CONFIDENTIAL* 2

SectionA [40 marks]

Answerall the questionsin fhissecfion.

composition
1. An orlanicacidhasthefollowing by mass'
C, 4O.OW 6.7%; .O' 53*3%'
-H,
ion)at the followingm/e
ItsmassspectrumshowErrjor pea'kt(inc[idingthe molecular
v a l u e s1:5,43 ,4 5 ,6 0 .
(a) (i) Calculate of the acid'
theempiricalformula [2 marks]
O
F\er"en\
ril
r)
&t #lr '
6'1 17i
pffo 3'13
*L r\
".l' zl
<
^p(eCi,,
Ir - \J
"
Srt'r^^y'
:. eqgdcat
formula'
to suggestits molecular
(ii) Usethe massspectrum [1 mark]
(cH"Q\=60
Qdn --oo
h:Z -Sr*u\q\9 C.Hl.0i
| . rno\ecrr\qn
t'/ (

(b) By suggestingtheirmolecular for the

formulae,identifythe sqgclgswhichis responsible
H-t*-Ofl [2 marks]
-
fottowingpeaksin the massspectrum.
"' *
^. ..^ Qctlrco) ,/

(c) (i) Whenmeasurements massof the acidin an

aremadeof the relativemolecular
for this
suggestan explanation
organicsolventlikepentane,a valueof 120is obtained.
observation.
-n* S,ojqqdd&*s in\end3rotlhdqsntsrdnq
+*=*tenr\s,- (d'*f,sN'e\g{ clHGdH)K - "ifitl

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CONFIDENTIAL* 4

formulafor the speciestonqO

(ii) Drawa displayed
SR ^i g-u Qa'--'iry:,,
..'?:i
H,5-'l-o-*r X ctk-c.ou
,r-*tt{:
r'\ t-l-ftt .
'
in waterandmadeupto 100cmt,the
(d) When1.00g of the pureacidis dissolved
thedissociation
pH is 2.55.Calculate
resulting K" of the acid.
constant, [3 marks]

?H--).ss ar(an\ddo"
* LW
\hQ add *
Y1r2
tH-l= 1p-2's5 = t4 -^, - W,t
SA-i
[ml'-''*t"tdt .ffifn
ffi ,,
thl.W- =016l^ "V-7
^
x.a= Ci'ttxratl
I'.
6lffidrn_1
-/

Ka=q-"r6xt01ry\4il 1/

2. (a) Define
tc\sa+A
-\*d.
(i) FirstelectronaffinitY {f
^/--
\s_ihe edih$l
"": J
gMS
E^ eldtun {" $nn q-): (
il ,^,rKS'q.vqsqhlet
affinity-\*A
(ii) Secondelectron qb$fo

\s {q $hqb\ drqnooo[ neqd{tt^

u'\en a
" " "t |"- f " "' " " c t : " " 'j " " " '
t: ftcr\
chqvrdlfl (X-) 1qd's9t gp(frnn

thefirstandsecondelectronaffinityfor an oxygen
(b) Writethe equationto represent
atom.
t g- ) 0 .S$...-...../
Firsterectronarrinity,....Q..$)
0.:.S.S)+{ )
seconderecrronarrinity, O-SC ?
/
[2 marks]

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CONFIDENTIAL-

(c) Thefirstelectron
affinity
for oxygenatomis -141kJmol-1
whereasthesecondelectron
affiiityforoxygenis +798kJmol'1.Explain
whythefirstelectron
affinity
is exothqrmic
while
thesecond etectron
affinity
is endothermic. tk<\^n \tGn&t(U)tz marrsl
1t( S.* eldro ct+{l'\nl
S edlqrnlckcry5pt\ea\[UerUH,
whe( on
€te!-nti qdids 4bgn,
su;'dd"il q$t{U
1ie'urtrr*r.
wh1.qr e\edr.on
buqnsn t o l.s{Nqsogd igls,
k 3ddgal
{l€r? t tii {Aflrio,r) -tt"r€kd*"
5qh"€eh r
(d) IntheContactProcess,
sulphurdioxideis changed
to sulphurtrioxideaccordingto the
reaction below;

4500c
+oz(s)
2so21g1 # 2so31s1 A H = -189kJ mol-1

(i)t/rite for the reactionabove. [1 mark]

Kt-ffil tF$l9-oression
/ I
(ii) Dsggllbethetemperature
andpressurerequiredto shiftthe equilibriumposition
(Rpkrt'r\
forwaro. [2 marks]
"'
ar\d tru terr\prrq\n.
hrq\ PTesgtnr
"l .' ' './" "' " '" ' "' "f
t

(iii) Usinga 'dot-cross'

diagram,
drawthestructure
of sulphurdioxide. [1 mark]

S\x"
tAs;G/ ,p.. v"
5 'hv V
qv
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CONFIDENTIAL-

3. (a)(i) Complete configuration

the electronic andits ionsin thefollowing
of manganese
[3 marks]

