June Holiday Assignment (Answers) Attempt the following questions on foolscap papers.

Topics: Mole Concept, Volumetric Analysis and Redox --------------------------------------------------------------------------------------------------------------------1. Assign oxidation numbers (oxidation state) to the underlined element in each of the following compounds: a. AlH3 (+3) b. KClO2 (+3) c. BiO3- (+5) d. Cr2(SO4)3 (+3) [4] 2. Write balanced ionic equations with state symbols, for the reduction of nitric acid, HNO3 a. by Cu to produce Cu2+ and NO2 b. by Al to produce Al3+ and NH4+ (Hint: the medium is acidic since an acid is involved) [4] a. [O] Cu(s) Cu2+(aq) + 2e ---(x1) + [R] NO3 (aq) + 2H (aq) + e NO2(g) + H2O(l) ---(x2) + 2+ Overall: 2NO3 (aq) + 4H (aq) + Cu(s) Cu (aq) + 2NO2(g) + 2H2O(l) b. [O] Al(s) Al3+(aq) + 3e ---(x8) + + [R] NO3 (aq) + 10H (aq) + 8e NH4 (aq) + 3H2O(l) ---(x3) + 3+ + Overall: 3NO3 (aq) + 30H (aq) + 8Al(s) 8Al (aq) + 3NH4 (aq) + 9H2O(l) 3. The yellow acidified dioxovandium (V) ion, VO2+, is reduced by zinc metal to blue VO2+ while zinc is oxidised to zinc (II) ions. Write a balanced ionic equation for the reaction. [2] [O] Zn(s) Zn2+(aq) + 2e ---(x1) + + 2+ [R] 2H (aq) + VO2 + e VO + H2O ---(x2) + + 2+ Overall: Zn(s) + 4H (aq) + 2VO2 (aq) Zn (aq) + 2VO2+(aq) + 2H2O(l) 4. In a titration, 25.0 cm3 of the solution containing tin (II) ions required 19.0 cm 3 of the 0.0200 moldm-3 of potassium manganate (VII) solution for oxidation. Calculate the concentration of tin (II) in the solution. (Hint: potassium manganate (VII) oxidises tin (II) ions to tin (IV) ions.)
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[5] [O] Sn (aq) Sn (aq) + 2e --- (x5) + 2+ [R] MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O(l) Overall: 2MnO4-(aq) + 16H+(aq) + 5Sn2+(aq) 2Mn2+(aq) + 5Sn4+(aq) + 8H2O(l) No. of moles of MnO4- = 19.0/1000 x 0.0200 = 3.8 x 10-4 MnO4- : Sn2+ = 2:5 No. of mole of Sn2+ = 3.80 x 10-4 x 5/2 = 9.50 x 10-4 Concentration of Sn2+ = 9.50 x 10-4 x 1000/25 = 0.038 moldm-3 5. A household bleach solution contains sodium chlorate, NaClO. The chlorate ion, ClO will be reduced to chloride ion, Cl, when it reacts with potassium iodide in acidic solution to give iodine. The amount of iodine can be estimated by titration with standard sodium thiosulphate, Na2S2O3 solution. a. State the change in oxidation number of chlorine when NaClO is reduced. b. Construct one half equation for the reduction of ClO and hence write the balanced chemical equation for the reaction between ClO and I. c. Write the equation for the reaction between iodine and thiosulphate ions. [4] (a) oxidation state of Cl atom changes from +1 in ClO- to -1 in Cl(b) 2I- I2 + 2e ClO + 2H+ + 2e Cl + H2O Overall: 2I + ClO + 2H+ I2 + Cl + H2O (c) I2 + 2S2O32 2I + S4O62 [1]
2+ 4+

[1] [1] [1]

6. Under different conditions, hydroxylamine, NH2OH, may be oxidized either to N2 or N2O. The half equation for the oxidation of NH2OH to N2 is 2 NH2OH N2 + 2H2O + 2H+ + 2e a. Construct a similar half-equation for the oxidation of NH2OH to N2O [1] b. In an experiment, 40.0cm3 of 0.100 moldm3 NH2OH(aq) was oxidized by 25.0cm3 of 0.320 moldm3 Fe3+ (aq). The Fe3+ was quantitatively reduced to Fe2+. Calculate the number of moles of i. NH2OH that reacted, ii. Fe3+ that reacted, iii. Fe3+ that would react with 1 mole of NH2OH [3]
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c. From your answers above, deduce whether NH2OH has been oxidized to N2 or N2O. Hence construct a balanced equation between NH2OH and Fe3+. [2] a) b) 2NH2OH N2O + H2O + 4H+ + 4e i) moles NH2OH = (40/1000) x 0.100 = 4.00 x 103 ii) moles Fe3+ = (25/1000) x 0.320 = 8.00 x 103 iii) ans(ii)/ans(i) = 2 c) 2Fe3+ gain 2e from each NH2OH (OR oxidation number of N : 1 to +1) => product is N2O => 2NH2OH + 4Fe3+ N2O + H2O + 4H+ + 4Fe2+ [1]

[1]

[1] [1] [] [] [1]

