MINISTRY OF EDUCATION, SINGAPORE in collaboration with UNIVERSITY OF CAMBRIDGE LOCAL EXAMINATIONS SYNDICATE General Certificate of Education Advanced Level

Higher 2

CHEMISTRY
Paper 1 Multiple Choice Additional Materials: Multiple Choice Answer Sheet Data Booklet

9647/01
October/November 2011 1 hour

READ THESE INSTRUCTIONS FIRST Write in soft pencil. Do not use staples, paper clips, highlighters, glue or correction fluid. Write your name, Centre number and index number on the Answer Sheet in the spaces provided unless this has been done for you. There are forty questions on this paper. Answer all questions. For each question there are four possible answers A, B, C and D. Choose the one you consider correct and record your choice in soft pencil on the separate Answer Sheet. Read the instructions on the Answer Sheet very carefully. Each correct answer will score one mark. A mark will not be deducted for a wrong answer. Any rough working should be done in this booklet.

This document consists of 17 printed pages and 1 blank page.

Singapore Examinations and Assessment Board

UCLES & MOE 2011

[Turn over

2 Section A For each question there are four possible answers, A, B, C and D. Choose the one you consider to be correct. 1 Use of the Data Booklet is relevant to this question. The sunlight-induced photolysis of water is being investigated as a useful source of the pollution-free fuel hydrogen. 2H2O o 2H2 + O2 It has been found that anatase, one of the three crystalline forms of the ionic compound TiO2, is a good catalyst for this reaction. How many electrons are associated with each titanium ion in the anatase lattice? A 18 B 19 C 20 D 22 Ti: 22 electrons Ti4+: (22 - 4) electrons

Why is the first ionisation energy of neon higher than that of fluorine? neon has one more proton than fluorine, i.e. greater nuclear charge; shielding effect remains constant B Neon has a complete octet, but fluorine does not. across the period; effective nuclear charge in neon is C The atomic radius of fluorine is less than that of neon. greater; D The nuclear charge in neon is greater than that in fluorine. more energy is required to remove the valence electron from neon than from fluorine Use of the Data Booklet is relevant to this question. A Fluorine is more electronegative than neon. Sodium percarbonate, (Na2CO3)x.y(H2O2), is an oxidising agent in some home and laundry cleaning products. 10.0 cm3 of 0.100 mol dm3 sodium percarbonate releases 48.0 cm3 of carbon dioxide at room conditions on acidification. n(CO32-) = 0.00100x mol = n(CO2) = 0.00200 mol x=2 An identical sample, on titration with 0.0500 mol dm 3 KMnO4, requires 24.0 cm3 before the first pink colour appears. KMnO4 reacts with H2O2 in the mole ratio 2 : 5. n(H2O2) = 0.00100y mol What is the ratio y/x? n(KMnO4) = 0.00120 mol A 1/3 B 2/3 C 3/2 D 3/1 0.00100y/0.00120 = 5/2 y=3

A given mass of ideal gas occupies a volume V and exerts a pressure p at 27C. At which temperature will the same mass of the ideal gas occupy the same volume V and exert a pressure 2p? pV/T = constant A 54C B 54 K C 600C D 600 K pV/(273+27) = (2p)(V)/T T = 600 K

UCLES & MOE 2011

9647/01/O/N/11

3 5 The standard enthalpy change of combustion of but-1-ene, C4H8(g), is x kJ mol1. The standard enthalpy change of the reaction 2C2H4(g) o C4H8(g) is y kJ mol1. What is the standard enthalpy change of combustion of ethene, C2H4(g)? A x/2 + y kJ mol1 B x + y/2 kJ mol
1

C4H8(g) + 6O2(g) y

4CO2(g) + 4H2O(l) y+x

C (x + y)/2 kJ mol1 D (x y)/2 kJ mol1

2C2H4(g) + 6O2(g)

standard enthalpy change of combustion: amount of energy released when 1 mole of ethene burns, i.e. (x + y)/2

The table shows the charge and radius of each of six ions. ion radius / nm J+ 0.14 L+ 0.18 M2+ 0.15 X 0.14 Y 0.18 lattice energy is Z2 proportional to product of 0.15 charges, inversely proportional to sum of ionic radii

The ionic solids JX, LY and MZ are of the same lattice type.