3d

Mn
1 1 1 1 1
Mn2* 1 1 1 1 1.
Mn3*
[];

1 Q- V'("'i!
(ii)Explainthe relativestabilityof Mn2*ion and Mn3*.,ion. I lZ marksl
>'[ ^, ..( 't\an \ rn flr\ | q r l.iT\
fY\n'*\s
" nror?
Me
rt ., .,n^ zf
CIA.* -
$nce
,^- *t
tA',lhosq. hq\$4\\ed Ug6\\
t,ri. ;;,";,i,;;";";;.;;;; r,,i,,ion,J;,
;;";;,.,",.;^;;;;H
for the colour?
responsible [1 markl
rntit foh}, ,{ (MnQro)*
(b)Thedecomposition of nitratesof Group2 elements(beryllium
temperature to barium)is
shownbelow.

Nitrate Be(NOg)z Mg(NO3)2 Ca(NO3)2 Sr(NO3)2 Ba(NOg)z

Temperature/K 320 390 460 670 820

) nrhqtsq

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CONFIDENTIAL*

4. Consider
thefollowing
reaction
scheme:

(A )
CaHeBr

KOHin alcohol
Reflux

c4Hloo ( B ) c c Ha (D)

Oxidation HBT

(C)
C+HeOz C+HgBr( E )

Compound A doesnothavea chiralcarbonatom.CompoundC producescarbon

dioxidewhenreactedwithsodiumhydrogencarbonate
aqueoussolution.
Compounds
B andC willreactundersuitable
conditions.
Compound
E exhibits
opticalactivity.

(a) Drawthestructuralformula
for compounds
A, B, C andD. [4 marks]

\ H $ r{ \-\I
F\-C-q-c*(*r-,r '-\ t J!_
H-!-C,
t\\\hL" h n \^yy r'
/

Compound
A Compound
B
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CONFIDENTIAL-

a \1 lt' F lil

$L C-O-\{

/
\-{-c-GC=i-H
J
'\ ./
,..
Compound
C Compound
D

tt *:,l" ti{"itins
unitrorthe
porvmer,?''T
tpry"'oound
D.

t,!,-.=[$^
n*Gh
[1 mark]

(c) (i) Namethe mechanism

involved
fortheconversion
of compound
A to
compound B.
,,- [1 mark]

(ii)statethe suitableconditions
requiredto to
gnvertcompound,B
comPound
c'
qg&tud ,/
| t marksl
Reasent:
, ...;.Kflt'0.'A . .- ..:...
condition:
,ffi teftlyZ t
(d)(i) Drawthe optical
€uisomers
ruuruels
for
rorComp
uompound
E. [1 mark]
fl
.'Ct.
c\a\i 'cHr
n ,l
|\)c- "t-cn,cf\3
A A A
{ . q E',/
(ii) Namethe mixturethatcontainsequimolar
quantities
of opticalisomers
ison butis
optically
inactive.
[1 mark]
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 CONFIDENTIAL* t4

SectionB [60 marksl

Answeranyfourquesfionsin this section.

s' i"l Giveanaccount

fortheformation
of lineemission
spectrum
of hydrogen
atom.
How can the ionisationenergyof hydrogenatom
be determinedfrom the line
emissionspectrum?
[6 marks]

(b) Thefrequencies,
f of the linesin the Lymanseriesof hydrogenspectrumaregiven
by theexpression
below.

f =cRuf1-1)
' \ 1'
nt)

wherec is thespeedof light, RH= 1.0g7x 107m-1and

n is an integer.
Thefrequencies of thefirstfourlinesin the Lymanseriesof the linespeclrum
of
hydrogen are:
2 .4 6 ,2 .9 2,3.09,
3.16 ( x 1015
Hz)
By usingthe expression
givenabove,plota suitablegraphto determine
the
ionization
energyof hydrogenin kJ mol-1.
[5 marks]

(c) Givetwo important

informations
thatcanbe obtainedfromthe linespectrumof the
hydrogenatom.
[2 marks]

(d) statetwo differences

betweenthe Lymanseriesandthe Balmerseries.
[2 marksJ

6. (a)(i) Definethetermstandarderectrode
potentiar.
[1 mark]

(ii)Usingthe DataBooklet,statethe celldiagram

andthe standardelectrode
potential
valuesfor thefollowingreactions:
Fe1"y + Pb2*1"q1 ---+ Fe2*1"qy+ pbt.l
and
2H'(aq) + Zn61 '-- Zn,*Gq) + Hz<s)

[4 marks]

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 CONFIDENTIAL"
16

(b)Predicttheproductthatwouldbe
obtainedfromthe etectrolysis
of thefollowing
aqueoussolutionsusingptatinum
electrodes: r{\
(i) Coppe(lt)chtoride
(ii) Hydrochlor.ic
acid
(iii) Potassium
hydroxide
[6 marksJ

(c) An industrially
importantsourceof hydrogenis the reaction
below:

CH{sl + 2H2O1e1 *, COzrsl+ 4HzGt

Usetheenthalpychangesof combustion
shownin the tablebelowto construct
an
energycycreanduseit to carcurate
the entharpy
changeof thisreaction.

