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SECTION A

Answer ALL questions. Write your answers in the spaces provided.


1. (a) (i) Draw a ‘dot-and-cross’ diagram to show the arrangement of the
outermost electrons in the species NH2-(g), and predict the shape of
this species.

V-shape (Bent) 1
*According to VSEPR, 2lone pair + 2bond pair = bent
(ii) Arrange the H-N-H bond angles in descending order for the three
species: NH2-(g), NH3(g) and NH4+(g). Explain your ordering.

– NH2- has lp-lp repulsion, NH3 has lp-bp repulsion, NH4+ has
bp-bp repulsion only ½
– As lp-lp repulsion > lp-bp > bp-bp ½
– greater repulsion = smaller H-N-H bond angles ½
– ∴ NH4+ >NH3 > NH2- ½

(iii) Excess NH3(g) reacts with Cl2(g) in two steps to give N2(g) and
NH4Cl(s). It is known that NH3(g) functions as a reducing agent and as
a base in the reaction. For each step, write the chemical equation and
state the function of NH3(g).

– 3Cl2 + 2NH3 → 6HCl + N2 (Reducing Agent) 1 + ½


– HCl + NH3 → NH4Cl (Base) 1 + ½

– Overall equation: 3Cl2 + 8NH3 → 6NH4Cl + N2

*This question is a bit difficult, esp. when you are nervous during
exam, just try your best.

(7 marks)

2008-AL-CHEM 1-1 1
1. (b) Both nickel(II) bromide and cobalt(II) bromide react with triethylphosphate,
PEt2 (Et represents C2H5), forming metal complexes with the general
formula M(PEt2)2Br2; where M is either Ni or Co.
(i) The nickel complex can occur in two forms, one of which has a net
dipole moment whereas the other does not. The cobalt complex,
however, occurs in only one form.

Account for the above results.

– Cobalt complex occurs in tetrahedral form ½


– Nickel complex exists in both cis and trans sq. planar complex ½

– Reason: Ni is d8 configuration (8 d e-) ½


– Co is d7 configuration ½
_______________________________________________________
The actual approach to explain is out of syllabus, just remember, d8
has high tendency to form sq. planar complex

Information:
1. The complex’s formula is ML4 (L = ligand), therefore, it must be
sq. planar for d8
2. Nickel occurs in 2 forms (1 with net dipole moment)
3. Cobalt only occurs in 1 form
_______________________________________________________
– Trans-sq. planar complex can cancel out dipole moment of Br ½
→ no net dipole moment
– Cis- sq.planar complex is not symmetrical ½
→has dipole moment
– d7 doesn’t favor the formation of sq.planar complex ½
→ tetrahedral only ½
(ii) Will the cobalt complex have a net dipole moment? Explain.

– Yes ½
– the dipole moment cannot cancel out in tetrahedral complex ½

*Don’t panic when you see an unknown ligand PEt2


(5 marks)

2008-AL-CHEM 1-2 2
2. (a) Three reagent bottles each containing 0.5 M KI(aq), 14 M HNO3(aq) and 0.02
M KMnO4(aq) have been kept in the laboratory for a long time. The table
below lists the observation for each of the bottles.
Solution Observation
0.5 M KI(aq) The liquid is pale yellow.
14 M HNO3(aq) There are brown fumes above the yellow
liquid.
0.02 M KMnO4(aq) There are brown stains on the interior wall of
the bottle.
In each case, account for the observation and write the relevant chemical
equation(s).

0.5 M KI(aq)

2I- → I2 + 2e- , I- + I2 → I3- ½


– Iodide combines with elemental iodine to form triiodide ½
*If you know triiodide is yellow, this shouldn’t be difficult
14 M HNO3(aq)

4HNO3 → 4NO2 + 2H2O + O2 ½


– Photodecomposition of conc. HNO3, brown NO2(g) is formed ½

* CE level, remember it is conc. (14M)

0.02 M KMnO4(aq)

2KMnO4 → K2MnO4 + MnO2 + O2 ½

– Photo/thermal decomposition, MnO2 (brown solid) is formed ½

* This is actually a combination of 2 half equations:


MnO4- + 4H+ + 3e- → MnO2(s) + 2H2O
MnO4- + 4OH- → MnO42- + 2H2O + O2 + 3e-

(6 marks)

2008-AL-CHEM 1-3 3
2. (b) The diagram below shows the design of a hydrogen-oxygen fuel cell:

(i) Describe the working principle of the fuel cell.

