1994 A-level chemistry paper I marking scheme

- - 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)

(b) (i) No. of atom A per unit-cell = 8 x 1/8 = 1

No. of atom B per unit-cell = 12 x 1/4 = 3
Therefore Empirical formula of the compound is AB3 [1m]

(ii) Coordination number of A = 6 [1/2m]

Coordination number of B = 2 [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 ]

2. (a)(i) Redox: one species is oxidized and another is reduced. [1m]

Disproportionation: single species is simultaneously oxidized and reduced. [1m]
(ii) 2KOH(aq) + Cl2(g) à KCl(aq) + KOCl(aq) + H2O(l) [1m]
or 6KOH(aq) + 3Cl2(g) à 5KCl(aq) + KClO3(aq) + H2O(l)
- - -
or 2OH (aq) + Cl2(g) à Cl (aq) + OCl (aq) + H2O(l)
- - -
or 6OH (aq) + 3Cl2(g) à 5Cl (aq) + ClO3 (aq) + 3H2O(l)
(Conditions are not necessary, the equation must be balanced.)
2+ + +
(b) (i) Ni higher charge density / more electronegative than K / more polarizing than K [1m]
(Or low-lying vacant d orbital, NOT accept effective nuclear charge argument)
∴ greater ability to form covalent bond / dative bond with ligand [1m]
(ii) one example, not name [1m]
(Correct charge; accept coordination numbers 4/6. Accept en etc.)
(c) (i) a proton donor [1m]
+ -
(ii) HNO3 + H2O à (or ) H3O + NO3 [1m]
+ -
HNO3 + HF à (or ) H2NO3 + F [1m]
(iii) HClO < HClO2 < HClO3 < HClO4 [2m]
(1m for 3 formulas, 1m for order of acidity)
(iv) HF is extensively hydrogen-bonded in water
+ -
(H-F)n + H2O(l) H3O (aq) + F (aq) + (H-F)n-1 [1m]
The equilibrium lying to LHS.
-
The Cl ion, having a large size, is highly polarizable, it is stable in water. Hence the equilibrium
+ -
HCl(aq) + H2O(l) H3O (aq) + Cl (aq)
lies to the right, so HCl is a strong acid.
or HX bond strength greater in H-F than H-Cl, H-F ionize less easily than H-Cl in water (1m), this
- -
outweighs the hydration energy from F to Cl . (1m)
(d) (i) H atom is situated between 2 small / electronegative atoms [1m]
One of these has a lone pair of electrons [1m]
or bond energy in range 2 - 10 kJ mol-1 (accept weak, or up to 50)
(ii) One example, must show X-H ... Y or X ... H ... X [1m]
(Accept bond between 2 different species, and δ+, δ- instead of dots. If lone pair is shown, but in
incorrect location 1/2m only)
(iii)(I) Boiling points expected to increase with number of electrons in the molecule (CH4 à SiH4) due to
increasing van der Waal's force [1m] (large surface area not enough)
(II) Boiling point of NH3 higher than expected (i.e. > PH3) due to increased intermolecular attraction
(hydrogen bonding) [1m]
(e) Cs, having a lower I.E. / a larger size, the e- in the outermost shell can be ionized easily by absorption
of visible light. Therefore it is more suitable to be used in making photo-electric cell. [1m]
(Not accept argument based on the effective nuclear charge.)
(f) In the periodic table, the elements are arranged in order of atomic number, but not in order of atomic
mass. Argon having no electron in the 4th shell is placed in group I. [1m]
(1 more proton 1/2m, Periodic table arranged in order of ascending atomic number 1/2m)

3. (a)(i) Add dil.(aq) HCl and (diethyl) ether to (C + D) [1m]

Separate the layers (using a separating funnel) [1/2m]
In aqueous HCl layer - D [1m]
In ether layer - C[1/2m]
(In place of HCl can use H2SO4. In place of ether can use CHCl3, CH2Cl2.
If D forms salt with HCl, soluble in H2O, C does not 2m

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

OR CH3CH2CH2N2+ N2 + CH 3CH2CH2+ CH3CH2CH2OH etc.

