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St. Paul’s Secondary School Mock Examination (2003-2004) Chemistry Paper I Suggested Answer Time allowed: 3 hours

Section A (60 marks) 1. Phenylboronic acid, C6H5B(OH)2, and benzoic acid, C6H5COOH, are both monobasic acids, with pKa values of 8.86 and 4.20 respectively. (a) State the relationship between the pKa of an acid and its acid dissociation constant, Ka. pKa =- log Ka (1) (1 mark) (b) Give the equation which represents the dissociation of phenylboronic acid. C6H5B(OH)2(aq)≒ C6H5BO2H-(aq) + H+(aq) (1) (1 mark) (c) Calculate the hydrogen ion concentration and the pH of 0.010M phenylboronic acid. Let x M be the [H+] at eqm Ka = [H+][A-]/[HA]~x2/0.01 = 10-8.86 (1) ∴x = 3.72 x 10-6 M pH =5.43 (1) (2 marks) (d) Which is the stronger of the two acids? Explain briefly. Benzoic acid (1) The smaller the pKa=> the larger the Ka, (1) ∴the eqm shifts to the right=> more acidic (2 marks) (e) A 10.0 cm3 sample of X, a solution containing both of these acids, was titrated against 0.050M NaOH using a mixture of two indicators, bromothymol blue and phenolphthalein. It was found that 8.6cm3 of NaOH(aq) were needed to change the colour of the first indicator and a further 7.1cm3 were needed to change the colour of the second indicator. (i) Sketch the shape of the pH curve during this titration. Correct graph shape (1) Correct end points with volume shown

(1)
2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-1 -1-

whereas BF3 readily reacts with water.1)(0. ∴ x = 4.5) (1.5) NF3: trigonal pyramidal (0. and give and equation for the reaction that occurs.05 Sn 33. of benzoic acid.03%.5) SiCl4(l) +4H2O(l) Si(OH)4(s) +4HCl(g) (1) (2 marks) (b) Predict the shapes of BF3. (8.5) It is because Si has low energy lying vacant d. 13.85%. Let x M be the conc. 30.5 marks) (c) NF3 is inert to hydrolysis.03 O 13. (1) BF3(aq) + 3H2O(l)  H3BO3(aq) +3HF(aq) (1) (2 marks) (d) When tin(IV) chloride reacts with potassium hydroxide in a small amount of water.5) CF4: tetrahedral (0. (0.6)(0.55%.(ii) Use the data to calculate the concentration of each of the two acids in X.05%. potassium chloride is produced. BF3 has a vacant p-orbital to accept e. Cl. Sn.22.H. CF4 and NF3 molecules.85 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-2 -1- . K % 22. SiCl4 is hydrolyzed in water but CCl4 does not. 33.55 Cl 30.55 x 10-2 M (1) 2. (i) Calculate the empirical formula of the salt. together with an anhydrous salt having the following composition by mass: K.05) =10 x .53%. BF3: trigonal planar (0.3 x 10-2 M (1) Let y M be the concentration of phenylboronic acid (7. O.from water molecule.05) = 10 y ∴ y = 3. (4 marks) (a) How and why do CCl4 and SiCl4 differ in their reactions with water? Include in your answer equations for any reactions that occur. Suggest a reason for this difference.53 H 0. 0.orbital which can accept efrom water molecule (0.

