RAFFLES INSTITUTION 2012 Year 6 H2 Chemistry Term 3 Common Test Suggested Solutions Section A 3 4 5 A C C 13 C 14 A 15 B

Question No. Answer Question No. Answer 1 angle of deflection ion

1 B 11 A

2 D 12 D

6 D 16 D

7 C 17 A

8 D 18 B

9 C 19 B

10 B 20 C

charge mass
79

Br+

81

Br+

81

Br2+

82

Br2+

charge mass

1 79

1 81

2 81

2 82

angle of deflection: 81Br+ < 79Br+ < 82Br2+ < 81Br2+ least most 2 SF4 is polar. These two dipoles cancel out.
F F

These two dipoles do not cancel out.

:S
F F

In addition to instantaneous dipole induced dipole (id-id) and permanent dipole permanent dipole (pd-pd) interactions between propanone and water molecules, the carbonyl oxygen of propanone can also form hydrogen bonds with water. Hence, propanone is soluble in water, i.e. these two liquids are miscible. Both I3 and N3 are linear, i.e. their bond angles are 180o.

+
H O: O H

Allene (or propadiene) is not planar. The two hydrogen atoms on the left lie on an equatorial plane while the two hydrogen atoms on the right lie on an axial plane.
H H C H H C C

Cu+ + e Cu2+ + e reduction: oxidation:

Cu Cu+

E = +0.52 V E = +0.15 V

Sn4+ + 2e Sn2+ + 2e reduction: oxidation:

Sn2+ Sn

E = +0.15 V E = 0.14 V

Cu+ + e Cu Cu+ Cu2+ + e

Sn2+ + 2e Sn Sn2+ Sn4+ + 2e

2Cu+ Cu2+ + Cu E cell = (+0.52) (+0.15) = +0.37 V Since E cell > 0 V, the disproportionation of Cu+ is energetically feasible under standard conditions. 2Sn2+ Sn4+ + Sn E cell = (0.14) (+0.15) = 0.29 V Since E cell < 0 V, the disproportionation of Sn2+ is not energetically feasible under standard conditions. 4 Amt of Cr(s) formed = 1.04 / 52.0 = 0.02 mol Cr3+ + 3e Cr Amt of electrons required to reduce 0.02 mol of Cr3+ to Cr = 3 x 0.02 mol = 0.06 mol Amt of charge transferred = 0.06 mol x 96 500 C mol1 = 5790 C Note: 1 A = 1 C s1 Time taken = Amt of charge transferred / Current = (5790 C) / (5 C s1) = 1158 s Let the solubility be z mol dm3. AlY3(s) Al3+(aq) + 3Y(aq) z 3z Ksp = K = [Al3+(aq)][Y(aq)]3 = (z)(3z)3 = 27z4

K . 27 K 81K = 4 = [Y(aq)] = 3 4 27 27
Hence, z =
4

3K

CH2ClCOOH + KOH CH2ClCOOK + H2O Let vol. of CH2ClCOOH added be V cm3. Amt of KOH left = initial amt of KOH amt of acid added = (5.0 x 103 x 0.10) (V x 103 x 0.05) = (5.0 x 105)(10 V), where 0 V 10 Amt of excess acid = (V 10) x 103 x 0.05 = (5.0 x 105)(V 10), where V > 10 Amt of KOH left / mol 5 x 104 2.5 x 104 0 0 Amt of CH2ClCOOK formed / mol 0 2.5 x 104 5 x 10
4

V / cm3 0 A B C 5 10 15

Amt of excess CH2ClCOOH / mol 0 0 0 2.5 x 104 5 x 104

Remarks only KOH(aq) present half-equivalence point reached equivalence point reached buffer formed, but [CH2ClCOOH < [CH2ClCOOK] max. buffering capacity as [CH2ClCOOH = [CH2ClCOOK]

5 x 104 5 x 104

20

A buffer solution has maximum buffering capacity when pH = pKa.

NaCl(s) Na+(aq) + Cl(aq), pH = 7 MgCl2(s) Mg2+(aq) + 2Cl(aq), pH = 6.5 due to slight hydrolysis of [Mg(H2O)6]2+ When a small amt of water is added: AlCl3(s) + 3H2O(l) Al(OH)3(s) + 3HCl(g) When a lot of water is added: AlCl3(s) + 6H2O(l) [Al(H2O)6]3+(aq) + 3Cl(aq)

SiCl4 + 4H2O Si(OH)4 + 4HCl PCl3 + 3H2O H3PO3 + 3HCl When a small amt of water is added: PCl5 + H2O POCl3 + 2HCl When a lot of water is added: PCl5 + 4H2O H3PO4 + 5HCl

MCln(l) Mn+(l) + nCl(l), where M = Na, Mg. Molten ionic chlorides conduct electricity. The other chlorides have simple molecular structures. They do not conduct electricity. 8 As the methyl group in methylbenzene is weakly activating, electrophilic substitution of the benzene ring will not occur. Use Br2 with FeBr3 (anhydrous condition) instead. HBr + H2O H3O+ and Br The ions form relatively strong ion-dipole interactions with water molecules. Propene is not nucleophilic enough to extract the H+ from H3O+. Use HBr(g) instead. Phenylmethanol would undergo free radical substitution if it reacted with Cl2(g) in the presence of uv light. Use Cl2 with FeCl3 (in the absence of water) instead. Sodium reacts with liquid ethanol to give sodium ethoxide, CH3CH2ONa+. In this case, the ethoxide ion functions as a base to bring about the elimination of HBr from bromocyclohexane. NOTE: the ethoxide ion can also function as a nucleophile.