What is the correct order of their lattice energies, placing the most exothermic first? A JX, MZ, LY B LY, MZ, JX C MZ, JX, LY D MZ, LY, JX

At temperatures below 13C, shiny, ductile metallic tin, known as white tin, changes slowly into a grey powder which is brittle. Data for each form of tin are given in the table. Hfo / kJ mol1 white grey 0 2.09 So / J K1 mol1 51.4 44.1

What is the expression for Gfo, in J mol1, for the formation of grey tin from white tin at 12C? A Gfo = 2.09 285(7.3) B Gfo = 2.09 12(+7.3) C Gfo = 2090 12(+7.3) D Gfo = 2090 285(7.3) standard entropy change = 44.1 - 51.4 = -7.3 J K-1 mol-1 standard enthalpy change = -2090 J mol-1

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

4 8 A student electrolyses concentrated aqueous sodium chloride using carbon electrodes. She ensures that the solution is continually stirred. What happens as the electrolysis proceeds? A H2 is produced at the anode. B HCl is formed. C NaClO is formed. D The NaCl gets more concentrated. chloride is oxidised to chlorine gas at the anode, water is reduced to H2 and OH- at the cathode, leaving NaOH in the solution; chlorine disproportionates in cold NaOH to produce NaClO

Use of the Data Booklet is relevant to this question. In many areas, tap water becomes slightly acidic due to dissolved carbon dioxide. By considering the relevant Eo values, which metal will not be dissolved by tap water containing carbon dioxide? A copper B iron C lead D zinc E(Cu2+/Cu) is the most positive, i.e. Cu has the least tendency to be oxidised

10 The diagram shows the apparatus needed to measure Eo for the reaction below. Fe3+(aq) + e hydrogen gas Y X Fe2+(aq)

platinum hydrochloric acid What are the identities of X and Y? X A B C D Fe Fe Pt Pt Y Fe3+(aq) Fe2+(aq) + Fe3+(aq) Fe3+(aq) Fe2+(aq) + Fe3+(aq)

UCLES & MOE 2011

9647/01/O/N/11

5 11 Soft drinks often have sodium citrate added to them to act as a buffer. Which statement about buffer solutions is correct? A The pH of a buffer solution changes slightly when very large amounts of acid or base are added. B The pH of a buffer solution increases very slightly when small amounts of acid are added. C The pH of a buffer solution increases very slightly when small amounts of base are added. D The pH of a buffer solution remains unchanged when small amounts of acid or base are added.

12 The reaction between NO2 and SO2 is a key stage in the formation of acid rain. NO2(g) + SO2(g) o NO(g) + SO3(g) The initial rate of this reaction was measured for different concentrations of reactants and the following results obtained. [NO2] / mol dm3 0.005 0.006 1.33 0.008 0.006 1.92 1.2 [SO2] / mol dm3 0.005 0.006 1.2 relative rate 1.00 1.44 1.33 1.44

Which row gives the correct orders of reaction with respect to the two reactants? order with respect to [NO2] A B C D 1 1 2 2 order with respect to [SO2] 0 1 0 1

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

6 13 The rate of the decomposition of the diazonium cation, C6H5N2+ + H2O o C6H5OH + H+ + N2 can be followed by measuring the time taken for the same volume of nitrogen to be produced from a range of diazonium cation concentrations. To find the order of the reaction with respect to the diazonium cation, which would be the most suitable graph to plot using the data? A [C6H5N2+] against time B [C6H5N2+] against 1 / time C volume N2 against time D volume N2 against 1 / time plot of [C6H5N2+] against time is the most straightforward method to determine order; if straight line with negative gradient obtained, zero order; if exponential curve with constant half-life obtained, first order; if curve with varying half-lives obtained, order is indeterminate, have to employ other methods to determine exact order

14 Which statement concerning only the elements in the third period, sodium to argon, is correct? A The element that has exactly four atoms in its molecule is sulfur. B The element with the highest electrical conductivity is aluminium. C The element with the highest melting point is aluminium. D The element with the largest anion is chlorine. electrical conductivity is directly related to the number of delocalised electrons in the 'sea of electrons' in metallic lattice

15 HCl is stable to heat, but HI decomposes into its elements when heated. What is responsible for this difference? A HI is a stronger reducing agent than HCl. B HI is more volatile than HCl. C The H-I bond is weaker than the H-Cl bond. D The I-I bond is weaker than the Cl-Cl bond. 16 Use of the Data Booklet is relevant to this question. What volume of oxygen, measured under room conditions, can be obtained from the complete thermal decomposition of 8.2 g of calcium nitrate (Mr = 164)? A 150 cm3 B 300 cm3 C 600 cm3 D 1200 cm3 thermal decomposition of HX involves breaking of H-X bonds; less energy required to break H-X bonds means easier to decompose