5) (4 marks) (b) The antiseptic TCP contains 2. (1) (3 marks) (c) Suggest the structural formulae for the organic products of the reactions of phenylmethanol with (i) HBr(aq).5. (0. Explain briefly.r. 6-trichlorophenol. C6H5O got the delocalisation of the –ve charge. Phenol and benzoic acid each dissolves in NaOH(aq). total=1. phenylmethanol and benzoic acid are three compounds containing benzene rings.m.564 2 118.843 3 K2[Sn(OH)3Cl3] (@row=0. (i) Which reagent and conditions are used to convert phenol to 2.5 marks) (a) Phenol. (0.847 3 16 0. (1) (4. C6H5OH C6H5CH2OH C6H5COOH Phenol Phenylmethanol Benzoic acid (i) Write equations for the reactions taking place. C6H5CH2Br (ii) 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-3 -1- . SnCl4(l) + 3KOH(aq)  K2[Sn(OH)3Cl3](aq) + KCl(aq) 3.gp is e.4.1 0.4.45 0.is delocalized and –COO.a. ∴ they withdraw e. 4. None of these compounds is particularly soluble in water. [Sn(OH)3Cl3]2(1) octahedral (1) (iii) Write an equation for the reaction. Relative no.withdrawing .5+0.283 1 35.5) Suggest whether 2.5) (ii) Deduce the structural formula of the anion and name its shape.7 0. Explain briefly.846 3 1. C6H5OH(aq) + NaOH(aq) C6H5ONa(aq) +H2O(l) (1) C6H5COOH(aq) + NaOH(aq)  C6H5COONa +H2O(l) C6H5COOH(aq) + Na2CO3(aq) 2 C6H5COONa(aq) +H2O(l) +CO2(g) (1) (ii) Arrange the trend in acidity of these compounds.from the benzene ring and stabilize the phenoxide ion. 6-trichlorophenol is more or less acidic than phenol. of moles Simplest ratio 39. It is more acidic than phenol (1) The EN of Cl is high. but only benzoic acid dissolves in Na2CO3(aq).008 0.5) ∵ e. C6H5COOH > C6H5OH > C6H5CH2OH (1) Benzoic acid is the most acidic.6trichlorophenol? Cl2(aq)/Fe(s) + reflux (0.

and draw their structures. (1) Propanone will not react with it. (1) (1 mark) 4. 0. These include propanone.5) (ii) 3-hydroxybutanoic acid.5 H C N 0. (a) Describe and name the mechanism of the reaction between ethanal and hydrogen cyanide. 3-oxobutanoic acid has a C=O gp which reacts with 2. Describe a separate simple test in each case to distinguish 3-oxobutanoic acid from (i) propanone. Enantiomers (1) OH C CH3 CN H H OH C CN CH3 (1+1) (3 marks) (c) As a consequence of starvation or diabetes.5 + OH H3C CH2 CN 1 Mechanism Nucleophilic addition (1) (4 marks) (b) The above reaction produces two isomeric products in equal amounts. 3-oxobutanoic acid.(1) (ii) Cr2O72-/H+(aq) C6H5COOH (1) (2 marks) (d) Suggest why phenol does not undergo a similar reaction to that in (c)(ii). (0. Name the type of isomerism involved. and 3-oxobutanoic acid reacts with sodium carbonate/hydrogencarbonate to give CO2(g). The ring has extra-stability due to the delocalization of Π e-s in the benzene ring.5 OH H3C CH CN0.5 O H3C CH 0. the blood plasma and urine of patients can contain large amounts of “ketone bodies”. 4-DNP -1- 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-4 . and 3-hydroxybutanoic acid.

5) (ii)Δ H = ΔHC-C + ΔHBr-Br – (ΔHC-Br) x 2 = 348+193-(276) x 2 = -11kJ mol-1 (0. (1) (1 mark) (c) What conclusions can you draw from the answers obtained in (a) and (b). (0. calculate △H for each of the reactions (i) and (ii) and hence show which reaction is energetically more favourable. (i)Δ H = ΔHC-H + ΔHBr-Br . (1) (ii) is kinetically more favourable. Give a reason for your choice. For the theoretical technique (1): (a) Using any of the mean bond enthalpy values. The following values of mean bond enthalpies in kJ mol-1 may be useful: C-C: 348. the aqueous solution is titrated with 0.g.5) (3 marks) 5. C-H: 412. The student decides to adopt two approaches: (1) a purely theoretical approach involving calculations based on mean bond enthalpies. In method (2) hexane and bromine are mixed in a 1:1 mole ratio in a stoppered container in the presence of water. (2) a practical approach using a titration approach.5) (1) ∴(i) is more energetically favourable (2 marks) (b) Considering only the mean bond enthalpy values for C-C and C-H. C6H14 + Br2  C6H13Br + HBr (i) However. it would seem possible that the reaction could also proceed as follows: C6H14 + Br2  2C3H7Br (ii) A student is given the task of discovering which reaction usually takes place or whether a combination of both reactions occurs.ΔHC-Br . Br-Br: 193. The container is placed in direct sunlight and shaken occasionally so that any HBr produced dissolves in the aqueous layer. H-Br: 366.1 mol dm-3 sodium hydroxide.(1) to give red/orange ppt. predict which of reactions (i) or (ii) seems more likely to occur. (1) (2 marks) 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-5 -1- . (i) is energetically more favourable. (ii) is the most likely because it involves less energy to break the C-C bond. Haloalkanes can be formed by reaction of a halogen with an alkane in the presence of sunlight e.ΔHHBr = 412+193-276-366 = -37 kJ mol-1 (0. C-Br: 276. When all the bromine has reacted.