7. 120.0 cm3 of hydrochloric acid reacted completely with calcium carbonate to liberate 11.00 g of carbon dioxide a. Write a balanced equation for the reaction between calcium carbonate and hydrochloric acid [1] b. How many molecules of carbon dioxide were formed in the reaction? [2] c. Determine the amount of hydrochloric acid present and hence find the concentration of the acid in moldm3. [2] a) b) CaCO3 + 2HCl CaCl2 + CO2 + H2O

Amount of CO2 = 11/44.0 = 0.250 mol No. of carbon dioxide molecules = 0.250 x 6.02 x 1023 = 1.51 x 1023 CO2 2HCl Amt of HCl in 120.0 cm3 = 0.250 x 2 = 0.500 mol Concentration of HCl = 0.50/0.12 = 4.17 mol dm3

c)

8. A fuel mixture used in the early days of rocketry is composed of two liquids, hydrazine (N2H4) and dinitrogen tetraoxide (N2O4), which ignite on contact to form nitrogen gas and water vapour.

a. Write a balanced equation, including state symbols, for the reaction between hydrazine and dinitrogen tetraoxide. [1] b. When 110 g of N2H4 and 220 g of N2O4 are mixed, 131g of nitrogen gas was obtained. i. What volume would the mass of nitrogen gas obtained occupy at s.t.p.? [2] ii. Determine the percentage yield of this reaction. [4] a) b) i) 2N2H4 (l) + N2O4 (l) 3N2 (g) + 4H2O (g)

Amt of N2 (g) = 131/28.0 = 4.68 mol Vol. of N2 (g) = 4.68 x 22.4 = 105 dm3 (3sf)

ii) Amt of N2H4 = 110/32.0 = 3.44 mol Amt of N2O4 = 220/92.0 = 2.39 mol N2H4 is limiting (or N2O4 in excess). Theoretical amt of N2 formed = 3.44 x 3/2 = 5.16 mol % yield = 4.68/5.16 x 100 = 90.7% (3sf) Topic: Atomic Structure --------------------------------------------------------------------------------------------------------------------1. Write the electronic configuration and electron-in-box diagram for the following atoms/ions. a. Cr2+ e. S b. Al c. Sc [5] + d. Cl

2. Complete the table below. Number of Particle Mass number Protons X Y 32 81 16 35 Electrons 16 36 Neutrons 16 46

a. Give the electronic configuration of particle Y. b. State, with reasons, how the radius of Y compare with that of 37Rb+. c. State, with reasons, whether the first ionisation energy of element X is higher or lower when compared with that of phosphorus. [5]
(i) electronic configuration of particle Y is

1s22s22p63s23p63d104s24p6 (not 1s22s22p63s23p64s23d104p6) (ii) Ionic radius of Y- is larger than that of Rb+ Reasons: 1. Y- and Rb+ are isoelectronic OR same number of total electrons 2. but nuclear charge of Y- is smaller than that of Rb+ as Y- has lesser number of protons. (iii) X: 1s22s2 2p63s23p4 P: 1s22s22p63s23p3 3p4 3p3

First ionization energy of X is lower than that of P due to the inter-electron repulsion between the paired electrons in a 3p orbital

3. The first eight ionization energies (in kJ mol-1) of an element, T are as follows: 966 (1st), 1950, 2730, 4850, 6020, 8220, 14330, 17830 a. State, giving reasons, the group of the Periodic Table to which T is likely to belong. b. Explain why the successive ionisation energies for element T increase as electrons are removed successively. [5]
(a) 966 984 1950 780 2730 2120 4850 6020 8220 2200 14330 6110 3500 17830

1170

There is a big increase in the I.E. upon the removal of the 7th electron OR the difference between the 6th and 7th I.E. is the largest. Hence, the first six electrons are in the outermost electron shell while the 7th electron is from the next inner electron shell. It can then be deduced that the element is in Group VI. (b) Ionisation energy involves removal of electron. The nuclear charge remains the same while the number of remaining electrons decreases Hence valence electrons are held more tightly by the positive nucleus and more energy is required to remove the next electron. The successive ionisation energy hence increases

Topic: Chemical Bonding --------------------------------------------------------------------------------------------------------------------1. Draw the dot-and-cross diagram for the following simple molecules/ions. a. NH3 d. NH4+ b. BeCl2 e. PF6c. H3O+ [5]

2. Complete the following table: Molecule/ Ion BeCl2 Lewis Structure No. of bond pairs 2 No. of lone pairs 0 Shape of Polar/nonmolecule/ion polar? (yes/no/n.a.) Linear Non-polar