Ca(NO3)2 CaO + 2NO2 + 0.5O2 n(Ca(NO3)2) = 0.050 mol n(O2) = 0.5 0.050 = 0.025 mol V(O2) = 0.025 24 000 = 600 cm3
UCLES & MOE 2011 9647/01/O/N/11

7 17 In acid solution, dichromate(VI) ions oxidise hydrogen peroxide, H2O2. In alkaline solution, hydrogen peroxide oxidises chromium(III) ions. Which conditions of oxidation produce oxygen gas? A both acid and alkaline oxidations B neither acid nor alkaline oxidation C only the acid oxidation D only the alkaline oxidation in order to produce oxygen gas, hydrogen peroxide must undergo oxidation; this occurs only in acid solution

18 The enthalpy change of fusion of a solid is defined as the amount of energy, in J or kJ, required to melt one mole of a solid at its melting point. The table shows the enthalpy changes of fusion of four successive elements, W to Z, in the third period (sodium to argon) of the Periodic Table. element enthalpy change of fusion / kJ mol1 W 10.8 X 46.4 Y 0.6 Z 1.4

Which sequence of elements is represented by W to Z? W A B C D Al Na P Si X Si Mg S P Y P Al Cl S Z S Si Ar Cl Si (giant covalent structure) has the highest m.p., followed by Al (metallic lattice); P and S (simple molecular structures) have low m.p. enthalpy change of fusion is directly related to melting point;

19 Which statement about the molecule but-2-yn-1-ol is not correct?

OH
4 3 2 1 but-2-yn-1-ol

A The centre carbon atoms (2 and 3) are sp hybridised. B The molecule decolourises warm acidified KMnO4. C The terminal carbon atoms (1 and 4) are sp2 hybridised. terminal carbon atoms are sp3 hybridised

D The terminal carbon atoms (1 and 4) have tetrahedral geometry.

UCLES & MOE 2011 9647/01/O/N/11

[Turn over

8 20 The complete combustion of alkanes to produce carbon dioxide and water is an important exothermic reaction. Which line on the graph shows the relationship between the number of carbon atoms in the alkane and the number of moles of oxygen gas needed for complete combustion of the alkane? A CxH2x+2 + (6x+2)/4 O2 xCO2 + (2x+2)/2 H2O B

number of moles of oxygen gas y = (6x+2)/4 = 1.5x + 0.5 i.e. straight line with gradient 1.5, y-intercept 0.5

D number of carbon atoms in alkane

21 Chloroethene, CH2=CHCl, is unreactive to CH2=CHCH2Cl, is very reactive by comparison. What explains the lack of reactivity of CH2=CHCl?

nucleophiles

whereas

3-chloropropene,

A Substituted alkenes undergo only electrophilic addition. B The C=C double bond and the Cl atom are both electron withdrawing which stabilises CH2=CHCl. C The electrons on the Cl atom delocalise into the S bond. D The presence of the S bond prevents free rotation of the C-Cl bond thus decreasing the reactivity. delocalisation of electrons from Cl into the pi bond results in partial double bond character, hence rendering it much less reactive

UCLES & MOE 2011

9647/01/O/N/11

9 22 Which species could be an intermediate in an S N1 substitution?

OH

A H3C

C O
-

Cl

CH2

SN1 mechanism proceeds with carbocation intermediate

CN

D HO

G -

H3C C
+

Br CH3

G -

H3C

23 The diagram shows a reaction.

O O

steam, H+

What could be the final products Z?

O OH

A
OH

B
OH

HO

OH

hydration of alkene, followed by hydrolysis of ester

OH

+
OH

HO

OH

HO

OH

+
O

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

10 24 A comparison is made of the rate of hydrolysis of four halogenocompounds by warm NaOH(aq). CH3CH2COCl W How will these rates compare? fastest A B C D W W X Z Y Z Z Y Z Y Y X slowest X X W W acid chloride is the most susceptible to hydrolysis due to its highly electron deficient carbonyl carbon (which is bonded to two electronegative O and Cl atoms); chlorobenzene is the least susceptible to hydrolysis due to partial double bond character of C-Cl; iodoalkane is more susceptible to hydrolysis than bromoalkane due to weaker H-I bond C6H5Cl X (CH3)3CBr Y (CH3)3CI Z

25 The reaction conditions for four different transformations are given below. Which transformation has a set of conditions that is not correct?
UV light

CH4(g) + Cl2(g)

CH3Cl + HCl
conc. H2SO4 55C
CH3

C6H6(l) + HNO3(conc.)
CH3

C6H5NO2 + H2O

(l) + Cl2(aq)

AlCl3(s) heat
Cl OH

+ HCl

conditions should be anhydrous for aluminium chloride to effectively act as Lewis acid catalyst

