CONFIDENTIAL • 2

Section A [40 marks]

Answer aU questions in this section

1. (a) The yellow gas, chlorine dioxide, CIOz, has been used for many years as flour-
improving agent in bread-making. It can be made in the laboratory by the following reaction.
2AgCI03(s) + Clz(g) , 2AgCI(s) + 2CI02(g) + Oz(g) ~H = 0 kJ
(i) Give the oxidation state ofCI in CIOz. [1 mark]
.

...................tt ........................................................................1. .................. .

(ii) Chlorine dioxide disproportionates to fonn a mixture of chlorate(III) and chlorate(V) ions in
alkaline solution. Write a balanced equation to iIlusbate the reaction that occurs. [1 mark]

... ?; .Cl.9~ .. j {.~ B. ~ ............ ~........~. ~ ~.~ ...... ~ ... ~ !.? ~ ...... i .... ~ .~ .. / ........j. ..... .
t
(iii) Given that the standard enthalpies of fonnation of AgCI03 and AgCI are -25 kJmor and
-127 kJ mort respectively, calculate and comment on the value of the standard enthalpy of
fonnation of chlorine dioxide. _ zs
- . 4.
;> CJ O.3(r) - - ( j j . [4 marks]
A,
\
~
S (j;)~) - - --- Q

(I)-f~.@ * C1?(~) _-7

O.
-( ?CIO~ -{;);>~ - @ J
-
Ov'V-a/ Pa(J..c;.d ;01-0
l
~ C 111 .
:l:l. + 01 > ~ (-15)-+ 0 - (-127)
c -+ I (:) 1 Ie J Vl-1o ( -,

Comment: ..... t~ ...... ~? ........ g~....... ~f.\ ~~ .l.~. ~~.~: ~ . . . . .~ f.-f!. 0.(? rJ.; ...... .~ ................................................ ~ . . .
.. .. .. .. . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. . .. .. .. .. . . . .. .. .. . .. . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .................................................................... .

(b) The standard electrode potentials of the following systems are given below:
Systems EO / V
CI02(aq) + 4H\aq) + 5e ~ cr (aq) + 2H20(l) + 1.50
S(s) + 2W(aq) + 2e ~ HzS(aq) +0.14
By using the standard electrode potentials given above, predict whether chlorine dioxide in an
acidic solution reacts with aqueous hydrogen sulphide. Give your reasoning. [4 marks]
L.il'·'tl r r Cl07 \11.0) Jl'w.\.-{l f "sH'IYe (C \j o/u.e
[.. LV-\:' 'c (aijo.() c;ll. - t" a~ 4 ,
+~" f..,~ u;f~ v<~J0 tr~v1c11 c""
-- +'.50 - {+o,14)/
wh,le U"S v(,11 ()y1~O
+ ,,3, V /
,
v~jHlY)

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*This question paper is CONFIDENTIAL until the examination is over CONFIDENTIAL *
CONFIDENTIAL • 3
2. Part of the process by which coal can be converted into a combustible mixture of gases
involves passing steam over white hot coke.
H20(g) + C(s) ~ H2(g) + CO(g) M1= +131 kJmorl
(a) For the reaction above, write an expression for the equilibrium constant, Kp.
~ p. [1 mark]

············ .. ~f...".... fu~~.~~.......................... ......................................................... (

(b) The system above is in equilibrium. State how the value of Kp and the equilibrium position
would be affected when [6 marks]
(i) the pressure of the system is increased .

.. J~....~~r. \\ ~r. ~~.~... X~~ (( .... ~k~f-!-....1.'?~.~..... ~0.:~P.'.~~ ... i~ ..... (f!~............. (

(ii) the tempemture is increased .

.T~ ...~\.I!.I: ?~~.~ Yr. .... ~~IJ~.... ! 9 .. ."7!:t ... .eJ': s:!~.!0.~. ~(.c; .. f': f?.cf! ?!". ;..E::rt.lf: ~ ~ .~........... .
.$h~ ~'.f,~ ....-f.~ ....~... ~1~:t1f:' _. Vr.... ~~. ~r.~.:........ .............................. _.... _. __ .... .
(iii) some carbon is added to the system. 1-
- y h'-' -
.~ ....~Ut k9.~V.~ ... shlifi... .19... ~r.~. ... -_. _kp.. ...;.I1.Y:.~-~~XeJ': ... ___ ... _. _....... ____ .____ '" __
/)
•••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••

(c) When steam was passed over coke at 700 °c, at equilibrium, the partial pressure of water
3
vapour was found to be 80 kPa and the equilibrium constant, Kp, was found to be 180 x 10 Pa.
Calculate the equilibrium partial pressure of hydrogen gas and carbon monoxide gas at 700°C.
[3 marks]
-+ C u) -:;:::"=~I (~) -f u.
Pl,j1 pco l
"
J /.I) -:- ~ ?(

XC" :>~ {.-;>( --

I QO x (0 ~ ;; -"----::
~ 3
x (0
~Ih 'f(~;: \' ~'+ )C [0
10
l;Va r
1 c
-[ ;( ( !. ;;E) :- /. U- 4 X lo (0

~ '7t- x:. \-'1. i- \0 ~ 5

~ H<::: 9(~ -:: \.1 y: \0

7
p~
• PO \cPo..
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CONFIDENTIAL • 4
3. (a). In the industrial preparation of aluminium from naturally occurring bauxite, the
following route is employed:

INSOLUBLE RESIDUE

IMPURE NaOH
BAUXITE

SOLUBLE INSOLUBLE
ALUMINIUM ALUMINIUM
COMPOUND A COMPOUND
added
B

ALUMINIUM el ELECTROLYTIC REFRACTORY ,

MELT COMPOUND
C
D

i. Give the of each of the compounds A, B, C, and D.