– O2 to cathode (reduced to O2-) ½


– H2 to anode (oxidized to H+) ½
– H2 + 2OH- → 2H2O + 2e- ½
– O2 + 4H2O + 4e- → 4OH- ½
– 2H2 + O2 → 2H2O ½
– NaOH acts as electrolyte ½
*H2 → 2H+ + 2e- is WRONG as the electrolyte is basic

(ii) One advantage of using hydrogen-oxygen fuel cells is that they do not
emit air pollutants. Suggest ONE other advantage of using
hydrogen-oxygen fuel cells.

Select one of the followings: ½ + elaborate ½

– Quiet (less moving parts compared with conventional combustion


engines)
– Effective (combustion of fossil fuels produce many by-products,
which reduces efficiency, hydrogen fuel cell only produces water
by redox, much higher efficiency)
– Sustainable energy alternative(H2 and O2 are abundant in nature,
while fossil fuels are non-regenerable fuels)

*Not difficult if you read beyond textbooks (esp. new way)

(4 marks)

2008-AL-CHEM 1-4 4
3. (a) Answer the following multiple-choice questions.
(i) Which one of the following ions is most ready to donate electrons?
A. Al3+
B. Fe2+
C. Cu2+
D. Zn2+
Answer: B
(ii) Which one of the following molecules has a zero dipole moment?
A. BF3
B. PH3
C. SO2
D. HCl
Answer: A
(iii) Which one of the following graphs represents the distribution of
molecular speeds of one mole of a gas at two different temperatures
T1 and T2, where T2 > T1?
A. B.

C. D.

Answer: C
Explanation: (i) Have you ever heard about Al , Cu or Zn3+? ☺
4+ 3+

(ii)
(iii) maxwell’s distribution, T2 must be flatter + higher average
molecular speed, both are from the origin (there must be molecules
with speed = 0)
(iv) by definition

2008-AL-CHEM 1-5 5
3. (a) (iv) Which one of the following equations represents the change
corresponding to the standard enthalpy change of atomization of
iodine?
A. ½ I2(s)→ I(g)
B. I2(l) → 2 I(g)
C. I2(s) → 2 I(g)
D. I2(g) → 2 I(g)
Answer: A
(4 marks)
(b) Account for the following observations:
(i) The boiling point of magnesium bromide is lower than that of sodium
bromide.

– Ionic bond strength of MgBr2 < NaBr ½


– Since MgBr2 carries more covalent character ½
– Weakens ionic bond strength ½
– Less energy is required to vaporize MgBr2 ½
– ∴ b.p. of MgBr2 < NaBr

(ii) The first ionization enthalpy of aluminium is smaller than that of


magnesium.

– Al: [Ne]3s2 3p1 ½


– Mg: [Ne]3s2 ½
– Al adopts extra stability when lose outermost e- ½
– Higher tendency (lower energy is needed) to lose outermost e- ½
– Lower first I.E.

*straightforward question

(4 marks)

2008-AL-CHEM 1-6 6
4. (a) Identify A, B, D, E, F and G in the following reactions:
(i)

A: 1
(ii)

B: 1
(iii)

D: 1
(iv)

E: 1
(v)

F: HCN 1 G: 1
(6 marks)

2008-AL-CHEM 1-7 7
4. (b) Consider the substitution reaction shown below:

(i) Outline a mechanism of the reaction.


Initiation

***
Propagation

***

***
Termination

***

Fishhook arrow ½ 3 steps ½ 4 key steps (***) ½ x 4


(ii) Suggest why the hydrogen atoms of the benzene ring will not be
substituted.
– Delocalized πelectrons stabilize the benzene ring ½
– For Benzylic radical (R-CH2‧), it is stabilized by donating
electron density through resonance by benzene ring, so it is
attacked by free radicals readily ½
– However, phenyl radical is not stabilized by this effect ½
– It does not form radical readily, therefore is not susceptible to
substitution ½

(5 marks)

2008-AL-CHEM 1-8 8
5. (a) Arrange the following compounds in order of increasing acidity. Explain
your ordering.

– More stable the conjugate base, more acidic ½


– Stability:
o-hydroxybenzoate(2nd) > benzoate > p-hydroxybenzoate(3rd) ½
– Para-position OH deactivates the carboxylate by donating e- 1
– Ortho-position OH stabilize carboxylate by forming intra H-bond 1

*looks like straightforward, yet a bit tricky


(3 marks)
(b) Consider reactions (1) and (2) shown below:

(i) Both reactions are of the same type. Name the type of reaction.

Electrophilic Aromatic Substitution 1

*Not (Friedal-Craft’s) Alkyl/Acylation

(ii) Suggest why reaction (2) gives a mixture of organic products while
reaction (1) gives only one monosubstitution product.

Acyl group deactivates (draws e-) benzene ½


→ benzene less susceptible to further substitution ½

Methyl group activates (donates e-) benzene ½


→ more susceptible to further substitution ½
→ *substitutes at ortho/para position
(3 marks)

2008-AL-CHEM 1-9 9
5. (c) Answer the following multiple-choice questions.
(i) Which one of the following compounds is most reactive towards Br2?