Br

Br

P is a ketone and Q is an amide. Only carbonyl compounds, e.g. P, react with 2,4-DNPH to form an orange ppt.
H C O2N N H NO2 N C H

+ C6H5COCH2I + 2I2 + 3NaOH warm C6H5COO Na + CHI3 + 2NaI + 2H2O

P reacts with alkaline aqueous iodine to give a yellow ppt, CHI3.

NaOH(aq) C6H5NHCOCH3 C6H5NH2 + CH3COONa+ heat

If heated strongly, Q may undergo hydrolysis. Both phenylamine and sodium ethanoate, the products of the alkaline hydrolysis, do not react with alkaline aqueous iodine to give a yellow ppt. Therefore, both 2,4-DNPH and alkaline aqueous iodine can be used to distinguish between P and Q. 10 Phenyl benzoate, C6H5OCOC6H5, undergoes acidic hydrolysis with concentrated sulfuric acid to give phenol, C6H5OH, and benzoic acid, C6H5COOH. Both products are dissolved in CCl4, a non-polar organic solvent. When aqueous sodium carbonate is mixed with the organic layer in the separatory funnel, the following equilibria are established. C6H5OH(org) C6H5COOH(org) C6H5OH(aq) C6H5COOH(aq)

Shaking the separatory funnel allows more phenol and benzoic acid molecules to migrate from the organic layer to the aqueous layer. Na2CO3 reacts with C6H5COOH to give sodium benzoate, C6H5COONa+ (as well as carbon dioxide and water). The ions of this salt are not well solvated by the non-polar CCl4. However, they are able to form ion-dipole interactions with water molecules. Since it is more energetically feasible for the ions to remain in the aqueous layer, the predominant species in the aqueous layer is C6H5COONa+. C6H5OH is slightly soluble in water, but it does not react with Na2CO3. There will be some phenol molecules in the aqueous layer. Since the phenyl group is hydrophobic, there will also be phenol molecules in the organic layer. As most of the benzoic acid molecules have reacted with sodium carbonate, there are very few of these molecules in the organic layer. Hence, the predominant species in the organic layer is C6H5OH. 11 Since N(II) and N(III) are bonded to carbon atoms of a benzene ring, we expect their lone pair electrons to be delocalised into the benzene ring (similar to the case of phenylamine). N(I) is bonded to two alkyl chains which are electron-donating. Hence, N(I) is the most basic and has the smallest pKb value. The fluoro group, which is in the vicinity of N(II), is able to withdraw some electron density from N(II) by inductive effect. N(III) is in the vicinity of an electron-withdrawing carboxylic group which can withdraw electron density by inductive effect. In addition, electron density is drawn away from N(III) by resonance. As a result, N(II) is more basic, and has a smaller pKb value, than N(III). + +

12

The peptide linkages (marked with arrows) will cleave when the tripeptide reacts with hot dilute NaOH.
H H2N C O C N H H C O C N H H C O C OH

CH2 COOH

CH2 OH

CH2

OH

Due to the alkaline conditions, the products obtained are:

Na+

H H2N C

O C

O C ONa
+

O Na+
+

H2N

CH2
Na COOH

CH2 OH

Na

13

For a fixed mass of gas, the no. of moles of gas, n, is constant. PV PV = nRT Case 1: constant n and V PV = nRT Grouping the constant terms together, we get P = (nR/V)T. P varies linearly with T. Hence, PV also varies linearly with T. Case 2: constant n and PV = nRT PV = (m/Mr)RT P = (m/V)(RT/Mr), where = m/V P = (R/Mr)T Taking reciprocal on both sides: (1/P) = (Mr /R)(1/T) 1/P varies linearly with 1/T. Case 3: constant n and P PV = nRT From Case 2, we get P = (m/V)(RT/Mr), where = m/V 1/T = (R/PMr) T varies inversely with . 1/P

1/T T

14 [ ] / mol dm3

Left half-cell Cu2+ + 2e 1.0

Cu

Right half-cell Cu2+ + 2e Cu 0.01

Since [Cu2+] in the left half-cell is higher, the Cu2+ ions in that half-cell are more likely to be reduced. Hence, electrons must flow from the right (anodic) half-cell to the left (cathodic) half-cell. 5

[Cu2+] at equilibrium = (1.0 0.01) / 2 = 0.495 = 0.5 mol dm3 (1 decimal place) When [Cu2+] in both half-cells are equal, the Cu2+ ions in each half-cell have equal tendency to undergo reduction (or the Cu atoms in each half-cell have equal tendency to undergo oxidation). The system is said to be at equilibrium. 15 From the graph, we know that at least 50 cm3 of HCl(aq) is required to neutralise 25.0 cm3 of the weak base; from 0 cm3 of HCl(aq) added to the point at which HCl(aq) is in excess (> 50 cm3), there is only one equivalence point on the titration curve. Based on the information, we could make the following deductions. The weak base has one pKb value, i.e. 1 mol of base reacts with 1 mol of HCl. Hence, the weak base cannot be H2NCH2CH2NH2, which has two pKb values and 1 mol of it requires 2 mol of HCl for complete neutralisation. Due to the hydrolysis of the conjugate acid of the weak base, the solution is acidic (pH < 7) at equivalence point. Methyl orange is a suitable indicator for the titration as its working range coincides with the region of rapid pH change (i.e. the region from just before to just after the equivalence point). At least 25 cm3 of HCl(aq) is required to reach half-equivalence point. When 25 cm3 of HCl(aq) is added to the weak base, the acid reacts completely and neutralises about half the total amount of weak base. At this point, the resulting solution contains unreacted weak base and the conjugate acid of the weak base. Hence, a buffer solution is formed. The highest oxides (i.e. an oxide in which the element exhibits its highest possible oxidation number) are Na2O, MgO, Al2O3, SiO2, P4O10, SO3 and Cl2O7. Basic oxides (ionic): Na2O, MgO Amphoteric oxide (ionic): Al2O3 Acidic oxides (covalent): SiO2, P4O10, SO3, Cl2O7 Na2O + H2O 2NaOH MgO + H2O Mg(OH)2 (pH > 12) (pH 9)

16

Note: MgO is sparingly soluble in water.