(Unstable)
CH3CH2CH2Cl
(If C is ignored - no mark for C. examples of products
If "only D reacts" award 1/2m for C. +
+ N2
If for D, CH3CH2CH2N N or award only 1m
Cl
If D or alone 1/2m each, max. 1m)
(iv) In the case of D colourless [1/2m] gas bubbles [1/2m] will be seen or N2 gas evolved with D.
(If "look for gas bubbles" with no mention of D or C 1/2m)
(b) (i)

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)

5. Chemical Knowledge (10 marks)

Core marks (7)
Discussion on the rate in the absence of an Fe surface

Probability of a simultaneous collision of (4 or gaseous) molecules in the gas phase is

extremely small. (1)
Breaking of the strong N ≡ N bond imposes high activation energy (Ea) on the process. (1)
Collision of molecules having high velocities should, in principle, provide the necessary Ea.
(1)
According to the (Boltzmann) distribution at moderate temperatures the number of such high-
velocity molecules is (very) small. (1)

(Looking for the graph, good organization of points)

Discussion of the rate in the presence of an Fe surface

The N ≡ N bond is significantly weakened in the Fe surface, and therefore providing a

different reaction path with smaller Ea.
OR Gaseous molecules covalent bond weakened. (1)
All the gases involved are only weakly adsorbed on the Fe surface. Thus N2 and H2

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)

(Looking for the adsorbed model, good organization of points)

The following diagrams are expected:

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.)

Organization ( 6 marks )(1/2 mark awarded)

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
(i) The essay should be clearly ORGANIZED, with suitable DIVISION, PARAGRAPHS AND SUB-
HEADINGS. [2m]
These should be clear to the reader. [2m]
(ii) Terms must be clearly defined. [1m]
(iii) The essay should be LOGICALLY organized. It must not be a list of facts. [2m]
(iv) No irrelevant / wrong material. [1m]
(v) 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

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]

6. Chemical knowledge (10 marks)

(Note: Emphasis on chemistry , e.g. preparation, reactions; not physical properties.)
Core Area
A. Composition (formulae), (natural abundances), (uses) [1m]
B. Bonding in chlorides, structures, (relative stabilities), (states) [2m]
C. Preparation, relation to chemical behaviour and bonding [3m]
D. Hydrolysis (mechanisms), (reactions with other species) [4m]
(Area in brackets: may be included to score up to 1m towards the area total)

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)

(One formula incorrect or mising, only 1/2m)

(For each chloride, if giving natural abundance / use è 1/2m; e.g. if the natural abundance / uses of
NaCl & Cl2 are discussed è 1m)

Area B (Max. 2m)

- State:
NaCl MgCl2 AlCl3 SiCl4 PCl3(l) S2Cl2(l) Cl2
(or PCl5(s)) (SCl2 or SCl4)
(---------- solid -------------------) (---------------- liquid*---------------------) gas [1m]
* state must be matched with the formula
or 2 examples of trend in states, melting points
- Structure/bonding (transformation from giant ionic to discrete covalent molecules) [1m]
(- amplifications of structures / bonding 2 x 1/2m = 1m)
- drawing of outer e- diagram / structure for NaCl & Cl2. 2 x 1/2m [1m]

Area C (Max. 3m)

(1/2m for general method + 1/2m for equation, up to 3m. Equation need not be balanced or complete)
- Covlanet chlorides: from elements by direct reaction with Cl2
e.g. Si(s) + 2Cl2(g) à SiCl4
P4(s) à PCl3(l) à PCl5(s)
2S(s) + Cl2(g) à S2Cl2(l) etc.
(or halogen exchange) [1m]
- Ionic chlorides: by reaction of HCl(aq) with oxides, carbonates, hydroxides
e.g. Na2CO3(s) + 2HCl(aq) à 2NaCl(aq) + H2O(l) + CO2(g)
AlCl3: 2Al(s) + 6HCl(g) à 2AlC3(s) + H2(g) [1m]
- Chlorine: HCl (conc) on oxidation by strong oxidizing agents
(KMnO4 or MnO2, NOT K2Cr2O7) gives Cl2(g)
e.g. MnO2(s) + 4HCl(aq) à MnCl2(aq) + Cl2(g) + 2H2O(l)
2KMnO4(s) + 16HCl(aq) à 2MnCl2(aq) + 5Cl2(g) + 2KCl(aq) + 8H2O(l)
or action of dil. acids on bleaching power
or 2NaCl + MnO2 + 2H2SO4 à 2NaHSO4 + 2H2O + Cl2 [1m]
Accept electrolysis of brine

