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- - 2-
1.(a) (i) O (g) + e à O (g) [1m]
-
(ii) Addition of an e to the O(g) atom is exothermic
- -
attraction between the nucleus and the incoming e outweighs the repulsion between e in O atom
-
and incoming e . [1m]
-
(if, attraction between the nucleus and the incoming e 1/2m)
- -
After addition of an e-, there is strong repulsion between the O (g) ion and the incoming e . [1m]
-
(if, the size of O expands, hence the attraction of another e is weakened 1/2m)
-
(iii) Screening effect of the stable electronic configuration of inert gases make the addition of an extra e an
unfavourable process [1m]
∴inert gases have +ve first E.A.
(if, addition of an e- destroys the extra stability of the electronic configuration of the inert gases 1/2m)
(c) (i)
F
Drawing [1m]
B Triangular planar [1/2m]
Zero dipole moment [1/2m]
F F
(ii)
F
Drawing [1m]
Cl F T-shaped [1/2m]
Non-zero dipole moment [1/2m]
F
(0m if shape of ClF3 is described as triangular planar.)
i.e.
..
F
F Cl
F
..
n+ -
(d) Ti + ne à Ti
No. of moles of Ti liberated = 5.60 / 47.90 = 0.1169 [1m]
No. of moles of e- passed = 5.00 x 2.50 x 60 x 60 / 96500
∴n = 4.663 x 10-1 / 1.167 x 10-1 = 3.989 = 4 [1m]
- - +
(e) (i) BrO3 (aq) + 5Br (aq) + 6H (aq) à 3Br2(aq) + 3H2O(l) [1.5m]
- - 2-
(ii) 2MnO4 (aq) + 3SO2(g) + 4OH (aq) à 2MnO2(s) + 3SO4 (aq) + 2H2O(l)
[1/2m for completing the equation, 1m for balancing the equation] )(No penalty on state symbols, max.
1m for multiples of the correct equation.)
2- - -
(f) (i) HPO4 (aq) + H2O(l) H2PO4 (aq) + OH (aq) [1m]
(ii) At pH 10,
1994-AL-CHEM P 1 - 1
- -4 -3
[OH (aq)] = 10 mol dm [1/2m]
2- -1 -3
[HPO4 (aq)] = 10 mol dm
+ 3 2- -
[Ag (aq)] [HPO4 (aq)][OH (aq)]
-22
= 2.84 x 10 or Kc [1/2m]
∴ [Ag+(aq)] = 2.84 x 10
3 -17
+ -6 -3
[Ag (aq)] = 3.05 x 10 mol dm [1m]
+
1 mole of Ag3PO4 produces 3 moles of Ag (aq) ions.
∴ solubility of Ag3PO4 = 1.017 x 10 mol dm [1m]
-6 -3
3 2- -
(Full mark should be awarded if the solubility x is solved by Kc=(3x) [HPO4 ][OH ]
1994-AL-CHEM P 1 - 2
If D may be recovered by addition of alkali (extracting with ether, drying and evaporation) - a BONUS
1/2m)
(ii)
E: [1m] F,G: [1m] [1m]
CH3CH2CH=CH2 CH3 CH3 CH3 H
or but-1-ene
C=C or C=C
or
H H H CH3
or cis-2-butene or trans-2-butene
H
1.O3 2. Zn, H3O+
CH3CH2CH=CH2 CH3CH2CHO + CH2O or C=O
[1/2m] [1/2m] H
(iii)
HNO2
C No reaction [1/2m]
HNO2
D CH3CH2CH2OH + N2
CH3CH=CH2
CH3CH-CH3 or Br
Br
or isopropyl bromide [1m]
or 2-bromopropane
(If CH3CH2Br 0m)
(ii) Mechanism:
+
-
Br
CH3CH=CH2 δ+H-Brδ− CH3CHCH3 CH3CHCH3
[1/2m] Br
[1/2m]
(If electrophilic additon only 1/2m)
Minor product is CH3CH2CH2Br [1m]
1994-AL-CHEM P 1 - 3
+
It is a minor product because its intermediate (CH3CH2CH2 ) is less stable than the secondary
carboncation (CH3CHCH3) [1/2m]
OR The carboncation formed exists as an equilibrium mixture
+ +
CH3CHCH3 CH3CH2CH2
(more stable) (less stable)
+
The secondary carboncation ( ) is more stable than the primary carboncation
+
( ) because the two electron releasing methyl groups disperse the charge more
and so stabilize the +ve secondary ion more effectively. [1/2m]
Bonus the electron release may be considered to be due to the inductive effect and the
hyperconjugative effect. (1/2m)
("The more stable ion will produce the major product" This should be stated or implied as in
above.)