Al2O3 is insoluble in water because the heat generated from its dissolution will not be sufficient to overcome the large amount of energy (i.e. highly exothermic lattice energy) required to break its giant ionic lattice. Thus, a solution containing solid aluminium oxide has a pH value of 7 (at 25 oC). SiO2 is insoluble in water because the heat generated from its dissolution will not be sufficient to overcome the large amount of energy required to break its giant molecular structure. Thus, a solution containing solid silicon dioxide has a pH value of 7 (at 25 oC). P4O10 + 6H2O 4H3PO4 SO3 + H2O H2SO4 Cl2O7 + H2O 2HClO4 Danger! Beware of highly exothermic reaction. Danger! Beware of hot, acidic mist. Note: Chloric(VII) acid is very acidic.

Electrical conductivity: Na < Mg < Al From Data Booklet: + As the number of valence electrons which can Na + e Na E = 2.71 V 2+ delocalise in the metallic lattice increases, the Mg + 2e Mg E = 2.38 V 3+ electrical conductivity also increases. Al + 3e Al E = 1.66 V Cl2 + 2e 2Cl E = +1.36 V Note: Cl2 is oxidising. reducing power: Na > Mg > Al > Cl2 (no E data for Si, P4 and S8) 6

17

MCO3(s) (s) + CO2(g) Hdecomp > 0; Sdecomp > 0 heat MO(s)

(M = Mg or Ba)

MgCO3 decomposes at a lower temperature because the higher charge density of Mg2+ polarises, , and hence weakens, the CO bond in carbonate ion to a greater extent than Ba2+ does. Depending on the temperature, MgCO3 may have decomposed to give CO2, but BaCO3 may not have begun decomposing. Gdecomp = Hdecomp TSdecomp The decomposition reaction does not occur spontaneously until the carbonate is heated to a certain temperature. At low temperatures, Gdecomp > 0 because |Hdecomp| is greater than |TSdecomp|. At high temperatures, Gdecomp < 0 because |TSdecomp| is greater than |Hdecomp|. 18

progesterone

aldosterone

Only progesterone reacts with alkaline aqueous iodine (see rectangle). Only aldosterone reacts with Fehlings solution (see oval). Neither of the two compounds reacts with sodium hydrogen carbonate (a weak base). 19
O OH O O
O OH OH

aspirin

salicylic acid

The phenol group of salicylic acid does not react with ethanoic acid to give the ester group in aspirin. Ethanoyl chloride should be used instead. Only salicylic acid forms a violet complex with neutral FeCl3(aq). 3RCOOH + PCl3 3RCOCl + H3PO3 Both aspirin and salicylic acid react with the same amt of PCl3. 20 At pH 7, the guanidino group will be protonated (i.e. positively charged), , so leupeptin cannot undergo nucleophilic acyl substitution with ethanoyl chloride. chloride In addition, with the exception of the guanidino group, the rest of the molecule is uncharged. Thus, at pH 7, leupeptin migrates to the negative tive electrode ( (cathode). guanidino group NH NH is isoelectronic with O, and NH2 is isoelectronic with O. Hence, this moiety is isoelectronic with COO , i.e. it can donate a lone pair to an H+ ion. At pH < 12.5, it exists as C(NH)(NH2)2+. 7

Section B B1 (a) Prediction: Solubility of cerium(IV) sulfate in sulfuric acid decreases when concentration of sulfuric acid increases. Explanation: As [H2SO4] increases, [SO42(aq)] also increases. By Le Chateliers Principle, the position of equilibrium of the reaction Ce(SO4)2(s) + aq Ce4+(aq) + 2SO42(aq) shifts to the left and the solubility of Ce(SO4)2 decreases. OR H2SO4(aq) is a strong acid which dissociates completely in aqueous solution to give H+ and SO42 ions. The SO42 ion is a common ion to both H2SO4 and Ce(SO4)2. Due to common ion effect, the solubility of Ce(SO4)2 decreases with increasing [H2SO4(aq)].

solubility of cerium(IV) sulfate

concentration of sulfuric acid (slight curve is also acceptable) (b) Temperature

Examiners Comments B1(a) The inverse relationship between the solubility of Ce(SO4)2 and the concentration of sulfuric acid must be clearly shown in your answer. Vague answers such as solubility decreases, which do not mention how solubility of Ce(SO4)2 varies with the acid concentration, are not given credit. The common ion, SO42, must be clearly identified in the explanation. Some students were able to give the expected prediction, but were unable to correctly display their prediction in the form of a graph. Many of these students did not seem to understand what they were doing. B1(b) Most students managed to identify temperature as the variable to be controlled since it is mentioned in the definition of solubility given at the beginning of the question. It is the temperature of water which should be kept constant, not the temperature of the surroundings.