Area D (Max. 4m)

(Name + arrow equation for each hydrolysis = 1m; or full equation. Reaction with OH- accepted for
AlCl3, MgCl2 or covalent chlorides.)
- Ionic chlorides form solvated ions in water which do not hydrolyse:
NaCl(s) + aq --> Na+(aq) + Cl-(aq)
With increasing polarization of cation undergoes slight hydrolysis:
MgCl2(s) + 2H2O(l) Mg(OH)2(aq) + 2HCl(aq)

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]

Organization ( 6 marks )(1/2 mark awarded)

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
(vi) The essay should be clearly ORGANIZED, with suitable DIVISION, PARAGRAPHS AND SUB-
HEADINGS. [2m]
These should be clear to the reader. [2m]
(vii) Terms must be clearly defined. (not relevant here) [0m]
(viii) The essay should be LOGICALLY organized. It must not be a list of facts. [2m]
(ix) No irrelevant / wrong material. [1m] (2 errors = -1)
(x) 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]

7. Chemical Knowledge (10 marks)

Unique properties of benzene ring (3)

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.

This part should include

Unique chemical properties:
Reaction expected of C=C - Electrophilic Addition (1/2)
Reaction Found for C6H6 - examples (some detail req.)
- Ar Electrophilic substitution (1)

Explanation - resonance
Evidence (Energy: Difference between experimental and theoretical, bond length, heat of
hydrogenation, heat of combustion) (1/2)

Effective of benzene ring on Reaction o Functional groups max 4

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:

Example: (max 11/2 mark for each example)

Ph-NH2: less basic than NH2 or RNH2 (1/2) due to interaction of lone pair with ring.
Resonance structures:

NH2 - NH2+ ...

Ph-OH: acidic (1/2) due to stability of Ph-O- ion (due to resonance; explain (1/2)),
ROH is not acidic (1/2).

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).

Other examples indicate the opposite:

+
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:

Accept other possible examples.

[This part of the question requires more ability as the details required are not stated specifically like
the other parts of the Q䀔 䀔 .hence 4 marks]

Source: from crude oil (1/2) following by refining (distillation (1/2)).

OR destructive distillation of coal (1/2).

Synthetic route of amino benzene

C6H6 conc.H2SO4/ conc.HNO3 (1/2) PhNO2 (1/2) Sn/HCl (1/2) PhNH2

Remaining (1/2) marks given to more detailed answer to any of the above 4 sections (1/2).
__________
(10)

Chemistry of benzene derivatives (21/2 marks)

Phenol- substitution (1) max
Nitrobenzene- substitution and others (1) max

Organization ( 6 marks )(1/2 mark awarded)

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
1994 A-level Chemistry paper II marking scheme
1.(a)(i) PAVA =nART
PBVB = nBRT [1m]
PA/PB = nA/nB(VB/VA) [1m]
= 1/2(1/2) = 1/4 [1m]
or PA = 1/4PB or PB = 4PA (1m)
(ii) P(CO2) < PA [1m]
Gas pressure is produced by the collision of gas molecules on wall of container [1m]. At low pressure,
the attraction / intermolecular force / van der Waal's force between CO2 molecules is a dominated
force, so the collision force on the wall is reduced.
2+ 2+
(b) FeNCS (aq) ions absorb visible light in electromagnetic spectrum, hence FeNCS (aq) can be
determined by measuring the absorbance of the solution. [1m]
Calibrate a colorimeter by measuring the absorbance of several solutions which contained known
2+
concentrations of FeNCS (aq) [1/2m + 1/2m]
-
(In these solutions, the NCS ions are in excess, so that Fe3+ ions present can be considered as existing
2+
in the complex form, FeNCS )
3+ -
By mixing comparable volumes of standard Fe (aq) and NCS (aq) solutions and measuring the
2+ 3+ - 2+
[FeNCS (aq)] formed with the colorimeter, [Fe (aq)], [NCS (aq)] and [FeNCS (aq)] at equilibrium can
be found. [1/2m + 1/2m]
Hence, the equilibrium constant
2+ 3+ -
Kc = [FeNCS ] / ([Fe (aq)][NCS (aq)]) [1m]
can be determined.
(c)(i)

