermal stability of Group II nitrates increases down the group; hence barium nitrate would decompose at a higher temperature compared to strontium nitrate.

56

(b)

(i)

Transition metals possess variable oxidation states due to the small energy difference between the 3d and 4s electrons. Thus different number of 3d and 4s electrons may be lost to form stable ions or compounds of different oxidation states.

(ii)

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Cu2+(aq) + 2OH-(aq) Cu(OH)2 (s) ----- (1)

When NH3(aq) is added gradually, [OH-] will increase Ionic product of Cu(OH)2 > Ksp of Cu(OH)2 Pale blue ppt, Cu(OH)2 is formed [Cu(H2O)6]2+(aq) + 4NH3(aq) [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l) -----(2) deep blue

When excess NH3 is added, NH3 ligands replaces the H2O ligands, forming a more stable deep blue [Cu(NH3)4(H2O)2]2+ complex with Cu2+(aq). [Cu2+] decreases as it is being used to form the complex, equilibrium position in (1) shifts left to increase [Cu2+] Pale blue ppt dissolves. (iii) The d orbitals of Cu2+ (aq) are split into two different energy level due to

presence of H2O ligands. The d electron undergoes d-d transition and is promoted to a higher energy d orbital. During the process, red wavelength of light energy from the visible region of the electromagnetic spectrum is absorbed and blue wavelength is transmitted which appears as the colour observed. 57 (d) In haemoglobin molecule, Fe(II) ion is octahedrally bonded to five nitrogen atoms and a water molecule. H2O ligand may be replaced by an oxygen (O 2) ligand in a reversible reaction allowing the haemoglobin to carry oxygen from one part of body to another. Stronger ligands like CO (or CN-) bond irreversibly with haemoglobin and this prevents the haemoglobin from carrying oxygen.

58

(d)

59

(a)

(b)

(i)

(ii)

(c)

(i) (ii)

60

(a)

(i)

NaCl: giant ionic crystal lattice, strong electrostatic forces of attraction between oppositely charged Na+ & Cl- ions. Large amount of energy required to break the strong ionic bonds hence high melting point. SiCl4: non-polar simple covalent molecule, weak induced dipole-induced dipole interactions between molecules. Small amount of energy required to break the weak induced dipole-induced dipole interactions hence low melting point.

(ii) 61 (a) (i)

Refer to Chemical Periodicity notes

23 23

1s2 2s2 2p6 3s2 3p6 4s2

V2+ 1s2 2s2 2p6 3s2 3p6 3d3

(ii)

In the presence of ligands, the 3d orbitals are split into two groups of slightly different energy levels. V2+ has a partially filled d orbitals, transition of electrons between the two different levels take place with abs orption of energy in the visible spectrum. The wavelengths that are transmitted correspond to the complementary colour observed. In Ca2+, there is no d-d transition due to absence of 3d electrons (or absence of partially filled 3d orbitals or electron transition takes place outside the visible region), hence it appears colourless.

(b)

The first ionization energy of the elements from scandium to copper remains relatively invariant as it involves the removal of 4s electrons. The significant screening effect of 3d electrons in the penultimate shell nullifies the increase in nuclear charge. The transition elements have higher 1st ionization energy than Ca since they have higher effective nuclear charge than Ca due to the fact that d electrons are poorly shielded. The increasing trend in third ionization energy is due to the increase in the effective nuclear charge and relatively constant shielding effect as 3d electrons are now in valence shell. Third ionization energy of calcium is much higher than that of the other transition elements as the electron to be removed is from inner 3p orbital which is closer to the nucleus and has lower energy, held more strongly by the nucleus (or electron is removed from a full octet to form Ca3+). Therefore, larger amount of energy is needed to remove it. The 3rd electron from Fe2+ is removed from an orbital containing a pair of electrons; less energy is expected due to inter-electronic repulsion.

62

(b)

(i) (ii)

Pb(OH)2.PbCO3(s) 2PbO(s) + CO2(g) +H2O(g) Mr of Pb(OH)2.PbCO3 = 508 % loss in mass = [(44.0 + 18.0)/508] x 100 = 12.2

(iii)

The decomposition temperature for Pb(OH)2.PbCO3 is expected to be higher. Pb2+ ion is larger in size than Ca 2+ hence charge density is lower resulting in lower polarizing power which leads to less distortion on anionic charge clouds, hence white lead is more stable.

63

(a)

Add excess NaOH(aq). Only aluminum oxide will dissolve to form a soluble complex: Al2O3 + 2NaOH + 3H2O 2NaAl(OH)4 The mixture is then filtered and the MgO residue is washed with distilled water.

64

(a)

(i)

NaCl electrostatic attraction exist between oppositely charged ions in an ionic lattice PCl3 covalent bonds exist between the P and Cl atoms to form discrete molecules. Large difference in electronegativity between Na and C l, hence, complete

transfer of electrons ionic compound; small difference in electronegativity between P and Cl, hence, atoms share electrons covalent compound. Large amount of energy required to overcome the strong ionic bonds between oppositely charged ions in NaCl, while much lesser energy is required to overcome weak intermolecular forces of attraction / vdw forces between PC l3 molecules. (ii) Electrical conductivity NaCl able to conduct electricity in molten state as the ions are free to carry the charge, while PCl3 does not contain mobile charge carriers in molten state (iii) (iv) [Mg(H2O)6]2+ [Mg(H2O)5(OH)]+ + H+ Observations: white fumes of HCl is produced

(at the beginning when water was first added) Reaction equation: PCl3 + 3H2O H3PO3 + 3HCl Or PCl3 hydrolyses completely in water to form HCl and H3PO3. pH between 0 to 2