(c)

Part 1 solubility of cerium(IV) sulfate in water Method 2: 1. Pour 60 cm3 of distilled water into a conical flask. Place the conical flask with the distilled water in a water bath which is maintained at the temperature at which the solubility of Ce(SO4)2 is to be found. 2. Add a little Ce(SO4)2 to the distilled water and stir the mixture with a glass rod. Continue adding Ce(SO4)2, with stirring, until some remained undissolved. Allow time (e.g. 10 min) for the mixture to reach equilibrium. 3. Weigh a clean and dry evaporating dish. Let its mass be m1. 4. Filter the mixture in the conical flask. Collect the filtrate and place it in the weighed evaporating dish. Weigh the filtrate and evaporating dish. Let the mass be m2. 5. Heat the evaporating dish to drive off all the water. Weigh the evaporating dish and the residue. Let the mass be m3. 6. Mass of Ce(SO4)2 in filtrate, mc = mass of residue = m3 m1 Mass of distilled water in filtrate, mw = m2 m3 m 7. Solubility of Ce(SO4)2 in water = m c x100
w

Method 1: 1. Weigh a clean and dry conical flask. Let its mass be m1. Place 60 cm3 of distilled water into the conical flask and obtain the new mass, m2. Mass of distilled water, mw = m2m1. 2. Place the conical flask with the distilled water in a water bath which is maintained at the temperature at which the solubility of Ce(SO4)2 is to be found. 3. Add a little Ce(SO4)2 to the distilled water and stir the mixture with a glass rod. Continue adding Ce(SO4)2 , with stirring, until some solid remains undissolved. Allow time (e.g. 10 min) for the mixture to reach equilibrium. 4. Weigh the conical flask with the saturated solution and undissolved Ce(SO4)2. Let the mass be m3. Filter this mixture. Collect the residue and leave it to dry. Weigh the dry residue. Let its mass be m4. Mass of saturated solution, ms = m3 m1 m4 5. The mass of Ce(SO4)2 which is soluble in 60 cm3 of distilled water, mc = ms m w m 6. Solubility of Ce(SO4)2 in water = m c x100
w

Key points: Description of a sequential method for preparing the saturated solution using 60 cm3 of distilled water and filtering off the excess solid Mention stirring and waiting time for equilibrium to be established Description of how temperature is controlled, e.g. using a water bath during the preparation of the saturated solution Description of how the mass of Ce(SO4)2 and mass of water could be found Examiners Comments for Part 1 Procedure lacks essential details, e.g. suitable apparatus, appropriate volume or mass, what measurements to take, when to stop adding the solid, how to maintain constant temperature, the need for equilibrium to be achieved before filtration, etc. Procedure lacks clarity, e.g. not labelling the steps, poor choice of words such as pour solid, illogical sequence such as not weighing the dry beaker before adding in water, etc. Ice-baths (you cannot dissolve a solid in ice!) and sand-baths (too hot!) are unsuitable for this experiment. A thermostat is not the same as a temperature-controlled (or thermostatically controlled) water bath. There is certainly no need for a thermodynamically controlled water bath in this experiment. Many students failed to recognise the need to either dry the residue or evaporate the filtrate to find the mass of solid dissolved. Some students dry the residue and then wash it with cold water, which defeats the purpose of drying the residue. Drying agents such as anhydrous calcium chloride should not be used as they contaminate the residue. The liquid obtained from filtration is a filtrate, not a distillate (which is obtained from distillation). Many students assumed the mass of 60 cm3 of water to be 60 g. Although this is a good approximation (since density of water is about 1 g/cm3), students should obtain the mass of water used by weighing. Although the definition of solubility is given in the question, it was generally ignored. Some students confused solubility with solubility product, Ksp. A filter funnel is not the same as a separating (or separatory) funnel. You do not use a separating funnel to separate a solid from a solution; a separating funnel is used to separate two immiscible layers. 9

Part 2 solubility of cerium(IV) sulfate in sulfuric acid 1. Using a burette, transfer 20.00 cm3, 40.00 cm3, 60.00 cm3 and 80.00 cm3 of the acid provided into four different 100 cm3 graduated volumetric flask labelled as S1, S2, S3 and S4. For each graduated flask, top up to the 100 cm3 mark with distilled water. Stopper and shake each flask to ensure that the dilute sulfuric acid prepared is homogeneous. Concentrations of the sulfuric acid are 1.00, 2.00, 3.00 and 4.00 mol dm3 in the flasks S1, S2, S3 and S4 respectively.

2.

Key points: An appropriate method for diluting the sulfuric acid described (means of measuring volume of acid and of water; sensible choice of volumes) Burettes/pipettes and graduated flasks (or other suitable precision apparatus) used to measure volumes Four solutions with different concentrations (to be specified) prepared and the range should cover at least a fourfold increase in concentration, e.g. 1 mol dm3 to 4 mol dm3, and at least one should be greater than 2.5 mol dm3. 5 mol dm3 should not be one of these because a decent scatter plot should contain 5 data points The volumes to be used must correspond to the desired concentrations to be attained Alternative method: Serial dilution Examiners Comments for Part 2 Language of procedure writing to include quantity and instrument used. o The key to doing well is to read as many laboratory procedures as possible. o Note that each step ideally should contain three parts: 1. Start with a verb (an action word). 2. Describe the variable with suitable quantities to be measured & recorded. 3. List the instrument to be used. o E.g. Weigh and record <the verb> about 2.5 g of Na2O (s) <the variable> using an electronic mass balance <the instrument>. [not required in this expt but for those that require weighing] E.g. Transfer <the verb> 25.0 cm3 of FA1 <the variable> using a pipette <the instrument> to a 250-ml graduated volumetric flask <follow up instrument for the verb transfer>. o Many students left the measuring instrument out! For those that stated the apparatus used, the apparatus used were not precise enough. E.g. Students suggested using measuring cylinders and beakers to measure volumes. Instead, burettes or pipettes should be used. To prepare a dilute solution of known concentration (standard solution), we have to use a standard volumetric flask (see comment below) instead of just placing the solution in a beaker. Adding up volumes o Generally, the total volume of a mixture of miscible solutions of different densities is not equal to the individual volumes. E.g. 10 cm3 of 5 mol dm3 H2SO4 + 10 cm3 of H2O 20 cm3 of combined solution o Hence, there is a need to use graduated standard volumetric flask to make standard solutions of known concentration, i.e. topping up to the mark to prepare a solution of a particular volume. Presentation o Students should try to tabulate their desired volumes to be used instead of writing all over the place. Calculation of concentration o A significant number of students do not know how to calculate the appropriate volumes of acid and water to make their desired concentrations of acid. [diluted solution] = volume of 5 mol dm3 H2SO4 x 5 mol dm3 total vol. of solution in standard flask 10