OH

NO2

(aq) + HNO3(dilute)

+ H2O

UCLES & MOE 2011

9647/01/O/N/11

11 26 Compound P, C4H10O2, is an alcohol containing two OH groups per molecule. It can be oxidised in stages to compound Q, C4H8O2, and then to compound R, C4H6O2, which is a diketone. Which pair of statements about the properties of P, Q and R is correct? has 2 chiral centres A B C D P only P only P and Q only P, Q and R reacts with alkaline aqueous iodine to give tri-iodomethane P, Q and R Q and R only Q and R only P, Q and R P: CH3C*H(OH)C*H(OH)CH3 Q: CH3COC*H(OH)CH3 R: CH3COCOCH3 chiral centres marked with * all give positive result with iodoform test

27 In the following two-step synthesis, Y a solid which is insoluble in water, is one of the components in the final reaction mixture.
O OH

PCl5, warm
OH

NH3 then heat

What is Y? A
O NH
NH3
+

B
O NH2

C
O O
-

D
O O NH4
+

OH

NH2

X: carboxylic acid converted to acid chloride; 1 alcohol converted to 1 chloroalkane Y: acid chloride converted to amide; 1 chloroalkane converted to 1 amine; 1 amine acts as a nucleophile and reacts with amide

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

12 28 Compounds X, Y and Z all react with sodium to release hydrogen but only one of them reacts with 2,4-dinitrophenylhydrazine reagent. Which combination could be X, Y and Z? X A Y Z CO2H CO2H

CH2OH CHO CH2OH CHO

CH2OH CH2OH CHO CH2OH CHO CO2H

CH2OH CH2OH CHO CHO CO2H CO2H CO2H CO2H X: 1 alcohol and carboxylic acid react with sodium Y: carboxylic acid reacts with sodium; aldehyde reacts with 2,4-DNPH Z: carboxylic acid reacts with sodium

CH2OH CHO CO2H CO2H

29 The compounds responsible for the umami flavour of soy sauce are salts of glutamic acid. HO2CCH2CH2CH(NH2)CO2H glutamic acid Glutamic acid has pKa values of 2.1, 4.1 and 9.5. pKa(alpha-carboxylic acid) = 2.1 < 7 pKa(R-carboxylic acid) = 4.1 < 7 pKa(alpha-amine) = 9.5 > 7

What is the structure of the major species in a solution of glutamic acid at pH 7? A

O 2C
-

B
NH2

O 2C

NH3

CO2

CO2

C
HO2C NH3
+

D
HO2C NH3
+

CO2

CO2H

UCLES & MOE 2011

9647/01/O/N/11

13 30 Oseltamivir is an anti-viral drug.

OR CONH H3C H2N

acidic hydrolysis of amide and ester to form protonated amine and carboxylic acid; protonation of amine
CO2CH2CH3

[OR is inert]

oseltamivir What is the product when oseltamivir is heated with HCl(aq)? A

OR CONH H3C H3N
+

B
OR H3N
+

CO2CH2CH3

H3N

CO2H

C
OR H3N
+

D
OR CONH H3C
CO2CH2CH3

H3N

H3N

CO2H

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

14 Section B For each of the questions in this section, one or more of the three numbered statements 1 to 3 may be correct. Decide whether each of the statements is or is not correct (you may find it helpful to put a tick against the statements that you consider to be correct). The responses A to D should be selected on the basis of A 1, 2 and 3 are correct B 1 and 2 only are correct C 2 and 3 only are correct D 1 only is correct

12 No other combination of statements is used as a correct response. 2. should be 1/12 of mass of a C atom 3. relative molecular mass is 31 Which statements about relative molecular mass are correct? compared with mass of a 12C atom 1 It is the sum of the relative atomic masses of all the atoms within the molecule.

2 3

It is the ratio of the average mass of a molecule to the mass of a

12

C atom. (D)

It is the ratio of the mass of 1 mol of molecules to the mass of 1 mol of 1H atoms.