A. B.

C. D.
Answer: B
(ii) Which one of the following compounds is most reactive towards
substitution with NaOH(aq)?

A. B. CH3(CH2)3Br

C. D.
Answer: A
(iii) Which one of the following compounds is most reactive towards
substitution with Cl2?

A. B.

C. CH3CH2CH2CH3 D.

Answer: B

(3 marks)

Explanation: (i) D is aromatic, B is tri-substituted (more stable intermediate)


A,C are di-substituted
(ii) C,D are stable aryl halide, A has more stable intermediate due to
resonance
(iii) Benzylic radicals are stabilized by resonance

2008-AL-CHEM 1-10 10
6. Read the passage below and answer the questions that follow:
Silicates and aluminosllicates
Silicates occur in a wide variety of structures. Orthosilicates contain discrete
tetrahedral SiO42- anions with O atoms at the corners. Other silicates can be
considered as formed from the tetrahedral by sharing oxygen atoms, e.g.
disilicates contain Si2O76- ions and cyclic silicates contain (SiO2)n2n+ ions, where n
is an integer greater than 2. Polymers of silicates also exist including
one-dimensional chain silicates, two-dimensional sheet silicates and
three-dimensional network silicates.

A type of aluminosilicate is formed when some of the Si(IV) in a


three-dimensional network silicate is replaced by Al(III) and another metal cation.
Figure 6.1 shows a part of the structure of such type of aluminosilicate, and
Figure 6.2 shows the framework representation of this part of the structure with
each vertex representation a Si or Al atom.

Zeolites belong to one of the above type of aluminosilicate. They have a


regular and opoen structure with cavities of a very precise size. As such, they can
function as molecular sieves (分子篩). Sodium zeolite A, one of the zeolites, is
commonly used as a water softener for reducing water hardness. The framework
representation of a part of the structure of sodium zeolite A is shown in Figure
6.3.

(a) Suggest TWO reasons for the occurrence of silicates in a wide variety of structures.
ANY TWO, each 1
– Si-O bond is exceptionally strong
– SiO4 tetrahedra similar to diamond structure → stable
– Silicates adopt giant covalent tetrahedral network → stable
(2 marks)

2008-AL-CHEM 1-11 11
6. (b) Some liquid detergents contain sodium orthosilicate, Na4SiO4, to maintain a
moderately high pH.
(i) Suggest why detergents need to have a moderately high pH.

– Detergents work as hydrophilic head ½


– Low pH → remove hydrophilic head ½
– No longer works
(ii) With the help of a chemical equation, explain how Na4SiO4 functions.

– Na4SiO4 + 4H+ → Si(OH)4 + 4Na+ ½


– Reacts with H+, so less acidic ½
(2 marks)
(c) Draw the structure of each of the following anions:
(i) Si2O76- (ii)(SiO3)612-

Represent SiO44- =

Si2O76- = 1 (SiO3)612- = 1
4-
*Remember to mention SiO4 = the triangle
(2 marks)
(d) Suggest why sodium zeolite A can function as a molecular sieve.

– It’s cavity has specific size ½


∴ only ions with suitable size and charge can fix into it ½
– Too large:blocked out, Too small:pass through it ½
– -ve charge from O:can only hold cations ½
(2 marks)
(e) Sodium zeolite A is commonly used as a water softener:
(i) Suggest why sodium zeolite A has a high affinity for Ca2+(aq) and
Mg2+(aq) ions.

Size and distribution of negative charge are suitable for these ions 1
(ii) Suggest ONE way to regenerate exhausted sodium zeolite A.

Wash with NaCl(brine) solution 1


(2 marks)
END OF SECTION A

2008-AL-CHEM 1-12 12
SECTION B
Answer ALL questions. Write your answers in the spaces provided.
7. (a) The diagram below shows the essential components of an instrument for
studying the kinetics of the reaction:

(i) What is this instrument?

Colorimeter 1
(ii) What physical parameter of the reaction mixture is measured by this
instrument?

Transmittance (or Absorbance) 1


(iii) Sketch a graph to show the variation of the measured physical
parameter with time.

OR
naming x y axis ½ suitable shape ½
(3 marks)
-
(b) (i) Hydride ion, H , is a strong Bronsted base. Write the chemical
equation for the reaction of H- with water.

H- + H2O -> OH- + H2 1

*Full equation: LiAlH4 + 4H2O → LiOH + Al(OH)3 + 4H2


*∴ LiAlH4 should not contact with water

2008-AL-CHEM 1-13 13
7. (b) (ii) Suggest why the following hazard warning labels should be displayed
on a bottle of LiAlH4(s).

