Answer ALL questions. MODULE 1: FUNDAMENTALS OF CHEMISTRY 1. (a) In 1808, John Dalton proposed his atomic theory. However, much of our current knowledge has disproven aspects of the theory. (i) Outline FOUR postulates of this theory. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Identify and explain which TWO of these postulates have been majorly disproven due to modern knowledge. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Refer to THREE criteria considered when a theory is accepted, and relate ONE of these to Dalton’s theory. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (b) The modern atom is known to comprise several species of subatomic particles. (i) Name and compare the THREE main subatomic particles within a neutral atom based on their relative charges, masses, location and behavior in magnetic fields. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Define the term ‘isotope,’ making reference to EACH of the subatomic particles mentioned above and variation in chemical and physical properties. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) A radioisotope of carbon, 146𝐶 , has a neutron to proton ratio higher than stable. Write one possible nuclear equation of its decay to form a nuclide of lower neutron to proton ratio. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (c) A sample of hydrogen gas is excited electrically and the resulting radiation passed through a prism, detected and analyzed. The result is a spectrum produced on a computer. (i) What is the name given to the spectrum produced? Give TWO characteristics of this spectrum as well. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) The analysis produced light in the visible spectrum. State the name given to this series and describe the nature of the electron transitions occurring. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Explain how the production of this spectrum gives evidence for the existence of energy levels in the atom, making specific reference to at least ONE assumption of the Bohr model. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (d) As period 3 of the periodic table is crossed from left to right, there is a general increase in first ionization energy, however an anomalous change occurs between the alkaline earth metal and the triel element, and again between the pnictogen and chalcogen of the period. (i) Define what is meant by ‘first ionization energy,’ and explain the general increase in first ionization energy across the period. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Explain the anomalous changes mentioned above. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) One of the anomalous changes referred to above can be explained based on the differences between TWO types of orbitals. Draw these orbitals, and state the name of the property that varies between them that results in the aforementioned anomalies. _______________________________________ (iv) The information above speaks to first ionization energies across DIFFERENT elements. Explain how SUCCESSIVE ionization energies of the same element provide evidence for shells in an atom. Using the axes provided, also show how ALL successive ionization energies vary for the sodium atom. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ 2. (a) Various forces of attraction exist between particles, and account for many properties of compounds. Account, or suggest an explanation, for EACH of the following observations (you have NO choice): (i) At very low temperatures (-248.6°C), Neon can solidify. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Water has the highest boiling point of the binary hydrides. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) n-pentane has a higher boiling point than 2,2-dimethylpropane. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) The density of ice is lower than the liquid state of water. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (v) The experimentally determined relative molecular mass of ethanoic acid (CH3COOH) was found to be 120. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vi) The boiling point of cis-1,2-dichloroethane is greater than that of trans-1,2dichloroethane. (Refer to the structures below): ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vii) Water can dissolve many polar and charged substances. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (viii) Boiling point of the halogens increases down the group. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (b) BF3 and NH3 react in a Lewis acid-base reaction to form the addition compound BF3NH3. Draw the structures of the THREE species mentioned, and name the bond formed between them. ________________________________________________________________________ (c) VSEPR Theory allows a prediction of the molecular geometry of compounds. (i) Give THREE principles upon which VSEPR Theory is based. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Describe and compare the electron and molecular geometries of methane (CH4) and ammonia (NH3). ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Explain the term ‘hybridization’ and relate it to the planarity of the ethene molecule. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) Define the terms ‘resonance’ and ‘𝜋 bonds’ and relate them to the structure of benzene. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (d) Reactions can be described as either endothermic or exothermic. (i) Differentiate between endothermic and exothermic reactions, using suitable energy profile diagrams and making reference to bond formation and bond dissociation. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Account for the following statements: The enthalpy of formation of Al2O3 cannot be easily experimentally determined. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ The enthalpy of formation of CO (carbon monoxide) cannot be experimentally determined. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Name and state the law that allows one to determine the enthalpy of formation of CO indirectly. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) Draw an energy cycle diagram to show how knowledge of the heats of combustion of Carbon and Carbon monoxide could permit determination of the enthalpy of formation using the law named above. (e) The lattice energy of an ionic compound is very difficult to determine experimentally. (i) Define ‘lattice energy.’ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Draw a Born-Haber Cycle for the formation of AlCl3. (iii) It was determined that the lattice energy of AlCl3 is significantly different from its experimental lattice energy. Explain what this suggests about its bonding. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) Give TWO main factors that affect lattice energy. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ MODULE 2: KINETICS AND EQUILIBRIA 3. (a) The following results were obtained for the hydrolysis of 2-bromo-2-methylpropane (CH3— C(CH3)Br—CH3), by aqueous sodium hydroxide at 298K. The equation is: CH3—C(CH3)Br—CH3 + OH- → CH3—C(CH3)(OH)—CH3 + BrConcentration of 2-bromo- Concentration of OH- Initial rate of hydrolysis/ 2-methylpropane/mol dm-3 ions/ mol dm-3 mol dm-3 s-1 0.100 0.500 0.0020 0.100 0.250 0.0020 0.075 0.250 0.0015 0.050 0.250 0.0010 0.025 0.250 0.0005 (i) Determine the order of the reaction with respect to: (a) 2-bromo-2-methylpropane (b) Hydroxide ions (ii) Write the rate expression for the reaction, and give the units of the rate constant. (v) Suggest ONE method by which the rate of this reaction could be determined in the laboratory, including at least TWO materials necessary. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vi) Apart from the one mentioned above, give FOUR other possible methods of determining the rate of a reaction. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (b) The following are two statements relevant to the issue of obtaining maximum yields in industrial processes as quickly as possible. ‘The equilibrium yields of exothermic reactions increase with decreasing temperatures.’ ‘The rates of all chemical reactions increase with increasing temperatures.’ (i) State Le Chatelier’s Principle. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Explain why both of these statements are correct. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Using a specific example, state how industrialists deal with the conflict between these statements. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) With reference to collision theory and drawing suitable graphs, explain the effect of temperature AND catalysts on rate of a reaction. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (v) Outline a suitable method to determine the equilibrium constant of the acid-catalyzed esterification reaction between ethanoic acid and ethanol. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ MODULE 3: CHEMISTRY OF THE ELEMENTS 4. (a) Group VII is unique in the periodic table as it is the only group that has elements in all three states of matter at standard conditions. (i) Explain the trend in density down the group. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Iodine produces different products when it reacts with thiosulphate (S2O32-) than the halogens above it. Using TWO relevant equations, describe these reactions AND describe the trend down the group that accounts for this difference. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) Fluorine gas cannot be used to displace other halide ions from solution. Give the reason for this and write ONE relevant equation. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) Write the ionic equation of fluorine gas with an alkali. ____________________________________________________________________ ____________________________________________________________________ (v) The other halogens react differently with potassium hydroxide, for example. Write THREE relevant reactions and the temperatures at which they occur to show the reactions of ONE halogen with potassium hydroxide solution. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vi) Describe the reactions of the halogens with hydrogen gas. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vii) State the trend in bond energy of the halogens in their homoatomic molecules (elemental states), and suggest ONE reason why fluorine has a LOWER bond energy than chlorine. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (viii) The trend in the strengths of the hydrohalic acids is directly related to the trend in their thermal stabilities. Explain these trends, making reference to bond energies. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ix) The reactions of the halide ions beneath chlorine with sulfuric acid result in the evolution of the halogen gases in addition to steamy fumes that form white fumes with ammonia gas. Explain why ONLY this fume product is produced with chlorine and write THREE equations to illustrate the difference between these reactions. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (x) On reaction with concentrated sulphuric acid, hydrogen iodide produces iodine gas and one of THREE sulphur-containing compounds. Name EACH of them, and write their chemical formulae. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (b) Transition elements exhibit very unique properties, such as the formation of coloured compounds. (i) Define ‘transition element.’ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ii) Give FOUR characteristics of transition elements, not including coloured compound formation. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iii) State and account for the differences between transition metals and calcium, a typical sblock element, with respect to EACH of the following properties: Melting point ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ Density ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ Atomic Radius ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ First Ionization Energy ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ Conductivity ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) The ionization energies and atomic radii of the transition metals vary across the d-block. Explain why this variation is relatively small. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (v) The transition elements in their neutral states do not all have filled 4s orbitals. Identify these elements and explain why this is so. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vi) In the space provided below, write the names and common oxidation states of FIVE transition elements. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (vii) Below is a series of reactions involving transition metals. In the blank boxes, write the chemical formulae of the species involved, then write their colours on the blank lines. (viii) State and explain the principle operating in the Cobalt, Copper and Chromium reactions above. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (ix) With reference to the above principle, explain the relationship between carbon monoxide, haemoglobin, and hypoxemia. Include mention of stability constants and a possible treatment for the above condition. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (x) State whether Fe2+ ions are good reducing or oxidizing agents, and, with writing its FULL electronic configuration in s, p, d, f notation, explain why this is so. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (xi) The scandium and zinc ions generate solutions of the same appearance, while each of the other transition metal ions exhibit solutions of varying colours. Explain, with reference to the colours of THREE aqueous transition metal ion colours, why these varying colours are observed and why scandium and zinc are different. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (xii) Compare the electronic configurations of Cu+ and Mn2+. Using the box notation for their valence shells, explain the paramagnetic and diamagnetic properties of either ion. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (xiii) Suggest ONE reason for the catalytic properties of transition metals, and give THREE specific examples of reactions catalysed by transition metals. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ 5. (a) A series of qualitative tests were carried out on a mixture, Z, of 2 soluble salts and one insoluble salt. The incomplete results are given in the table below. TABLE 1: QUALITATIVE TESTS CARRIED OUT ON A MIXTURE OF TWO SOLUBLE SALTS AND ONE INSOLUBLE SALT Qualitative Test Observation Inference Z was mixed with adequate distilled water and stirred. This mixture was filtered and the filtrate, A, divided into 5 equal volume portions. The residue, B, was washed and dried. Ba2+ present. To one portion of A, sodium White precipitate formed Al3+, Pb2+, or Zn2+ ions hydroxide was added until in A platinum wire was cleaned, dipped in dilute HCl, then dipped into B. This wire was then placed into the flame of a Bunsen burner. present. excess. The resulting solution was warmed, and any gas Colourless, pungent gas evolved tested with moist red evolved which turns moist litmus paper. red litmus blue. reaction required To another portion of A, White precipitate formed aqueous ammonia was added Al3+ or Pb2+ ions present. until in excess. No precipitate formed. Al3+ ions present. Another portion of A was No gas was evolved. mixed with concentrated Solution turned orange in sulfuric acid. colour. reaction required This portion was added to a NO3- present. separating funnel, and a solution of FeSO4 was added reaction required to form a layer on top of the portion of A. To another portion of A, Colourless, pungent gas granulated zinc and aqueous evolved which turns moist sodium hydroxide were red litmus blue. added, and the mixture heated. reaction required The final portion of A was Red-brown precipitate mixed with aqueous silver formed. nitrate. (i) Complete the table above to indicate any missing tests, observations, or inferences- writing equations where necessary. (ii) Suggest the identities of the THREE salts in the mixture Z. ____________________________________________________________________ ____________________________________________________________________ (iii) The first test involves a Bunsen burner. Explain the principle upon which this test is based. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ (iv) A student has accidentally mislabelled three bottles containing soluble salt solutionssodium sulphate, sulphite and carbonate. Outline a method allowing him to differentiate between the three solutions. ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ ____________________________________________________________________ END OF TEST IF YOU FINISH BEFORE TIME IS CALLED, CHECK YOUR WORK ON THIS TEST.