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UPCSE chemistry 2006 mark scheme - 1 -

1 redox titration / 8
2 IE / 6
3 covalent bonding /14
4 Born-Haber cycle /14
5 acids /16
6. organic /13
7 rates /11
8 organic unknown /10
9 organic /09
10 equilibria /10
total 111
section B
1 /18
2
total 129
UPCSE chemistry 2006 mark scheme - 2 -
UPCSE chemistry 2006 mark scheme
1 (a) (i) +7 (1)
(ii) +2 (1)
(b) first appearance of permanent pink colouration due to presence of excess
manganate (VII) ion/self indicating (1)
(c) n
MnO4
= cV = 0.0100 x 11.80 = 1.18 x 10
-4
moles (1)
n
Fe
= 5 x n
MnO4
= 5.90 x 10
-4
(in 25 cm
3
) (1)
= 5.90 x 10
-3
in the standard solution (1)
(d) mass of Fe in solution = 56 x 5.90 x 10
-3
g (1)
% Fe = 56 x 5.90 x 10
-3
/2.40 x 100% = 13.77% (1)
2)
(a) Energy change when one mole of electrons is removed form 1 mole of gas phase
atoms (2)
(b) X
+
(g) = X
2+
(g) + e
-
(1)
(c) Group V (1)
Large increase in ionisation energy between fifth and sixth implying five electrons
in outer shell and remainder in an inner shell (1)
3)
nitrogen chloride
(2)
boron chloride
(2)
(b) nitrogen chloride bond is polarised and moleculae has a permanent dipole moment
due to unsymmetric shape (1)
permanent dipole interactions occur (1)
these intermolecular forces have to be overcome by thermal motion before substance
boils (1)
boron chloride bond is polarised but molecule has no overall dipole moment due to
symmetry (1)
only weak Van der Waal's forces between molecules (1)
Little thermal energy needed to break these (1) hence low boiling point
(c) 1/2N
2
+ 3/2Cl
2
= NCl
3
(1)
N
Cl
Cl
Cl
104
o
B
Cl
Cl
Cl
120
o
UPCSE chemistry 2006 mark scheme - 3 -
H
f
(NCl
3
) = 1/2E (NN) + 3/2 E(ClCl) - 3E(NCl) (1)
= 1/2 x 945.5 + 3/2 x 432 - 3 x 305.5
= +230 kJ mol
-1
(1)
Positive enthalpy of formation indicates thermal instability/will readily decompose (1)
4) (a)
H
latt
= H
f
- (H
at
(Ag) +(H
at
(Br)+ IE (Ag) + EA(Br)) (1)
-100.4 -(284.6 + 111.9 + 731.0 - 324.6) = -903.3 kJ mol
-1
(2)
(b) Calculated value assumes only ionic bonding (1)
Silver chloride contains some covalent bonding (1)
due to small electronegativity difference/polarising power of Ag (1)
additional bonding gives stronger lattice (1)
(c) H
sol
= H
hyd
(Ag
+
) +H
hyd
(Cl
-
) - H
latt
(1)
= -464 -364 + 905
= +117 kJmol
-1
(1)
(ii) The compound is highly insoluble (1) and the positive enthalpy of solution (1)
indicates that the dissolving process is not thermodynamically feasible (1)
(d) The high concentration of ammonia movew the equilibrium to the right, reducing
[Ag
+
] (1) The equilibrium AgCl(s) = Ag
+
+ Cl
-
then moves to the right (1) . If this
moves far enough all the AgCl goes into solution. (1)
5)
(a) A strong acid fully dissociates into ions (1) a weak acid only partially
dissociates.(1)
(b)(i) pH = -log (0.15) (1)
= 0.82 (1)
(ii) pH = 1/2(pK
a
- log[A]) or derived from K
a
expression (1)
= 1/2(4.87-(-0.82) (1)
= 2.85 (1)
(c) (i) curve : starts at pH 2.85 (1)
sharp rise after addition of 25 cm
3
alkali (1)
mid-point of sharp rise at pH~8.5 (>7) (1)
pH 13.2 after addition of excess alkali (1)
(ii) phenolphthalein - it changes colour in the pH range 8 - 10 suitable for a titration of
a weak acid with a strong base.
(d)

acid
salt
log pK pH
a
(1)

acid
salt
log . 87 4 5 (1)
UPCSE chemistry 2006 mark scheme - 4 -


13 0.
acid
salt
log (1)