*From the equation mentioned above:


LiAlH4 + 4H2O → LiOH + Al(OH)3 + 4H2
– LiAlH4 decomposes upon contact with water
– Forms corrosive LiOH 1
– Explosive H2 1
*Difficult if you don’t know the full equation
(3 marks)
(c) (i) Outline how you would prepare a sample of dry CuSO4·5H2O crystals
from copper turnings in a laboratory.

– Dissolve Cu turnings in minimum amount of conc. H2SO4 ½


– Stir until fully dissolved + filtrate to obtain CuSO4(aq) ½
– Evaporate at room temperature (form crystals) ½
– Filtrate to obtain crystals ½
– Rinse with little cold water ½
– Air-dry the crystals ½

(ii) Suggest suitable reagent(s) for the determination of the purity of a


sample of the dry CuSO4·5H2O crystals by titrimetric analysis.

– Standardized Na2S2O3 solution ½


– Excess but known amount of KI solution ½
– Starch Indicator (better write it out)

*Redox + Back titration


*Cu(OH)2 does not work as the end pt is hard to determine

(4 marks)

2008-AL-CHEM 1-14 14
8. (a) Super glue works as an adhesive by addition polymerization as shown below:

(i) The progress of this polymerization was monitored by infra-red


spectroscopy. Figure 8.1 shows the change of transmittance with time
(t) for the reaction system. Assign the functional group corresponding
to the absorption at 1614cm-1. Account for the change of
transmittance of this peak with time.

– C=C double bond ½


– C=C undergoes addition as the polymerization
proceeds ½
– [C=C] decreases ½
– The intensity of characteristic peak decrease ½

(ii) The experiments were carried out to study the effects of NaOH(aq)
and H2O(l) on the polymerization. The conditions of the experiments
were the same except that one was conducted in the presence of
NaOH(aq) and the other in the presence of H2O(l). Figure 8.2 shows
the change of temperature of the two reaction mixtures with time.

(I) Account for the increase and decrease in temperature of the


reaction mixtures.
– NaOH↑ the reaction rate ½ and therefore the reaction is more
exothermic ½, rate of change of temperature↑
– [polymer]↓½ rate↓½ rate of change of T↓as reaction proceeds
(II) Suggest a reason for the significant difference in the two curves.
– OH- is a stronger nucleophile than H2O 1
– Increases rate of reaction
***The mechanism is NOT free radical polymerization!!! *** (5 marks)

2008-AL-CHEM 1-15 15
(b) Propenamide, the monomer of polypropenamide (also known as
polyacrylamide) is a potential carcinogen. The melting point of
propenamide is 84C and its solubility in water is 2.16gcm-3 at 30C.

(i) Polyacrylamide gel (PAAG) is polyacrylamide saturated with water. A


sample of PAAG for breast augmentation is suspected to contain
about 1% propenamide. Suggest a chemical test to show the presence
of propenamide in the sample.

Test for C=C: ANY ONE, test ½ + observation ½


– Br2 → decolorization OR
– Cold acidified KMnO4 → decolorization

Test for amide: ANY ONE, test ½ + observation ½


– NaOH → gives off ammonia (bubbles) on heating OR
– Br2/NaOH → gives off CO2 (bubbles) (hofmann degradation)

(ii) Propenamide can be identified by converting it to a solid derivative


and determining the melting point of the derivate. With the help of a
chemical equation, suggest ONE solid derivative of propenamide
suitable for this purpose.

2,3-dibromopropanamide ½

+ Br2 → ½
(iii) Suggest an instrumental method for the further characterization of the
derivative suggested in (ii). State clearly the expected results.

– Mass Spectroscopy ½
– Isotopic abundance of 79Br : 81Br = 1:1 ½
– Relative intensity of e/m M:M+2:M+4 = 1:2:1 ½
– Name a few other peaks ½
(M=molecular mass)

(5 marks)
END OF SECTION B

2008-AL-CHEM 1-16 16
SECTION C
Answer ONE question only, and write your answer in the AL(D) Answer Book.

Marks will be allocated approximately as follows:


Chemical knowledge 50%
Organization 30%
Presentation (including use of language) 20%

Use equations, diagrams and examples where appropriate.

The examiners are looking for the ability to analyse, to evaluate and to express ideas.

9. Write an essay on the chemistry of chlorine including its industrial manufacture


and applications in daily life.
(20 marks)

10. Write an essay on the application of the principle of green chemistry in industry.
(20 marks)
* everyone writes 12 principles + 2 applications in Q.10
if you are familiar with green chem. + only wants C-E grades, choose Q.10
if you aim higher grades + not bad in chlorine, better choose Q.9 as it is easier to
show how extraordinary you are

END OF PAPER

2008-AL-CHEM 1-17 17