A: .......... ~.\... ~.~.~~.~................~.............................................................................................. .

B: ......... ~.1. W.H1. :. ~. ~...S. ~1.:?) .. ?:. ............................................................................................

c: .....~.\~.~.~~~~ ...........................................................................................................................
D: ........ (.%9.\\~.~......... _............................................................................................................ .
ii. What type of chemical bonding would you expect to be present in the reftactory compound
C? [5 marks]

.............. ~~.~~~.... ~r)~t~........................................................................................................

(b). (i) Draw the structure and name the shape of the hydrated aluminium ion. [2 marks]
O~ .-
Structure: \
,
A\
~: ;/ fj/ \ ~ ot
~ DI1

,
~~fl=='
~~~: ..•..••.•..•.•..•. .
.... ...... ~ ..... . ..~ ..... ~~.~!:.~~.~ ...........................................................

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CONFIDENTIAL • 5
ii. Write an equation to show the hydrolysis of the hydrated aluminium ion in water.

............... ~J.(~~h......... i .... .~:.~ .............?...... L~.~~~~!.~.~ .... ~ ..... --H..~................. ~.~.~.l_~~~~ .....
(c) Give one physical property of the aluminium metal and state one use of the metal related to
this property. [2 marks]

~~..:::..~~ .....~.~ ....~~~.~.... I~ .... ~~l!1.~

......~f?)~ ................................................................... .
Use: ...................Q.~...... ~.~ ... .. y.e.~ \-!.u~

o /

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CONFIDENTIAL • 6
4. (a) Write the structural formulae of the products fonned when the following compound
OH
I

reacts with

(i) sodium metal [1 mark]

01./

~ ~ ~
c - c ~C -0"1 •

~ ~ ~

(ii) sodium hydroxide solution [1 mark]

•
04
H
i
'"
I I
it
Cpj-( - c.: - OM
I I I
L./ WI J;1

(iii) ethanoic acid in the presence of concentrated sulphuric (VI) acid and wanned.
[1 mark]

(iv) dilute nitric(V) acid [1 mark]

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 CONFIDENTIAL • 7
4. (b) Write the structural formulae of the following compounds.
(i) P, CSHIOO, reacts with phosphorous(V) chloride to release white fumes ofHCI and
forms iodoforlIl with alkaline iodine solution.
(ii) Q, CSHIOO, reacts with phosphorous(V) chloride to release white fumes ofHCI and
forIllS dicarboxylic acid when oxidised by acidified potassium manganate(VII) solution.
(iii) R, C4Hs~, which after hydrolysis with dilute acid, produces an alcohol which gives
a positive iodoforIll test, and a carboxylic acid which can decolourise acidified potassium
manganate(VII) solution.
(iv) S, C3H7NO, does not react with cold aqueous sodium hydroxide but liberates
ammonia when the reaction mixture is heated.
P Q
011
I 4 ~I
0\ c-
, (I,b I .

,
u-( J
0 >-C'- 0
\-\ ~ ~ ~

R S
•
1,I
I
11 , Q
II ~ ~
0
II ~
I'! - C- C - 0- c -/1 \
.'~-L-C-(
_N -t1
I I I
/
H
lJ- C-~
I
J \...\
I
11

[4 marks]

(c) o CHO

T u v ,
~- /

Which of the the above compounds can be converted to

OH
I
o
•

>-CH2-C-COOH
/ I
/ CH3

(1·)
v
•••••••••••••••••••••••••••• •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• ••••••••••••••••••••••••••••

[1 mark]
(ii) Write the structural forIllula of the intermediate compound.
J.,.1 0 l.f H
[1 mark]
\ 1 f.
o (-C-c-/,J
- \ \ I

H eN Y
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 CONFIDENTIAL· 8

Section B [60 marks]

.Answer any four questions in this section.

•
5. (a) Chlorine consists of two isotopes, 35CI and 37CI in the abundance ratio of 3: 1.
Apart from the lines due to atomic ions, the mass spectrum of a chloride of phosphorus contains
9 lines arranged in 3 groups. The sample consists only phosphorous-31.

Group mle value

A 66,68
B . 101,103,105
C 136,138,140,142

(i) Give the fOlmula of the single ion responsible for the lines fOlllled in Group A, Group B and
Group C. [3 marks]
(ii) Give the fOllllula of the ion responsible for the lines formed at mle 136, 138, 140 and 142.
[4 marks]
(iii) Predict the abundance ratio of the various mle values shown in Group C.
[2 marks]
(b) (i) Give two reasons why Xenon shows the greatest deviation from ideal behaviour
compared with other elements in Group 18. [2 marks]
(ii) State two conditions when real gases behave almost like ideal gases. [2 marks]
3
(iii) At a temperature of 300 K, 2.79 g of a mixture of gases occupies a volume of 1.00 dm at a
4
pressure of 8.0 x 10 Pa. Calculate the average relative molecular mass of this mixture of gases.
[2 marks]