The graph of log [C] versus t is not a straight line

∴ order ≠ 1 [1/2m]
The graph of 1/[C] versus t is a straight line
∴ order = 2 [1/2m]
[2m for the two graphs]
(ii) For second order reaction,
1994 AL CHEM P II – Page 1
 1/[C] = 1/[C]o - kt
From the slope of graph,
-2 -3 -1
k=1.997x10 (mol dm ) s [1m for ans.; 1m for unit]
-2 -2 -3 -1 -1
(1.95 x 10 to 2.05 x 10 (mole dm ) s )

(iii) Arrhenius Equation

ln k = C - Ea/RT
ln k = C - Ea/R(1/298) ...... (1)
ln k + ln 2 = C - Ea/R(1/306) ......(2)
(2) - (1)
ln 2 = Ea/R(1/298 - 1/306) [1m]
∴ Ea = 65.7 kJ [1/2m for answer; 1/2m for unit]

2.(a)(i) ∆H298 = -393.5 + 2(-285.9) - (-75.0) [1m]

= -890.3 kJ [1/2m for answer; 1/2m for unit]
(ii) CH4(g) + 2O2(g) à 2H2O(g) + CO2(g) ∆H= -801.7 kJ
-) CH4(g) + 2O2(g) à 2H2O(l) + CO2(g) ∆H = -890.3 kJ
2H2O(l) à 2H2O(g) ∆H = 88.6 kJ [1m]
∆Hvaporization(H2O) = +44.3 kJ [1m]
(iii) ∆Hcomb.[C(diamond)] = -395.4 kJ mol .
-1

∆Hcomb.[C(graphite)] = -393.5 kJ mol .

-1

∴ graphite is relatively more stable allotrope [1m]

Conversion from diamond to graphite involves the rearrangement atoms in giant covalent network
would require a high activation energy. ∴ conversion does not occur at room temperature. [1m]

(b)(i) In H3PO4, the intermolecular force is H-bond. [1m]

The structure of H3PO4 is
OH
/
O=P-O-H [1/2m]
\
OH
(or H3PO4 is capable of forming 3-H-bonds with its neighbours 1/2m) With strong intermolecular forces,
H3PO4 has a high viscosity [1/2m]
(ii) In ice the intermolecular attraction is H-bond, each H2O molecule is tetrahedrally surrounded by 4 other
H2O molecules or (C.N. = 4) [1/2m + 1/2m]
i.e. an open structure [1/2m]
In liquid water, the molecules are packed closer together
∴ water has a higher density than ice [1/2m]
For the endothermic reaction,
H2O(s) H2O(l)
Increase in pressure, shifts the equilibrium to the right [1m]
∴ m.p. of ice decreases with increases in pressure
(c)(i)

[1m for labelling the two axes; 1/2m for the line drawn]
Mole fraction of F = 4/(4+1) = 4/5 [1/2m]
From the graph,
V.P. of mixture = 1.8Po [1m]
or, by calculation
PE = 0.2 Po PF = 0.8(2Po)
= 1.6Po
∴ V.P. of mixture = 1.8Po (1m)
1994 AL CHEM P II – Page 2
 (ii) If deviation is negative P < 1.8Po
If deviation is positive P > 1.8Po [1m]
Explanation: In case of negative (positive) deviation, the interaction between E and F is stronger
(weaker) than the average of interaction between E and E and between F and F. [1m]
The molecules have a smaller (greater) chance to escape, [1m] thus resulting in a lower
(higher) vapour pressure.
(Max. 2m, if only one of the cases is discussed.)

3.(a)(i) From the graph

+
When [Ag (aq)] = 1.0 M, e.m.f. of cell = +0.46 V [1m]
∴ Standard electrode potential of Ag(s)|Ag (aq) half-cell = +0.46 + (0.34) V
+