BCl3

Trigonal Planar

Non-polar

CH3+

Trigonal Planar

na

PCl6-

Octahedral

na

ICl4-

Square Planar

na

[5] 3. State the structure and type of bonding(s) of the following: e. Aluminum oxide (Al2O3) a. Ammonia (NH4) b. Sodium oxide (Na2O) f. Diamond (C) c. Hydrogen chloride (HCl) g. Sulfur dioxide (SO2) d. Magnesium chloride h. Sodium (Na) (MgCl2) [8] Structure Simple molecular Giant ionic Simple molecular Type of Bonding Strong covalent bond between atoms and hydrogen bonds between molecules Strong electrostatic forces of attraction between oppositely charged ions Strong covalent bonds between atoms and weak van der waals forces of attractions between molecules Strong electrostatic forces of attraction between oppositely charged ions Strong electrostatic forces of attraction between oppositely charged ions Strong covalent bonds between atoms Strong covalent bonds between atoms and weak van der waals forces of attractions between molecules Strong electrostatic forces of attraction between the positively cations and the sea of delocalized electrons
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Ammonia (NH4) Sodium oxide (Na2O) Hydrogen chloride (HCl) Magnesium chloride (MgCl2) Aluminum oxide (Al2O3) Diamond (C) Sulfur dioxide (SO2) Sodium (Na)

Giant ionic Giant ionic Giant molecular Simple molecular

metallic

4. State the type of intermolecular forces (Hint: permanent dipole permanent dipole, temporary induced dipole, hydrogen bonding) present in the following: a. HCl pd-pd b. CO2 temp induced dipole c. HF hydrogen bonding d. NF3 pd-pd e. H2O hydrogen bonding [5] 5. Explain the following in terms of their bonding and structure. a. At standard conditions, carbon dioxide exists as a gas while silicon dioxide exists as a solid. b. NH3 is soluble in water by PH3 is not soluble in water. c. Silicon dioxide is often used as an industrial abrasive. [5] a) Silicon dioxide has a giant molecular structure with strong covalent bonding between the atoms while carbon dioxide has a simple molecular structure with weak van der waals forces of attraction between molecules. More energy is required to break the strong covalent bonds between the silicon ad oxygen atoms than the weak intermolecular forces between carbon dioxide molecules. Hence, silicon dioxide exist as a solid at room temperature while carbon dioxide exist as a gas. b) Both NH3 and PH3 have simple molecular structure. Hydrogen bonds exisit between NH3 molecules while weak van der waals forces of attraction exist between PH 3 molecules. In water, NH3 has the ability to form hydrogen bonds with the water molecules and are thus soluble in water. However the hydrogen bonds between water molecules is stronger than the weak intermolecular forces of attraction between PH 3 molecules, favourable interaction between water and PH3 molecules cannot be formed thus PH3 is not so soluble in water. c) silicon dioxide has a giant molecular structure and the bonds that exist between the atoms are extensive and strong covalent bonds. A large amount of energy is required to overcome these strong bonds and therefore it is a very hard material. It is therefore suitable to be used as an abrasive.

Topic: Gas Laws --------------------------------------------------------------------------------------------------------------------1. A given mass of gas at a temperature of 20oC has a volume of 240m3 at 120,500 N/M2. What would be its volume at room temperature and pressure? [2]
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Since the number of moles of gas remains constant, = = V2 = 290 m3 2. A gas initially 5.5 dm3, 1.5 atm and 50oC was compressed to a volume of 4.0 dm3. If the final pressure of the gas is 180 kPa, what is the final temperature of the gas? [2] Using = = Final Temp = 279 K 3. Cylinder A contains 2.5 dm3 of helium at 3 kPa. Cylinder B contains 5 dm3 of argon at 4.5 kPa. If the 2 cylinders are connected at constant temperature, what is the final pressure of the combined setup? [2] At constant temperature, PTVT = P1V1 + P2V2 PT(2.5 + 5) = (3)(2.5) + (4.5)(5) PT = 4.0 kPa 4. A mixture of gases consisted of 20 cm3 methane (CH4) and 60 cm3 of ethane (CH3CH3). The mixture was exploded with 310 cm3 of oxygen and the products were cooled to room temperature. All volumes were measured at room temperature and pressure. a. Calculate the partial pressure (in atm) of each in the mixture. [2] b. Calculate the volume of oxygen needed for the complete combustion of the mixture. [3] c. Calculate the partial pressure of carbon dioxide in the final mixture. [3]

a) Mole fraction of CH4 =

= 0.25
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Partial Pressure of CH4 = 0.25 x 1 atm = 0.25 atm Mole fraction of CH3CH3 = = 0.75

Partial Pressure of CH3CH3 = 0.75 x 1 atm = 0.75 atm b) Avogardos Law states that mole ratio = volume ratio at constant temperature and pressure. CH4 + 2O2 CO2 + 2H2O 20: 2(20) = 40 cm3 of O2 CH3CH3 + O2 2CO2 + 3H2O 60: (60) = 210 cm3 of O2 Total volume of O2 needed = 40 + 210 = 250 cm3 c) The final mixture contains unreacted O2 and CO2 formed CH4 + 2O2 CO2 + 2H2O 20 20 cm3 of CO2 CH3CH3 + O2 2CO2 + 3H2O 60 2(60) = 120 cm3 of CO2

Volume of CO2 formed = 20 + 120 = 140 cm3 Partial Pressure of CO2 in final mixture = x 1 atm = 0.7 atm

5. Draw the graphs showing the relationship of the following conditions of an ideal gas: a. P against V b. P against c. V against d. PV against e. PV against P [5]

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a)

b)

c)

d)

e)

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