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AHS Examinations
Semester 4

Other names

Centre Number

Chemistry

Candidate Number

Grade

Advanced Level
GeneralPrinciples
Principlesof
ofyChemistry
II Transition Metals
Unit 5: General
I,
and Organic
Nitrogen
Chemistry
(including synoptic assessment)
Equilibria
and Further
Organic
Chemistry
(including synoptic assessment)

April 2012
Time: 1 hour 40 minutes
You do not need any other materials.

Paper Reference

6CH05/01
Total Marks

Instructions

Use black ink or ball-point pen.

Fill in the boxes at the top of this page with your name, centre number and candidate number.
Answer all questions.
Answer the questions in the spaces provided
there may be more space than you need.

Information

The total mark for this paper is 90.

The marks for each question are shown in brackets
use this as a guide as to how much time to spend on each question.
Questions labelled with an asterisk (*) are ones where the quality of your written
communication will be assessed
you should take particular care with your spelling, punctuation and grammar, as well as the
clarity of expression, on these questions.
A data booklet is provided with this paper.

Advice

Read each question carefully before you start to answer it.

Keep an eye on the time.
Try to answer every question.
Check your answers if you have time at the end. Check your answer if you have time at the end.

A37964H
2012 Addu High School.

SECTION A
Answer ALL questions.
For questions 110, in Section A, select one answer from A to D and put a cross in the box.
If you change your mind, put a line through the box

and then mark your new answer with a cross.

1. What is the value of E0 for the half-cell:

(1)

MnO4- + 8H+ + 5e- Mn2+ + 4H2O

A

1.50 V

B 1.86 V

C 1.44 V

D 1.58 V

2. Consider the standard voltaic (or galvanic) cell: Fe,Fe2+ // Ag,Ag+. Which answer identifies the cathode and gives
the Eo for the cell?
(1)
A Ag, 0.80 V

B Fe, 1.06 V

C Ag, 1.06 V

D Fe, 1.94 V

3. Which of the following is the strongest oxidizing agent?

A Pb2+

B Ag+

(1)
C Cu2+

D Zn2+

4. On the basis of the definition which of these ions have an electronic configuration of a transition metal.
A SC3+

5.

B Zn 2+

C Cu+

D Cu2+

6. Which transition metal shows the greatest variation in possible oxidation numbers
A

B Cr

C Mn

(1)
D Fe

6. Which of the following statements about catalyst is true.

A

Catalysts change the equilibrium position of a reaction

Catalysts are always used to slow down reaction rates

Catalysts are not consumed by the reaction they take part in

DD

(1)

(1)

Catalysts can be recovered from a reaction and regenerated by performing a simple chemical reaction

7. What is meant by the term 'ligand' ?

A

A substance that can donate a lone pair of electrons to form a dative bond

A substance that can accept a lone pair of electrons to form a dative bond

A substance that can donate lone pair of electrons to form hydrogen bond

(1)

D A substance that can accept a lone pair of electrons to form hydrogen bond
AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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8. Given the list of ligands and their corresponding names, choose the pair that disagrees.
-

A OH

hydroxo

B CN

Cyanide

C Cl

Chloro

(1)
D H2O Aqua

9. What is the oxidation number of the central metal atom in the coordination compound [Pt(NH3)3Cl]Cl?
A 1

B 2

(1)

D 4

10. When aqueous ammonia is added to a solution of copper II sulphate the pale blue solution changes to a dark blue
colour. What is the formula of the complex formed?
A [Cu(H2O)6]2+(aq)

B [Cu(NH3)4(H2O)2]2+(aq)

(1)
C [ Cu(NH3)2(H2O)4]2+(aq)

D [ Cu(NH3)6]2+(aq)

11. Which statement about benzene is incorrect?

(1)

A The empirical formula is C1H1

B The C6 ring is planar.

B The CC -bonding is delocalized.

D The reactivity reflects the presence of C=C bond

12. How many signals do you expect to see in the 1H NMR spectrum of benzene?
A 1

B 2

C 3

(1)
D 6

13. In the nitration of benzene using a mixture of conc. H2SO4 and conc. HNO3, the species which initiates the reaction
is .
(1)
A NO2

B NO+

C NO2+

D NO2

14. The possible number of isomeric mono substituted benzene derivatives is

A 4

B 3

C 2

(1)
D 1

15. The nitration of benzene results in a mixture of different products. Select the odd one out.
A nitrobenzene

B 1,2-dinitrobenzene

C 1,3,5-trnitrobenzene

(1)
D 1,3 dinitroenzene

16. Which statement about phenol is correct

(1)

A. No catalyst is required for its reaction with bromine

It behaves like a typical alcohol

C. It is a crystalline solid at 298 K

D It reacts with NaOH to give sodium phenoxide

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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17. The reaction of aniline with bromine water gives:

(1)

A 2-bromoaniline

B 4-bromoaniline

C 2,4-dibromoaniline

D 2,4,6-tribromoaniline

18. Ethanamine , CH3CH2NH2, reacts with ethanoyl chloride to form

(1)

A CH3CH2NH3+Cl

B CH3CH2NH CH2CH3

D CH3CH2COCH3

CH3CH2NHCOCH3

19. The gas evolved when methylamine reacts with nitrous acid is
A NH3

(1)

B N2

C H2

D C2H6

20. Organic solids are often purified by recrystallization. This technique works on the basis that
A the impurities must be insoluble in the solvent used.
B the impurities must react with the solvent used.
C the impurities crystallize first when the hot solution is cooled.
D the cooled solution is saturated with the desired material but not with the
(Total for section A = 20 Marks)

SECTION B
Answer ALL questions.
Answer the questions in the space provided.
21. The pain-relieving drug ibuprofen has the formula

CH 3
H

C
CH 3

CH 3
CH 2

CO 2 H

(a) The drug ibuprofen can be synthesised from benzene by the route shown below.

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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CH3

CH3

CH3

CH3

HCCH3

HCCH3

HCCH3

HCCH3

CH2

CH2

CH2

CH2

Step A

Step B

CO /Pd
catalyst

Step C

CH3

HCOH
CH3

HCCO2H
CH3
Ibuprofen

(i) Name the type and mechanism of the reaction in Step A, and suggest a suitable reagent and catalyst.
Type and mechanism:

(3)

-----------------------------------------------------------------------------------------------------------------------------------------------Name of the reagent for Step A

-----------------------------------------------------------------------------------------------------------------------------------------------Catalyst

------------------------------------------------------------------------------------------------------------------------------------------------

(ii) Give the mechanism for the reaction in step 1, including the equation for the formation of the secies
responsible for this reaction.
Equation for formation of the reacting species

(1)

Mechanism

(3)

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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(b) The alkyl benzene formed in step A generally reacts in a similar way to benzene but faster, as the ring is said to
be activated.
(i) Explain how the presence of alkyl group activates the benzene ring.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) Use your answer to (i) to explain why alkyl benzene reacts faster.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(c) Step C is a reduction.

Give ONE reason why lithium tetrahydridoaluminate,LiAlH4, is preferred to hydrogen as a reducing agent in this
reaction

(2)

--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(d)

A sample of the final product was analysed by combustion. 1.00 g was burnt in oxygen. It produced 2.78 g
carbon dioxide and 0.786 g water.
State the molecular formula of ibuprofen and show that these results are consistent with it

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

(4)
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Molecular formula

-----------------------------------------------------------------------------------------------------------------------------------------------Calculations:-

(e) Ibuprofen can be analysed by instrumental methods. The infrared spectra of ibuprofen and two other drugs,
aspirin and paracetamol, not necessarily in that order, are shown opposite.

Ibuprofen

Paracetamol,

Aspirin

(i) Explain, referring to the structure of each molecule, why infrared spectroscopy is not a good technique to
distinguish aspirin from ibuprofen
.
(1)
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) Deduce which of X, Y or Z is the infrared spectrum of paracetamol, giving a piece of evidence from the
spectrum you select.

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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Reasoning:

(2)

--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(f) (i) Ibuprofen and aspirin can be distinguished using their mass spectra.
A line at mass/charge ratio 57 occurs only in the mass spectrum of ibuprofen.
AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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Give the formula of the ion which produces this line.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(iii) Suggest the mass/charge ratio of one line which occurs in the mass spectrum of aspirin but not ibuprofen, and
the formula of the species which produces it.
(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(g) Ibuprofen is almost insoluble in aqueous solutions at pH 3 but if the pH is raised to 8 then the ibuprofen
becomes reasonably soluble. Account for these observations.

(3)

---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(h) Under the appropriate conditions ibuprofen reacts with ethanol to produce a substance with a characteristic
odour.
(i)

Identify the functional group in ibuprofen that would react with the ethanol.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) Suggest the conditions needed for the reaction to take place and identify the product.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(Total Question 21 = 25 Marks)

22. Alanine, 2-aminopropanoic acid, is the simplest chiral amino acid found in nature and is optically active.

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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(a) (i)Explain the meaning of the term chiral.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) How is optical activity detected experimentally?

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(iv) If alanine is made from propanoic acid the product mixture does not show optical activity. Explain why this is
so.