(d)

Corrosive nature of concentrated sulfuric acid OR toxicity of cerium compounds

Examiners Comments for B1(d) Students need to differentiate risk from precautionary measures. o Risk: potentially health-threatening o Precautionary measure: methods to reduce the risk

B2

(a)

(i) (ii) (iii)

Lead metal E
cell

= +1.69 (0.36) = +2.05 V

2PbSO4(s) + 2H2O(l) PbO2(s) + 4H+(aq) + 2SO42(aq) + Pb(s) Anode: Zn(s) + 4OH(aq) [Zn(OH)4]2(aq) + 2e Cathode: O2(g) + 2H2O(l) + 4e 4OH(aq) Overall: 2Zn(s) + 4OH(aq) + O2(g) + 2H2O(l) 2[Zn(OH)4]2(aq) +1.62 = +0.40 E E anode = 1.22 V
anode

(b)

(i)

(ii) (iii)

Things to include: Voltmeter Salt bridge Labelled electrodes Standard conditions (T = 298K, P = 1 atm and concentrations = 1 mol dm-3)

T = 298 K H2 (1 atm)
K+ NO3

salt bridge
Pt

Zn

H+ [H (aq)] = 1 mol dm
+ 3

[Zn(OH)4]2 [Zn(OH)4]2 = 1 mol dm3

(iv)

Mass of Zn used = 0.60 x 40 = 24 g Amt of Zn used = 24/65.4 = 0.3670 mol Amt of e = 2 x 0.3670 = 0.7339 mol Quantity of charge = 0.7339 x 96500 = 7.08 x 104 C Time needed = 7.08 x 104 / 13.7 x 103 = 5.17 x106 s

Examiners Comments for B2 Question a(iii) seemed to be a problem for many students. These students failed to understand that the process of charging required electrical power and thus the overall equation is in the opposite direction to the reaction which took place to give the positive E cell in a(ii). A few students define rather than determine the E cell in a(ii). Please read the question carefully. For Questions b(i) and (ii), many students did not analyse the information given in the question. It is an alkaline/neutral medium and thus the half equation O2 + 4H+ + 4e 2H2O should not be chosen for the cathode reaction. Some students who chose the correct half-equation made careless mistakes and did not balance the overall equation correctly. The arrows used in the equations for the anodic, cathodic and overall processes should point in one direction only (oxidation at anode and reduction at cathode). Reversible arrows should not be used. 11

Examiners Comments for B2 (continued) Students who revised their work answered Question b(iii) well. The diagram should be constructed using a ruler. Please note that the standard hydrogen electrode is used as a reference electrode and has a voltage of 0.00 V. The electrode to be used for this half-cell should be platinised platinum. Using a graphite electrode in this half-cell will lead to a potential difference. Question b(iv) was generally well-answered. Some students did not use 40 g of Zn as given on pg 15 for their calculations. Quite a number of students forgot to calculate the quantity of electricity passing through the cell and calculated only the length of time. Some students incorrectly thought that the number of moles of electrons transferred was 4 times that of zinc. Many students did not know that 13.7 mA = 13.7 x 103 A. Almost all students omitted the units for quantity of electricity, which was C (coulombs). A number of students used the Ar of Cu instead of Zn. In many cases, rounding-off errors were spotted. Please do not copy the entire string of numbers from your calculator. Round-off intermediate and final answers to 4-5 and 3-4 significant figures respectively. B3 (a) (i) A titration curve with three vertical sections at 10, 20 and 30 cm3 and three pKa values of 2.1, 4.1 and 9.5 at 5, 15 and 25 cm3 respectively as shown below: Additional information:
(1) pKa associated with glu are as shown: pH 9.5

H pKa = 2.1 -COOH has a smaller pKa 1 + than side-chain COOH as it H3N C CO2H is closer to the electron pKa = 9.5 CH2 withdrawing NH3+ group 3 CH2 which stabilises its anion. pK = 4.1 CO2H a2
(2) As pH increases, glu is progressively deprotonated, forming 4 species:

4.1 2.1

A
0 5 10 15 20 3 Volume of aq NaOH/ cm 25 30

H + + C CO H H N H 3N 3 2 CH2 CH2 CO2H glu+

H + C CO2 H3N CH2 CH2 CO2H glu

H C CO2 CH2 CH2 CO2 glu

H H2N C CO2 CH2 CH2 CO2 glu2

Note that acid with lower pKa is deprotonated first. (3) The species present at different parts of the titration curve are shown below: C 3.1 glu D 4.1 (pKa2) Equal amt of glu and glu E 7.8 glu F 9.5 (pKa3) Equal amt of glu and glu2 G 11 glu2

Region pH Dominant species

A 1.5 glu+

B 2.1 (pKa1) Equal amt of glu+ and glu

Hence, at pH 2.5, as required by question (a)(ii), the species present would be glu+ and glu. (ii)

O HO

O OH NH 3+ HO

O O NH 3+

cationic form (glu+)

zwitterionic form (glu)

12

Using Henderson-Hasselbalch equation, 2.5 = 2.1 + lg {[zwitterionic form]/[cationic form]} Hence, the ratio of zwitterionic form to cationic form is 2.51. (OR cationic form : zwitterionic form = 0.398) (b)

N H 2N NH O O OH OH
(zwitterionic form also accepted) (c) Any one of the following: van der Waals interaction (ala with ala, pro with pro, or ala with pro) hydrogen bonding (ser with ser, ser with glu, or ser with lys) ionic bonding (glu with lys)

Examiners Comments for B3(a)(c) Most students did not give a complete sketch of the pH titration curve. Please show 3 vertical (or near vertical) regions and label their corresponding equivalence volumes. More often, the half-equivalence points and their corresponding pKa values and volumes were not well-labelled. General formation of amide bond is as shown: RCOOH + RNH2 RCONHR + H2O. The N of amine group loses an H. Since proline is a secondary amine, it has no more H attached to it after amide bond formation. Note that if C is written in the structure, all H atoms attached to it should be shown. Hence, the following structure would be wrong. The correct structure is shown on the right.

