RAFFLES INSTITUTION 2011 YEAR 6 PRELIMINARY EXAMINATION HIGHER 2

CHEMISTRY
Paper 1 M !"#p!e C$%#&e

9647/01
26 Sep"e'(er 2011 1 $% r

Additional Materials: Multiple Choice Answer Sheet Data Booklet

REA) THESE INSTRUCTIONS FIRST )% *%" %pe* "$#+ , e+"#%* (%%-!e" *"#! .% are "%!/ "% /% +%0 Write in soft pencil. Do not use staples, paper clips, highlighters, glue or correction fluid. Write your name, class and inde num!er in the spaces pro"ided on the Answer Sheet. #here are 1%r". $uestions on this paper. Answer a!! $uestions. %or each $uestion there are four possi!le answers A, 2, C and ). Choose the one you consider to !e correct and record your choice with a soft pencil on the separate Answer Sheet. Rea/ "$e #*+"r &"#%*+ %* "$e A*+3er S$ee" 4er. &are1 !!.0 &ach correct answer will score one mark. A mark will not !e deducted for a wrong answer. Any rough working should !e done in this !ooklet.

#his document consists of 17 printed pages. '('

Se&"#%* A %or each $uestion there are four possi!le answers, A, 2, C, and ). Choose the %*e you consider to !e correct. 1 ).* g of a metal, M, com!ines with +.* g of o ygen to form the o ide M,. #he metal, M, also forms a second o ide in which the metal and o ygen are present in the ratio -:. !y mass. What is the formula of the second o ide/ A 2 M,) 2 M), C M),. ) M.,)

Use of the Data Booklet is relevant to this question. When x mol of "anadium is added to a solution containing y mol of "anadium0III1 ions, "anadium0II1 ions are formed in the resultant solution. Which of the following are possi!le "alues of x and y if "anadium reacts completely and the resultant solution contains e$ual num!er of moles of "anadium0 III1 ions and "anadium0II1 ions/ x A 2 C ) ( ( ( ) y ) . 2 .

Bromine trifluoride is a li$uid at room temperature. 3t shows an electrical conducti"ity high enough to indicate that some auto'ionisation occurs, which is usually represented !y the following e$uation: )Br%. Br%)4 4 Br%56 Which of the following is correct regarding Br%., Br%)4 and Br%56/ A 2 C ) Br%. is planar while Br%56 is non'planar. Br%)4 is linear while Br%56 is tetrahedral in shape. #he %6Br6% !ond angle in Br%. is smaller than that in Br%56. #here are more lone pairs of electrons around the Br atom in Br% . than that in Br%)4.

Which of the following &a**%" !e e plained !y hydrogen !onding/ A 2 C ) the e istence of the hydrogen'difluoride anion, 7%) the difference in "olatility !etween pentan'('ol and he an'('ol the difference in melting point !etween )'nitrophenol and 5'nitrophenol the higher than e pected relati"e molecular mass of ethanoic acid in !en8ene

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Buckminsterfullerene has the formula, C9+. 3ts structure is shown !elow.

#he !onding in !uckminsterfullerene is similar to that in graphite. Which of the following is correct/ A 2 C ) 6 All the !ond angles in !uckminsterfullerene are ()+o. #here are delocalised electrons in !uckminsterfullerene. #he melting point of !uckminsterfullerene is higher than that of graphite. ,n complete com!ustion, !uckminsterfullerene forms car!on dio ide and water.

Deuterium, )7, is an isotope of hydrogen. 3n an e periment, ..- g of a gas X at )2 oC was found to occupy the same "olume as +..9* g of deuterium gas at (- oC. Both gases were at the same pressure. What is the relati"e molecular mass of the gas X/ A C
).+ ..- )2 +..9* (5.+ ..- ):+ +..9* ):*

2 )

..- ):* ).+ +..9* ):+ 5.+ ..- ):* +..9* ):+

#he diagram shows the Ma well'Bolt8mann energy distri!ution cur"es for molecules of a sample of a gas at two different temperatures. Which letter on the a es represents the most pro!a!le energy of the molecules at the lower temperature/ C )

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Use of the Data Booklet is relevant to this question. 3n an e periment to determine the enthalpy change of solution of ammonium nitrate in water, *.++ g of solid ammonium nitrate 0Mr ; *+.+1 was added to 2+ g of water and the temperature of the resultant solution monitored at "arious time inter"als. <sing data from the a!o"e e periment, the following graph was o!tained.

time of mi ing of reactants What is the enthalpy change of solution of ammonium nitrate !ased on the data from the a!o"e e periment/ A 2 C ) 4(:.5 k= mol6( 4)+.( k= mol6( 4)+.: k= mol6( 4)).9 k= mol6(

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3n (:55, #. &llingham pu!lished plots of Go against temperature # for a num!er of reactions. #oday, such plots are called &llingham diagrams. An &llingham diagram for three reactions in"ol"ing the o idation of C and C, is shown !elow.