(c) (i) Chromatography or thin layer chromatography
Paper chromatography: a small spot of solution of protein hydrolysate is placed near the bottom of
a sheet of chromatography paper. In the same horizontal line is placed spots of all the likely known
amino acids. After drying the paper is placed in a tank with a layer of suitable solvent below the line
of spots. [Method 1m]
After the solvent has reached near the top of the paper it is removed from the tank, dried and
sprayed with ninhydrin (or stained) [1/2m]
OR use of diagram to explain the method.
(There are many ways of answering "method".)
The amino acids in the mixture are identified from their Rf values when compared with that of the
known amino acids. [1m]
Rf is relative distance travelled [1/2m]
(ii)
NH3+
|
CH3 - C - CO2- or R-CH(NH3+)CO2- [1m]
(If not an α-amino acid 1/2m)
NH 2
|
(If just RNH3+ or RCO2-, or R - CH - CO2H 0m)
+
(iii) This is the H ion concentration [1/2m] of solution in which a particular amino acid [1/2m] of
solution in which a particular amino acid [1/2m] does not migrate [1/2m] under the influence of an
electric field. [1/2m]
OR pH at which no ion migration occurs
OR pH at which cationic form and anionic form of an amino acid are in equal concentration.
4.(a) Addition of Na2CO3(aq) [or NaHCO3(aq)] to CH3COOH(aq) gives CO2(g) / effervescence [1m]
Addition of Na2CO3(aq) [or NaHCO3(aq)] to phenol does not give CO2(g) / effervescence [1m]
(Correct reagent, but result incorrect, 1/2m only. No need to use lime water. Accept also reactions with
insoluble basic oxides, or magnesium.)
(b) Clean test tube [1/2m]
to AgNO3(aq) [1/2m] add NH3(aq) (excess) [1/2m] in test tube until initial precipitate dissolves.
+
(If Ag(NH3)2 or ammoniacal silver nitrate, total 1/2m only, Tollens' reagent 0 m)
Add a few drops of aldehyde [1/2m]
Place tube in a beaker of warm water (or warm water bath) [1/2m]
(Direct - gentle heating or heating 0m)
An explosion may occur [1/2m]
(c)(i) Carcinogenic / toxic
(ii) Oxidizing [3m, deduct 1m for each incorrect
answer, down to zero]
(iii) Corrosive
(iv) Flammable
st
(Accept 1 answer written down, if several answers.)