(ANY 2) (1+1) (d)t is meant by the van der Waals’ radius of an atom (lines 40-41)? How does it differ from the covalent radius? (3 marks) Half the distance between two identical atoms which are attracted to each other by van der Waals’ foces. (1) Section B (20 marks) 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-6 -1- .9) =3.13 x 10-3 (1) ∴ no.A. Used these figures to show that reaction is occurring only by equation (i).50g of bromine was added to suitable volumes of hexane and water. If reaction (i) occurs. of moles of NaOH = 1:1 it follows route (i) (1) (2 marks) 6.5/2(79. calculate the percentage composition of F. of moles of NaOH = (0. (1) The C-C bond is shielded from attack by the F atoms. How can this explain the unreactivity of Teflon.For the practical technique (2): (d) How would you know when the reaction between hexane and bromine was complete? The bromine will be decolorized.13 x 10-3 No. (2 marks) For teflon to react. (2 marks) CClF2CF2Cl(s) +Zn(s)  CF2CF2(g) + ZnCl2(s) (1)  CHF2CF2Cl(l) CF2CF2(g) +HCl(g) (1) (b) From the empirical formula given in line 9. very strong C-F bonds must be broken. No. Slipperiness – will not wear as the hip moves. of moles of Br2 : No. of moles of Br2 = 0.M. ∴ there is a high activation energy. (1+1) It is larger than the covalent radius. (1) (e) Consider the molecular data given in the diagrams and the last paragraph. (1) (1 mark) (e) Explain concisely why sodium hydroxide can used to show that reaction (i) is occurring rather than reaction (ii). F=19) (1 mark) % of F = 38/50 x 100% = 76% (1) (c) Which two properties of Teflon described in the second paragraph make it particularly suitable for artifical hip joints? (2 marks) Unreactivity – will not ract in the body. 0. Titration of the aqueous layer required 31. Name an indicator which could be used for this titration. Insolubility – will not dissolve in body fluids.25 cm 3 of the sodium hydroxide.25/1000) = 3.1)(31. (1) Any indicators. the HBr produced will neutralize with NaOH. Comprehension (a) Write balanced equations for the two reactions described in lines 2-4. (1) (2 marks) (f) In such an experiment.: C=12. (R.