H2N wrong

C C C N C O O

NH OH

O OH

CH2 H2N

CH2

N C NH O H O O OH correct OH

CH2

For (c), marks are awarded for the type of R group interaction only if the amino acid residues that give rise to it are correctly given. o For van der Waals (or id-id) interactions, the R group should be non-polar. Glycine is not acceptable as its R group (which is an H atom) is too small to result in significant vdw interactions. o Hydrogen bonding can occur between 2 ser residues (OH - - - OH), glu and ser (COO- - - HO) and lys and ser (NH3+ - - - OH). Note that R groups of lys and glu exist as (CH2)4NH3+ and (CH2)2COO respectively. Hence, the interaction between lys and glu is ionic interactions and not hydrogen bonding. o Some students thought that electrostatic attraction is the same as ionic bonding. Do note that electrostatic attraction is an attraction that arises from unequal distribution of charges. Hence, ionic bonds, ion-dipole interactions, hydrogen bonding, pd-pd and id-id interactions are all electrostatic in nature and electrostatic attraction is not the same as ionic bonding.

13

(d) (e) (f)

quaternary structure Glycine is small so it can fit into the space within the helix and still allows the chains to come close together. Papaya juice contains enzymes that can digest or break down the covalent bonds in the protein. Boiled papaya juice is ineffective as the heat has denatured the enzyme.

(g)

Choose a sensible method such as using an acidic/basic medium (such as lemon juice or bicarbonate powder) or mechanically breaking the bonds through hammering/hitting the meat or gentle heating. Methods that will result in the meat becoming inedible, e.g. using mineral acids or heavy metal ions, are not accepted.

(h)

OH O
2

O OH
+ [O]

HS NH2

NH2 S S H2N HO
+ H2O

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B4

(a)

Mg(NO3)2 decomposed first. The ionic size of Mg2+ is smaller than that of Ba2+. As a result, the charge density of Mg2+ is higher than that of Ba2+. Mg2+ has a higher polarising power compared to Ba2+ and is able to polarise the electron cloud of the NO3 ion to a greater extent. The NO bond in the NO3 ion is weakened to a greater extent in Mg(NO3)2. Thus, Mg(NO3)2 is thermally less stable. Mg(NO3)2(s) MgO(s) + 2NO2(g) + O2(g)

(b)

(i) (ii)

X to Y: Volume increase is due only to increase in temperature of the gases. V T since P is constant. W to X: From W to X, the volume is affected by not only an increase in the temperature but also the increase in the no. of moles of gas resulting from the decomposition of Mg(NO3)2. Since both n and T are changing, the volume increases exponentially instead of linearly.

Examiners Comments for B4 4(a) Some students had the misconception that thermal decomposition involves the breaking of the ionic bonds between the cations and the anions. As a result, some students thought that Ba(NO3)2 will decompose first since it has a less exothermic lattice energy. Please note that in thermal decomposition, it is the covalent bond in the anion (in this case, the N-O bond) that will be broken. Students were not very careful / specific with the terms used. For example, there were flawed statements like: Mg has a higher charge density than Ba. (Note: Mg does NOT have a charge!) or Magnesium nitrate polarises the anion to a greater extent (Note: It is the cation, Mg2+, that polarises the anion, not magnesium nitrate or Mg). Some students did not compare Mg2+ and Ba2+ specifically. Instead, they either gave general trends down the group without clearly stating the relative positions of Mg and Ba, or just simply stated that Mg2+ has a high charge density and was able to polarise the electron cloud of the anion. 4(b)(i) Many students wrongly explained that the volume increase from X to Y was due to the thermal decomposition of barium nitrate. They failed to see that the question hinted that they should make use of the ideal gas equation to deduce the relationship between V and T. Also, some students did not read the question stem properly and hence missed out the fact that P was kept constant. 4(b)(ii) Very few students could see that the volume increase from W to X results from a combination of 2 factors: temperature increase as well as an increase in the no. of moles of gas in the system (due to thermal decomposition of magnesium nitrate).

15

Section C C1 (a) (i) (ii) A nucleophile is an electron-rich species that donates a pair of electrons (to an electron deficient species) to form a covalent bond. I II IV - nucleophilic addition - elimination - acid-base reaction/proton transfer

(iii)

LiAlH4 reacts violently with water (to form H2 gas). Note: LiAlH4 + 4H2O LiOH + Al(OH)3 + 4H2 dry ether (or any non-protic solvent such as CCl4, followed by water as proton source) Note: A non-protic solvent is a solvent that cannot donate H+ ions.