Which of the following shows correctly the three reactions corresponding to I, II and III in the a!o"e &llingham diagram/

I
A 2 C ) )C, 4 ,) )C,) )C 4 ,) )C, C 4 ,) C,) )C, 4 ,) )C,)

II
C 4 ,) C,) )C, 4 ,) )C,) )C, 4 ,) )C,) )C 4 ,) )C,

III
)C 4 ,) )C, C 4 ,) C,) )C 4 ,) )C, C 4 ,) C,)

10

A chemical plant illegally dumped some radioacti"e waste in a landfill. #his waste composed of two radioacti"e isotopes M and N. #he half'life of M is . days whereas that of N is ) days. #he authorities found out a!out this illegal dumping only when the waste had !een in the landfill for () days. #hey did an immediate analysis on a sample of the waste and found e$ual amounts of M and N. Considering that the decay of radioacti"e isotopes follows first'order kinetics, what is the molar ratio of M to N if the waste had !een in the landfill for 9 days/ M : N A 2 C ) ( ( ) 5 : : : : 5 ) ( (

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#he kinetics of the reaction !elow was studied using the method of initial rates. ,76 I 0a$1 4 Cl, 0a$1 I,60a$1 4 Cl60a$1
6 6

& periment ( ) . 5

3nitial >I6? @ mol dm6. +.++(. +.++)9 +.++(. +.++)9

3nitial >Cl,6? @ mol dm6. +.+() +.+() +.+(* +.+(*

3nitial >,76? @ mol dm6. +.(++ +.(++ +.(++ +.+2+

3nitial rate @ mol dm6. s6( :.5 (+6. (*.- (+6. (5.+ (+6. 29.( (+6.

What is the o"erall order of the reaction/ A C ( . 2 ) ) 5

12

At a temperature T A, +.*+ mol of S,) and +.5+ mol of , ) were introduced into a (+ dm. "essel and allowed to come to e$uili!rium. )S,)0g1 4 ,)0g1 )S,.0g1 7 B + #he graph !elow shows the "ariations in the amounts of S, ) and S,. in the system with time. A change was made to the system at time t.

What was the change made at time t/ A 2 C ) a catalyst was added the temperature was decreased an inert gas was added at constant "olume +.+2 mol of ,) was added at constant "olume

15

#he p7 of pure water is 9.** at .) oC. #he p7 of a saturated solution of a Croup II hydro ide is ((.-+ at the same temperature. What is the numerical "alue of the solu!ility product of this hydro ide at .) oC/ A C 9.. (.. (+6* (+62 2 ) ... ..* (+6(+62

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3n an e periment, a cell was set up to o!tain pure copper from a copper'sil"er alloy as shown !elow.

electrode P

electrode : CuS,50a$1

When a current of 5+.+ A flows through the electrolyte for )9.* minutes, the mass of the anode changes !y )9.5- g. Which of the following statements is correct/ A 2 C ) &lectrode P is pure copper and electrode : is the copper'sil"er alloy. #he concentration of CuS,50a$1 decreases during the e periment. #he mass of the cathode changes !y )9.5- g during the e periment. #he copper'sil"er alloy contains )+D sil"er !y mass.

17

X, Y and ; are consecuti"e elements in Eeriod . of the Eeriodic #a!le. &lement ; has the lowest melting point and the highest second ionisation energy among the three elements. What could !e the atomic num!ers of X, Y and ; respecti"ely/ A 2 C ) ((, () and (. (), (. and (5 (., (5 and (2 (5, (2 and (9

16

Which of the following statements is correct for Croup II elements and its compounds/ A 2 C ) #he reducing power of strontium is greater than that of !arium. #he solu!ility product of magnesium hydro ide is smaller than that of calcium hydro ide. #he thermal decomposition temperature of calcium nitrate is higher than that of strontium nitrate. #he co"alent character in !arium o ide is greater than that in magnesium o ide.