NaOH is corrosive. Benzoic acid has a melting point of 121 ℃. (1) (4) Ethanol is flammable. EtOH is collected by distillation and sodium hydroxide is left in the flask. Give reagents. therefore a water bath is used. H2SO4(l). Its solubility in water is about 0.3g/100cm-3 at 18℃ and about 3g/100cm-3 at 100℃. conc.: room temp. State necessary safety precautions. C6H5COOC2H5(aq) + NaOH(aq)  C6H5COONa(aq) C2H5OH(l) (1) Alkaline hydrolysis of ester (Saponification) (1) (2 marks) (c) Can sodium hydroxide be replaced by dilute sulphuric acid? Explain briefly. But the yield is lower because (1) (i) the reaction is reversible: R’COOR +H2O ≒R’COOH + ROH (1) (ii) separation of acid and ethanol is difficult ∵ benzoic acid is quite soluble in hot water. H2SO4. Ethyl benzoate. is a colourless liquid immiscible with water. C6H5COOC2H5. (1) Known volumes of water and sodium hydroxide solution are put into a pearshape flask. how to carry out this experiment. Ethanol has a boiling point of 78℃ and forms an azeotrope with water containing 96% ethanol which boils at 78. . (1) (2) Add anti-bumping granules to the mixture to ensure smooth boiling.7. (1) (3) Fir the water-condenser to the pear shape flask and reflux the mixture by using a water bath. Test for SO32. therefore gloves should be worn. Cr2O72-/H+ (1) Gas given out (SO2) which turns Cr2O72-/H+ from orange to green.5℃. reaction conditions an expected observations for the tests. (1) (5) When the reaction is complete. FeSO4(aq) solution. 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-7 -1- . with full practical details. A brown ring is formed in the interface between the aqueous layer and conc. It reacts slowly with aqueous with aqueous sodium hydroxide to form sodium benzoate solution and ethanol. Yes or No. room temp. (1) (5 marks) (b) Give the equation and state the type of reaction taking place.: (1) 8. (1) Test for NO3. (1) (3 marks) (a) Outline laboratory tests to identify the cation and the anions in NaSO3(s) and NaNO3(s). (a) Describe.

When solid sulphur containing the radioactive isotopes 35S is boiled with sodium sulphite. The resulting solution contains non-radioactive sulphite ions. (5 marks) (b) The average oxidation number of the two sulphur atoms in sodium thiosulphate. Na232SO3. Adding HCl(aq) to this sample causes all the 35S to precipitate as sulphur. (i) Draw the structural formula of the sulphite ion. S O O O S O (ii) O O (1) Use your answer in (i) and the reactions described to suggest a structure for the thiosulphate ion produced.Test for Na (1) + : (1) golden yellow flame under burning in flame test. a radioactive sample of sodium thiosulphate is produced. Na2S2O3. On your structure. S S O O S35* S O O O O (iii) (1+1) Deduce the oxidation number for each sulphur atom in the thiosulphate ion. label any radioactive atom. is +2. 0 S35* 4 O S O O (1+1) (5 marks) Section C (20 marks) 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-8 -1- .

Answer ONE question in this section. 10. X Y CH CO2H D Discuss the chemical reactions of D in which X = C2H5. Give an account of the general features shown by transition metals. and the remainder of the light reflected in the visible region accounts for the specific colour of that ion. For each of your specific examples indicate their use. Marks will be allocated approximately as follows: Chemical knowledge Organization Presentation (including proper use of English) 50% 30% 20% 9. Illustrate this with 2 examples containing nitrogen. and outline the chemical reactions involved in obtaining each compound. Y = H.S (2) (ii) complex formation (2) (iii) coloured compounds of transition metals . Guidelines only: Introduction: Transition Metals: elements which form compounds in which there is an incomplete subshell of d-electrons in more than one of its compounds. the 3d e. a man-made example of great industrial importance for making large molecules. one of which occurs in nature. Illustrate your answer with suitable examples. As sufficient light energy is absorbed. the 3d orbitals split into two groups with small energy difference. and also comment on how the acidic and physical properties of D may be modified by different substituents X and Y.they are usually coloured ∵under the influence of a ligand in a complex. The general features of transition metals are as follows: (i) variable O. Several examples of D (with appropriate substituents) are of great benefit to man.of a lower energy level to a higher energy level. d-block Elements: atoms/elements with electron configuration in which the d-orbitals are being filled. This resulting d-d transition causes for light absorption. (2) (iv) catalytic properties (2) (v) magnetic properties (2) 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-9 -1- . Copper(II) sulpahte-5-water is blue in colour. and the other.g. E.

END OF PAPER 2004-SUGGESTED ANSWER-AL-SPSS-CHEM-I-10 -1- .

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