71 0.
acid
salt
(1)
since concentrations are the same, volume of salt = 0.71 x 50 = 35.5 cm
3
(1)
6)
(a) chlorine gas (1) UV light (1)
(b) nucleophilic (1) substitution (1)
(c) warm (1) with acidified potassium dichromate solution (1)
(d) Benedicts (1)- blue solution to red precipitate (1)
or Tollen's (1) Silver mirror formed on heating colourless solution(1)
(e) NaBH
4
or LiAlH
4
(1)
(f) (i) chlorine (1) and iron/iron(III) chloride catalyst (1)
(ii) electrophilic (1) substitution (1)
7) (i) first order (1)
(ii) first order (1)]
(iii) rate = k[[C
4
H
9
Br][OH
-
] (1)
(iv)
1 3 1 4
10 28 1

s dm mol .
OH-] [[C4H9Br][ [
rate
k (1) units (1)
(v) bimolecular (1)
(b) unimolecular (1)
(c) slower, (1) C-Cl bond is stronger, (1) therefore the reaction would have a higher
activation energy (1)
8) (i) C H O
41.4/12 3.4/1 55.2/16 (1)
3.45 3.4 3.45
CHO (1)
(ii) CHO = 29; 116/29 = 4 (1) hence C
4
H
4
O
4
(1)
(iii) carbon carbon double bond
(iv) carboxylic acid
(v) 2.90/116 = 0.025 moles; 0.0025 moles in titration
UPCSE chemistry 2006 mark scheme - 5 -
n
NaOH
= 0.050 x 0.10 = 0.005 ` (1)
therefore one mole acid reacts with 2 moles alkali, therefore two acid groups (1)
(vi) cis and trans butenedioic acid (2)
9) (a) (1)
(b) curly arrows from H
+
(1)
intermediate cabocation (1)
curly arrow from Br
-
(1)
product formed (1)
(c) tertiary (consequential on (a)) (1)
(d) (i) colourless gas evolved /sodium dissolves (1)
(ii) acidic fumes evolved (1)
(iii) no reaction (1) (or consequential)
10
(a) (i)
2
2
3
2
2
SO
O
p
p
p p
K
SO

(ii) partial pressure = mole fraction x total pressure (1)


(or pressure gas would exert if it occupied to container on its own)
(iii) if n
SO3
= 0.25; n
SO2
= 0.75 n
O2
= 0.75/2 (1)
n
total
= 1.375 (1)
p
SO3
= 0.25/1.375; p
SO2
= 0.75/1.375; p
O2
= 0.375/1.375 (1)
K
p

p
SO
2
2
p
O
2
p
SO
3
2

(0.75/1.375)
2
(0.375/1.375)
(0.25/1.375)
2
2.45atm(1) (1) for units
(b) (i) K remains the same (1)
(ii) increasing pressure sends equilibrium to the left, (1) to the side with fewer
molecules (1) so increase percentage of sulphur trioxide
(iii) increasing temperature moves equilibrium in endothermic direction (1) to give
more sulphur dioxide (1)
(iv).amount of catalyst would not affect position of equilibrium (1)
Br
UPCSE chemistry 2006 mark scheme - 6 -
Section B question 1
(a) e.m.f. of a cell with sstandard hydrogen electrode as left hand electrode and
electrode in question as right hand electrode. (1) Standard conditions are 1 mol dm
-3
concentrations for solutions, 298 K and 1 atm pressure of hydrogen gas (1)
(b) It is not possible to measure the effect of a single electrode since two electrodes
are needed to form a cell. (1)The reference cell is required so a common comparison
can be made. (1)
(c) (i) Ag|Ag
+
||Au
3+
|Au (1)
E
cell
= E
right
- E
left
= 1.41 0.80 = +0.61V (Au positive electrode) (1)
(ii) 3Ag + Au
3+
= 3Ag
+
+ Au (1)
from sign of emf (1) equilibrium lies well to the right (1)
3Au
+
= 2Au + Au
3+
(1) E
cell
= +1.69 1.29 = +0.40 (1)
Au disproportionation reaction is feasible
(c) (i) number of electrons lost by an atom of an element (1)
(ii) n
TlI3
= 0.585/204 + 3 x 127) = 0.01 (1)
n
AgI
= 0.235/(108 + 127) = 0.01 (1)
therefore one TlI
3
releases one I
-
(1) therefore Tl must be in +1 oxidation state
(iii) I
2
(I 0) is oxidizing agent, (1) oxidizes Tl
+
to Tl
3+
and is reduced to I
-
question 2
(a)
(i) IR produces excitation of vibrational energy levels (1) different bond types absorb
at different frequencies (1) frequency of absorbtion can be used to identify particular
bond types (1)
(ii) carbonyl (1)
(iii) no strong absorption at 3100 3300 cm
-1
(1)
(b) (i) parent ion is ion formed from molecule without fragmentation (1) 150 (1)
(ii) 107 (1) 43 (1) CH
3
CO (1)
(iii) C
6
H
5
+
(1)
UPCSE chemistry 2006 mark scheme - 7 -
(c) (i) shift in resonance frequency (1) due to (magnetic field of circulating electrons )
of chemical environment (1)
(ii) 2ppm CH
3
C (1) 5ppm CH
2
O (1) 7.3ppm C
6
H
5
(1)
(d) C
6
H
5
CH
2
OCOCH
3
(1)
benzene ring from mass spec, IR and nmr
CO from IR no OH suggests ester
Benzyl from mass spec (2)