1994-AL-CHEM P 1 - 4
(d)
Substance Reaction method Expected observation(s) Main products
CH3COOH(l) and Warm/reflux with conc. Miscible, fruity odour CH3COOC2H5(l)
C2H5OH(l) H2SO4
2+
Cu(s) and conc HNO3 Add acid dropwise at room Green / blue solution Cu [1/2m]
temperature [1/2m] brown fumes [1/2m] NO2 [1/2m]
or Cu dissolves [1/2m]
CH3CHBr2(l) and 4M Gently heat mixture in a Pungent odour [1m] / CH3CHO(aq)
NaOH test tube miscible
CuSO4(aq) and 2NH3 Add NH3(aq) dropwise Pale blue precipitate, deep Cu(OH)2(s)
2+
[1m] (slowly) blue solution [Cu(NH3)4] (aq)
Pb(NO3)2(aq) and 2M HCl Add acid dropwise at room White ppt [1m] milky PbCl2 [1m]
temperature [1/2m]m / cloudy [1/2m] /
turbid [1/2m]
(Each box total = 1m, state symbol not necessary. Deduct 1/2m for mistake(s) in same box)
2- +
(e)(i) S2O3 (aq) + 2H (aq) à H2O(l) + SO2(g) + S(s) [1m]
or Na2S2O3 + 2HCl à 2NaCl + S + SO2 + H2O
2-
(ii) Make [S2O3 ] solutions of known molarities and place equal volumes of these solutions in conical
flasks. [1m]
Measure temperature of solutions/set thermostat at 298 K. [1m]
Add a fixed volume of acid to Na2S2O3 (using measuring cylinder), start stop-clock [1m]
Note time, t, when a black "X" marked on a cardboard becomes invisible when lookng through the
flask. [1m]
Points are:
2-
- solutions of different molarities of S2O3
- equal volumes of these solutions
- flasks
- 298 K
- add fixed volume of acid
- start stop clock
- note time
- black X disappearts
[1/2m for each point]
-1 2- -3
(iii) (1/t) / s and [S2O3 (aq)] / mole dm [1m]
concentration
(Accept log both sides)
1994-AL-CHEM P 1 - 5
molecules are quite mobile on the Fe surface, (and may encounter each other on this 2-
dimensional plane or higher concentration of reactants on the surface, therefore surface
becomes better meeting place) (1)
Instead of a 4-body collision in a 3-dimensional space in the gas phase, the presence of the
Fe surface requires only that the adsorbed species be higher than the former event.
OR 3-dimensional collision à 2-dimensional collision à higher frequency collision. (1)
(7)
Optional Mark (3; any 3 of the following)
As a result of weak interaction of the product with the surface, NH2 desorbs easily. (1)
Fe has (numerous) 3-d electrons and many vacant 3-d orbitals, and is therefore capable of
temporarily donating or accepting electrons from adsorbed species, making it (one of the
best catalyst in heterogeneous catalysis.)
OR Variable oxidation state (1)
(Steric effect) is more important in the gas phase: the (4) colliding molecules have to be in
the correct orientations to yield the product.
(1)
The gas phase reaction may be speeded up by raising the temperature, but at high
temperatures decomposition of NH3 is favoured, thus lowered the yield. (1)
Specifically, N2 dissociates into (weakly adsorbed/ absorbed) N atoms at around (500 °C )
and H2 dissociates at temperatures as low as (-196 °C ) as weakly adsorbed H atoms. These
atoms are highly reactive, and they form NH3 readily. (1)
Breaking of the strong ( N ≡ N triple bond or resist breaking) (1)
(3)
Diagram for Boltzmann distribution, change of reaction path in the presence of the catalyst, (pictorial
illustration of gas phase collision and formation of ammonia on the Fe surface.)
Presentation ( 4 marks )
This mark is awarded for the ability to PRESENT the organized Chemical Knowledge in a suitable,
meaningful and readable form.
NOTE: Marks awarded should be related to Chemical Knowledge.
Marks for chemical knowledge Max. for presentation
10 ’ 8 4
7’ 6 3
5’ 4 2
1994-AL-CHEM P 1 - 6
<3 1
The followings are looked for:
EQUATIONS, DIAGRAMS AND EXAMPLES. [1 ꙷ 2m]
ENGLISH This mark is for the ability to express clearly in English [2 ꙷ 3 m]
A more detailed break down of the marks for each of the core areas:
Area A (Max. 1m)
- Composition: Must give 1 formula for each element
NaCl MgCl2 AlCl3 SiCl4 PCl3(l) S2Cl2(l) Cl2 [1m]
(or PCl5(s)) (SCl2 or SCl4)
1994-AL-CHEM P 1 - 7
Reversible hydrolysis of highly polarizing cation:
AlCl3(s) + 6H2O(l) [Al(H2O)6]3+(aq) + 3Cl-(aq)
then [Al(H2O)6]3+(aq) + H2O(l) H3O+(aq) + [Al(H2O)5(OH)]2+
à ...
