(ii)
(iii)
2008-AL-CHEM 2-1
Low toxicity
Environmentally friendly
Stable to the coffee bean sample
(iv)
No
The supercritical CO2 used is recycled
(7 marks)
1.
(b) Both Sodium and Chloride are elements of Period 3 of the Periodic Table.
(i)
(ii)
(iii)
2008-AL-CHEM 2-2
1.
(c) The table below lists the standard enthalpy change of formation of four
compounds
HfO298/kJ mol-1
Compound
H2O(l)
HCl(g)
SiO2(s)
SiCl4(l)
(i)
-286
-92
-910
-640
(ii)
2008-AL-CHEM 2-3
2.
(7 marks)
(a) The gaseous reaction below takes place at 750 C in a closed container with a
fixed volume.
o
(ii)
The table below lists three sets of experimental data of the reaction at
750oC:
Experiment
1
2
3
0.0250
0.0250
0.0125
Deduce the rate equation for the reaction, and calculate the rate
constant at 750oC.
0.5/0.25 = [0.01/0.005]x , x = 1, order w.r.t. [H2] = 1
0.5/0.125 = [0.025/0.0125]x , x = 2, order w.r.t. [NO] = 2
rate = k[NO(g)]2[H2(g)]
0.5 = k (0.025)2(0.01) , k = 8 x 104 mol-2 dm6 s-1
2008-AL-CHEM 2-4
(iii)
2.
No
Very difficult for 4 molecules to simultaneously collide + react
The molecularity is different from the reaction order
Fe2+(aq)
Cr3+(aq)
(6 marks)
ions.
(ii)
2008-AL-CHEM 2-5
Since the first step has +ve Eo as well, the activation energy of
catalyzed rxns is most likely to be lower than the uncatalyzed one
5
(iii)
Sketch, in the same diagram, the energy profile of the reaction with
and without Fe2+(aq) ions.
(iv)
2.
(c)
(10 marks)
The following four substances all exist in the form of white powder:
Baking soda(NaHCO3), cornstarch, finely ground sugar, and plaster of
Paris (CaSO4.H2O)
Suggest how you would do experiments at home to distinguish the
four substances from one another. (You are not allowed to taste the
substances)
Baking Soda: add acid (HCl/vinegar) effervescence
Cornstarch: add small amt of iodine dark blue
Sugar: add sulphuric acid black solid
Plaster of Paris: add water release large amt of heat
2008-AL-CHEM 2-6
(a) (i)
(ii)
(4 marks)
Sketch the variation of pH when 25.0cm3 of 0.05mol dm Na2CO3(aq)
is titrated against 0.10mol dm-3 HCl(aq)
-3
2008-AL-CHEM 2-7
(b) (i)
(7 marks)
Mercury(I) chloride, Hg2Cl2(s), is sparingly soluble in water, and gives
Hg22+(aq) and Cl-(aq) ions
The solubility products Ksp of Hg2Cl2(s) is 2.4 x 10-18 mol3 dm-9 at
298K. Calculate, at 298K, the solubility of Hg2Cl2(s)
(I) in pure water, and
Let x be the solubility of Hg2Cl2(s) in pure water
Ksp = [Hg22+(aq)][Cl-(aq)]2
= x(2x)2
2.4 x 10-18 = 4x3
x = 8.43 x 10-7 mol dm-3
(II) in 0.10 mol dm-3 KCl(aq)
Let y be the solubility of Hg2Cl2(s) in 0.1M KCl(aq)
Ksp = y(0.1 + 2y)2
= y x 0.01
y = 2.4 x 10-16 mol dm-3
(ii)
2 Hg(l) + 2 Cl-(aq)
2008-AL-CHEM 2-8
(8 marks)
(c) Account for each of the following:
(i)
(ii)
2008-AL-CHEM 2-9
4.
(a)
I2(aq) + I-(aq)
I3-(aq)
(1)
State ONE safety precaution when shaking the liquid mixture in the
separating funnel.
(ii)
2008-AL-CHEM 2-10
10
(b)
11
4.
(5 marks)
(c) Both diamond and graphite are allotropes of carbon. A unit cell of diamond
and a part of the structure of graphite are shown below:
(i)
(ii)
2008-AL-CHEM 2-12
12
(iii)
(8 marks)
2008-AL-CHEM 2-13
13
5.