Enthalpy
changeof combustion
,
AH" / kJmol-l

[4 marksJ
7. (a)(i) statethetwoindustriar
stagesof preparing
nitrogengasfromair.

(ii)what factorenablesthe separation

of oxygenandnitrogengasespresentin
the
atmosphere?
[3 marks]
(b)(i)when brownNoz(g)is cooled,
colourlessNzo+(9)is formed.A gassyringeis filled
withNo2(g)andthe endsealed.when
the gasis compressed,the browncorourfades.
Warmingthe syringerestoresthecolour.
\ Explainthe observations
described.
[3 marks]
(ii)suggesthowNoz is formedin
a carengineandhowit maybe removed
from
exhaustgases.
[2 marksJ
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CONFIDENTIAL- l8

q0
v:)?..
(c) At temperature
of 320K anda pressure of 1.0x105Pa,0.50g of thegaseous
d{"1]
No2/N2o4 mixturetakesup a vorumeof 190cm! o'*9
Calculate
theaveragerelative molecular Giveyouranswer 0'\%7"
massof themixture.
correctto 3 significant
figures. [2 marks]

(d) Theequation
for the decomposition pentoxide,
of dinitrogen NzOs,
is as shownbelow.

NzOu(9) -+ 2NOz(g)+ Y,OzG)

Thereaction
aboveis a firstorderreaction
andthe half-life
is 2.7x 103s.
(i) Writethe rateequationfor the reaction.
(ii) Determinetherateconstant.
(iii) Determine
therateof reaction
whentheconcentration
of NzOsis
3.1x 102moldm-3. [5 marks]

8. (a) Discusswith equationswhat happensin eachof the experimentbelow.

(i)Aluminium chloride is addedto watercontaining

a fewdropsof methyl
orangeindicator.
(ii)A strongalkaliis boiledvigorously
in an aluminiumpot. [7 marks]

(b)Givetwousesof aluminium
andrelatetheusesto itsproperties [4 marks]

(c ) Explain
whyan aqueous
solution
of ammonia
doesnotcontainNHooH
molecules. [2 marks]

(d)Writean equation
to showthe roleof ammonia
as a
(i) base and
(ii) complexing
agent [2 marks]

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CONFIDENTIAL- 20

9. (a) Methylbenzene
reactswithchlorineundertwodifferentsetsof conditions
to give
compound
A or compound
B.

ra
Y
fn,

cl
A
6' B

(i) Describetheconditions
usedto produce
A andB respectively.
(ii) Describe
a reaction
bywhichyoucoulddistinguish
between
A andB. Statethe
reagents
andtheobservations
witheachcompound. [5 marks]

(b)Duringaromaticsubstitution,
theposition
of theincoming group,the neWsubstituent,
is determinedbythe natureof thegrouparreadypresentin thering.
Usethisknowledge to devisetwostepsyntheses of 3-nitrobenzoic
acid,startingwith
methylbenzene.
ldentifythe reagentsat eachstep,anddrawthe structural
formulaeof the
intermediates.
[3 marks]

(c)Benzocaine
canbe synthesized
from4-nitrobenzoic
acidin twostages.

PooH cooH
PoocH,cH3
rb
>a
c
--------) lol
-^t.
DrA
---.---+Y
NO,
YNHz
NHz

Suggestreagents
andconditions
forstepsC andD. [3 marks]

(d)Foreachof thefollowing
compounds,
describe
onesimplechemical
testbywhichyou
coulddistinguish
it frompropanone,
CH3COCH3.
(i) methylethanoate, CH3COOCH3
(ii) propanal,
CH3CH2CHO.
Foreachteststatethereagents
youwoulduse,andtheobservations
youwould
makewitheachcompound undergoing
thetest.
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CONFIDENTIAL* 22

10.Thestructure
belowshowspartof a proteinmolecule.

---- NH --- cH ----- CO -*- NH --__CH___-co ----NH----CH-__CO_-___

CHz
7 I I
CHz CHz
I I I
OH cooH CH,
I
CH,
I
CH,
I
NHz

(a) (i) Statethe reagentsandreactions

conditions
neededto hydrolpethisproteininto
aminoacids.
[2 marks]
(ii)Drawthe structurefor all THREEaminoacidsformed
whenthisproteinis
hydrolysed.
[3 marks]

(iii) statethe specificteststo differentiate

eachof thethreeaminoacidsfromone
another.
[6 marks]

(b) Electrophoresisis usedto separatea mixtureof aminoacids.Theelectrophoresis

cellconsistsof a cathodeandan anode.To whichelectrode wouid'aphenylalanine
ionmovewhenit is placedin a solution of
( i ) pH =1

( i i )p H= 1 3
[4 marks]

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