(2)

---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(b) Alanine reacts with both acids and bases. Give the structural formulae of the compounds you would expect if
alanine reacts with
(1)
hydrochloric acid

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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sodium hydroxide

(1)

(c) Alanine has a high melting temperature of 300 C, much higher than would be expected for the structure given at
the start of the question.
Draw the structure that is actually present in the solid, and explain why the melting temperature is so high.
Structure

(1)

Explanation

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(Total Question 22 = 8 Marks)

21. The following scheme shows some reactions of chromium compounds in aqueous solution.
[Cr(H2O)6]3+

Cr2O72-

Reaction 7
CH3CH2OH + H2SO4 (aq)

Reaction 1
NaOH(aq)

Grey- Green precipitate A

Reaction 6
Zn + H2SO4 (aq)

Blue solution C

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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Reaction 2

Reaction 4
Excess NH3(aq)

[Cr(OH)6]3-

[Cr(NH3)6]3+

Reaction 3

Reaction 5

EDTA 4-

CrO42-

Chromium containing species

(a) (i) Explain why the [Cr(H2O)6]3+ ion is coloured.

(3)

-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(b) Identify the grey-green precipitate A formed in reaction 1. Write an equation for this reaction.
Green precipitate

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------Equation :

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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(c) (i) Identify a reagent for Reaction 2.

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------(ii) Deduce the oxidation state of chromium in CrO

2
4

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------(iii) Identify a reagent needed for Reaction 3.

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------(d) (i) Draw the structure of the chromium-containing species C formed in Reaction 5. Indicate the charge on
species C.

(2)

(ii)Explain, by reference to the changes in bonding, why the enthalpy change, H, in Reaction 5 is close to zero.
(1)
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(iii) Explain why the free-energy change, G, for Reaction 5 is negative.

(2)

--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(e) Identify the chromium-containing species present in the blue solution D formed in Reaction 6 and state the role
of zinc in its formation.
AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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Chromium species formed

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------Role of zinc in this reaction

(1)

-----------------------------------------------------------------------------------------------------------------------------------------------(f) Two organic compounds are formed in Reaction 7.

One of these compounds has a low boiling point and can be distilled readily from the reaction mixture. The other
compound has a higher boiling point and is the main organic product formed when the reaction mixture is
refluxed.
(i) Identify the organic product which has a low boiling point.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) Identify the main organic product formed when the mixture is refluxed.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(Total For Question 23 = 17 Marks)

(Total for section B = 50 Marks)

SECTION C

The hexagonal ring structure of benzene was first suggested by Kekul in 1865, but the nature of the bonding was not
elucidated until the 1930s. This question concerns aspects of the structure of benzene.
(a) The enthalpy of hydrogenation of cyclohexene to give cyclohexane is 120 kJ mol1 and that of cyclohexa-1,4diene is 240 kJ mol1 .

(i) What would you expect the value of the enthalpy of hydrogenation to be for the hypothetical molecule
cyclohexa-1,3,5-triene, on the basis of these data?

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

(1)

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----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) The hydrogenation enthalpy of benzene to give cyclohexane is 208 kJ mol1.

Use your result from (i) and this information to draw an enthalpy level diagram to show that benzene is
thermodynamically more stable than the hypothetical cyclohexa-1,3,5-triene.

(2)

Label the stabilisation energy on your diagram.

(iii) Explain in terms of bonding why benzene would be less reactive with bromine than the hypothetical
cyclohexa-1,3,5-triene.

(2)

------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(b) Both cyclohexa-1,3,5-triene & benzene reacts with bromine in an appropriate solvent to form the same product
(i) Name the type & mechanism of the reaction of cyclohexene with bromine and name the product of the
reaction

(2)

Type
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Mechanism
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) Explain why benzene does not undergo reactions with the same mechanism as in (b)(i).

(2)

---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

(iii) Name the condition necessary for benzene to undergo the same type of reaction with bromine.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(iv) Name the mechanism for the reaction in which benzene undergoes but cyclohexene does not.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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(v) Draw the structural formulae of the product formed in this reaction

(1)

(d) This question concerns the reaction scheme shown below.

(i) Give the reagents needed for the reduction of nitrobenzene in step 1.

(2)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(ii) In step 1 when reduction is complete, the reaction mixture must be made alkaline to liberate the phenylamine
product.
Give the equation for the reaction that occurs when the alkali is added.

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(iii) In step 2, a mixture of sodium nitrite and hydrochloric acid is used at a temperature between 0 C and 10 C.
Explain why the reaction mixture must not be cooler or warmer than these limits.
AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

(2)
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--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(iv) Complete the structure of the cation in compound A, showing all the bonds.

(1)

(v) In step 3, compound A reacts with phenol. What conditions are necessary?

(1)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------(vi)

Draw the structure of compound B, showing all the bonds.

(1)

(Total for section C = 20 Marks)

AHS/Dept of Science / Semester- 4(April 2012)/ Grade 12/Chemistry - Unit 5

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