= + 0.80 V
[1/2m for answer, 1/2m for unit]
(ii)(I) From the graph, when e.m.f. = +0.27 V,
+
log10 [Ag (aq)] = -3.2 (-3.1 to -3.3) [1/2m]
+ -4 -3
i.e. [Ag (aq)] = 6.31 x 10 mol dm [1/2m]
-4 -4 -3
(7.94 x 10 to 5.01 x 10 mol dm )
+ -
(II) Ksp[AgBrO3] = [Ag (aq)][BrO3 (aq)] [1m]
-4
= (6.31 x 10 )(0.1)
-5 2 -6
= 6.31 x 10 mol dm [1m]
-5 -5 2 -6
(5.01 x 10 to 7.94 x 10 mol dm )
(b)(i) The dissociation of water
+ -
2H2O(l) H3O (aq) + OH (aq)
is an endothermic process / ∆H = +ve [1m]
+
Increase in temperature, the equilibrium shifts to the right [1/2m] and hence [H3O (aq)] increases. In
pure water, [H3O (aq)] at 323 K is higher than that at 298 K, ∴ pH of pure water at 323 K is less than
+

7.0. [1/2m]
(ii) Acid-base indicators are weak acids/bases.
The dissociation of which can be represented by:
+ -
HIn(aq) + H2O(l) H3O (aq) + In (aq) [1m]
The colour of an indicator depends on the relative concentrations of the acidic form. HIn and the
alkaline form In-(aq) which are of different colours. [1/2m]
The dissociation constant Ki for different acid-base indicators are different, [1/2m] thus they change
colour over different pH range.
The pH range of methyl orange is below 7, [1/2m]
while that of phenolphthalein is above 7, [1/2m]
∴ at pH 7, methyl orange shows its alkaline colour, while phenolphthalein shows its acidic colour.
+ -
(c)(i) Ka = [H ][PrCOO ] / [PrCOOH]
+ -
Assuming [H ] = [PrCOO ], [PrCOOH] = 0.1 M
-5 + 2
1.5 x 10 = [H ] / 0.1 [1m]
-3
[H+] = 1.225 x 10 M
pH = 2.91 [1m]
(ii) Assuming [PrCOOH] = 0.05 M
-
[PrCOO ] = 0.05 M
-5 +
1.5 x 10 = [H ] x 0.05/0.05 [1m]
+ -5
[H ] = 1.5 x 10 M
pH = 4.82 [1m]
( > 2 d.p. or < 2 d.p. -1/2m)
(iii) After addition of 1.0 x 10-3 moles solid NaOH
-3
[PrCOOH] = 0.05 - 1.0 x 10 }
- -3
[PrCOO ] = 0.05 + 1.0 x 10 } [1m]
-5 +
1.5 x 10 = [H ](0.051) / (0.049) [1m]
-5
[H+] = 1.44 x 10 M
pH = 4.84 [1m]
(> 2 decimal places or < 2 decimal places -1/2m)

4.(a) Heating conc. HCl in the presence of manganese(IV) oxide [1/2m + 1/2m]
∆
MnO2(s) + 4HCl(aq) à MnCl2(aq) + 2H2O(l) + Cl2(g) [1m]
or add conc. HCl to solid KMnO4 (1/2m + 1/2m)
- + 2+
10HCl + 2MnO4 + 6H à 5Cl2 + 8H2O + 2Mn (1m)
Pass the Cl2 produced through cold water to remove HCl, [1m] dry the gas by passing through conc.
H2SO4 and collect by downward delivery [1/2m + 1/2m]
1994 AL CHEM P II – Page 3
 The experiment should be carried out in a fume cupboard. [1m]
(b) The anomalous boiling point of HF is due to extensive H-bonding between HF molecules [1/2m + 1/2m]

(diagram showing H-bonds in HF) [1m]

(Accept alternative answers such as in HCl, HBr, HI there are no extensive H-bonds.)
(c) Highest O.S. of I = +7 [1m]
-
Example: IF7, IO4 [1m]
(d)(i) NaCl + H2SO4(l) à NaHSO4 + HCl [1m]
(ii) NaI + H2SO4 à HI + NaHSO4
8HI(g) + H2SO4(l) à I2(s) + H2S(g) + 4H2O(l) [1m]
or 2HI(g) + H2SO4(l) à I2(s) + SO2(g) + 2H2O(l) (1m)
HI, being a stronger reducing agent than HCl, will be oxidized by conc. H2SO4 to give I2. [1/2m + 1/2m]
-
(e)(i) ∵ NH2NH2 : IO3 = 1 : 1
- -
In the reduction of IO3 , O.S. of I decreases from +5 (in IO3 ) to +1 (in ICl) [1/2m]
∴ In the oxidation of NH2NH2, 4 moles of e should be released from each mole of NH2NH2 [1/2m]
-

In 1 mole of NH2NH2 there are 2 moles of N atoms.