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#he element astatine, At), is radioacti"e with a short half'life. 3t is !elow iodine in the Eeriodic #a!le. Which of the following statements is most likely to !e correct for astatine or its compounds/ A 2 C ) At) reacts with S),.)6 to produce S,5)6. AgAt is solu!le in concentrated a$ueous F7.. AAt reacts with concentrated 7)S,5 to produce 7)S and At). 7At0a$1 has a lower p7 than 7Cl0a$1 of the same concentration.

19

Which of the following reactions of first row transition metal ions is correct/ A 2 C ) addition of Fa)C,.0a$1 to CrCl.0a$1 produces a green precipitate of Cr)0C,.1. addition of AI0a$1 to %e)0S,51.0a$1 produces a !rown precipitate of %eI. addition of Fa,70a$1 to A)Cr,50a$1 produces an orange solution of A)Cr),addition of concentrated 7Cl to CuS,50a$1 produces a yellow solution of 7)>CuCl5?

19

Which of the following reagents, upon reaction with compound E, gi"es only one sp) hy!ridised car!on atom in the product molecule/

compound E A C S,Cl) GiAl75 in dry ether 2 ) 7Cl0a$1, heat FaB75 in methanol

20

Taxol is a drug isolated from the Eacific yew tree and is used in the treatment of lung and o"arian cancers. #he tricyclic core of Taxol has the following structure.

3n the reactions gi"en !elow, the

ring remains unaltered.

#he tricyclic core was first reacted with 7 ) and Et catalyst, followed !y hot acidified A)Cr),-. 7ow many chiral centres are present in the product of reaction/ A C 2 : 2 ) ((

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& traction is a techni$ue which makes use of a separatory funnel to separate organic compounds !ased on their different solu!ilities or different acid'!ase properties. Higorous shaking allows compounds in the different layers to react. An ether solution of phenol, !en8oic acid and he ylamine was shaken with dilute 7Cl0a$1 and the organic layer was separated from the a$ueous layer.

add 7Cl0a$1

"igorous shaking

remo"e a$ueous layer

organic layer containing phenol, !en8oic acid and he ylamine

a$ueous layer containing 7Cl0a$1

#he series of steps was repeated with a$ueous Fa)C,. and a$ueous Fa,7 in separate e periments. Which organic compound0s1 will remain in the %r<a*#& !a.er after treatment with the different a$ueous solutions/ "rea"'e*" 3#"$ HCl=a,> A 2 C ) he ylamine !en8oic acid phenol and he ylamine !en8oic acid and phenol "rea"'e*" 3#"$ Na2CO5=a,> !en8oic acid phenol and !en8oic acid he ylamine he ylamine and phenol "rea"'e*" 3#"$ NaOH=a,> !en8oic acid and phenol he ylamine !en8oic acid he ylamine

22

Which of the following transformations will occur under the gi"en conditions/ A

2 C

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Compound X was su!Iected to the following se$uence of reactions.

Which of the following could !e the structure of X/ A 2

24

Dia8omethane 0C7)F)1 is a highly e plosi"e yellow gas which is known to e plode upon gentle impact or e posure to light. Despite the risks associated with its use, it is well known as an effecti"e and efficient reagent in the preparation of methyl esters. 3ts mechanism is shown !elow.

What types of reaction took place in S"ep+ 1 and 2/ S"ep 1 A 2 C ) nucleophilic su!stitution acid6!ase reaction nucleophilic su!stitution acid'!ase reaction S"ep 2 elimination elimination electrophilic addition nucleophilic su!stitution

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Compound F is an isomer of Citral.

#he reaction of F with hot acidified potassium manganate0VII1 yields three products, G, H and I. G can !e con"erted to H with the use of a$ueous alkaline iodine followed !y acidification with a$ueous sulfuric acid. Which of the following shows the structure of compound F/ A 2

26

Which of the following reactions yields an organic compound which has *% deuterium incorporated/ 0Deuterium, D ; )71

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#he following information is rele"ant to $uestions 27 and 29. #he Wittig reaction in"ol"es the reaction of a car!onyl compound with a phosphorus ylide to gi"e an alkene. #he reaction occurs !ecause of an important o aphosphetane intermediate.

phosphorus ylide

o aphosphetane

27

Which one of the following structures shows the product of the reaction !etween the following compound and the phosphorus ylide shown/

29

Jeagents similar to the phosphorus ylide ha"e !een in"estigated to carry out the same reaction. Which of the following atoms can !e used in place of phosphorus to carry out the reaction/ A 2 C ) F , B Si