END OF SECTION A
SECTION B
(a) Upon irradiation of visible light, 0.450 g of 2,4-dimethylpentane undergoes
monochloro-substitution to give 0.200 g of 1-chloro-2,4-dimethylpentane,
0.167 g of 2-chloro-2,4-dimethylpentane and 0.117 g of
3-chloro-2,4-dimethylpentane.
(i)
Draw the structure of 2,4-dimethylpentane.
(ii)
(I)
2008-AL-CHEM 2-14
14
(iii)
You are provided with the following bond dissociation enthalpy data:
Bond
H-Cl
+432
Cl-Cl
+243
H-CH2CH3
+420
H-CH(CH3)2
+401
H-C(CH3)3
+390
Cl-CH2CH3
+338
Cl-CH(CH3)2
+339
Cl-C(CH3)3
+330
General formula:
H + 432 + y = 243 + x
H = x - y - 189
substitute +420, +401, +390 into x respectively
substitute +338, +339, +330 into y respectively
primary: -107 kJ mol-1
secondary: -127 kJ mol-1
tertiary: -129 kJ mol-1
2008-AL-CHEM 2-15
15
(iv)
(I)
Steric factor
Relative stability of alkyl radicals
Enthalpy change of different monochlorination reactions
Statistical factor
(II) Which of these factors is dominating in accounting for the higher
yield of 1-chloro-2,4-dimethylpentane? Explain.
Statistical factor
There are 12 primary H, 2 secondary H, 2 tertiary H in
2,4-dimethylpentane
Leads to higher probability of forming primary monochlorinated
product
(v)
2008-AL-CHEM 2-16
16
5.
(13 marks)
(b) Outline a synthetic route, with no more than five steps, to accomplish each of
the following transformations. For each step, give the reagent(s), conditions
and the structure of the organic product.
(i)
A=
Step 2: Br2
B=
Hint:
A=
Step 2: LiAlH4
B=
Step 3: SOCl2
Step 4: heat
C=
2008-AL-CHEM 2-17
17
6.
(7 marks)
(a) Figure 6.1 and Figure 6.2 below respectively show the mass spectrum and
infra-red spectrum of compound A (C4H8O2). Based on the information in the
figures, deduce ONE possible structure of A.
18
(6 marks)
6.
(b) Consider the reaction between compound B and water in mole ratio of 1:1 as
shown below:
(i)
(ii)
Give the structure of the major organic product(s) if B and water are
allowed to react in mole ratio of 1:2.
2008-AL-CHEM 2-19
19
(4 marks)
(c) Ibuprofen, an over-the counter analgesic drug, can be synthesized from
compound E in three steps as shown below:
(i)
For each of Steps 1,2 and 3, suggest the reagent(s) used and the
reaction condition.
Step 1: NH2OH Step 2: heat OR dehydrating agent Step 3: H3O+/heat
(ii)
(5 marks)
(d) Morphine, a potent analgesic drug, is obtained from the latex extracted from
opium poppy.
(i)
Given that the pKa of the phenolic hydroxyl group of morphine is 9.8
and that of its ammonium salt is 7.9, outline how morphine can be
obtained from the latex extracted from opium poppy.
Add HCl(aq) to latex to convert morphine to its ammonium salt
Add CCl4 to extract non-ionic organic compounds
Obtain the ammonium salt in aqueous layer by crystallization
(ii)
Both morphine and its ammonium salt sublime upon heating. Suggest
why it is necessary to add quicklime, CaO(s), to morphine before it is
disposed of by incineration.
Quicklime is a strong base, it reacts with morphine to form its calcium
phenoxide, which is non-volatile and will not sublime
2008-AL-CHEM 2-20
20
(5 marks)
7.
(a) Deduce the structure of isomeric compounds F and G, with formula C6H12,
that have the following characteristics:
Compound
Characteristics
Structure:
Enantiomers:
G is an alkene (undergoes addition)
As it gives a single achiral compound only, each double bond C
should have same substitutents
Structure:
Achiral product:
2008-AL-CHEM 2-21
21
(6 marks)
(b) (i)
(I)
J:
K:
(ii)
(I)
22
(c) Compounds M, N, P, Q and R are all colourless liquids. Without the aid of
instrumental analysis, suggest how you would differentiate the five
compounds from one another.
CH3CH2OH CH3COCH3 (CH3)3COH CH3(CH2)3NH2
CH3(CH2)7OH
M
2008-AL-CHEM 2-23
23