∴ O.S. of N in the reaction product is 0. [1/2m]
The colourless gas is probably N2 [1/2m]
- + -
(ii) IO3 + 5H + HCl + 4e à ICl + 3H2O [1m]
+) NH2NH2 à ICl + N2 + 3H2O [1m]
- +
IO3 + H + HCl + NH2NH2 à ICl + N2 + 3H2O [1m]
- + -
Or, IO3 + 5H + HCl + 4e à ICl + 3H2O (1m)
+) NH2NH2 à ICl + N2 + 3H2O (1m)
- 2+ +
IO3 + NH3NH3 + HCl à ICl + N2 + 3H2O + H (1m)

5.(a)(i) Elements with valence electrons in d-orbitals [1/2m + 1/2m]

(ii)

[1m] each
2+
(iii) Mn with half-filled 3d orbitals is relatively stable. [1m]
Removing e disturbs this stable configuration: relative high energy is required. ∴, Mn is not readily
- 2+
3+
oxidized to Mn . [1m]
2+ 6
Fe with an electronic configuration of d , after removal of an e- from the outermost shell will attain the
relatively stable e- configuration with half-filled 3d orbitals. ∴, the Fe ions are easily oxidized to Fe .
2+ 3+

[1m]
(iv) Variable oxidation states of d-block elements [1m] allow electron transfer between reactants and
products by means of catalyst changing betwen two oxidation states. [1m]
Any one example of transition metals or its compound as catalyst
V2O5
e.g. 2SO2 + O2 à 2SO3 [1m]
(example must involve redox process, accept Haber process, but not accept hydrogenation of alkene.)
(v)

[1m]
-
(b)(i) MnO4 is unstable in the presence of sunlight / undergoes photodecomposition; [1m]
it will decompose to form a brown solid / MnO2 [1m]
(ii) Cobalt(II) chloride, in anhydrous state is blue [1/2m] in colour. After absorption of water / forming
complex with water, [1m] it changes colour to pink. [1/2m]
3+
(iii) In aqueous solution, Fe exists as aquo-complex.
-
Addition of OH causes the formation of a brown ppt.
3+ -
[Fe(H2O)6] + 3OH à Fe(OH)3(s) + 6H2O(l) [1m]
- 3+ 3- 3+
In the presence of excess CN , Fe forms a very stable complex [Fe(CN)6] , concentration of free Fe
ions is lowered [1m]
∴ addition of 2M NaOH cannot cause [Fe ][OH ] to exceed the Ksp of Fe(OH)3. [1m]
3+ - 3

1994 AL CHEM P II – Page 4

6.(a) Sodium hydrogencarbonate in the self-raising flour undergoes thermal decomposition to give CO2 gas.
[1m]
∆
2NaHCO3(s) à Na2CO3(s) + CO2(g) + H2O(g)
[1/2m for product; 1/2m for balanced equation]
The CO2 gas produced causes the cakes to rise. [1m]
+ -
(b) The small size of Li ion and the relatively large HCO3 ions do not favour the formation of a stable crystal
lattice. [1m]
- +
(accept explanation in terms of the polarization of HCO3 ion by Li ion)
+
The highly exothermic hydration energy of Li ion, causes lithium hydrogencarbonate to exist in solutions
only. [1m]
(c) 2PbO2(s) à 2PbO(s) + O2(g) [2m]
(Award 1 mark for an unbalanced equation)
(d)(i) Tin(II) chloride hydrolyses in water to give insoluble Sn(OH)Cl [1/2m + 1/2m]
SnCl2 + H2O Sn(OH)Cl + HCl [1m]
thus the solution appears cloudy.
+
Addition of H shifts the equilibrium to the left, the solution becomes clear. [1m]
- 2-
Addition of OH forms Sn(OH)4 [1m]
(Since Sn(OH)2 in amphoteric), thus the solution becomes clear.
-
(ii) Hydrolysis of SnCl4 involves the attack e pairs in H2O: on the vacant lower energy d orbitals of Sn [1m]