(iv) (b) (i) (ii) (iii) (c) (d) H2O Q R S T U -

NaH is a strong base / H is least polarisable / H is a poor nucleophile C6H7NO2 x = 120o ; y = 104.5o 1 = nitrile; 2 = alkene; 3 = ester (allow 104o105o for y)

CH2=C(CH2NH2)CH2OH CH3CH2OH CH2=C(CH2NHCOCH3)CH2OCOCH3 CH3CH2OCOCH3 CH3CH(CH2NH2)CO2CH2CH3

Reactions of Q and R with ethanoyl chloride: 1:2 ratio with Q as both NH2 and OH are acylated 1:1 ratio with R as only one OH group is acylated No hydrogenation of alkene with LiAlH4 No reduction of ester with hydrogen/Ni

Examiners Comments C1(a)(i) The majority of the students are unable to give the full definition of a nucleophile. Many students thought that nucleophiles must be negatively charged and they failed to recognise that what a nucleophile must possess is a lone pair of electrons for donation to form a covalent bond with an electron deficient species. C1(a)(ii) Students should understand the difference between state and describe so that they do not waste time by giving too much detail. When asked to state type of reaction, it is not sufficient to just say addition/substitution. The word nucleophilic or electrophilic is crucial. The term neutralisation should be avoided here as it involves the formation of a salt. The reaction in step IV is NOT hydrolysis. Hydrolysis usually involves the rupturing of a chemical bond by the addition of water.

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Examiners Comments C1(a)(iii) Many students had the wrong impression that water is a stronger nucleophile and hence will hydrolyse the ester. They failed to recall that the hydrolysis of esters does not take place so readily and it requires heating. Some students suggested methane or ethane as another suitable solvent without realising that these compounds exist as gases at rtp and hence cannot be used as solvents. C1(a)(iv) Many students failed to recognise that NaH is an ionic compound and there is no such thing as NaH bond in this context. Some students also have the serious misconception that H+ from NaH is a poor nucleophile. They failed to realise that H+ can never serve as a nucleophile as it is electron deficient and has NO lone pairs of electrons. It should be the H ion from NaH that is a poor nucleophile because its electron cloud is less polarisable. C1(b)(i) About half the cohort did not answer to the question. They gave the structural formula instead of the molecular formula. This is shocking! C1(b)(ii) When asked to state the bond angle, please state a value. Signs like </> are not acceptable. Do not state a range of values too. Students failed to link 1(d) to 1(a) and thought that the reaction of LiAlH4 with an ester is similar to the hydrolysis of an ester. Students also need to learn the correct names of functional groups (e.g. cyanide is not acceptable for the CN group). When students encounter a C=O group, they should always check if the C=O is part of an ester or amide linkage before concluding the functional group is a ketone. The explanations for 1(d) are also unclear be explicit and explain how the mole ratios of ethanoyl chloride to Q and R help to identify the structures (i.e. say Q has two groups (alcohol and amine) that will react with CH3COCl and not Q may have alcohol or amine functional groups). Students also need to remember which functional groups are affected by the various reducing agents. Many failed to recognise that LiAlH4 does not reduce alkenes and hydrogen gas reduces nitriles. Just because hydrogen gas does not reduce esters does not mean it is a weak reducing agent! C2 (a) (i)

(ii)

React with 2,4-DNPH and then determining the melting points of the hydrazones. Reagents: I2(aq) / NaOH(aq) Condition: warm Observation: Pentan-2-one gave a yellow ppt, but not pentan-3-one. Organic products: CHI3 and CH3CH2CH2COONa+

(iii)

17

(iv)

Type of reaction: Nucleophilic Addition Condition: trace amounts of NaCN or NaOH(aq) Mechanism:

B1

Examiners Comments for C2(a) This question was generally high-scoring. However, there are also many students who did not take care when reading the question and as a result, lost marks unnecessarily. (a)(i) The question asked for a balanced equation. Many students did not balance the equation with H2O. Please take note that the structure of the product has to be clear. CH3CH2CH2 cannot be replaced with C3H7 because it represents two possible structures, CH3CH2CH2 and (CH3)2CH. (a)(iii) While many students stated correctly the use of the iodoform test to distinguish the ketones, very few students gave the correct products. CH3CH2CH2CO2Na+ was usually just given as the anion without the counter ion. Note that the sodium ion is required. (a)(iv) Please note the use of curved/curly arrows in the writing of mechanisms and their significance. To many students, arrows show the movement of attacking species. However, arrows show movement of electrons, with a half arrowhead representing one electron and a full arrowhead representing a pair of electrons. And the arrows must be curved! Dont be flippant when drawing mechanisms. Respect the convention. Arrows should also start from the electron pair and end close to where the pair of electrons goes. Dont leave your arrow hanging in midair. And please DONT draw arrows starting from negative charges and ending them at positive charges. These charges are drawn in by humans; they dont physically exist. Note that the intermediate must also show correct structure so the condensed C3H7 is not allowed and such answers were penalised again. The question also did not ask you to address the stereochemistry of the product so there is no need to show the attack of the carbonyl carbon by the cyanide ion from either side of the plane around the carbonyl group.

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(b)

+ O H O C C H
cis

O + C OH C H

H C C HOOC
trans

COOH H

(hydrogen bonds not required) In the cis isomer, the COOH COOH groups are oriented close enough to form intramolecular hydrogen bonding. bonding Hence, the cis isomer has less extensive intermolecular hydrogen bonding and a lower melting point. OR The cis isomer cannot pack as efficiently or closely as the trans isomer can, and thus, , the cis isomer has a lower melting point. (c) (i) Li+, Na+ and K+ belong to Group I. Down the group, nuclear charge increases but electrons are added to a higher principal quantum s shell which is further fu away from the nucleus. Hence, valence electrons experience weaker attractive force and ionic radius increases.