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29

Which of the following se$uences ranks the gi"en species in order of decreasing K! "alues/
6 6

A 2 C ) 50

II, IV, I, III III, IV, I, II III, I, IV, II II, I, IV, III

#he following diagram shows the structural components of o yhaemoglo!in, the o ygenated form of haemoglo!in,

Which of the following statements a!out o yhaemoglo!in is correct/

A
2 C )

&ach o yhaemoglo!in holds only one o ygen molecule. , yhaemoglo!in comprises two K'helices and two 'sheets. A co"alent !ond helps to hold the haem group in each su!unit. #he su!units are held together !y hydrogen !onds !etween the peptide linkages.

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Se&"#%* 2 %or each of the following $uestions, one or more of the three num!ered statements 1 to 5 may !e correct. Decide whether each of the statements is or is not correct 0you may find it helpful to put a tick against the statements that you consider to !e correct1. #he responses A to ) should !e selected on the !asis of A 1, 2 and 5 are correct 2 1 and 2 only are correct C 2 and 5 only are correct ) 1 only is correct

Fo other com!ination of statements is used as a correct response.

51

%or which of the following pairs does the first species contain fewer unpaired electrons than the second species/ 1 2 5 C4, FL ,L, S)4 %e.4, Cr

52

Which of the enthalpy changes of the following reactions can %*!. !e o!tained !y application of 7essM Gaw/ 1 2 5 the com!ustion of glucose, C97(),9 the formation of methane from its elements the hydration of anhydrous copper sulfate to form crystals of CuS,5 27),

55

Why does a mi ture of hydrogen gas and !romine gas react together faster at a temperature of 52+ A than it does at a temperature of .2+ A/ 1 2 5 A higher proportion of effecti"e collisions occurs at 52+ A. 7ydrogen molecules and !romine molecules collide more fre$uently at 52+ A. #he acti"ation energy of the reaction is lower at 52+ A.

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A 1, 2 and 5 are correct

2 1 and 2 only are correct

C 2 and 5 only are correct

) 1 only is correct

54

A gas P decomposes to two other gases, : and R, according to the e$uation: 2P0g1 5:0g1 4 R0g1 #he graph !elow represents the decomposition of (.+ mole of P in the presence of a catalyst at "arious temperatures.

Amount of P present@mol #( A #) A #. A time Which of the following statements a!out the a!o"e system are correct/ 1 2 5 57 #he e$uili!rium constant, Kp, for the decomposition reaction increases with increasing temperature. At #( A, the mole fraction of P is greater than that of R at e$uili!rium. #he decomposition reaction is spontaneous at all temperatures.

A sample of a$ueous ammonia is diluted at constant temperature to a "olume H. Which of the following diagrams are correct with regard to this solution/ 1 p7 2 5
degree of ionisation

K!

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A 1, 2 and 5 are correct 56

2 1 and 2 only are correct

C 2 and 5 only are correct

) 1 only is correct

Use of the Data Booklet is relevant to this question. Which of the following are chemically sta!le when left to stand in the atmosphere/ 1 2 5 a solution of potassium he acyanoferrate0III1 a solution of chromium0II1 chloride a mi ture of a$ueous sodium hydro ide and iron0II1 sulfate

57

Eotassium phthalimide is used in the preparation of primary amines from halogenoalkanes.

Which of the following statements a!out the a!o"e reaction are correct/ 1 2 5 59 #he use of C7.C7)I instead of C7.C7)Br in Step 1 increases the reaction rate. Y is !en8ene'(,)'dicar!o ylic acid. Ehenylamine can !e prepared using this method.

3n a su!stitution reaction, when the product is more reacti"e than the original reactant, polysu!stitution may occur. 3n which of the following reactions will polysu!stitution !e likely to occur/ 1

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A 1, 2 and 5 are correct

2 1 and 2 only are correct

C 2 and 5 only are correct

) 1 only is correct

59

Which of the following synthetic routes will gi"e the following ester as the product/

ECl2

40

Compound X is a synthetic precursor of meloscine, an alkaloid isolated from the Few Caledonian plant Melodinus Scandens Forst.

Which of the following statements a!out its reactions are correct/ 1 2 5 ( mol of X reacts with 2 mol of 7Br0g1 when heated. ( mol of X reacts with 5 mol of Br)0a$1 at room temperature ( mol of X reacts with ) mol of C7.C,Cl at room temperature.

E*/ %1 Paper

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