6. (a) A student on a field trip investigates some disused lead workings which have been
flooded for some time. The presence of lead(II) ions in the water is to be demonstrated by
precipitating yellow lead(IJ) iodide.
(i) Write an expression for the solubility product oflead(II) iodide. [1 mark]
9
(ii) At 15°C, the solubility product oflead(H) iodide is 4.0 x 10- moedm-9 • Find the solubility of
3
lead(II) iodide in a 0.20 moldm- solution of sodium iodide solution at the same temperature.
[2 marks]
(iii) If an equal volume of the water from the flooded lead workings, and potassium iodide '
3 3
solution of concentration 4.0 x 10- mol dm- , are mixed at 15°C, determine the minimum
concentration of lead(II) ions which might be detected in the flood water.
[2 marks]
(b) Trichloromethane (b.p = 61.2 0c) and propanone (b.p=56.4 0c) fOlll1S an azeotropic mixture.
The azeotropic mixture has a boiling point of 64.7 °c and contains 80% by mass of
trichloromethane .
•

(i) Explain why a mixture of trichloromethane-propanone does not f01'1I1 an ideal solution
[4 marks]
(ii) Sketch a vapour pressure-composition phase diagram for the trichloromethane-propanone
system. [4 marks]

(iii) What is obtained when 20% by mass of trichloromethane is fractionally distilled ?

[2 marks]
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 CONFIDENTIAL • 9
7. (a). Explain how the following changes down Group 2 (beryllium to barium) of the
/Periodic Table. Write equations for the reactions involved.
(i) Reactivity towards water [3 marks]
(ii) Thellllal stability of the nitrates [5 marks]

(b) Some properties of two substances X and Yare given below. Identify each of these
substances and explain the chemistry of the reactions involved.
(i) X is a colourless aqueous solution that leaves no residue on evaporation. It forIns a
blue solid with an aqueous solution of copper(II) ions, and upon excess turns into a deep blue
solution. [4 marks]
(ii) Y is a compound of Group 14 elements, which exists as a colourless liquid at room
temperature. It is stable to heat even at high temperatures. It reacts with water to fonn an acidic
solution. [3 marks]

8. (a). Why does cobalt show variable oxidation states? [3 marks]

(b) What do you understand by the tenn complex ion? [4 marks]

(c) A complex compound, triammminetrichlorocobalt(III) exists as two isomers.

( i) What is the chemical fOllllula of triammrninetrichlorocobalt(III)?
[I mark]
(ii) Draw the structures of the two isomers and name them. State the type of isomerism
shown.
[5 marks]
(iii) Explain what happens when an aqueous solution of silver nitrate is added to an
aqueous solution of triammrninetrichlorocobalt(III)
[2 marks]

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 CONFIDENTIAL • 10
9. (a) Carbonyl compounds react with hydrogen cyanide to fonn cyanohydrins. Starting
from a suitable carbonyl compound of your choice, and using a cyanohydrin as an intermediate,
devise a 3-stage synthesis of compound B.

CompoundB

Suggest reagents and conditions for each step, and draw the sb uctural formula of every
intermediate compound. [6 marks]

(b) Compound K, C4H 1002, reacts with sodium metal but is insoluble in aqueous sodium
hydroxide. On treatment with hot acidified sodium dichromate(VI), K gives L, which is soluble
in aqueous sodium hydroxide. L can also be formed from fumaric acid, H02CCH=CHC02H, by
treatment with hydrogen over a nickel catalyst. Compounds K and L can be co-polymerised to
produce a polyester. Identify K and L and explain the above reactions.
. [9 marks]

, 1'6. (a) The compound 4-ethylphenol, E, and chlorinated products derived from it have useful
antiseptic properties.

-OH

E
Depending on the conditions of the reaction, compound E can react with chlorine in two
different ways, giving the two isomers F and G. In these reactions chlorine reacts in a similar
manner to bromine.

I II
CgHgChO .. E CgHgChO
F G

Compound F reacts with NaOH(aq)to give H, CgH1003, which immediately loses water to give
J, CgHg~. Compound J is insoluble in water but it dissolves in NaOH(aq). It reacts with 2,4-
dinitrophenylhydrazine and with alkaline aqueous iodine, but not with Fehling's solution.
(i) Identify and draw the structural formulae of compounds F, H and J. Explain the reactions
described and write equations where appropriate. [11 marks]
(ii) Suggest a structural formula for G. [1 mark]

(b) Describe one reaction which could be used to distinguish aniline from phenol.
[3 marks]

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*This question paper is CONFIDENTIAL until the examination is over CONFIDENTIAL *
 NO:..... .. DATE:
----

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