dative bonds

(ii) The crown ether complexes with the K+ ions and carries the ions into the organic solvent since the CH2CH2 chains of the ether can form instantaneous dipole-induced dipole induced dipole interactions with the organic solvent. HOOCCH2CH2CH2CH2COOH In the organic solvent, the K+ ions are complexed with the crown ether, and the MnO4 ions are unsolvated or naked (as compared to aqueous medium, medium where the MnO4 ions are surrounded by a dense hydration shell.) AlBr3 AlBr3 will hydrolyse water instead. AlBr3 + 3H2O Al(OH)3 + 3HBr

(iii)

(iv) (v)

(vi) (vii)

19

Examiners Comments C2(b) Many students did not draw diagrams to illustrate the proximity of COOH groups in the cis isomer or the more symmetrical arrangement in the trans isomer. A number of students mixed up the cis and trans isomers. Most of the answers were lengthy and did not have the key points. C2(c)(i) For trends down a group, please do not explain using effective nuclear charge, which is for comparing trends across a period. Some students mistook effective nuclear charge for nuclear charge, which is determined by the number of protons. C2(c)(ii) Many students could not draw the correct complex with six dative bonds. The cavity of the crown ether is not large enough to accommodate multiple K+ ions! C2(c)(iii) Most students wrongly explained the increased solubility solely based on overcoming the ionic bonds in KMnO4. The more important point here is the id-id interaction between the alkyl chains of the crown ether and the benzene ring as the question asks why it is soluble in benzene. Many students used the term hydrophobic, which is not accepted. Please describe the molecules as non-polar and the interactions as id-id (not hydrophobic interactions). C2(c)(v) Most students gave incorrect responses for this question. Many students suggested that the reactants did not dissolve as well in water, which does not explain the enhanced oxidising strength of purple benzene. C2(d)(i) Some students suggested CH3CH2+ as the Lewis acid, but the question requires identification of a reagent. C2(d)(ii) Most students described the hydrolysis reaction as AlBr3 dissociates in water. AlBr3 is a covalent compound, so hydrolysis describes the breaking of its covalent bonds more accurately. Dissociate is a term often used for ionic compounds.

C3

(a)

(i)

Titanium dioxide exists as oppositely charged ions held together by strong ionic bonds / electrostatic forces. Octocrylene exists as molecules held together by relatively weaker van der Waals forces. More energy is required to overcome the stronger electrostatic forces of attraction in titanium dioxide and thus it has a higher boiling point.

(ii)

Phenylbenzimidazole sulfonic acid has polar OH and NH groups that can form hydrogen bonds with water molecules. Thus, it is watersoluble and is not a suitable sunscreen. Octocrylene has a large hydrophobic hydrocarbon chain that makes it water-resistant, and thus, is a suitable sunscreen.

20

(iii)

COO-Na+ O-Na+ O

(iv)

correct reagents and conditions + correct observations Any one of the following tests. Test 1: Reagents and conditions: 2,4-dinitrophenylhydrazine Observations: Orange ppt formed with oxybenzone and no orange ppt obtained with octocrylene. Test 2: Reagents and conditions: Sodium Observations: With oxybenzone, effervescence of H2 was observed. Gas evolved gave a pop sound with a lighted splint. No effervescence of H2 gas observed with octocrylene. Test 3: Reagents and conditions: KMnO4(aq), dilute H2SO4(aq), heat Observations: Decolourisation of purple MnO4 with octocrylene and no decolourisation of purple MnO4 with oxybenzone Test 4: Reagents and conditions: neutral FeCl3 Observations: Purple colouration observed with oxybenzone and no purple colouration observed with octocrylene

Examiners Comments C3(a)(i) Ionic bonding involves electrostatic attraction between ions, NOT attraction between molecules or between atoms. Confusing terms like intermolecular ionic bonding also surfaced. Octocrylene is incapable of hydrogen bonding between its molecules. C3(a)(ii) Many students only focus on the solubility of phenylbenzimidazole sulfonic acid, but ignored octocrylene. Some merely said that octocrylene is incapable of forming hydrogen bonding with water and hence it is insoluble. However, the focus should be on the bulky hydrophobic alkyl groups and the benzene ring. In fact, the nitrile and ester groups are capable of hydrogen bonding with water molecules! C3(a)(iv) Some students used Br2(aq) with the intention of reacting it with the phenol group in oxybenzone. However, the presence of an alkene in octocrylene would also bring about decolourisation of Br2.

21

(b)

(i) (ii)

sp2

+ +

Examiners Comments C3(b) The two molecules must be orientated in such a way that three H-bonds can be drawn. Students often left out the lone pair of electrons on the donor atom. The partial charges + and must be placed, respectively, on the H and N atoms of the H-N bond. (c) (i) 9 Note: no. of orbitals in a sub-shell = 2l + 1, where l = angular momentum quantum number. For s orbital, l = 0; p orbital, l = 1; d orbital, l = 2; f orbital, l = 3; g orbital, l = 4. Hence, (2 x 4) + 1 = 9.

(ii)

18 Note: Each orbital can accommodate 2 electrons, so 9 orbitals can accommodate up to 18 electrons. Thus, there are 18 elements. 4p 5s 4d 5p 6s 4f 5d (Use Aufbau Principle. You may refer to Understanding Advanced Physical Inorganic Chemistry by Jeanne Tan & Kim Seng Chan.) 6d 7p 8s 5g Two g electrons

(iii)

(iv) (v) (d)

1 ppm = 1 m3 of gas in 106 m3 of air 100 ppm = 100 m3 of gas in 106 m3 of air = 100/106 x 25.5 = 0.00255 m3 of gas in 25.5 m3 of air in laundry room pV = nRT = mRT / Mr m = pV (Mr) / RT = 101 x 103 x 0.00255 x 166 / (8.31 x 303) = 17.0 g

Examiners Comments 3(d) Some students cannot answer this question is because they did not convert ppm to m3 correctly.

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