32 Which conditions are necessary when an electrode potential is measured using a standard hydrogen electrode as the reference electrode? 1. standard pressure = 1 atm 1 2 3 the use of hydrogen gas at 101 kPa (1 atm) 2. when current flows, measured voltage across terminals is no longer e.m.f. but p.d.

measurement of the e.m.f. when the current delivered by the cell is effectively zero
+ -3 a pH of 1.0 for the solution at the hydrogen electrode 3. [H ] = 0.10 mol dm , standard (B) conc. should be 1 mol dm-3

33 The three compounds X, Y and Z have the following structures.

HO N N OH
CO2CH3

N N

CH=CH2

N O

C12H10O2N2 X

C12H10O2N2 Y

C6H5ON

Which statements about X, Y and Z are correct? 1 2 3 X and Z have the same empirical formula. X and Y are isomers. The Mr of Y is exactly twice that of Z.
9647/01/O/N/11

(A)

UCLES & MOE 2011

15 34 The kinetics of the zero order reaction P o Q were investigated under different conditions. The table shows pairs of quantities that were plotted as graphs. Which pairs gave the following graph?

y-axis

0 0 y-axis 1 2 3 rate rate constant rate constant x-axis time time temperature zero order kinetics: rate is independent of [P] and hence does not vary with time rate constant is dependent on temperature and presence of catalyst, and hence does not vary with time (B) x-axis

35 What factors explain why a solution of aluminium chloride is acidic? 1 2 Chloride ions react with water to form hydrochloric acid. Aluminium ions have a large charge / surface area ratio. aluminium chloride is acidic because aluminium ions, having high charge density, hydrolyse in 3 The HO bonds are weaker in [Al(H2O)6]3+ than in H2O. water to produce hydrogen ions 1. chloride, being the conjugate base of a strong acid (weak (C) conjugate base), does not react with water 36 1-Bromopropane may be prepared by slowly adding concentrated sulfuric acid to a mixture of propan-1-ol and sodium bromide, and keeping the reaction mixture cool. CH3CH2CH2OH + HBr o CH3CH2CH2Br + H2O What would be a by-product of this reaction if the temperature is allowed to rise? 1 2 3 Br2 SO2 CH3CH(OH)CH3 1. bromide is oxidised by conc. sulfuric acid to bromine 2. conc. sulfuric acid is reduced by bromide to sulfur dioxide 3. 1-bromopropane can undergo dehydration in the presence of conc. sulfuric acid to produce propene, which then reacts with steam (high temperature) to produce the Markovnikov's product, propan-2-ol (A)

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

16 The responses A to D should be selected on the basis of A 1, 2 and 3 are correct B 1 and 2 only are correct C 2 and 3 only are correct D 1 only is correct

No other combination of statements is used as a correct response. 37 Swine flu has caused great concern internationally. One widely used treatment is the anti-viral drug Tamilflu. ester O
OCH2CH3

* (CH3CH2)2CHO
H3C O

*
NH

*
NH2

amide Which statements about the Tamilflu molecule are correct? 1 2 3 It contains an amide group. It contains two ester groups. It contains four chiral centres. (D)

38 A catalytic converter is part of the exhaust system of many modern cars. Which reactions occur in a catalytic converter? 1 2 3 2CO + 2NO o 2CO2 + N2 CO2 + NO o CO + NO2 2SO2 + 2NO o 2SO3 + N2 catalytic converter converts toxic exhaust to harmless gases, hence should not produce CO, NO2 and SO3 (D)

UCLES & MOE 2011

9647/01/O/N/11

17 39 Baeyers reagent is used to detect carbon-carbon double bonds: a dilute alkaline solution of KMnO4 loses its pink colour in the presence of such a bond. In which tests does a positive result involve a reduction in the oxidation number of the metal present in the reagent? 1 2 3 Baeyers test Fehlings test Tollens test 1. Baeyer's reagent oxidises alkene to diol, it itself being reduced from MnO4- to MnO2 2/3. Both Fehling's solution and Tollens' reagent oxidise aldehyde to carboxylate, and are being reduced in the process

(A)

40 Spider silk is a protein composed mainly of the three amino acids alanine, glycine and serine. NH2CH(CH3)CO2H alanine NH2CH2CO2H glycine NH2CH(CH2OH)CO2H serine

Which type of bonding can occur in the tertiary structure of spider silk? 1 2 3 van der Waals forces hydrogen bonding ionic bonding (B) van der Waals' forces between R-groups of alanine/glycine; hydrogen bonding between R-groups of serine

UCLES & MOE 2011

9647/01/O/N/11

[Turn over

18 BLANK PAGE

Permission to reproduce items where third-party owned material protected by copyright is included has been sought and cleared where possible. Every reasonable effort has been made by the publisher (UCLES) to trace copyright holders, but if any items requiring clearance have unwittingly been included, the publisher will be pleased to make amends at the earliest possible opportunity. University of Cambridge International Examinations is part of the Cambridge Assessment Group. Cambridge Assessment is the brand name of University of Cambridge Local Examinations Syndicate (UCLES), which is itself a department of the University of Cambridge.

UCLES & MOE 2011

9647/01/O/N/11