[1m]
In C, there is no low energy vacant 3d orbitals for the incoming water molecule ∴ No low energy
hydrolysis reaction path for CCl4. [1m]
(e) Reaction with acidified KMnO4 [1m for method]
-
SnCl2 decolorizes the purple colour of MnO4
while SnCl4 does not. [2m for observation]
or pass H2S(g) into aqueous solutions of the two chlorides (1m)
SnCl2 gives a brown ppt. while (1m)
SnCl4 gives a yellow ppt. (1m)

7.(a) Structural isomerism - occurence of more than one structure for a given molecular formula. [1/2m
+1/2m]
Stereoisomerism - occurence of more than one configuration (different arrangements of groups in space)
for a given structural formula. [1/2m + 1/2m]
Examples to illustrate the two types of isomers. [1/2m + 1/2m]
(b)(i)

Empirical formula of G is C2H4O

Since, relative molecular mass of G is between 80 to 100
∴ molecular formula of G is C4H8O2 [1m]
G is a sweet smelling liquid ∴ it is an ester [1m]
Possible structures of G (any 3 of the structure shown below):

(any 3) [2m]
(ii) Structure possesses a chiral carbon. [1m]

1994 AL CHEM P II – Page 5

 H H H3C H
H2C CHCH2 C *
CH3 H3C HC CH C* CH3 H2C C C* CH3
Cl Cl Cl

H CH3
H2C CH C* C2H5 H2C CH C* CH2Cl
Cl H
(iii) J reacts with PCl5 to give HCl
∴ J carries an -OH group [1/2m]
Strong oxidation of J gives , J is a 1,2-disubstituted aromatic compound. [1m]
Mild oxidation of J gives a ketone,
J is a 2° alcohol [1/2m]
Possible structures of J

[2m]
Iodoform test / I2 in NaOH [1m]
Observation:

and will gives a pale yellow ppt. while will not [1m]

8.(a) (Any chemically reasonable transformation are acceptable.)

(i)

[3m]
(ii)

[3m]
(iii)
O O CH3 O
NaOH
CH3CH2 C CH2CH3 CH3CH2 C CH
_ CH3CH2 C CH2CH3
O CH3 OH
O CH3 O CH3
CH3CH2 C C C CH2CH3
H H
CH3CH2 C C C CH2CH3 H2/Ni CH3CH2 C C C CH2CH3 CH2CH3
H conc.H2SO4
CH2CH3 CH2CH3 180oC
[OUT]
(b)(i) e.g. CH3CH2Br
_
H3C CH3
CH3
C Br NC C Br NC C
_ H H + Br
CN H H H H

[3m]
-
(ii) No, HCN is a weak acid, it ionizes only slightly in water. In HCN(aq), [CN (aq)] is low, hence rate of
SN2 reaction with R-Br is low.[2m]
(c)(i) 4,5-dimethylhex-1-ene [1m]
1994 AL CHEM P II – Page 6
 (ii) propyl butanoate [1m]
(iii) 4-hydroxyhexan-3-one

9.(a)(i) P:

[1m]
(ii) Q:

(iii) R:
[1m]

(iv)

[1m]
- +
(v) U & V: (CH3)3CCOO Na & (CH3)3CCH2OH [2m]
2
(b)(i) There are 4 C-H bonds and 1 C=C bond is an ethene molecule. The C's in ethene are sp hybridized.
2
The C-H bond is formed by overlapping of a sp hybrid oribtal with an atomic orbital of H. [1m]
The C=C bond consisted of a sigma bond and a pi bond. These bonds are formed by the overlapping
of two unhybridized p orbitals on C's respectively. [1m]

2
Since for sp hybridization, the hybrid orbitals are arranged on a triangular plane.
∴ Ethene molecule is planar and C-C-H bond angles are 120° [1m]
or C=C π bond (1/2m) by overlapping of Pz orbitals (1/2m)
C-C σ bond (1/2m) by overlapping of sp orbitals (1/2m)
2

shape - planar (1/2m); triangular or the angle is 120° (1/2m)

1994 AL CHEM P II – Page 7

(ii)

(iii)

[2m]
(iv) The structure of PVC can be represented by

The attraction between polymer chain of PVC is dipolar attraction while that between PE polymers is
van der Waal's force which is weaker when compared with former. Hence PVC is more rigid and more
durable than PE. [1m]
(v) Incineration of PVC produces CO2, H2O ... and also HCl(g) which causes more serious pollution
problem than the incineration of PE (no HCl is produced). [1m]

1994 AL CHEM P II – Page 8