[1m for statement, equation not necessary, up to 2m]
- For covalent chlorides SCl2, SiCl4, PCl3, PCl5, (XCln), the hydrolysis proceeds by nucleophilic attack
-
by a lone pair of e on O in H2O: upon X, which if less electronegative than Cl.
e.g. PCl3(l) + 3H2O(l) à P(OH)3(aq) + 3HCl(aq)
2S2Cl2(l) + 2H2O(l) à 3S(s) + SO2(aq) + 4HCl(aq)
- Hydrolysis of chlorine
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
[1m for each example & equation, up to 2m]
- Trend:
Pure ionic chloride - neutral / not hydrolysed;
Covalently bonded - acidic / hydrolysed [1m]
- Mechanisms of hydrolysis for one example [1m]
- Reaction of the chlorides IF THEY ARE OF COMPARATIVE NATURE
[1m each for 2 comparative chlorides, e.g. PCl3 + PCl5]
Presentation ( 4 marks )
This mark is awarded for the ability to PRESENT the organized Chemical Knowledge in a suitable,
meaningful and readable form.
NOTE: Marks awarded should be related to Chemical Knowledge.
Marks for chemical knowledge Max. for presentation
10 ’ 8 4
7’ 6 3
5’ 4 2
<3 1
The followings are looked for:
EQUATIONS, DIAGRAMS AND EXAMPLES. [1 ꙷ 2m]
ENGLISH This mark is for the ability to express clearly in English [2 ꙷ 3 m]
the benzene ring with 3 π bonds is electron rich. The usual reactions are not electrophilic
addition (like alkenes) because of the unusual stability of the ring- seen in the difference
between calculated and measured heats of hydrogenation and combustion which is the
-1
resonance energy (approx. 154 KJ mol )
1994-AL-CHEM P 1 - 8
(Definition and formulae to explain resonance using correct arrows are expected.)
Electrophilic substitution reactions being the common reactions.
Examples: with electrophiles
e.g. nitration, bromination, sulphonation.
Explanation - resonance
Evidence (Energy: Difference between experimental and theoretical, bond length, heat of
hydrogenation, heat of combustion) (1/2)
Some answers may refer to the benzene ring as a SINK for electrons. The following examples are
due to the interaction of lose pairs of electrons on a hetero-atom with the benzene ring. The ring
appears to the attract electrons:
Ph-Cl: The Cl is very unreactive compared to HCl and won…t react with AgNO3 (due to
stronger C-Cl bond - by lone pair interaction).
+
The unusual stability of the Phenyldiazoniun ion Ph − N ≡ N (1/2) compared with
unstable alkyl type. These results in a coupling reaction (1/2) - only observed with aryl case:
Remaining (1/2) marks given to more detailed answer to any of the above 4 sections (1/2).
__________
(10)
1994-AL-CHEM P 1 - 9
NOTE: The marks should be related to chemical knowledge
General guidelines for Organization:
Mark for chemical knowledge Maximum for organization
10 - 9 6
9-7 5
7-5 4
5-4 3
3-2 2
2-1 1
0 0
(xi) The essay should be clearly ORGANIZED, with suitable DIVISION, PARAGRAPHS AND SUB-
HEADINGS. [2m]
These should be clear to the reader. [2m]
(xii) Terms must be clearly defined. [1m]
(xiii) The essay should be LOGICALLY organized. It must not be a list of facts. [2m]
(xiv) No irrelevant / wrong material. [1m]
(xv) No error in labels of diagrams, spelling etc. [1m]
Presentation ( 4 marks )
This mark is awarded for the ability to PRESENT the organized Chemical Knowledge in a suitable,
meaningful and readable form.
NOTE: Marks awarded should be related to Chemical Knowledge.
Marks for chemical knowledge Max. for presentation
10 ’ 8 4
7’ 6 3
5’ 4 2
<3 1
The followings are looked for:
EQUATIONS, DIAGRAMS AND EXAMPLES. [1 ꙷ 2m]
ENGLISH This mark is for the ability to express clearly in English [2 ꙷ 3 m]
1994-AL-CHEM P 1 - 10